JP2001026506A - Sulfonamide derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agricultural and horticultural microbiocide useful as a controlling agent for blast, or the like, of rice plants by including a specific safe sulfonamide derivative having microbiocidal actions, slight influences on mammals, natural enemies and environments and excellent controlling effects even on chemical-resistant microorganisms. SOLUTION: This agricultural and horticultural microbiocide is obtained by including a compound represented by the formula (A1 is an aryl or a heterocyclic ring; X1 is a chemical bond, methylene or vinylene; B1 is a five-membered heterocyclic ring or a condensed heterocyclic ring; Z1 is a hydrocarbon, an acyl, or the like) or its salt. The compound is obtained by reacting a sulfonylating agent represented by the formula A1-X1-SO2-L (L is an eliminable group) with amines represented by the formula Z1HN-B1 or salts thereof. The resultant compound is preferably uniformly mixed with a suitable liquid carrier or a suitable solid carrier, as necessary, various additives, and the like, to provide a microbiocidal composition, which is then applied to a paddy field, an upland, or the like, by, e.g. treatment of nursery boxes or foliar spraying on crops so as to provide 0.3-3,000 g of the compound represented by the formula or its salt per hectare.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a sulfonamide derivative useful as a microbicide for agricultural and horticultural use.

[0002]

2. Description of the Related Art Conventionally, a large number of compounds having a microbicidal activity have been synthesized and used as microbicides for agricultural and horticultural use, thereby contributing to a stable supply of agricultural products. But,
It is well known that a large number of compounds in a limited range have been used, and thus, a drug-resistant microorganism has been generated and poses a problem. Also, with the increasing demand for safety of chemical substances and influence on the environment, development of safer microbicides for agricultural and horticultural use has been desired. For this reason, search research for a compound having a novel microbicidal activity has been conducted. Attention has also been paid to the biological or chemical properties of sulfonamide derivatives, and many compounds have been synthesized to date.
However, most are synthetic intermediates, pharmaceuticals, compounds or reagents synthesized for elucidation of chemical reactions. Examples of sulfonamide derivatives related to microbicides include JP-A-61-286366 and JP-A-63-286366.
JP-A-239264, JP-A-63-238006, JP-A-63-307851, JP-A-1-15
6952, J. Med. Chem. 1983, 26, 1741, DE1
9725447 and the like have been reported.

[0003]

However, humans and livestock,
Sulfonamide derivatives that have a small impact on natural enemies and the environment, are safe, and have an excellent control effect on drug-resistant microorganisms have not yet been developed.

[0004]

The present inventors Means for Solving the problems] In order to solve the above problems, in order to find compounds having an excellent microbicidal activity, have continued extensive studies for many years results, the formula (I ⁰⁾

Embedded image Wherein A ⁰ represents (1) an optionally substituted aryl group or (2) an optionally substituted heterocyclic group, X ⁰ represents (1) a chemical bond, (2) an optionally substituted A good methylene group or (3) an optionally substituted vinylene group, B ⁰ is an optionally substituted heterocyclic group or an optionally substituted aryl group, and Z ⁰ is (1) an optionally substituted Good hydrocarbon groups, (2)
An optionally substituted acyl group, (3) a formyl group, (4) an optionally substituted amino group, (5) -N = CR ¹ R ² (R ¹
And R ² each represent a hydrogen atom or an optionally substituted hydrocarbon group; (6) a cyclic amino group; (7) —OR ³ (R ³ is a hydrogen atom; A hydrocarbon group, an optionally substituted acyl group, a formyl group or an optionally substituted alkylsulfonyl group) or (8) -S (O) _n R ⁴ (n is An integer of 0 to 2; R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted); a compound represented by the following formula (I ⁰ ) Or a salt thereof, in particular, compounds (I) to (V) described below or a salt thereof have a surprisingly strong microbicidal action,
Moreover, they found that their toxicity to humans, fish and natural enemies was low. As a result of further intensive studies based on these findings, the present invention has been completed.

That is, the present invention provides: [1] Formula (I)

Embedded image Wherein A ¹ is (1) an optionally substituted aryl group or (2) an optionally substituted heterocyclic group, X ¹ is (1) a chemical bond, (2) an optionally substituted A good methylene group or (3) an optionally substituted vinylene group, B ¹ is an optionally substituted 5-membered heterocyclic group (excluding isoxazolyl group) or an optionally substituted fused heterocyclic group The group
¹ is (1) an optionally substituted hydrocarbon group, (2) an optionally substituted acyl group, (3) a formyl group, (4) an optionally substituted amino group, (5) -N = CR ¹ R ² (R ¹ and R
² represents a hydrogen atom or a hydrocarbon group which may be substituted), a group represented by (6) a cyclic amino group, (7)-
A group represented by OR ³ (R ³ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group, or an optionally substituted alkylsulfonyl group) or ( 8) —S (O) _n R ⁴ (n represents an integer of 0 to 2, and R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted). Agricultural or horticultural microbicides containing the compound or a salt thereof,

[2] B ¹ is a 5-membered heterocyclic group in which a ring-constituting atom other than an optionally substituted carbon atom is a heteroatom selected from a nitrogen atom and a sulfur atom, or an optionally substituted condensation The agricultural and horticultural microbicide according to the above [1], which is a heterocyclic group,

[3] A ¹ is (1) (i) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di-C _1-4 alkylhydrazono and C _1-4 A C _1-4 alkyl group which may be substituted with 1 to 5 substituent (s) selected from alkylthio, (i
i) a C _3-6 cycloalkyl group optionally substituted with 1 to 5 halogens, (iii) a C _3-6 optionally substituted with 1 to 5 substituents selected from halogen, cyano and nitro
_2-4 alkenyl group, (iv) C _3-6 cycloalkenyl group optionally substituted with 1 to 5 halogens, (v) 1
(Vi) an optionally substituted _C2-4 alkynyl group,
A hydroxy group, (vii) a C-substituent optionally substituted with 1 to 5 substituents selected from halogen and _C1-4 alkoxy
_1-4 alkoxy group, (viii) formyloxy group, (ix) C _1-4 alkyl- which may be substituted with 1 to 5 halogens.
Carbonyloxy group, (x) C _1-4 alkoxy-carbonyloxy group optionally substituted with 1 to 5 halogens,
(xi) a mercapto group, (xii) a C _1-4 alkylthio group optionally substituted with 1 to 5 halogens, (xiii) a C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens A thio group, (xiv) a C _1-4 alkoxy-carbonylthio group optionally substituted with 1 to 5 halogens, (xv) a C _1-4 alkylsulfinyl group optionally substituted with 1 to 5 halogens (Xvi) a C _1-4 alkylsulfonyl group optionally substituted with 1 to 5 halogens, (xvii) a sulfamoyl group, (xviii) a mono- or di-C _1-4 alkylsulfamoyl group, (xix )

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, hydroxy, C _1-4 alkoxy , Formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl,
Or two optionally substituted amino groups, (xxi) 3
A 6-membered cyclic amino group, (xxii) a formyl group, (xxiii) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, and (xxiv) 1 to 5 substituted with halogens. A C _1-4 alkoxy-carbonyl group, (xxv) C
_1-4 alkylthio - carbonyl group, (xxvi) C _1-4 alkoxy - thiocarbonyl group, (xxvii) C _1-4 alkylthio - thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- - or di -C _{1 -4} alkylcarbamoyl group, (xxx)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxxiii)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
xxviii) a substituent consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group, (xliv) azoxycyano group and (xlv) sulfo group A C _6-14 aryl group which may be substituted with 1 to 5 substituents selected from the group (T) or (2) 1 to 5 substituents selected from the substituent group (T) X ¹ represents a (1) chemical bond, (2)
A substituent selected from C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, halogen atom and cyano;
Or a methylene group which may be substituted two or
(3) a substituent selected from C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, a halogen atom and cyano;
Alternatively, two optionally substituted vinylene groups are represented by B ¹
Is (1) a ring atom other than a carbon atom which is optionally substituted with 1 to 5 substituents selected from the substituent group (T), and is a hetero atom selected from a nitrogen atom and a sulfur atom. 5-6, which may be substituted with a membered heterocyclic group or (2) 1 to 5 substituents selected from the above substituent group (T).
Membered heterocycle and benzene ring or 5-6 membered heterocycle and 5-6
A fused heterocyclic group formed with a membered heterocyclic ring, Z ¹ is (1) (i) (a)
Halogen, (b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f ) Mercapto, (g) C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl, (i) C _1-4 alkylsulfonyl, (j) cyano, (k) C
_1-4 alkoxy-carbonyl, (l) carbamoyl and
(m) 1-5 C-substituents which may be substituted with a substituent selected from mono- or di-C _1-4 alkyl-carbamoyl
_1-6 alkyl group, (ii) (a) halogen, (b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy,
(e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f) mercapto, (g) C _1-4 alkylthio, (h) C
_1-4 alkylsulfinyl, (i) _C1-4 alkylsulfonyl, (j) cyano, (k) _C1-4 alkoxy-carbonyl, (l)
Carbamoyl and (m) a C _2-6 alkenyl group optionally substituted by 1 to 5 substituents selected from mono- or di-C _1-4 alkyl-carbamoyl, (iii) (a) halogen, (b ) Amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f) mercapto, g)
C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl,
(i) a substitution selected from C _1-4 alkylsulfonyl, (j) cyano, (k) C _1-4 alkoxy-carbonyl, (1) carbamoyl and (m) mono- or di-C _1-4 alkyl-carbamoyl. A C _2-6 alkynyl group optionally substituted with 1 to 5 groups, (iv) (a) a C _1-4 alkyl optionally substituted with 1 to 5 halogens, (b) a halogen, (c ) Amino, (d) mono- or di-C _1-4 alkylamino, (e) hydroxy, (f) C _1-4 optionally substituted with 1 to 5 halogens.
Alkoxy, (g) mercapto, (h) C _1-4 alkylthio,
(i) C _1-4 alkylsulfinyl, (j) C _1-4 alkylsulfonyl, (k) cyano, (1) C _1-4 alkoxy-carbonyl, (m) carbamoyl and (n) mono- or di-C
_1-4 substituents selected from alkyl-carbamoyl
5 optionally substituted C _3-6 cycloalkyl groups, (v)
(a) halogen, (b) amino, (c) mono- or di-C _1-4
Alkylamino, (d) hydroxy, (e) halogen with 1 to 5
Optionally substituted C _1-4 alkoxy, (f) mercapto, (g) C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl, (i) C _1-4 alkylsulfonyl, (j) Cyano, (k) C
_1-4 alkoxy-carbonyl, (l) carbamoyl and
(m) 1-5 C-substituents which may be substituted with a substituent selected from mono- or di-C _1-4 alkyl-carbamoyl
_3-6 alkadienyl group and (vi) (a) C _1-4 alkyl optionally substituted with 1 to 5 halogens, (b) halogen,
(c) amino, (d) mono- or di-C _1-4 alkylamino, (e) hydroxy, (f) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (g) mercapto , (H) C _1-4
Alkylthio, (i) C _1-4 alkylsulfinyl, (j) C
_1-4 alkylsulfonyl, (k) cyano, (l) C _1-4 alkoxy-carbonyl, (m) carbamoyl and (n) mono- or di-C _1-4 alkyl-carbamoyl A hydrocarbon group selected from five optionally substituted C _6-14 aryl groups, (2) a C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens, (i)
i) C _1-4 alkoxy-carbonyl, (iii) C _1-4 alkylthio-carbonyl, (iv) C _1-4 alkoxy-thiocarbonyl, (v) C _1-4 alkylthio-thiocarbonyl, (vi) mono- Or di-C _1-4 alkyl-carbamoyl and
(vii) an acyl group selected from mono- or di-C _1-4 alkyl-thiocarbamoyl, (3) formyl group, (4) (a) C
_1-4 alkyl, (b) C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens, (c) C _1-4 alkoxy-carbonyl, (d) mono- or di-C _{1- 4} alkyl-
Carbamoyl and (e) an amino group optionally substituted by one or two substituents selected from mono- or di-C _1-4 alkyl-thiocarbamoyl, (5) -N = CR ¹ R
² (R ¹ and R ² each represent a hydrogen atom or a C _1-4 alkyl group), (6) a 3- to 6-membered cyclic amino group, (7) —OR ³ (R ³ is hydrogen An atom, a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms, 1 halogen atom
_1-4 to five optionally substituted C alkyl - carbonyl group, an optionally C _1-4 be 1-5 substituted by halogen
An alkoxy-carbonyl group, a formyl group or a C _1-4 alkylsulfonyl group optionally substituted with 1 to 5 halogen atoms) or a group represented by (8) -S (O) _n R ⁴
(N is an integer of 0 to 2, R ⁴ is (a) a hydrogen atom, (b) a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms or (c) a C _1-4 alkyl group. The agricultural chemicals for agricultural and horticultural use according to the above-mentioned [1], which represents a group represented by 1 to 5 optionally substituted C _6-14 aryl groups);

[4] A ¹ represents a C _6-14 aryl group which may be substituted with 1 to 3 C _1-4 alkyl groups, X ¹ represents a chemical bond, and B ¹ represents ¹ to 5 halogens. 1-5 selected from optionally substituted C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, cyano, halogen and nitro
Number of which may be substituted with a substituent, a thienyl group, a pyrazolyl group, an isothiazolyl group, an imidazolyl group, a thiazolyl group, thiadiazolyl group, a dioxabicycloctane sign mite group or imidazopyridyl group, Z ¹ is C _1-6 alkyl The agricultural or horticultural microbicide according to the above [1], which represents a group or a C _1-4 alkoxy group,

[5] Formula (II)

Embedded image Wherein A ² is (1) (i) halogen, hydroxy, imino,
Hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono - or di -C _1-4 alkyl hydrazono or C _1-4 optionally C _1-4 be 1-5 substituted with a substituent selected from alkylthio An alkyl group, (ii) a _C3-6 cycloalkyl group optionally substituted with 1 to 5 halogens, (iii) 1 to 5 optionally substituted substituents selected from halogen, cyano and nitro C _2-4 alkenyl group, (iv) C which may be substituted by 1 to 5 halogens
_3-6 cycloalkenyl group, (v) _C2-4 alkynyl group optionally substituted with 1 to 5 halogens, (vi) hydroxy group, (vii) halogen and ₁ to ₄ alkoxy selected from _C1-4 alkoxy. A C _1-4 alkoxy group optionally substituted with 5 substituents, (viii) a formyloxy group, (ix)
5 optionally substituted C _1-4 alkyl-carbonyloxy groups, (x) _1-5 optionally substituted C _1-4 alkoxy-carbonyloxy groups with halogen, (xi) mercapto group, xii) C _1-4 alkylthio group optionally substituted with 1 to 5 halogens, (xiii) C _1-4 alkyl-carbonylthio group optionally substituted with 1 to 5 halogens, (xiv) halogen 1 to 5 optionally substituted C
_1-4 alkoxy-carbonylthio group, (xv) 1 halogen
To five an optionally substituted C _1-4 alkylsulfinyl group, (xvi) a halogen with 1-5 optionally substituted C _1-4 alkyl sulfonyl group, (xvii) sulfamoyl group, (xviii) mono- -Or di-C _1-4 alkylsulfamoyl group, (xix)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, hydroxy, C _1-4 alkoxy , Formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl,
Or two optionally substituted amino groups, (xxi) 3
A 6-membered cyclic amino group, (xxii) a formyl group, (xxiii) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, and (xxiv) 1 to 5 substituted with halogens. A C _1-4 alkoxy-carbonyl group, (xxv) C
_1-4 alkylthio - carbonyl group, (xxvi) C _1-4 alkoxy - thiocarbonyl group, (xxvii) C _1-4 alkylthio - thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- - or di -C _{1 -4} alkylcarbamoyl group, (xxx)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxx
iii)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) halogen atom, (xxxv) carboxyl group, (xxxvi) thiocyanato group, (xxxvii) isothiocyanato group, (xxxviii) cyano Group, (xxxix) isocyano group, (xl)
Azide group, (xli) nitroso group, (xlii) nitro group, (xliii)
An aryl group which may be substituted with 1 to 5 substituents selected from a substituent group (T ') consisting of an azocyano group and (xliv) sulfo group, or (2) a heterocyclic group which may be substituted. , X ² is (1) chemical bond, (2) methylene substituted group or (3) a good vinylene group which may be substituted, an aryl group which may be B ² is substituted, Z ² Is
(1) mono- or di-C _1-6 alkylamino, hydroxy, halogen, C _1-6 alkoxy, C _1-6 alkoxy-carbonyl, C _1-6 alkylthio and substituted with a substituent selected from cyano Alkyl group, (2) vinyl group, (3) allyl group, (4) propadienyl group, (5) optionally substituted alkynyl group, (6) optionally substituted cycloalkyl group, (7 Optionally substituted aryl groups, (8) optionally substituted acyl groups, (9) formyl groups, (10) optionally substituted amino groups, (11) -N = C
A group represented by R ¹ R ² (R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group which may be substituted), (12)
A cyclic amino group, (13) -OR ³ (R ³ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group, or an optionally substituted alkylsulfonyl group ), Or (14) -S
(O) _n R ⁴ (n represents an integer of 0 to 2, and R ⁴ represents a hydrogen atom or an optionally substituted hydrocarbon group)] or a salt thereof. An agricultural and horticultural microbicide containing

[6] A ² is (1) (i) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di-C _1-4 alkylhydrazono and C _1-4 A C _1-4 alkyl group optionally substituted with 1 to 5 substituent (s) selected from alkylthio, (i
i) a C _3-6 cycloalkyl group optionally substituted with 1 to 5 halogens, (iii) a C _3-6 optionally substituted with 1 to 5 substituents selected from halogen, cyano and nitro
_2-4 alkenyl group, (iv) C _3-6 cycloalkenyl group optionally substituted with 1 to 5 halogens, (v) 1
(Vi) an optionally substituted _C2-4 alkynyl group,
A hydroxy group, (vii) a C-substituent optionally substituted with 1 to 5 substituents selected from halogen and _C1-4 alkoxy
_1-4 alkoxy group, (viii) formyloxy group, (ix) C _1-4 alkyl- which may be substituted with 1 to 5 halogens.
Carbonyloxy group, (x) C _1-4 alkoxy-carbonyloxy group optionally substituted with 1 to 5 halogens,
(xi) a mercapto group, (xii) a C _1-4 alkylthio group optionally substituted with 1 to 5 halogens, (xiii) a C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens A thio group, (xiv) a C _1-4 alkoxy-carbonylthio group optionally substituted with 1 to 5 halogens, (xv) a C _1-4 alkylsulfinyl group optionally substituted with 1 to 5 halogens (Xvi) a C _1-4 alkylsulfonyl group optionally substituted with 1 to 5 halogens, (xvii) a sulfamoyl group, (xviii) a mono- or di-C _1-4 alkylsulfamoyl group, (xix )

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, hydroxy, C _1-4 alkoxy , Formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl,
Or two optionally substituted amino groups, (xxi) 3
A 6-membered cyclic amino group, (xxii) a formyl group, (xxiii) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, and (xxiv) 1 to 5 substituted with halogens. A C _1-4 alkoxy-carbonyl group, (xxv) C
_1-4 alkylthio - carbonyl group, (xxvi) C _1-4 alkoxy - thiocarbonyl group, (xxvii) C _{1- 4} alkylthio - thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- - or di -C _{1 -4} alkylcarbamoyl group, (xxx)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxxiii)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
xxviii) a substituent group (T ′) consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group and (xliv) sulfo group
A C _6-14 aryl group optionally substituted with 1 to 5 substituents selected from or (2) (i) halogen, hydroxy,
Imino, hydroxyimino, C _1-4 alkoxyimino,
A substituent selected from hydrazono, mono- or di-C _1-4 alkylhydrazono and C _1-4 alkylthio;
Selected from a C _1-4 alkyl group optionally substituted with 5 to 5 carbon atoms, (ii) a C _3-6 cycloalkyl group optionally substituted with 1 to 5 halogen atoms, (iii) halogen, cyano and nitro A C _2-4 alkenyl group optionally substituted by 1 to 5 substituents, (iv) a C _3-6 cycloalkenyl group optionally substituted by 1 to 5 halogens, (v) 1 to 5 halogens 5 an optionally substituted C _2-4 alkynyl group, (vi) hydroxy group, (vii) halogen and C _1-4 optionally C ₁ optionally substituted with 1 to 5 substituents selected from alkoxy _-4 alkoxy group, (viii) formyloxy group, (ix) which may be 1-5 substituted by halogen C _1-4 alkyl - carbonyl group, optionally be 1-5 substituted with (x) halogen which may C _1-4 alkoxy - carbonyl group, (xi) a mercapto group, a 1-5 substituted with (xii) halogen Optionally have C _1-4 alkylthio group, 1-5 in (xiii) halogen
Optionally substituted C _1-4 alkyl-carbonylthio group, (xiv) 1 to 5 optionally substituted C _1-4 alkoxy-carbonylthio groups, (xv) 1 to 5 halogen pieces optionally substituted C _1-4 alkyl sulfinyl group, (xvi) may be 1-5 substituted by halogen C _1-4 alkylsulfonyl group, (xvii) sulfamoyl group, (xviii) mono- - or Di-C _1-4 alkylsulfamoyl group, (xix)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, hydroxy, C _1-4 alkoxy , Formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl,
Or two optionally substituted amino groups, (xxi) 3
A 6-membered cyclic amino group, (xxii) a formyl group, (xxiii) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, and (xxiv) 1 to 5 substituted with halogens. A C _1-4 alkoxy-carbonyl group, (xxv) C
_1-4 alkylthio - carbonyl group, (xxvi) C _1-4 alkoxy - thiocarbonyl group, (xxvii) C _1-4 alkylthio - thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- - or di -C _{1 -4} alkylcarbamoyl group, (xxx)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxxiii)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
xxviii) a substituent consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group, (xliv) azoxycyano group and (xlv) sulfo group X ² represents a heterocyclic group which may be substituted with 1 to 5 substituents selected from the group (T), wherein X ² is (1) a chemical bond, (2) C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, a methylene group optionally substituted by one or two substituents selected from a halogen atom and cyano, or (3) C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, A vinylene group which may be substituted with one or two substituents selected from a halogen atom and cyano is represented by B
² is a C _6-14 aryl group _optionally substituted with 1 to 5 substituents selected from the above substituent group (T), and Z ² is (1)
1-5 substituted with a substituent selected from mono- or di-C _1-4 alkylamino, hydroxy, halogen, C _1-4 alkoxy, C _1-4 alkoxy-carbonyl, C _1-4 alkylthio and cyano. C _1-6 alkyl group, (2) vinyl group, (3) allyl group, (4) propadienyl group, (5) (a) halogen, (b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f)
Mercapto, (g) C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl, (i) C _1-4 alkylsulfonyl, (j) cyano, (k) C _1-4 alkoxy-carbonyl, (l) Carbamoyl and (m) a C _2-6 alkynyl group optionally substituted with 1 to 5 substituents selected from mono- or di-C _1-4 alkyl-carbamoyl, (6) (a) Optionally substituted C _1-4 alkyl, (b) halogen, (c)
Amino, (d) mono- or di-C _1-4 alkylamino,
(e) hydroxy, (f) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (g) mercapto, (h) C _1-4 alkylthio, (i) C _1-4 alkylsulfinyl, (j) C _1-4 alkylsulfonyl, (k) cyano, (l) C _1-4 alkoxy-
Carbonyl, (m) carbamoyl and (n) a C _3-6 cycloalkyl group optionally substituted with 1 to 5 substituents selected from mono- or di-C _1-4 alkyl-carbamoyl, (7) ( a) C optionally substituted with 1 to 5 halogens
_1-4 alkyl, (b) halogen, (c) amino, (d) mono- or di-C _1-4 alkylamino, (e) hydroxy, (f) optionally substituted with 1 to 5 halogens C _1-4 alkoxy, (g) mercapto, (h) C _1-4 alkylthio, (i) C _1-4
Alkylsulfinyl, (j) C _1-4 alkylsulfonyl,
(k) cyano, (l) C _1-4 alkoxy-carbonyl, (m) carbamoyl and (n) mono- or di-C _1-4 alkyl-
A C _6-14 aryl group _optionally substituted with 1 to 5 substituent (s) selected from carbamoyl, (8) a C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogen (s). (Ii) C _1-4 alkoxy-carbonyl, (iii) C _1-4 alkylthio-carbonyl, (iv) C _1-4 alkoxy-thiocarbonyl, (v) C _1-4 alkylthio-thiocarbonyl,
(vi) mono- or di-C _1-4 alkyl-carbamoyl and (vii) an acyl group selected from mono- or di-C _1-4 alkyl-thiocarbamoyl, (9) formyl group, (1
0) (a) C _1-4 alkyl, (b) C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens, (c) C _1-4 alkoxy-carbonyl, (d) mono- Or di-C _1-4 alkyl-carbamoyl and (e) mono- or di-C
_An amino group optionally substituted by one or two substituents selected from _1-4 alkyl-thiocarbamoyl, (11)-
A group represented by N = CR ¹ R ² (R ¹ and R ² each represent a hydrogen atom or a C _1-4 alkyl group), (12) a 3- to 6-membered cyclic amino group, and (13) —OR ³ (R ³ is a hydrogen atom, a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms,
C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, C _1-4 alkoxy-carbonyl group optionally substituted with 1 to 5 halogens, 1-5 _Represents an optionally substituted C _1-4 alkylsulfonyl group) or (14)-
S (O) _n R ⁴ (n is an integer of 0 to 2, R ⁴ is (C) _1-4 which may be substituted with (a) a hydrogen atom and (b) halogen.
The microorganism for agricultural and horticultural use according to the above [5], which represents a group represented by an alkyl group or (c) a C _6-14 aryl group which may be substituted with 1 to 5 C _1-4 alkyl groups). Agent,

[7] A ² is (1) (i) a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms, and (ii) a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms. _1-4 alkoxy group, (ii
i) an amino group optionally substituted by one or two C _1-4 alkyl-carbonyl, (iv) a C _1-4 alkoxy-carbonyl group, (v) a halogen atom, (vi) a cyano group and (vii)
C _6-14 aryl group optionally substituted with 1 to 5 substituents selected from nitro group, (2) (i) C _1-4 alkyl group, (ii) C _1-4 alkoxy-carbonyl group (Iii) carbamoyl group, (iv) mono- or di-C _1-4 alkylcarbamoyl group, (v) C _1-4 alkylsulfonyl group, (vi) halogen atom, (vii) carboxyl group and (viii) cyano Thienyl group, triazolyl group, imidazolyl group, isoxazolyl group, pyrazolyl group, pyridyl group, quinolyl group, benzothiadiazolyl group, imidazothiazolyl which may be substituted with 1 to 5 substituents selected from X ² represents (1) a chemical bond, (2) C 2
One or two optionally substituted methylene group or (3) C _1-4 alkyl with one or two optionally substituted vinylene group _1-4 alkyl, B ² is (1) halogen, hydroxy , Imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di-C _1-4 alkylhydrazono and C _1-4 alkylthio, which may be substituted by 1 to 5 carbon atoms which may be substituted. _1-4 alkyl group, (2) C _2-4 alkynyl group, (3) hydroxy group, (4) halogen and C _1-4 optionally substituted with 1 to 5 substituents selected from C _1-4 alkoxy _1-4 alkoxy group, (5) C
_1-4 alkyl-carbonyloxy group, (6) C _1-4 alkylthio group, (7) C _1-4 alkyl sulfinyl group, (8) C _1-4 alkyl sulfonyl group, (9) mono- or di-C _1-4 alkylsulfamoyl group, (10) amino group, (11) a formyl group, (12) C _1-4 alkoxy - carbonyl group, (13) carbamoyl group, (14) mono- - or di -C _{1- 4 selected from} alkylcarbamoyl group, (15) thiocarbamoyl group, (16) halogen atom, (17) carboxyl group, (18) thiocyanato group, (19) cyano group, (20) nitroso group and (21) nitro group A C _6-14 aryl group optionally substituted with 1 to 5 substituents, Z ² represents (1) mono- or di-C _1-4 alkylamino, hydroxy, halogen, C _1-4 alkoxy, C
_C1-4 alkoxy - carbonyl, C _1-4 alkylthio and 1-5 optionally substituted C _1-6 alkyl group with a substituent selected from cyano, (2) vinyl group, (3) allyl group, ( Four)
Propadienyl group, (5) C _2-6 alkynyl group optionally substituted with 1 to 5 halogens, (6) C _3-6 cycloalkyl group, (7) C _6-14 aryl group, (8) halogen 1-5 optionally substituted C _1-4 alkyl-carbonyl, (9) C
_1-4 alkyl, C _1-4 alkyl-carbonyl and C _1-4
An amino group optionally substituted by one or two substituents selected from alkoxy-carbonyl, (10) -N = CR
A group represented by ¹ R ² (R ¹ and R ² each represent a C _1-4 alkyl group); (11) —OR ³ (R ³ is a C _1-4 alkyl group or a C _1-4 alkyl-carbonyl); Or (12) —S (O) _n R ⁴ (n is an integer of 0 to 2, and R ⁴ is (a) 1 to 5 carbon atoms which may be substituted with halogen. Agriculture and horticulture according to the above-mentioned [5], which represents a group represented by a _1-4 alkyl group or (b) a C _6-14 aryl group which may be substituted with 1 to 5 C _1-4 alkyl groups). Microbicides,

[8] A ² is a phenyl group which may be substituted by 1 to 3 substituents selected from a C _1-4 alkyl group, halogen and cyano, X ² is a chemical bond, B ² is ( 1) C _1-4 alkyl group optionally substituted with 1 to 3 halogens, (2) C _1-4 alkoxy group, (3) C _1-4 alkylthio group,
(4) thiocarbamoyl group, (5) halogen atom, (6) cyano group and (7) 1-5 optionally substituted phenyl group optionally substituted by a group selected from nitro group, Z ² is (1 ) C _1-4 1 to 3 amino substituted C _1-6 optionally alkyl alkoxy, (2) C _3-6 cycloalkyl group, (3) allyl group or
(4) The agricultural and horticultural microbicide according to the above-mentioned (5), which represents a C _1-4 alkoxy group,

[0013]

[9] The compound or a salt thereof is 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide, 2 ', 4'-dinitro-N-ethyl-p-toluenesulfonanilide, 2', 4 '-Dicyano-N-ethyl-p-toluenesulfonanilide, 4'-chloro-N-
Isopropyl-2'-nitro-p-toluenesulfonanilide, 4'-fluoro-N-isopropyl-2'-nitro-p-toluenesulfonanilide, 4'-cyano-N
-Isopropyl-2'-nitro-p-toluenesulfonanilide, 4'-chloro-N-isopropyl-2'-cyano-p-toluenesulfonanilide, 2 ', 4'-dinitro-N-isopropyl-p-toluenesulfone Anilide, 4'-nitro-N-isopropyl-2'-cyano-p
The above-mentioned [5] which is -toluenesulfonanilide, 2'-cyano-N-methoxy-4'-nitro-p-toluenesulfonanilide or 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof; Agricultural and horticultural microbicides according to the item,

[10] Formula (III)

Embedded image Wherein A ³ represents (1) an optionally substituted aryl group or (2) an optionally substituted heterocyclic group, X ³ represents (1) a chemical bond, and (2) an optionally substituted A good methylene group or (3) a vinylene group which may be substituted, B ³ represents (i) a halogen,
1 to 5 substituents selected from hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di-C _1-4 alkylhydrazono and C _1-4 alkylthio may be substituted. A C _1-4 alkyl group, (ii) a C 1-5 optionally substituted with halogen
_3-6 cycloalkyl group, (iii) _C2-4 alkenyl group _optionally substituted with 1 to 5 substituents selected from halogen, cyano and nitro, (iv) 1 to 5 substituted with halogen which may be C _{3 -6} cycloalkenyl group, (v) 1 to 5 amino optionally substituted C _2-4 alkynyl group with halogen,
(vi) a hydroxy group, (vii) a C _1-4 alkoxy group optionally substituted with 1 to 5 substituents selected from halogen and C _1-4 alkoxy, (viii) a formyloxy group, (ix)
A C _1-4 alkyl-carbonyloxy group optionally substituted with 1 to 5 halogens, (x) a C _1-4 alkoxy-carbonyloxy group optionally substituted with 1 to 5 halogens, (xi) A mercapto group, (xii) a C _1-4 alkylthio group optionally substituted with 1 to 5 halogens, (xiii) a C _1-4 alkyl-carbonylthio group optionally substituted with 1 to 5 halogens, (xiv) a C _1-4 alkoxy-carbonylthio group optionally substituted with 1 to 5 halogens, (xv)
Halogen with 1-5 optionally substituted C _1-4 alkylsulfamoyl also be alkylsulfonyl group, (xvi) 1-5 optionally substituted C _1-4 alkylsulfonyl group halogen, (xvii) sulfamoyl group, ( xviii) mono- or di-C _1-4 alkylsulfamoyl group, (xix)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, hydroxy, C _1-4 alkoxy , Formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl,
Or two optionally substituted amino groups, (xxi) 3
A 6-membered cyclic amino group, (xxii) a formyl group, (xxiii) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, and (xxiv) 1 to 5 substituted with halogens. A C _1-4 alkoxy-carbonyl group, (xxv) C
_1-4 alkylthio - carbonyl group, (xxvi) C _1-4 alkoxy - thiocarbonyl group, (xxvii) C _1-4 alkylthio - thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- - or di -C _{1 -4} alkylcarbamoyl group, (xx
x)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, and (xxxii) a mono-
Or a di-C _1-4 alkyl-thiocarbamoyl group, (xx
xiii)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
(xxviii) a substituent consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group, (xliv) azoxycyano group and (xlv) sulfo group 6 having a substituent selected from group (T)
Membered heterocyclic group, Z ³ is (1) an optionally substituted hydrocarbon group, (2) an optionally substituted acyl group, (3) a formyl group, (4) an optionally substituted amino Group, (5) -N = CR
¹ R ² (R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group which may be substituted); (6) a cyclic amino group; (7) —OR ³ (R ³ is hydrogen Atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group or an optionally substituted sulfonyl group) or (8) -S (O) _n R ⁴ (n
Represents an integer of 0 to 2, and R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted)), or a microbicidal agricultural or horticultural microorganism containing a compound represented by the formula: Agent,

[11] A ³ is (1) (i) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di-C _1-4 alkylhydrazono and C _1-4 A C _1-4 alkyl group which may be substituted with 1 to 5 substituent (s) selected from alkylthio, (i
i) a C _3-6 cycloalkyl group optionally substituted with 1 to 5 halogens, (iii) a C _3-6 optionally substituted with 1 to 5 substituents selected from halogen, cyano and nitro
_2-4 alkenyl group, (iv) C _3-6 cycloalkenyl group optionally substituted with 1 to 5 halogens, (v) 1
(Vi) an optionally substituted _C2-4 alkynyl group,
A hydroxy group, (vii) a C-substituent optionally substituted with 1 to 5 substituents selected from halogen and _C1-4 alkoxy
_1-4 alkoxy group, (viii) formyloxy group, (ix) C _1-4 alkyl- which may be substituted with 1 to 5 halogens.
Carbonyloxy group, (x) C _1-4 alkoxy-carbonyloxy group optionally substituted with 1 to 5 halogens,
(xi) a mercapto group, (xii) a C _1-4 alkylthio group optionally substituted with 1 to 5 halogens, (xiii) a C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens A thio group, (xiv) a C _1-4 alkoxy-carbonylthio group optionally substituted with 1 to 5 halogens, (xv) a C _1-4 alkylsulfinyl group optionally substituted with 1 to 5 halogens (Xvi) a C _1-4 alkylsulfonyl group optionally substituted with 1 to 5 halogens, (xvii) a sulfamoyl group, (xviii) a mono- or di-C _1-4 alkylsulfamoyl group, (xix )

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, hydroxy, C _1-4 alkoxy , Formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl,
Or two optionally substituted amino groups, (xxi) 3
A 6-membered cyclic amino group, (xxii) a formyl group, (xxiii) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, and (xxiv) 1 to 5 substituted with halogens. A C _1-4 alkoxy-carbonyl group, (xxv) C
_1-4 alkylthio - carbonyl group, (xxvi) C _1-4 alkoxy - thiocarbonyl group, (xxvii) C _{1- 4} alkylthio - thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- - or di -C _{1 -4} alkylcarbamoyl group, (xxx)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxxiii)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
xxviii) a substituent consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group, (xliv) azoxycyano group and (xlv) sulfo group A C _6-14 aryl group which may be substituted with 1 to 5 substituents selected from the group (T) or (2) 1 to 5 substituents selected from the substituent group (T) X ³ represents a (1) chemical bond, (2)
A substituent selected from C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, halogen atom and cyano;
Or a methylene group which may be substituted two or
(3) a substituent selected from C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, a halogen atom and cyano;
Alternatively, two optionally substituted vinylene groups are represented by B ³
Is a 6-membered heterocyclic group substituted with 1 to 5 substituents selected from the above substituent group (T), Z ³ is (1) (i) (a) halogen,
(b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f) mercapto , (G) C _1-4
Alkylthio, (h) C _1-4 alkylsulfinyl, (i) C
_1-4 alkylsulfonyl, (j) cyano, (k) C _1-4 alkoxy-carbonyl, (l) carbamoyl and (m) mono- or di-C _1-4 alkyl-carbamoyl 5-substituted C _1-6 alkyl group, (ii) (a) halogen, (b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e ) halogen with 1-5 substituents which may be C _1-4 alkoxy,
(f) mercapto, (g) C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl, (i) C _1-4 alkylsulfonyl, (j)
C-5 optionally substituted with 1 to 5 substituents selected from cyano, (k) _C1-4 alkoxy-carbonyl, (1) carbamoyl and (m) mono- or di- _C1-4 alkyl-carbamoyl. _2-6 alkenyl group, (iii) (a) halogen, (b) amino, (c) mono- or di-C _1-4 alkylamino,
(d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f) mercapto, (g) C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl, (i) C _1-4 alkylsulfonyl, (j) cyano, (k) C _1-4 alkoxy-
Carbonyl, (l) carbamoyl and (m) mono- - or di -C _1-4 alkyl - 1-5 optionally substituted C _2-6 alkynyl group with a substituent selected from carbamoyl,
(iv) (a) C _1-4 optionally substituted with 1 to 5 halogens
Alkyl, (b) halogen, (c) amino, (d) mono- or di-C _1-4 alkylamino, (e) hydroxy, (f) 1 to 5 halogen-substituted C _{1- 4} alkoxy, (g) mercapto, (h) C _1-4 alkylthio, (i) C _1-4
Alkylsulfinyl, (j) C _1-4 alkylsulfonyl,
(k) cyano, (l) C _1-4 alkoxy-carbonyl, (m) carbamoyl and (n) mono- or di-C _1-4 alkyl-
A C _3-6 cycloalkyl group optionally substituted with 1 to 5 substituents selected from carbamoyl, (v) (a) halogen,
(b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f) mercapto , (G) C _1-4
Alkylthio, (h) C _1-4 alkylsulfinyl, (i) C
_1-4 alkylsulfonyl, (j) cyano, (k) C _1-4 alkoxy-carbonyl, (l) carbamoyl and (m) mono- or di-C _1-4 alkyl-carbamoyl 5 optionally substituted C _3-6 alkadienyl group, and (vi) (a) halogen with 1-5 substituents on these C _1-4 alkyl, (b) halogen, (c) amino, ( d)
Mono- or di-C _1-4 alkylamino, (e) hydroxy, (f) C _1-4 optionally substituted with 1 to 5 halogens.
Alkoxy, (g) mercapto, (h) C _1-4 alkylthio,
(i) C _1-4 alkylsulfinyl, (j) C _1-4 alkylsulfonyl, (k) cyano, (1) C _1-4 alkoxy-carbonyl, (m) carbamoyl and (n) mono- or di-C
_1-4 substituents selected from alkyl-carbamoyl
A hydrocarbon group selected from a 5-substituted C _6-14 aryl group, (2) a C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogen atoms, (ii) ) C _1-4 alkoxy-carbonyl, (iii) C _1-4 alkylthio-carbonyl, (iv) C _1-4 alkoxy-thiocarbonyl, (v) C
_1-4 alkylthio-thiocarbonyl, (vi) mono- or di-C _1-4 alkyl-carbamoyl and (vii) mono-
Alternatively, ₁ to 5 acyl groups selected from di-C _1-4 alkyl-thiocarbamoyl, (3) formyl group, (4) (a) C _1-4 alkyl, and (b) halogen may be substituted. C _1-4
Selected from alkyl-carbonyl, (c) C _1-4 alkoxy-carbonyl, (d) mono- or di-C _1-4 alkyl-carbamoyl and (e) mono- or di-C _1-4 alkyl-thiocarbamoyl. An amino group optionally substituted by one or two substituents, represented by (5) -N = CR ¹ R ² (R ¹ and R ² each represent a hydrogen atom or a C _1-4 alkyl group) Group, (6) 3- to 6-membered cyclic amino group, (7)-
OR ³ (R ³ is a hydrogen atom, a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms, a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogen atoms, halogen Represents a C _1-4 alkoxy-carbonyl group, a formyl group or a C _1-4 alkylsulfonyl group optionally substituted with 1 to 5 halogens which may be substituted by 1 to 5) Or (8) -S (O) _n R ⁴ (n is 0 to
R ⁴ is (a) a hydrogen atom and (b) halogen is 1 to 5
Optionally substituted C _1-4 alkyl group or (c) C
Agricultural and horticultural microbicide described in [10], wherein indicating a group represented by _1-4 alkyl shows a 1-5 optionally substituted C _6-14 aryl group),

[0016] [12] A ³ is a 1-5 substituted 1 phenyl group or a C _1-4 alkyl optionally or two optionally substituted imidazolyl group by C _1-4 alkyl, X ³ Is a chemical bond, and B ³ is substituted with 1 to 5 substituents selected from C _1-4 alkyl, C _1-4 alkoxy, halogen, nitro and cyano which may be substituted with 1 to 5 halogens. A pyridyl group, a pyridazinyl group or a pyrimidinyl group, and Z ³ represents a C _1-6 alkyl group, a C _3-6 cycloalkyl group or a C _1-4 alkoxy group.
0] The agricultural and horticultural microbicide according to the above,

[13] Formula (IV)

Embedded image Wherein A ⁴ represents (1) an optionally substituted aryl group or (2) an optionally substituted heterocyclic group, X ⁴ represents (1) a chemical bond, (2) an optionally substituted A good methylene group or (3) a optionally substituted vinylene group, B ⁴ is a pyridazinyl group or a pyrazinyl group, Z ⁴ is (1) an optionally substituted hydrocarbon group, (2) a substituted Good acyl group, (3)
Formyl group, (4) optionally substituted amino group, (5)-
A group represented by N = CR ¹ R ² (R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group which may be substituted), (6) a cyclic amino group, and (7) —OR ³ (R ³ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group or an optionally substituted sulfonyl group) or a group represented by (8) -S ( O) _n R
⁴ (n represents an integer of 0 to 2; R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted);
An agricultural or horticultural microbicide containing a compound represented by or a salt thereof,

[14] Equation (V)

Embedded image Wherein A ⁵ represents a 4-methylphenyl group, X ⁵ represents a chemical bond, B ⁵ represents a pyridyl group or a pyrimidinyl group, and Z ⁵ represents a C
_1-4 represents an alkyl group] agricultural or horticultural microbicide containing a compound or a salt thereof represented by

[15] Formula (VI)

Embedded image Wherein A ⁶ is a phenyl group which may be substituted with a substituent selected from C _1-4 alkyl, halogen and cyano, X ⁶ is a chemical bond, and B ⁶ is a halogen atom, nitro and cyano is a 2-nitrophenyl group or a 2-cyanophenyl group which is substituted with a substituent, Z ⁶ is an ethyl group, an isopropyl group, a cyclopropyl group, a methoxy group,
An ethoxy group or an isopropoxy group) or a salt thereof,

[16] A ⁶ represents a phenyl group which may be substituted with a substituent selected from C _1-4 alkyl, halogen and cyano, X ⁶ represents a chemical bond, B ⁶ represents a halogen atom,
2 substituted with a substituent selected from nitro and cyano
The compound of the above-mentioned [15], wherein Z ⁶ represents an ethyl group, an isopropyl group or a cyclopropyl group, or a salt thereof,

[17] 4'-chloro-N-ethyl-2'-
Nitro-p-toluenesulfonanilide, 2 ′, 4′-dinitro-N-ethyl-p-toluenesulfonanilide,
2 ', 4'-dicyano-N-ethyl-p-toluenesulfonanilide, 4'-chloro-N-isopropyl-2'-nitro-p-toluenesulfonanilide, 4'-fluoro-N-isopropyl-2'- Nitro-p-toluenesulfonanilide, 4'-cyano-N-isopropyl-2'-
Nitro-p-toluenesulfonanilide, 4'-chloro-N-isopropyl-2'-cyano-p-toluenesulfonanilide, 2 ', 4'-dinitro-N-isopropyl-p-toluenesulfonanilide, 4'-nitro -N-
Isopropyl-2'-cyano-p-toluenesulfonanilide, 2'-cyano-N-methoxy-4'-nitro-p
The compound of the above-mentioned [15], which is -toluenesulfonanilide or 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof, or a salt thereof;

[18] Equation (1)

Embedded image (Each symbol in the formula has the same meaning as described in the above [15].)
And a salt thereof and a compound represented by the formula Z ⁶ -L ″
L ″ represents a leaving group, and Z ⁶ represents an electrophilic agent represented by the above [15]), or (2) a compound represented by the formula A ⁶ -X ⁶ -SO _2-. L (wherein L represents a leaving group, and other symbols have the same meanings as described in the above item [15]) or a salt thereof, and a compound represented by the formula Z ⁶ HN-B ⁶ (each of the formulas The symbols have the same meanings as described in the above [15].) Or a salt thereof,
⁶ -X ⁶ -SO ₂ -NHZ ⁶ (Each symbol in the formula is the above [15]
Shows the compound or a salt thereof represented by the indicating section, wherein the same meaning), the formula L'-B ⁶ (wherein L 'is a leaving group, and other symbols are as defined above [15], wherein Or a salt thereof, or (4)

Embedded image (In the formula, B ⁷ is a phenyl group substituted with at least one of the 2-position and 6-position substituted with a substituent selected from a halogen atom, nitro and cyano, and other symbols are described in the above [15]. Wherein the compound or its salt is nitrated.

Embedded image (Each symbol in the formula has the same meaning as described in the above [15].)
Or a salt thereof.

The compound (I ⁰ ) which is a sulfonamide derivative may exist in an optically active form, a diastereomer and / or a geometric isomer, and the present invention relates to each of these isomers and their isomers. And mixtures. “Aryl group which may be substituted” in A ⁰
Examples of the aryl group in phenyl and naphthyl (eg,
And C _6-14 aryl groups such as 1-naphthyl and 2-naphthyl). As the substituent of the aryl group, (1) (i)
Halogen, hydroxy, imino, hydroxyimino, C
_1-4 alkoxyimino (e.g., methoxyimino, ethoxyimino), hydrazono, mono- - or di -C _1-4 alkyl hydrazono (e.g., methyl hydrazono, ethyl hydrazono, dimethyl hydrazono) and C _1-4 alkylthio (Eg, 1 substituent with a substituent selected from methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio)
Up to 5 optionally substituted C _1-4 alkyl groups (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl,
sec-butyl, isobutyl, tert-butyl), (ii) a C _3-6 cycloalkyl group optionally substituted with 1 to 5 halogens (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), (iii) halogen , A _C2-4 alkenyl group _optionally substituted by 1 to 5 substituents selected from cyano and nitro (eg, vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl), (i
v) a C _3-6 cycloalkenyl group optionally substituted with halogen (eg, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl), (v) a C _3-6 cycloalkenyl group optionally substituted with halogen Good C _2-4 alkynyl groups (eg, ethynyl, 1-propynyl, 2-propynyl,
1-butynyl, 2-butynyl, 3-butynyl), (vi) a hydroxy group, (vii) halogen and a C _1-4 alkoxy (eg, methoxy, ethoxy) substituted with 1 to 5 substituents. C _1-4 alkoxy group (eg,
Methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), (viii) formyloxy group, (ix) halogen
An optionally substituted C _1-4 alkyl-carbonyloxy group (eg, acetyloxy, propionyloxy,
Butyryloxy, isobutyryloxy),

(X) a C _1-4 alkoxy-carbonyloxy group which may be substituted by 1 to 5 halogen atoms (for example, methoxycarbonyloxy, ethoxycarbonyloxy, n-
Propoxycarbonyloxy, isopropoxycarbonyloxy), (xi) mercapto group, (xii) halogen
An optionally substituted C _1-4 alkylthio group (eg,
Methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio), (xiii) C _1-4 alkyl-carbonylthio optionally substituted by 1 to 5 halogens Groups (eg, acetylthio, propionylthio, butyrylthio, isobutyrylthio), (xiv) a C _1-4 alkoxy-carbonylthio group optionally substituted with 1 to 5 halogens (eg, methoxycarbonylthio, ethoxycarbonylthio, n -Propoxycarbonylthio, isopropoxycarbonylthio), (xv) a C _1-4 alkylsulfinyl group optionally substituted with 1 to 5 halogens (eg, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl) , (xvi) optionally C _1-4 Al be 1-5 substituted by halogen Rusuruhoniru group (e.g., methylsulfonyl, ethylsulfonyl, n- propylsulfonyl, isopropylsulfonyl), (xvii)
A sulfamoyl group, (xviii) a mono- or di-C _1-4 alkylsulfamoyl group (eg, methylsulfamoyl,
Ethylsulfamoyl, n-propylsulfamoyl, dimethylsulfamoyl, ethylmethylsulfamoyl,
Diethylsulfamoyl), (xix)

Embedded image A group represented by [Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group (eg, aziridino, azetidino, pyrrolidino, piperidino, morpholino, thiomorpholino)];

(Xx) C _1-4 alkyl (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl), C _2-4 alkenyl (eg, vinyl, allyl) , Propenyl, isopropenyl,
2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl), C _2-4 alkynyl (eg, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl,
2-butynyl, 3-butynyl), hydroxy, C _1-4 alkoxy (eg, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), formyloxy, C _{1 -4} alkyl-carbonyloxy (eg, acetyloxy, propionyloxy, butyryloxy, isobutyloxy), formyl and C _1-4 alkyl-carbonyl (eg, acetyl, propionyl, butyryl, isobutyryl); An optionally substituted amino group, (xxi) a 3- to 6-membered cyclic amino group (eg, aziridino, azetidino, pyrrolidino, piperidino, morpholino, thiomorpholino), (xxii) formyl group, (xxiii) halogen to five optionally substituted C _1-4 alkyl - carbonyl group (e.g., acetyl, propionitrile Le, butyryl, isobutyryl), (xxiv) a halogen with 1-5 optionally substituted C _1-4 alkoxy - carbonyl group (e.g.,
Methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl), (xxv) C
_1-4 alkylthio-carbonyl group (eg, (methylthio)
Carbonyl, (ethylthio) carbonyl, (n-propylthio) carbonyl, (isopropylthio) carbonyl,
(N-butylthio) carbonyl, (isobutylthio) carbonyl, (sec-butylthio) carbonyl, (tert-butylthio) carbonyl), (xxvi) C _1-4 alkoxy-thiocarbonyl group (eg, (methoxy) thiocarbonyl, ( (Ethoxy) thiocarbonyl, (n-propoxy) thiocarbonyl, (isopropoxy) thiocarbonyl), (xxvii)
C _1-4 alkylthio-thiocarbonyl group (eg, (methylthio) thiocarbonyl, (ethylthio) thiocarbonyl, (n-propylthio) thiocarbonyl, (isopropylthio) thiocarbonyl, (n-butylthio) thiocarbonyl, (isobutylthio) ) Thiocarbonyl, (sec-butylthio) thiocarbonyl, (tert-butylthio) thiocarbonyl), (xxviii) carbamoyl group, (xxix) mono- or di-C _1-4 alkylcarbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl) , N-propylcarbamoyl, dimethylcarbamoyl, ethylmethylcarbamoyl, diethylcarbamoyl),

(Xxx)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group (eg, aziridino, azetidino, pyrrolidino, piperidino, morpholino, thiomorpholino)), (xxxi) thiocarbamoyl group, (xxxii) mono- Or di-C _1-4 alkyl-
Thiocarbamoyl group (eg, (methyl) thiocarbamoyl, (ethyl) thiocarbamoyl, (n-propyl) thiocarbamoyl, (dimethyl) thiocarbamoyl, (ethylmethyl) thiocarbamoyl, (diethyl) thiocarbamoyl), (xxxiii)

Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group (eg, aziridino, azetidino, pyrrolidino, piperidino, morpholino, thiomorpholino)), (xxxiv) a halogen atom (eg, fluorine, chlorine, Bromine, iodine), (xxxv) carboxyl group, (xxxvi) thiocyanato group, (xxxvii) isothiocyanato group, (xxxviii) cyano group, (xxxix) isocyano group,

(Xl) azide group, (xli) nitroso group, (xlii)
Nitro group, (xliii) azocyano group, (xliv) azoxycyano group (-NO = N-CN) and (xlv) sulfo group. Hereinafter, the substituent groups (i) to (xlv) may be abbreviated as a substituent group (T). In addition, the above (i) to (xliii)
And (xlv) may be abbreviated as a substituent group (T ′). ("Halogen" in the above substituents includes fluorine, chlorine, bromine and iodine.) The number of substituents in the aryl group is 1 to 5 (preferably 1 to 3).

Examples of the heterocyclic group in the “optionally substituted heterocyclic group” in A ⁰ include a heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom, from 1 to 4
5 to 6 membered heterocyclic group, or 5 to 6 membered heterocyclic ring and benzene ring containing 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, or nitrogen, oxygen and sulfur 5 to 6-membered heterocyclic ring containing 1 to 4 heteroatoms selected from the group consisting of a 5 to 6-membered heterocyclic ring containing 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur atoms Represents a group. Specifically, pyrrolyl (eg, 1-, 2- or 3-pyrrolyl), pyrazolyl (eg, 1-, 3-, 4- or 5-pyrazolyl), imidazolyl (eg, 1-, 2-, 4-) Or 5-imidazolyl), triazolyl (eg, 1,2,3-triazol-1-, 4- or 5-yl, 1,2,4-triazol-1-, 3-, 4- or 5-yl), Tetrazolyl (eg, tetrazol-1-, 2- or 5-yl), furyl (eg, 2- or 3-furyl), thienyl (eg, 2
-Or 3-thienyl), oxazolyl (eg, 2-, 4
-Or 5-oxazolyl), isoxazolyl (eg, 3
-, 4- or 5-isoxazolyl), oxadiazolyl (eg, 1,2,3-oxadiazole-4- or 5
-Yl, 1,2,4-oxadiazole-3- or 5
-Yl, 1,2,5-oxadiazol-3-yl,
1,3,4-oxadiazol-2-yl), thiazolyl (eg, 2-, 4- or 5-thiazolyl), isothiazolyl (eg, 3-, 4- or 5-isothiazolyl),
Thiadiazolyl (eg, 1,2,3-thiadiazole-4
-Or 5-yl, 1,2,4-thiadiazole-3-
Or 5-yl, 1,2,5-thiadiazol-3-yl, 1,3,4-thiadiazol-2-yl), pyrrolidinyl (eg, 1-, 2- or 3-pyrrolidinyl), pyridyl (eg, 2 -, 3- or 4-pyridyl), pyridazinyl (eg, 3- or 4-pyridazinyl), pyrimidinyl (eg, 2-, 4- or 5-pyrimidinyl), pyrazinyl, piperidinyl (eg, 1-, 2-, 3) -Or 4
-Piperidinyl), piperazinyl (eg, 1- or 2-
Piperazinyl), indolyl (eg, 3H-indole-
2-, 3-, 4-, 5-, 6- or 7-yl), pyranyl (eg, 2-, 3- or 4-pyranyl), thiopyranyl (eg, 2-, 3- or 4-thiopyranyl), Morpholinyl (eg, 2-, 3- or 4-morpholinyl),
Thiomorpholinyl, quinolyl (eg, 2-, 3-, 4-,
5-, 6-, 7- or 8-quinolyl), isoquinolyl, pyrido [2,3-d] pyrimidinyl (eg, pyrido [2,3-d] pyrimidin-2-yl), 1,5-,
1,6-, 1,7-, 1,8-, 2,6- or 2,7
-Naphthyridinyl such as naphthyridinyl (eg, 1,5-
Naphthyridin-2- or 3-yl), thieno [2,3
-D] pyridyl (eg, thieno [2,3-d] pyridine-
3-yl), pyrazinoquinolyl (eg, pyrazino [2,3
-D] quinolin-2-yl), chromenil (eg, 2H-
Chromen-2-, 3-, 4-, 5- or 6-yl),
Chromanil (eg, 1-, 2-, 3-, 4-, 5-, 6
-, 7- or 8-chromanyl), isochromanil (eg, 1-, 3-, 4-, 5-, 6-, 7- or 8-
Isochromanyl), benzofuryl (eg, 2-, 3-, 4
-, 5-, 6- or 7-benzofuryl), benzothienyl (eg, 2-, 3-, 4-, 5-, 6- or 7-benzothienyl), benzimidazolyl (eg, 2-, 4)
-, 5-, 6- or 7-benzimidazolyl), indazolyl (eg, 1H-indazole-1-, 3-, 4)
-, 5-, 6- or 7-yl), benzoxazolyl (eg, 2-, 4-, 5-, 6- or 7-benzoxazolyl), benzisoxazolyl (eg, 3- , 4-, 5
-, 6- or 7-benzoisoxazolyl), benzothiazolyl (eg, 2-, 4-, 5-, 6- or 7-benzothiazolyl), benzothiadiazolyl (eg, benzo-
1,2,3-thiadiazole-4-, 5-, 6- or 7-yl, benzo-1,2,4-thiadiazole-3
-, 4-, 5-, 6- or 7-yl, benzo-1,
2,5-thiadiazole-3-, 4-, 5-, 6- or 7-yl, benzo-1,3,4-thiadiazole-2
-, 4-, 5-, 6- or 7-yl,), benzoisothiazolyl (eg, 3-, 4-, 5-, 6- or 7-benzoisothiazolyl), benzotriazolyl (example) , 4
-, 5-, 6-, 7- or 8-benzo-1,2,3-
Triazolyl, 3-, 5-, 6-, 7- or 8-benzo-1,2,4-triazolyl), cinnolyl (eg, 3
-, 4-, 5-, 6-, 7- or 8-cinnolyl),
Phthalazinyl (eg, 1-, 5- or 6-phthalazinyl), quinazolinyl (eg, 2-, 4-, 5-, 6-, 7)
-Or 8-quinazolinyl), quinoxalinyl (eg, 2
-, 5- or 6-quinoxalinyl), imidazopyridyl (eg, imidazo [1,2-a] pyridin-2-yl,
Imidazo [1,2-a] pyridyl such as imidazo [1,2-a] pyridin-3-yl), imidazothiazolyl (eg, imidazo [2,1-b] thiazol-5-yl and the like imidazo [ 2,1-b] thiazolyl), dioxaindanyl (eg, 1,3-dioxaindan-2-, 4
-, 5-, 6- or 1,3-dioxaindanyl such as 7-yl) and the like. Among these heterocyclic groups, isoxazolyl, triazolyl, pyridyl, quinolyl, thienyl, isoxazolyl, pyrazolyl, imidazolyl, benzothiadiazolyl, imidazopyridyl, imidazothiazolyl and the like are particularly preferable.

The substituent of the heterocyclic group is preferably a substituent contained in the above-mentioned substituent group (T). The number of the substituents is 1 to 5 (preferably 1 to 3). Preferred substituents on the aryl group in the “optionally substituted aryl group” or the heterocyclic group in the “optionally substituted heterocyclic group” of A ⁰ are (1) 1 to 5 halogen-substituted groups. _C1-4 alkyl which may be substituted, (2) amino optionally substituted with 1 or 2 _C1-4 alkyl-carbonyl, (3) nitro, (4) 1 to 5 substituted with halogen. C _1-4 alkoxy, (5) halogen, (6) C _1-4 alkoxy-carbonyl, (7) cyano, (8) mono- or di-C _1-4 alkylcarbamoyl, (9) C _{1 -4alkylsulfonyl} , (10) carbamoyl and (11) carboxyl. A ⁰ is preferably a phenyl group which may be substituted with 1 to 3 substituents selected from C _1-4 alkyl, halogen and cyano, and particularly preferably 1 to 3 selected from C _1-4 alkyl and halogen. A phenyl group which may be substituted with two substituents is preferred. It is particularly preferable that the substituent is substituted on the 4-position of the phenyl group.

As the substituent of the methylene group in X ^0,
(1) C _1-4 alkyl (eg, methyl, ethyl, n-propyl,
Isopropyl, n-butyl, isobutyl, sec-butyl, te
rt-butyl), (2) C _1-4 alkoxy (eg, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
Isobutoxy, sec-butoxy, tert-butoxy), (3) C
_1-4 alkylthio (eg, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio), (4) halogen atom (eg, fluorine, chlorine, bromine, iodine) and
(5) Cyano is preferred. The number of the substituents is one or two. Examples of the substituent of the vinylene group for X ⁰ include the same substituents as those for the methylene group for X ⁰ . The number of the substituents is one or two. The X ^0, a chemical bond (a single bond or a bond), C _1-4 alkyl with one or two optionally substituted methylene group, it may be one or two substituted with C _1-4 alkyl Vinylene groups are preferred. Particularly, a chemical bond is preferable.

As the "optionally substituted heterocyclic group" for B ^{0, the same as} the "optionally substituted heterocyclic group" for A ⁰ can be mentioned. Preferred heterocyclic groups are thienyl, pyrazolyl, imidazolyl, thiazolyl,
Isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, imidazopyridyl, dioxaindanyl. Preferred as the substituent of the heterocyclic group are nitro, halogen, cyano, C _1-4 alkyl optionally substituted with 1 to 5 halogens, C _1-4 alkoxy, C
_1-4 alkylthio. As the “optionally substituted aryl group” for B ^{0, the same as} the “optionally substituted aryl group” for A ⁰ can be mentioned. As the aryl group, a phenyl group is particularly preferred. Examples of the substituent of the aryl group include (1) halogen, (2) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di-C _1-4 alkylhydrazono, and C ₁ C _1-4 alkyl optionally substituted with 1 to 5 substituents selected from _-4 alkylthio, (3) C _2-4 alkynyl, (4) a substituent selected from halogen and C _1-4 alkoxy. 1 to 5 optionally substituted alkoxy, (5) _C1-4 alkylthio, (6) _C1-4 alkylsulfinyl, (7) _C1-4 alkylsulfonyl, (8)
C _1-4 alkyl-carbonyloxy, (9) C _1-4 alkoxy-carbonyl, (10) carboxyl, (11) cyano, (12)
Nitro, (13) nitroso, (14) formyl, (15) carbamoyl, (16) mono- or di-C _1-4 alkylcarbamoyl, (17) thiocarbamoyl, (18) hydroxy, (19) mono- or di- -C _1-4 alkylsulfamoyl, (20) thiocyanato, (21) azoxycyano and (22) amino are preferred.

The "hydrocarbon group" in the "optionally substituted hydrocarbon group" for Z ⁰ includes (i) a C _1-6 alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl), (ii) a C _2-6 alkenyl group (eg, vinyl, allyl, propenyl, isophenyl) A linear _C2-6 alkenyl group such as propenyl, 1-butenyl, 2-butenyl or 3-butenyl; 2-methyl-1-
Propenyl, 2-methyl-2-propenyl, 1-methyl-2-propenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1,2-dimethyl-2-propenyl, 1,1-dimethyl- 2-propenyl, 1-methyl-
2-butenyl, 3-methyl-2-butenyl, 2-methyl-2-butenyl, 1-methyl-3-butenyl, 1-ethyl-2-propenyl, 2-methyl-3-butenyl, 3-
Methyl-3-butenyl, 2-methyl-1-pentenyl,
3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-
Pentenyl, 3-methyl-2-pentenyl, 4-methyl-3-pentenyl, 1,1-dimethyl-2-butenyl,
1,2-dimethyl-2-butenyl, 1,3-dimethyl-
2-butenyl, 2,3-dimethyl-2-butenyl, 1-
Methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1,1-dimethyl-3-butenyl, 1,2-
Dimethyl-3-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-3-butenyl, 1-methyl-4-pentenyl, 2
-Ethyl-1-butenyl, 2-ethyl-2-butenyl,
A branched C _2-6 alkenyl group such as 1-ethyl-1-butenyl and 1-ethyl-2-butenyl), (iii) a C _2-6 alkynyl group (eg, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl), (i
v) C _3-6 cycloalkyl group (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), (v) C
_3-6 alkadienyl group (eg, 1,2-propadienyl,
1,2-butadienyl, 1,3-butadienyl, 3-methyl-1,2-dienyl, 1,2-pentadienyl,
2,4-pentadienyl, 1-methyl-1,2-pentadienyl, 1-methyl-1,3-pentadienyl), and (vi) a C _6-14 aryl group (eg, phenyl; 1-naphthyl, 2-naphthyl and the like) Of naphthyl).

When the hydrocarbon group is an alkyl group, an alkenyl group, an alkynyl group, or an alkadienyl group, the substituent of the hydrocarbon group includes (a) a halogen atom (eg, fluorine, chlorine, bromine, iodine), ( b) amino group, (c) mono- or di-C _1-4 alkylamino group (eg, methylamino, ethylamino, dimethylamino, methylethylamino), (d) hydroxy group, (e) halogen (eg, 1 to 5 (preferably 1 to 3) fluorine, chlorine, bromine, iodine)
Optionally substituted C _1-4 alkoxy (eg, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), (f) mercapto, (g) C _{1 -4} alkylthio (eg, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio), (h) C _1-4 alkylsulfinyl (eg, methylsulfinyl, ethylsulfinyl) , N-
Propylsulfinyl, isopropylsulfinyl),
(i) C _1-4 alkylsulfonyl (eg, methylsulfonyl,
Ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl), (j) cyano, (k) C _1-4 alkoxy-carbonyl (eg, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl), (l) carbamoyl And (m) mono- or di-C
_1-4 alkyl-carbamoyl (eg, methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, dimethylcarbamoyl, ethylmethylcarbamoyl, diethylcarbamoyl). The number of the substituents is 1 to
5 (preferably 1 to 3). When the hydrocarbon group is a cycloalkyl group or an aryl group, the substituent of the hydrocarbon group includes (a) halogen (eg, fluorine, chlorine,
C _1-4 alkyl _optionally substituted with 1 to 5 (preferably 1 to 3) bromine or iodine (eg, methyl, ethyl, propyl, isopropyl, tert-butyl, chloromethyl, trifluoromethyl) , (B) a halogen atom (eg,
(Fluorine, chlorine, bromine, iodine), (c) amino group, (d) mono- or di-C _1-4 alkylamino group (eg, methylamino, ethylamino, dimethylamino, methylethylamino), (e) Hydroxy group, (f) halogen (eg, fluorine,
1-5 (chlorine, bromine, iodine) (preferably 1-3)
) Optionally substituted C _1-4 alkoxy (eg, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), (g) mercapto, (h) C _1-4 alkylthio (eg, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio), (i) C _1-4 alkylsulfinyl (eg, methylsulfinyl, Ethyl sulfinyl, n-
Propylsulfinyl, isopropylsulfinyl),
(j) C _1-4 alkylsulfonyl (eg, methylsulfonyl,
Ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl), (k) cyano, (l) C _1-4 alkoxy-carbonyl (eg, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl), (m) carbamoyl And (n) mono- or di-C
_1-4 alkyl-carbamoyl (eg, methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, dimethylcarbamoyl, ethylmethylcarbamoyl, diethylcarbamoyl). The number of the substituents is 1 to
5 (preferably 1 to 3).

The "optionally substituted acyl group" for Z ⁰
Examples of the “acyl group” in (i) include (i) a C _1-4 alkyl-carbonyl group (eg, acetyl, propionyl, butyryl, isobutyryl), (ii) a C _1-4 alkoxy-carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl), (i
ii) C _1-4 alkylthio-carbonyl group (eg, (methylthio) carbonyl, (ethylthio) carbonyl, (n-propylthio) carbonyl, (isopropylthio) carbonyl, (n-butylthio) carbonyl, (isobutylthio)
Carbonyl, (sec-butylthio) carbonyl, (tert-
Butylthio) carbonyl), (iv) a C _1-4 alkoxy-thiocarbonyl group (eg, (methoxy) thiocarbonyl,
(Ethoxy) thiocarbonyl, (n-propoxy) thiocarbonyl, (isopropoxy) thiocarbonyl), (v)
C _1-4 alkylthio-thiocarbonyl group (eg, (methylthio) thiocarbonyl, (ethylthio) thiocarbonyl, (n-propylthio) thiocarbonyl, (isopropylthio) thiocarbonyl, (n-butylthio) thiocarbonyl, (isobutylthio) ) Thiocarbonyl, (sec-butylthio) thiocarbonyl, (tert-butylthio) thiocarbonyl), (vi) mono- or di-C _1-4 alkyl-
A carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, dimethylcarbamoyl, ethylmethylcarbamoyl, diethylcarbamoyl), and (vii) a mono- or di-C _1-4 alkyl-
And thiocarbamoyl groups (eg, (methyl) thiocarbamoyl, (ethyl) thiocarbamoyl, (n-propyl) thiocarbamoyl, (dimethyl) thiocarbamoyl, (ethylmethyl) thiocarbamoyl, (diethyl) thiocarbamoyl). As the substituent for the acyl group, halogen (eg, fluorine, chlorine, bromine, iodine) is preferable. The number of the substituents is 1 to 5 (preferably 1 to 3).

Examples of the substituent of the “optionally substituted amino group” in Z ⁰ include (a) C _1-4 alkyl (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. -Butyl, tert-butyl), (b) C _1-4 alkyl-carbonyl ( _optionally substituted with 1 to 5 (preferably 1 to 3) halogens (eg, fluorine, chlorine, bromine, iodine) Eg, acetyl, propionyl, butyryl, isobutyryl), (c) C _1-4 alkoxy-carbonyl (eg, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl),
(d) mono- or di-C _1-4 alkyl-carbamoyl (eg, methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, dimethylcarbamoyl, ethylmethylcarbamoyl, diethylcarbamoyl), and
(e) mono- or di-C _1-4 alkyl-thiocarbamoyl (eg, (methyl) thiocarbamoyl, (ethyl) thiocarbamoyl, (n-propyl) thiocarbamoyl, (dimethyl) thiocarbamoyl, (ethylmethyl) thio Carbamoyl, (diethyl) thiocarbamoyl). The number of the substituents is one or two.

As the "optionally substituted hydrocarbon group" for R ¹ , R ² , R ³ and R ^{4, the same as} the "optionally substituted hydrocarbon group" for Z ⁰ described above can be mentioned. . As the “optionally substituted hydrocarbon group” for R ¹ and R ^{2, a} C _1-4 alkyl group (eg,
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl) are preferred. “Optionally substituted hydrocarbon group” for R ³
Among them, C _1-4 alkyl groups (eg, methyl, ethyl, n-propyl) which may be substituted by 1 to 5 (preferably 1 to 3) halogens (eg, fluorine, chlorine, bromine, iodine) , Isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl). Examples of the “optionally substituted hydrocarbon group” for R ⁴ include (1) 1 to 5 (preferably 1 to 3) halogen (eg, fluorine, chlorine, bromine, and iodine) substituted. Good C _1-4 alkyl groups (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl), and (2) C _1-4 alkyl (eg, methyl, ethyl ,
n-propyl, isopropyl, n-butyl, isobutyl, se
1 to 5 (preferably 1 to 5)
3) C _6-14 aryl group which may be substituted (eg, naphthyl such as phenyl, 1-naphthyl and 2-naphthyl)
Is preferred.

Examples of the cyclic amino group for Z ⁰ include a 3- to 6-membered cyclic amino group (eg, aziridino, azetidino, pyrrolidino, piperidino, morpholino, thiomorpholino). As the “optionally substituted acyl group” for R ^3, the same as the aforementioned “optionally substituted acyl group” for Z ⁰ can be mentioned. Among them, halogen (eg,
A C _1-4 alkyl-carbonyl group (eg, acetyl, propionyl, butyryl, isobutyryl) which may be substituted by 1 to 5 (preferably 1 to 3) with fluorine, chlorine, bromine, iodine), and halogen ( For example, a C _1-4 alkoxy-carbonyl group (eg, fluorine, chlorine, bromine, iodine) which may be substituted with 1 to 5 (preferably 1 to 3)
Methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl) are preferred. As the “alkylsulfonyl” in the “optionally substituted alkylsulfonyl group” for R ³ , methylsulfonyl, ethylsulfonyl, n-propylsulfonyl,
C _1-4 alkylsulfonyl groups such as isopropylsulfonyl. As a substituent of the alkylsulfonyl group, halogen (eg, fluorine, chlorine, bromine, iodine) is preferable. The number of the substituents is 1 to 5 (preferably 1 to 3).
).

As Z ⁰ , among the above, (1) hydroxy, halogen, cyano, C _1-4 alkylthio, C _1-4 alkoxy, C _1-4 alkoxy-carbonyl and mono- or di-C _1-4 alkylamino A C _1-6 alkyl group which may be substituted by 1 to 3 substituent (s), (2) C
_2-6 alkenyl group, (3) C _2-6 alkynyl group optionally substituted with 1 to 3 halogens, (4) C _3-6 cycloalkyl group, (5) C _3-6 alkadienyl group, 6) phenyl group, (7) C _1-4 alkyl-carbonyl group _optionally substituted with 1 to 3 halogen atoms, (8) C _1-4 alkyl, C _1-4 alkyl-
An amino group optionally substituted by one or two substituents selected from carbonyl and C _1-4 alkoxy-carbonyl, (9) -N ＝ CR ¹ R ² (R ¹ and R ² are each a hydrogen atom or C _{A (1-4} ) alkyl group), a (10) _C1-4 alkoxy group, (11) a _C1-4 alkyl-carbonyloxy group (12) A good C _1-4 alkylthio group, (13) a C _1-4 alkylsulfinyl group optionally substituted with 1 to 5 halogens,
(14) a C _1-4 alkylsulfonyl group, and (15) a phenylsulfonyl group optionally substituted with 1 to 3 C _1-4 alkyl groups.

The salt of compound (I ⁰ ) may be any salt that is acceptable in agrochemical chemistry. When the compound (I ⁰ ) has basic properties, for example, salts of inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, nitric acid, perchloric acid, for example, formic acid, Salts of organic acids such as acetic acid, propionic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, benzoic acid, picric acid, methanesulfonic acid, p-toluenesulfonic acid and the like can be mentioned. When the compound (I ⁰ ) has acidic properties, for example, alkali metal salts such as lithium, sodium and potassium, for example, alkaline earth metal salts such as magnesium and calcium, for example, ammonia, methylamine, dimethylamine, trimethylamine And ammonium salts such as triethylamine, ethylenediamine, TMEDA (tetramethylethylenediamine), aniline, N, N-dimethylaniline, pyridine, lutidine, collidine and hydrazine, and salts with urea, guanidine and the like.

Among the compounds contained in compound (I ⁰ ) or a salt thereof, compound (I), compound (II), compound (III), compound (IV) and compound (V) or a salt thereof are shown below. preferable. [1] Compound (I) or a salt thereof has the formula

Embedded image Wherein A ¹ is (1) an optionally substituted aryl group or (2) an optionally substituted heterocyclic group, X ¹ is (1) a chemical bond, (2) an optionally substituted A good methylene group or (3) an optionally substituted vinylene group, B ¹ is an optionally substituted 5-membered heterocyclic group (excluding isoxazolyl group) or an optionally substituted fused heterocyclic group The group
¹ is (1) an optionally substituted hydrocarbon group, (2) an optionally substituted acyl group, (3) a formyl group, (4) an optionally substituted amino group, (5) -N = CR ¹ R ² (R ¹ and R
² represents a hydrogen atom or a hydrocarbon group which may be substituted), a group represented by (6) a cyclic amino group, (7)-
A group represented by OR ³ (R ³ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group, or an optionally substituted alkylsulfonyl group) or ( 8) —S (O) _n R ⁴ (n represents an integer of 0 to 2, and R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted). A compound or a salt thereof. Each substituent of A ¹ , X ¹ and Z ^{1 has} the same meaning as A ⁰ , X ⁰ and Z ⁰ , respectively.

Examples of the 5-membered heterocyclic group in the “optionally substituted 5-membered heterocyclic group” of B ¹ include pyrrolyl (eg, 1-, 2- or 3-pyrrolyl), pyrazolyl (eg, 1- , 3-, 4- or 5-pyrazolyl), imidazolyl (eg, 1-, 2-, 4- or 5-imidazolyl), triazolyl (eg, 1,2,3-triazole-)
1-, 4- or 5-yl, 1,2,4-triazol-1-, 3-, 4- or 5-yl), tetrazolyl (eg, tetrazol-1-, 2- or 5-yl), thienyl (Eg, 2- or 3-thienyl), thiazolyl (eg, 2-, 4- or 5-thiazolyl), isothiazolyl (eg, 3-, 4- or 5-isothiazolyl), thiadiazolyl (eg, 1, 2, 3) -Thiadiazole-4-
Or 5-yl, 1,2,4-thiadiazol-3- or 5-yl, 1,2,5-thiadiazol-3-yl, 1,3,4-thiadiazol-2-yl), pyrrolidinyl (eg, 1 -, 2- or 3-pyrrolidinyl) and other ring-constituting atoms other than carbon atoms are nitrogen atoms or sulfur atoms, and 1 to 4 (preferably 1 to 3) heteroatoms selected from nitrogen and sulfur atoms. And a 5-membered heterocyclic group contained therein. Particularly preferred are thienyl, pyrazolyl, isothiazolyl, imidazolyl, thiazolyl and thiadiazolyl.

The substituent of the 5-membered heterocyclic group is preferably a substituent selected from the above-mentioned substituent group (T). The number of substituents is 1 to 5 (preferably 1 to 3). As the substituent, halogen, nitro, cyano, and halogen are particularly preferable.
5 (preferably 1 to 3) optionally substituted C
_1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio are preferred. As the “fused heterocyclic group” in the “optionally substituted fused heterocyclic group” of B ^1, a 5- to 6-membered heterocycle and a benzene ring or a 5- to 6-membered heterocycle and a 5- to 6-membered heterocycle are formed. And specifically preferred are indolyl (eg, 3H-indole-2-, 3-, 4-, 5
-, 6- or 7-yl), quinolyl (eg, 2-, 3
-, 4-, 5-, 6-, 7- or 8-quinolyl), isoquinolyl, pyrido [2,3-d] pyrimidinyl (eg,
Pyrido [2,3-d] pyrimidin-2-yl), 1,5
Naphthyridinyl such as-, 1,6-, 1,7-, 1,8-, 2,6- or 2,7-naphthyridinyl (eg,
1,5-naphthyridin-2- or 3-yl), thieno [2,3-d] pyridyl (eg, thieno [2,3-d] pyridin-3-yl), pyrazinoquinolyl (eg, pyrazino [2,3 -D] quinolin-2-yl), chromenyl (eg, 2H-chromen-2-, 3-, 4-, 5- or 6-yl), chromanyl (eg, 1-, 2-, 3-, 4)
-, 5-, 6-, 7- or 8-chromanyl), isochromanyl (eg, 1-, 3-, 4-, 5-, 6-, 7- or 8-isochromanyl), benzofuryl (eg, 2-,
3-, 4-, 5-, 6- or 7-benzofuryl), benzothienyl (eg, 2-, 3-, 4-, 5-, 6- or 7-benzothienyl), benzimidazolyl (eg, 2
-, 4-, 5-, 6- or 7-benzimidazolyl), indazolyl (eg, 1H-indazole-1-,
3-, 4-, 5-, 6- or 7-yl), benzoxazolyl (eg, 2-, 4-, 5-, 6- or 7-benzoxazolyl), benzoisoxazolyl ( For example, 3-,
4-, 5-, 6- or 7-benzoisoxazolyl),
Benzothiazolyl (eg, 2-, 4-, 5-, 6- or 7-benzothiazolyl), benzothiadiazolyl (eg,
Benzo-1,2,3-thiadiazole-4-, 5-, 6
-Or 7-yl, benzo-1,2,4-thiadiazole-3-, 4-, 5-, 6- or 7-yl, benzo-
1,2,5-thiadiazole-3-, 4-, 5-, 6-
Or 7-yl, benzo-1,3,4-thiadiazole-2-, 4-, 5-, 6- or 7-yl,), benzoisothiazolyl (eg, 3-, 4-, 5-, 6 -Or 7
-Benzoisothiazolyl), benzotriazolyl (eg,
4-, 5-, 6-, 7- or 8-benzo-1,2,3
-Triazolyl, 3-, 5-, 6-, 7- or 8-benzo-1,2,4-triazolyl), cinnolyl (eg,
3-, 4-, 5-, 6-, 7- or 8-cinnolyl), phthalazinyl (eg, 1-, 5- or 6-phthalazinyl), quinazolinyl (eg, 2-, 4-, 5-, 6)
-, 7- or 8-quinazolinyl), quinoxalinyl (eg, 2-, 5- or 6-quinoxalinyl), imidazopyridyl (eg, imidazo [1,2-a] pyridine-2)
-Yl, imidazo [1,2-a] pyridyl such as imidazo [1,2-a] pyridin-3-yl), imidazothiazolyl (eg, imidazo [2,1-b] thiazole-5-
Imidazo [2,1-b] thiazolyl such as yl), dioxaindanyl (eg, 1,3-dioxaindan-2)
-, 4-, 5-, 6- or 7-yl and the like, 1,3-dioxaindanyl). Among them, imidazopyridyl and dioxaindanyl are preferred. As the substituent of the “condensed heterocyclic group”, a substituent selected from the above substituent group (T) is preferable. The number of substituents is 1 to 5 (preferably 1 to 3). Nitro is particularly preferred as the substituent.

As the compounds contained in the compound (I), in the above formula (I), A ¹ represents a C _6-14 aryl group which may be substituted by 1 to 3 C _1-4 alkyl groups, ¹ is a chemical bond,
B ¹ is substituted by 1 to 5 substituents selected from C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, cyano, halogen and nitro which may be substituted by 1 to 5 halogens. A thienyl group, a pyrazolyl group, an isothiazolyl group, an imidazolyl group, a thiazolyl group, a thiadiazolyl, a dioxaindanyl group or an imidazopyridyl group, and Z ¹ is a C _1-6 alkyl group or C _1-4
Compound (I) showing an alkoxy group or a salt thereof is preferred.

Further preferred embodiments of the compound (I) or a salt thereof are shown below. (1) As A ¹ , phenyl which may be substituted by 1 to 3 C _1-4 alkyls is preferable, and 4-methylphenyl group is particularly preferable. (2) B ¹ is selected from (i) C _1-4 alkyl optionally substituted with 1 to 5 halogens, C _1-4 alkoxy, C _1-4 alkylthio, cyano, halogen and nitro.
A thienyl group optionally substituted with up to 5 substituents,
A pyrazolyl group, isothiazolyl group, imidazolyl group, thiazolyl group or thiadiazolyl group, or (ii) a dioxaindanyl group or an imidazopyridyl group optionally substituted by 1 to 3 nitro groups is preferred. More preferred B
¹ is (i) a thienyl group optionally substituted with 1 to 3 substituents selected from halogen and nitro, (ii) 1 to 3 substituents selected from C _1-4 alkyl, nitro and cyano A pyrazolyl group optionally substituted with (iii) C _1-4
An imidazolyl group optionally substituted with 1 to 3 substituents selected from alkyl and nitro, (iv) a C _1-4 alkyl optionally substituted with 1 to 5 halogens, a C _1-4 alkylthio, A thiazolyl group optionally substituted with 1 to 3 substituents selected from halogen, nitro and cyano, (v) a C _1-4 optionally substituted with 1 to 5 halogens
Thiadiazolyl group (preferably 1,3,4-thiadiazolyl group) optionally substituted with alkyl, (vi) C _1-4 alkyl optionally substituted with 1 to 5 halogen atoms, C
_1-4 selected from alkoxy, nitro and cyano
An isothiazolyl group optionally substituted with 3 substituents, (vi) 1,3 optionally substituted with 1 to 3 nitro groups,
A dioxaindanyl group, and (vii) nitro with 1-3
An imidazo [1,2-a] pyridyl group which may be individually substituted; (3) Z ¹ is preferably a C _1-6 alkyl group or a C _1-4 alkoxy group. (4) X ¹ is preferably a chemical bond (single bond or bond). A ¹ , B ¹ , Z ¹ and X ¹ shown in the above (1) to (4)
May be combined arbitrarily.

[2] The compound (II) or a salt thereof has the formula (II)

Embedded image [Wherein A ² is (1) 1 selected from the above substituent group (T ′)
X ² represents an aryl group which may be substituted with up to 5 (preferably 1 to 3) substituents or (2) a heterocyclic group which may be substituted, X ² represents (1) a chemical bond, (2) An optionally substituted methylene group or (3) an optionally substituted vinylene group, B ² represents an optionally substituted aryl group, and Z ² represents
(1) mono- or di-C _1-6 alkylamino, hydroxy, halogen, C _1-6 alkoxy, C _1-6 alkoxy-carbonyl, C _1-6 alkylthio and substituted with a substituent selected from cyano Alkyl group, (2) vinyl group, (3) allyl group, (4) propadienyl group, (5) optionally substituted alkynyl group, (6) optionally substituted cycloalkyl group, (7 Optionally substituted aryl groups, (8) optionally substituted acyl groups, (9) formyl groups, (10) optionally substituted amino groups, (11) -N = C
A group represented by R ¹ R ² (R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group which may be substituted), (12)
A cyclic amino group, (13) -OR ³ (R ³ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group, or an optionally substituted alkylsulfonyl group ), Or (14) -S
(O) _n R ⁴ (n represents an integer of 0 to 2, R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted)) or a salt thereof. It is. A ²
Examples of the aryl group in phenyl and naphthyl (eg,
And C _6-14 aryl groups such as 1-naphthyl and 2-naphthyl). Particularly, a phenyl group is preferred. Heterocyclic group which may be substituted in the A ² is as defined heterocyclic group which may be substituted at A ^0. Each substituent of X ^{2 has} the same meaning as X ⁰ described above.

The aryl group which may be substituted in the B ² have the same meanings as the aryl group which may be substituted in the B ^0. As the aryl group, a phenyl group is particularly preferred. Z ^{2 represents} a mono- or di-C _1-6 alkylamino, hydroxy, halogen, C _1-6 alkoxy, C _1-6
Examples of the alkyl group in the "alkyl group which may be substituted with a substituent selected from alkoxy-carbonyl, C _1-6 alkylthio and cyano" include methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, se
c-butyl, tert-butyl, n-pentyl, sec-pentyl,
Examples include C _1-6 alkyl groups such as isopentyl, neopentyl, n-hexyl, and isohexyl. The number of substituents in the alkyl group is 1 to 5, preferably 1 to 3. As the mono- or di-C _1-6 alkylamino in the substituent, methylamino, ethylamino, n-propylamino, dimethylamino, ethylmethylamino,
Examples thereof include diethylamino and the like, and particularly preferred is mono- or di-C _1-4 alkylamino. Halogen includes fluorine, chlorine, bromine and iodine. C _1-6 alkoxy includes methoxy, ethoxy, n-propoxy,
Examples include isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like, with C _1-4 alkoxy being particularly preferred. Examples of the C _1-6 alkoxy-carbonyl include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and the like, and C _1-4 alkoxy-carbonyl is particularly preferable.
As C _1-6 alkylthio, methylthio, ethylthio, n
-Propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio and the like, with C _1-4 alkylthio being particularly preferred. The alkynyl in the “optionally substituted alkynyl” for Z ² includes a C _2-6 alkynyl group such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl and 3-butynyl. Examples of the cycloalkyl in the “optionally substituted cycloalkyl” include C _3-6 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. As the aryl in the “aryl group which may be substituted”, phenyl, naphthyl (eg, 1-naphthyl,
And C _6-14 aryl such as 2-naphthyl). As the substituent of the alkynyl group, cycloalkyl group or aryl group, each of the alkynyl group, cycloalkyl group or aryl group exemplified in the hydrocarbon group of the aforementioned “optionally substituted hydrocarbon group” of Z ⁰ is The same substituents as the substituents that may be included are mentioned. The number of substituents in the alkynyl group, cycloalkyl group or aryl group is 1 to 5, preferably 1 to 3, respectively.

The "optionally substituted acyl group" for Z ^2, "optionally substituted amino group", "- N =
Group represented by CR ¹ R ² ”,“ cyclic amino group ”,“ —OR
^The “group represented by ³ ” and the “group represented by —S (O) _n R ⁴ ” are respectively the “optionally substituted acyl group” and the “optionally substituted amino group” in Z ⁰ . "
“A group represented by —N ＝ CR ¹ R ² ”, “cyclic amino group”,
The same meaning as "group represented by -OR ^3" and "-S (O) group represented by _n R ^4".

As the compounds contained in the compound (II), in the above formula (II), A ² is (1) (i) a C _1-4 alkyl group which may be substituted with 1 to 5 halogens; ii) 1 to 5 with halogen
Optionally substituted C _1-4 alkoxy group, (iii) C
_From an amino group optionally substituted by one or two _1-4 alkyl-carbonyl, (iv) a C _1-4 alkoxy-carbonyl group, (v) a halogen atom, (vi) a cyano group and (vii) a nitro group. A C _6-14 aryl group optionally substituted with 1 to 5 selected substituents or (2) (i) a C _1-4 alkyl group,
(ii) C _1-4 alkoxy-carbonyl group, (iii) carbamoyl group, (iv) mono- or di-C _1-4 alkylcarbamoyl group, (v) C _1-4 alkylsulfonyl group, (vi) halogen atom , (Vii) a carboxyl group and (viii) a thienyl group, a triazolyl group, an imidazolyl group, an isoxazolyl group, a pyrazolyl group, a pyridyl group, a quinolyl group which may be substituted with 1 to 5 substituents selected from a cyano group. A benzothiadiazolyl group, an imidazothiazolyl group or an imidazopyridyl group, X ² represents (1) a chemical bond, (2) a methylene group optionally substituted by one or two C _1-4 alkyl or ( 3) a vinylene group which may be substituted by one or two C _1-4 alkyls; B ² is (1) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di- −C _{1 A} C _1-4 alkyl group which may be substituted with 1 to 5 substituent (s) selected from _-4 alkylhydrazono and C _1-4 alkylthio, (2)
C _2-4 alkynyl group, (3) hydroxy group, (4) halogen and C _1-4 1 to 5 amino optionally substituted with a substituent C _1-4 alkoxy group selected from alkoxy, (5) C _1-4 alkyl-carbonyloxy group, (6) C _1-4 alkylthio group, (7) C _1-4 alkylsulfinyl group, (8) C _1-4 alkylsulfonyl group, (9) mono- or di- C _1-4 alkylsulfamoyl group, (10) amino group, (11) formyl group, (1
2) C _1-4 alkoxy-carbonyl group, (13) carbamoyl group, (14) mono- or di-C _1-4 alkylcarbamoyl group, (15) thiocarbamoyl group, (16) halogen atom, (1
7) one selected from a carboxyl group, (18) thiocyanato group, (19) cyano group, (20) nitroso group and (21) nitro group
A C _6-14 aryl group optionally substituted with up to 5 substituents, Z ² represents (1) mono- or di-C _1-4 alkylamino, hydroxy, halogen, C _1-4 alkoxy, C _C1-4 alkoxy - carbonyl, C _1-4 alkylthio and 1-5 optionally substituted C _1-6 alkyl group with a substituent selected from cyano, (2) vinyl group, (3) allyl group, ( 4) propadienyl group, (5) C _2-6 alkynyl group optionally substituted with 1 to 5 halogens, (6) C _3-6 cycloalkyl group, (7) C _6-14 aryl group, (8 ) C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens, (9) C
_1-4 alkyl, C _1-4 alkyl-carbonyl and C _1-4
An amino group optionally substituted by one or two substituents selected from alkoxy-carbonyl, (10) -N = CR
A group represented by ¹ R ² (R ¹ and R ² each represent a C _1-4 alkyl group); (11) —OR ³ (R ³ is a C _1-4 alkyl group or a C _1-4 alkyl-carbonyl); Or (12) —S (O) _n R ⁴ (n is an integer of 0 to 2, and R ⁴ is (a) 1 to 5 carbon atoms which may be substituted with halogen. (II) or a salt thereof, which is a group represented by a _1-4 alkyl group or (b) a C _6-14 aryl group which may be substituted with 1 to 5 C _1-4 alkyl). .

Further preferred embodiments of the compound (II) or a salt thereof are shown below. (1) A ² is (a) C _1-4 alkyl optionally substituted with 1 to 3 halogen, halogen, nitro, cyano, acetylamino, C ₁ to 3 optionally substituted with halogen
_A phenyl group optionally substituted with 1 to 3 substituents selected from _1-4 alkoxy and C _1-4 alkoxy-carbonyl, (b) naphthyl group, (c) C _1-4 alkyl group 3
An optionally substituted isoxazolyl group, (d) mono-
Or a triazolyl group optionally substituted with 1 to 3 di-C _1-4 carbamoyl, (e) pyridyl group, (f) quinolyl group, (g) a substituent selected from C _1-4 alkyl and halogen. 1 to 3 optionally substituted thienyl groups, (h)
C _1-4 alkyl, C _1-4 alkoxy - carbonyl, carboxyl, carbamoyl, cyano and 1-3 optionally substituted pyrazolyl group with a substituent selected from halogen, 1 (i) C _1-4 alkyl Imidazolyl group which may be substituted by 3 to 3, (j) benzothiadiazolyl group (preferably 2,1,3-benzothiadiazolyl group), and (k) 1 to 3 substituted by halogen May be substituted with 1 to 3 substituents selected from imidazothiazolyl groups (preferably imidazo [2,1-b] thiazolyl groups) or (l) halogen and C _1-4 alkylsulfonyl. An imidazopyridyl group (preferably an imidazo [1,2-
a] pyridyl group) is preferred, and a C _1-4 alkyl group, C _1-4
A phenyl group or a thienyl group, which may be substituted with 1 to 3 alkoxy groups, halogen or cyano groups, is more preferred. Among them, a phenyl group which may be substituted with 1 to 3 substituents selected from C _1-4 alkyl and halogen is preferable, and phenyl in which the 4-position of the phenyl group is substituted with a methyl group or a chlorine atom is particularly preferable. .

(2) B ² is the one wherein the 2- or 4-position of the phenyl group is (a) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di-C _1-4 A C _1-4 alkyl group which may be substituted by 1 to 5 substituent (s) selected from alkylhydrazono and C _1-4 alkylthio, (b) a C _2-4 alkynyl group, (c) a hydroxy group, (d A) a C _1-4 alkoxy group optionally substituted with 1 to 5 substituents selected from halogen and C _1-4 alkoxy, (e) a C _1-4 alkyl-carbonyloxy group,
(f) C _1-4 alkylthio group, (g) C _1-4 alkyl sulfinyl group, (h) C _1-4 alkyl sulfonyl group, (i) mono- or di-C _1-4 alkyl sulfamoyl group, (j) formyl group, (k) C _1-4 alkoxy-carbonyl group, (l) carbamoyl group, (m) mono- or di-C _1-4 alkylcarbamoyl group, (n) thiocarbamoyl group, (o) Halogen atom,
A phenyl group substituted with a substituent selected from (p) a carboxyl group, (q) thiocyanato group, (r) cyano group, (s) nitroso group and (t) nitro group is preferred. As B ² is

Embedded image (M ¹ represents a nitro group, a cyano group, a trifluoromethyl group or a thiocarbamoyl group, and M ² represents a halogen atom, a cyano group, a nitro group or a trifluoromethyl group).

(3) Z ² is selected from (a) mono- or di-C _1-4 alkylamino, hydroxy, halogen, C _1-4 alkoxy, C _1-4 alkoxy-carbonyl, C _1-4 alkylthio and cyano 1 to 5 C _1-6 alkyl groups which may be substituted with 1 to 5 substituents selected, (b) vinyl group, (c) allyl group, (d) propadienyl group, (e) 1 to 5 substituted with halogen An optionally substituted C _2-6 alkynyl group, or (f) C _3-6
A cycloalkyl group or (g) a C _1-4 alkoxy group is preferred. Particularly, a C _1-6 alkyl group, C _3-6 cycloalkyl group, vinyl group, allyl group, C _2-6 alkynyl group or C _2-6
1-4 alkoxy groups are preferred. (4) X ² is preferably a chemical bond (single bond or bond). The preferred embodiments of A ² , B ² , Z ² and X ² shown in the above (1) to (4) may be arbitrarily combined.

In another embodiment, as the compound (II) or a salt thereof, A ² is a phenyl group which may be substituted by 1 to 3 substituents selected from a C _1-4 alkyl group, halogen and cyano. X ² is a chemical bond, B ² is (1) halogen,
Three optionally substituted C _1-4 alkyl groups, (2) C _1-4
Alkoxy group, (3) C _1-4 alkylthio group, (4) thiocarbamoyl group, (5) halogen atom, (6) cyano group and (7)
A phenyl group which may be substituted with 1 to 5 substituents selected from a nitro group, Z ² is (1) C _1-4 alkoxy,
Up to 3 optionally substituted C _1-6 alkyl groups, (2) C
A compound showing a _3-6 cycloalkyl group, (3) allyl group or (4) C _1-4 alkoxy group or a salt thereof is preferable.

[3] The compound (III) or a salt thereof has the formula (I)
II)

Embedded image Wherein A ³ represents (1) an optionally substituted aryl group or (2) an optionally substituted heterocyclic group, X ³ represents (1) a chemical bond, and (2) an optionally substituted A good methylene group or (3) an optionally substituted vinylene group, B ³ is a substituted 6-membered heterocyclic group, Z ³ is (1) an optionally substituted hydrocarbon group, (2) An optionally substituted acyl group, (3) a formyl group, (4) an optionally substituted amino group, (5) -N = C
A group represented by R ¹ R ² (R ¹ and R ² each represent a hydrogen atom or an optionally substituted hydrocarbon group), (6)
Cyclic amino group, (7) -OR ³ (R ³ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group or an optionally substituted sulfonyl group) Or a group represented by the formula (8) -S (O) _n R ⁴ (n
Represents an integer of 0 to 2, R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted)) or a salt thereof. A ³ , X ³ and Z ³
Have the same meanings as A ⁰ , X ⁰ and Z ⁰ , respectively.

[0054] Examples of the "6-membered heterocyclic group" of B ³ in the "6-membered heterocyclic group having a substituent" include 1 to 4 hetero atoms selected from nitrogen atom, oxygen atom and sulfur atom 6
Membered heterocyclic groups. Specifically, pyridyl (e.g.,
2-, 3- or 4-pyridyl), pyridazinyl (eg,
3- or 4-pyridazinyl), pyrimidinyl (eg, 2
-, 4- or 5-pyrimidinyl), pyrazinyl, piperidinyl (eg, 1-, 2-, 3- or 4-piperidinyl), piperazinyl (eg, 1- or 2-piperazinyl) and the like. Of these 6-membered heterocyclic groups, pyridyl, pyridazinyl and pyrimidinyl are particularly preferred. As the substituent of the 6-membered heterocyclic group, a substituent included in the above substituent group (T) is preferable. The number of the substituents is 1 to 5 (preferably 1 to 3).

Compounds included in compound (III) include:
In the formula (III), A ³ is a 1-5 substituted 1 phenyl group or a C _1-4 alkyl optionally or two optionally substituted imidazolyl group by C _1-4 alkyl, X
³ a chemical bond, B ³ is substituted with 1-5 substituents selected from C _1-4 alkyl, C _1-4 alkoxy, halogen and nitro, pyridyl group, pyridazinyl group or pyrimidinyl group, Z ³ is preferably a compound (III) showing a C _1-6 alkyl group or a C _3-6 cycloalkyl group or a salt thereof. A ³ is more preferably a phenyl group which may be substituted with 1 to 5 C _1-4 alkyls, and more preferably a 4-methylphenyl group.

[4] The compound (IV) or a salt thereof is represented by the formula (I)
V)

Embedded image Wherein A ⁴ represents (1) an optionally substituted aryl group or (2) an optionally substituted heterocyclic group, X ⁴ represents (1) a chemical bond, (2) an optionally substituted A good methylene group or (3) a optionally substituted vinylene group, B ⁴ is a pyridazinyl group or a pyrazinyl group, Z ⁴ is (1) an optionally substituted hydrocarbon group, (2) a substituted Good acyl group, (3)
Formyl group, (4) optionally substituted amino group, (5)-
A group represented by N = CR ¹ R ² (R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group which may be substituted), (6) a cyclic amino group, and (7) —OR ³ (R ³ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group or an optionally substituted sulfonyl group) or a group represented by (8) -S ( O) _n R
⁴ (n represents an integer of 0 to 2; R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted);
Or a salt thereof. Each substituent of A ⁴ , X ⁴ and Z ^{4 has} the same meaning as A ⁰ , X ⁰ and Z ⁰ , respectively.

[5] The compound (V) or a salt thereof has the formula (V)

Embedded image [Wherein, A ⁵ represents a 4-methylphenyl group, X ⁵ represents a chemical bond (single bond or a bond), B ⁵ represents a pyridyl group or a pyrimidinyl group, and Z ⁵ represents a C _1-4 alkyl group (eg, Methyl, ethyl, n-propyl, isopropyl)] or a salt thereof.

Among the above-mentioned compounds (I) to (V), compounds
(I) to (III) or salts thereof are preferred, and compound (II) or a salt thereof is particularly preferred. Among the above-mentioned compound (I ⁰ ) or a salt thereof, the following compound (VI) or a salt thereof is a novel compound and is particularly preferably used. The compound (VI) or a salt thereof is a compound included in the compound (II) or a salt thereof. Formula (VI)

Embedded image Wherein A ⁶ is C _1-4 alkyl (eg, methyl, ethyl, n-
Propyl, isopropyl), halogen (eg, fluorine, chlorine, bromine, iodine) and cyano which may be substituted with a substituent selected from cyano, X ⁶ represents a chemical bond (single bond or bond), B ⁶ is a 2-nitrophenyl group (or 6-nitrophenyl group) or a 2-cyanophenyl group (or 6) substituted with a halogen atom (eg, fluorine, chlorine, bromine, iodine), a substituent selected from nitro and cyano. -Cyanophenyl group), and Z ⁶ represents an ethyl group, an isopropyl group, a cyclopropyl group, a methoxy group, an ethoxy group or an isopropoxy group] or a salt thereof. In particular, A ⁶ represents a phenyl group which may be substituted with a substituent selected from C _1-4 alkyl, halogen and cyano, X ⁶ represents a chemical bond, and B ⁶ represents a substituent selected from a halogen atom, nitro and cyano. A compound or a salt thereof, wherein a 2-nitrophenyl group substituted with a group, and Z ⁶ represents an ethyl group, an isopropyl group or a cyclopropyl group. The number of substituents in the phenyl group of A ⁶ is 1 to 3. As the substituent, methyl and chlorine are particularly preferred. The phenyl group preferably has a substituent at the 4-position of the phenyl group. The number of substituents of the 2-nitrophenyl group (or 6-nitrophenyl group) or the 2-cyanophenyl group (or 6-cyanophenyl group) of B ⁶ is 1 to 3. As the substituent, halogen and cyano are particularly preferred. Such a substituent is preferably at the 4-position of a 2-nitrophenyl group (or 6-nitrophenyl group) or a 2-cyanophenyl group (or 6-cyanophenyl group).

Compounds (I ⁰ ), (I), (II), (III),
When using (IV), (V) or (VI) or a salt thereof (hereinafter sometimes abbreviated as “compound (I ⁰ ) or a salt thereof”) as a microbicide composition, a general pesticide must be used. It is used as a known form of the composition.
That is, one or more (preferably one or more, three or less) of the compound (I ⁰ ) or a salt thereof is mixed or dispersed as an active ingredient with an appropriate liquid carrier depending on the purpose of use, or with an appropriate solid carrier. Mix or adsorb,
Emulsions, oils, aqueous suspensions, emulsions, solutions, ULV
Powder, wettable powder, powder, DL (driftless) powder, granule,
Of fine granules, fine granules F, flowables, dry flowables, tablets, jumbo, sprays, ointments, pastes, foams, aerosols, microcapsules, seed coatings, smokers, sticks for irrigation of crops Use as a dosage form. These preparations may be used, if necessary, for example, emulsifiers, suspensions,
Spreading agents, penetrants, wetting agents, dispersants, mucilage agents, stabilizers, binders, flow aids, anti-caking agents, flocculants, antioxidants, floating agents, defoamers, antifreeze agents, Preservatives, moisture removing agents, ultraviolet absorbers, ultraviolet scattering agents, coloring agents, suspension stabilizers and the like may be added, and can be prepared by a method known per se.
That is, it can be produced by uniformly mixing the compound (I ⁰ ) or a salt thereof, a liquid carrier or a solid carrier, the above-mentioned various additives, and other pesticidal active ingredients, if necessary. For example, an emulsion can be produced by uniformly mixing and dissolving the compound (I ⁰ ) or a salt thereof, an emulsifier, an organic solvent and the like. For example, granules, wettable powders and the like are produced by uniformly mixing the compound (I ⁰ ) or a salt thereof, a dispersant (surfactant), a binder, a bulking agent (or a solid carrier), and granulating the mixture. it can. For example, a powder (such as a DL powder) can be produced by uniformly mixing and pulverizing the compound (I ⁰ ) or a salt thereof, a bulking agent (or a solid carrier), and the like. For example, a flowable agent is obtained by mixing and dispersing components such as compound (I ⁰ ) or a salt thereof, and a dispersant using a stirrer,
It is manufactured by wet pulverization using a dyno mill or the like. For example, a jumbo agent can be produced by uniformly mixing the compound (I ⁰ ) or a salt thereof, a dispersant (surfactant), a binder, a suspending agent, a bulking agent (or a solid carrier) and the like, and granulating the mixture. Jumbo powders, powders, granules, water dispersible granules, wettable powders, etc., are used for easy spraying.
The water-soluble film may be packaged and used in units of 200 g. Examples of the water-soluble film include polyvinyl alcohol, carboxymethylcellulose, starch, gelatin, polyvinylpyrrolidone, polyacrylic acid and its salts, pullulan (trade name: starch-based polysaccharide), and paogen (trade name: thermoplastic water-soluble polymer). No.

Examples of the liquid carrier (solvent) to be used include water, alcohols such as methanol, ethanol, propanol, isopropanol, and ethylene glycol; ketones such as acetone and methyl ethyl ketone; such as 1,4-dioxane, tetrahydrofuran, and ethylene glycol Ethers such as monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc., for example, kerosene, kerosene, fuel oil, machine oil, edible oil, etc., aliphatic hydrocarbons, for example, benzene, toluene, xylene, solvent naphtha, methyl naphthalene, etc. Aromatic hydrocarbons, for example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and the like, for example, N, N-dimethylformamide, N, N-dimethylacetamide Solvents such as acid amides such as ethyl acetate, butyl acetate, esters such as fatty acid glycerin ester, and nitriles such as acetonitrile and propionitrile are suitable, and one or more (preferably one or more) , Three or less) in an appropriate ratio and used as appropriate.

Examples of solid carriers (diluents, extenders) include vegetable powders such as soybean flour, tobacco flour, wheat flour and wood flour, such as clays such as kaolin, bentonite and acid clay.
For example, talc such as talc powder, waxite powder, for example, diatomaceous earth,
Mineral powders such as silica such as mica powder, calcium carbonate, alumina, sulfur powder, activated carbon and the like are used, and these may be used alone or in combination of two or more (preferably one or more and three or less) in an appropriate ratio. Can be used. Ointment bases include, for example, polyethylene glycol, pectin, polyhydric alcohol esters of higher fatty acids such as glyceryl monostearate, for example, cellulose derivatives such as methylcellulose, sodium alginate, bentonite, and higher alcohols such as glycerin. Alcohol, petrolatum, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hardened oil, one or more (preferably one or more, three or less) of resins, or various types shown below What added a surfactant etc. is used suitably. Surfactants used as emulsifiers, spreading agents, penetrants, wetting agents and dispersants include soaps, polyoxyethylene alkyl ethers (Newcalgen D15
04 ^™ (TM indicates a registered trademark), Neugen ET65 ^™ , Neugen ET83 ^™ , Neugen ET15
7 ^™ ), polyoxyethylene alkyl phenyl ethers, polyoxyethylene nonyl phenyl ethers (Nonipol 20 ^™ , Nonipol 100 ^™, etc.), polyoxyethylene alkyl allyl ethers [eg, Neugen EA142 ^™ , Neugen EA92 ^™ ; Nonal ^TM ; manufactured by Toho Kagaku Co., Ltd.], polyethylene glycol ethers [eg, Nonipol 85 ^™ , Nonipol 160 ^™ ; manufactured by Sanyo Chemical Co., Ltd.], polyhydric alcohol esters [eg, Tween 20 ^TM , Tween 80
^TM ; manufactured by Kao Corporation], polyoxyethylene polyoxypropylene ethers, polyoxyethylene distyrenated phenyl ether (Neugen EA87 ^™ , Neugen EA
177 ^™, etc.), polyoxyethylene alkyl esters (ionet MO20 ^™ , ionet MO600)
^TM ), sorbitan fatty acid esters (Reodol SP-
S10 ^™ , Reodol TW-S20 ^™, etc.), polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide (Newpol PE
64 ^TM), higher fatty acid alkanolamide, a nonionic surfactant such as an alkyl maleic acid copolymer (Demol EP ^TM, etc.); alkyl amine salts, cationic surfactants such as quaternary ammonium salts, alkyl sulfate Salts [eg, Emar 10 ^™ , Emar 40 ^™ ; Kao Corporation
Alkyl sulfonates [eg, Neogen ^™ , Neogen T ^™ ; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neoperex; manufactured by Kao Corporation], naphthalenesulfonic acid polycondensate metal salt,
High molecular compounds such as formalin condensates of naphthalene sulfonates (eg, Newcalgen FS4 ^™ ), alkyl naphthalene sulfonates (eg, Solpol 5115 ^™ ), metal salts of lignin sulfonic acid, alkyl allyl sulfonates, and alkyl allyl sulfonate sulfates , Polynaphthyl methanesulfonate, polystyrenesulfonate sodium salt, polycarboxylate metal salt, polyoxyethylene histyl phenyl ether sulfate ammonium, higher alcohol sulfonate, higher alcohol ether sulfonate, dialkyl sulfosuccinate (new Anionic surfactants such as Kalgen EP70P ^™ ) and alkali metal salts of higher fatty acids are used. As the salt, sodium salt, potassium salt, ammonium salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, to the extent that the performance of the surfactant is not hindered,
Diisopropanolamine salts, triisopropanolamine salts, and other tertiary amine salts such as dialkyldimethylammonium salts are used. As the spreading agent, anionic surfactants containing a tertiary amine as a cation among the above-mentioned surfactants [eg, dialkyldimethylammonium polynaphthyl methanesulfonate such as Needs ^TM (Kumiai Chemical Sales, Kao Pharmaceutical Co., Ltd.) Are preferred. As a stabilizer, a compound having an epoxy group, an antioxidant [eg, dibutylhydroxytoluene (BH
T), butylhydroxyanisole (BHA), tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (Irganox 1010), DL-tocopherol, propyl gallate, erythorbic acid , Sodium erythorbate,
Isopropyl citrate, etc.], phosphoric acid, PAP auxiliary agent (isopropyl acid phosphate), cyclodextrin (Toyoderin P), tall oil fatty acid (Hator fatty acid) and the like, and one or more of these (preferably (One or more, three or less) can be mixed and used at an appropriate ratio. As a binder, dextrin, pregelatinized starch, polyvinyl alcohol, gum arabic, sodium alginate, polyvinylpyrrolidone,
Glucose, sucrose, mannitol, sorbitol and the like are used, and these can be used alone or as a mixture of two or more (preferably one or more and three or less) at an appropriate ratio. As the fluidity aid, a PAP aid (eg, isopropyl acid phosphate), talc, or the like is used, and these may be used alone or in a combination of two or more (preferably one or more, three or less) at an appropriate ratio. can do. As the anti-caking agent, white carbon, diatomaceous earth, magnesium stearate, aluminum oxide, titanium dioxide and the like are used, and these may be used alone or in combination of two or more (preferably one or more and three or less) in an appropriate ratio. It can be used as appropriate. As the coagulant, liquid paraffin, ethylene glycol, diethylene glycol, triethylene glycol, isobutylene polymer (eg, IP solvent) and the like are used, and these are one kind or two or more kinds (preferably one kind or more, three kinds or less).
May be mixed at an appropriate ratio and used as appropriate. As antioxidants, dibutylhydroxytoluene, 4,
4-thiobis-6-tert-butyl-3-methylphenol, butylhydroxyanisole, paraoctylphenol, mono (or di or tri) (a-methylbenzyl) phenol, 2,6-di-tert-butyl-4 -Methylphenol, tetrakis [3- (3,5-di-tert-
[Butyl-4-hydroxyphenyl) propionyloxymethyl] methane and the like, and one or more of them (preferably one or more and three or less) can be mixed and used at an appropriate ratio. Suspending agents are used particularly for producing jumbo agents, and have a specific gravity of 1 or less (preferably 1
To 0.5) are preferred. The powder base has a particle diameter of 600 μm or less, preferably 600 μm.
m to 10 μm are preferable. Inorganic materials obtained by firing natural glassy material and having one or more independent bubbles therein, for example, pearlite or shirasu made of perlite or obsidian Shirasu balloon (trade name) made of vermiculite made of vermiculite, and a fine hollow phyllite (trade name) obtained by similarly firing in an aluminosilicate system. In addition, organic materials include higher fatty acids such as stearic acid and palmitic acid that are solid at ordinary temperature, higher alcohols such as stearyl alcohol, and paraffin wax, which are generally called waxy substances. Therefore, it is difficult for water to penetrate, the pesticidal active ingredient may be entrapped in the waxy substance for a long time, and it may be difficult to disperse the substance in water. Therefore, it is preferably used by mixing with the above-mentioned glassy hollow body. As the defoaming agent, a silicon-based defoaming agent (for example, anti-home E20) or the like is used, and these are used singly or in combination of two or more (preferably one or more, three or less) in an appropriate ratio. be able to. Antifreeze agents include ethylene glycol, diethylene glycol, polyethylene glycol,
Glycerin and the like are used, and one or two or more (preferably one or more and three or less) can be mixed at an appropriate ratio and used appropriately. As the preservative, butyl paraben, potassium sorbate and the like are used, and these can be used alone or in a combination of two or more (preferably one or more and three or less) at an appropriate ratio. As the water removing agent, anhydrous gypsum, silica gel powder and the like are used, and these can be used alone or in a mixture of two or more (preferably one or more and three or less) at an appropriate ratio. As the ultraviolet absorber, 2- (2 ′)
-Hydroxy-5'-methylphenyl) benzotriazole, 2-ethoxy-2'methyloxalic acid bisanilide, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6 -Tetramethylpiperidine polycondensate and the like can be used, and these can be used as appropriate by mixing one kind or two or more kinds (preferably one kind or more and three kinds or less) at an appropriate ratio. As the ultraviolet scattering agent, titanium dioxide or the like is used, and these are one kind or two or more kinds (preferably one kind or more, three kinds or less).
Can be mixed at an appropriate ratio and used as appropriate. Coloring agents include Cyanine Green G, Erio Green B
400 or the like can be used, and these can be used as appropriate by mixing one kind or two or more kinds (preferably one kind or more, three kinds or less) at an appropriate ratio. Examples of the suspension stabilizer include polyvinyl alcohol (such as Gohsenol GH17), clay minerals (such as Kunipia F, VEEGUM R), and silicon dioxide (such as Aerosil COK84), and one or more of these (preferably one or more). , Three or less) in an appropriate ratio and used as appropriate. Jumbo, powders, granules, wettable powders, wettable powders and the like may be used by being packaged in a water-soluble film in a unit of 20 to 200 g for easy application. Examples of the water-soluble film include polyvinyl alcohol, carboxymethyl cellulose, starch, gelatin, polyvinyl pyrrolidone,
Examples include polyacrylic acid and its salts, pullulan (trade name: starch-based polysaccharide), paogen (trade name: thermoplastic water-soluble polymer), and the like.

Further, the compound (I ⁰ ) or a salt thereof may be used together with, for example, an insecticide, an acaricide, a nematicide, a herbicide, a plant hormone, a plant growth regulator, a fungicide, a synergist, an attractant, It is also possible to mix a repellent, a pigment, a fertilizer, and the like and use it as appropriate. That is, the present invention includes an agricultural and horticultural microbicide containing the compound (I ⁰ ) or a salt thereof and another agricultural chemical active ingredient. Other pesticidal active ingredients are compounds (I
⁰ ) or a salt thereof may be contained in the same preparation.
Moreover, after formulating into separate preparations, they may be mixed at the time of use. Representative examples of insecticides, acaricides, and nematicides that can be used by mixing with the compound (I ⁰ ) or a salt thereof are shown below.
Acephate, acetamiprid
d), acrinathrin, alanicarb (alan)
ycarb), aldrin, allethri
n), aluminum phosphide (Aluminium phosphide), amitraz (amitraz), arsenite (Arsenic acid), avermectin (avermectin-B), bendiocarb (bendiocarb),
Benfuracarb, Bensultap
tap), benzoximate, bifenthrin, bromopropylat
e), buprofezin, lime nitrogen (Calcium c
yanamide), lime sulfur mixture (Calcium polysulfide), carbaryl (carbaryl: NAC), carbofuran (carbofuran), carbosulfan (carbosulfan), cartap (cartap),
Chlordane, chlorfenvinphos (chlorf
envinphos: CVP), chlorfluazuro
n), chlorphenapyr, chlorpyrifos-methyl, chromafenozide
(chromafenozide), clofentezine,
Clothianidin, cyanophos (cyanopho)
s: CYAP), cycloprothrin (cycloprothrin), cyfluthrin (cyfluthrin), cyhalothrin (cyhalothrin), cypermethrin (cypermethrin), cyromazine (cyromazine),
DCIP (dichlorodiisopropyl ether), DD (1,3-Di
chloropropene), DDT, deltamethri
n), diafenthiuron, diazinon, diclofenthion,
Dichlorvos (DDVP), dicofol (dicofol),
Dieldrin, dienochlor,
Diflubenzuron (diflubenzuron), dimethoate (dime
thoate), dimethylvinphos, disulfoton, DSP, endosulfan
ulfan), EPN, esfenvalerat
e), ethion, ethofenprox (ethofen
prox), ethoprophos, etoxazole (e
toxazole), fenbutatin oxide,
Fenitrothion (MEP), Fenobucarb
(fenobucarb), phenothiocarb (fenothiocarb), fenoxycarb (fenoxycarb), fenpropatrin (fenpr
opathrin), fenpyroximate, fenvalerate, fipronil
l), fluazinam (fluazinam), flucitrinate (fluc
ythrinate), flufenoxuron, flupyrazofos, fluvalina
te), formetanate, formotione (for
mothion), fosthiazate, furathiocarb, halfenprox
x), hexaflumuron (hexaflumuron), hexthithiazox (hexythiazox), hydrogen phosphide (Hydrogen phosphide),
Imidacloprid, isofenphos (iso
fenphos), isoprocarb, isoxathion, malathion, mesulfenfos, metham ammonium
monium), metam-sodium, methidathion, methiocarb, methocarb, methomyl, methoxychlor, methoxyfenozide, methyl bromide
yl bromide), metolcarb (MTMC), milbemycin-A, monocrotophos (monocroto
phos), nared (naled: BRP), nicotine sulfate (nicotine-
sulfate, nidinotefuran, nitenpyram, oxamyl, oxydeprofos (ESP), parathion, permethrin, phenthoate:
PAP), phosalone, phosmet (PM
P), pirimicarb (pirimicarb), pirimiphos-methyl (p
irimiphos-methyl), potassium oleate (Potassium ol
eate), profenofos, propafos (prop
aphos), propargite (propargite: BPPS), propoxur (propoxur), prothiofos (prothiofos), protrifenbute (protrifenbute), pymetrozine (pymetr)
ozine), pyraclofos, pyrethrin (pyret)
hrins), pyridaben, pyridafenthion
(pyridafenthion), pyrimidifen, pyriproxyfen, quinalphos
hos), resmethrin (resmethrin), salicion (salithi)
on), silafluofen, sulfur,
Sulprofos, tebufenozi
de), tebufenpyrad (tebufenpyrad), teflubenzuron (teflubenzuron), tefluthrin (tefluthrin), temephos (temephos), tetrachlorvinphos (tetrachlorv
inphos), tetradifon, thiacloprid
(thiacloprid), thiamethoxam, thiocyclam, thiodicarb, thiometon, tolfenpyra
d), tralomethrin, trichlorfon (t
richlorfon: DEP), triflumuron, vamidothion, XMC.

Representative examples of fungicides which can be used in admixture with compound (I ⁰ ) or a salt thereof are shown below. For example, acetic acid (ace
tic acid), Acibenzolar S-methyl (acibenzolar-
S-methyl), ambam, anilazine
e), azoxystrobin, benomyl (ben
omyl), benthiazole, bitertanol
(bitertanol), blasticidin-S
S), Bordeaux mixture, Bromconazole
(bromuconazole), butiobate, calcium hypochlorite, lime sulfur combination
(Calcium polysulfide), captan, carbendazol, carpropamido
d), IKF-916 (4-chloro-2-cyano-N, N-dimethyl-5
-p-tolylimidazole-1-sulfonamide), chloroneb (chlor
oneb), chloropicrin, chlorothalonil (TPN), cinnamaldehyde (Cinnamaldeh
yde), RH-7281 (3,5-dichloro-N- (3-chloro-1-et
hyl-1-methyl-2-oxopropyl) 4-methylbenzamide), CN
A (2,6-Dichloro-4-nitroaniline), cupric hydroxide (Copp
er hydroxide), Copper sulfate, AC382
042 (N- (1-cyano-1,2-dimethylpropyl) -2- (2,4-dichl
orophenoxy) propionamide (R, S) -and (R, R) -and (S, R) -and
(S, S)), cymoxanil, cyproconazole
(cyproconazole), cyprodinil (cyprodinil), dazomet (dazomet), diclofluanid (dichlofluanid), D
-D (1,3-Dichloropropene), diclosimet (diclocym
et), diclomezine, dietofencarb
(diethofencarb), difenoconazol
e), diflumetorim, dimethilimol (d
imethirimol), dimethomorph, diniconazole-M, dinocap,
Nickel dimethyldithiocarbamate, etridiazole, famoxadone, fenarimol, fenbuconazole
ole), Fendazosulam, Fenhexamid, Fenoxanil (NNF-9425: fenoxani)
l), fenpiclonil, fenthiazone
(fentiazon), triphenyltin hydroxide (fentinhydroxid
e), ferimzone, fluazina
m), Fludioxonil, Flumetova (RP
A-403397: flumetover), fluoroimid
e), fluquinconazole, flusulfamide, flutolanil,
Fosetil (fosetyl-Al), fthalide (fthalide), furametpyr (furametpyr), hexaconazol (hexaconazol)
e), hymexazol, imazali (imazali)
l), imibenconazole, iminoctadine-albesilate, iminoctadine-triacetate, iodocarb, ipconazole, iprodione, isoprothiolane
lane), kasugamycin, kresoxim
Methyl (kresoxim-methyl), mancozeb (mancozeb), maneb (maneb), mepanipyrim (mepanipyrim), mepronil (mepronil), metalaxyl (metalaxyl), metalaxyl M (metalaxyl-M), metam sodium (metam-sodi
um), metasulfocarb, methyl bromide
(Methyl bromide), RPA407213 ((s) -5-methyl-
2-methylthio-5-phenyl-3-phenylamino-3,5-dihydroimi
dazol-4-one), metominostrobi (metominostrobi)
n), Mildiomycin, Milneb (miln
eb), microbutanil (myclobutanil), nabam (naba
m), oxadixyl, oxolinic acid (oxo
linic acid), oxpoconazole, oxycarboxin, oxytetracycline, pefurazoate
e), penconazole, penclon (penc
ycuron), picoxystrobin, polycarbamate, polyoxin
n), potassium hydrogen carbonate (Potassium hydrogen carbonat
e), probenazole, prochloraz (proc
hloraz), procymidone, propamocarb-hydrochloride, propiconaole, propineb, pyrazophos
(pyrazophos), pyributicarb, pyrifenox, pyrimethanil
l), pyroquilon, quinoxyphen
fen), quintozene (PCNB), silthiopharm (MON65500: silthiopham), sipconazole (sipconazo
le), sodium bicarbonate (Sodium bibarbonate), sodium hypochlorite (Sodium hypochlorite), SSF-1
29 ((E) -2 [2- (2,5-dimethylphenoxymethyl) phenyl] -2-
methoxyimino-N-methylacetamide), Streptomycin, Sulfur, Tebuconazole (teb
uconazole), tecloftalam, tetraconazole, thiabendazole
azole), thiram (TMTD), thifluzamide (thiflu
zamide), thiophanate-methy
l), triadimefon, triadimenol
(triadimenol), tricyclazole (tricyclazole), tridemorph (tridemorph), triflumizole (triflumiz
ole), trifloxystrobin, triforine, validamycin,
Vinclozolin, zineb, ziram
(ziram).

Representative examples of herbicides, phytohormones and plant growth regulators which can be used in admixture with compound (I ⁰ ) or a salt thereof are shown below. Abscisic acid,
Acetochlor (acetochlor), acifluorfen (aci
fluorfen-sodium), alachlor (alachlor), alloxydim (alloxydim), amethrin (ametryn), amidosulfuron, amidoprofosmethyl (amiprofos-
methyl), ancimidol (ancymidol), ashram (asu
lam), atrazine, azimsulfuron (azims
ulfuron), benfluralin, benfuresate, and bensulfu methyl
ron-methyl), bensulide (SAP), bentazone
(bentazone), benthiocarb, benzamizole, benzfendison
izone), benzofenap, benzyladenine, bialaphos, bifenox, brassinolide
e), bromacil, bromobutid
e), butachlor, butafenacyl (butafe)
nacil), butamifos, butylat
e), cafenstrole, calcium carbonate (Calcium carbonate), calcium peroxide (Calcium pe
roxide), carbaryl, chloromethoxynil (ch
lomethoxynil), chloridazon, chlorimuron-ethyl, chlorophthalim (ch
lorphthlim), chlorpropham, chlorsulfuron, chlortal dimethyl
(chlorthal-dimethyl), chlorthiamid (chlorthiamid:
DCBN), choline chloride, cinmethylin
(cinmethylin), sinosulfuron (cinosulfuron), clethodim (clethodim), clomeprop (clomeprop), cloxyfonac-sodium, 4-CPA (4-chlo
rophenoxyacetic acid), cumyluron, cyanazine, cyclosulfa
mron), cyhalofop-butyl, 2,
4-D salt (2,4-Dichlorophenoxyacetic acid salts), dichlorprop (2,4-DP),
muron), dalapon (DPA), daminosit (damino
zide), dazomet (dazomet), decyl alcohol (n-Dec
yl alcohol), dicamba-sodium (MDBA), dichlobenil (dichlobenil: DBN), diflufenican (diflufen
ican), dimepiperate, dimethametryn, dimethenamid, diquat, diquat, dithiopyr, diuron
(diuron), endothal (endothal), esprocarb (e
sprocarb), ethephon, ethidimlon (ethidi)
muron), ethoxysulfuron, ethychlozate, etobenzani
d), fenarimol, fenoxaprop
Ethyl (fenoxaprop-ethyl), fentrazamide (fentraz
amide), flazasulfuron, florasulam, fluazifop-buty
l), Flumioxazin, Flupropanate-sodium, Flurprimidol, Fluthiacet-methyl
iacet-methyl), forchlorfenulon
ron), homesafen (formesafen), gibberellin (gibbere)
llin), glufosinate, glyphosate (g
lyphosate), halosulfuron-me
thyl), hexazinone, imazamox (im
azamox), imazapyr (imazapyr), imazakin (imazaqui
n), imazosulfuron, inabenfide, indole acetic acid:
IAA), indole butyric acid, ioxynil-octanoate, isouron,
Carbutilate, lactofen
n), lenacil, linuron, maleic hydrazide, mecoprop (mec
oprop: MCPP), MCP salt (2-Methyl-4-chlorophenoxyacet)
ic acid salts), MCPA-thioethy
l), MCPB (2-Methyl-4-chlorophenoxybutanoic acid
ethyl ester), mefenacet (mefenacet), mefluidide (mefluidide), mepiquat (mepiquat), methyl daimuron (methyl daimuron), metolachlor (metolachlo
r), metribuzin, metsulfuron-methyl, molinate, NA
D (1-naphthaleneacetamide), naproanilide (naproan
ilide), napropamide, nicosulfuron
(nicosulfuron), orbencarb (orbencarb), oxadiazon (oxadiazon), oxadiclomehon (oxaziclome)
fone), oxine-sulfate, paclobutrazol, paraquat, pelargonic acid, pendimethalin (pendim
ethalin), pentoxazone, pethoxamide, phenmedipha
m), picloram, piperonyl butoxide (pip
eronyl butoxide), piperophos, pretilachlor, primisulfon
uron-methyl), procarbazone, prodiamine, prohexadione calcium (p
rohexadione-calcium), promethrin (prometryn), propanil (propanil), propizamide (propyzamide), pyraflufen-ethyl (pyraflufen-ethyl), pyrazolate (pyrazolate), pyrazosulfuron ethyl (pyrazosul)
furon-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyriminobac-methyl, pyriminobac, pyrithiobac, quinclorac, quinoclamine, quinoclamine, quizalofop-ethyl
zalofop-ethyl), rimsulfuron, sethoxydim, siduron, simazine, simethrin (simetryn), sodium chlorate (Sodium chlorate), sulfosulfuron (sulfosulfuro)
n), swep (MCP), tebuthiuro (tebuthiuro
n), terbacil, terbucarb (terbucarb: M
BPMC), thenylchlor, thiazafluron
(thiazafluron), thifensulfuron-methyl (thifens
(ulfuron-methyl), triaziflam, triclopyr, tridiphane, trifluralin, trinexapac-ethyl, tritosulfuron
on), uniconazole-P (uniconazole-P), vernalate (vemolate: PPTC).

Among the above-mentioned "other pesticidal active ingredients", a bactericidal active ingredient and an insecticidal active ingredient are particularly preferred. Also,
As the fungicidal active compound, in addition to azoxystrobin, chlorothalonil, hexaconazole, iminoctadine, mepanipyrim, kresoxim-methyl, iprodione, a soil treatment agent for rice, a seed treatment agent, or carpropamide as a surface application agent, Diclosimet, probenazole, tricyclazole, pyroquinone, isoprothiolane, acibenzol-S-methyl; carpropamide, diclosimet, probenazole as foliar spray
Tricyclazole, pyroquilon, isoprothiolane, acibenzolar-S-methyl, validamycin A, ferimzone, fusalide and the like are preferably used. Validamycin A, ferimzone, fusalide and the like are particularly preferably used. In addition, as the insecticidal active ingredient, particularly, clothianidin [1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine], nitenpyram [(E) -N- (6-chloro-3) -Pyridylmethyl) -N-ethyl-N'-methyl-2-nitrovinylidenediamine], cartap hydrochloride [1,3-bis (carbamoylthio) -2- (N, N-dimethylamino) propane hydrochloride], Bensultap [S, S'-2-dimethylaminotrimethylene = di (benzenethiosulfonate)], pyraclofos [(RS)-[O-1- (4-chlorophenyl) pyrazol-4-yl] = O-ethyl =
[S-propyl phosphorothioate] and the like are preferably used. That is, the present invention relates to a microbicide for agricultural and horticultural use containing [1] the compound (I) or a salt thereof and another pesticide active ingredient, and [2] a compound (II) or a salt thereof and another pesticide active ingredient. Agricultural and horticultural microbicides containing [3] compounds
(III) or an agricultural and horticultural microbicide containing a salt thereof and another pesticidal active ingredient; [4] an agricultural and horticultural microbicide containing the compound (IV) or a salt thereof and another pesticidal active ingredient;
[5] Agricultural and horticultural microbicide containing the compound (V) or a salt thereof and another pesticidal active ingredient, [6] Agricultural and horticultural containing the compound (VI) or a salt thereof and another pesticidal active ingredient A microbicide, [7] an agricultural and horticultural microbicide containing the following compound (II ') or a salt thereof and another pesticidal active ingredient, [8] the above-mentioned [2], wherein the other pesticidal active ingredient is an insecticidal ingredient. 1] to [7]
[10] The agricultural or horticultural microbicide according to [8], wherein the insecticidal component is at least one selected from bensultap, cartap, clothianidin, nitenpyram and pyraclopos. The microbicide for agricultural and horticultural use according to the above [1] to [7], wherein the other pesticidal active ingredient is a bactericidal ingredient; [11] The bactericidal ingredient is azoxystrobin, chlorothalonil, hexaconazole, iminoctadine, mepanipyrim , Cresoxime-methyl, iprodione, ferimzone, fusalide, and validamycin, the microbicide for agricultural and horticultural use according to the above [10], and [12] compounds (I), (II),
(III), (IV), (V), (VI) or a compound (II ′) described below, or a salt thereof and a pesticidal active ingredient in combination, characterized in that the compound (I), ( II), (III), (IV),
Methods for enhancing the microbicidal effect of (V), (VI) or (II ') are included. Among the above compounds (I), (II), (III), (IV), (V), (VI) or the compounds (II ') described below or salts thereof in combination with other agrochemical active ingredients,
(I), (II), (III), (VI) or (II ′) or a salt thereof is preferred, and compound (II), (VI) or (II ′) or a salt thereof is particularly preferred. Specifically, 4′-chloro-N-ethyl-2′-nitro-p-toluenesulfonanilide,
2 ', 4'-dinitro-N-ethyl-p-toluenesulfonanilide, 2', 4'-dicyano-N-ethyl-p-toluenesulfonanilide, 4'-chloro-N-isopropyl-2'-nitro- p-toluenesulfonanilide,
4'-fluoro-N-isopropyl-2'-nitro-p-
Toluenesulfonanilide, 4'-cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilide, 4'-chloro-N-isopropyl-2'-cyano-p
-Toluenesulfonanilide, 2 ', 4'-dinitro-N
-Isopropyl-p-toluenesulfonanilide, 4 '
-Nitro-N-isopropyl-2'-cyano-p-toluenesulfonanilide, 2'-cyano-N-methoxy-
4'-Nitro-p-toluenesulfonanilide or 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof is preferred. Compound (I ⁰ )
(Examples, compounds (I), (II), (III), (IV), (V), (VI) or the compound (II ') described below) or a salt thereof and a composition containing nitenpyram, For the purpose of improving the stability of the composition, nitenpyram may be added to, for example,
An inclusion may be included in the composition with a cyclodextrin such as (trade name). These compositions may further contain one or more (preferably one or more and three or less) other pesticidal active ingredients (for example, the above-described insecticidal active ingredient, acaricidal active ingredient, and fungicidal active ingredient). For example, compound (I ⁰ ) [eg, compounds (I), (II), (III), (IV), (V),
(VI) or a compound (II ′) described below) or a salt thereof, ferrimzone and fusalide; a compound (I ⁰ ) [eg, compounds (I), (II), (III), (IV), (V), (V
I) or the following compound (II ′)] or a salt thereof, a composition containing validamycin, ferimzone and fusalide.

Preferred embodiments of the composition containing other pesticidal active ingredients are shown below. (i) An agricultural and horticultural microbicide containing 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or a salt thereof and ferimzone. (ii) An agricultural and horticultural microbicide containing 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or a salt thereof and fusalide. (iii) An agricultural and horticultural microbicide containing 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or a salt thereof and validamycin. (iv) An agricultural and horticultural insecticide / microbicide containing 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or a salt thereof and bensultap. (v) An agricultural and horticultural insecticide / microbicide containing 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or a salt thereof and cartap. (vi) An agricultural and horticultural insecticide / microbicide containing 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or a salt thereof and clothianidin. (vii) An agricultural and horticultural insecticide / microbicide containing 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or a salt thereof and nitenpyram. (viii) An agricultural and horticultural insecticide / microbicide containing 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or a salt thereof and pyraclofos. (ix) An agricultural and horticultural microbicide containing 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof and ferimzone. (x) An agricultural and horticultural microbicide containing 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof and fusalide. (xi) An agricultural and horticultural microbicide comprising 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof and validamycin. (xii) An agricultural and horticultural insecticide / microbicide containing 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof and bensultap. (xiii) An agricultural and horticultural insecticide / microbicide containing 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof and cartap. (xiv) An agricultural and horticultural insecticide / microbicide containing 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof and clothianidin. (xv) An agricultural and horticultural insecticide / microbicide containing 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof and nitenpyram. (xvi) An agricultural and horticultural insecticide / microbicide containing 2 ', 4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt thereof and pyraclofos. Regarding the above [12], the present inventors have determined that the compounds (I), (II), (III), (IV), (V), (VI) or (II ′) described below or salts thereof in the present invention. Have found that, in combination with other pesticidal active ingredients, the microbicidal effect may be synergistically enhanced as compared with the case of using each as a single agent. Sulfonamide derivatives of the present invention as described above (e.g., compounds (I), (II), (III), (IV), (V), (V
A microbicide obtained by combining (I) or the compound (II ') described below) with another pesticidal active ingredient is more effective in disinfecting, killing insects, killing mites, and killing the insecticide than when (1) each agent is applied alone. The efficacy of nematodes may be enhanced, (2) immediate sterilization, insecticidal, acaricidal, nematicidal effects are imparted, and (3) existing sterilization, insecticidal,
Broad disinfection, insecticidal, acaricidal and nematicidal spectrum not found in miticides and nematicides, and long residual effects are induced. (4)
Compared to the case of using each drug alone, it can reduce the amount of drug dropped and (5) exerts excellent effects such as expecting a more reliable control effect against various pests than using each drug alone I do.

The disease which is controlled by the compound (I ⁰ ) or a salt thereof includes, for example, blast ( Pyricul
aria oryzae ), sesame leaf blight ( Helminthosporium oryzae ,
Cochliobolus miyabeanus ), idiot disease ( Gibberella fuji)
kuroi ), seedling blight ( Rhizopusoryzae ), sheath blight ( Rhizocton )
ia solani ) and other diseases of rice, for example, crown rust ( Puccini a cor
onata ) and other diseases of oats such as powdery mildew ( Erysiphe
graminis ), scald disease ( Rhynchsporium secalis ), spot disease ( C
ochliobolus sativus ), leaf spot disease ( Helminthosporium gram )
ineum, Pyrenophora gramineum), net blotch (Pyrenophra t
eres ), Tilletia caries , naked smut ( Ustil
ago nuda) of barley, such as diseases, for example powdery mildew (Erysiphe
graminis ), Fusarium wilt ( Leptosphaeria nodorum , Septoria
nodorum ), yellow rust ( Puccinia striiformis ), brown granules ( Typhula incarnata ), eye spot disease ( Pseudocercosporella )
herpotrichoides ), red snow rot ( Calonectria graminico
la , Fusarium nivale ), black rust ( Puccinia graminis ),
Typhula ishikariensis , Fusarium head blight ( Gibber
ella zeae ), leaf rust ( Puccinia recondita , Puccinia t
riticina ), spot leaf disease ( Helminthosporium gramineum ), nettle smut ( Tilletia caries ), leaf blight ( Septoria tritic)
i ), disease of wheat such as naked smut ( Ustilago tritici ), for example, disease of corn such as seedling blight ( Pythium debaryanum ), disease of rye such as red snow rot ( Fusarium nivale ), such as plague ( Phytophthor) a infestans ) and other potato diseases such as downy mildew ( Peronospora tabacina ), plague ( Phytophthora parasitica var ), and white scab ( Cercospora ).
nicotianae ), mosaic disease (tobacco mosaic virus), tobacco disease, brown spot ( Cercospora beticola ), seedling damping off ( Pythium debaryanum , Rhizoctonia solani ), damping off
( Pythium aphanidermatum ) and other sugar beet diseases such as gray mold ( Botrytis cinerea ) and other paprika diseases such as gray mold ( Botrytis cinerea ) and sclerotium ( Sclerotin
ia sclerotiorum ), bean diseases such as white silk disease ( Corticium rolfsii ), such as powdery mildew ( Erysiphepolygoni , Sp
haerotheca fuliginea ), rust ( Uromyces fabae , Uromy
ces phaseoli ), gray mold ( Botrytis cinerea ), and other diseases of broad bean such as brown spot ( Mycosphaerella arachidi).
cola) peanut diseases such as, for example, seedling blight (Rhizocto
nia solani ) and other cabbage diseases such as powdery mildew ( Sp
haerotheca fuliginea ), vine disease ( Fusarium oxysporu)
m ), vine blight ( Mycosphaerella melonis ), downy mildew ( Pseud
operonospora cubensis ), gray mold ( Botrytis cinere)
a ), sclerotium disease ( Sclerotiniasclerotiorum ), anthracnose ( Collet
otrichum lagenarium ), seedling blight ( Fusarium oxysporum ,
Pythium aphanidermatum , Rhizoctonia solani ), mosaic disease (Cucumber mosaic virus), and other cucumber diseases such as black spot ( Alternaria brassicicola ), clubroot ( Pl
asmodiophora brassicae) Diseases of Brassica campestris, such as, for example, leaf blotch (Septoria APII) Diseases of celery such as, for example, chlorosis disease (Fusarium oxysporum) radish diseases such as, for example, wilt (Fusarium oxysporum), plague (Phytophthora Infest
ans ), ring spot ( Alternaria solani ), gray mold ( Botryt
is cinerea ), gray plague ( Phytophthora capsici ), black spot ( Alternaria tomato ) and other tomato diseases, for example, brown rot ( Phytophthora capsici ), half body wilt ( Verticill
ium albo - atrum ) and other eggplant diseases such as black spot ( Altern
aria japonica ), clubroot ( Plasmodiophora brassicae )
Diseases of Chinese cabbage such as plague ( Phytophthora capsic
i ), gray mold ( Botrytis cinerea ) and other pepper diseases, such as gray mold ( Botrytis cinerea ) and other lettuce diseases, such as black spot ( Diaporthe citri ) and citrus diseases such as black scab ( Venturia nashicola ), Black spot ( Alt
ernaria kikuchiana ), Scab ( Gymnosporangium haraea)
num ) and other pear diseases such as downy mildew ( Plasmopara vitico
la ), gray mold ( Botrytis cinerea ), black mold ( Elsino
e ampelina ), grape diseases, leaf blight (Taphrina defor
mans), drilling disease (Mycosphaerella cerasella) peach diseases such as, for example, powdery mildew (Podosphaera leucotria), scab (Cladsporium carpophilum), gray mold (Botryt
is cinerea ), scab ( Venturia inaequalis ), scab ( G
ymnosporangium yamadae ), white root rot ( Rosellinia nectr)
ix ), apple diseases such as spot leaf rot ( Alternaia mali ),
Oilseed rape, sunflower, carrot, pepper, strawberry,
Diseases of cereal fruits and vegetables such as melon, kiwifruit, onion, leek, sweet potato, fig, plum, asparagus, oyster, soybean, adzuki, watermelon, oyster, shungiku, spinach, tea and the like are included. Especially Pyricularia
Genus, Cochliobolus , Curvularia , Pyrenophora , A
Lternaria genus, and show high activity against diseases derived from fungi belonging to these closely related genera, such as such diseases, such as rice blast, sesame leaf blight, brown rice disease, barley spot disease, Leaf spot, net spot, wheat leaf spot, spot disease, corn leaf blight, potato summer blight, komatsuna black spot, tomato ring spot, black spot, Chinese cabbage spot And black spot of pear, leaf spot of apple and the like.

In the above compound (I ⁰ ) or a salt thereof, a compound wherein Z ⁰ is a group represented by —OR ³ or a salt thereof is a cruciferous plant (for example, canola, turnip, cauliflower, cabbage, komatsuna, rapeseed, Chinese cabbage) It has an excellent control effect on clubroot disease. Among them, in the above compounds (I), (II) and (III), a compound wherein Z ¹ , Z ² or Z ³ is a group represented by —OR ³ or a salt thereof is preferable, and particularly the following compound (II ′) or Its salts are preferred. Formula (II ')

Embedded image Wherein, A ² ', X ^2' above and B ² 'are respectively A ^2, X ²
And B ² and the same meaning, Z ² 'is -OR ³ (R ³ is. Which as defined above) a group represented by. Or a salt thereof.

Among the compounds contained in the compound (II '),
A ² ′ is (1) (i) a C _1-4 alkyl group optionally substituted with 1 to 5 halogens, (ii) a C _1-4 alkoxy group optionally substituted with 1 to 5 halogens. (Iii) C _1-4 alkyl-
1 to 5 selected from an amino group optionally substituted by one or two carbonyl groups, (iv) a C _1-4 alkoxy-carbonyl group, (v) a halogen atom, (vi) a cyano group and (vii) a nitro group. C _6-14 aryl group or (2) (i) C _1-4 alkyl group, (ii) C _1-4 alkoxy-carbonyl group, (iii) carbamoyl group, iv) mono- or di-C _1-4 alkylcarbamoyl, (v) C
_1-4 alkylsulfonyl groups, (vi) halogen atoms, (vii) carboxyl groups and (viii) 1-5 selected from cyano groups
May be substituted with thienyl group, triazolyl group, imidazolyl group, isoxazolyl group, pyrazolyl group, pyridyl group, quinolyl group, benzothiadiazolyl group, imidazothiazolyl group or imidazopyridyl group, X ² ′ represents (1) a chemical bond, (2) a methylene group optionally substituted by one or two C _1-4 alkyl, or (3) C
One or two optionally substituted vinylene group _1-4 alkyl, B ² 'is (1) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono - or di -C _1-4 substituents selected from alkyl hydrazono and C _1-4 alkylthio
Optionally substituted C _1-4 alkyl group, (2) C _2-4 alkynyl group, (3) hydroxy group, (4) halogen and C
1-5 may be substituted with a substituent C _1-4 alkoxy group selected from _C1-4 alkoxy, (5) C _1-4 alkyl - carbonyl group, (6) C _1-4 alkylthio group , (7)
C _1-4 alkylsulfinyl group, (8) C _1-4 alkylsulfonyl group, (9) mono- or di-C _1-4 alkylsulfamoyl group, (10) amino group, (11) formyl group, ( 12) C
_1-4 alkoxy-carbonyl group, (13) carbamoyl group,
(14) mono- or di-C _1-4 alkylcarbamoyl group, (15) thiocarbamoyl group, (16) halogen atom, (17)
Carboxyl group, (18) thiocyanato group, (19) cyano group,
1 to 5 selected from (20) nitroso group and (21) nitro group
The number of optionally substituted C _6-14 aryl group optionally substituted with a group, Z ² 'is -OR ³ (R ³ is C _1-4 alkyl or C _1-4
Which represents an alkyl-carbonyl group)
A compound showing the group represented by or a salt thereof is preferred.

Further preferred embodiments of the compound (II ') or a salt thereof are shown below. (1) A ² ′ is (a) 1 selected from C _1-4 alkyl optionally substituted with 1 to 3 halogens, halogen and nitro
A phenyl group optionally substituted with up to 3 substituents,
(b) a thienyl group optionally substituted with 1 to 3 halogen atoms, or (c) a pyrazolyl group optionally substituted with 1 to 3 substituent groups selected from C _1-4 alkyl and halogen. Particularly, phenyl in which the 4-position of the phenyl group is substituted with a methyl group is preferable.

(2) B ² ′ is (a) a C _1-4 alkyl group _optionally substituted with 1 to 5 (preferably 1 to 3) halogens, (b) a halogen atom, (c) cyano And a phenyl group substituted with a substituent selected from a nitro group and (d) a nitro group. Compounds in which the substituent is at the 2- or 4-position of the phenyl group are particularly preferred.

(3) Z ² is preferably a C _1-4 alkoxy group or a C _1-4 alkyl-carbonyloxy group, particularly preferably a methoxy group and an ethoxy group. (4) X ² is preferably a chemical bond (single bond or bond). The preferred embodiments of A ² ′, B ² ′, Z ² ′ and X ² ′ shown in the above (1) to (4) may be arbitrarily combined.

The compound (I ⁰ ) or a salt thereof has a microbicidal action, has very low toxicity and is safe, and can be used as an excellent microbicidal composition. The composition of the present invention can be used in the same manner as a conventional microbicide, and as a result, it can exhibit excellent effects as compared with conventional products. For example, the composition of the present invention can be used by spraying it on a paddy field, a field, an orchard, a non-agricultural land, or the like by a method known per se. More specifically, it can be used by, for example, nursery box treatment, foliage application of crops, underwater application in paddy fields, seed treatment or soil treatment, direct application to fruit tree trunks, and the like. The application rate can be varied over a wide range according to the application time, application place, application method, etc., but generally, the active ingredient (compound (I)
⁰ ) or its salt) is desirably 0.3 g to 3,000 g, preferably 50 g to 1,000 g. When the composition of the present invention is a wettable powder,
The active ingredient may be diluted and used so that the final concentration of the active ingredient is in the range of 0.1 to 1,000 ppm, preferably 10 to 500 ppm. The content ratio of the compound (I ⁰ ) or a salt thereof is as follows:
It is usually about 0.1 to 80% by weight, preferably about 1 to 20% by weight, based on the total amount of the preparation. Specifically, emulsions,
When used in solutions, wettable powders (eg, water-dispersible granules), aqueous suspension preparations, microemulsions, and the like, usually about 1 to 8
About 0% by weight, preferably about 1 to 20% by weight is suitable. When used in oils, powders, etc., it is usually 0.1 to 5
About 0% by weight, preferably about 1 to 20% by weight is suitable. When used in granules, tablets, jumbo and the like, usually about 5 to 50% by weight, preferably about 1 to 20% by weight
The degree is appropriate. Other pesticidal active ingredients (eg, insecticides, acaricides, herbicides and / or microbicides) incorporated in the composition of the present invention are usually about 1 to 80% by weight based on the total amount of the preparation, Preferably, it is used in the range of about 1 to 20% by weight. The content of the additives other than the above-mentioned active ingredients varies depending on the kind or content of the pesticidal active ingredient or the dosage form of the preparation, but is usually about 0.001 to 99.9% by weight, preferably about 1 to 99% by weight. It is. More specifically, a surfactant is usually added in an amount of 1 to the total amount of the composition.
About 20% by weight, preferably about 1 to 15% by weight,
It is preferable to add about 1 to 20% by weight of a flow aid and about 1 to 90% by weight, preferably about 1 to 70% by weight of a carrier. Specifically, when producing a liquid preparation, the surfactant is usually added in an amount of about 1 to 20% by weight, preferably 1 to 20% by weight.
It is preferable to add about 10% by weight and about 20 to 90% by weight of water. Emulsions, wettable powders (eg, water-dispersible granules) and the like may be appropriately diluted with water or the like before use (eg, about 10
(0 to 5,000 times).

Compound (I ⁰ ) or a salt thereof is, for example,
It can be produced according to the following reaction formulas (A), (B), (C) or synthesis method (D). [Reaction formula (A)]

Embedded image The compound (I ⁰ ) or a salt thereof is represented by the formula (VII): A ⁰ -X ⁰ -SO ₂ -L (A ⁰ and X ⁰ are as defined above, and L represents a leaving group)
Reaction of a sulfonylating agent represented by the formula with an amine represented by the formula (VIII): H ₂ N—B ⁰ (B ⁰ has the same meaning as described above) or a salt thereof, or a compound represented by the formula (IX): A sulfonamide compound represented by A ⁰ -X ⁰ -SO ₂ -NH ₂ (the symbols in the formula have the same meanings as described above) or a salt thereof, and a formula (X): L′-B ⁰ (wherein: L ′ represents a leaving group, and B ⁰ has the same meaning as described above) or a compound thereof represented by the formula (X
I):

Embedded image (Wherein each symbol is as defined above) or a salt thereof represented by the formula (XII): Z ⁰ -L ″ (where L ″ represents a leaving group, and Z ⁰ represents As defined above)
By reacting with an electrophile represented by the following formula: Examples of the sulfonylating agent represented by the formula (VII) include sulfonyl chloride, sulfonyl bromide, sulfonic anhydride and the like. As the leaving group for L, L ′ or L ″, for example, a halogen atom such as fluorine, chlorine, bromine and iodine, for example, a lower alkoxy group such as methoxy, ethoxy and propoxy (preferably a C _1-4 alkoxy group), a phenoxy group, such as methylthio, ethylthio, lower alkylthio group (preferably a C _1-4 alkylthio group) such as propylthio, for example methylsulfinyl, ethylsulfinyl, propyl sulfinyl lower alkylsulfinyl group (preferably C _1-4 alkylsulfinyl group Le etc. ), Lower alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl and propylsulfonyl (preferably C _1-4 alkylsulfonyl groups), and lower alkylsulfonyloxy groups such as methylsulfonyloxy, ethylsulfonyloxy and propylsulfonyloxy (preferably Kuha C
_1-4 alkylsulfonyloxy group), trifluoromethylsulfonyloxy group, benzenesulfonyloxy group,
and p-toluenesulfonyloxy group. The reaction between the sulfonylating agent (VII) and the amines (VIII) can be carried out, for example, in Japanese Society of Pesticides 21:31 (1996).
Year), Japanese Patent Publication No. 45-6836, Japanese Patent Publication No. 40-19
199, JP-A-57-31655, JP-A-58-219159, and JP-A-61-197553.
JP, JP-A-61-271270, JP-A-63-271270
-57565, JP-A-1-272566,
JP-A-1-156953, JP-A-2-72151
JP, JP-A-2-96560, JP-A-2-23
The method can be carried out according to the methods described in JP-A No. 1465, JP-A-2-212467, JP-A-4-54161, JP-A-4-145060 and the like.

The reaction between the sulfonamide (IX) and the compound (X) is usually carried out in a solvent or without a solvent. As a solvent when a solvent is used, for example, hydrocarbons such as petroleum ether, pentane, hexane, cyclohexane, benzene, toluene, xylene, such as dichloromethane,
Chloroform, carbon tetrachloride, 1,2-dichloroethane,
Halogenated hydrocarbons such as 1,2-dichloroethylene, trichloroethylene, and chlorobenzene, for example, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, for example, ethyl acetate ,
Esters such as butyl acetate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone For example, sulfoxides such as dimethyl sulfoxide, sulfones such as sulfolane, nitro compounds such as nitromethane and nitrobenzene, alcohols such as methanol, ethanol, isopropanol, 1-butanol, ethylene glycol, carbon disulfide, water and the like Is mentioned. The reaction temperature is -100 to 300C, preferably -50 to 200C.
The reaction time is 1 minute to 1 week, preferably 5 minutes to 24 hours. Acids or bases may be added to promote the reaction, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid,
Inorganic acids such as nitric acid and perchloric acid, for example, formic acid, acetic acid, propionic acid, trifluoroacetic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, benzoic acid, picric acid, methanesulfonic acid, p-toluenesulfone Acids, organic acids such as trifluoromethanesulfonic acid, and the like. Examples of the base include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide, for example, sodium carbonate, potassium carbonate, and carbonic acid. Sodium hydrogen, metal carbonates such as potassium hydrogen carbonate, such as sodium hydride, potassium hydride, metal hydrides such as calcium hydride, such as lithium diisopropylamide, sodium amide, metal amides such as potassium amide, such as methyl lithium, n-butyllithium, sec-butyllithium, ter Organic lithium reagents such as butyllithium and phenyllithium; organic magnesium reagents such as methylmagnesium bromide and ethylmagnesium chloride (Grignard reagent); metals such as lithium metal, sodium metal and potassium potassium, such as trimethylamine and triethylamine , Diisopropylethylamine, N, N-dimethylaniline, pyridine, lutidine, collidine, DMAP (4-dimethylaminopyridine), TMEDA (tetramethylethylenediamine), DBU (1,8-diazabicyclo [5.4.
0] undes-7-ene) and the like.
In order to promote the reaction, for example, titanium, vanadium,
Chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium,
Metal salts such as rhodium, palladium, silver, cadmium, tungsten, platinum, gold, mercury (eg, oxides, fluorides, chlorides, bromides, iodides, sulfides, sulfates, nitrates, phosphates, perchloric acid) Salt, etc.) or a metal simple substance as a catalyst in an amount of 0.000001 to 1000 equivalents, preferably 0.1 to 1000 equivalents.
001 to 10 equivalents may be added.

Sulfonamide (XI) and electrophile (XII)
Is usually carried out in a solvent or without a solvent. When a solvent is used, the same solvent as the solvent used in the above reaction can be used. Reaction temperature is -10
The reaction is carried out at 0 to 300 ° C, preferably at -50 to 200 ° C, for a reaction time of 1 minute to 1 week, preferably 5 minutes to 24 hours. An acid or a base may be added for accelerating the reaction. Examples of such an acid or a base include the same acids and bases as those used in the above reaction. In order to promote the reaction, for example, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, tungsten, platinum, gold,
Metal salts such as mercury (eg, oxides, fluorides, chlorides, bromides, iodides, sulfides, sulfates, nitrates, phosphates,
Perchlorate) or a simple metal as a catalyst
001 to 1000 equivalents, preferably 0.001 to 10 equivalents may be added. Electrophile (XII) is a sulfonamide
It is possible to use a large excess as long as the reaction does not adversely affect (XI), but it is preferable to use 1.0 to 10 equivalents. Such electrophiles include, for example, methyl iodide, ethyl iodide, propyl bromide, propyl iodide, isopropyl iodide, cyclopropyl bromide, butyl bromide, isobutyl bromide, allyl chloride, allyl bromide, Halides such as propargyl bromide, 1,2-dibromoethane, acetyl chloride, propargyl chloride, methyl chloroformate, ethyl chloroformate, methanesulfonyl chloride, benzenesulfonyl chloride, and p-toluenesulfonyl chloride, such as dimethyl sulfate and diethyl sulfate Sulfonates such as methylmethanesulfonate, ethylbenzenesulfonate, isopropyl p-toluenesulfonate and the like sulfonic acid esters such as acetic anhydride, trifluoroacetic anhydride, trifluoromethanesulfonic anhydride, acetic acid-formic acid mixed anhydride and the like. Acid anhydrides I can do it.

[Reaction formula (B)]

Embedded image The compound (I ⁰ ) or a salt thereof is represented by the sulfonylating agent represented by the formula (VII) and the formula (XIII): Z ⁰ HN-B ⁰ (wherein each symbol has the same meaning as described above). Obtained by reacting with an amine or a salt thereof.
Such a reaction is usually performed in a solvent or without a solvent. When a solvent is used, the same solvent as the solvent described in the above reaction formula (A) can be used. The reaction temperature is -100 to 300C, preferably -5.
The reaction is carried out at 0 to 200 ° C. for 1 minute to 1 week, preferably for 5 minutes to 24 hours. An acid or a base may be added to promote the reaction. Examples of such an acid or a base include the same acids and bases as those described in the above reaction formula (A). In order to promote the reaction, for example, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, tungsten, platinum, gold, mercury And the like, or a metal salt (eg, oxide, fluoride, chloride, bromide, iodide, sulfide, sulfate, nitrate, phosphate, perchlorate, etc.) or a simple metal as a catalyst in an amount of 0.000001 to 1000 equivalents. , Preferably 0.001 to 10 equivalents.

[Reaction formula (C)]

Embedded image The compound (I ⁰ ) or a salt thereof is a sulfonamide derivative represented by the formula (XIV): A ⁰ -X ⁰ -SO ₂ -NHZ ⁰ (wherein each symbol has the same meaning as described above) or a salt thereof. And a compound represented by the above formula (X) or a salt thereof.
Such a reaction is usually performed in a solvent or without a solvent. When a solvent is used, the same solvent as the solvent described in the above reaction formula (A) can be used. The reaction temperature is -100 to 300C, preferably -5.
The reaction is carried out at 0 to 200 ° C. for 1 minute to 1 week, preferably for 5 minutes to 24 hours. An acid or a base may be added to promote the reaction. Examples of such an acid or a base include the same acids and bases as those described in the above reaction formula (A). In order to promote the reaction, for example, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, tungsten, platinum, gold, mercury And the like, or a metal salt (eg, oxide, fluoride, chloride, bromide, iodide, sulfide, sulfate, nitrate, phosphate, perchlorate, etc.) or a simple metal as a catalyst in an amount of 0.000001 to 1000 equivalents. , Preferably 0.001 to 10 equivalents.
When compounds (VII) to (XIV) form a salt, examples of the salt include those similar to the salt of compound (I ⁰ ). [Synthesis Method (D)] When the compound (I ⁰ ) or a salt thereof has a nitro group as a substituent on B ⁰ , the corresponding raw material (a compound in which the position where the nitro group is introduced is not substituted) is nitrated. It can also be obtained by nitrating with an agent [synthesis method (D)]. 30 as nitrating agent
-100% nitric acid and fuming nitric acid are widely used, for example, alkali metal nitrates such as sodium nitrate and potassium nitrate, alkyl nitrates such as ethyl nitrate and amyl nitrate, and nitronium tetrafluoroborate (NO ₂ B
F ₄ ), nitronium trifluoromethanesulfonate
(NO ₂ CF ₃ SO ₃ ), nitrogen oxides (eg, NO ₂ , N ₂ O
₃ , N ₂ O ₄ , N ₂ O ₅ ) and the like. Especially 50 to 10
0% nitric acid is preferred. The nitrating agent is used in an amount of about 1.0 to 20 with respect to the raw material in which the nitro group is not introduced.
The equivalent amount can be used, but preferably 1.0 to 10 equivalents when nitric acid is used. When 90% or more of nitric acid is used, about 1.0 to 3.0 equivalents are preferable. The nitration reaction may be performed without a solvent, but usually, sulfuric acid,
The reaction is performed in the presence of an acidic solvent such as acetic acid, acetic anhydride, trifluoroacetic anhydride, and trifluoromethanesulfonic acid. If desired, a solvent which does not adversely influence the reaction or a mixture thereof may be used. Examples of such a solvent include the same solvents as those described in the reaction formula (A), in addition to the acidic solvents described above. These solvents can be used alone or, if necessary, two or more (preferably two to three) in a suitable ratio, for example, a ratio of about 1: 1 to 1:10 (volume ratio). May be used as a mixture. When the reaction solvent is not uniform, for example, phase transfer of quaternary ammonium salts such as triethylbenzylammonium chloride, tri-n-octylmethylammonium chloride, trimethyldecylammonium chloride, tetramethylammonium bromide, cetylpyridinium bromide, and crown ethers. The reaction may be performed in the presence of a catalyst. Particularly preferred solvents are acetic acid and acetic anhydride.
The reaction temperature is usually about -50 to 200C, preferably about -2.
The range is from 0 to 130 ° C. Reaction times range from about 1 minute to 24 hours, preferably from about 15 minutes to 3 hours. Here, the compound (VI) or a salt thereof is synthesized according to the above-mentioned synthesis method (D).
When manufacturing according to, for example, the formula

Embedded image (Where B ⁷ is a halogen atom (eg, fluorine, chlorine, bromine,
Iodine), a phenyl group substituted with a substituent selected from nitro and cyano and at least one of the 2- or 6-positions is not substituted, and other symbols are as defined above) Alternatively, it can be obtained by nitrating a salt thereof. The number of substituents selected from halogen atoms, nitro and cyano in the “phenyl group in which at least one of the 2-position and 6-position is not substituted” of B ⁶ is 1 to 3. When compound (I ⁰ ) or a salt thereof has a substituent, the substituent can be introduced in advance into the starting material or intermediates (VII) to (XIV), or compound (I ⁰ ) or a salt thereof After the synthesis, a known functional group conversion method, for example, Organic Reactions
(Organic Reactions), Organic Synthesis (Organic Reactions)
ic Syntheses), Synthetic methods of Organic chemistry
nic Chemistry), Compendium of Organic Synthetic Methods
Synthetic Methods) can be used to introduce or convert necessary substituents. As such a substituent conversion reaction, for example, the following synthesis method (E)
To (T), but should not be limited to the following examples. [Synthesis Method (E)] A compound having an alkylthio group synthesized from a known raw material by the method of Reaction Formula (A), (B) or (C) is converted to a suitable oxidizing agent (eg, hydrogen peroxide, peracetic acid). , Perbenzoic acid, metachloroperbenzoic acid, potassium permanganate, etc.) 0.5 to 2.0 equivalents, preferably 0.8 to 2.0 equivalents
By reacting with 1.5 equivalents, it can be converted to a compound having an alkylsulfinyl group. Also,
The compound having an alkylsulfonyl group can be converted by reacting the above oxidizing agent with 1.5 equivalents or more, preferably 2.0 to 3.0 equivalents. [Synthesis Method (F)] A compound having an alkoxycarbonyl group synthesized from a known raw material by the method of Reaction Formula (A), (B) or (C) is converted into a base (for example, sodium hydroxide,
The compound can be converted to a compound having a carboxyl group by subjecting it to a hydrolysis reaction in the presence of a base such as potassium hydroxide or an acid (eg, an acid such as sulfuric acid or hydrochloric acid). [Synthesis method (G)] The compound having a carboxyl group is esterified by reacting the compound with an alcohol (eg, methanol, ethanol, etc.) in the presence of a suitable acid (eg, sulfuric acid, p-toluenesulfonic acid). can do. Further, the carboxyl group is activated (for example, conversion to an acid chloride with thionyl chloride or phosphorus oxychloride, for example, conversion to an acid anhydride with carboxylic acid chloride or chloroformate, for example, dicyclocarbodiimide, methylpyridinium chloride, etc.) After carboxylic acid activation), the compound can be converted to a compound having an ester by reacting with an alcohol, and can be converted to a compound having an amide group by reacting with an amine. [Synthesis method (H)] A compound having an amide group (CONH ₂ ) is dehydrated (eg, acetic anhydride, trifluoroacetic anhydride, thionyl chloride, oxychloride) in the presence or absence of a base (eg, pyridine, triethylamine, etc.). (Phosphorus, diphosphorus pentoxide) can be converted to a compound having a cyano group. [Synthesis Method (I)] A compound having an amide group and a Lawesson's reagent (2,4-bis (4-methoxyphenyl) -1,3-
The compound can be converted to a compound having a thioamide group by reacting it with dithia-2,4-diphosphetane-2,4-disulfide) or phosphorus pentasulfide, or by adding hydrogen sulfide to a compound having a cyano group. [Synthesis method (J)] Compound having a carboxyl group synthesized by synthesis method (F), compound having ester group or amide group synthesized by synthesis method (G), or synthesis method (H) The compound having a cyano group to be synthesized is subjected to a reduction reaction with a suitable reducing agent (eg, hydrogenation, diborane, silanes, sodium borohydride, lithium aluminum hydride, diisobutylaluminum, etc.) to give a compound having a formyl group. Can be converted. Further, a compound having a methyl group or a hydroxymethyl group synthesized from a known raw material is converted to an oxidizing agent (for example, chromic acids, dichromic acids, manganese dioxide, potassium permanganate) by the methods of Reaction Formulas (A) to (C). ,
The compound can be converted to a compound having a formyl group by performing an oxidation reaction with selenium dioxide, dimethylsulfoxide-oxalic acid chloride-triethylamine [swern oxidation] or the like. [Synthesis Method (K)] A compound (a compound in which the formyl group is not substituted at the position where a formyl group is introduced) synthesized from a known raw material by the method of Reaction Formula (A), (B) or (C) is formylated ( For example, phosphorus oxychloride-N, N-dimethylformamide [Vilsmeier reaction], zinc chloride-hydrogen cyanide-hydrogen chloride [Gatterman
n) reaction], chloroform-sodium hydroxide [Lymer-
Reimer-Tiemann reaction], formylation with dichloromethoxymethane-aluminum chloride, etc.) to obtain a compound having a formyl group. [Synthesis method (L)] Synthesis of oximes or hydrazones by reacting a compound having a formyl group synthesized by the synthesis method (J) or the synthesis method (K) with hydroxylamines or hydrazines. Can be. [Synthesis Method (M)] A compound having a haloalkyl group synthesized from a known raw material by the method of Reaction Formula (A), (B) or (C) and a suitable nucleophile (for example, methyl mercaptan, ethyl mercaptan, etc.) The presence of mercaptans, for example, amines such as ammonia, methylamine, dimethylamine and the like, for example, alcohols such as methanol and ethanol, and an appropriate base (for example, sodium hydroxide, sodium hydride, sodium carbonate, potassium carbonate, etc.) Below, various functional groups can be converted by subjecting to a substitution reaction. [Synthesis Method (N)] A compound having a haloethyl group synthesized from a known raw material by the method of Reaction Formula (A), (B) or (C) is subjected to a dehydrohalogenation reaction by a base treatment to form a vinyl group. Can be converted to [Synthesis Method (O)] A compound having a terminal acetylene group synthesized from a known raw material by the method of Reaction Formula (A), (B) or (C) is converted into a suitable base (for example, sodium hydroxide, sodium hydride, Reaction with a halogen source (eg, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, chlorine, bromine, iodine, etc.) in the presence of sodium carbonate, potassium carbonate, n-butyllithium, etc. It can be converted to a compound having a haloacetylene group. [Synthesis method (P)] Reaction formula (A), (B) or (C),
Alternatively, a compound having an amino group can be obtained by reducing a compound having a nitro group obtained by the synthesis method (D) with a reducing agent (for example, hydrogenation, iron, tin, zinc, ferrous chloride, stannous chloride, and the like). Can be converted. [Synthesis method (Q)] A compound having an amino group synthesized by the synthesis method (P) or the like is combined with an oxidizing agent (for example, hydrogen peroxide, peracetic acid, perbenzoic acid, metachloroperbenzoic acid, potassium permanganate, etc.). By reacting, it can be converted to a compound having a nitroso group. [Synthesis method (R)] A compound having a nitroso group synthesized by the synthesis method (Q) or the like is reacted with an N-oxidizing agent (eg, N-chlorosuccinimide, N-bromosuccinimide, iodobenzene diacetate, etc.). Then, the compound can be converted to a compound having an azoxycyano group (-N (O) = N-CN) by reacting with cyanamide in the presence of a base (eg, sodium carbonate, potassium carbonate, sodium hydroxide, etc.). [Synthesis method (S)] Protecting groups (for example, methoxymethyl group, dihydropyranyl group, acetyl group, methoxycarbonyl group, and the like) synthesized from known raw materials by the method of reaction formula (A), (B) or (C) Compounds having a hydroxy group protected with a benzyl group, a tert-butyldimethylsilyl group, etc., can be used, for example, in Protective Groups in Organic Synthesis.
The compound can be converted to a compound having a hydroxyl group by subjecting it to a deprotecting group reaction according to a method described in Synthesis). [Synthesis method (T)] An electrophilic agent is prepared by reacting a compound having a hydroxy group synthesized by the synthesis method (S) or the like in the presence of a suitable base (eg, sodium hydroxide, sodium hydride, sodium carbonate, potassium carbonate, etc.). (Eg methyl iodide,
Dimethyl sulfate, ethyl iodide, isopropyl iodide, propyl bromide, 1,2-dibromoethane, acetic anhydride, acetyl chloride, methyl chloroformate, trifluoroacetic anhydride,
Methanesulfonyl chloride, p-toluenesulfonyl chloride, etc.)
(Substitution reaction) to obtain various substituents.

[0079]

The compound (I ⁰ ) or a salt thereof, in particular, the compounds (I) to (V) or a salt thereof have a microbicidal action,
Since it is a safe sulfonamide derivative that has little effect on humans, animals, natural enemies and the environment and has an excellent control effect on drug-resistant microorganisms, it is useful as an excellent agricultural and horticultural microbicide. In particular, rice blast, sesame leaf blight, brown rice disease, barley leaf spot, leaf spot, net spot, wheat leaf spot, spot disease, corn leaf spot, potato summer blight, It is effective as an agent for controlling black spot of Komatsuna, ring spot of tomato, black spot of Chinese cabbage, black spot of Chinese cabbage, black spot of pear, and spot leaf spot of apple.

[0080]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, Preparation Examples and Test Examples, but the scope of compound (I ⁰ ) or a salt thereof should not be construed as being limited to the Examples. Elution in the silica gel column chromatography of the synthesis example was performed under observation by TLC (Thin Layer Chromatograph, thin layer chromatography). TLC
In observation, Merck (Merc) was used as a TLC plate.
k) Kieselgel 60F254 (70-230 mesh) manufactured by K.K., a solvent used as an eluting solvent in column chromatography was used as a developing solvent, and a UV detector or an iodine coloring method was used as a detection method. The silica gel for the column is Kieselgel 60 (70-230) manufactured by Merck.
Mesh). When a mixed solvent is used as the developing solvent, the numerical values shown in parentheses are the volume mixing ratios of the respective solvents. NMR (nuclear magnetic resonance) spectrum is proton NMR
Shows, using tetramethylsilane as an internal standard,
Measured with a Bruker AC-200P (200 MHz) spectrometer and all δ values are given in ppm. The abbreviations used in the following Reference Examples, Examples and Tables have the following meanings. s: singlet, d: doublet, t: triplet, q: quartet, m: multi-pellet, dd: double doublet, dt: double triplet, dq: double quartet, septet: septet, br: broad (wide) , Brs: Broad singlet, ddd: Double double doublet, ddt: Double double triplet, b
rd: Broad doublet, brq: Broad quartet, J: Coupling constant, J _HF : Coupling constant between hydrogen and fluorine atoms, Hz: Hertz, CDCl ₃ : Deuterated chloroform, DMSO-d ₆ : Deuterated dimethyl sulfoxide, DMF :
N, N-dimethylformamide,%: wt%, mp: melting point, room temperature means 15 to 25 ° C.

[0081]

EXAMPLES Example 1 2 ', 4'-Dichloro-N-methyl-p-toluenesulfonanilide (Compound No. 5
Synthesis of 1) 0.07 g (1.75 mmol) of 60% sodium hydride was added to DMF 2.0 ml
And 0.50 g (1.58 mmol) of 2 ', 4'-dichloro-p-toluenesulfonanilide was added with stirring at room temperature. After stirring at room temperature for 15 minutes, dimethyl sulfate 0.17 ml
(1.80 mmol) was added dropwise. After stirring at room temperature for 15 hours, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The precipitated crystals were collected by filtration and washed with diisopropyl ether to give the title compound (0.38 g, 73%) as white crystals. _{Mp: 86.0-87.0 ℃ NMR (CDCl 3)} δ: 2.44 (3H, s), 3.17 (3H, s), 7.13 (1H, d, J =
8.6Hz), 7.22 (1H, dd, J = 8.6 & 2.3Hz), 7.30 (2H, d, J = 8.4
Hz), 7.42 (1H, d, J = 2.3Hz), 7.65 (2H, d, J = 8.4Hz).

Example 2 N, 4'-dimethyl-3'-nitro-p-toluenesulfonanilide (Compound No. 1
26) 0.14 g (3.50 mmol) of 60% sodium hydride in DMF 3.0 ml
4′-methyl-3′- while stirring at room temperature.
Nitro-p-toluenesulfonanilide 1.00 g (3.26 mmo
l) was added. After stirring at room temperature for 15 minutes, dimethyl sulfate
0.34 ml (3.56 mmol) was added dropwise. After heating and stirring at room temperature for 1 hour, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Ether was added to the residue and filtered,
By washing, the title compound was obtained as pale yellow crystals in an amount of 0.
79 g (76%) were obtained. _{Mp: 103.5-106.0 ℃ NMR (CDCl 3)} δ: 2.43 (3H, s), 2.59 (3H, s), 3.17 (3H, s),
7.27 (2H, d, J = 8.3Hz), 7.31 (1H, d, J = 8.2Hz), 7.43 (2H, d, J
J = 8.3Hz), 7.45 (1H, dd, J = 8.2 & 2.3Hz), 7.58 (1H, d, J =
2.3Hz).

Example 3 N-ethyl-4'-fluoro-
Synthesis of 2′-nitro-p-toluenesulfonanilide (Compound No. 263) 0.05% (1.25 mmol) of 60% sodium hydride in DMF 2.0 ml
4′-Fluoro-2 ′ while stirring at room temperature.
-Nitro-p-toluenesulfonanilide 0.31 g (1.00 m
mol) was added. After stirring at room temperature for 15 minutes, ethyl iodide
0.30 ml (3.75 mmol) was added dropwise. After heating and stirring at 100 ° C. for 30 minutes, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Diisopropyl ether was added to the residue, and the precipitated crystals were collected by filtration and washed to give 0.25 g (74%) of the title compound as pale yellow crystals. Melting point: 93.0-94.5 ° C NMR (CDCl ₃ ) δ: 1.18 (3H, s), 2.44 (3H, s), 3.67 (2H, brq,
J = 7.2Hz), 7.10 (1H, dd, J = 8.9Hz, J _HF = 5.1Hz), 7.23 (1H, d
dd, J = 8.9 & 2.9Hz, J _HF = 7.2Hz), 7.27 (2H, d, J = 8.4Hz),
7.53 (2H, d, J = 8.4Hz), 7.60 (1H, dd, J = 2.9Hz, J _HF = 7.7Hz).

Example 4 4'-chloro-N-ethyl-
Synthesis of 2′-nitro-p-toluenesulfonanilide (Compound No. 289) 0.05% (1.25 mmol) of 60% sodium hydride in DMF 2.0 ml
4'-chloro-2'- while stirring at room temperature.
Nitro-p-toluenesulfonanilide 0.30 g (0.92 mmo
l) was added. After stirring at room temperature for 15 minutes, ethyl iodide
0.50 ml (6.25 mmol) was added dropwise. After heating and stirring at 100 ° C. for 1 hour, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and ethyl acetate-hexane (1: 1).
By eluting in 3), 0.24 g (74%) of the title compound was obtained as pale yellow crystals. Melting point: 132.5-134.0 ° C NMR (CDCl ₃ ) δ: 1.18 (3H, t, J = 7.2 Hz), 2.44 (3H, s), 3.66
(2H, q, J = 7.2Hz), 7.05 (1H, d, J = 8.6Hz), 7.28 (2H, d, J = 8.
2Hz), 7.50 (1H, dd, J = 8.6 & 2.5Hz), 7.53 (2H, d, J = 8.2H
z), 7.86 (1H, d, J = 2.5Hz).

Example 5 Synthesis of 4'-methoxy-2'-nitro-N-isopropyl-p-toluenesulfonanilide (Compound No. 207) 0.10 g (2.50 mmol) of 60% sodium hydride and 2.0 ml of DMF
4'-methoxy-2 'while stirring at room temperature.
-Nitro-p-toluenesulfonanilide 0.65 g (2.02 m
mol) was added. After stirring at room temperature for 15 minutes, 1.00 g (5.88 mmol) of isopropyl iodide was added dropwise. After heating and stirring at 130 ° C. for 5 hours, the reaction solution was poured into water and extracted with ethyl acetate.
The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 2) to give 0.21 g (28.5%) of the title compound as pale brown crystals. Melting point: 148.0-149.5 ° C NMR (CDCl ₃ ) δ: 1.04 (3H, d, J = 6.7 Hz), 1.11 (3H, d, J = 6.7H)
z), 2.43 (3H, s), 3.89 (3H, s), 4.36 (1H, septet, J = 6.7H
z), 7.06 (1H, dd, J = 8.8 & 2.8Hz), 7.16 (1H, d, J = 8.8Hz),
7.28 (2H, d, J = 8.3Hz), 7.38 (1H, d, J = 2.8Hz), 7.67 (2H, d
d, J = 8.3Hz).

Example 6 4-Chloro-4'-cyano-
Synthesis of 2′-nitro-N- (isopropyl) benzenesulfonanilide (Compound No. 413) (1) Dissolve 2.36 g (20.0 mmol) of 4-aminobenzonitrile in 10 ml of pyridine and cool in a water bath (15 ° C.) 4-
4.35 g (20.6 mmol) of chlorobenzenesulfonyl chloride were added. After stirring at room temperature for 18 hours, 100 ml of water was added, and stirring was continued to precipitate crystals. Filter out these crystals,
By washing with water, 4.45 g (76%) of 4-chloro-4′-cyanobenzenesulfonanilide was obtained as pale orange crystals. _{Mp: 182.5-184.0 ℃ NMR (CDCl 3)} δ: 7.11 (1H.s), 7.18 (2H, d, J = 8.8Hz), 7.47
(2H, d, J = 8.8Hz), 7.56 (2H, d, J = 8.8Hz), 7.78 (2H, d, J = 8.
(2) 4.03 g (13.8 mmol) of 4-chloro-4'-cyanobenzenesulfonanilide was suspended in 15 ml of acetic anhydride, and 0.61 ml (14.3 mmol) of 97% fuming nitric acid was added dropwise with stirring at room temperature. After stirring at 50 ° C. for 1 hour, the reaction solution was poured into water to precipitate crystals. By filtering and washing the crystals with water,
4.30 g (93%) of 4-chloro-4'-cyano-2'-nitrobenzenesulfonanilide was obtained as pale yellow crystals. Melting point: 193.0-195.0 ° C NMR (CDCl ₃ ) δ: 7.53 (2H, d, J = 8.8 Hz), 7.81 (1H, dd, J = 8.8)
& 1.9Hz), 7.88 (2H, d, J = 8.8Hz), 7.95 (1H, d, J = 8.8Hz),
8.50 (1H, d, J = 1.9 Hz), 10.28 (1H, brs). (3) 0.10 g (2.50 mmol) of 60% sodium hydride in DMF
4.0 ml of 4-chloro-
4'-cyano-2'-nitrobenzenesulfonanilide
0.70 g (2.07 mmol) was added. After stirring at room temperature for 15 minutes,
0.50 ml (5.01 mmol) of isopropyl iodide was added dropwise. 130
After heating and stirring at 3 ° C. for 3 hours, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 2) to give the title compound (0.11 g, 14%) as pale-yellow crystals. Melting point: 167.5-168.5 ° C NMR (CDCl ₃ ) δ: 1.07 (3H, d, J = 6.7 Hz), 1.19 (3H, d, J = 6.7H)
z), 4.39 (1H, septet, J = 6.7Hz), 7.46 (1H, d, J = 8.3Hz),
7.50 (2H, d, J = 8.8Hz), 7.72 (2H, d, J = 8.8Hz), 7.89 (1H, d
d, J = 8.3 & 2.0Hz), 8.20 (1H, d, J = 2.0Hz).

Example 7 N-allyl-4'-chloro-
Synthesis of 2'-nitro-p-toluenesulfonanilide (Compound No. 299) 0.05% (1.25 mmol) of 60% sodium hydride in 2.0 ml of DMF
4'-chloro-2'- while stirring at room temperature.
Nitro-p-toluenesulfonanilide 0.30 g (0.92 mmo
l) was added. After stirring at room temperature for 15 minutes, allyl bromide 0.5
0 ml (5.78 mmol) was added dropwise. After stirring at 50 ° C. for 30 minutes and at room temperature for 15 hours, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Diisopropyl ether was added to the residue, and the precipitated crystals were collected by filtration, washed,
0.21 g (62%) of the title compound was obtained as pale yellow crystals. Melting point: 77.0-78.0 ° C NMR (CDCl ₃ ) δ: 2.44 (3H, s), 4.22 (2H, dt, J = 6.9 & 1.2H
z), 5.05 (1H, ddt, J = 17.0 & 2.5 & 1.2Hz), 5.11 (1H, ddt,
J = 10.1 & 2.5 & 1.2Hz), 5.89 (2H, ddt, J = 17.0 & 10.1 &
6.9Hz), 7.05 (1H, d, J = 8.5Hz), 7.28 (2H, d, J = 8.4Hz), 7.
48 (1H, dd, J = 8.5 & 2.4Hz), 7.54 (2H, d, J = 8.4Hz), 7.84 (1
(H, d, J = 2.4Hz).

Example 8 Synthesis of N-acetyl-4'-methoxy-2'-nitro-p-toluenesulfonanilide (Compound No. 213) 60% sodium hydride 0.08 g (2.00 mmol) was added to DMF 3.0 ml
4'-methoxy-2 'while stirring at room temperature.
-Nitro-p-toluenesulfonanilide 0.50 g (1.55 m
mol) was added. After stirring at room temperature for 15 minutes, acetic anhydride 0.2
0 ml (2.12 mmol) was added dropwise. After stirring at room temperature for 1 hour, water was poured into the reaction solution, which was extracted with ethyl acetate. Wash the extract with water,
After washing with a saturated saline solution, the extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Ether was added to the precipitated crystals, and the mixture was filtered and washed to give the title compound as pale yellow crystals in an amount of 0.51.
g (90%). Melting point: 172.5-174.0 ° C NMR (CDCl ₃ ) δ: 2.08 (3H, s), 2.45 (3H, s), 3.94 (3H, s),
7.22 (1H, dd, J = 8.8 & 2.9Hz), 7.32 (2H, d, J = 8.5Hz), 7.3
7 (1H, d, J = 8.8Hz), 7.56 (1H, d, J = 2.9Hz), 7.82 (2H, d, J =
8.5Hz).

Example 9 Synthesis of N, N-bis (p-toluenesulfonyl) -4-methoxy-2-nitroaniline (Compound No. 214) 4'-methoxy-2'-nitro-p-toluenesulfonanilide 0.32 g (1.00 mmol) dissolved in pyridine (1.0 ml) and stirred at room temperature, p-toluenesulfonyl chloride 0.20 g
(1.05 mmol) was added. After stirring at room temperature for 15 hours, the mixture was poured into water, and the precipitated crystals were collected by filtration and washed with water to give 0.34 g (83%) of the title compound as pale yellow crystals. _{Mp: 180.5-182.0 ℃ NMR (CDCl 3)} δ: 2.46 (6H, s), 3.90 (3H, s), 6.95-7.15 (2
H, m), 7.33 (4H, d, J = 8.4Hz), 7.45-7.55 (1H, m), 7.83 (4
(H, d, J = 8.4Hz).

Example 10 4-Chloro-2-nitro-N
Synthesis of -methyl-N-[(trans) -β-styrenesulfonyl] aniline (Compound No. 282) 0.13 g (3.25 mmol) of 60% sodium hydride in 7.0 ml of DMF
And 1.00 g (2.95 mmol) of 4-chloro-2-nitro-N-[(trans) -β-styrenesulfonyl] aniline was added with stirring at room temperature. After stirring at room temperature for 15 minutes, 0.32 ml (3.38 mmol) of dimethyl sulfate was added. 3 at 80 ° C
After stirring for an hour, the reaction solution was poured into water and extracted with ether. The extract was washed with 1% aqueous sodium hydroxide, washed with water, and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. A small amount of ether was added to the residue, and the precipitated crystals were collected by filtration, washed and 0.99 g of the title compound as pale yellow crystals
(95%). Melting point: 162.0-164.0 ° C NMR (CDCl ₃ ) δ: 3.28 (3H, s), 6.74 (1H, d, J = 15.4 Hz), 7.3
5-7.60 (7H, m), 7.60 (1H, dd, J = 8.6 & 2.3Hz), 7.87 (1H,
d, J = 2.3Hz).

Example 11 2 ', 4'-Dinitro-N-
Methylbenzenesulfonanilide (Compound No. 42
5) Synthesis of 60% sodium hydride 0.12 g (3.00 mmol) in DMF 4.0 ml
And stirred at room temperature while adding N-methyl-2,4-
0.39 g (1.98 mmol) of dinitroaniline was added. Room temperature 15
After stirring for 30 minutes, 0.38 ml of benzenesulfonyl chloride (2.98
mmol) was added dropwise. After stirring at room temperature for 2 hours, the reaction solution was poured into water and extracted with ether. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 2) to give 0.52 g (78%) of the title compound as pale yellow crystals. Melting point: 151.5-153.0 ° C NMR (CDCl ₃ ) δ: 3.28 (3H, s), 7.38 (1H, d, J = 8.8 Hz), 7.45
-7.75 (5H, m), 8.39 (1H, dd, J = 8.8 & 2.6Hz), 8.73 (1H, d,
J = 2.6Hz).

Example 12 2 ', 4'-Dinitro-N-
Ethyl-p-toluenesulfonanilide (Compound No.
435) Synthesis of 60% sodium hydride 0.12 g (3.00 mmol) in DMF 4.0 ml
And stirred at room temperature with 2,4-dinitro-N-
0.42 g (1.99 mmol) of ethylaniline was added. After stirring at room temperature for 15 minutes, p-toluenesulfonyl chloride 0.57 g (2.9
9 mmol) was added. After stirring at room temperature for 2 hours, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 2) to give the title compound (0.47 g, 65%) as pale-yellow crystals. Melting point: 135.0-136.5 ° C NMR (CDCl ₃ ) δ: 1.21 (3H, t, J = 7.2 Hz), 2.45 (3H, s), 3.69
(2H, q, J = 7.2Hz), 7.30 (2H, d, J = 8.4Hz), 7.30 (1H, d, J = 8.
8Hz), 7.52 (2H, d, J = 8.4Hz), 8.38 (1H, dd, J = 8.8 & 2.6H
z), 8.74 (1H, d, J = 2.6Hz).

Example 13 Synthesis of 4'-chloro-N-cyclopropyl-2'-nitro-p-toluenesulfonanilide (Compound No. 292) (1) 2.00 g (10.4 mmol) of 2,5-dichloronitrobenzene
After a mixture of l) and 2.0 ml of cyclopropylamine was heated under reflux for 60 hours, excess cyclopropylamine was removed by concentration under reduced pressure. The residue was dissolved in ethyl acetate and washed sequentially with a 1% aqueous sodium hydroxide solution and saturated saline. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1:10) to give 4-chloro-N-cyclopropyl-2. 1.30 g (59%) of nitroaniline were obtained as orange crystals. _{Mp: 65.0-66.0 ℃ NMR (CDCl 3)} δ: 0.60-0.75 (2H, m), 0.85-1.00 (2H, m), 2.
50-2.65 (1H, m), 7.29 (1H, d, J = 9.5Hz), 7.42 (1H, dd, J = 9.
5 & 2.4Hz), 8.05 (1H, brs), 8.15 (1H, d, J = 2.4Hz). (2) 0.10 g (2.50 mmol) of 60% sodium hydride in DMF
Suspension in 3.0 ml and stirring at room temperature with 4-chloro-N-
0.40 g (1.88 mmol) of cyclopropyl-2-nitroaniline
Was added. After stirring at room temperature for 15 minutes, 0.38 g (1.99 mmol) of p-toluenesulfonyl chloride was added. After stirring at room temperature for 1 hour, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 3) to give the title compound as yellow crystals (0.42 g, 61%). Melting point: 98.5-100.0 ° C NMR (CDCl ₃ ) δ: 0.55-0.85 (2H, m), 0.85-1.20 (2H, m), 2.
45 (3H, s), 2.60-2.80 (1H, m), 7.02 (1H, d, J = 8.6Hz), 7.3
2 (2H, d, J = 8.2Hz), 7.48 (1H, dd, J = 8.6 & 2.4Hz), 7.60 (2
H, d, J = 8.2Hz), 7.81 (1H, d, J = 2.4Hz).

Example 14 2 ', 4'-Dinitro-N-
Methoxy-p-toluenesulfonanilide (compound N
o. Synthesis of 545) (1) 4.05 g (20.0 mmo) of 2,4-dinitrochlorobenzene
l) and 2.00 g (23.9 mmol) of methoxylamine hydrochloride were dissolved in 15 ml of acetonitrile, and 7.00 ml (50.2 mmol) of triethylamine was added dropwise with stirring under ice cooling. After continuing stirring at room temperature for 24 hours, the obtained black solution was concentrated under reduced pressure. After adding water and diluted hydrochloric acid to the residue, the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, eluting with ethyl acetate-hexane (1: 5) to give N
2.26 g (53%) of-(2,4-dinitrophenyl) -O-methylhydroxylamine were obtained as yellow crystals. Melting point: 109.5-111.5 ° C NMR (CDCl ₃ ) δ: 3.92 (3H, s), 7.47 (1H, d, J = 9.5 Hz), 8.38
(1H, dd, J = 9.5 & 2.6Hz), 9.11 (1H, d, J = 2.6Hz), 10.23 (1
H, brs). (2) 0.24 g (6.00 mmol) of 60% sodium hydride in DMF
8.0 ml and suspended under ice-cooling while stirring N- (2,4-
Dinitrophenyl) -O-methylhydroxylamine
0.85 g (3.99 mmol) was added. After stirring under ice cooling for 15 minutes,
1.15 g (6.03 mmol) of p-toluenesulfonyl chloride were added. After returning to room temperature and stirring for 18 hours, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 3) to give the title compound (0.30 g, 21%) as orange crystals. Melting point: 146.0-148.0 ° C NMR (CDCl ₃ ) δ: 2.47 (3H, s), 3.90 (3H, s), 7.31 (1H, d, J =
9.0Hz), 7.32 (2H, d, J = 8.3Hz), 7.54 (2H, d, J = 8.3Hz), 8.
28 (1H, dd, J = 9.0 & 2.5Hz), 8.71 (1H, d, J = 2.5Hz).

Example 15 Synthesis of N- (5-chloro-3-nitropyridin-2-yl) -N-methyl-p-toluenesulfonamide (Compound No. 494) 0.05% of 60% sodium hydride (1.25 mmol) ) In DMF 2.0ml
And 0.20 g (1.07 mmol) of 5-chloro-2-methylamino-3-nitropyridine was added while stirring under ice-cooling. After stirring for 15 minutes under ice cooling, 0.23 g (1.21 mmol) of p-toluenesulfonyl chloride was added. 30 minutes at room temperature under ice cooling
After stirring for 30 minutes, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 3) to give 0.16 g (44%) of the title compound as pale yellow crystals. Melting point: 141.0-143.0 ° C NMR (CDCl ₃ ) δ: 2.44 (3H, s), 3.22 (3H, s), 7.29 (2H, d, J =
8.3Hz), 7.48 (2H, d, J = 8.3Hz), 8.28 (1H, d, J = 2.4Hz), 8.
48 (1H, d, J = 2.4Hz).

Example 16 Synthesis of 4 ′, 5-dichloro-N-methyl-2′-nitro-2-thiophene sulfoneanilide (Compound No. 370) 0.15 g (3.75 mmol) of 60% sodium hydride was added to 5.0 ml of DMF.
And 0.34 g (1.82 mmol) of 4-chloro-N-methyl-2-nitroaniline was added while stirring at room temperature. After stirring at room temperature for 30 minutes, 0.67 g (3.11 mmol) of 5-chloro-2-thiophenesulfonyl chloride was added. After stirring at room temperature for 24 hours, the mixture was poured into water and extracted with chloroform. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and acetone-hexane (1: 4) was used.
Elution with the title compound as pale yellow crystals
0.11 g (16%) was obtained. Melting point: 85.0-86.0 ° C NMR (CDCl ₃ ) δ: 3.31 (3H, s), 6.96 (1H, d, J = 4.0 Hz), 7.17
(1H, d, J = 8.5Hz), 7.26 (1H, d, J = 4.0Hz), 7.56 (1H, dd, J =
8.5 & 2.5Hz), 7.90 (1H, d, J = 2.5Hz).

Example 17 Synthesis of N- (6-chloro-3-pyridazinyl) -N-methyl-p-toluenesulfonamide (compound No. 420) 0.42 g (10.5 mmol) of 60% sodium hydride and 10.0 ml of DMF
While stirring under ice-cooling, 1.85 g (9.99 mmol) of N-methyl-p-toluenesulfonamide was added. below freezing
After stirring for 15 minutes, 3,49-dichloropyridazine 1.49 g
(10.0 mmol) was added. After stirring at room temperature for 1 hour, the resulting solution was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 3) to give 1.41 of the title compound as white crystals.
g (47%) was obtained. Melting point: 80.0-81.0 ° C NMR (CDCl ₃ ) δ: 2.41 (3H, s), 3.38 (3H, s), 7.27 (2H, d, J =
8.4Hz), 7.47 (2H, d, J = 8.4Hz), 7.48 (1H, d, J = 9.3Hz), 8.
02 (1H, d, J = 9.3Hz).

Example 18 N, 2'-dimethyl-4'-
Nitro-p-toluenesulfonanilide (Compound No.
125) Synthesis of 60% sodium hydride 0.08 g (2.00 mmol) in DMF 2.0 ml
While stirring at room temperature, 0.37 g (2.00 mmol) of N-methyl-p-toluenesulfonamide was added. At room temperature
After stirring for 15 minutes, 0.31 g (2.00 mmol) of 2-fluoro-5-nitrotoluene was added. 2 at room temperature
After stirring for an hour, the resulting solution was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Diisopropyl ether was added to the residue, and the precipitated crystals were collected by filtration, washed,
0.22 g (36%) of the title compound was obtained as pale yellow crystals. _{Mp: 103.0-104.0 ℃ NMR (CDCl 3)} δ: 2.47 (3H, s), 2.51 (3H, s), 3.13 (3H, s),
6.77 (1H, d, J = 8.7Hz), 7.34 (2H, d, J = 8.3Hz), 7.58 (2H, d,
J = 8.3Hz), 7.92 (1H, dd, J = 8.7 & 2.6Hz), 8.17 (1H, d, J =
2.6Hz).

Example 19 5-chloro-N-methyl-N
Synthesis of-(p-toluenesulfonyl) anthranilic acid (Compound No. 71) (1) Methyl 5-chloroanthranilate 10.50 g (56.6 mmol)
l) was dissolved in 30 ml of pyridine, and the mixture was stirred at 5 ° C.
-12.00 g (62.9 mmol) of toluenesulfonyl were added. After continuing stirring at room temperature for 18 hours, 200 ml of water was added, and the precipitated crystals were collected by filtration and washed with water to give 4′-chloro-2′-.
18.20 g (95%) of methoxycarbonyl-p-toluenesulfonanilide was obtained as white crystals. Melting point: 112.5-113.5 ° C NMR (CDCl ₃ ) δ: 2.37 (3H, s), 3.88 (3H, s), 7.23 (2H, d, J =
8.4Hz), 7.40 (1H, dd, J = 9.0 & 2.6Hz), 7.67 (1H, d, J = 9.0
Hz), 7.72 (2H, d, J = 8.4Hz), 7.88 (1H, d, J = 2.6Hz), 10.48
(1H, s). (2) 0.43 g (10.8 mmol) of 60% sodium hydride was added to DMF10
4'-chloro-2 'while stirring under ice-cooling.
-Methoxycarbonyl-p-toluenesulfonanilide
3.33 g (9.80 mmol) was added. After stirring under ice cooling for 15 minutes,
1.02 ml (10.8 mmol) of dimethyl sulfate was added dropwise, and stirring was continued at room temperature for 16 hours. After the reaction solution was poured into water and extracted with ethyl acetate, the extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 3) to give 4′-chloro-2′-methoxycarbonyl-N-methyl-p-toluenesulfonanilide as white crystals. 2.95 g (85%) were obtained. Melting point: 65.5-67.0 ° C NMR (CDCl ₃ ) δ: 2.43 (3H, s), 3.23 (3H, s), 3.85 (3H, s),
6.85 (1H, d, J = 8.5Hz), 7.27 (2H, d, J = 8.3Hz), 7.37 (1H, d
d, J = 8.5 & 2.6Hz), 7.52 (2H, d, J = 8.3Hz), 7.82 (1H, d, J =
2.6Hz). (3) 4'-chloro-2'-methoxycarbonyl-N-
13.3 g of methyl-p-toluenesulfonanilide (37.5 mmo
l) was suspended in 30.0 ml of methanol and stirred at room temperature.
30.0 ml of a 0% aqueous sodium hydroxide solution was added dropwise. 48 at room temperature
After stirring for an hour, the mixture was concentrated under reduced pressure. After water was added to the residue to make a homogeneous solution, 10.0 ml of concentrated hydrochloric acid was added to precipitate crystals. After extraction by adding ethyl acetate, the extract was washed with water and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, ether was added to the precipitated crystals, which was filtered and washed to obtain 10.4 g (82%) of the title compound as white crystals. _{Mp: 175.0-177.0 ℃ NMR (CDCl 3)} δ: 2.44 (3H, s), 3.25 (3H, s), 5.70-6.60 (1
H, br), 6.86 (1H, d, J = 8.5Hz), 7.31 (2H, d, J = 8.3Hz), 7.4
2 (1H, dd, J = 8.5 & 2.6Hz), 7.55 (2H, d, J = 8.3Hz), 7.98 (1
(H, d, J = 2.6Hz).

Example 20 Synthesis of 4'-chloro-2'-carbamoyl-N-methyl-p-toluenesulfonanilide (Compound No. 79) 5-Chloro-N-methyl-N- (p-toluenesulfonyl) anthranyl 5.00 g (14.7 mmol) of acid and 1.33 m of pyridine
l (16.4 mmol) was dissolved in 70.0 ml of acetonitrile, and 2.00 g (16.3 mmol) of isopropyl chloroformate was added dropwise with stirring under ice cooling. After stirring for 30 minutes under ice cooling, ammonia gas
About 1.25 g (73.4 mmol) was blown. After stirring for 30 minutes under ice-cooling and for 20 hours at room temperature, the mixture was concentrated under reduced pressure. Water was poured into the residue, extracted with ethyl acetate, washed with water, washed with dilute aqueous sodium hydroxide, and washed with water in this order. After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure to obtain crude crystals. Ether was added to the crystals, followed by filtration and washing to obtain 1.70 g (34%) of the title compound as white crystals. Melting point: 176.5-178.0 ° C NMR (CDCl ₃ ) δ: 2.49 (3H, s), 3.17 (3H, s), 5.92 (1H, br
s), 6.44 (1H, d, J = 8.5Hz), 7.24 (1H, dd, J = 8.5 & 2.6Hz),
7.37 (2H, d, J = 8.4Hz), 7.44 (1H, br), 7.61 (2H, d, J = 8.4H
z), 7.84 (1H, d, J = 2.6Hz).

Example 21 Synthesis of 4'-chloro-2'-cyano-N-methyl-p-toluenesulfonanilide (Compound No. 94) 4'-chloro-2'-carbamoyl-N-methyl-p-
0.70 g (2.07 mmol) of toluenesulfonanilide in pyridine
After dissolving in 3.0 ml and stirring under ice-cooling, 0.40 ml (2.83 mmol) of trifluoroacetic anhydride was added dropwise. After returning to room temperature and stirring for 2 hours, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with dilute hydrochloric acid, washed with water, and washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Diisopropyl ether was added to the residue, and the precipitated crystals were collected by filtration and washed to give 0.63 g (95%) of the title compound as white crystals. Melting point: 145.0-147.0 ° C NMR (CDCl ₃ ) δ: 2.46 (3H, s), 3.22 (3H, s), 7.24 (1H, d, J =
8.7Hz), 7.33 (2H, d, J = 8.3Hz), 7.54 (1H, dd, J = 8.7 & 2.5
Hz), 7.63 (1H, d, J = 2.5Hz), 7.64 (2H, d, J = 8.3Hz).

Example 22 4'-chloro-N-methyl-
Synthesis of 2'-thiocarbamoyl-p-toluenesulfonanilide (Compound No. 83) 4'-chloro-2'-carbamoyl-N-methyl-p-
1.05 g (3.10 mmol) of toluenesulfonanilide and 95% Lawesson's reagent (2,4-bis (4-methoxyphenyl)-
1.70 g (3.99 mmol) of 1,3-dithia-2,4-diphosphetane-2,4-disulfide in 1,4-dioxane 1
In 0.0 ml, the mixture was heated and stirred at 100 ° C. for 1 hour. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography and eluted with chloroform to give 0.51 g (46%) of the title compound as pale yellow crystals. Melting point: 180.5-182.5 ° C NMR (CDCl ₃ ) δ: 2.50 (3H, s), 3.17 (3
H, s), 6.34 (1H, d, J = 8.5 Hz),
7.16 (1H, dd, J = 8.5 & 2.5H
z), 7.38 (2H, d, J = 8.3 Hz),
7.64 (2H, d, J = 8.3 Hz), 7.74
(1H, d, J = 2.5 Hz), 8.04 (1H, br)
s), 8.68 (1H, brs).

Example 23 4'-Chloro-N-methyl-
Synthesis of 2'-methanesulfinyl-p-toluenesulfonanilide (Compound No. 63) 4'-chloro-N-methyl-2'-methylthio-p-toluenesulfonanilide 0.35 g (1.02 mmol)
l) was suspended in 2.0 ml of acetic acid, and 0.12 g (1.06 mmol) of 30% aqueous hydrogen peroxide was added dropwise with stirring at room temperature. After stirring at 50 ° C. for 15 minutes to form a homogeneous solution, stirring was continued at room temperature for 18 hours. The obtained solution was dissolved in ethyl acetate, washed with an aqueous sodium hydroxide solution, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain crude crystals. Diisopropyl ether was added to the crystals, and the crystals were collected by filtration and washed to give 0.27 g (74%) of the title compound as white crystals. Melting point: 142.0-143.5 ° C NMR (CDCl ₃ ) δ: 2.49 (3H, s), 2.98 (3H, s), 3.12 (3H, s),
6.59 (1H, d, J = 8.5Hz), 7.33 (1H, dd, J = 8.5 & 2.3Hz), 7.37
(2H, d, J = 8.3Hz), 7.60 (2H, d, J = 8.3Hz), 8.06 (1H, d, J = 2.3H
z).

Example 24 Synthesis of 4'-fluoro-N-methyl-2'-nitro-p-toluenesulfonanilide (Compound No. 262) (1) 0.31 g (7.75 mmol) of 60% sodium hydride was added to DMF1
While suspending in 0.0 ml and stirring at room temperature, 2.00 g (7.54 mmol) of 4'-fluoro-p-toluenesulfonanilide was added. After stirring at room temperature for 15 minutes, 0.75 ml of dimethyl sulfate
(7.93 mmol) was added dropwise, and stirring was continued at room temperature for 1 hour. After the reaction solution was poured into water and extracted with ethyl acetate, the extract was washed with water and saturated saline in this order, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Diisopropyl ether was added to the residue, and the precipitated crystals were collected by filtration and washed to give 4'-
1.96 g (93%) of fluoro-N-methyl-p-toluenesulfonanilide was obtained as pale yellowish gray crystals. Melting point: 92.0-94.5 ° C NMR (CDCl ₃ ) δ: 2.43 (3H, s), 3.14 (3H, s), 6.90-7.15 (4
H, m), 7.25 (2H, dt, J = 8.3 & 0.6Hz), 7.43 (2H, dt, J = 8.3 &
1.8 Hz). (2) 1.00 g (3.58 mmol) of 4'-fluoro-N-methyl-p-toluenesulfonanilide was dissolved in 5.0 ml of acetic acid, and 0.35 ml (8.19 mmol) of 97% fuming nitric acid was stirred at room temperature while stirring. It was dropped. After heating and stirring at 100 ° C. for 1 hour, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain crude crystals. Ether was added to the crystals, followed by filtration and washing to obtain 0.81 g (70%) of the title compound as yellow crystals. Melting point: 93.5-94.5 ° C NMR (CDCl ₃ ) δ: 2.45 (3H, s), 3.25 (3H, s), 7.11 (1H, dd, J
= 8.8Hz, J _HF = 4.9Hz), 7.15-7.40 (3H, m), 7.50-7.65 (3H,
m).

Example 25 N- (2-bromoethyl)-
4′-Chloro-2′-nitro-p-toluenesulfonanilide (Compound No. 305) 0.20 g (5.00 mmol) of 60% sodium hydride was suspended in 7.0 ml of DMF and 4′-chloro was stirred at room temperature while stirring. 1.20 g (3.67 mmol) of -2'-nitro-p-toluenesulfonanilide
Was added. After stirring at room temperature for 15 minutes, 1,2-dibromoethane (2.00 ml, 23.2 mmol) was added, and the mixture was heated and stirred at 130 ° C for 1 hour. After cooling to room temperature, the reaction solution was poured into water and extracted with ether. The extract was washed successively with a 1% aqueous sodium hydroxide solution and a saturated saline solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to crystallize the residue. Hexane was added and the crystals were collected by filtration while washing, to give 1.12 g (70%) of the title compound as pale yellow crystals. Melting point: 70.0-72.0 ° C NMR (CDCl ₃ ) δ: 2.44 (3H, s), 3.61 (2H, t, J = 8.1 Hz), 3.97
(2H, t, J = 8.1Hz), 7.15 (1H, d, J = 8.6Hz), 7.28 (2H, d, J = 8.
4Hz), 7.50 (2H, d, J = 8.4Hz), 7.54 (1H, dd, J = 8.6 & 2.5H
z), 7.89 (1H, d, J = 2.5Hz).

Example 26 Synthesis of 4'-chloro-N- (2-methylthioethyl) -2'-nitro-p-toluenesulfonanilide (Compound No. 307) N- (2-bromoethyl) -4'-chloro Dissolve 0.30 g (0.69 mmol) of -2'-nitro-p-toluenesulfonanilide in 3.0 ml of acetonitrile and stir at room temperature for 15%
Methyl mercaptan sodium salt aqueous solution 0.50 g (1.07 mmo
l) was added dropwise. After stirring at room temperature for 15 hours, the mixture was concentrated under reduced pressure. After water was added to the residue and the mixture was extracted with ethyl acetate, the extract was washed with water and washed with saturated saline. After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure, and diisopropyl ether was added to the residue to precipitate crystals. The crystals were collected by filtration and washed to give the title compound as pale yellow crystals 0.22 g (79%)
Obtained. Melting point: 94.5-95.5 ° C NMR (CDCl ₃ ) δ: 2.09 (3H, s), 2.44 (3H, s), 2.77 (2H, dd, J
= 7.9 & 5.9Hz), 3.78 (2H, dd, J = 7.9 & 7.5Hz), 7.13 (1H,
d, J = 8.6Hz), 7.28 (2H, d, J = 8.3Hz), 7.51 (2H, d, J = 8.3H
z), 7.52 (1H, dd, J = 8.6 & 2.5Hz), 7.87 (1H, d, J = 2.5Hz).

Example 27 Synthesis of 4'-chloro-2'-nitro-N-vinyl-p-toluenesulfonanilide (Compound No. 298) 0.04 g (1.00 mmol) of 60% sodium hydride and 5.0 ml of DMF
And stirred at room temperature with 1,2,4-triazole 0.0
8 g (1.16 mmol) were added. After stirring at room temperature for 15 minutes, N-
(2-bromoethyl) -4′-chloro-2′-nitro-
0.35 g (0.81 mmol) of p-toluenesulfonanilide was added. After stirring at room temperature for 18 hours, the reaction solution was poured into water and extracted with ethyl acetate. After washing the extract with water and saturated saline,
The extract was dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 3) to give the title compound as pale-yellow crystals (0.052 g, 18%). Melting point:> 108.0 ° C (decomposition) NMR (CDCl ₃ ) δ: 2.45 (3H, s), 3.88 (1H, dd, J = 15.5 & 1.7H)
z), 4.40 (1H, dd, J = 8.9 & 1.7Hz), 6.96 (1H, d, J = 8.5Hz),
7.12 (1H, dd, J = 15.5 & 8.9Hz), 7.30 (2H, d, J = 8.3Hz), 7.
54 (1H, dd, J = 8.5 & 2.4Hz), 7.57 (2H, d, J = 8.3Hz), 7.99
(1H, d, J = 2.4Hz).

Example 28 4'-methoxymethoxy-N
Synthesis of -methyl-2'-nitro-p-toluenesulfonanilide (Compound No. 219) (1) 2.70 g (67.5 mmol) of 60% sodium hydride in THF10
Suspended in 0.0 ml of ice, and stirred under ice-cooling.
10.0 g (64.9 mmol) of nitrophenol were added. Under ice cooling 10
After stirring for 5 minutes, 5.50 g of chloromethyl methyl ether (6
(8.3 mmol) was added dropwise. After stirring at 5 ° C for 1 hour and at room temperature for 1 hour, the mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate, washed with water and saturated aqueous sodium bicarbonate in that order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with chloroform-ethanol (100: 1) to give 7.69 g of 4-methoxymethoxy-2-nitroaniline as a red oil.
(60%). NMR (CDCl ₃ ) δ: 3.48 (3H, s), 5.12 (2H, s), 5.92 (2H, br
s), 6.77 (1H, d, J = 9.0Hz), 7.15 (1H, dd, J = 9.0 & 2.9Hz),
7.78 (1H, d, J = 2.9 Hz). (2) 4-methoxymethoxy-2-nitroaniline 7.69
g (38.8 mmol) was dissolved in 19.0 ml of pyridine, and while stirring at room temperature, 8.14 g (42.7 mmol) of p-toluenesulfonyl chloride was added. After stirring at room temperature for 18 hours, 200.0 ml of water was added, and the mixture was extracted with chloroform. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with chloroform-ethanol (100: 1) to give 4.46 g (63%) of 4'-methoxymethoxy-2'-nitro-p-toluenesulfonanilide as a yellow oil. %)Obtained. NMR (CDCl ₃ ) δ: 2.38 (3H, s), 3.46 (3H, s), 5.16 (2H, s),
7.23 (2H, d, J = 8.4Hz), 7.29 (1H, dd, J = 9.1Hz & 2.7Hz),
7.64 (2H, dt, J = 8.4 & 2.0Hz), 7.70 (1H, d, J = 2.7Hz), 7.7
9 (1H, d, J = 9.1Hz), 9.34 (1H, brs). (3) 0.40 g (10.0 mmol) of 60% sodium hydride in DMF
The suspension was suspended in 15.0 ml and stirred at room temperature, and 3.00 g (8.51 mmol) of 4'-methoxymethoxy-2'-nitro-p-toluenesulfonanilide was added. After stirring at room temperature for 15 minutes, 1.0 ml (10.6 mmol) of dimethyl sulfate was added dropwise and the mixture was stirred at room temperature for 15 minutes.
Stirring was continued for hours. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 2) to give 2.91 g of the title compound as yellow crystals.
(93%). Melting point: 110.5-112.0 ° C NMR (CDCl ₃ ) δ: 2.44 (3H, s), 3.24 (3
H, s), 3.49 (3H, s), 5.21 (2
H, s), 7.01 (1H, d, J = 8.8 Hz),
7.15 (1H, dd, J = 8.8 & 2.8H
z), 7.29 (2H, d, J = 8.3 Hz),
7.50 (1H, d, J = 2.8 Hz), 7.57
(2H, d, J = 8.3 Hz).

Example 29 Synthesis of 4'-hydroxy-N-methyl-2'-nitro-p-toluenesulfonanilide (Compound No. 156) 4'-methoxymethoxy-N-methyl-2'-nitro-
2.70 g of p-toluenesulfonanilide (7.37
mmol) was suspended in 20.0 ml of methanol, and 5.0 ml of 35% hydrochloric acid was added with stirring at room temperature. After stirring at room temperature for 15 hours, the mixture was concentrated to dryness under reduced pressure. Ether was added to the remaining solid,
Filtration and washing gave 2.30 g (97%) of the title compound as pale red crystals. _{Mp: 173.0-174.0 ℃ NMR (CDCl 3)} δ: 2.45 (3H, s), 3.22 (3H, s), 6.37 (1H, br
s), 6.90-7.05 (2H, m), 7.25 (1H, d, J = 2.3Hz), 7.31 (2H, m
d, J = 8.4Hz), 7.59 (2H, d, J = 8.4Hz).

Example 30 N-methyl-2'-nitro-
Synthesis of 4 ′-(n-propoxy) -p-toluenesulfonanilide (Compound No. 216) 0.05% (1.25 mmol) of 60% sodium hydride in DMF 1.0 ml
4'-hydroxy-N
0.32 g (0.99 mmol) of -methyl-2'-nitro-p-toluenesulfonanilide was added. After stirring at room temperature for 15 minutes, 0.20 ml (2.20 mmol) of n-propyl bromide was added dropwise.
After stirring at room temperature for 15 hours, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Diisopropyl ether was added to the residue, and the precipitated crystals were collected by filtration and washed to give the title compound as pale yellow crystals in an amount of 0.15%.
g (42%). Melting point: 93.0-94.0 ° C NMR (CDCl ₃ ) δ: 1.05 (3H, t, J = 7.3 Hz), 1.83 (2H, tq, J = 6.5
& 7.3Hz), 2.44 (3H, s), 3.24 (3H, s), 3.96 (2H, t, J = 6.5H
z), 6.90-7.10 (2H, m), 7.20-7.35 (3H, m), 7.56 (2H, d, J =
(8.3Hz).

Example 31 4'-bromo-N-methyl-
Synthesis of 2′-nitro-p-toluenesulfonanilide (Compound No. 398) (1) 0.18 g (4.50 mmol) of 60% sodium hydride was added to DMF5.
0 'and suspended at room temperature while stirring.
1.30 g (3.99 mmol) of toluenesulfoneanilide were added. After stirring at room temperature for 15 minutes, 0.40 ml of dimethyl sulfate (4.2
3 mmol) was added dropwise, and stirring was continued at room temperature for 24 hours. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to crystallize the residue. Diisopropyl ether was added, and the crystals were washed and filtered to give 4'-bromo-N-methyl-p-toluenesulfonanilide as white crystals, 1.17.
g (86%). Melting point: 82.5-83.5 ° C NMR (CDCl ₃ ) δ: 2.42 (3H, s), 3.13 (3H, s), 6.98 (2H, d, J =
8.9Hz), 7.25 (2H, d, J = 8.4Hz), 7.42 (2H, d, J = 8.9Hz), 7.
42 (2H, d, J = 8.4 Hz). (2) Dissolve 0.90 g (2.65 mmol) of 4'-bromo-N-methyl-p-toluenesulfonanilide in 5.0 ml of acetic acid, and stir at room temperature with 97% fuming nitric acid. 0.64 ml (15.0 mmol) was added dropwise. After heating and stirring at 100 ° C. for 1.5 hours, the mixture was cooled to room temperature, and the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with saturated aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 3) to give 0.64 g (63%) of the title compound as pale yellow crystals.
%)Obtained. Melting point: 108.0-110.5 ° C NMR (CDCl ₃ ) δ: 2.45 (3H, s), 3.24 (3H, s), 7.00 (1H, d, J =
8.5Hz), 7.31 (2H, d, J = 8.4Hz), 7.56 (2H, d, J = 8.4Hz), 7.
65 (1H, dd, J = 8.5 & 2.3Hz), 7.99 (1H, d, J = 2.3Hz).

Example 32 4'-Chloro-N-ethyl-
Synthesis of 2′-methoxycarbonyl-p-toluenesulfonanilide (Compound No. 76) In (2) of Example 19, the reaction was carried out at 80 ° C. for 1 hour using diethyl sulfate instead of dimethyl sulfate.
The title compound was obtained as white crystals in 72% yield. Melting point: 105.0-107.0 ° C NMR (CDCl ₃ ) δ: 1.15 (3H, t, J = 7.1 Hz), 2.42 (3H, s), 3.67
(2H, q, J = 7.1Hz), 3.81 (3H, s), 6.86 (1H, d, J = 8.5Hz), 7.
25 (2H, d, J = 8.4Hz), 7.38 (1H, dd, J = 8.5 & 2.6Hz), 7.50 (2
H, d, J = 8.4Hz), 7.84 (1H, d, J = 2.6Hz).

Example 33 Synthesis of 4'-chloro-N-isopropyl-2'-methoxycarbonyl-p-toluenesulfonanilide (Compound No. 77) In Example 19 (2), iodide was used instead of dimethyl sulfate. The reaction was carried out at 130 ° C. for 1 hour using isopropyl to give the title compound as white crystals in a yield of 19%. _{Mp: 113.5-115.5 ℃ NMR (CDCl 3)} : 1.04 (3H, d, J = 6.7Hz), 1.06 (3H, d, J = 6.7H
z), 2.42 (3H, s), 3.87 (3H, s), 4.49 (1H, septet, J = 6.7H
z), 6.94 (1H, d, J = 8.5Hz), 7.26 (2H, d, J = 8.4Hz), 7.41 (1
H, dd, J = 8.5 & 2.6Hz), 7.60 (2H, d, J = 8.4Hz), 7.89 (1H,
d, J = 2.6Hz).

Example 34 5-Chloro-N-ethyl-N
Synthesis of-(p-toluenesulfonyl) anthranilic acid (compound No. 72) In Example 19 (3), 4 ''-Chloro-N-ethyl-2'-
By using methoxycarbonyl-p-toluenesulfonanilide, the title compound was obtained as white crystals in a yield of 68%. Melting point: 163.0-165.0 ° C NMR (CDCl ₃ ) δ: 1.12 (3H, t, J = 7.2 Hz), 2.44 (3H, s), 3.20
-3.80 (1H, br), 3.50-4.10 (1H, br), 4.00-5.20 (1H, br),
6.77 (1H, d, J = 8.6Hz), 7.30 (2H, d, J = 8.3Hz), 7.41 (1H, d
d, J = 8.6 & 2.6Hz), 7.55 (2H, d, J = 8.3Hz), 7.99 (1H, d, J =
2.6Hz).

Example 35 Synthesis of 5-chloro-N-isopropyl-N- (p-toluenesulfonyl) anthranilic acid (Compound No. 73) In Example 19 (3), 4'-chloro-2'-methoxy 4'-chloro-N-isopropyl-instead of carbonyl-N-methyl-p-toluenesulfonanilide
By using 2'-methoxycarbonyl-p-toluenesulfonanilide, the title compound was obtained as white crystals.
% Yield. Melting point: 175.0-176.5 ° C NMR (CDCl ₃ ) δ: 1.02 (3H, d, J = 6.7 Hz), 1.10 (3H, d, J = 6.7H)
z), 2.46 (3H, s), 4.67 (1H, septet, J = 6.7Hz), 6.61 (1H,
d, J = 8.6Hz), 7.32 (2H, d, J = 8.3Hz), 7.36 (1H, dd, J = 8.6 &
2.6Hz), 7.61 (2H, d, J = 8.3Hz), 7.91 (1H, d, J = 2.6Hz).

Example 36 Synthesis of 4'-chloro-2'-carbamoyl-N-ethyl-p-toluenesulfonanilide (Compound No. 80) 5-Chloro-N-ethyl-N- (p-toluenesulfonyl) anthranyl 3.40 g (9.61 mmol) of acid and 5.0 of thionyl chloride
0 ml (68.5 mmol) of the mixture was mixed with 50.0 ml of chloroform
The mixture was heated and stirred at 0 ° C. for 1 hour. After allowing to cool to room temperature, the mixture was concentrated under reduced pressure to obtain crude crystals of acid chloride. A solution of acid chloride in 25.0 ml of acetonitrile was added dropwise to a solution of 5.00 g (73.4 mmol) of 25% aqueous ammonia in 25.0 ml of acetonitrile under ice-cooling. After stirring for 30 minutes under ice cooling,
It was concentrated under reduced pressure. After water was added to the residue to precipitate crystals, the crystals were filtered and washed with water to give 3.14 g (93%) of the title compound as white crystals. Melting point: 148.5-150.0 ° C NMR (CDCl ₃ ) δ: 1.05 (3H, t, J = 7.2Hz), 2.49 (3H, s), 2.90
-3.70 (1H, br), 3.60-4.40 (1H, br), 5.93 (1H, brs), 6.37
(1H, d, J = 8.5Hz), 7.24 (1H, dd, J = 8.5 & 2.6Hz), 7.36 (2
H, d, J = 8.3Hz), 7.61 (2H, d, J = 8.3Hz), 7.63 (1H, brs), 7.
82 (1H, d, J = 2.6Hz).

Example 37 Synthesis of 4'-chloro-2'-carbamoyl-N-isopropyl-p-toluenesulfonanilide (Compound No. 81) 5-Chloro-N-ethyl-N- (p- 5-chloro-N-isopropyl-N- (p-toluenesulfonyl) instead of toluenesulfonyl) anthranilic acid
The use of anthranilic acid provided the title compound as white crystals in 94% yield. Melting point: 177.0-178.5 ° C NMR (CDCl ₃ ) δ: 0.84 (3H, d, J = 6.7 Hz), 1.14 (3H, d, J = 6.7H)
z), 2.48 (3H, s), 4.65 (1H, septet, J = 6.7Hz), 5.87 (1H, b
rs), 6.43 (1H, d, J = 8.6Hz), 7.25 (1H, dd, J = 8.6 & 2.6Hz),
7.35 (2H, d, J = 8.3Hz), 7.67 (2H, d, J = 8.3Hz), 7.78 (1H,
d, J = 2.6Hz), 7.82 (1H, brs).

Example 38 Synthesis of 4'-chloro-2'-cyano-N-ethyl-p-toluenesulfonanilide (Compound No. 95) 4'-Chloro-2'-carbamoyl-N- of Example 21
4 'instead of methyl-p-toluenesulfonanilide
The title compound was obtained as white crystals in 84% yield by using -chloro-2'-carbamoyl-N-ethyl-p-toluenesulfonanilide. Melting point: 138.5-140.5 ° C NMR (CDCl ₃ ) δ: 1.10 (3H, t, J = 7.2Hz), 2.45 (3H, s), 3.64
(2H, q, J = 7.2Hz), 7.20 (1H, d, J = 8.6Hz), 7.32 (2H, d, J = 8.
4Hz), 7.55 (1H, dd, J = 8.6 & 2.5Hz), 7.60-7.75 (3H, m).

Example 39 Synthesis of 4'-chloro-2'-cyano-N-isopropyl-p-toluenesulfonanilide (Compound No. 97) 4'-chloro-2'-carbamoyl-N- of Example 21
4 'instead of methyl-p-toluenesulfonanilide
-Chloro-2'-carbamoyl-N-isopropyl-p
-The title compound was obtained as white crystals in a yield of 90% by using toluenesulfonanilide. Melting point: 129.5-130.5 ° C NMR (CDCl ₃ ) δ: 1.14 (6H, d, J = 6.7 Hz), 2.44 (3H, s), 4.49
(1H, septet, J = 6.7Hz), 7.26 (1H, d, J = 8.6Hz), 7.31 (2H,
d, J = 8.5Hz), 7.57 (1H, dd, J = 8.6 & 2.5Hz), 7.68 (1H, d, J
= 2.5Hz), 7.74 (2H, d, J = 8.5Hz).

Example 40 4'-Chloro-N-ethyl-
Synthesis of 2′-thiocarbamoyl-p-toluenesulfonanilide (Compound No. 84) 4′-Chloro-2′-carbamoyl-N- of Example 22
4 'instead of methyl-p-toluenesulfonanilide
By using -chloro-2'-carbamoyl-N-ethyl-p-toluenesulfonanilide, the title compound was obtained as pale yellow crystals in a yield of 91%. Melting point: 180.0-182.0 ° C NMR (CDCl ₃ ) δ: 1.06 (3H, t, J = 7.2 Hz), 2.49 (3H, s), 3.21
(1H, dq, J = 7.0 & 7.2Hz), 3.88 (1H, dq, J = 7.0 & 7.2Hz),
6.29 (1H, d, J = 8.6Hz), 7.17 (1H, dd, J = 8.6 & 2.5Hz), 7.3
7 (2H, d, J = 8.4Hz), 7.63 (2H, d, J = 8.4Hz), 7.84 (1H, d, J =
2.5Hz), 8.01 (1H, brs), 9.04 (1H, brs).

Example 41 Synthesis of 4'-chloro-N-isopropyl-2'-thiocarbamoyl-p-toluenesulfonanilide (Compound No. 85) 4'-Chloro-2'-carbamoyl-N- of Example 22
4 'instead of methyl-p-toluenesulfonanilide
-Chloro-2'-carbamoyl-N-isopropyl-p
-The title compound was obtained as pale yellow crystals in a yield of 34% by using toluenesulfoneanilide. Melting point: 189.0-191.0 ° C NMR (CDCl ₃ ) δ: 0.85 (3H, d, J = 6.8 Hz), 1.23 (3H, d, J = 6.8H)
z), 2.48 (3H, s), 4.59 (1H, septet, J = 6.8Hz), 6.36 (1H,
d, J = 8.6Hz), 7.19 (1H, dd, J = 8.6 & 2.6Hz), 7.35 (2H, d, J
= 8.4Hz), 7.65 (2H, d, J = 8.4Hz), 7.98 (1H, d, J = 2.6Hz),
7.99 (1H, brs), 9.29 (1H, brs).

Example 42 Synthesis of 2'-cyano-N-methoxy-4'-nitro-p-toluenesulfonanilide (Compound No. 535) (1) 9.00 g (108 mmol) of methoxylamine hydrochloride was added to 30.0 ml of pyridine. After suspending and stirring under ice cooling, 19.07 g (100 mmol) of p-toluenesulfonyl chloride was added. After stirring for 30 minutes under ice cooling and 2 hours at room temperature, 200.0 ml of water was poured to precipitate crystals. After stirring for 30 minutes, the crystals were collected by filtration and washed with water to obtain 20.26 g (99%) of N-methoxy-p-toluenesulfonamide as white crystals. Melting point: 116.0-117.0 ° C NMR (CDCl ₃ ) δ: 2.45 (3H, s), 3.79 (3H, s), 7.14 (1H, s),
7.35 (2H, d, J = 8.3 Hz), 7.84 (2H, d, J = 8.3 Hz). (2) 0.09 g (2.25 mmol) of 60% sodium hydride was added to DMF 3.
0-ml and stirred under ice-cooling with N-methoxy-p-
0.45 g (2.20 mmol) of toluenesulfonamide was added. After stirring for 15 minutes under ice cooling, 0.37 g (2.03 mmol) of 2-chloro-5-nitrobenzonitrile was added. After stirring for 1 hour under ice cooling and 18 hours at room temperature, the mixture was poured into water and extracted with ether. The extract was washed twice with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 5) to give the title compound as pale-yellow crystals (0.48 g, 68%). Melting point: 148.0-149.5 ° C NMR (CDCl ₃ ) δ: 2.48 (3H, s), 3.84 (3H, s), 7.32 (1H, d, J =
9.0Hz), 7.35 (2H, d, J = 8.3Hz), 7.62 (2H, d, J = 8.3Hz), 8.
32 (1H, dd, J = 9.0 & 2.5Hz), 8.54 (1H, d, J = 2.5Hz).

Example 43 Synthesis of 2'-chloro-N-ethoxy-4'-nitro-p-toluenesulfonanilide (Compound No. 533) (1) Instead of methoxylamine hydrochloride in Example 42 (1) By using ethoxylamine hydrochloride, N-ethoxy-p-toluenesulfonamide was obtained as white crystals in a yield of 91%. Melting point: 94.0-95.0 ° C NMR (CDCl ₃ ) δ: 1.20 (3H, t, J = 7.0 Hz), 2.45 (3H, s), 4.03
(2H, q, J = 7.0Hz), 6.89 (1H, s), 7.35 (2H, d, J = 8.3Hz), 7.
82 (2H, d, J = 8.3 Hz). (2) 0.18 g (4.50 mmol) of 60% sodium hydride was added to DMF6.
0 ml and suspended under ice-cooling while stirring N-ethoxy-p.
0.90 g (4.18 mmol) of toluenesulfonamide were added.
After stirring for 15 minutes under ice cooling, 0.70 g (3.99 mmol) of 3-chloro-4-fluoronitrobenzene was added. 1 hour under ice cooling,
After stirring at room temperature for 18 hours, the reaction solution was poured into water and extracted with ether. The extract was washed twice with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain crude crystals. The crystals were washed with diisopropyl ether and collected by filtration to obtain 1.06 g (72%) of the title compound as pale yellow crystals. Melting point: 133.5-135.0 ° C NMR (CDCl ₃ ) δ: 1.15 (3H, t, J = 7.0 Hz), 2.49 (3H, s), 4.10
(2H, q, J = 7.0Hz), 6.89 (1H, d, J = 8.9Hz), 7.34 (2H, d, J = 8.
4Hz), 7.62 (2H, d, J = 8.4Hz), 7.95 (1H, dd, J = 8.9 & 2.5H
z), 8.35 (1H, d, J = 2.5Hz).

Example 44 Synthesis of 2'-chloro-N-isopropoxy-4'-nitro-p-toluenesulfonanilide (Compound No. 534) (1) Preparation of methoxylamine hydrochloride in Instead of using isopropoxylamine hydrochloride, N-isopropoxy-p-toluenesulfonamide was obtained as pale yellow crystals in a yield of 96%. Melting point: 103.5-104.5 ° C NMR (CDCl ₃ ) δ: 1.18 (6H, d, J = 6.2 Hz), 2.45 (3H, s), 4.24
(1H, septet, J = 6.2Hz), 6.75 (1H, s), 7.34 (2H, d, J = 8.3H
z), 7.81 (2H, d, J = 8.3 Hz). (2) In Example 43 (2), N-ethoxy-p-
The title compound was obtained as pale yellow crystals in 80% yield by using N-isopropoxy-p-toluenesulfonamide instead of toluenesulfonamide. Melting point: 160.5-162.0 ° C NMR (CDCl ₃ ) δ: 1.14 (6H, d, J = 6.2 Hz), 2.49 (3H, s), 4.42
(1H, septet, J = 6.2Hz), 6.86 (1H, d, J = 9.0Hz), 7.34 (2H,
d, J = 8.3Hz), 7.59 (2H, d, J = 8.3Hz), 7.94 (1H, dd, J = 9.0 &
2.5Hz), 8.35 (1H, d, J = 2.5Hz).

Example 45 Synthesis of 2 ′, 4-dichloro-N-methoxy-4′-nitrobenzenesulfonanilide (Compound No. 526) (1) In place of p-toluenesulfonyl chloride in (1) of Example 42 By using 4-chlorobenzenesulfonyl chloride, 4-chloro-N-methoxybenzenesulfonamide was obtained as pale yellow crystals in a yield of 97%. Melting point: 81.0-82.5 ° C NMR (CDCl ₃ ) δ: 3.81 (3H, s), 7.23 (1H, s), 7.53 (2H, dt, J
= 8.7 & 2.5Hz), 7.87 (2H, dt, J = 8.7 & 2.5Hz). (2) In Example 43 (2), N-ethoxy-p-
By using 4-chloro-N-methoxybenzenesulfonamide instead of toluenesulfonamide, the title compound was obtained as pale yellow crystals in a yield of 49%. Melting point: 150.0-151.0 ° C NMR (CDCl ₃ ) δ: 3.84 (3H, s), 6.91 (1H, d, J = 8.9 Hz), 7.54
(2H, d, J = 8.5Hz), 7.70 (2H, d, J = 8.5Hz), 8.00 (1H, dd, J =
(8.9 & 2.5Hz), 8.37 (1H, d, J = 2.5Hz).

Example 46 2 ', 4'-dicyano-N-
Synthesis of isopropyl-p-toluenesulfonanilide (Compound No. 114) (1) 47.5 g (0.30 mol) of potassium permanganate was added to 500.0 m of water.
20.0 g of 3-methyl-4-nitrobenzoic acid (0.13 m
ol) and stirred at 70 ° C. overnight. Potassium permanganate 2
An additional 4.5 g (0.16 mol) was added and stirring was continued at 70 ° C. for 2 days. While the reaction solution was warm, insolubles were removed by filtration, and after cooling, the solution was acidified with concentrated hydrochloric acid to precipitate crystals. The crystals were collected by filtration and washed with water to give 11.9 g (51%) of 4-nitroisophthalic acid as white crystals. Mp: 256.8-258.5 ℃ NMR (DMSO-d 6) δ: 8.07 (1H, dd, J = 8.3 & 0.3Hz), 8.27 (1
H, dd, J = 8.3 & 1.9Hz), 8.34 (1H, dd, J = 1.9 & 0.3Hz), 1
3.80 (2H, brs). (2) A mixture of 11.9 g (56.4 mmol) of 4-nitroisophthalic acid and 20.0 ml of thionyl chloride was heated and stirred at 70 ° C. for 2 days, and then concentrated under reduced pressure. The residue was diluted with 30.0 ml of acetonitrile and added dropwise to 30.0 ml of ice-cooled 25% aqueous ammonia.
The precipitated crystals were collected by filtration and washed with water to obtain 11.9 g (100%) of 4-nitroisophthalamide as white crystals. Melting point: 287.0-289.0 ° C NMR (DMSO-d ₆ ) δ: 7.77 (2H, br), 8.00-8.20 (3H, m), 8.25
(2H, br). (3) Dissolve 6.0 g (28.7 mmol) of 4-nitroisophthalamide in 150.0 ml of ethanol, and add 20.02 g (86.1 mmo) of stannous chloride.
l) was added and the mixture was stirred at 70 ° C. overnight. After allowing to cool, the mixture was neutralized with a saturated aqueous solution of sodium bicarbonate, and the resulting insolubles were removed by filtration. The aqueous layer was extracted with ethyl acetate, and the extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 2.59 g (50%) of 4-aminoisophthalamide as pale yellow crystals. Melting point: 177.0-197.5 ° C NMR (DMSO-d ₆ ) δ: 6.68 (1H, d, J = 8.6 Hz), 6.90-7.30 (4H,
m), 7.40-7.80 (2H, m), 7.65 (1H, dd, J = 8.6 & 1.9Hz), 8.
11 (1H, d, J = 1.9 Hz). (4) Dissolve 1.00 g (5.58 mmol) of 4-aminoisophthalamide in 10.0 ml of pyridine and, with stirring at room temperature, p-chloride.
1.06 g (5.58 mmol) of toluenesulfonyl were added. Room temperature 3
After stirring for an hour, water was added to precipitate crystals. The crystals are collected by filtration, washed with water and washed with ethyl acetate to give 2 ′,
0.94 g (51%) of 4′-dicarbamoyl-p-toluenesulfonanilide was obtained as white crystals. Melting point: 212.0-215.0 ° C NMR (DMSO-d ₆ ) δ: 2.33 (3H, s), 7.35 (2H, d, J = 8.3 Hz), 7.
40 (1H, brs), 7.53 (1H, d, J = 8.6Hz), 7.70 (2H, d, J = 8.3H
z), 7.79 (1H, brs), 7.90 (1H, dd, J = 8.6 & 1.8Hz), 7.97
(1H, brs), 8.26 (1H, d, J = 1.8Hz), 8.38 (1H, brs), 12.30
(1H, s). (5) To 5.00 g of phosphorus oxychloride was added 0.30 g (0.90 mmol) of 2 ', 4'-dicarbamoyl-p-toluenesulfonanilide, and the mixture was heated with stirring at 50 ° C for 4 hours. After cooling, water was added and the mixture was stirred, whereby an insoluble solid precipitated. The crystals were collected by filtration, washed with water, and recrystallized from ethyl acetate-hexane to give 0.16 g (60%) of 2 ', 4'-dicyano-p-toluenesulfonanilide as light brown crystals. Melting point: 200.0-206.0 ° C NMR (DMSO-d ₆ ) δ: 2.38 (3H, s), 7.31 (1H, d, J = 8.7 Hz), 7.
41 (2H, d, J = 8.3Hz), 7.73 (2H, d, J = 8.3Hz), 8.01 (1H, dd, J
= 8.7 & 2.0Hz), 8.40 (1H, d, J = 2.0Hz). (6) 0.12 g (3.30 mmol) of 65% sodium hydride in DMF 6.
The suspension was suspended in 0 ml, and 0.49 g (1.65 mmol) of 2 ', 4'-dicyano-p-toluenesulfonanilide was added with stirring at room temperature. After stirring at room temperature for 10 minutes, isopropyl iodide
0.50 ml (4.94 mmol) was added and the mixture was heated and stirred at 130 ° C. for 6 hours. After cooling, the reaction solution was poured into water and extracted with ether. Extract
After washing with a 1% aqueous sodium hydroxide solution and a saturated saline solution, the mixture was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (3: 7) to give the title compound as white crystals (0.07 g, 13%). Melting point: 157.2-157.7 ° C NMR (CDCl ₃ ) δ: 1.16 (6H, d, J = 6.7 Hz), 2.45 (3H, s), 4.48
(1H, q, J = 6.7Hz), 7.33 (2H, d, J = 8.4Hz), 7.49 (1H, d, J = 8.
3Hz), 7.74 (2H, d, J = 8.4Hz), 7.89 (1H, dd, J = 8.3 & 2.0H
z), 8.01 (1H, d, J = 2.0Hz).

Example 47 2′-Cyano-N-ethyl-
Synthesis of 4'-nitro-p-toluenesulfonanilide (Compound No. 420) (1) Dissolve 2.36 g (20.0 mmol) of 2-aminobenzonitrile in 10.0 ml of pyridine and, with stirring at room temperature, p-toluenesulfonyl chloride 4.20 g (22.0 mmol) was added. 15 at room temperature
After stirring for 10 hours, 100.0 ml of water was poured, and stirring was continued for 30 minutes. The precipitated crystals were collected by filtration and washed with water. The obtained crystal was once dissolved in chloroform, and a soluble matter was extracted in a 1% aqueous sodium hydroxide solution. The aqueous layer was acidified with hydrochloric acid, extracted again with chloroform, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure for crystallization. The crystals are washed with diisopropyl ether and collected by filtration to give 2'-cyano-p-.
4.83 g (89%) of toluenesulfonanilide as white crystals
Obtained. Melting point: 134.5-136.5 ° C NMR (CDCl ₃ ) δ: 2.39 (3H, s), 7.06 (1H, brs), 7.10-7.35
(3H, m), 7.40-7.60 (2H, m), 7.60-7.80 (3H, m). (2) 2'-cyano-p-toluenesulfonanilide 2.
67 g (9.80 mmol) was suspended in 7.0 ml of acetic anhydride, and 0.45 ml (10.5 mmol) of 97% fuming nitric acid was added dropwise with stirring at room temperature. 50
After stirring at ℃ for 1 hour, crystals began to precipitate. After pouring water to decompose acetic anhydride, the crystals were collected by filtration and washed with water. After drying the crystals, they are washed with ether and filtered to give 2'-cyano-4'-.
3.05 g (98%) of nitro-p-toluenesulfonanilide was obtained as pale yellow crystals. Melting point: 165.5-167.0 ° C NMR (CDCl ₃ ) δ: 2.43 (3H, s), 7.34 (2H, d, J = 8.4 Hz), 7.62
(1H, s), 7.81 (2H, d, J = 8.4Hz), 7.80-7.95 (1H, m), 8.25-
8.45 (2H, m). (3) 0.12 g (3.00 mmol) of 60% sodium hydride was added to DMF3.
2'-cyano-4 'while stirring at room temperature.
-Nitro-p-toluenesulfonanilide 0.80 g (2.52 mm
ol). After stirring at room temperature for 15 minutes, diethyl sulfate
0.40 ml (3.05 mmol) was added dropwise, and the mixture was heated and stirred at 80 ° C. for 2 hours and at 100 ° C. for 2 hours. After allowing to cool to room temperature, the reaction solution was poured into water and extracted with ether. Extract solution with 1% aqueous sodium hydroxide
After washing three times, the extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 2) to give the title compound as white crystals (0.23 g, 26%). Melting point: 135.0-136.5 ° C NMR (CDCl ₃ ) δ: 1.13 (3H, t, J = 7.2 Hz), 2.46 (3H, s), 3.72
(2H, q, J = 7.2Hz), 7.34 (2H, d, J = 8.4Hz), 7.50 (1H, d, J = 8.
8Hz), 7.65 (2H, d, J = 8.4Hz), 8.43 (1H, dd, J = 8.8 & 2.2H
z), 8.54 (1H, d, J = 2.2Hz).

Example 48 4′-Chloro-N-ethyl-
Synthesis of 2′-nitro-p-toluenesulfonanilide (Compound No. 289) (1) Dissolve 500 g (3.84 mol) of 4-chloroaniline (98%) in 338 ml of pyridine and 800 ml of acetonitrile, and stir at 15 ° C. or lower. 807.8 g of p-toluenesulfonyl chloride (4.11mo
l) was added. After stirring at room temperature for 16 hours, add 4000 ml of water
Stirring was continued for 3 hours to precipitate crystals. Filter these crystals,
After washing with water, 1100 g (102%) of 4'-chloro-p-toluenesulfonanilide was obtained as pale red crude crystals. _{Mp: 122.0-123.0 ℃ NMR (CDCl 3)} δ: 2.39 (3H, s), 6.73 (1H, brs), 7.00 (2H, d,
J = 8.8Hz), 7.20 (2H, d, J = 8.8Hz), 7.24 (2H, d, J = 8.3Hz),
7.64 (2H, d, J = 8.3 Hz). (2) 4'-chloro-p-toluenesulfonanilide 11
00g (3.90 mol) was suspended in 2200 ml of acetic acid, and 273.9 g (4.22 mol) of fuming nitric acid was added dropwise over 40 minutes while stirring at 50 ° C. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours to complete the reaction. After allowing to cool to room temperature, 7000 ml of water was added and the mixture was stirred to crystallize. The precipitated crystals were filtered and washed with water to obtain 1261 g (99%) of 4'-chloro-2'-nitro-p-toluenesulfonanilide as yellow crystals. Melting point: 110.0-111.0 ° C NMR (CDCl ₃ ) δ: 2.40 (3H, s), 7.27 (2H, d, J = 8.4 Hz), 7.54
(1H, dd, J = 9.0 & 2.4Hz), 7.71 (2H, d, J = 8.4Hz), 7.83 (1H,
d, J = 9.0Hz), 8.09 (1H, d, J = 2.4Hz), 9.72 (1H, s). (3) 164.0g (3.94mol) of 96% sodium hydroxide in 390ml of water
The mixture was dissolved in a mixed solvent of 1600 ml of ethanol and ethanol and stirred at 10 to 25 ° C., and 1261 g (3.86 mol) of 4′-chloro-2′-nitro-p-toluenesulfonanilide was added. After stirring at room temperature for 4 hours, the mixture was cooled on ice, and the crystals were filtered and washed with ethanol to give 1253 g (93%) of 4'-chloro-2'-nitro-p-toluenesulfonanilide sodium salt as orange crystals. Melting point: 267.0-284.0 ° C NMR (DMSO-d ₆ ) δ: 2.29 (3H, s), 7.06 (1H, dd, J = 9.1 & 2.7)
Hz), 7.17 (2H, d, J = 8.3Hz), 7.25 (1H, d, J = 9.1Hz), 7.42
(1H, d, J = 2.7Hz), 7.59 (2H, d, J = 8.3Hz). (4) 1046 g (3.00 mol) of 4'-chloro-2'-nitro-p-toluenesulfonanilide sodium salt and DMF11
While heating the mixture of 00 ml in an oil bath at 100 ° C., 733.8 g (4.50 mol) of diethyl sulfate was added dropwise over 1 hour.
The mixture was aged and stirred at the same temperature for 1.5 hours. After allowing to cool to room temperature, a 1.5% aqueous sodium hydroxide solution was poured and stirred for 1 hour. The solid was filtered, washed with water, dried and recrystallized from 1450 ml of ethyl acetate to obtain 858 g (81%) of the title compound as pale yellow crystals. Melting point: 132.5-134.0 ° C NMR (CDCl ₃ ) δ: 1.18 (3H, t, J = 7.2 Hz), 2.44 (3H, s), 3.66
(2H, q, J = 7.2Hz), 7.05 (1H, d, J = 8.6Hz), 7.28 (2H, d, J = 8.
2Hz), 7.50 (1H, dd, J = 8.6 & 2.5Hz), 7.53 (2H, d, J = 8.2H
z), 7.86 (1H, d, J = 2.5Hz).

Example 49 Synthesis of 4′-chloro-N-isopropyl-2′-nitro-p-toluenesulfonanilide (Compound No. 291) In Example 48 (4), isopropyl iodide was used in place of diethyl sulfate. By heating on an oil bath at 120 ° C for 3 hours to give the title compound as pale yellow crystals.
% Yield. Melting point: 112.0-114.0 ° C NMR (CDCl ₃ ) δ: 1.06 (3H, d, J = 6.7 Hz), 1.13 (3H, d, J = 6.7H)
z), 2.44 (3H, s), 4.38 (1H, septet, J = 6.7Hz), 7.22 (1H,
d, J = 8.5Hz), 7.29 (2H, d, J = 8.4Hz), 7.54 (1H, dd, J = 8.5 &
2.5Hz), 7.66 (2H, d, J = 8.4Hz), 7.88 (1H, d, J = 2.5Hz).

Example 50 Synthesis of 4'-fluoro-N-isopropyl-2'-nitro-p-toluenesulfonanilide (Compound No. 265) (1) 200.0 g (1.80 mol) of 4-fluoroaniline was added to 155.0 g of pyridine (1.96 mol) and dissolved in 155 ml of acetonitrile while stirring under ice cooling, p-toluenesulfonyl chloride 360.3 g
(1.89 mol) was added. After stirring at room temperature for 20 hours, water 1500m
l was added to precipitate crystals. Filter the crystals, wash with water and 4 '
486.6 g (102%) of -fluoro-p-toluenesulfonanilide was obtained as pale red crude crystals. Melting point: 78.0-79.5 ° C NMR (CDCl ₃ ) δ: 2.39 (3H, s), 6.61 (1H, brs), 6.85-7.10
(4H, m), 7.23 (2H, dt, J = 8.3 & 0.6Hz), 7.60 (2H, dt, J = 8.
3 & 1.8Hz). (2) 4'-fluoro-p-toluenesulfonanilide
While suspending 486.6 g (1.80 mol) in 955 ml of acetic acid and stirring at an internal temperature of 45 ° C., 128.6 g (1.98 mol) of 97% fuming nitric acid was added dropwise over 40 minutes, and after completion of the addition, the mixture was stirred at 50 ° C. for 2 hours. did. After allowing to cool to room temperature, 2000 ml of water was poured and stirring was continued for 30 minutes. The precipitated crystals are filtered and washed with water to give 4'-fluoro-2'-nitro-p
543.5 g of toluenesulfonanilide as yellow crystals (9
7%). Melting point: 117.5-118.5 ° C NMR (CDCl3) δ: 2.39 (3H, s), 7.25 (2H, d, J = 8.4Hz), 7.35
(1H, ddd, J = 9.3 & 3.0Hz, J _HF = 6.9Hz), 7.66 (2H, d, J = 8.4H
z), 7.79 (1H, dd, J = 3.0Hz, J _HF = 8.2Hz), 7.89 (1H, dd, J = 9.
(3 Hz, J _HF = 4.9 Hz), 9.51 (1H, s). (3) Dissolve 12.0 g (291 mmol) of 97% sodium hydroxide in a mixed solvent of 24 ml of water and 89 ml of methanol, and stir at room temperature with 4'-fluoro. 89.16 g (287 mmol) of -2'-nitro-p-toluenesulfonanilide were added. The resulting mixed suspension was stirred at room temperature for 30 minutes, cooled with ice, filtered, and washed with methanol to give 79.31 g of 4'-fluoro-2'-nitro-p-toluenesulfonanilide sodium salt as orange crystals. (83%). Melting point: 276.0-278.0 ° C NMR (DMSO-d ₆ ) δ: 2.29 (3H, s), 6.97 (1H, ddd, J = 9.3 & 3.
2Hz, J _HF = 8.3Hz), 7.16 (2H, d, J = 8.3Hz), 7.20-7.40 (2H,
m), 7.58 (2H, d, J = 8.3 Hz). (4) 66.46 g (200 mmol) of 4'-fluoro-2'-nitro-p-toluenesulfonanilide sodium salt in DM
F2.0 ml of isopropyl iodide was added dropwise over 20 minutes while dissolving in F66 ml and heating on an oil bath at 120 ° C. After cooling to room temperature, a 1% aqueous sodium hydroxide solution was added and stirred. After the precipitated crystals were filtered, they were sequentially washed with water and ethanol. The obtained crude crystals were recrystallized from ethyl acetate to give 30.58 g (43%) of the title compound as pale yellow crystals. _{Mp: 129.0-130 ℃ NMR (CDCl 3)} δ: 1.05 (3H, d, J = 6.7Hz), 1.13 (3H, d, J = 6.7H
z), 2.44 (3H, s), 4.38 (1H, septet, J = 6.7Hz), 7.20-7.40
(4H, m), 7.55-7.75 (3H, m).

Example 51 Synthesis of 4'-cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilide (Compound No. 409) (1) 500.0 g (4.15 mol) of 4-aminobenzonitrile (98%) )
Is dissolved in a mixed solvent of 360 ml of pyridine and 900 ml of acetonitrile, and stirred at room temperature, and p-toluenesulfonyl chloride is dissolved.
872.3 g (4.44 mol) were added. After stirring at room temperature for 16 hours,
4000 ml of water was added to precipitate crystals. The crystals were filtered and washed with water to obtain 1153 g (98%) of 4'-cyano-p-toluenesulfonanilide as pale red crude crystals. Melting point: 182.0-184.0 ° C NMR (CDCl ₃ ) δ: 2.40 (3H, s), 7.18 (2H, dt, J = 8.8 & 2.3H)
z), 7.28 (2H, d, J = 8.4Hz), 7.52 (2H, dt, J = 8.8 & 2.0Hz),
7.59 (1H, s), 7.75 (2H, dt, J = 8.4 & 1.7 Hz). (2) 4'-cyano-p-toluenesulfonanilide 11
53 g (4.23 mol) was suspended in 2306 ml of acetic anhydride, and 294.3 g (4.53 mol) of fuming nitric acid was added dropwise over 100 minutes while stirring at 50 ° C. After the dropwise addition, stirring was continued at 50 ° C. for 1.5 hours, fuming nitric acid (1.75 ml, 0.042 mol) was added, and stirring was continued at 50 ° C. for 1 hour. After allowing to cool to room temperature, 7000 ml of water was poured to precipitate crystals. After stirring for 1 hour under ice cooling, the crystals were filtered and washed with water to obtain 1305 g (97%) of 4'-cyano-2'-nitro-p-toluenesulfonanilide as yellow crystals. Melting point: 150.0-152.0 ° C NMR (CDCl ₃ ) δ: 2.42 (3H, s), 7.33 (2H, d, J = 8.5 Hz), 7.78
(1H, dd, J = 8.8 & 2.3Hz), 7.82 (2H, d, J = 8.5Hz), 7.95 (1H,
d, J = 8.8Hz), 8.46 (1H, d, J = 2.3Hz), 10.60 (1H, brs). (3) A mixed solvent of 174.8 g (4.20 mol) of 96% sodium hydroxide in 420 ml of water and 1950 ml of methanol And 1305 g (4.11 mol) of 4'-cyano-2'-nitro-p-toluenesulfonanilide was added while stirring under ice-cooling. After stirring at 5 to 12 ° C. for 75 minutes, the precipitated crystals were filtered and washed with methanol to give 4′-cyano-2′-nitro-p-toluenesulfonanilide sodium salt as yellow crystals.
30 g (95%) were obtained. Melting point: 300 ° C. or higher NMR (DMSO-d ₆ ): 2.31 (3H, s), 7.22 (2H, d, J = 8.1 Hz), 7.29
(1H, d, J = 8.9Hz), 7.39 (1H, dd, J = 8.9 & 2.0Hz), 7.61 (2
(H, d, J = 8.1Hz), 7.85 (1H, d, J = 2.0Hz). (4) 1330 g (3.92 mol) of 4'-cyano-2'-nitro-p-toluenesulfonanilide sodium salt and DMF30
While heating 00 ml of the mixture on a 110 ° C. oil bath,
2019 g (11.8 mol) of isopropyl iodide was added dropwise over 1.5 hours. After completion of the dropwise addition, heating and stirring were continued at the same temperature for 3 hours.
After allowing to cool to room temperature, 1500 ml of water was poured to precipitate crystals. The crystals were filtered, washed with water, dried, suspended in ether and stirred for 4 hours. After removing insoluble components by filtration, the ether solution was removed.
The material 4'-cyano-2'-nitro-p-toluenesulfonanilide was removed by washing with a 0.1% aqueous sodium hydroxide solution. The ether layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a crude crystal. The crystals were washed with ethanol and recrystallized from ethyl acetate to give 124 g (8.8%) of the title compound as pale yellow crystals. _{Mp: 125.0-126.0 ℃ NMR (CDCl 3)} δ: 1.07 (3H, d, J = 6.7Hz), 1.15 (3H, d, J = 6.7H
z), 2.45 (3H, s), 4.40 (1H, septet, J = 6.7Hz), 7.31 (2H,
d, J = 8.4Hz), 7.44 (1H, d, J = 8.3Hz), 7.66 (2H, d, J = 8.4H
z), 7.86 (1H, dd, J = 8.3 & 1.9Hz), 8.19 (1H, d, J = 1.9Hz).

Example 52 N-methyl-2'-nitro-
p-Toluenesulfonanilide (Compound No. 38) and N, N-bis (p-toluenesulfonyl) -2′-
Synthesis of Nitroaniline (Compound No. 39) (1) 2-Nitroaniline (2.15 g, 15.6 mmol) was added to pyridine 1
After dissolving in 0.0 ml and stirring at room temperature, 3.55 g (18.6 mmol) of p-toluenesulfonyl chloride was added. After stirring at room temperature for 15 hours, 100 ml of water was poured to precipitate crystals. The crystals were filtered, washed with water, dried and subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (2: 3) to give 2.88 g (53%) of 2′-nitro-p-toluenesulfonanilide as yellow crystals. ), N, N-bis (p-toluenesulfonyl) -2'-nitroaniline (Compound No. 39) as pale yellow crystals (1.17 g, 17%). Physical properties of 2'-nitro-p-toluenesulfonanilide Melting point: 115.0-116.5 ° C NMR (CDCl ₃ ) δ: 2.39 (3H, s), 7.15 (1H, dt, J = 1.3 & 8.5H)
z), 7.26 (2H, d, J = 8.3Hz), 7.58 (1H, dt, J = 1.5 & 8.5Hz),
7.73 (2H, d, J = 8.3Hz), 7.85 (1H, dd, J = 8.5 & 1.3Hz), 8.1
Compound No. 1 (1H, dd, J = 8.5 & 1.5 Hz), 9.85 (1H, s). Physical properties of 39 Melting point: 184.5-186.5 ° C NMR (CDCl ₃ ) δ: 2.47 (6H, s), 7.15 (1H, dd, J = 7.6 & 2.0H)
z), 7.33 (4H, d, J = 8.5Hz), 7.56 (1H, dt, J = 2.0 & 7.5Hz),
7.62 (1H, dt, J = 1.9 & 7.6Hz), 7.84 (4H, dt, J = 8.5 & 1.9H
z), 8.02 (1H, dd, J = 7.5 & 1.9 Hz). (2) 0.15 g (3.75 mmol) of 60% sodium hydride in DMF 3.
2'-nitro-p-
1.00 g (3.42 mmol) of toluenesulfoneanilide was added.
After stirring at room temperature for 15 minutes, dimethyl sulfate 0.4 ml (4.22 mmo
l) was added dropwise. After stirring was continued for 2 hours, water was added to precipitate crystals. The crystals were filtered, washed with water, dried, and then subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 2 → 1: 1) to give N-methyl-2′-nitro-p-toluenesulfonanilide ( Compound No. 38) was obtained as pale yellow crystals (0.93 g, 89%). Melting point: 131.5-132.5 ° C NMR (CDCl ₃ ) δ: 2.44 (3H, s), 3.26 (3H, s), 7.11 (1H, dd, J
= 7.1 & 2.2Hz), 7.29 (2H, d, J = 8.5Hz), 7.40-7.60 (2H,
m), 7.55 (2H, d, J = 8.5Hz), 7.85 (1H, dd, J = 7.5 & 2.3Hz).

Example 53 2'-chloro-N-ethyl-
Synthesis of 4′-nitro-p-toluenesulfonanilide (Compound No. 275) (1) 1.73 g (10.0 mmol) of 2-chloro-4-nitroaniline
l) was dissolved in 5.0 ml of pyridine, and 1.91 g (10.0 mmol) of p-toluenesulfonyl chloride was added with stirring at room temperature. After stirring at room temperature for 18 hours, 50 ml of water was poured to precipitate crystals. The crystals were filtered, washed with water, dissolved in an aqueous sodium hydroxide solution, and washed with ether. The aqueous layer was acidified with hydrochloric acid,
After extraction with ethyl acetate, the extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 2′-chloro-4 ′.
2.61 g (80%) of -nitro-p-toluenesulfonanilide was obtained as pale yellow crystals. Melting point: 167.0-168.5 ° C NMR (CDCl ₃ ) δ: 2.41 (3H, s), 7.30 (2H, d, J = 8.4 Hz), 7.41
(1H, s), 7.77 (1H, d, J = 9.0Hz), 7.77 (2H, d, J = 8.4Hz), 8.
09 (1H, dd, J = 9.0 & 2.5Hz), 8.21 (1H, d, J = 2.5Hz). (2) 0.07 g (1.75mmol) of 60% sodium hydride was added to DMF3.
2'-chloro-
0.50 g of 4'-nitro-p-toluenesulfonanilide (1.
53 mmol) was added. After stirring for 15 minutes under ice cooling, 0.23 ml (1.76 mmol) of diethyl sulfate was added dropwise, and the mixture was heated and stirred at 100 ° C. for 2 hours. After allowing to cool to room temperature, water was poured and extracted with ether.
The extract was washed with water, washed with 1% aqueous sodium hydroxide, and dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography, eluting with ethyl acetate-hexane (1: 3). The obtained crystals were recrystallized from ethyl acetate to give 0.31 g (57%) of the title compound as pale yellow crystals. Melting point: 118.0-119.0 ° C NMR (CDCl ₃ ) δ: 1.10 (3H, t, J = 7.2Hz), 2.45 (3H, s), 3.67
(2H, q, J = 7.2Hz), 7.30 (2H, d, J = 8.3Hz), 7.39 (1H, d, J = 8.
7Hz), 7.64 (2H, d, J = 8.3Hz), 8.11 (1H, dd, J = 8.7 & 2.6H
z), 8.31 (1H, d, J = 2.6Hz).

Example 54 Synthesis of 2′-chloro-N-isopropyl-4′-nitro-p-toluenesulfonanilide (Compound No. 272) In Example 53 (2), isopropyl iodide was used in place of diethyl sulfate. And heated at 130 ° C. for 2 hours to give the title compound as pale yellow crystals in 24% yield. _{Mp: 154.0-157.0 ℃ NMR (CDCl 3)} δ: 1.09 (3H, d, J = 6.7Hz), 1.14 (3H, d, J = 6.7H
z), 2.45 (3H, s), 4.46 (1H, septet, J = 6.7Hz), 7.31 (2H,
d, J = 8.4Hz), 7.33 (1H, d, J = 8.7Hz), 7.69 (2H, d, J = 8.4H
z), 8.11 (1H, dd, J = 8.7 & 2.6Hz), 8.38 (1H, d, J = 2.6Hz).

Example 55 Synthesis of 2'-chloro-4'-cyano-N-ethyl-p-toluenesulfonanilide (Compound No. 92) (1) 1.50 g of 4-amino-3-chlorobenzonitrile (9.
(83 mmol) dissolved in 5.0 ml of pyridine and stirred under ice-cooling.
1.90 g (9.97 mmol) of p-toluenesulfonyl chloride were added. After stirring was continued at room temperature for 18 hours, 100 ml of water was poured to precipitate crystals. The crystals were filtered, washed with water, dissolved in an aqueous sodium hydroxide solution, and washed with ether. The aqueous layer was returned to acidic with hydrochloric acid and extracted with chloroform. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 2′-
1.65 g (55%) of chloro-4'-cyano-p-toluenesulfonanilide were obtained as white crystals. _{Mp: 186.0-187.0 ℃ NMR (CDCl 3)} δ: 2.41 (3H, s), 7.20-7.40 (1H, br), 7.29 (2
H, d, J = 8.4Hz), 7.49 (1H, dd, J = 8.7 & 1.7Hz), 7.58 (1H,
d, J = 1.7Hz), 7.72 (1H, d, J = 8.7Hz), 7.75 (2H, d, J = 8.4H
(2) 0.07 g (1.75 mmol) of 60% sodium hydride was added to DMF3.
2'-chloro-
0.50 g of 4'-cyano-p-toluenesulfonanilide (1.
63 mmol) was added. After stirring for 15 minutes under ice cooling, 0.25 ml (1.91 mmol) of diethyl sulfate was added dropwise, and the mixture was heated and stirred at 100 ° C. for 2 hours. After allowing to cool to room temperature, water was poured and extracted with ether.
The extract was washed with water, washed with 1% aqueous sodium hydroxide, and dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the obtained crystals were recrystallized from ether to give 0.33 g (61%) of the title compound as white crystals. Melting point: 112.0-114.0 ° C NMR (CDCl ₃ ) δ: 1.08 (3H, t, J = 7.1H)
z), 2.44 (3H, s), 3.64 (2H,
q, J = 7.1 Hz), 7.29 (2H, d, J =
8.4 Hz), 7.31 (1H, d, J = 8.3H)
z), 7.55 (1H, dd, J = 8.3 & 1.
9 Hz), 7.63 (2H, d, J = 8.4 Hz),
7.73 (1H, d, J = 1.9 Hz).

Example 56 Synthesis of 2'-chloro-4'-cyano-N-isopropyl-p-toluenesulfonanilide (Compound No. 93) In Example 55 (2), isopropyl iodide was used in place of diethyl sulfate. And heated at 130 ° C. for 2 hours to give the title compound as pale yellow crystals in 19% yield. Melting point: 118.0-119.0 ° C NMR (CDCl ₃ ) δ: 1.06 (3H, d, J = 6.7 Hz), 1.12 (3H, d, J = 6.7H)
z), 2.45 (3H, s), 4.45 (1H, septet, J = 6.7Hz), 7.26 (1H,
d, J = 8.3Hz), 7.30 (2H, d, J = 8.4Hz), 7.56 (1H, dd, J = 8.3 &
1.9Hz), 7.68 (2H, d, J = 8.4Hz), 7.81 (1H, d, J = 1.9Hz).

Example 57 Methyl 5-chloro-2-
(N-ethyl-Np-toluenesulfonyl) aminobenzthioimidate hydroiodide (Compound No. 8
Synthesis of 7) 4'-chloro-N-ethyl-2'-thiocarbamoyl-
A mixture of 0.30 g (0.81 mmol) of p-toluenesulfonanilide and 1.0 ml (16.1 mmol) of methyl iodide was mixed with 3.0 ml of chloroform.
The mixture was heated under reflux for 5 hours. After allowing to cool to room temperature, the mixture was concentrated under reduced pressure to obtain crude crystals. After adding ether and stirring, the mixture was filtered and washed with ether to obtain 0.41 g (99%) of the title compound as pale yellow crystals. Melting point:> 160 ° C (decomposition) NMR (CDCl ₃ ) δ: 1.03 (3H, t, J = 7.2 Hz), 2.47 (3H, s), 3.30
(3H, s), 3.00-3.50 (1H, br), 3.50-4.10 (1H, br), 6.72 (1
H, d, J = 8.6Hz), 7.38 (2H, d, J = 8.3Hz), 7.49 (1H, dd, J = 8.6Hz)
& 2.4Hz), 7.62 (2H, d, J = 8.3Hz), 7.82 (1H, d, J = 2.4Hz),
10.50-12.50 (2H, br).

Example 58 Ethyl 5-chloro-2-
(N-ethyl-Np-toluenesulfonyl) aminobenzthioimidate hydroiodide (Compound No. 8
8) Synthesis In Example 57, the title compound was obtained as pale yellow crystals in 94% yield by heating under reflux for 6 hours using ethyl iodide instead of methyl iodide. Melting point:> 161 ° C (decomposition) NMR (CDCl ₃ ) δ: 1.03 (3H, t, J = 7.1 Hz), 1.56 (3H, t, J = 7.5H)
z), 2.47 (3H, s), 2.90-3.50 (1H, br), 3.50-4.00 (1H, b
r), 3.93 (2H, q, J = 7.5Hz), 6.74 (1H, d, J = 8.6Hz), 7.38 (2H, d, J = 8.6Hz)
H, q, J = 8.4Hz), 7.49 (1H, dd, J = 8.6 & 2.4Hz), 7.63 (2H,
d, J = 8.4Hz), 7.79 (1H, d, J = 2.4Hz), 10.50-12.50 (2H, b
r).

Example 59 Synthesis of N-ethyl-4'-methylthio-2'-nitro-p-toluenesulfonanilide (Compound No. 227) (1) 10.0 g (66.6 mmol) of 4-aminophenyl thiocyanate
l) was dissolved in 70 ml of pyridine, and
12.7 g (66.6 mmol) of toluenesulfonyl were added. After stirring at room temperature for 16 hours, water was added, and the mixture was extracted with ethyl acetate.
The extract was washed with diluted hydrochloric acid and saturated saline, and then dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure to obtain 19.4 g (96%) of 4'-thiocyano-p-toluenesulfonanilide as pale yellow crystals. Melting point: 122.0-123.5 ° C NMR (CDCl ₃ ) δ: 2.40 (3H, s), 7.16 (2H, dt, J = 8.7 & 2.0H
z), 7.20-7.30 (2H, m), 7.37 (1H, brs), 7.40 (2H, dt, J = 8.
(7 & 2.0Hz), 7.71 (2H, d, J = 8.3Hz). (2) Dissolve 19.2g (63.2mmol) of 4'-thiocyano-p-toluenesulfonanilide in 60ml of acetic acid and stir at room temperature with fuming nitric acid. 3.04 ml (75.9 mmol) was added dropwise. 4 at 50 ° C
After stirring for an hour, the mixture was poured into water, and the precipitated crystals were filtered and washed with water. The crystals were dissolved in ethyl acetate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give 2'-nitro-4'-thiocyano-p-toluenesulfonanilide as pale yellow crystals.
1.8 g (99%) were obtained. Melting point: 121.0-122.5 ° C NMR (CDCl ₃ ) δ: 2.42 (3H, s), 7.32 (2H, d, J = 8.6 Hz), 7.73
(1H, dd, J = 9.0 & 2.3Hz), 7.78 (2H, d, J = 8.6Hz), 7.95 (1H,
d, J = 9.0 Hz), 8.33 (1 H, d, J = 2.3 Hz). (3) Dissolve 5.0 g (14.3 mmol) of 2'-nitro-4'-thiocyano-p-toluenesulfonanilide in 20 ml of methanol and ice. While stirring under cooling, sodium borohydride 2.80
g (66.7 mmol) was added. After stirring for 30 minutes, 3.67 ml (59.0 mmol) of methyl iodide was added dropwise under ice cooling. After stirring at room temperature for 20 hours, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 4). The obtained crystals were recrystallized from ethyl acetate to give 2.27 g (47%) of 2'-nitro-4'-methylthio-p-toluenesulfonanilide as orange crystals. _{Mp: 116.0-117.0 ℃ NMR (CDCl 3)} δ: 2.39 (3H, s), 2.48 (3H, s), 7.25 (2H, d, J =
8.4Hz), 7.44 (1H, dd, J = 8.8 & 2.3Hz), 7.68 (2H, d, J = 8.4
Hz), 7.78 (1H, d, J = 8.8Hz), 7.88 (1H, d, J = 2.3Hz). (4) 0.21 g (5.76 mmol) of 65% sodium hydride in DMF4.
2'-nitro-4 'while stirring at room temperature.
1.50 g of methylthio-p-toluenesulfonanilide (4.
43 mmol) was added. After stirring at room temperature for 30 minutes, 0.52 ml (6.21 mmol) of ethyl iodide was added dropwise, and the mixture was stirred at room temperature for 16 hours. After the reaction solution was poured into water and extracted with ethyl acetate, the extract was washed successively with saturated aqueous sodium hydrogen carbonate, diluted hydrochloric acid, and saturated saline. The ethyl acetate layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with chloroform to give 1.04 g (64%) of the title compound as pale yellow crystals. Melting point: 135.0-136.5 ° C NMR (CDCl ₃ ) δ: 1.18 (3H, t, J = 7.2 Hz), 2.43 (3H, s), 2.53
(3H, s), 3.50-3.80 (2H, m), 6.96 (1H, d, J = 8.5Hz), 7.20-
7.40 (3H, m), 7.53 (2H, d, J = 8.3Hz), 7.62 (1H, d, J = 2.3H
z).

Example 60 Synthesis of N-isopropyl-4'-methylthio-2'-nitro-p-toluenesulfonanilide (Compound No. 229) In Example 59 (4), iodide was used instead of ethyl iodide. The title compound was obtained as pale yellow crystals in 31% yield by heating and stirring at 80 ° C. for 7 hours using isopropyl. _{Mp: 124.5-126.0 ℃ NMR (CDCl 3)} δ: 1.05 (3H, d, J = 6.7Hz), 1.11 (3H, d, J = 6.7H
z), 2.43 (3H, s), 2.54 (3H, s), 4.37 (1H, septet, J = 6.7H
z), 7.14 (1H, d, J = 8.5Hz), 7.28 (2H, d, J = 8.2Hz), 7.36 (1
(H, dd, J = 8.5 & 2.3Hz), 7.60-7.70 (3H, m).

Example 61 2'-Cyano-N-methyl-
Synthesis of 4′-methylthio-p-toluenesulfonanilide (Compound No. 99) (1) 4.00 g (33.9 mmol) of 2-aminobenzonitrile and 3.00 g (37.0 mmol) of sodium thiocyanate in methanol 20.
Dissolved in 0 ml and stirred under ice-cooling, bromine 5.50 g (34.4 mmol)
Was dissolved in 5.0 ml of methanol dropwise over 40 minutes. After stirring for 30 minutes under ice cooling, the mixture was neutralized with saturated aqueous sodium hydrogen carbonate and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with chloroform to give 2
4.21 g (71%) of -amino-5-thiocyanobenzonitrile was obtained as pale yellowish white crystals. Melting point: 123.5-125.0 ° C NMR (CDCl ₃ ) δ: 4.77 (2H, br), 6.81 (1H, d, J = 8.8 Hz), 7.5
4 (1H, dd, J = 8.8 & 2.2Hz), 7.64 (1H, d, J = 2.2Hz). (2) 1.20 g (29.1 mmol) of 97% sodium hydroxide in 4.0 ml of water
And methanol in a mixed solvent of 20.0 ml while stirring and
5.03 g of 2-amino-5-thiocyanobenzonitrile (28.7
mmol) was added. After stirring for 30 minutes under ice cooling, 0.60 g (14.3 mmol) of 90% sodium borohydride was added, and stirring was continued for 30 minutes. 3.0 ml (30.0 mmol) of 95% dimethyl sulfate was added dropwise, and the mixture was stirred under ice cooling for 30 minutes and at room temperature for 30 minutes, and then concentrated under reduced pressure. Pour water into the residue and extract with ether.
After washing twice with water, drying over anhydrous magnesium sulfate and concentration under reduced pressure yielded 4.73 g (100%) of 2-amino-5-methylthiobenzonitrile as pale yellow crystals. Melting point: 50.0-54.0 ° C NMR (CDCl ₃ ) δ: 2.41 (3H, s), 3.20-4.60 (2H, br), 6.70 (1
H, ddd, J = 9.1 & 2.2 & 1.1Hz), 7.30-7.45 (2H, m). (3) 2-amino-5-methylthiobenzonitrile 4.60
g (28.0 mmol) was dissolved in 20.0 ml of pyridine, and 5.60 g (29.4 mmol) of p-toluenesulfonyl chloride was added while stirring under ice cooling. After stirring for 30 minutes under ice-cooling and 1 hour at room temperature, water 200
The mixture was poured into the mixture and stirred for 30 minutes to precipitate crystals. Filter the crystals,
By washing with water, 2'-cyano-4'-thiomethyl-
8.33 as p-toluenesulfonanilide as pale yellow crystals
g (93%). Melting point: 170.0-173.0 ° C NMR (CDCl ₃ ) δ: 2.40 (3H, s), 2.45 (3H, s), 7.20-7.35 (3
H, m), 7.40 (1H, dd, J = 8.9 & 2.3Hz), 7.64 (1H, d, J = 8.9H
z), 7.67 (2H, d, J = 8.3 Hz). (4) 0.27 g (6.75 mmol) of 60% sodium hydride was added to DMF 7.
2'-cyano-
4'-thiomethyl-p-toluenesulfonanilide 2.00
g (6.28 mmol) was added. After stirring at room temperature for 15 minutes, 0.70 ml (7.38 mmol) of dimethyl sulfate was added dropwise. After stirring at room temperature for 18 hours, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with chloroform to give 1.63 g (78%) of the title compound as white crystals. Melting point: 139.0-140.0 ° C NMR (CDCl ₃ ) δ: 2.45 (3H, s), 2.51 (3H, s), 3.22 (3H, s),
7.17 (1H, d, J = 8.4Hz), 7.25-7.45 (4H, m), 7.65 (2H, d, J =
(8.3Hz).

Example 62 2'-Cyano-N-ethyl-
Synthesis of 4′-methylthio-p-toluenesulfonanilide (Compound No. 100) In (4) of Example 61, the title compound was heated and stirred at 100 ° C. for 1 hour using diethyl sulfate instead of dimethyl sulfate. Was obtained as white crystals in 43% yield. Melting point: 136.0-137.0 ° C NMR (CDCl ₃ ) δ: 1.10 (3H, t, J = 7.2 Hz), 2.44 (3H, s), 2.51
(3H, s), 3.63 (2H, q, J = 7.2Hz), 7.12 (1H, d, J = 8.5Hz), 7.
31 (2H, d, J = 8.4Hz), 7.38 (1H, dd, J = 8.5 & 2.3Hz), 7.44 (1
(H, d, J = 2.3Hz), 7.66 (2H, d, J = 8.4Hz).

Example 63 Synthesis of 2'-cyano-4'-methanesulfonyl-N-methyl-p-toluenesulfonanilide (Compound No. 105) 2'-cyano-N-methyl-4'-methylthio-p- Dissolve 0.29 g (0.87 mmol) of toluenesulfonanilide in 2.0 ml of chloroform and, with stirring under ice-cooling, 70% mCPBA
0.43 g (1.74 mmol) of (m-chloroperbenzoic acid) was added.
After stirring under ice cooling for 30 minutes and at room temperature for 2 hours, the mixture was diluted with chloroform and washed with an aqueous solution of sodium bisulfite and an aqueous solution of 1% sodium hydroxide in that order. The chloroform layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 0.31 g (97.5%) of the title compound as white crystals. Melting point: 179.0-180.5 ° C NMR (CDCl ₃ ) δ: 2.47 (3H, s), 3.12 (3H, s), 3.26 (3H, s),
7.36 (2H, d, J = 8.3Hz), 7.56 (1H, d, J = 8.5Hz), 7.67 (2H, d,
J = 8.3Hz), 8.13 (1H, dd, J = 8.5 & 2.2Hz), 8.23 (1H, d, J =
2.2Hz).

Example 64 Synthesis of N-methoxy-4'-nitro-2 ', 3,4-trichlorobenzenesulfonanilide (Compound No. 527) (1) 0.93 g (11.1 mmol) of methoxylamine hydrochloride was added to pyridine 5.0 suspended in ice-cooled water and stirred under ice-cooling.
2.73 g (11.1 mmol) of dichlorobenzenesulfonyl were added. After stirring for 1 hour under ice cooling and 18 hours at room temperature, water 50.0 ml
And crystallized out. The crystals are filtered and washed with water,
2.69 g (95%) of 4-dichloro-N-methoxybenzenesulfonamide was obtained as pale yellow crystals. Melting point: 146.0-147.0 ° C NMR (CDCl ₃ ) δ: 3.82 (3H, s), 7.63 (1H, dd, J = 8.4 & 0.3H)
z), 7.76 (1H, dd, J = 8.4 & 2.1Hz), 7.86 (1H, s), 8.02 (1H,
(dd, J = 2.1 & 0.3 Hz). (2) 0.09 g (2.25 mmol) of 60% sodium hydride was added to DMF3.
0.54 g (2.19 mmol) of 3,4-dichloro-N-methoxybenzenesulfonamide while stirring under ice-cooling.
l) was added. After stirring under ice cooling for 15 minutes, 3-chloro-4
0.35 g (1.99 mmol) of -fluoronitrobenzene was added, and stirring was continued for 1 hour under ice cooling and for 3 hours at room temperature. After adding water and extracting with ether, the extract was washed twice with water. The ether layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 0.56 g (68%) of the title compound as pale yellowish white crystals. Melting point: 132.0-133.0 ° C NMR (CDCl ₃ ) δ: 3.87 (3H, s), 6.95 (1H, d, J = 8.8 Hz), 7.53
(1H, dd, J = 8.4 & 2.1Hz), 7.64 (1H, dd, J = 8.4 & 0.3Hz),
7.88 (1H, dd, J = 2.1 & 0.3Hz), 8.03 (1H, dd, J = 8.8 & 2.5H
z), 8.39 (1H, d, J = 2.5Hz).

Example 65 N-methoxy-4′-nitro-2,2 ′, 5-trichlorobenzenesulfonanilide (Compound No. 528) (1) In Example 64 (1), 3,4-dichloro Using 2,5-dichlorobenzenesulfonyl chloride instead of chlorobenzenesulfonyl, 2,5-dichloro-N-
Methoxybenzenesulfonamide as pale yellow crystals 93
% Yield. Melting point: 127.0-128.5 ° C NMR (CDCl ₃ ) δ: 3.80 (3H, s), 7.48 (1H, dd, J = 8.5 & 0.4H)
z), 7.55 (1H, dd, J = 8.5 & 2.3Hz), 8.14 (1H, dd, J = 2.3 &
(0.4Hz), 8.14 (1H, s). (2) In (2) of Example 64, 2,2 was used instead of 3,4-dichloro-N-methoxybenzenesulfonamide.
The title compound was obtained as pale yellowish white crystals in a yield of 68% using 5-dichloro-N-methoxybenzenesulfonamide. Melting point: 132.0-133.0 ° C NMR (CDCl ₃ ) δ: 3.83 (3H, s), 7.23 (1H, d, J = 9.0 Hz), 7.50
(1H, dd, J = 8.6 & 0.3Hz), 7.59 (1H, dd, J = 8.6 & 2.4Hz),
7.96 (1H, dd, J = 2.4 & 0.3Hz), 8.06 (1H, dd, J = 9.0 & 2.
5Hz), 8.37 (1H, d, J = 2.5Hz).

Example 66 Synthesis of 2'-chloro-N-methoxy-4'-nitro-3-trifluoromethylbenzenesulfonanilide (Compound No. 529) (1) In Example 64, (1) N-methoxy-3 using 3-trifluoromethylbenzenesulfonyl chloride instead of 2,4-dichlorobenzenesulfonyl
-Trifluoromethylbenzenesulfonamide was obtained as pale yellow crystals in 97% yield. Melting point: 78.0-81.0 ° C NMR (CDCl ₃ ) δ: 3.83 (3H, s), 7.27 (1
H, s), 7.72 (1H, t, J = 7.8 Hz),
7.92 (1H, dt, J = 7.8 & 0.6H
z), 8.13 (1H, dt, J = 7.8 & 0.
6 Hz), 8.20 (1H, t, J = 0.6 Hz). (2) In (2) of Example 64, instead of 3,4-dichloro-N-methoxybenzenesulfonamide, N-
The title compound was obtained as white crystals in a 57% yield using methoxy-3-trifluoromethylbenzenesulfonamide. Melting point: 95.5-96.5 ° C NMR (CDCl ₃ ) δ: 3.86 (3H, s), 6.86 (1H, d, J = 9.0 Hz), 7.73
(1H, t, J = 7.9Hz), 7.90-8.10 (4H, m), 8.39 (1H, d, J = 2.5H
z).

Example 67 Synthesis of 2′-chloro-3,4′-dinitro-N-methoxybenzenesulfonanilide (Compound No. 530) (1) In Example 64 (1), 3,4-dichloro N-methoxy-3-nitrobenzenesulfonamide was obtained as pale yellow crystals in 85% yield using 3-nitrobenzenesulfonyl chloride instead of chlorobenzenesulfonyl. Mp: 1110.-113.0 ℃ NMR (CDCl 3) δ: 3.86 (3H, s), 7.28 (1H, s), 7.80 (1H, t, J =
8.3Hz), 8.26 (1H, ddd, J = 8.3 & 1.8 & 1.1Hz), 8.52 (1H,
ddd, J = 8.3 & 2.2 & 1.1Hz), 8.77 (1H, dd, J = 2.2 & 1.8H
z). (2) In (2) of Example 64, instead of 3,4-dichloro-N-methoxybenzenesulfonamide, N-
The title compound was obtained as pale yellow crystals in 80% yield using methoxy-3-nitrobenzenesulfonamide. Melting point: 167.5-169.0 ° C NMR (CDCl ₃ ) δ: 3.89 (3H, s), 6.90 (1H, d, J = 8.8 Hz), 7.80
(1H, t, J = 8.2Hz), 7.95-8.10 (2H, m), 8.40 (1H, d, J = 2.5H
z), 8.55-8.70 (2H, m).

Example 68 2 ', 4-Dichloro-3,
Synthesis of 4'-dinitro-N-methoxybenzenesulfonanilide (Compound No. 531) (1) 0.90 g (10.8 mmol) of methoxylamine hydrochloride was suspended in 3.0 ml of pyridine, and stirred under ice-cooling. 2.56 g (10.8 mmol) of chloro-3-nitrobenzenesulfonyl
Was added. After stirring for 1 hour under ice cooling and 3 hours at room temperature, water 5
0.0 ml was poured and extracted with ethyl acetate. The extract is diluted with hydrochloric acid,
After sequentially washing with water, the extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 2.02 g (76%) of 4-chloro-N-methoxy-3-nitrobenzenesulfonamide as pale yellowish white crystals.
%)Obtained. Melting point: 69.5-71.0 ° C NMR (CDCl ₃ ) δ: 3.86 (3H, s), 7.29 (1H, s), 7.77 (1H, d, J =
8.4Hz), 8.05 (1H, dd, J = 8.4 & 2.1Hz), 8.41 (1H, d, J = 2.1
(2) Dissolve 0.53 g (1.99 mmol) of 4-chloro-N-methoxy-3-nitrobenzenesulfonamide and 1.05 g (5.98 mmol) of 3-chloro-4-fluoronitrobenzene in 5.0 ml of DMF and stir under ice-cooling. While doing, 0.09 g of 60% sodium hydride
(2.25 mmol) was added in small portions. After stirring for 1 hour under ice-cooling and for 2 hours at room temperature, water and ether were added, and insolubles were removed by filtration. After allowing the filtrate to stand, the layers were separated and the organic layer was washed with water. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 5) to give the title compound (0.10 g, 12%) as pale-yellow white crystals. Melting point: 138.0-139.0 ° C NMR (CDCl ₃ ) δ: 3.89 (3H, s), 6.96 (1H, d, J = 8.9 Hz), 7.70
-7.90 (2H, m), 8.05 (1H, dd, J = 8.9 & 2.5Hz), 8.26 (1H, d,
J = 1.5Hz), 8.40 (1H, d, J = 2.5Hz).

Example 69 4-Chloro-2'-fluoro-N-methoxy-4'-nitro-3- (trifluoromethyl) benzenesulfonanilide (Compound No. 52)
Synthesis of 4) (1) In (1) of Example 68, 4-chloro-
4-chloro-3- (trifluoromethyl) benzenesulfonyl chloride was used instead of 3-nitrobenzenesulfonyl to give 4-chloro-N-methoxy-3- (trifluoromethyl) benzenesulfonamide as white crystals, 92%.
In a yield of Melting point: 88.0-90.5 ° C NMR (CDCl ₃ ) δ: 3.84 (3H, s), 7.20 (1H, s), 7.72 (1H, d, J =
8.4Hz), 8.03 (1H, dd, J = 8.4 & 2.2Hz), 8.23 (1H, d, J = 2.2
(2) 0.58 g (2.00 mmol) of 4-chloro-N-methoxy-3- (trifluoromethyl) benzenesulfonamide and 0.66 ml (5.96 mmol) of 3,4-difluoronitrobenzene were dissolved in 5.0 ml of DMF and iced. While stirring under cooling, 0.09 g (2.25 mmol) of 60% sodium hydride was added little by little. After stirring for 1 hour under ice cooling, the temperature was returned to room temperature, water was added, and the mixture was extracted with ether. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 0.32 g (37%) of the title compound as pale yellow crystals. Melting point: 104.5-105.5 ° C NMR (CDCl ₃ ) δ: 3.92 (3H, s), 7.03 (1H, dd, J = 9.0 Hz, J _HF =
7.0Hz), 7.60-7.85 (2H, m), 7.90-8.15 (3H, m).

Example 70 4-Chloro-2'-cyano-
N-methoxy-4'-nitro-3- (trifluoromethyl) benzenesulfonanilide (Compound No. 536)
The title compound was obtained as pale yellowish white crystals in a yield of 38% by using 2-chloro-5-nitrobenzonitrile instead of 3,4-difluoronitrobenzene in Example 69 (2). Melting point: 140.5-142.0 ° C NMR (CDCl ₃ ) δ: 3.88 (3H, s), 7.36 (1H, d, J = 9.0 Hz), 7.72
(1H, d, J = 8.4Hz), 7.82 (1H, dd, J = 8.4 & 2.1Hz), 8.07 (1
H, d, J = 2.1Hz), 8.39 (1H, dd, J = 9.0 & 2.5Hz), 8.58 (1H,
d, J = 2.5Hz).

Example 71 5-Chloro-1,3-dimethyl-N- (2,4-dinitrophenyl) -N-methoxy-4-pyrazolesulfonamide (Compound No. 55)
Synthesis of 2) (1) 0.90 g (10.8 mmol) of methoxylamine hydrochloride was suspended in 2.0 ml of pyridine and stirred under ice-cooling while stirring 5-chloro-1,3-dimethyl-4-pyrazolesulfonyl chloride.
A solution of 29 g (10.0 mmol) in 2.0 ml of acetonitrile was added dropwise. After stirring for 1 hour under ice cooling and 1 hour at room temperature, water 5
0.0 ml was poured to precipitate crystals. The crystals were filtered, washed with water, dried and then subjected to silica gel column chromatography, eluting with ethyl acetate-hexane (1: 1) to give 5-
1.72 g (72%) of chloro-1,3-dimethyl-N-methoxy-4-pyrazolesulfonamide as white crystals were obtained. Melting point: 120.0-122.5 ° C NMR (CDCl ₃ ) δ: 2.43 (3H, s), 3.82 (3H, s), 3.83 (3H, s),
7.09 (1H, s). (2) 5-chloro-1,3-dimethyl-N-methoxy-
0.48 g (2,00 mmol) of 4-pyrazole sulfonamide and 2,2
0.49 g (2.42 mmol) of 4-dinitrochlorobenzene in DMF
After dissolving in 3.0 ml and stirring under ice cooling, 0.09 g (2.25 mmol) of 60% sodium hydride was added little by little. After stirring for 1 hour under ice-cooling and 1 hour at room temperature, water was poured and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with chloroform-hexane (10: 1) to give 0.65 g of the title compound as pale yellow crystals.
(87%). Melting point: 189.0-191.0 ° C (decomposition) NMR (CDCl3) δ: 2.14 (3H, s), 3.81 (3H, s), 3.99 (3H, s),
7.59 (1H, d, J = 9.0Hz), 8.35 (1H, dd, J = 9.0 & 2.5Hz), 8.6
7 (1H, d, J = 2.5Hz).

Example 72 Synthesis of 5-chloro-N- (2-cyano-4-nitrophenyl) -N-methoxy-2-thiophene sulfonamide (Compound No. 537) (1) Example 1 (1) In the above, 5-chloro- chloride
By using 5-chloro-2-thiophenesulfonyl chloride instead of 1,3-dimethyl-4-pyrazolesulfonyl, 5-chloro-N-methoxy-2-thiophenesulfonamide was obtained as white crystals in a yield of 69%. Obtained. Melting point: 65.5-66.5 ° C NMR (CDCl ₃ ) δ: 3.86 (3H, s), 6.99 (1H, d, J = 4.1 Hz), 7.08
(1H, s), 7.53 (1H, d, J = 4.1Hz). (2) 0.46 g (2.02 mmol) of 5-chloro-N-methoxy-2-thiophene sulfonamide and 2-chloro-5-nitrobenzonitrile Dissolve 0.45 g (2.46 mmol) in DMF (3.0 ml) and stir under ice-cooling while adding 60% sodium hydride 0.09 g (2.25 m
mol) was added in small portions. After stirring for 1 hour under ice-cooling and 1 hour at room temperature, water was poured and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 3) to give the title compound (0.41 g, 54%) as pale-yellow crystals. Melting point: 144.0-146.0 ° C NMR (CDCl ₃ ) δ: 3.99 (3H, s), 7.03 (1H, d, J = 4.1 Hz), 7.29
(1H, d, J = 4.1Hz), 7.37 (1H, d, J = 9.0Hz), 8.37 (1H, dd, J =
9.0 & 2.5Hz), 8.57 (1H, d, J = 2.5Hz).

Example 73 Synthesis of 2′-chloro-4′-cyano-N-methoxy-p-toluenesulfonanilide (Compound No. 566) 0.09 g (2.25 mmol) of 60% sodium hydride was suspended in DMF (3.0 ml). 0.45 g (2.20 mmol) of N-methoxy-p-toluenesulfonamide was added while the mixture was turbid and stirred under ice-cooling. Under ice cooling 1
After stirring for 5 minutes, 0.31 g (1.99 mmol) of 3-chloro-4-fluorobenzonitrile was added. 1 hour under ice cooling, 50 ° C
After stirring for 18 hours, water was added and extracted with ether. The extract was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 0.54 g (81%) of the title compound as white crystals. Melting point: 145.0-147.0 ° C NMR (CDCl ₃ ) δ: 2.49 (3H, s), 3.81 (3H, s), 6.82 (1H, d, J =
8.3Hz), 7.34 (2H, d, J = 8.3Hz), 7.39 (1H, dd, J = 8.3 & 1.8
Hz), 7.63 (2H, d, J = 8.3Hz), 7.77 (1H, d, J = 1.8Hz).

Example 74 Synthesis of 2-chloro-2 ′, 4′-dinitro-N-methoxybenzenesulfonanilide (Compound No. 563) (1) 0.95 g (11.4 mmol) of methoxylamine hydrochloride was added to 4.0 ml of pyridine. 2.11 g (10.0 mmol) of 2-chlorobenzenesulfonyl chloride was added to the suspension with stirring under ice cooling. After stirring for 1 hour under ice cooling and at room temperature for 1 hour, 50.0 ml of water was added, and the mixture was extracted with ethyl acetate. The extract was washed with water, diluted hydrochloric acid and saturated saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 1.41 g (64%) of 2-chloro-N-methoxybenzenesulfonamide as pale yellow crystals. Was. _{Mp: 92.5-94.0 ℃ NMR (CDCl 3)} δ: 3.80 (3H, s), 7.40-7.70 (3H, m), 7.86 (1
H, s), 8.17 (1H, ddd, J = 7.7 & 1.6 & 0.8Hz). (2) 0.09 g (2.25 mmol) of 60% sodium hydride was added to DMF3.
2-chloro-N-
0.48 g (2.17 mmol) of methoxybenzenesulfonamide was added. After stirring for 15 minutes under ice cooling, 0.41 g (2.02 mmol) of 2,4-dinitrochlorobenzene was added. After stirring for 1 hour under ice cooling and 1 hour at room temperature, water was added and the mixture was extracted with ether.
The extract was washed with water, diluted hydrochloric acid and saturated saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 0.49 g (62%) of the title compound as pale yellow crystals. Melting point: 112.5-114.0 ° C NMR (CDCl ₃ ) δ: 3.93 (3H, s), 7.40-7.70 (4H, m), 7.96 (1
H, dd, J = 7.9 & 1.7Hz), 8.34 (1H, dd, J = 8.9 & 2.5Hz), 8.
67 (1H, d, J = 2.5Hz).

Example 75 3-Chloro-2 ', 4'-dinitro-N-methoxybenzenesulfonanilide (Compound No. 564) (1) In Example 74 (1), instead of 2-chlorobenzenesulfonyl chloride, By using 3-chlorobenzenesulfonyl chloride, 3-chloro-N-methoxybenzenesulfonamide was obtained as pale yellow crystals in a yield of 38%. Melting point: 72.0-74.5 ° C NMR (CDCl ₃ ) δ: 3.83 (3H, s), 7.10 (1H, s), 7.50 (1H, dd, J
= 8.0 & 7.7Hz), 7.63 (1H, ddd, J = 8.0 & 2.0 & 1.2Hz),
7.82 (1H, dd, J = 7.7 & 1.7 & 1.2Hz), 7.92 (1H, dd, J = 2.0
& 1.7Hz). (2) In (2) of Example 74, 2-chloro-N-
By using 3-chloro-N-methoxybenzenesulfonamide instead of methoxybenzenesulfonamide, the title compound was obtained as pale yellow crystals in a yield of 76%. Melting point: 157.0-159.0 ° C NMR (CDCl ₃ ) δ: 3.94 (3H, s), 7.35 (1H, d, J = 8.9 Hz), 7.45
-7.55 (2H, m), 7.65-7.75 (2H, m), 8.32 (1H, dd, J = 8.9 &
2.7Hz), 8.73 (1H, d, J = 2.7Hz).

Example 76 2'-Cyano-N-methoxy-4'-nitro-4- (trifluoromethyl) benzenesulfonanilide (1) In Example 74 (1), instead of 2-chlorobenzenesulfonyl chloride, By using 4- (trifluoromethyl) benzenesulfonyl chloride, N-methoxy-4- (trifluoromethyl) benzenesulfonamide was obtained as pale yellowish white crystals in a yield of 22%. _{Mp: 96.0-97.0 ℃ NMR (CDCl 3)} δ: 3.84 (3H, s), 7.15 (1H, s), 7.83 (2H, d, J =
8.2 Hz), 8.07 (2H, d, J = 8.2 Hz). (2) 0.09 g (2.25 mmol) of 60% sodium hydride was added to DMF4.
0-ml and stirred under ice-cooling while adding N-methoxy-4.
-(Trifluoromethyl) benzenesulfonamide 0.55
g (2.16 mmol) was added. After stirring for 15 minutes under ice-cooling, 2-
0.37 g (2.03 mmol) of chloro-5-nitrobenzonitrile was added. After stirring for 1 hour under ice cooling and 1 hour at room temperature, water was added and the mixture was extracted with ether. The extract was washed with water, diluted hydrochloric acid, and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 4) to give 0.51 g (63%) of the title compound as white crystals. Melting point: 133.5-135.0 ° C NMR (CDCl ₃ ) δ: 3.87 (3H, s), 7.34 (1H, d, J = 9.0 Hz), 7.84
(2H, d, J = 8.6Hz), 7.91 (2H, d, J = 8.6Hz), 8.37 (1H, dd, J =
9.0 & 2.7Hz), 8.57 (1H, d, J = 2.7Hz).

Example 77 2 ', 4'-Dinitro-N-
Synthesis of methoxy-3-methylbenzenesulfonanilide (Compound No. 562) -3-Methylbenzenesulfonamide was obtained as pale yellow crystals in a yield of 53%. Melting point: 90.0-92.0 ° C NMR (CDCl ₃ ) δ: 2.45 (3H, s), 3.80 (3H, s), 7.05 (1H, s),
7.40-7.55 (2H, m), 7.70-7.80 (2H, m). (2) In (2) of Example 74, 2-chloro-N-
By using N-methoxy-3-methylbenzenesulfonamide instead of methoxybenzenesulfonamide, the title compound was obtained as pale yellow crystals in a yield of 77%. Melting point: 147.5-149.5 ° C NMR (CDCl ₃ ) δ: 2.42 (3H, s), 3.90 (3H, s), 7.32 (1H, d, J =
9.0Hz), 7.35-7.45 (2H, m), 7.45-7.60 (2H, m), 8.29 (1H,
(dd, J = 9.0 & 2.5Hz), 8.72 (1H, d, J = 2.5Hz).

Example 78 Synthesis of N-methoxy-4'-methylthio-2'-nitro-p-toluenesulfonanilide (Compound No. 572) (1) 0.57 g (9.79 mmol) of dried potassium fluoride was dissolved in dimethyl Suspended in 10.0 ml of sulfoxide, 2-chloro-5
1.88 g (9.23 mmol) of-(methylthio) nitrobenzene was added, and the mixture was stirred at 170 ° C for 3 hours. Since the reaction was not completed, 0.68 g (11.7 mmol) of dried potassium fluoride was added, and the mixture was stirred at 170 ° C. for 3 hours. The reaction mixture was poured into water and extracted with ether. The extract was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was distilled in a glass tube oven under reduced pressure to obtain a fraction (110-160 ° C / 0.8 mmHg) of 2-fluoro-5- (methylthio) nitrobenzene and 2-chloro-5- (methylthio) nitrobenzene.
1.39 g of a 3: 2 mixture was obtained as a yellow oil. (2) 0.33 g (8.17 mmol) of 60% sodium hydride was added to DMF1
Suspended in 0.0 ml of N-methoxy-
1.63 g (8.17 mmol) of p-toluenesulfonamide were added. After stirring at room temperature for 15 minutes, 1.39 g of a 3: 2 mixture of 2-fluoro-5- (methylthio) nitrobenzene and 2-chloro-5- (methylthio) nitrobenzene was added. After stirring at room temperature overnight, the mixture was poured into water and extracted with ether. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, eluted with ethyl acetate-hexane (1: 6 → 1: 4), and recrystallized from ethyl acetate-hexane to obtain 0.60 g of the title compound as yellow crystals. Melting point: 110.3-110.8 ° C NMR (CDCl ₃ ) δ: 2.46 (3H, s), 2.52 (3H, s), 3.82 (3H, s),
6.89 (1H, d, J = 8.6Hz), 7.23 (1H, dd, J = 8.6 & 2.2Hz), 7.
30 (2H, d, J = 8.0Hz), 7.50-7.70 (3H, m).

Example 79 Synthesis of 2'-cyano-N-methoxy-4'-methylthio-p-toluenesulfonanilide (Compound No. 571) (1) 2.00 g of 2-amino-5- (thiocyanato) benzonitrile 11.4 mmol) and 7.16 g of 42% borofluoric acid (3
0.87 g (12.6 mmol) of sodium nitrite dissolved in 1.2 ml of water was added dropwise to a 10.0 ml solution of 4.2 mmol) in ethanol under ice-cooling. After stirring for 2 hours under ice cooling, the precipitated crystals were collected by filtration, and the solid was washed with water, methanol and ether. The obtained solid was dried under reduced pressure to obtain 2.98 g (95%) of 2-cyano-4- (thiocyanato) benzenediazonium fluoborate as white crystals. Melting point: 191 ° C. (decomposition) NMR (DMSO-d ₆ ) δ: 8.47 (1H, dd, J = 8.9 & 2.1 Hz), 8.82 (1
(H, d, J = 2.1Hz), 9.01 (1H, d, J = 8.9Hz). (2) Heating 2.98 g (10.9 mmol) of 2-cyano-4- (thiocyanato) benzenediazonium fluoborate with a heat gun to decompose I let it. When the whole became black, it was heated at 200 ° C. for 30 minutes using an oil bath. After cooling, water was added and extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Distill the residue in a glass tube oven (180-240 ° C / 0.2
mmHg), 0.29 g (15%) of 2-fluoro-5- (thiocyanato) benzonitrile as pale yellowish white crystals. Melting point: 39.0-41.0 ° C NMR (CDCl ₃ ) δ: 8.36 (1H, ddd, J = 9.4 & 8.1 & 1.2Hz), 7.
7-7.9 (2H, m), 7.67 (1H, d, J = 2.2Hz). (3) 0.41 g (9.76 mmol) of 90% sodium borohydride was suspended in 10 ml of ethanol, and stirred under ice-cooling. -Fluoro-5- (thiocyanato) benzonitrile 0.29 g (1.63 mm
ol). After stirring at room temperature for 1 hour, methyl iodide
0.11 ml (1.71 mmol) was added, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (3: 7).
0.25 g (92%) of -fluoro-5- (methylthio) benzonitrile was obtained as pale yellowish white crystals. Melting point: 61.7-62.7 ° C NMR (CDCl ₃ ) δ: 2.50 (3H, s), 7.05-7.2 (1H, m), 7.4-7.55
(4) 60% sodium hydride 0.07 g (1.64 mmol) in DMF 5.0 ml
And 0.33 g (1.64 mmol) of N-methoxy-p-toluenesulfonamide was added with stirring under ice cooling. After stirring at room temperature for 15 minutes, 0.25 g (1.50 mmol) of 2-fluoro-5- (methylthio) benzonitrile was added, and the mixture was stirred at room temperature overnight. Since the reaction did not proceed, 3
Stirred for days. After cooling, the reaction mixture was poured into water and extracted with ether. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and ethyl acetate-hexane (1: 1).
After elution in 4), the residue was purified by recrystallization with ethyl acetate-hexane.
0.34 g (65%) of the title compound was obtained as white crystals. Melting point: 146.8-147.6 ° C NMR (CDCl ₃ ) δ: 2.47 (3H, s), 2.51 (3H, s), 3.76 (3H, s),
6.96 (1H, d, J = 8.7Hz), 7.2-7.4 (3H, m), 7.44 (1H, d, J = 2.2
Hz), 7.66 (2H, d, J = 8.3Hz).

Example 80 Synthesis of N- (4-cyano-3-methoxy-5-isothiazolyl) -N-methoxy-p-toluenesulfonanilide (Compound No. 560) 0.09 g (2.25 mmol) of 60% sodium hydride Was suspended in 3.0 ml of DMF, and 0.45 g (2.20 mmol) of N-methoxy-p-toluenesulfonamide was added while stirring under ice cooling. Under ice cooling 1
After stirring for 5 minutes, 0.44 g (2.02 mmol) of 4-cyano-5-methanesulfonyl-3-methoxyisothiazole was added. After stirring for 30 minutes under ice-cooling and 30 minutes at room temperature, water was poured into the reaction solution, which was extracted with ethyl acetate. The extract was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with ethyl acetate-hexane (1: 3) to obtain 0.44 g (64%) of the title compound as white crystals. Melting point: 115.5-118.0 ° C NMR (CDCl ₃ ) δ: 2.46 (3H, s), 4.00 (3H, s), 4.14 (3H, s),
7.35 (2H, d, J = 8.3Hz), 7.77 (2H, d, J = 8.3Hz).

Example 81 4'-Chloro-4-ethyl-
Synthesis of N-isopropyl-2'-nitrobenzenesulfonanilide (Compound No. 328) (1) 4.25 g of 90% 4-ethylbenzenesulfonyl chloride (20.
(8 mmol) in pyridine 10.0 ml and stirring at room temperature,
2.55 g (20.0 mmol) of 4-chloroaniline was added. 1 at room temperature
After stirring for 8 hours, 100.0 ml of water was added, and the mixture was extracted with ethyl acetate. The extract was washed with diluted hydrochloric acid, water, and saturated saline in this order, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
5.26 g (89%) of 4'-chloro-4-ethylbenzenesulfonanilide was obtained as white crystals. Melting point: 119.5-121.5 ° C NMR (CDCl ₃ ) δ: 1.23 (3H, t, J = 7.6 Hz), 2.68 (2H, q, J = 7.6H)
z), 6.90 (1H, s), 7.02 (2H, d, J = 8.8Hz), 7.20 (2H, d, J = 8.
8Hz), 7.26 (2H, d, J = 8.4Hz), 7.68 (2H, d, J = 8.4Hz). (2) 4'-chloro-4-ethylbenzenesulfonanilide 4.70 g (15.9 mmol) in acetic acid 15.0 ml While stirring at room temperature, 0.69 ml (16.1 mmol) of 97% fuming nitric acid was added dropwise. After stirring at 50 ° C for 30 minutes, the mixture is allowed to cool to room temperature and water 100.
0 ml was poured to precipitate crystals. Filter the crystals, wash with water,
4.35 g (99%) of 4′-chloro-4-ethyl-2′-nitrobenzenesulfonanilide was obtained as pale yellow crystals. Melting point: 104.5-105.5 ° C. NMR (CDCl ₃ ) δ: 1.23 (3H, t, J = 7.6 Hz), 2.69 (2H, q, J = 7.6H)
z), 7.30 (2H, d, J = 8.4Hz), 7.54 (1H, dd, J = 9.0 & 2.5Hz),
7.74 (2H, d, J = 8.4Hz), 7.84 (1H, d, J = 9.0Hz), 8.10 (1H,
d, J = 2.5 Hz), 9.73 (1H, brs). (3) 0.12 g (3.00 mmol) of 60% sodium hydride in DMF 7.
0 'and suspended at room temperature while stirring.
-Ethyl-2'-nitrobenzenesulfonanilide 1.00
g (2.93 mmol) was added. After stirring at room temperature for 15 minutes, 0.70 ml (7.01 mmol) of isopropyl iodide was added dropwise, and the mixture was heated and stirred at 130 ° C. for 2 hours. After allowing to cool to room temperature, the mixture was extracted into water with ether. The extract was washed with a 1% aqueous sodium hydroxide solution and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 3) to give the title compound as pale red crystals (0.41 g, 37%). Melting point: 117.0-118.5 ° C NMR (CDCl ₃ ) δ: 1.06 (3H, d, J = 6.7 Hz), 1.13 (3H, d, J = 6.7H)
z), 1.27 (3H, t, J = 7.6Hz), 2.74 (2H, q, J = 7.6Hz), 4.37 (1
H, septet, J = 6.7Hz), 7.23 (1H, d, J = 8.6Hz), 7.32 (2H, d, J
= 8.4Hz), 7.55 (1H, dd, J = 8.6 & 2.5Hz), 7.69 (2H, d, J = 8.
4Hz), 7.89 (1H, d, J = 2.5Hz).

Example 82 Synthesis of 4,4'-dichloro-N-ethyl-2'-nitrobenzenesulfonanilide (Compound No. 338) (1) In place of 4-ethylbenzenesulfonyl chloride in (1) of Example 81 Then, using 4-chlorobenzenesulfonyl chloride, 4,4′-dichlorobenzenesulfonanilide was obtained as pale red crystals in a yield of 86%. Melting point: 144.5-145.5 ° C NMR (CDCl ₃ ) δ: 6.71 (1H, s), 7.01 (2H, d, J = 8.9 Hz), 7.23
(2H, d, J = 8.9Hz), 7.43 (2H, d, J = 8.8Hz), 7.68 (2H, d, J = 8.
(2) 4′-chloro-4 in (2) of Example 81.
4,4 'instead of ethylbenzenesulfonanilide
4, using dichlorobenzenesulfonanilide,
4′-Dichloro-2′-nitrobenzenesulfonanilide was obtained with a 96% yield. Melting point: 122.0-123.0 ° C NMR (CDCl ₃ ) δ: 7.46 (2H, d, J = 8.8 Hz), 7.57 (1H, dd, J = 9.0)
& 2.5Hz), 7.77 (2H, d, J = 8.8Hz), 7.83 (1H, d, J = 9.0Hz),
8.12 (1H, d, J = 2.5 Hz), 9.74 (1H, s). (3) 0.13 g (3.25 mmol) of 60% sodium hydride was added to DMF7.
1.00 g (2.88 g) of 4,4'-dichloro-2'-nitrobenzenesulfonanilide while suspending in 0 ml and stirring at room temperature.
mmol) was added. After stirring at room temperature for 15 minutes, 0.45 ml (3.44 mmol) of diethyl sulfate was added dropwise, and the mixture was heated and stirred at 100 ° C. for 2 hours. After allowing to cool to room temperature, the reaction solution was poured into water and extracted with ether. The extract was washed with a 1% aqueous sodium hydroxide solution and saturated saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give the title compound as pale yellow crystals (0.51 g, 47%).
%)Obtained. _{Mp: 121.5-123.0 ℃ NMR (CDCl 3)} δ: 1.20 (3H, t, J = 7.2Hz), 3.68 (2H, q, J = 7.2H
z), 7.09 (1H, d, J = 8.6Hz), 7.47 (2H, d, J = 8.7Hz), 7.54 (1
H, dd, J = 8.6 & 2.5Hz), 7.60 (2H, d, J = 8.7Hz), 7.88 (1H,
d, J = 2.5Hz).

Example 83 Synthesis of 4′-chloro-2′-hydroxymethyl-N-methyl-p-toluenesulfonanilide (Compound No. 65) 5-chloro-N-methyl-N- (p-toluenesulfonyl) 5.20 g (15.3 mmol) of anthranilic acid in chloroform 20.
Dissolve in 0ml and stir at room temperature, while stirring thionyl chloride 2.00ml
(27.4 mmol) was added dropwise. After heating and stirring at 50 ° C for 2 hours,
It was concentrated under reduced pressure. The residue was dissolved in 20.0 ml of acetonitrile, and 1.30 g (30.9 mmol) of 90% sodium borohydride was added to water 2
The solution dissolved in 0.0 ml was added dropwise under ice cooling. After stirring at room temperature for 1 hour, 100.0 ml of water was added, and the mixture was extracted with ethyl acetate. The extract was washed with dilute hydrochloric acid, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 4.40 g (88%) of the title compound as white crystals. Melting point: 130.0-132.0 ° C NMR (CDCl ₃ ) δ: 2.47 (3H, s), 2.70-3.20 (1H, br), 3.12 (3
H, s), 4.61 (1H, brs), 4.94 (1H, brs), 6.37 (1H, d, J = 8.5H
z), 7.10 (1H, dd, J = 8.5 & 2.5Hz), 7.32 (2H, d, J = 8.3Hz),
7.54 (2H, d, J = 8.3Hz), 7.60 (1H, d, J = 2.5Hz).

Example 84 Synthesis of 5-chloro-2- (N-methyl-Np-toluenesulfonyl) aminobenzaldehyde (Compound No. 66) 4′-chloro-2′-hydroxymethyl-N-methyl-
p-toluenesulfonanilide 3.83 g (11.8 mmol) and manganese dioxide 5.11 g (58.8 mmol) in acetonitrile 30.0 ml
The mixture was stirred at room temperature for 3 hours. Manganese dioxide 5.11g (58.8m
mol) was added and stirring was continued for another 20 hours, followed by filtration.
The filtrate was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography.
Elution with 0: 1) gave 2.33 g (61%) of the title compound as white crystals. Melting point: 123.0-124.0 ° C NMR (CDCl ₃ ) δ: 2.46 (3H, s), 3.22 (3
H, s), 6.64 (1H, d, J = 8.6 Hz),
7.30 (2H, d, J = 8.4 Hz), 7.41
(1H, dd, J = 8.6 & 2.6 Hz), 7.
44 (2H, d, J = 8.4 Hz), 7.97 (1
H, d, J = 2.6 Hz), 10.39 (1H, s).

Example 85 Synthesis of 5-chloro-2- (N-methyl-Np-toluenesulfonyl) aminobenzaldehyde methoxime (Compound No. 68) 5-Chloro-2- (N-methyl-N-p- 0.30 g (0.93 of toluenesulfonyl) aminobenzaldehyde
mmol) and 0.10 g (1.20 mmol) of methoxylamine hydrochloride
Was stirred in 0.50 ml of pyridine at room temperature for 18 hours. The reaction solution was concentrated under reduced pressure, dissolved in ether, and washed with water. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 0.30 g (92%) of the title compound as white crystals. _{Mp: 123.5-124.5 ℃ NMR (CDCl 3)} δ: 2.45 (3H, s), 3.11 (3H, s), 3.99 (3H, s),
6.56 (1H, d, J = 8.6Hz), 7.18 (1H, dd, J = 8.6 & 2.5Hz), 7.3
1 (2H, d, J = 8.4Hz), 7.54 (2H, d, J = 8.4Hz), 7.96 (1H, d, J =
2.5Hz), 8.38 (1H, s).

Example 86 Synthesis of 2'-amino-4'-chloro-N-methyl-p-toluenesulfonanilide (Compound No. 61) 4'-chloro-N-methyl-2'-nitro-p-toluene 7.11 g (20.9 mmol) of sulfoneanilide and stannous chloride 14.
7 g (62.6 mmol) was stirred in 100.0 ml of ethanol at room temperature for 45 minutes and at 50 ° C. for 16 hours. After allowing to cool to room temperature, the mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution, and insoluble solids were removed by filtration. The filtrate was extracted with ethyl acetate, and the extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and eluted with acetone-chloroform-hexane (1: 3: 5) to give 5.22 g (81%) of the title compound as white crystals. _{Mp: 101.5-102.5 ℃ NMR (CDCl 3)} δ: 2.46 (3H, s), 3.10 (3H, s), 3.65 (2H, br
s), 6.21 (1H, d, J = 8.5Hz), 6.50 (1H, dd, J = 8.5 & 2.3Hz),
6.81 (1H, d, J = 2.3Hz), 7.31 (2H, d, J = 8.3Hz), 7.58 (2H, d,
J = 8.3Hz).

Example 87 4′-Chloro-N-methyl-
Synthesis of 2'-nitroso-p-toluenesulfonanilide (Compound No. 284)
Dissolve in 0 ml and stir at room temperature with 70% mCPBA (m-
2.38 g of chloroperbenzoic acid) were added. After stirring at room temperature for 3 days, saturated aqueous sodium hydrogen carbonate was added, and the mixture was extracted with chloroform. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 6) to give 1.15 g (73%) of the title compound as blue-green crystals. Melting point: 113.0-114.5 ° C NMR (CDCl ₃ ) δ: 2.40 (3H, s), 3.63 (3H, s), 6.09 (1H, dd, J
= 1.8 & 1.1Hz), 7.17 (2H, m), 7.45 (2H, d, J = 8.3Hz), 7.6
6 (1H, d, J = 1.8Hz), 7.66 (1H, d, J = 1.1Hz).

Example 88 2'-azoxycyano-4 '
Synthesis of -chloro-N-methyl-p-toluenesulfonanilide (Compound No. 393) 4'-chloro-N-methyl-2'-nitroso-p-toluenesulfonanilide 0.50 g (1.54 mmol) in DMF 6.0 ml While dissolving and stirring at room temperature, 0.28 g (1.54 mmol) of NBS (N-bromosuccinimide) was added. After stirring at room temperature for 20 minutes, a solution of 0.10 g (2.31 mmol) of cyanamide dissolved in 1.0 ml of water was added dropwise. After stirring at room temperature for 2 days, water was added to the reaction solution, which was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with acetone-chloroform-hexane (1: 3: 8) to give 0.32 g (57%) of the title compound as pale yellowish white crystals. Melting point: 140.0-142.0 ° C NMR (CDCl ₃ ) δ: 2.46 (3H, s), 3.24 (3H, s), 7.11 (1H, d, J =
8.6Hz), 7.31 (2H, d, J = 8.4Hz), 7.52 (2H, d, J = 8.4Hz), 7.
57 (1H, d, J = 8.6Hz), 7.84 (1H, d, J = 2.5Hz).

Example 89 4′-Cyano-N-ethyl-
Synthesis of p-toluenesulfonanilide (Compound No. 29) 3.39 g (91.8 mmol) of 65% sodium hydride was suspended in 60.0 ml of DMF and 10.0 g of 4'-cyano-p-toluenesulfonanilide was stirred at room temperature. (36.7 mmol) was added. After stirring at room temperature for 1 hour, diethyl sulfate (12.0 ml, 91.8 mmol) was added dropwise, and the mixture was heated and stirred at 75 ° C. for 4 hours. After allowing to cool to room temperature, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with diluted hydrochloric acid and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with chloroform to give 9.8 g (89%) of the title compound as white crystals. Melting point: 85.4-86.6 ° C NMR (CDCl ₃ ) δ: 1.08 (3H, t, J = 7.1 Hz), 2.43 (3H, s), 3.63
(2H, q, J = 7.1Hz), 7.15-7.30 (4H, m), 7.44 (2H, dt, J = 8.4
& 2.0Hz), 7.62 (2H, dt, J = 8.4 & 2.0Hz).

Example 90 Synthesis of 5-chloro-N- (4-cyano-2-nitrophenyl) -N-ethyl-2-thiophene sulfonamide (Compound No. 415) (1) 4′-cyano-N- 1.00 ml (23.4 mmol) of 97% fuming nitric acid was added dropwise to a solution of 6.95 g (23.1 mmol) of ethyl-p-toluenesulfonanilide dissolved in 20.0 ml of concentrated sulfuric acid under ice-cooling. After stirring for 30 minutes under ice cooling, the mixture was poured into ice water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 3) to give 1.25 g (28%) of 4-cyano-N-ethyl-2-nitroaniline as yellow crystals. Melting point: 130.0-131.5 ° C NMR (CDCl ₃ ) δ: 1.41 (3H, t, J = 7.2 Hz), 3.42 (2H, dq, J = 5.1
& 7.2Hz), 6.91 (1H, d, J = 9.0Hz), 7.61 (1H, dd, J = 9.0 &
2.0Hz), 8.33 (1H, br), 8.52 (1H, d, J = 2.0Hz). (2) Suspension of 0.10 g (2.50 mmol) of 60% sodium hydride in 3.0 ml of tetrahydrofuran (THF) and room temperature While stirring, 4-cyano-N-ethyl-2-nitroaniline 0.1.
38 g (1.99 mmol) were added. After stirring at room temperature for 15 minutes to form a deep purple solution, 0.55 g (2.53 mmol) of 5-chloro-2-thiophenesulfonyl chloride was added, and the mixture was stirred at room temperature for 18 hours. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 3) to give 0.22 g (30%) of the title compound as pale yellow crystals.
%)Obtained. Melting point: 101.5-103.0 ° C. NMR (CDCl ₃ ) δ: 1.24 (3H, t, J = 7.2 Hz), 3.75 (2H, q, J = 7.2H)
z), 6.96 (1H, d, J = 4.1Hz), 7.25 (1H, d, J = 4.1Hz), 7.36 (1H, d, J = 4.1Hz)
H, d, J = 8.3Hz), 7.88 (1H, dd, J = 8.3 & 1.9Hz), 8.22 (1H,
d, J = 1.9Hz).

Example 91 5-chloro-N- (4-chloro-2-nitrophenyl) -N, 1,3-trimethyl-
4-pyrazole sulfonanilide (Compound No. 37
Synthesis of 7) 65% sodium hydride was suspended in 5.0 ml of DMF, and 0.48 g (2.57 mmol) of 4-chloro-N-methyl-2-nitroaniline was added with stirring at room temperature. After stirring at room temperature for 1 hour to form a dark purple solution, 0.70 g (3.06 mmol) of 5-chloro-1,3-dimethyl-4-pyrazolesulfonyl chloride was added, and the mixture was stirred at room temperature for 16 hours. Water was added to the reaction solution to precipitate a solid. The solid was filtered, washed with water, dried and then subjected to silica gel column chromatography to give acetone-chloroform-
Elution with hexane (1: 3: 8 → 1: 0: 5) gave 0.55 g (56%) of the title compound as white crystals. Melting point: 102.0-103.0 ° C NMR (CDCl ₃ ) δ: 2.14 (3H, s), 3.33 (3H, s), 3.81 (3H, s),
7.41 (1H, d, J = 8.6Hz), 7.57 (1H, dd, J = 8.6 & 2.4Hz), 7.8
2 (1H, d, J = 2.4Hz).

Example 92 Synthesis of N- (4-chloro-2-nitrophenyl) -N, 3,5-trimethyl-4-isoxazolesulfonamide (Compound No. 376) (1) 0.18 g of potassium carbonate ( 1.28 mmol) in acetonitrile
While suspending in 5.0 ml and stirring at room temperature, 0.33 g (2.56 mmol) of 4-chloroaniline, 0.50 g (2.56 mmol) of 3,5-dimethyl-4-isoxazolesulfonyl chloride, 0.20 g of 18-crown-6 (0.77 mmol) was added and stirred for 16 hours. Water 1
After adding 5.0 ml and extracting with ethyl acetate, the extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with chloroform to give N- (4-chlorophenyl)-
0.68 g (92%) of 3,5-dimethyl-4-isoxazolesulfonamide was obtained. Melting point: 143.5-144.3 ° C NMR (CDCl3) δ: 2.31 (3H, s), 3.46 (3H, s), 6.92 (1H, br
s), 7.04 (2H, d, J = 8.8 Hz), 7.29 (2H, d, J = 8.8 Hz). (2) N- (4-chlorophenyl) -3,5-dimethyl-4-isoxazolesulfone Amide 1.10 g (3.84 mmol)
Was dissolved in 4.0 ml of acetic acid and stirred at room temperature, while fuming nitric acid 0.2
0 ml (4.68 mmol) was added dropwise. After stirring at 50 ° C. for 1 hour, 20.0 ml of water was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed with an aqueous sodium hydroxide solution and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with acetone-chloroform-hexane (1: 3: 8) to give N- (4-chloro-2-nitrophenyl) -3,
0.82 g (64%) of 5-dimethyl-4-isoxazolesulfonamide was obtained as yellow crystals. Melting point: 129.5-130.7 ° C NMR (CDCl ₃ ) δ: 2.18 (3H, s), 2.35 (3H, s), 7.44 (1H, d, J =
8.7Hz), 7.81 (1H, dd, J = 8.7 & 2.5Hz), 8.10 (1H, d, J = 2.5
Hz), 10.70 (1H, brs). (3) 0.05 g (1.36 mmol) of 65% sodium hydride was added to DMF3.
The mixture was suspended in 0 ml and stirred at room temperature, and 0.30 g (0.90 mmol) of N- (4-chloro-2-nitrophenyl) -3,5-dimethyl-4-isoxazolesulfonamide was added.
After stirring at room temperature for 1 hour, dimethyl sulfate 0.13 ml (1.36 mmo
l) was added dropwise and stirring was continued for 16 hours. 20.0 ml of water was poured into the reaction solution, and extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and acetone-hexane (1: 1) was used.
By elution in 4), 0.11 g (35%) of the title compound was obtained as white crystals. Melting point: 99.0-101.0 ° C NMR (CDCl ₃ ) δ: 2.21 (3H, s), 2.40 (3H, s), 3.33 (3H, s),
7.40 (1H, d, J = 8.6Hz), 7.61 (1H, dd, J = 8.6 & 2.4Hz), 7.8
6 (1H, d, J = 2.4Hz).

Example 93 4'-Chloro-4-cyano-
Synthesis of N-ethyl-2′-nitrobenzenesulfonanilide (Compound No. 356) 0.10 g (2.50 mmol) of 60% sodium hydride was suspended in 3.0 ml of tetrahydrofuran (THF) and stirred at room temperature while stirring.
0.40 g of 4-chloro-N-ethyl-2-nitroaniline (1.
99 mmol) was added. After stirring at room temperature for 30 minutes,
0.50 g (2.48 mmol) of cyanobenzenesulfonyl were added.
After stirring at room temperature for 3 hours, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and ethyl acetate-
Elution with hexane (1: 2) gave 0.47 g (64%) of the title compound as pale yellow crystals. Melting point: 146.0-148.0 ° C NMR (CDCl ₃ ) δ: 1.22 (3H, t, J = 7.2 Hz), 3.71 (2H, q, J = 7.2H)
z), 7.16 (1H, d, J = 8.5Hz), 7.58 (1H, dd, J = 8.5 & 2.5Hz),
7.78 (4H, s), 7.89 (1H, d, J = 2.5Hz).

The same method as in Examples 1 to 93 or a method analogous thereto (for example, the reaction formulas (A) to (D) described above)
And the compounds (I ⁰ ) which can be produced by the synthesis methods (D) to (T) are shown in Table 1. The abbreviations in the table have the following significance. Me: methyl group, Et: ethyl group, n-Pr: n-propyl group, i-Pr: isopropyl group, c-Pr: cyclopropyl group, n-Bu: n-butyl group, i-Bu: isobutyl group, sB
u: s-butyl group, t-Bu: t-butyl group, Ph: phenyl group, Ac: acetyl group.

Embedded image

[Table 1]

Formulation Example 1 Compound No. 171 (20% by weight), xylene (75% by weight), and polyoxyethylene glycol ether (Nonipol 85 ^™ ) (5% by weight) are mixed well to prepare an emulsion.

Formulation Example 2 Compound no. 226 (30% by weight), sodium ligninsulfonate (5% by weight), polyoxyethylene glycol ether (Nonipol 85
^TM ) (5% by weight), white carbon (30% by weight),
Clay (30% by weight) is mixed well to produce a wettable powder.

Formulation Example 3 Compound no. 263 (3% by weight), white carbon (3% by weight) and clay (94% by weight) are mixed well to produce a powder.

Formulation Example 4 Compound no. 291 (10% by weight), sodium ligninsulfonate (5% by weight), and clay (85% by weight) are thoroughly pulverized and mixed, water is added and kneaded well, and the mixture is granulated and dried to produce granules.

Formulation Example 5 Compound no. 289 (11% by weight), ethylene glycol (12% by weight), anti-home E20 (0.2% by weight), butylparaben (0.1% by weight), Neugen EA-177 (2% by weight), Neucalgen FS- 7 (2% by weight), Kunipia F (1% by weight), polyvinyl alcohol 224 (1% by weight) and water (70.7% by weight), and then wet-pulverized with Dynomill KDL to obtain a uniform suspension (flowable). Agent).

Formulation Example 6 Compound no. 409 (11% by weight), ethylene glycol (12% by weight), anti-home E20 (0.2% by weight), butylparaben (0.1% by weight), Neugen EA-177 (2% by weight), Newcalgen FS- 7 (2% by weight), Kunipia F (1% by weight), cellogen 7A (1.5% by weight) and water (70.2% by weight), and then wet-milled with Dynomill KDL to obtain a uniform suspension ( Flowable agent).

Formulation Example 7 Compound no. 292 (2% by weight), ferimzone (2% by weight), white carbon (3% by weight) and clay (93% by weight)
Manufacture mixed powder.

Formulation Example 8 Compound no. 289 (11
Parts), ferimzone (20 parts), ethylene glycol (12 parts), anti-home E20 (0.2 parts), butylparaben (0.1 parts), Neugen EA-177 (2 parts)
Part), New Cargen FS-7 (2 parts), Kunipia F
(1 part), polyvinyl alcohol (1 part), water (50.
7 parts), and then wet-milled with Dynomill KDL to produce a uniform suspension (flowable agent).

Formulation Example 9 Compound no. 289 (11
Parts), azoxystrobin (2 parts), ethylene glycol (12 parts), antihome E20 (0.2 parts), butyl paraben (0.1 parts), Neugen EA-177 (2 parts)
Part), New Cargen FS-7 (2 parts), Kunipia F
(1 part), polyvinyl alcohol (1 part), water (68.
7 parts), and then wet-milled with Dynomill KDL to produce a uniform suspension (flowable agent).

Formulation Example 10 Compound No. 289 (4
Part), validamycin A (0.3 part), ferimzone
(2 parts), Fusaride (1.5 parts), IP solvent
(0.2 parts), New Calgen EP-60P (2
Parts), white carbon (1.5 parts), butylparaben (0.05 parts), Newcalgen D-1504 (3 parts)
Parts), Hartole fatty acid (0.25 parts) and calcium carbonate (85.2 parts) are uniformly mixed, and then crushed to obtain D.
L powder is obtained.

Formulation Example 11 Compound no. 421 (15
Parts), chlorothalonil (15 parts), sodium lignin sulfonate (5 parts), polyoxyethylene glycol ether (Nonipol 85 ^™ ) (5 parts), white carbon (30 parts), and clay (30 parts). Produces wettable powder.

Formulation Example 12 Compound no. 289 (17
Parts), clothianidin (8 parts), xylene (70 parts),
Polyoxyethylene glycol ether (Nonipol 8
5 ^™ ) (5 parts) is mixed well to produce an emulsion.

Formulation Example 13 Compound no. 289 (17
Parts), clothianidin (8 parts), Neugen EA-17
7 (0.5 parts), Newkargen FS-4 (2 parts),
Gohsenol GH-17 (2 parts), butyl paraben
(0.1 parts) and water (70.4 parts) were sufficiently mixed and dispersed using a high-speed stirrer, and then Dynomill (manufactured by Shinmaru Enterprise, 1.0 mm glass beads, filling rate 80%, peripheral speed 15 m / s) was used. To produce a uniform suspension (flowable agent).

Formulation Example 14 Compound no. 437 (5
Part), clothianidin (1 part), Newpole PE-
After uniformly mixing 64 (0.5 parts), dextrin NDS (4 parts) and clay (89.5 parts), 5 to 10 parts of water are added and kneaded, and the mixture is extruded from a 0.8 mmφ screen and granulated. The obtained granules are dried at 60 ° C. for 1 hour to obtain granules.

Formulation Example 15 A solution prepared by dissolving 20 parts of nitenpyram and 80 parts of toyoderin P in 400 parts of water is spray-dried to obtain a cyclodextrin clathrate A of nitenpyram. Compound No. After uniformly mixing 1 part of 274, 5 parts of cyclodextrin clathrate A, 2 parts of Newcalgen EP-70P, 10 parts of dextrin NDS and 82 parts of clay, 5 to 10 parts of water is added and kneaded. Extrude and granulate. The obtained granulated product is
Dry for hours to obtain granules.

Formulation Example 16 Compound no. 545 (4
Parts), clothianidin (0.15 parts), Newcalgen EP-70P (2 parts), IP solvent (0.2 parts)
Parts), white carbon (1 part), clay (92.65)
Part) is uniformly kneaded, and then pulverized to obtain a DL powder.

Formulation Example 17 Compound no. 409 (4
Part), cyclodextrin clathrate A (1.25 parts),
New Kalgen EP-70P (2 parts), IP Solvent (0.2 parts), White Carbon (1.5 parts), Clay (91.05 parts) are uniformly kneaded, then pulverized and mixed.
L powder is obtained.

Formulation Example 18 Compound no. 545 (4
Parts), cartap hydrochloride (2 parts), Hartoll fatty acid
(1 part), IP solvent (0.2 part), white carbon (1.5 parts) and clay (91.3 parts) are uniformly kneaded, and then pulverized to obtain a DL powder.

Formulation Example 19 Compound no. 525 (60
Parts), clothianidin (15 parts), Hytenol NE-15
(5 parts), Vanillex N (10 parts), and white carbon carplex # 80D (10 parts) were uniformly mixed and pulverized, and then a small amount of water was added, followed by stirring, mixing and kneading, followed by granulation by an extrusion granulator. And dried to obtain a wettable powder (dry flowable).

Test Example 1 Rice blast ( Pyricularia oryza)
e ) Preventive effect on test compounds to be tested (indicated by compound No. shown in Table 1 above)
Was dissolved in dimethylformamide (final concentration 1% by weight), and xylene (final concentration 0.02% by weight) and Tween 20 (trade name) (final concentration 0.02% by weight) were added thereto. (200 ppm) with water. To this solution was added a spreading agent Dyne (trade name, manufactured by Takeda Pharmaceutical Co., Ltd., polyoxyethylene nonyl phenyl ether 20% by weight and calcium lignin sulfonate 12).
(Including the weight%) at a ratio of 0.05% by weight (final concentration) to prepare a spray liquid, and 10 ml / pot of rice (variety: Asahi No. 4) seedlings cultivated in a greenhouse for 2 to 3 weeks. Sprayed in proportions. After air-drying, blast-infected rice was placed between treated rice and inoculated by natural infection. After 24 hours, the diseased rice was removed and 25
Cultivated in a greenhouse at ~ 35 ° C (humidity 70% or more) for 1 week,
The ratio of the lesion area of the test compound-treated section to the lesion area of the untreated section was investigated, and the results were expressed using the following control values. Control value 3: Ratio to non-treated section 14% or less Control value 2: Ratio to untreated section 15 to 29% Control value 1: Ratio to untreated section 30 to 55% Control value 0: Ratio to untreated section 56% or more As a result, Compound No. 43, 174, 201, 26
2,305,519,276,361,362,39
3,538 compounds gave a control value of 3.

Test Example 2 Rice Bacterial Leaf Blight ( Cochliobolus mi
Preventive effect on yabeanus ) In the same manner as in Test Example 1, the concentration of the specified active ingredient (200pp
m) was applied to rice (cultivar: Nipponbare or Asahi No. 4) seedlings cultivated for 3-4 weeks in a greenhouse.
Sprayed at a rate of ml / pot. 3-5 × 10 ^{5 after} air drying
The suspension was spray-inoculated with a suspension of spores of the blast fungus of rice sesame seeds, and kept in a moist chamber at 28 ° C. for 2 days. Thereafter, the cells were cultivated in a greenhouse for 5 days, and the ratio of the lesion area of the test compound-treated section to the lesion area of the untreated section was investigated. The results were expressed using the following control values. Control value 3: Lesion area rate 10% or less Control value 2: Lesion area rate 11 to 20% Control value 1: Lesion area rate 21 to 50% Control value 0: Lesion area rate 51% or more As a result, the compound No. 171, 207, 262, 28
Compounds of 8, 289, 292 gave a control value of 3.

Test Example 3 Apple Leaf Spot ( Alternaria)
Preventive effect against mali ) A prescribed concentration of the active ingredient (200pp
m) apples cultivated in a greenhouse for 3 to 4 weeks with the spray liquid prepared to become m) (variety: Starking Delicious)
Young plants were sprayed at a rate of 10 ml / pot. One day after treatment,
A suspension containing 1% yeast extract, 1% sucrose, 5 × 10 ⁵ cells / ml spores of apple spot leaf rot fungus was spray-inoculated at a rate of 1 ml / pot. After keeping in a 28 ° C moist chamber for 4 days after inoculation,
The lesion area ratio of the treated leaves was investigated, and the results were expressed using the following control values. Control value 3: Lesion area rate 10% or less Control value 2: Lesion area rate 11 to 20% Control value 1: Lesion area rate 21 to 50% Control value 0: Lesion area rate 51% or more As a result, the compound No. 12,23,25,30,4
0, 51, 84, 94, 116, 118, 119, 12
5, 126, 127, 163, 171, 172, 17
7, 194, 195, 205, 206, 207, 20
9, 210, 211, 213, 214, 216, 21
8, 219, 226, 262, 263, 264, 26
5, 266, 273, 274, 276, 277, 27
9, 282, 288, 289, 290, 291, 29
2,295,298,299,300,305,30
7, 308, 309, 311, 322, 324, 32
6, 332, 337, 338, 340, 370, 38
7, 396, 398, 404, 406, 407, 40
9, 411, 412, 413, 423, 425, 42
6, 429, 434, 435, 438, 545, 44
8, 449, 450, 456, 464, 494, 50
3,504,511,517,26,61,65,6
7, 69, 80, 83, 85, 86, 87, 88, 8
9, 95, 97, 99, 100, 101, 105, 11
1, 112, 113, 114, 227, 229, 34
8, 354, 356, 414, 415, 419, 42
0, 421, 437, 455, 457, 522, 52
3, 525, 533, 535, 538, 539, 54
0, 554, 563, 565, 566, 567, 57
1,572 compounds gave a control value of 3.

Test Example 4 Plasmodioph
ora brassicae ) Test compound (compound No. of the compound shown in Table 1 above)
Was dissolved in dimethylformamide (final concentration 1% by weight), and xylene (final concentration 0.02% by weight) and Tween 20 (trade name) (final concentration 0.02% by weight) were added thereto, followed by dilution with water. The prepared drug solution was irrigated into soil contaminated with clubroot so that the active ingredient was 353.7 mg / m ² , mixed well, and then seeded with Komatsuna. After cultivation in a greenhouse for 4 to 6 weeks, the roots of Komatsuna were washed out and examined for disease severity, and the results were expressed using the following control values. Control value 3: Disease severity 25% or less Control value 2: Disease severity 26 to 50% Control value 1: Disease severity 51 to 75% Control value 0: Disease severity 76% or more As a result, Compound No. 115, 312, 525, 52
8, 529, 535, 536, 537, 545, 55
2,560 compounds gave a control value of 3.

The evaluation of the bactericide in Test Examples 5 to 9 was performed by measuring the lesion area ratio (percentage) and converting it to a control value. The control value was calculated by the following formula. Control value = (1− (lesion area ratio of drug-treated area / lesion area rate of non-treated area)) × 100 The predicted control value of the mixture of active ingredients was calculated using Colby's formula (Colby's formula).
s formula) [R. S. Colby, Weeds 1
5, 20-22 (1967)] and compared with the actual control value. Colby's formula: E = x + y-xy / 100 where E is the expected control value (additive effect) when a mixture of active ingredients A and B is used at concentrations a and b, and x is the active ingredient A Represents the control value when using at the concentration a, and y represents the controlling value when using the active ingredient B at the concentration b. When the control value obtained by the test shows a value larger than the expected effect E, there is a synergistic effect. In addition, the control value 0 corresponds to the control standard in which the lesion area ratio of the test plant is untreated. Control value 100
Means that the test plant is not diseased.

Test Example 5 Apple Spot Leaf Spot ( Alternaria)
Preventive effect against mali ) The test compound (indicated by the compound No. shown in Table 1 above), chlorothalonil, hexaconazole and azoxystrobin, alone or in combination, were added to dimethylformamide (final concentration 1% by weight). After dissolving, xylene (final concentration 0.02% by weight) and Tween 20 (trade name) (final concentration 0.02% by weight) were added, and the mixture was diluted with water to a predetermined active ingredient concentration (ppm). . This liquid is added to the spreading agent Syndyne (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.)
20% by weight of polyoxyethylene nonyl phenyl ether
And 12% by weight of calcium ligninsulfonate) were added at a ratio of 0.05% by weight (final concentration) to adjust the spraying liquid, and apples (cultivar: Starking Delicious) cultivated in a greenhouse for 3 to 4 weeks ) Young plants were sprayed at a rate of 10 ml / pot. 1 day after treatment, 1% yeast extract, 1% sucrose,
A suspension containing 5 × 10 ⁵ spores of apple spot rot fungus was spray-inoculated at a rate of 1 ml / pot. After being kept in a moist chamber at 28 ° C. for 4 days after inoculation, the lesion area ratio of the treated leaves was examined, and the results were expressed using the above control values. The results are shown in Table 2. Compound No. 289 and No. 421 exhibited a higher controlling effect when used in combination with chlorothalonil, hexaconazole and azoxystrobin than when each compound was used alone, and a synergistic effect due to the mixture was observed.

[Table 2]

Test Example 6 Apple Leaf Spot ( Alternaria)
Preventive effect against mali ) The test compound (indicated by No. of the compound shown in Table 1 above), iminoctadine, mepanipyrim and kresoxim-methyl alone or as a mixture, and the lesion area ratio of the treated leaves in the same manner as in Test Example 4. And the results were expressed using the above control values. The results are shown in Table 3. Compound No. 28
9 is mepanipyrim and No. 9 When 97 was used in combination with iminoctadine, 97 exhibited a higher control effect than the case where each compound was used alone, and synergistic action due to mixing was observed.

[Table 3]

Test Example 7 Rice Blast ( Pyricularia oryza)
e ) Preventive effect on test compounds to be tested (indicated by compound No. shown in Table 1 above)
And azoxystrobin, alone or mixed, dissolved in dimethylformamide (final concentration 1% by weight), and further dissolved in xylene (final concentration 0.02% by weight), Tween 20 (trade name) (final concentration 0.02%). % By weight)
It was diluted with water to a predetermined concentration of the active ingredient. This liquid is added to the spreading agent Syndyne (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.)
20% by weight of polyoxyethylene nonyl phenyl ether
And 12% by weight of calcium ligninsulfonate) were added at a ratio of 0.05% by weight (final concentration) to prepare a spray liquid, and rice (cultivar: Asahi 4) cultivated in a greenhouse for 2 to 3 weeks
No.) Young plants were sprayed at a rate of 10 ml / pot. After air drying,
Rice plants with blast disease were placed between treated rice plants and inoculated by natural infection. Twenty-four hours later, the diseased rice was removed, cultivated in a greenhouse at 25 to 35 ° C. (humidity of 70% or more) for one week, and the lesion area of the present sulfonamide-treated section and the area treated with other drugs with respect to the lesion area of the untreated section The area ratio was investigated and the results were expressed using the above control values. The results are shown in Table 4. Compound No. 289
Is used by mixing with azoxystrobin,
A higher controlling effect was exhibited than when each compound was used alone, and a synergistic effect by mixing was observed.

[Table 4]

Test Example 8 Rice sesame leaf blight ( Cochliobolus mi
Preventive effect on yabeanus ) Test compound (indicated by compound No. shown in Table 1 above)
And ferimzone alone or mixed and dissolved in dimethylformamide (final concentration 1% by weight).
Xylene (final concentration 0.02% by weight), Tween 20
(Trade name) (final concentration: 0.02% by weight) was added, and the mixture was diluted with water to a predetermined active ingredient concentration (200 ppm). In this solution, a spreading agent Syndyne (trade name, manufactured by Takeda Pharmaceutical Co., Ltd., 20% by weight of polyoxyethylene nonylphenyl ether and 12% by weight of calcium ligninsulfonate)
Was added at a rate of 0.05% by weight (final concentration) to prepare a spray liquid, and 10 ml / pot of rice (cultivar: Nihonbare or Asahi No. 4) seedling cultivated in a greenhouse for 3 to 4 weeks. Sprayed at a rate. After air-drying, a suspension of 3 to 5 × 10 ⁵ cells / ml of spore suspension of rice sesame leaf blight was spray-inoculated and kept in a 28 ° C. moist chamber for 2 days. Thereafter, the ratio of the lesion area of the present sulfonamide-treated section and the area treated with another drug to the lesion area of the untreated section was investigated after cultivation in a greenhouse for 5 days, and the results were expressed using the above control values. Table 5 shows the results. Compound No. 289
When used as a mixture with ferimzone, a higher control effect was exhibited than when each compound was used alone, and a synergistic effect due to the mixture was observed.

[Table 5]

Test Example 9 Cucumber Gray Mold ( Botrytis
Preventive effect on cinerea ) Test compound (indicated by compound No. shown in Table 1 above)
And azoxystrobin, mepanipyrim or iprodione alone or as a mixture, dissolved in dimethylformamide (final concentration 1% by weight), and further dissolved in xylene (final concentration 0.02% by weight), Tween 20 (trade name) (final (A concentration of 0.02% by weight) and diluted with water to a predetermined active ingredient concentration (200 ppm). This liquid is applied to the spreading agent Syndyne (trade name, Takeda Pharmaceutical Co., Ltd.)
(Including 20% by weight of polyoxyethylene nonyl phenyl ether and 12% by weight of calcium ligninsulfonate) at a ratio of 0.05% by weight (final concentration) to prepare a spray liquid, and 3 to 4% in a greenhouse. Cucumber (cultivar: four leaf) seedlings cultivated for a week were sprayed at a rate of 10 ml / pot. After air-drying, a microflora disk was punched out of the PSA medium in which the gray mold fungus had grown on the entire surface, placed on cucumber leaves, inoculated with mycelia, and kept in a 28 ° C. moist chamber for 3 days. afterwards,
The ratio of the lesion area of the present sulfonamide-treated section and the other drug-treated section to the lesion area of the untreated section was investigated, and expressed using the above control value. The results are shown in Table 6. Compound N
o. When 289 was used in combination with azoxystrobin, mepanipyrim or iprodione, a higher controlling effect was exhibited than when each compound was used alone, and a synergistic effect due to the mixture was observed.

[Table 6]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 43/824 C07C 311/21 C07C 311/21 321/28 321/28 C07D 213/71 C07D 213/71 213 / 76 213/76 215/36 215/36 231/18 231/18 233/84 233/84 237/12 237/12 237/20 237/20 237/24 237/24 249/02 249/02 249/12 512 249/12 512 261/10 261/10 277/52 275/03 277/58 277/52 285/10 277/58 285/14 285/10 333/34 285/14 333/42 333/34 403/12 333/42 471/04 108A 403/12 513/04 331 471/04 108 A01N 43/82 101C 513/04 331 C07D 275/02

Claims (18)

[Claims] (1) Formula (I) Wherein A ¹ is (1) an optionally substituted aryl group or (2) an optionally substituted heterocyclic group, X ¹ is (1) a chemical bond, (2) an optionally substituted A good methylene group or (3) an optionally substituted vinylene group, B ¹ is an optionally substituted 5-membered heterocyclic group (excluding isoxazolyl group) or an optionally substituted fused heterocyclic group The group
¹ is (1) an optionally substituted hydrocarbon group, (2) an optionally substituted acyl group, (3) a formyl group, (4) an optionally substituted amino group, (5) -N = CR ¹ R ² (R ¹ and R
² represents a hydrogen atom or a hydrocarbon group which may be substituted), a group represented by (6) a cyclic amino group, (7)-
A group represented by OR ³ (R ³ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group or an optionally substituted alkylsulfonyl group) or ( 8) —S (O) _n R ⁴ (n represents an integer of 0 to 2, and R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted). An agricultural and horticultural microbicide containing a compound or a salt thereof. 2. A 5-membered heterocyclic group wherein B ¹ is a heteroatom in which a ring-constituting atom other than an optionally substituted carbon atom is selected from a nitrogen atom and a sulfur atom, or a condensed heterocyclic group which may be optionally substituted. The agricultural and horticultural microbicide according to claim 1, which is a cyclic group. 3. A ¹ is (1) (i) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di-C _1-4 alkylhydrazono and C _1-4 alkylthio. 1 to 5 with a substituent selected from
An optionally substituted C _1-4 alkyl group, (ii) a C _3-6 cycloalkyl group optionally substituted with 1 to 5 halogens, (iii) a substituent selected from halogen, cyano and nitro 1 to 5 optionally substituted C _2-4 alkenyl groups, (iv) 1 to 5 halogen optionally substituted C _3-6 cycloalkenyl groups, (v) 1 to 5 halogens optionally substituted C _2-4 alkynyl group, (vi) hydroxy group, (vii) halogen and C _1-4 optionally C _1-4 optionally substituted with 1-5 substituents selected from alkoxy Alkoxy group, (viii) formyloxy group, (ix) halogen
5 optionally substituted C _1-4 alkyl-carbonyloxy groups, (x) _1-5 optionally substituted C _1-4 alkoxy-carbonyloxy groups with halogen, (xi) mercapto group, xii) C _1-4 alkylthio group optionally substituted with 1 to 5 halogens, (xiii) C _1-4 alkyl-carbonylthio group optionally substituted with 1 to 5 halogens, (xiv) halogen 1 to 5 optionally substituted C
_1-4 alkoxy-carbonylthio group, (xv) 1 halogen
To five an optionally substituted C _1-4 alkylsulfinyl group, (xvi) a halogen with 1-5 optionally substituted C _1-4 alkyl sulfonyl group, (xvii) sulfamoyl group, (xviii) mono- — Or di-C _1-4 alkylsulfamoyl group, (xix) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, hydroxy, C _1-4 alkoxy , Formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl,
Or two optionally substituted amino groups, (xxi) 3
A 6-membered cyclic amino group, (xxii) a formyl group, (xxiii) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, and (xxiv) 1 to 5 substituted with halogens. A C _1-4 alkoxy-carbonyl group, (xxv) C
_1-4 alkylthio - carbonyl group, (xxvi) C _1-4 alkoxy - thiocarbonyl group, (xxvii) C _1-4 alkylthio - thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- - or di -C _{1 -4} alkylcarbamoyl group, (xxx) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxxiii) Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
xxviii) a substituent consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group, (xliv) azoxycyano group and (xlv) sulfo group A C _6-14 aryl group which may be substituted with 1 to 5 substituents selected from the group (T) or (2) 1 to 5 substituents selected from the substituent group (T) X ¹ represents a (1) chemical bond, (2)
A substituent selected from C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, halogen atom and cyano;
Or a methylene group which may be substituted two or
(3) a substituent selected from C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, a halogen atom and cyano;
Alternatively, two optionally substituted vinylene groups are represented by B ¹
Is (1) a ring atom other than a carbon atom which is optionally substituted with 1 to 5 substituents selected from the substituent group (T), and is a hetero atom selected from a nitrogen atom and a sulfur atom. 5-6, which may be substituted with a membered heterocyclic group or (2) 1 to 5 substituents selected from the above substituent group (T).
Membered heterocycle and benzene ring or 5-6 membered heterocycle and 5-6
A fused heterocyclic group formed with a membered heterocyclic ring, Z ¹ is (1) (i) (a)
Halogen, (b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f ) Mercapto, (g) C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl, (i) C _1-4 alkylsulfonyl, (j) cyano, (k) C
_1-4 alkoxy-carbonyl, (l) carbamoyl and
(m) 1-5 C-substituents which may be substituted with a substituent selected from mono- or di-C _1-4 alkyl-carbamoyl
_1-6 alkyl group, (ii) (a) halogen, (b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy,
(e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f) mercapto, (g) C _1-4 alkylthio, (h) C
_1-4 alkylsulfinyl, (i) _C1-4 alkylsulfonyl, (j) cyano, (k) _C1-4 alkoxy-carbonyl, (l)
Carbamoyl and (m) a C _2-6 alkenyl group optionally substituted by 1 to 5 substituents selected from mono- or di-C _1-4 alkyl-carbamoyl, (iii) (a) halogen, (b ) Amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f) mercapto, g)
C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl,
(i) a substitution selected from C _1-4 alkylsulfonyl, (j) cyano, (k) C _1-4 alkoxy-carbonyl, (1) carbamoyl and (m) mono- or di-C _1-4 alkyl-carbamoyl. A C _2-6 alkynyl group optionally substituted with 1 to 5 groups, (iv) (a) a C _1-4 alkyl optionally substituted with 1 to 5 halogens, (b) a halogen, (c ) Amino, (d) mono- or di-C _1-4 alkylamino, (e) hydroxy, (f) C _1-4 optionally substituted with 1 to 5 halogens.
Alkoxy, (g) mercapto, (h) C _1-4 alkylthio,
(i) C _1-4 alkylsulfinyl, (j) C _1-4 alkylsulfonyl, (k) cyano, (1) C _1-4 alkoxy-carbonyl, (m) carbamoyl and (n) mono- or di-C
_1-4 substituents selected from alkyl-carbamoyl
5 optionally substituted C _3-6 cycloalkyl groups, (v)
(a) halogen, (b) amino, (c) mono- or di-C _1-4
Alkylamino, (d) hydroxy, (e) halogen with 1 to 5
Optionally substituted C _1-4 alkoxy, (f) mercapto, (g) C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl, (i) C _1-4 alkylsulfonyl, (j) Cyano, (k) C
_1-4 alkoxy-carbonyl, (l) carbamoyl and
(m) 1-5 C-substituents which may be substituted with a substituent selected from mono- or di-C _1-4 alkyl-carbamoyl
_3-6 alkadienyl group and (vi) (a) C _1-4 alkyl optionally substituted with 1 to 5 halogens, (b) halogen,
(c) amino, (d) mono- or di-C _1-4 alkylamino, (e) hydroxy, (f) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (g) mercapto , (H) C _1-4
Alkylthio, (i) C _1-4 alkylsulfinyl, (j) C
_1-4 alkylsulfonyl, (k) cyano, (l) C _1-4 alkoxy-carbonyl, (m) carbamoyl and (n) mono- or di-C _1-4 alkyl-carbamoyl A hydrocarbon group selected from five optionally substituted C _6-14 aryl groups, (2) a C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens, (i)
i) C _1-4 alkoxy-carbonyl, (iii) C _1-4 alkylthio-carbonyl, (iv) C _1-4 alkoxy-thiocarbonyl, (v) C _1-4 alkylthio-thiocarbonyl, (vi) mono- Or di-C _1-4 alkyl-carbamoyl and
(vii) an acyl group selected from mono- or di-C _1-4 alkyl-thiocarbamoyl, (3) formyl group, (4) (a) C
_1-4 alkyl, (b) C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens, (c) C _1-4 alkoxy-carbonyl, (d) mono- or di-C _{1- 4} alkyl-
Carbamoyl and (e) an amino group optionally substituted by one or two substituents selected from mono- or di-C _1-4 alkyl-thiocarbamoyl, (5) -N = CR ¹ R
² (R ¹ and R ² each represent a hydrogen atom or a C _1-4 alkyl group), (6) a 3- to 6-membered cyclic amino group, (7) —OR ³ (R ³ is hydrogen An atom, a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms, 1 halogen atom
_1-4 to five optionally substituted C alkyl - carbonyl group, an optionally C _1-4 be 1-5 substituted by halogen
An alkoxy-carbonyl group, a formyl group or a C _1-4 alkylsulfonyl group optionally substituted with 1 to 5 halogen atoms) or a group represented by (8) -S (O) _n R ⁴
(N is an integer of 0 to 2, R ⁴ is (a) a hydrogen atom, (b) a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms or (c) a C _1-4 alkyl group. 1 to 5 C _6-14 aryl groups which may be substituted).
The agricultural and horticultural microbicide according to the above. 4. A¹Is C_1-41-3 substituted with an alkyl group
May be C_6-14An aryl group is represented by X¹Represents a chemical bond,
B¹Is a C optionally substituted with 1 to 5 halogens _1-4A
Luquil, C_1-4Alkoxy, C_1-4Alkylthio, shea
1 to 5 substitutions selected from no, halogen and nitro
Optionally substituted with a thienyl group, a pyrazolyl group
Group, isothiazolyl group, imidazolyl group, thiazolyl
Group, thiadiazolyl group, dioxaindanyl group or i
A midazopyridyl group represented by Z¹Is C_1-6Alkyl group or C
_1-4The agricultural and horticultural microbicidal composition according to claim 1, which represents an alkoxy group.
Materials. 5. A compound of the formula (II) Wherein A ² is (1) (i) halogen, hydroxy, imino,
Hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono - or di -C _1-4 alkyl hydrazono or C _1-4 optionally C _1-4 be 1-5 substituted with a substituent selected from alkylthio An alkyl group, (ii) a _C3-6 cycloalkyl group optionally substituted with 1 to 5 halogens, (iii) 1 to 5 optionally substituted substituents selected from halogen, cyano and nitro C _2-4 alkenyl group, (iv) C which may be substituted by 1 to 5 halogens
_3-6 cycloalkenyl group, (v) _C2-4 alkynyl group optionally substituted with 1 to 5 halogens, (vi) hydroxy group, (vii) halogen and ₁ to ₄ alkoxy selected from _C1-4 alkoxy. A C _1-4 alkoxy group optionally substituted with 5 substituents, (viii) a formyloxy group, (ix)
5 optionally substituted C _1-4 alkyl-carbonyloxy groups, (x) _1-5 optionally substituted C _1-4 alkoxy-carbonyloxy groups with halogen, (xi) mercapto group, xii) C _1-4 alkylthio group optionally substituted with 1 to 5 halogens, (xiii) C _1-4 alkyl-carbonylthio group optionally substituted with 1 to 5 halogens, (xiv) halogen 1 to 5 optionally substituted C
_1-4 alkoxy-carbonylthio group, (xv) 1 halogen
To five an optionally substituted C _1-4 alkylsulfinyl group, (xvi) a halogen with 1-5 optionally substituted C _1-4 alkyl sulfonyl group, (xvii) sulfamoyl group, (xviii) mono- — Or a di-C _1-4 alkylsulfamoyl group, (xix) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4
Alkynyl, hydroxy, C _1-4 alkoxy, formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl, one or two amino groups which may be substituted with a substituent selected from (xx
i) a 3- to 6-membered cyclic amino group, (xxii) formyl group, (xxii
i) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, (xxiv) a C _1-4 alkoxy-carbonyl group optionally substituted with 1 to 5 halogens, (xxv)
C _1-4 alkylthio-carbonyl group, (xxvi) C _1-4 alkoxy-thiocarbonyl group, (xxvii) C _1-4 alkylthio-
Thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- or di-C _1-4 alkylcarbamoyl group, (xxx) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxxiii) Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
xxviii) a substituent group (T ′) consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group and (xliv) sulfo group
X ² represents (1) a chemical bond, (2) a substituted or unsubstituted aryl group which may be substituted with 1 to 5 substituents selected from A methylene group or (3) a vinylene group which may be substituted,
B ² represents an optionally substituted aryl group; Z ² represents (1) a mono- or di-C _1-6 alkylamino, hydroxy,
An alkyl group optionally substituted with a substituent selected from halogen, C _1-6 alkoxy, C _1-6 alkoxy-carbonyl, C _1-6 alkylthio and cyano, (2) a vinyl group, (3) an allyl group, (4) propadienyl group, (5) optionally substituted alkynyl group, (6) optionally substituted cycloalkyl group, (7) optionally substituted aryl group, (8) substituted Acyl group, (9) formyl group, (10) optionally substituted amino group, (11) -N = C
A group represented by R ¹ R ² (R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group which may be substituted), (12)
A cyclic amino group, (13) -OR ³ (R ³ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group, or an optionally substituted alkylsulfonyl group ), Or (14) -S
(O) _n R ⁴ (n represents an integer of 0 to 2, and R ⁴ represents a hydrogen atom or an optionally substituted hydrocarbon group)] or a salt thereof. A microbicide for agricultural and horticultural use. Wherein A ² is (1) (i) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono - or di -C _1-4 alkyl hydrazono or C _1-4 alkylthio 1 to 5 with a substituent selected from
An optionally substituted C _1-4 alkyl group, (ii) a C _3-6 cycloalkyl group optionally substituted with 1 to 5 halogens, (iii) a substituent selected from halogen, cyano and nitro 1 to 5 optionally substituted C _2-4 alkenyl groups, (iv) 1 to 5 halogen optionally substituted C _3-6 cycloalkenyl groups, (v) 1 to 5 halogens optionally substituted C _2-4 alkynyl group, (vi) hydroxy group, (vii) halogen and C _1-4 optionally C _1-4 optionally substituted with 1-5 substituents selected from alkoxy Alkoxy group, (viii) formyloxy group, (ix) halogen
5 optionally substituted C _1-4 alkyl-carbonyloxy groups, (x) _1-5 optionally substituted C _1-4 alkoxy-carbonyloxy groups with halogen, (xi) mercapto group, xii) C _1-4 alkylthio group optionally substituted with 1 to 5 halogens, (xiii) C _1-4 alkyl-carbonylthio group optionally substituted with 1 to 5 halogens, (xiv) halogen 1 to 5 optionally substituted C
_1-4 alkoxy-carbonylthio group, (xv) 1 halogen
To five an optionally substituted C _1-4 alkylsulfinyl group, (xvi) a halogen with 1-5 optionally substituted C _1-4 alkyl sulfonyl group, (xvii) sulfamoyl group, (xviii) mono- — Or di-C _1-4 alkylsulfamoyl group, (xix) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, hydroxy, C _1-4 alkoxy , Formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl,
Or two optionally substituted amino groups, (xxi) 3
A 6-membered cyclic amino group, (xxii) a formyl group, (xxiii) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, and (xxiv) 1 to 5 substituted with halogens. A C _1-4 alkoxy-carbonyl group, (xxv) C
_1-4 alkylthio - carbonyl group, (xxvi) C _1-4 alkoxy - thiocarbonyl group, (xxvii) C _1-4 alkylthio - thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- - or di -C _{1 -4} alkylcarbamoyl group, (xxx) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxxiii) Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
xxviii) a substituent group (T ′) consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group and (xliv) sulfo group
A C _6-14 aryl group optionally substituted with 1 to 5 substituents selected from or (2) (i) halogen, hydroxy,
Imino, hydroxyimino, C _1-4 alkoxyimino,
A substituent selected from hydrazono, mono- or di-C _1-4 alkylhydrazono and C _1-4 alkylthio;
Selected from a C _1-4 alkyl group optionally substituted with 5 to 5 carbon atoms, (ii) a C _3-6 cycloalkyl group optionally substituted with 1 to 5 halogen atoms, (iii) halogen, cyano and nitro A C _2-4 alkenyl group optionally substituted by 1 to 5 substituents, (iv) a C _3-6 cycloalkenyl group optionally substituted by 1 to 5 halogens, (v) 1 to 5 halogens 5 an optionally substituted C _2-4 alkynyl group, (vi) hydroxy group, (vii) halogen and C _1-4 optionally C ₁ optionally substituted with 1 to 5 substituents selected from alkoxy _-4 alkoxy group, (viii) formyloxy group, (ix) 1 to 5 halogen-substituted C _1-4 alkyl-carbonyloxy group, (x) 1 to 5 halogen-substituted which may C _1-4 alkoxy - carbonyl group, (xi) a mercapto group, a 1-5 substituted with (xii) halogen Optionally have C _1-4 alkylthio group, 1-5 in (xiii) halogen
Optionally substituted C _1-4 alkyl-carbonylthio group, (xiv) 1 to 5 optionally substituted C _1-4 alkoxy-carbonylthio groups, (xv) 1 to 5 halogen pieces optionally substituted C _1-4 alkyl sulfinyl group, (xvi) may be 1-5 substituted by halogen C _1-4 alkylsulfonyl group, (xvii) sulfamoyl group, (xviii) mono- - or Di-C _1-4 alkylsulfamoyl group, (xix) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, hydroxy, C _1-4 alkoxy , Formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl,
Or two optionally substituted amino groups, (xxi) 3
A 6-membered cyclic amino group, (xxii) a formyl group, (xxiii) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, and (xxiv) 1 to 5 substituted with halogens. A C _1-4 alkoxy-carbonyl group, (xxv) C
_1-4 alkylthio - carbonyl group, (xxvi) C _1-4 alkoxy - thiocarbonyl group, (xxvii) C _1-4 alkylthio - thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- - or di -C _{1 -4} alkylcarbamoyl group, (xxx) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxxiii) Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
xxviii) a substituent consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group, (xliv) azoxycyano group and (xlv) sulfo group X ² represents a heterocyclic group which may be substituted with 1 to 5 substituents selected from the group (T), wherein X ² is (1) a chemical bond, (2) C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, a methylene group optionally substituted by one or two substituents selected from a halogen atom and cyano, or (3) C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, A vinylene group which may be substituted with one or two substituents selected from a halogen atom and cyano is represented by B
² is a C _6-14 aryl group _optionally substituted with 1 to 5 substituents selected from the above substituent group (T), and Z ² is (1)
1-5 substituted with a substituent selected from mono- or di-C _1-4 alkylamino, hydroxy, halogen, C _1-4 alkoxy, C _1-4 alkoxy-carbonyl, C _1-4 alkylthio and cyano. C _1-6 alkyl group, (2) vinyl group, (3) allyl group, (4) propadienyl group, (5) (a) halogen, (b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f)
Mercapto, (g) C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl, (i) C _1-4 alkylsulfonyl, (j) cyano, (k) C _1-4 alkoxy-carbonyl, (l) Carbamoyl and (m) a C _2-6 alkynyl group optionally substituted with 1 to 5 substituents selected from mono- or di-C _1-4 alkyl-carbamoyl, (6) (a) Optionally substituted C _1-4 alkyl, (b) halogen, (c)
Amino, (d) mono- or di-C _1-4 alkylamino,
(e) hydroxy, (f) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (g) mercapto, (h) C _1-4 alkylthio, (i) C _1-4 alkylsulfinyl, (j) C _1-4 alkylsulfonyl, (k) cyano, (l) C _1-4 alkoxy-
Carbonyl, (m) carbamoyl and (n) a C _3-6 cycloalkyl group optionally substituted with 1 to 5 substituents selected from mono- or di-C _1-4 alkyl-carbamoyl, (7) ( a) C optionally substituted with 1 to 5 halogens
_1-4 alkyl, (b) halogen, (c) amino, (d) mono- or di-C _1-4 alkylamino, (e) hydroxy, (f) optionally substituted with 1 to 5 halogens C _1-4 alkoxy, (g) mercapto, (h) C _1-4 alkylthio, (i) C _1-4
Alkylsulfinyl, (j) C _1-4 alkylsulfonyl,
(k) cyano, (l) C _1-4 alkoxy-carbonyl, (m) carbamoyl and (n) mono- or di-C _1-4 alkyl-
A C _6-14 aryl group _optionally substituted with 1 to 5 substituent (s) selected from carbamoyl, (8) a C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogen (s). (Ii) C _1-4 alkoxy-carbonyl, (iii) C _1-4 alkylthio-carbonyl, (iv) C _1-4 alkoxy-thiocarbonyl, (v) C _1-4 alkylthio-thiocarbonyl,
(vi) mono- or di-C _1-4 alkyl-carbamoyl and (vii) an acyl group selected from mono- or di-C _1-4 alkyl-thiocarbamoyl, (9) formyl group, (1
0) (a) C _1-4 alkyl, (b) C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens, (c) C _1-4 alkoxy-carbonyl, (d) mono- Or di-C _1-4 alkyl-carbamoyl and (e) mono- or di-C
_An amino group optionally substituted by one or two substituents selected from _1-4 alkyl-thiocarbamoyl, (11)-
A group represented by N = CR ¹ R ² (R ¹ and R ² each represent a hydrogen atom or a C _1-4 alkyl group), (12) a 3- to 6-membered cyclic amino group, and (13) —OR ³ (R ³ is a hydrogen atom, a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms,
C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, C _1-4 alkoxy-carbonyl group optionally substituted with 1 to 5 halogens, 1-5 _Represents an optionally substituted C _1-4 alkylsulfonyl group) or (14)-
S (O) _n R ⁴ (n is an integer of 0 to 2, R ⁴ is (C) _1-4 which may be substituted with (a) a hydrogen atom and (b) halogen.
The agricultural and horticultural microbicide according to claim 5, wherein the alkyl group or (c) a C _6-14 aryl group which may be substituted with 1 to 5 C _1-4 alkyl groups). A ² is (1) (i) a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms, and (ii) 1 to 5 halogen atoms.
Optionally substituted C _1-4 alkoxy group, (iii) C
_From an amino group optionally substituted by one or two _1-4 alkyl-carbonyl, (iv) a C _1-4 alkoxy-carbonyl group, (v) a halogen atom, (vi) a cyano group and (vii) a nitro group. A C _6-14 aryl group optionally substituted with 1 to 5 selected substituents or (2) (i) a C _1-4 alkyl group,
(ii) C _1-4 alkoxy-carbonyl group, (iii) carbamoyl group, (iv) mono- or di-C _1-4 alkylcarbamoyl group, (v) C _1-4 alkylsulfonyl group, (vi) halogen atom , (Vii) a carboxyl group and (viii) a thienyl group, a triazolyl group, an imidazolyl group, an isoxazolyl group, a pyrazolyl group, a pyridyl group, a quinolyl group which may be substituted with 1 to 5 substituents selected from a cyano group. A benzothiadiazolyl group, an imidazothiazolyl group or an imidazopyridyl group, X ² represents (1) a chemical bond, (2) a methylene group optionally substituted by one or two C _1-4 alkyl or ( 3) a vinylene group which may be substituted by one or two C _1-4 alkyls; B ² is (1) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di- −C _{1 A} C _1-4 alkyl group which may be substituted with 1 to 5 substituent (s) selected from _-4 alkylhydrazono and C _1-4 alkylthio, (2)
C _2-4 alkynyl group, (3) hydroxy group, (4) halogen and C _1-4 1 to 5 amino optionally substituted with a substituent C _1-4 alkoxy group selected from alkoxy, (5) C _1-4 alkyl-carbonyloxy group, (6) C _1-4 alkylthio group, (7) C _1-4 alkylsulfinyl group, (8) C _1-4 alkylsulfonyl group, (9) mono- or di- C _1-4 alkylsulfamoyl group, (10) amino group, (11) formyl group, (1
2) C _1-4 alkoxy-carbonyl group, (13) carbamoyl group, (14) mono- or di-C _1-4 alkylcarbamoyl group, (15) thiocarbamoyl group, (16) halogen atom, (1
7) one selected from a carboxyl group, (18) thiocyanato group, (19) cyano group, (20) nitroso group and (21) nitro group
A C _6-14 aryl group optionally substituted with up to 5 substituents, Z ² represents (1) mono- or di-C _1-4 alkylamino, hydroxy, halogen, C _1-4 alkoxy, C _C1-4 alkoxy - carbonyl, C _1-4 alkylthio and 1-5 optionally substituted C _1-6 alkyl group with a substituent selected from cyano, (2) vinyl group, (3) allyl group, ( 4) propadienyl group, (5) C _2-6 alkynyl group optionally substituted with 1 to 5 halogens, (6) C _3-6 cycloalkyl group, (7) C _6-14 aryl group, (8 ) C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogens, (9) C
_1-4 alkyl, C _1-4 alkyl-carbonyl and C _1-4
An amino group optionally substituted by one or two substituents selected from alkoxy-carbonyl, (10) -N = CR
A group represented by ¹ R ² (R ¹ and R ² each represent a C _1-4 alkyl group); (11) —OR ³ (R ³ is a C _1-4 alkyl group or a C _1-4 alkyl-carbonyl); Or (12) —S (O) _n R ⁴ (n is an integer of 0 to 2, and R ⁴ is (a) 1 to 5 carbon atoms which may be substituted with halogen. _{And a} (b) C _6-14 aryl group which may be substituted with 1 to 5 C _1-4 alkyl groups). Microbial agents. 8. A ² is a phenyl group which may be substituted by 1 to 3 substituents selected from a C _1-4 alkyl group, halogen and cyano, X ² is a chemical bond, B ² is (1 C) alkyl group _optionally substituted with 1 to 3 halogen atoms, (2)
C _1-4 alkoxy group, (3) C _1-4 alkylthio group, (4) thiocarbamoyl group, (5) halogen atom, (6) cyano group and
(7) 1-5 optionally substituted phenyl group optionally substituted by a group selected from nitro group, Z ² is (1) C _1-4 optionally C ₁ be 1-3 alkoxy substituted _-6 alkyl group, (2)
The agricultural and horticultural microbicide according to claim 5, which represents a _C3-6 cycloalkyl group, (3) an allyl group, or (4) a _C1-4 alkoxy group. (9) the compound or a salt thereof is 4'-chloro-N-
Ethyl-2'-nitro-p-toluenesulfonanilide, 2 ', 4'-dinitro-N-ethyl-p-toluenesulfonanilide, 2', 4'-dicyano-N-ethyl-p
-Toluenesulfonanilide, 4'-chloro-N-isopropyl-2'-nitro-p-toluenesulfonanilide, 4'-fluoro-N-isopropyl-2'-nitro-
p-Toluenesulfonanilide, 4'-cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilide, 4'-chloro-N-isopropyl-2'-cyano-
p-Toluenesulfonanilide, 2 ', 4'-dinitro-
N-isopropyl-p-toluenesulfonanilide,
4'-nitro-N-isopropyl-2'-cyano-p-toluenesulfonanilide, 2'-cyano-N-methoxy-4'-nitro-p-toluenesulfonanilide or 2 ', 4'-dinitro-N- The microbicide for agricultural and horticultural use according to claim 5, which is methoxy-p-toluenesulfonanilide or a salt thereof. 10. A compound of the formula (III) Wherein A ³ represents (1) an optionally substituted aryl group or (2) an optionally substituted heterocyclic group, X ³ represents (1) a chemical bond, and (2) an optionally substituted A good methylene group or (3) a vinylene group which may be substituted, B ³ represents (i) a halogen,
1 to 5 substituents selected from hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di-C _1-4 alkylhydrazono and C _1-4 alkylthio may be substituted. A C _1-4 alkyl group, (ii) a C 1-5 optionally substituted with halogen
_3-6 cycloalkyl group, (iii) C _2-4 alkenyl group _optionally substituted with 1 to 5 substituents selected from halogen, cyano and nitro, (iv) 1 to 5 substituted with halogen An optionally substituted C _3-6 cycloalkenyl group, (v) a C _2-4 alkynyl group _optionally substituted with 1 to 5 halogens,
(vi) a hydroxy group, (vii) a C _1-4 alkoxy group optionally substituted with 1 to 5 substituents selected from halogen and C _1-4 alkoxy, (viii) a formyloxy group, (ix)
A C _1-4 alkyl-carbonyloxy group optionally substituted with 1 to 5 halogens, (x) a C _1-4 alkoxy-carbonyloxy group optionally substituted with 1 to 5 halogens, (xi) A mercapto group, (xii) a C _1-4 alkylthio group optionally substituted with 1 to 5 halogens, (xiii) a C _1-4 alkyl-carbonylthio group optionally substituted with 1 to 5 halogens, (xiv) a C _1-4 alkoxy-carbonylthio group optionally substituted with 1 to 5 halogens, (xv)
Halogen with 1-5 optionally substituted C _1-4 alkylsulfamoyl also be alkylsulfonyl group, (xvi) 1-5 optionally substituted C _1-4 alkylsulfonyl group halogen, (xvii) sulfamoyl group, ( xviii) mono- or di-C _1-4 alkylsulfamoyl group, (xix) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4
Alkynyl, hydroxy, C _1-4 alkoxy, formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl, one or two amino groups which may be substituted with a substituent selected from (xx
i) a 3- to 6-membered cyclic amino group, (xxii) formyl group, (xxii
i) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, (xxiv) a C _1-4 alkoxy-carbonyl group optionally substituted with 1 to 5 halogens, (xxv)
C _1-4 alkylthio-carbonyl group, (xxvi) C _1-4 alkoxy-thiocarbonyl group, (xxvii) C _1-4 alkylthio-
Thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- or di-C _1-4 alkylcarbamoyl group, (xxx) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxxiii) Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
(xxviii) a substituent consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group, (xliv) azoxycyano group and (xlv) sulfo group 6 having a substituent selected from group (T)
Membered heterocyclic group, Z ³ is (1) an optionally substituted hydrocarbon group, (2) an optionally substituted acyl group, (3) a formyl group, (4) an optionally substituted amino Group, (5) -N = CR
¹ R ² (R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group which may be substituted); (6) a cyclic amino group; (7) —OR ³ (R ³ is hydrogen Atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group or an optionally substituted sulfonyl group) or (8) -S (O) _n R ⁴ (n
Represents an integer of 0 to 2, and R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted)). Agent. 11. A ³ is (1) (i) halogen, hydroxy, imino, hydroxyimino, C _1-4 alkoxyimino, hydrazono, mono- or di-C _1-4 alkylhydrazono and C _1-4 alkylthio. 1 to 1 substituents selected from
5-substituted C _1-4 alkyl group, (ii) C _3-6 cycloalkyl group optionally substituted with 1-5 halogen, (iii) substitution selected from halogen, cyano and nitro A C _2-4 alkenyl group optionally substituted with 1 to 5 groups, (iv) a C _3-6 cycloalkenyl group optionally substituted with 1 to 5 halogens, (v) 1 to 5 pieces optionally substituted C _2-4 alkynyl group, (vi) hydroxy group, (vii) halogen and C _1-4 optionally substituted with 1-5 substituents selected from alkoxy C _{1- 4} alkoxy group, (viii) formyloxy group, (ix) halogen
A C _1-4 alkyl-carbonyloxy group which may be substituted with 5 to 5 carbon atoms, (x) a C _1-4 alkoxy-carbonyloxy group which may be substituted with 1 to 5 halogen atoms, (xi) a mercapto group, (xii) a C _1-4 alkylthio group optionally substituted with 1 to 5 halogens, (xiii) a C _1-4 alkyl-carbonylthio group optionally substituted with 1 to 5 halogens, (xiv) C that may be substituted with 1 to 5 halogen atoms
_1-4 alkoxy-carbonylthio group, (xv) 1 halogen
To five an optionally substituted C _1-4 alkylsulfinyl group, (xvi) a halogen with 1-5 optionally substituted C _1-4 alkyl sulfonyl group, (xvii) sulfamoyl group, (xviii) mono- — Or di-C _1-4 alkylsulfamoyl group, (xix) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xx) C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, hydroxy, C _1-4 alkoxy , Formyloxy, C _1-4 alkyl-carbonyloxy, formyl and C _1-4 alkyl-carbonyl,
Or two optionally substituted amino groups, (xxi) 3
A 6-membered cyclic amino group, (xxii) a formyl group, (xxiii) a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogens, and (xxiv) 1 to 5 substituted with halogens. A C _1-4 alkoxy-carbonyl group, (xxv) C
_1-4 alkylthio - carbonyl group, (xxvi) C _1-4 alkoxy - thiocarbonyl group, (xxvii) C _1-4 alkylthio - thiocarbonyl group, (xxviii) carbamoyl group, (xxix) mono- - or di -C _{1 -4} alkylcarbamoyl group, (xxx) (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxi) a thiocarbamoyl group, (xxxii) a mono- or di-C _1-4 alkyl-thiocarbamoyl group, (xxxiii) Embedded image (Ring C represents a 3- to 6-membered nitrogen-containing heterocyclic group), (xxxiv) a halogen atom, (xxxv) a carboxyl group, and (xx
(xvi) thiocyanato group, (xxxvii) isothiocyanato group, (x
xxviii) a substituent consisting of a cyano group, (xxxix) isocyano group, (xl) azide group, (xli) nitroso group, (xlii) nitro group, (xliii) azocyano group, (xliv) azoxycyano group and (xlv) sulfo group A C _6-14 aryl group which may be substituted with 1 to 5 substituents selected from the group (T) or (2) 1 to 5 substituents selected from the substituent group (T) X ³ represents a (1) chemical bond, (2)
A substituent selected from C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, halogen atom and cyano;
Or a methylene group which may be substituted two or
(3) a substituent selected from C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, a halogen atom and cyano;
Alternatively, two optionally substituted vinylene groups are represented by B ³
Is a 6-membered heterocyclic group substituted with 1 to 5 substituents selected from the above substituent group (T), Z ³ is (1) (i) (a) halogen,
(b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f) mercapto , (G) C _1-4
Alkylthio, (h) C _1-4 alkylsulfinyl, (i) C
_1-4 alkylsulfonyl, (j) cyano, (k) C _1-4 alkoxy-carbonyl, (l) carbamoyl and (m) mono- or di-C _1-4 alkyl-carbamoyl 5-substituted C _1-6 alkyl group, (ii) (a) halogen, (b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e ) halogen with 1-5 substituents which may be C _1-4 alkoxy,
(f) mercapto, (g) C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl, (i) C _1-4 alkylsulfonyl, (j)
C-5 optionally substituted with 1 to 5 substituents selected from cyano, (k) _C1-4 alkoxy-carbonyl, (1) carbamoyl and (m) mono- or di- _C1-4 alkyl-carbamoyl. _2-6 alkenyl group, (iii) (a) halogen, (b) amino, (c) mono- or di-C _1-4 alkylamino,
(d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f) mercapto, (g) C _1-4 alkylthio, (h) C _1-4 alkylsulfinyl, (i) C _1-4 alkylsulfonyl, (j) cyano, (k) C _1-4 alkoxy-
Carbonyl, (l) carbamoyl and (m) mono- - or di -C _1-4 alkyl - 1-5 optionally substituted C _2-6 alkynyl group with a substituent selected from carbamoyl,
(iv) (a) C _1-4 optionally substituted with 1 to 5 halogens
Alkyl, (b) halogen, (c) amino, (d) mono- or di-C _1-4 alkylamino, (e) hydroxy, (f) 1 to 5 halogen-substituted C _{1- 4} alkoxy, (g) mercapto, (h) C _1-4 alkylthio, (i) C _1-4
Alkylsulfinyl, (j) C _1-4 alkylsulfonyl,
(k) cyano, (l) C _1-4 alkoxy-carbonyl, (m) carbamoyl and (n) mono- or di-C _1-4 alkyl-
A C _3-6 cycloalkyl group optionally substituted with 1 to 5 substituents selected from carbamoyl, (v) (a) halogen,
(b) amino, (c) mono- or di-C _1-4 alkylamino, (d) hydroxy, (e) C _1-4 alkoxy optionally substituted with 1 to 5 halogens, (f) mercapto , (G) C _1-4
Alkylthio, (h) C _1-4 alkylsulfinyl, (i) C
_1-4 alkylsulfonyl, (j) cyano, (k) C _1-4 alkoxy-carbonyl, (l) carbamoyl and (m) mono- or di-C _1-4 alkyl-carbamoyl 5 optionally substituted C _3-6 alkadienyl group, and (vi) (a) halogen with 1-5 substituents on these C _1-4 alkyl, (b) halogen, (c) amino, ( d)
Mono- or di-C _1-4 alkylamino, (e) hydroxy, (f) C _1-4 optionally substituted with 1 to 5 halogens.
Alkoxy, (g) mercapto, (h) C _1-4 alkylthio,
(i) C _1-4 alkylsulfinyl, (j) C _1-4 alkylsulfonyl, (k) cyano, (1) C _1-4 alkoxy-carbonyl, (m) carbamoyl and (n) mono- or di-C
_1-4 substituents selected from alkyl-carbamoyl
A hydrocarbon group selected from a 5-substituted C _6-14 aryl group, (2) a C _1-4 alkyl-carbonyl optionally substituted with 1 to 5 halogen atoms, (ii) ) C _1-4 alkoxy-carbonyl, (iii) C _1-4 alkylthio-carbonyl, (iv) C _1-4 alkoxy-thiocarbonyl, (v) C
_1-4 alkylthio-thiocarbonyl, (vi) mono- or di-C _1-4 alkyl-carbamoyl and (vii) mono-
Alternatively, ₁ to 5 acyl groups selected from di-C _1-4 alkyl-thiocarbamoyl, (3) formyl group, (4) (a) C _1-4 alkyl, and (b) halogen may be substituted. C _1-4
Selected from alkyl-carbonyl, (c) C _1-4 alkoxy-carbonyl, (d) mono- or di-C _1-4 alkyl-carbamoyl and (e) mono- or di-C _1-4 alkyl-thiocarbamoyl. An amino group optionally substituted by one or two substituents, represented by (5) -N = CR ¹ R ² (R ¹ and R ² each represent a hydrogen atom or a C _1-4 alkyl group) Group, (6) 3- to 6-membered cyclic amino group, (7)-
OR ³ (R ³ is a hydrogen atom, a C _1-4 alkyl group optionally substituted with 1 to 5 halogen atoms, a C _1-4 alkyl-carbonyl group optionally substituted with 1 to 5 halogen atoms, halogen Represents a C _1-4 alkoxy-carbonyl group, a formyl group or a C _1-4 alkylsulfonyl group optionally substituted with 1 to 5 halogens which may be substituted by 1 to 5) Or (8) -S (O) _n R ⁴ (n is 0 to
R ⁴ is (a) a hydrogen atom and (b) halogen is 1 to 5
Optionally substituted C _1-4 alkyl group or (c) C
The agricultural and horticultural microbicidal agent according to claim 10, wherein the C _6-14 aryl group which may be substituted with 1 to 5 _1-4 alkyl groups). 12. A ³ is a 1-5 substituted 1 phenyl group or a C _1-4 alkyl optionally or two optionally substituted imidazolyl group by C _1-4 alkyl, X ³
Is a chemical bond, B ³ is C _1-4 alkyl optionally substituted with 1 to 5 halogens, C _1-4 alkoxy, halogen,
A pyridyl group, a pyridazinyl group or a pyrimidinyl group substituted with 1 to 5 substituents selected from nitro and cyano, Z ³ represents a C _1-6 alkyl group, a C _3-6 cycloalkyl group or a C _1-4 The microbicide for agricultural and horticultural use according to claim 10, which represents an alkoxy group. 13. A compound of the formula (IV) Wherein A ⁴ represents (1) an optionally substituted aryl group or (2) an optionally substituted heterocyclic group, X ⁴ represents (1) a chemical bond, (2) an optionally substituted A good methylene group or (3) a optionally substituted vinylene group, B ⁴ is a pyridazinyl group or a pyrazinyl group, Z ⁴ is (1) an optionally substituted hydrocarbon group, (2) a substituted Good acyl group, (3)
Formyl group, (4) optionally substituted amino group, (5)-
A group represented by N = CR ¹ R ² (R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group which may be substituted), (6) a cyclic amino group, and (7) —OR ³ (R ³ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a formyl group or an optionally substituted sulfonyl group) or a group represented by (8) -S ( O) _n R
⁴ (n represents an integer of 0 to 2; R ⁴ represents a hydrogen atom or a hydrocarbon group which may be substituted);
A microbicide for agricultural and horticultural use containing the compound represented by the formula or a salt thereof. 14. A compound of the formula (V) Wherein A ⁵ represents a 4-methylphenyl group, X ⁵ represents a chemical bond, B ⁵ represents a pyridyl group or a pyrimidinyl group, and Z ⁵ represents a C
_Which represents a _1-4 alkyl group] or a salt thereof, for agricultural and horticultural use. 15. A compound of the formula (VI) Wherein A ⁶ is a phenyl group which may be substituted with a substituent selected from C _1-4 alkyl, halogen and cyano, X ⁶ is a chemical bond, and B ⁶ is a halogen atom, nitro and cyano is a 2-nitrophenyl group or a 2-cyanophenyl group which is substituted with a substituent, Z ⁶ is an ethyl group, an isopropyl group, a cyclopropyl group, a methoxy group,
Ethoxy group or isopropoxy group] or a salt thereof. 16. A ⁶ is a phenyl group which may be substituted by a substituent selected from C _1-4 alkyl, halogen and cyano, X ⁶ is a chemical bond, and B ⁶ is a halogen atom, nitro and cyano. The compound according to claim 15 or a salt thereof, wherein the 2-nitrophenyl group substituted with a selected substituent, and Z ⁶ represents an ethyl group, an isopropyl group or a cyclopropyl group. 17. A 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide, 2 ', 4'-dinitro-N-ethyl-p-toluenesulfonanilide, 2',
4'-dicyano-N-ethyl-p-toluenesulfonanilide, 4'-chloro-N-isopropyl-2'-nitro-p-toluenesulfonanilide, 4'-fluoro-N
-Isopropyl-2'-nitro-p-toluenesulfonanilide, 4'-cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilide, 4'-chloro-N
-Isopropyl-2'-cyano-p-toluenesulfonanilide, 2 ', 4'-dinitro-N-isopropyl-p
-Toluenesulfonanilide, 4'-nitro-N-isopropyl-2'-cyano-p-toluenesulfonanilide, 2'-cyano-N-methoxy-4'-nitro-p-toluenesulfonanilide or 2 ', 4' -Dinitro-
The compound according to claim 15, which is N-methoxy-p-toluenesulfonanilide or a salt thereof, or a salt thereof. 18. The formula (1) (Wherein each symbol is as defined in claim 15) or a salt thereof and a compound of the formula Z ⁶ -L ″ (wherein L ″
Is a leaving group, and Z ⁶ has the same meaning as defined in claim 15), or (2) a compound represented by the formula A ⁶ −
A compound represented by X ⁶ -SO ₂ -L (wherein L represents a leaving group, and other symbols have the same meanings as defined in claim 15) or a salt thereof, and a compound represented by the formula Z ⁶ HN-B ⁶ ( Each symbol in the formula has the same meaning as in claim 15.) or a salt thereof, or (3) a compound represented by the formula A ⁶ -X ⁶ -SO _2-
A compound represented by NHZ ⁶ (wherein each symbol is as defined in claim 15) or a salt thereof, and a compound represented by the formula L′-B
⁶ (wherein L 'represents a leaving group and the other symbols have the same meanings as defined in claim 15) or a salt thereof, or (4) a compound represented by the formula (4): (Wherein B ⁷ is a phenyl group substituted with at least one of the 2- or 6-position substituted with a substituent selected from a halogen atom, nitro and cyano, and the other symbols are the same as those in claim 15) Wherein the compound represented by the formula: or a salt thereof is nitrated. (Each symbol in the formula has the same meaning as described in claim 15) or a method for producing a salt thereof.