CA1340949C - Imidazole compounds and biocidal composition comprising the same for controlling harmful organisms - Google Patents

Abstract

This invention relates to intermediate compounds represented by a compound as an intermediate represented by the following general formula (II'):

(see formula I) wherein R2 an R3 each represents a hydrogen atom; a halogen atom; a nitro group; a cyano group; a trimethylsilyl group; a C3-6 cycloalkyl group; a naphthyl group; an unsubstituted C1-12 alkyl group or a substituted C1-12 alkyl group which substituent is selected from the group consisting of one or more halogen atoms, hydroxyl groups, acetoxy groups, C1-4 alkoxy groups, halogenated C1-4 alkoxy groups, phenyl groups, halogenated phenyl groups, or C1-4 alkylated phenyl groups; an unsubstituted C2-10 alkenyl group or a substituted C2-10 alkenyl group which substituent is selected from the group consisting of one or more halogen atoms; an unsubstituted C1-6 alkoxy group or a substituted C1-6 alkoxy group which substituent is selected from the group consisting of one or more halogen atoms; an unsubstituted phenyl group or a substituted phenyl group which substituent is selected from the group consisting of one or more halogen atoms, C1-4 alkyl groups, halogenated C1-4 alkyl groups, C1-4 alkoxy groups, halogenated C1-4 alkoxy groups, alkylthio groups, halogenated C1-4 alkylthio groups, nitro groups, cyano groups, or 3,4-methylenedioxy groups; an unsubstituted furyl group or a substituted furyl group which substituent is selected from the group consisting of one or more halogen atones or C1-4 alkyl groups; an unsubstituted thienyl group or a substituted thienyl group which substituent is selected from the group consisting of one or more halogen atoms or C1-4 alkyl groups; an unsubstituted pyridyl group or a substituted pyridyl group which substituent is selected from the group consisting of one or more halogen atoms or C1-4 alkyl groups; an -SO n R7 group, wherein R7 represents a C1-6 alkyl group, a C2-6 alkenyl group, an unsubstituted phenyl group or a substituted phenyl group which substituent is selected from the group consisting of one or more halogen atoms, a benzyl group, an unsubstituted pyridyl group or a substituted pyridyl group which substituent is selected from the group consisting of one or more halogen atoms, C1-4 alkyl groups, or halogenated C1-4 alkyl groups, or an -NR8R9 group, wherein R8 and R9 each represents a C1-4 alkyl group, and n is 0, 1 or 2; or a -CO(NH)m R10 group, wherein R10 represents an unsubstituted C1-4 alkyl group or a substituted C1-4 alkyl group which substituent is selected from the group consisting of one or more halogen atoms, an unsubstituted C1-4 alkoxy group or a substituted alkoxy group which substituent is selected from the group consisting of one or more halogen atoms, or an unsubstituted phenyl group or a substituted phenyl group which substituent is selected from the group consisting of one or more halogen atoms; and m is 0 or 1; provided that compounds represented by the general formula (II"):

(see formula II) wherein R2' and R3' area simultaneously a hydrogen atom, an unsubstituted phenyl group or a phenyl group which substituent is selected from the group consisting of the same or different C1-2 alkoxy group or C1-2 alkylthio group at the para-position, an unsubstituted C1-4 alkyl group or a substituted C1-4 alkyl group which substituent is selected from the group consisting of one or more halogen atoms, hydroxyl groups, acetoxy groups, C1-4 alkoxy groups, halogenated C1-4 alkoxy groups, phenyl groups, halogenated phenyl groups, or C1-4 alkylated phenyl groups, wherein R2' and R3' are each independently selected from the group consisting of a halogen atom, a cyano group, or a nitro group; and wherein one of R2' and R3' is a hydrogen atom and the other is a halogen atom, a methyl group or a phenyl group, are excluded.

These compounds are useful intermediates for the production of novel imidazole compounds and biocidal compounds for controlling harmful organisms.

Description

1~4a9 49 THIS IS A DIVISIONAL APPLICATION OF CANADIAN PATENT APPLICATION
SERIAL DfUMBER 560,436 FILED ON MARCH 3, 1988 The present invention relates to novel imidazole compounds and biocidal compositions comprising the same for controlling harmful organisms.
BACKGROUND OF THE INVENTION
Imidazole type compounds proposed so far are exemplified below.
Belgian Patient 852313 (published Sept. 12, 1977) discloses (4,!5)-dichloro-imidazole(2)-carboxylic acid derivatives having the formula XYZC -~~ wherein CXYZ

H
represents a (: atom with 3 bonds attached to hetero atoms, and Japanese Patent Publication No. 15625/85 (published Apr. 20, 1985) discloses the following reaction scheme, C1 ,\ C1 C1 Ni C1 N C1 while no compound having other substituents than chlorine atoms at the 4 and 5-positions in the imidazole ring and having a substituted sulfonyl group in the imidazole ring is disclosed in both of the above references.

1 3 ~ 09 49 1 Recl. Tr;~v. Chim. Pays-Bas ,1973, 92(3), 449-59 phenyl . ~ phenyl discloses NC -< ~ , NC -~ ~ , etc. ;
N~ H N phenyl H H
DT-OS 2317453 (published Oct. 11, 1973) discloses CN ~ CN
quaternary ammonium salts of NC ~ or N02--N CN N CN
H H
etc.; J. Org. Chem., Vol. 44, No. 16, 1979, 2902-2906 _. ~ , R
discloses NC -~ ~ (R: H, CH3), etc.; EP 31086 N' H
X
(published July 1, 1987.) discloses R'--C~~ (R': -CQZR, N y H
CN); J. Orct. Chem., Vol. 51, No. 10, 1986, 1891-1894 discloses 2-cyano innidazole, etc.; and Research Disclosure, June (1986), 323-324 (C. A., 106, 49942e) phenyl-X
discloses NC-~~'~ , etc.; while no N phenyl-X' H
compound having a substituted sulfonyl group in the imidazole ring is disclosed in any of the above-described references.
Japanese Patent Application (OPI) No. 4303/80 (published Jan. 12, 1980) (the term "OPI" as used herein 1 means a "publi.shed unexamined patent application") discloses 1-(N,N-~dimethyl-S02N(CH3)2 I
N CN
sulfamoylj-4,5-d:icyanoimidazole ~ ~ ; C.A., 95:
N CN
7283q [Japanese Patent Application (OPI) No. 157570/80 (published Dec. 8, 1981))] discloses sulfamoylimidazole :i OZN ( Cla3 ) 2 S02N ( CH3 ) 2 N CN N CONHZ
derivatives of ~ ~ and ~ ~ ; C.A., 101:
rl CO1NH2 N . CN
7092u (J.Chem. Soc., PE~rkin Trans. 1, 1984, (3), 481-6) SO,~N ( CH3 ,) 2 N Li discloses Li~ ~ , etc.; and C.A., 106: 138324x N' (Tetrahedron, 19f.6, 42(8), 2351-8) discloses S02N(CH3)2 I
Li (Et)3Si~ ~ . etc.; while no compounds having other N
than a hydrogen atom, a lithium atom, or an -Si(Et)3 group at the 2-position in i=he imidazole ring as a substituent are disclosed.
Japanese Patent Application (OPI) No. 142164/87 (published June 25, 1987) discloses 4,5-dichloro-imidazole compounds having the formula R3 -~~ , while no I

1 compounds having other substituents than chlorine atoms at the 4 and 5-posit:ions in the imidazole ring are disclosed.
References li~;ted below disclose imidazopyridine compounds- and/or benz;imidazole compounds in which the compounds contain a condensed ring of an imidazole ring with a benzene ring and/or a pyridine ring in their chemical structures.
U.S. Patent 36179157 (issued Sept. 28, 1971) U.S. Patent 3681369 (issued Aug. 1, 1972) . Belgian Patent 830719 (published Dec. 29, 1975) Belgian Patent 845641 (published Feb. 28, 1977) U.S. Patent 4536502 (issued Aug. 20, 1985) U.S. PatE~nt 45;79853 (issued Apr. 1, 1986) French Patent :?559150 (published Aug. 9, 1985) Japanese Patent: Application (OPI) No. 103873/86 (published May 22, 1086) Japanese Patent: Application (OPI) No. 22782/87 (published Jan.. 30, 1987)' EP 219192 (pubT~ished Apr. 22, 1987) Japanese Patent: Application (OPI) No. 195379/87 (published Aug. 28, 1987) EP 239508~ (publ.ished Sept. 30, 1987) SUMMARY OF THE INVENTION
An object: of the present invention is to provide imidazole compounds of the following general formula (I) and biocidal compositions comprising the same for controlling harmful organisms:

13~09.4~

_ i S0,2R4 wherein:
R1 represents a cyano group or a -CSNHRS group, wherein R5 represents .a hydrogen atom, a C1-4 alkyl group, or a -CORE group, wherein R6 represents a Cl_4 alkyl group, a halogenated C1_4 alkyl group, or a~phenyl group;
R2 and R3 each represents a hydrogen atom; a halogen atom; a nitro group; a cyano group; a trimeth-ylsilyl group; a C;;_6 cycloalkyl group; a naphthyl group; a C1-12 alkyl group which is optionally substituted with one or more halogen atoms, hydroxyl groups, acetoxy groups, Cl_4 alkoxy groups, halogenated C1_4 alkoxy groups, phenyl groups, halogenated phenyl groups, or C1_4 alkylated phenyl groups; a C2_lo alkenyl group which is optionally substituted with one or more halogen atoms; a Cl_6 alkoxy group which is optionally substituted with one or more halogen atoms; a phenyl group which is optionally substituted with one or more halogen atoms, C:1_4 a7Lky1 groups, halogenated Cl_4 alkyl groups, C1_4 alkoxy groups, halogenated C1_9 alkoxy groups, C1_q alkylthio groups, halogenated C1_4 alkylthio groups, nitro groups, cyano groups, or 3,4-methylenedioxy groups;

~~~409 49 1 a furyl group which is optionally substituted with one or more halogen atoms or C1_q alkyl groups; a thienyl group which is optionally substituted with one or more halogen atoms or -C1_q alkyl .groups; a pyridyl group which is optionally substituted. with one or more halogen atoms or Cl_q alkyl groups; an -SOnR7 group, wherein R~ represents a Cl_6 alkyl group, a C2_6 alkenyl group, a phenyl group which is optionally substituted with one or more halogen atoms, a benzyl <iroup, a pyridyl group which is optionally . substituted with one or more halogen atoms, C1_q alkyl groups, or halogenated Cl_q alkyl groups; or an -NR$R9 group, wherein I~g and R9 each represents a Cl_q alkyl group, and n is 0, 7., or 2; or a -CO(NH)mRlp group, wherein Rlp represents a Cl_q alkyl group which is optionally substituted with one or more halogen atoms, a Cl_q alkoxy group which is optionally substituted with one or more halogen atoms, or a phenyl group which is optionally substituted with one or more halogen atoms;
and m is 0 or 1; and Rq represents a C1_6 alkyl group which is optionally substituted with one or more halogen atoms; a C3_6 cycloalkyl group; a phenyl group; a thienyl group;
or an -NR11R12 group, wlherein R11 and R12 each represents a hydrogen atom, a~ Cl_q alkyl group which is optionally substituted with one or more halogen atoms, a C2_q alkenyl group, or R11 and R;~2 are combined with each other 1 together with a nitrogen atom adjacent thereto to form a pyrrolidinyl grc>up, a piperidinyl group, a morpholino group, or a thiomorpholino group, provided that R11 and R12 are not simultaneously a hydrogen atom;
provided that R2 and R3 are not simultaneously a halogen atom.
Another object: of the present invention is to provide a process; for preparing the imidazole compounds of the formula (I) hereinabove.
_ . A further object of the present invention is to provide intermediate compounds of the following general formula (II'):

NC (II') H
wherein R2 and R.3 each represents a hydrogen atom; a halogen atom; a nitro group; a cyano group; a trimeth-ylsilyl group; a Cg._6 cycloalkyl group; a naphthyl group; a Cl-12 alkyl group which is optionally substituted with one or more halogen atoms, hydroxyl groups, acetoxy groups, Cl_q alkoxy groups, halogenated Cl_4 alkoxy groups, phenyl groups, halogenated phenyl groups, or Cl_4 aLkylat~ed phenyl groups; a C2_lo alkenyl group which is optionally substituted with one or more 1 halogen atoms; a Cl_6 alkoxy group which is optionally substituted with one or more halogen atoms; a phenyl group which is optionally substituted with one or more halogen atoms, C:1_4 alkyl groups, halogenated Cl_4 alkyl groups, C1_4 alkoxy groups, halogenated Cl_4 alkoxy groups, C1_4 alkylthio groups, halogenated Cl_4 alkylthio groups, nitro groups, cy~ano groups, or 3,4-methylenedioxy groups;
a furyl group which is optionally substituted with one or more halogen atoms or C1_4 alkyl groups; a thienyl group _ which is optionally substituted with one or more halogen atoms or C1_4 alkyl groups; a pyridyl group which is optionally substituted with one or more halogen atoms or Cl_4 alkyl groups; an -SOnR7 group, wherein R~ represents a Cl_6 alkyl group, a CZ_6 alkenyl group, a phenyl group which is optionally substituted with one or more halogen atoms, a benzyl o~roup, a pyridyl group which is optionally substituted with one or more halogen atoms, Cl_4 alkyl groups, or halogenated Cl_4 alkyl groups; or an -NR8R9 group, wherein R$ and R9 each represents a C1_4 alkyl group, and n is 0, l, or 2; or a -CO(NH)mRlp group, wherein Rlp represents a Cl_4 alkyl group which is optionally substituted with one or more halogen atoms, a C1_4 alkoxy group which is optionally substituted with one or more halogen atoms, or a phenyl group which is optionally substituted with one or more halogen atoms;
and m is 0 or 1, _ g _ provided that compoundls represented by the following general formula (II"):
R ' v rIC ~ ' (II") p- ~R

wherein RZ' and l~3' are simultaneously a hydrogen atom, an unsubstituted phenyl group or a phenyl group which substituent is selected from i=he group consisting of the same or different C~_2 alkoxy group or C~_2 alkylthio group at the para-position, an unsubstituted C~_4 a:Lkyl group or a substituted C~_4 alkyl group which substituent is selected from the group consisting of one or more halogen atoms, hydroxyl groups, acetoxy groups, C~_4 alkoxy groups, halogenated C~_4 alkoxy groups, phenyl groups, halogenat:ed phenyl groups, or C~_4 alkylated phenyl ~> ~ groups, ~ wherein RZ' and R3' are each independently selected from the group consisting of a halogen atom, a cyano group, or a nitro group; and wherein one of RZ' and R3' is a hydrogen atom and the other is a halogen atom, a methyl group or a phenyl group, are excluded.
Among the imiolazole compounds represented by the general formula (I), preferred compounds of the present invention are illustraterd below.
- g _ B

Compounds of the general formula ( I ) wherein R, is a cyano group;
Compounds of the general formula (I) wherein RZ
and R~ each represents a hydrogen atom; a halogen atom; a nitro group; a c:yano group; a C1_~Z alkyl group which is optionally substituted with one or more halogen atoms, hydroxyl groups, C1_4 alkoxy groups, phenyl groups, halogenated phenyl groups, or C1_' alkylated phenyl groups;
a CZ_,o alkenyl group which is optionally substituted with one or more halogen atoms; a phenyl - 9a -~3~09 49 1 group which is optionally substituted with one or more halogen atoms, C1_4 alkyl groups, C1_4 alkoxy groups, halogenated Cl_q alkoxy groups or vitro groups; an -SOnR~
group, wherein R;. represents a Cl_6 alkyl group, a phenyl group which is optionally substituted with one or more halogen atoms; or an -NRgRg group, wherein Rg and Rg each represents a Cl_q alkyl. group, and n is 0, 1, or 2; or a -CONHRIO group, wherein Rlo represents a phenyl group which is optiona:Lly su~.bstituted with one or more halogen _ atoms, provided that R2 and R3 are not simultaneously a halogen atom;
Compounds of the general formula (I) wherein R4 is a Cl_6 alkyl group or an -NR11Ri2 group, wherein R11 and R12 each represents a C1_4 ;alkyl group;
Compounds of the general formula (I) wherein R2 is a hydrogen atom; a C1_12 alkyl group which is optionally substituted with one or more halogen atoms, phenyl groups, or halogenated phenyl groups; a C2_4 alkenyl group; a phenyl group which is optionally substituted with one or more halogen atoms, C1_4 alkyl groups, Cl_4 alkoxy groups, or halogenated C1_.4 alkoxy groups; a Cl_6 alkylthio group;
or a phenylthio group which is optionally substituted with one or more haloge n atoms;
Compounds of the general formula (I) wherein R3 is a hydrogen atom, a halogen atom, or a cyano group;

~3~09 49 1 Compound, of the general formula (I) wherein R4 is an -N(CH3)2 group;
Compounds of the general formula (I) wherein RZ is a Cl-12 alkyl group which is optionally substituted with one or more halogen atoms, phenyl groups, or halogenated phenyl groups; a C2._4 alkenyl group; a phenyl group which is optionally substituted with one or more halogen atoms; or a Cl_6 alkylthio group;
Compounds of t:he general formula {I) wherein R3 is l0 . a halogen atom; and ' Compounds of ithe general formula (I) wherein Rl represents a cyano group; R2 represents a C1_12 alkyl group or a phenyl group; R3 represents a chlorine atom;
and R4 represents an -D~(CH3)2 group.
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (I) described above, definitions of C~._4 alk:yl group and alkyl moieties of Cl_4 alkoxy group and Cl_4 ,alkylthio group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl groups. Definition of C1_6 alkyl group may include n-pentyl and n-hexyl groups in addition to the exemplified Cl_4 alkyl groups hereinabove. Definition of Ci_12 alkyl group may include heptyl, octyl, nonyl, and decyl groups in addition to the exemplified Cl_6 alkyl groups hereinabove. Definition of C3_6 cycloalkyl group may include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl group:. Df~finition of CZ_q alkenyl group may include an allyl group, etc. Definition of C2_6 alkenyl group may include a pe~ntenyl group, etc. in addition to the exemplified C2_4 alkenyl groups hereinabove.
Definition of C2_lo al.kenyl group may include a geranyl group, etc. in addition to the exemplified C2_6 alkenyl groups hereinabove. Definition of halogen atom may include chlorine, bromine, fluorine, and iodine atoms.

The novel imidazole compound represented by the general formula (I) described above can be prepared specifically by t:he following process:
(A]

Ri / I + Y-SOZR4 N~ ~R
H 3 (III) (II) to 150°C
Ri 1 to ~48 hours N

(I) wherein Ri, R2, R3, and R4 have the same meanings as described above; and Y is a halogen atom.
In the general formula (I) described above, compounds wherein Ri is a cyano group can also be prepared l0 by the following process: .

°

~340~ ~g [B]
R2 , Step-1 NC
NC -N' Y-S02R4 (III) N
H 10 to 150°C SOZR4 1 to 48 hours (II 1) (I-1) Step-2 _ RZ
n-C4H9Li/tetrahydrofuran NC
R3_.I N R3 -~80 to 30°C
1. to 24 hours S02Ra (I-2) In the general formula (I-2) described above wherein R3 is an -SR.i group, R~SSR~ can also be used instead of R3-I in Step-2 of the process [B] described above. In the foregoing formulae, R2, R3, R4, R~, and Y
have the same meanings as described above.
In the ~genera~l formula (I) described above, compounds wherein R1 is a cyano group, and R3 is a hydrogen atom, a chlorine atom, or a bromine atom can also be prepared by the' following process:

~~4~09 ~49~
, 102R4 - / R2n Step-1 R2..
1 NC I _ NC
N ,R ~~ Y-S02Rq ( I I I ) N R n H 3 10 t0 150°C
1 to 48 hours (II_2) (I-3) Step-2 n-C4H9Li/'tetrahydrofuran NC
R2._y ~ N R n -80 to~ 30°C
1 to 24 hours (I-4) In the general formula (I-4) described above wherein R2 is a.n -SP:~ group, R~SSR~ can also be used instead of R2-Y' in Step-2 of the process (C] described above; and wherein R2 is a -CH(OH)-813 group (wherein 813 is an alkyl group or an optionally substituted phenyl group), 813-CHO can also be used instead of R2-Y' in Step-2 of the process [C] described above. In the foregoing formulae, R2, R4, a,nd R~ have the same meanings as described above; R~," and R3" are simultaneously a ~3~Or ~~
1 hydrogen atom, a chlorine atom or a bromine atom; and Y' is a chlorine atom, a bromine atom, or a iodine atom.
In the general formula (I) described above, compounds- wherein R~, is a -CSNHZ group or a -CSNHCOR6 group can also be prepared by the following process:
[D]
R2 Step-1 R2 _. NC ~ I - NC
_ Y-SOZR4 (IrI) N R
'R3 10 t0 150°C
1 to 48 hours S02R4 (II 3) (I-5) Step-2 dioxane, triethylamine N R3 t0 70°C S02R4 0.1 t~o 5 hours (I-6) Step-3 _~ R6CHNC
acetone,, pyridine N ~R3 0 t0 li 0 ° C S02R4 0.5 to 5 hours (I-7) wherein R2, R3, R4, RE,, and Y have the same meanings as described above.
The process [A] and Step-1 of the processes [B]
through [D] described above are carried out, if necessary and desired, in the presence of a solvent and an acid acceptor.
Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, chloro-l0 benzene, etc.; cyclic: or acyclic aliphatic hydrocarbons such as chloro:Eorm, carbon tetrachloride, methylene chloride, dichloroetlnane, trichloroethane, n-hexane, cyclohexane, etc.; ethers such as diethyl ether, dioxane, tetrahydrofuran, etc.; ketones such as acetone, methyl 15 ethyl ketone, methyl isobutyl ketone, etc.; nitriles such as acetonitrile, propionitrile, etc.; and aprotic polar solvents such asc dime~thylformamide, N-methylpyrrolidone, dimethyl sulfoxide, su7.folane, etc.
As the acid acceptor, any of inorganic bases and 20 organic bases can be used. Examples of the inorganic base 134ag ~9 1 include alkali metal lhydroxides such as sodium hydroxide, potassium hydroxide, e~tc.; alkali metal or alkaline earth metal carbonates such as anhydrous potassium carbonate, anhydrous-calcium carbonate, etc.; alkali metal hydrides such as sodium hydride; alkali metals such as metallic sodium; etc. Further, as the organic base, metion may be made of triethylamine, etc.
The reaction described above can be carried out in the presence of a suitable catalyst. As the catalyst, l0 _ mention may be made of, for example, a phase transfer catalyst such as a quaternary ammonium derivative.
As the halogen atom shown by Y in the general formula (III) described above, mention may be made of a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom; of these, preferred is a chlorine atom.
In the reaci:ion scheme described above, the compounds represented by the general formula (III) are known compounds, and the compounds represented by the general formula (II) c:an be prepared by either one of the following processes.
(1) C1;i02R4 N R K2C~3. CH3CN N R3 g 3 10 to 150°C
1 to 48 hours S~2R4 - 1$ -v~409 4~
n-C4H9Li, RSNCS S R2 RSNHC
tetrahydrofuran ' -80 to 30°C N R3 1_ to 24 hours S02Rq RSNHC
50 to 100°C
1 to 12 hours H R3 (2) R2 n-C,iH Li O R2 dimet~ylformamide HC
N R tetrahydrofuran N R
-.BO to 30°C
S02R9 1 to 24 hours SO2R4 NH20H~HC1 .
HON=CH
pyridine N R
50 to 150°C
1 to 24 hours S~2Rq acetic anhydride NC
pyridine 50 to 1~i0°C H R3 1 to 24 hours H2S ~) R2 triethylamine pyridine N R3 to 70°C H
0.1 to 5 hours '~~~09 ~9 (3) R2 C1CH20CZH4Si(CH3)3 R2 dimethylformamide N R
R3 NaH, 10 to 70°C
1 to 12 hours CH20C2H4Si(CH3)3 C1CN, CH3C;N R2 HC1 --~- NC i -30 to 70°C ' 50 to 100°C
1 to 12 hours N R3 1 to 12 hours CH20C2H4Si(CH3)3 »2 Nc N 'R3 H
(4) 2 -halogenating agent ~ R2 NC I NC
-50 to 100°C
N 1 to 24 hours N
H H
(5) R

NC ~ I -- NC
to 150°C N
N 1 to 48 hours ~~~09 ~9 n-C4H9Li, R3-I ~ RZ HCl water NC
tetrahydrofuran 30 to 100°C
-80 to 30°C i R3 0.5 to 2 hours 1 to 24 hours l~2 NC
N ~R3 H
R
R~Z NH40H ~ 2 NC
:10 to 120°C
N R3 :L to 60 hours ~ R3 H

(7) /NH
RZ R3 ( CH30 ) ZCHC/~\ ~ HC1 ~CH3 CH3 \ R2' CH
CH3OH, 0 to 70°C
C2H50 NH:2 1 to 12 hours CH30 / N R3 H
(i) HC1 ii ) NH20H~HC1/pyridine Rz (iii)acetic anhydride NC
50 to 150°C N R3 1 to 24 hours H

~3~09 ~9 c8) O R2 ;NH40H . ~) R2 CH OC

!i0 to 150°C
H 'R3 :L to 100 hours H R3 I
50 to 110°C
1 to 12 hours H R3 O )Z2 ~R5NH2 ~~ R2 CH30'C ~ I - RSNH ~ I
0 to 150°C
'R3 1 to 50 hours H R3 ~) i~S
CH30 -O- P\, / --«OCH3 S R2 S ~S (I
RSNH
toluene N R3 H
(10) R
R2 NH3/02 ~ 2 CH3 ~ ( - ~- NC I
N N
H H

cll) R
;R2 - K2S208 : ~ 2 CH I --~ HOCH2 -N N
H H

Mn02 ~~ ~ ~'' RZ NH20H ~ HC1 HC - I HON=CH
N ~ N
H H

acetic anhydride NC
N
H
(12) R
C12~HC1 w 2 HC1 CH3 ~ I -~ C12C

H
R2 NH.40H ~ R2 CC13 ~ I --~ NC
N 'C1 N ~Cl H H

~34Q9 ~9 (13) R2 R2 .
NaCN
N - Q ~N electrode reaction H
R., R
ac5.d or alkali NC I NC

H
(14) R2 halogenating agent R2 n-C4H9Li ~ CuCN
Y

NC I acid or alkali NC
N
N
H

°

~~409 ~9 (15) C1COORa O R2 n-C4H9Li ~~ acid or alkali RaOC
S2 N S2 ..N
R~' ( i ) SOC12/ ( i i ) NH40H il R2 -- N . N
H ' H
POC13 or SOC1,, R2 ~ NC:
N
H
(16) ( CH20 ) n ~ Mn02 ~. HOCH2 O F;2 RZ
NH20H ~ HC1 HC I _~ HON=C
N Q N

~~~09 ~~
R2 acetic acid or alkali ~ anhydride HON=CH
N
H

NC
N
H
(17) . R2 dimethylformamide ~ I' . R2 n-C9H91Li HC
N Q N
R
NH20H~HCl 2 acid or alkali H:ON=CH-i~ N
acetic R
anhydride HON=CH ( - ~ NC
N~ N
H H

(la) R.2 Na/NH3 . R2 Mn02 HOCH2 . I HOCH2 r Q N N
H
R2 acetic NH20H~HC1 ~ ~ anhydride HON=CH-N
H

NC
N
H
(19) (i)CS2/(ii) acid or alkali - HSC
N N
H
R2 acetic NH20H~HC1 ~ ~ anhydride HON=CH
N
H

°

NC
N
H
(20) II R2 H2~~2 II / RZ
HSC ~ I -~ HOC
N N
H H
(i) SOC12/(ii) NH4OH O R2 II

N
H
POC13 or SOC_L2 R2 NC
N
H
(21) O
O

R Q ~ CIC1 o- CIHN R2 N Na013 ~HN
H II
O

~~~09 4~
trifluoro-acetic R2 _ R2 anhydride / NHg CF3 ( ~ NC /

N N
H H
(22) . CF3I / R2 _ NH3 :~ CF3 N by H N
_. H , .

N~ /
N
H
In the foregoing formulae, R2, R3, R4, R5, and Y
have the same n~eaninc~s as described above; X is a CF3 group or a CC13 group; Ra is an alkyl group; and Q is a protective group.
As the :protective groups for Q, an -SOZRb group, wherein Rb is a dialk:ylamino group, an alkyl group, or an optionally alky7.ated phenyl group; a -CH(Rc)-Rd group, wherein Rc is a hydrogen atom or a methyl group, and Rd is an alkoxy group, a phenyl group which is optionally substituted with, an alkyl group or an alkoxy group, or a -OC2HQSi(CH3)3, e~tc. are exemplified.
In each of the processes as described above, the reaction conditions such as reaction temperature, reaction _ 29 -~~~409 ~49 time, solvent, acid acceptor, alkali acceptor, etc, can appropriately be chosen from the conventionally known reaction conditions.
Further, the compounds of the formula CH3 ~ I in the reaction schemes of the processes N
H
( 10 ) , ( 11 ) , and ( 12 ) described above can be prepared by, for example, the following methods:
(23) or O
(24) R2 i~H3 Aq (25) R
NH2 CH -A ~ 2 oxidation 3 g ~ CH3 H
NH2 . H
H

~~~09 ~~
(26) R2 .
CH3 ~ I - TiCl3 - N
OH
Still further, the compounds of the formula in the reaction schemes of the processes N
H . ' (13), (21), and (22) described above can be prepared by, for example, the following methods:
(27) or ~O
(28) R2 R;Z Al HCONHZ R2 HCONH2 or ~O O

~~409 49 (29) R2 ~ ~ R2 R,2 A KSCN / ~ HN03 or 1 ~ HS
Al N
H
(30) R~, A1 guanidine or g _ A1 . N
' ~0 H
( i ) diazot~zatio;n/( ii ) reduction (31) A4-H:
\0 NH3 (32) oxidation H

H H

(33) Z'iCl3 N
OH
In the foregoing formulae, RZ has the same meanings as described above; Al is a halogen atom, an amino group, a hydroxyl group, or an alkanoyloxy group;
A2 is a -CONH2 group, a -C(NH)NH2.group, or a -C(NH)-A3 group, wherein A3 is an alkoxy group or an alkylthio group: and AQ is a fo:rmyl group.
The carbonyl group included in the above described formulae may bE~ in the latent form of, for example, acetal, thioacetal, cyclic acetal, cyclic thioacetal, etc.
Further, the formyl group represented by A4 may be in the latent form of, Eor example, acetal, hemiacetal, etc.
In each of the processes as described above, the reaction conditions such as reaction temperature, reaction time, solvent, acid acceptor, alkali acceptor, etc. can appropriately be chosen from the conventionally known reaction conditions.

Typical e~xampl~es of the intermediate' compounds represented by the general formula (II), for the imidazole compounds of the present invention represented by the general formula (I) are shown in Table 1.
Table 1 RZ
Ri- ~ I (I=) H
Intermediate Melting No. R~ R2 R3 Point (oC) 2 CN 3-trifluoromethyl- g 160-168 phenyl .

3 " C1 CH3 194-196 4 " 4-me~thoxyphenyl C1 150-155 " phen,~rl CH3 222-225 6 " " Hr 120-125 7 " 4-fluorophenyl H 211-213 " 4-met:hylphenyl " 228-232 9 " " Hr 142-144 " 4-fluorophenyl " 176-178 11 " 3,4-dichlorophenyl H 115-121 12 " 4-met;hylphenyl Cl 124-129 14 " n-C3H~ Cl 107-109 " phenyl " 149-151 C

a Table 1 (cont'd Intermediate , Melting No. R1 R2 R3 Point - -C~) 16 CN 3-methylphenyl C1 140-142 17 " 3,4-dimethylphenyl " 150-152 18 ~ " 4-fluorophenyl " 153-155 19 " 4-bromophenyl " 162-167 20 " 4-ethylphenyl " 141-145 21 " " . H 214-217 '22 " 3-methoxyphenyl " 218-220 23 " 4-nitrophenyl " 230-235 24 " 5-chloro-2-thienyl " 202-206 25 " SCH3 "

26 " phenylthio " 166-169 ~

27 " phenyl CN 207-215 29 " 2-naphthyl C1 196-149 30 " " H 253-255 31 " 4-nitrophenyl C1 189-191 32 " 4-chlorophenyl 8 215-224 33 " 4-chlorophenyl C1 ~ 178-181 34 " 2-chlorophenyl " 145-152 35 " " Br 152-156 36 " 4-isopropylphenyl Ii 180-184 37 " 4-methylthiophenyl " 217-219 B

~~~o~ ~~
'fable 1 (cont'd Intermediate ' M
g No . R:1 R2 R3 point -- (C) 3g CN 4-(2',2',2'-trifluoro- H 195-198 ethoxy)phenyl 39 ~~ CHa N02 125-130 40 " tert-C4H9 Br 120-127 41 " 2-methylphenyl H

4 2 ~ ~~ ~~ C1 43 " 5-methyl-2-furyl ' H 169-171 44 " 3,4-dimethoxyphenyl " 188-190 45 " 4-~ethoxyphenyl " 218-219 46 " 3-methyl-4-methoxy- " 199-205 phenyl 47 " 2-~thienyl " 195-203 4g " 4-(2',2',2'-trifluro- C1 164-166 et:hoxy ) phenyl 49 " " Br 150-155 50 " 3--methyl-4-methoxy- C1 145-149 phenyl 51 " 3--chloro-4-methyl- Br 190-194 phenyl 52 " CH3 CN 142-145 53 " C~,HS H 127-129 54 " " C1 138-140 55 ~~ n._C3g~ H 52-54 56 " ." I 106-109 57 " n._C4H9 H 83-85 Table 1 ( cont' d ) Intermediate , Melting No. R1- R2 R3 Point (oC) 58 CN n-C4H9 C1 107-109 59 " n-C5H11 H 89-92 60 " n-CSH11 C1 109-110 61 " iso-C3H~ H 88-91 62 " " C1 84-87 - 63 " iso-C4H9 . . H

~64 " " C1 142-145 65 " tert-C4H9 H 130-135 66 " " C1 120-124 67 " iso-C5H11 H 144-146 68 ~ " " C1 104-107 69 " cyclopropyl " 170-183 70 " cyclohexyl H 185-190 71 " " C1 130-133 72 " 3-chloropropyl " 117-120 7 3 " CH2(~CH3 "

74 " CH2l7C2H5 75 " ben:zyl " 144-146 76 " phenethyl " 147-152 77 " SCZH5 H 112-115 78 " " C1 128-131 79 " S-w-CQH9 H 97-99 80 " " C1 95-99 T<~ble 1 ( cont' d ) Intermediate , Melting No. Rl_ R2 Rg Point (°C) 81 CN 3-fluoropropyl Cl 82 " SOZN(CH3)2 H 175-180 83 " 3-chlorophenyl " 140-143 84 " " C1 124-128 85 " 2,3-dichlorophenyl H 202-206 -- 86 " " C1 198-204 87 " 3-chloro-4-methoxy- " 158-160 phenyl 88 " " Br 161-163 89 " 3-chloro-4-methyl- C1 165-169 phenyl 90 " 4-cyanophenyl H 240-244 91 " " C1 250-255 92 " " Br 239-244 93 " 4-ethoxyphenyl C1 151-153 94 " " Br 140-145 95 " 2-fluorophenyl H 190-195 96 " " C1 155-159 97 " 2-methoxyphenyl H 155-159 98 " " C1 223-230 99 " 3,4-methylenedioxy- H 228-231 . phenyl 100 " " C1 149-152 101 " " Br 166-169 ~~~09 49 The following three compounds are reference compounds and are specifically excluded from the present invention.
Table 11 R.1 ~ I III) N ~R3 H
' Intermediate Melting No. R1_ R2 R3 Point C°C) 1 CN Br H 196-201 13 " C1 H 150-153 28 " H F
- 38a -~~409 ~9 In the case that R2 and R3 are different from each other, the intEarmediate compounds represented by the general formula (II) described above include tautomers represented by the general formulae (II-a) and (II-b) described below:
H

R1 ~ I R1 ~ I
'R3 N 'R3 H
- . (II_a) ~ (II-b) wherein Rl, R2, a.nd R3 have the same meanings as described hereinabove. Ac<:ordingly, in the case that the imidazole compounds of the present invention represented by the general formula (I) are prepared using the compounds represented by t:he gE~neral formula ( II ) as a starting material, the imidazole compounds represented by the general formulae (I-a) and/or (I-b) described below can be obtained.
S02Rq w R2 R2 Rl ~ ( and/or Rl ~ I
i'' ~R3 N ~R3 S02:R4 (I_a) (I_b) ~34a9 4~
1 wherein Rl, R2, R3, and R4 have the same meanings as described hereinabove. In the case that R2 and R3 are different from each other, the imidazole compounds represented by the general formulae (I-a) and (I-b) are tautomers each other. The same also applies to the compounds represErnted ~by the general formulae (I-1), (I-5), (I-6). and (I-7) in. the processes [B] to [D] described hereinabove, etc.
The imidazole compounds represented by the general . formula (I-a) or (I-b) described- hereinabove can be separated concretely, for example, by methods [E-1] to [E
3] described below:
[E-1] Method by means of chromatography:
Each compound can be separated from a mixture of isomers of the general formulae (I-a) and (I-b) described above, by means of silica gel column chromatography, preparative high performance liquid chromatography, flash chromatography, etc. In the case of silica gel column chromatography, for example, n-hexane, carbon tetrachloride, methyle ne chloride, chloroform, ethyl acetate, or a mixture thereof can be used as a developing solvent.
[E-2] Method by means of recrystallization:
Each compound c:an be separated from a mixture of isomers of the general formulae (I-a) and (I-b) described above, using as a solvent fox recrystallization, for ~3~09 49 1 example, carbon tetrac:hloride, methylene chloride, chloro-form, 1,2-dichloroeth.ane, ethyl ,acetate, diethyl ether, tetrahydrofuran, acetone, or a mixture thereof.
[E-3] Method by means of decomposition:
Either compound can be separated from a mixture of isomers of the c~enera:~l formulae (I-a) and (I-b) described above, by the selective hydrolysis under conditions of from 0 to 80°C (preferably from room temperature to 50°C) for from 1 to 48 hours (preferably from 5 to 24 hours).
_ As the m.ixture~ of isomers used . in the methods [E-1] to [E-3] described above, it is preferred to use the mixture having a mixing ratio of both isomers as large as possible by appropriately choosing reaction conditions previously in ithe process [A] described above, for example, kind o1. solvent and acid acceptor and amounts thereof to be u:>ed, reaction temperature, reaction time, etc.
Further, in the case of preparing imidazole compounds wherein R1 is a -CSNHZ group or a -CSNHRS group, wherein R5 has the sarne meaning as described hereinabove from compounds wherein R, is a cyano group in the compounds represented by the general formula (I-b) separated by the method [E-1], [E-2], or [E-3] described above, such compounds c:an be obtained, for example, by the following method:

'134 09 49 [F]
SO,~R4 - S02R4 R2 g g S I R2 1 NC \ H2NC
N ~ R3 dioxane N R3 triethylamine R

_. R6CHNC
acei;.one - pyr:idine N Rg wherein R2, R3, R4, and R6, have the same meanings as described hereinabove.
Specific examples of synthesizing the imidazole compounds of the present invention are described below.
Synthesis Example 1 Synthesis of 2-cya,no-1-dimethylsulfamoylimidazole (Compound No,. 1) Thirty grams of 2-cyanoimidazole, 53.4 g of an-hydrous potassium carbonate and 600 ml of acetonitrile were mixed at room temperature. After reacting for 2 hours at the ref:luxincf temperature, the reaction mixture was cooled, and 55.6 g of dimethylsulfamoyl chloride was added thereto. The mixture was reacted again at the refluxing tempera~.ture f:or 2 hours.

After completion of the reaction, the reaction mixture was poured into water. Extraction with methylene chloride was carried out. After 'washing with water, the extract was driE~d ovE~r anhydrous sodium sulfate. The solvent was removed by distillation. The obtained residue was purified by ~;ilica gel column chromatography (develop-ing solvent: mE~thylene chloride) to give 28.0 g of 2-cyano-1-dimethylsulfamoylimidazole (Compound No. 1) having a melting point of from 74 to 76°C.
-- Synthesis Example 2 'Synthesis of 2-cyano-1-dimethylsulfamoyl-5-phenylthioimidazoler (Compound No. 10-b) In a four-necked flask were charged 12.0 g of 2 cyano-1-dimethylsulfamoylimidazole (Compound No. 1) and 240 ml of dry tetrahydrofuran in a nitrogen flow. While maintaining the mixture at -75°C or below with dry ice-acetone, 41.3 m:L of a 1.6 M n-butyl lithium hexane solution (manufac:tured by Aldrich) was gradually added dropwise to the mixture. After completion of the dropwise addition, the system was kept at the same temperature for 15 minutes. Then, a solution of 17 g of diphenyl disulfide in 30 ml of tetrahydrofuran was added dropwise to the mixture at ~-70°C or below. While stirring overnight, the temperature was gradually reverted to room temperature.
After completion of the reaction, the reaction mixture was poured into water. Extraction with 500 ml of ethyl acetate was carried out. After washing with water, '~~409 4~
1 the extract was dried over anhydrous sodium sulfate. The ethyl acetate wars removed by distillation, and the residue was purified by silica gel column chromatography (develop-ing solvent: methylE~ne chloride) to give 4.3 g of 2-cyano-1-dimethyl:~ulfamoyl-5-phenylthioimidazole (Compound No. 10-b) having a melting point of from 106 to 107°C.
ythesis Example 3 Synthesis of 4-chloro-2-cyano-1-dimethyl-sulfamoyl-5-n-prop:ylimidazole (Compound No. 16-b) -. [1] 4.8 g of 2-cyano-1-dimethylsulfamoyl-5-n-propylimidazole having a melting point of from 51 to 52°C
(Compound No. 3-b) was synthesized by the reaction of 12.0 g of 2-cyano-1-d:imethylsulfamoylimidazole (Compound No. 1) and 15.3 g of n-propyl iodide in a manner similar to Synthesis Example 2 described above.
[2] 4.8 g of 2-cyano-1-dimethylsulfamoyl-5-n-propylimidazo~e as obtained in [1] above, 40 ml of pyridine, and 11..4 g of pyridinium chloride were mixed, and the mixture was stirred at 90°C for 4 hours. After completion of th,e reaction, the pyridine was removed by distillation from the reaction mixture, and the residue was extracted wiith ethyl acetate. The extract was washed with water and then dried over anhydrous sodium sulfate.
Thereafter, the f:thyl acetate was removed by distillation, and the residue was purified by silica gel column chromatography (developing solvent: a mixture of ethyl acetate and n-he:Kane) and separated to give 2.46 g of 2-~3~09v9 1 cyano-4(5)-n-propylimidazole (Intermediate No. 55) having a melting point of from 52 to 54°C,.
[3] 2.3:5 g of 2-cyano-4(5)-n-propylimidazole as obtained in [2] above, 80 ml of chloroform, and 2.6 g of N-chlorosuccinimide were mixed, and the mixture was reacted at the refluxing temperature for 4 hours. After completion of the reaction, 200 ml of water was added to the reaction mixture. The resulting organic layer was washed with watE~r and then dried over anhydrous sodium _ sulfate. After drying, the chloroform was removed by distillation, and the residue was purified by silica gel column chromatography (developing solvent: a 1:1 mixture of ethyl acetate and n-hexane) and separated to give 2.2 g of 4(5)-chloro-~2-cyano-5(4)-n-propylimidazole (Inter-mediate No. 14) having a melting point of from 107 to 109°C
[4] 2.0 g of 4(5)-chloro-2-cyano-5(4)-n-propyl-imidazole as obtained :in [3] above, 30 ml of acetonitrile, 1.95 g of anhydrous potassium carbonate, and 1.86 g of dimethylsulfamoyl. chloride were mixed, and after gradually elevating the temperature, the mixture was reacted at the refluxing temperature for 1 hours. After completion of the reaction, the acetonitrile was removed by distillation from the reaction mixture. After pouring 100 ml of water into the residue, the :resulting mixture was extracted with 50 ml of methylene chloride. The extract was washed with 1 water and dried over anhydrous sodium sulfate. There-after, the methylene chloride was removed by distillation.
The residue was allowed to stand overnight, and the analysis thereof revea:Led that one of the two isomers in the mixture decomposed and returned to the starting 4(5)-chloro-2-cyano-5(4)-n--propylimidazole. The residue containing the other isomer was purified by silica gel column chromatography (developing solvent: methylene chloride) and sep~aratecl to give 1.1 g of 4-chloro-2-cyano-_ 1-dimethylsulfamoyl-5-n-propylimidazble (Compound No. 16-b) having a melting point of from 64 to 66°C.
Synthesis Example 4 Synthesis oi= 2-c,yano-1-dimethylsulfamoyl-4(5)-phenylimidazo~le (Cc>mpound No. 4) I11 In 320 ml of acetone was dissolved 23.04 g of 4(5)-phenylimidazole, and 12.14 g of anhydrous potassium carbonate was added to the solution. The mixture was heated at the re~fluxirig temperature for 2 hours. After cooling, 45 ml of an acetone solution containing 25.25 g of dimethylsulfarnoyl chloride was added dropwise to the mixture. After completion of the dropwise addition, the mixture was heated at the refluxing temperature for 4.5 hours to complete the reaction.
After completion of the reaction, the reaction mixture was cooled, and solid substances were removed by filtration. After the solvent was removed by distillation under reduced pressure, the residue was purified b~~ s~lica 1 gel column chromatography (developing solvent: methylene chloride) to gave 1'7.8 g of 1-dimethylsulfamoyl-4(5)-phenylimidazole having a melting point of from 96 to 100°C.
[2] In 290 ml. of tetrahydrofuran was dissolved 17 g of 1-dimethylsulfamoyl-4(5)-phenylimidazole as obtained in [1] above. The solution was cooled to -70°C in a nitrogen flow, and 51 ml of a 1.6 M n-butyl lithium hexane solution was added dropwise to the mixture over 30 _ minutes. After completion of the dropwise addition, the reaction mixturE~ was stirred at -70°C for 30 minutes.
Then, 12 ml of .a tetrahydrofuran solution containing 6 g of N,N-dimethylformamide was added dropwise to the mixture. After completion of the dropwise addition, the reaction mixture was reacted for 15 hours with stirring while slowly elevating the temperature to room temperature.
After completion of the reaction, the reaction mixture was poured into ice water and extracted with ethyl acetate. After washing the extracted layer with water, the extracted :Layer was dried over anhydrous sodium sulfate. The aolvent was distilled off under reduced pressure, and t:he residue was purified by silica gel column chromatography (developing solvent: a 1:2 mixture of ethyl acetate anf, n-hexane) to give 12.8 g of 1-1~4~09 49 1 dimethylsulfamoyl-2-formyl-4(5)-phenylimidazole having a melting point of from 86 to 89°C.:
[3] In 120 ml of pyridine were dissolved 11.16 g of 1-dimethylsulfamoyl-2-formyl-4(5)-phenylimidazole as obtained in [2] above and 5.56 g of hydroxylamine hydrochloride, and 24 ml of acetic anhydride was added dropwise to the solution at room temperature. After completion of t:he dropwise addition, the temperature was gradually raised, and the mixture was reacted at 100°C for . 12 hours.
After completion of the reaction, the solvent in the reaction mixture was removed by distillation under reduced pressure. Then, 125 ml of water was added to the residue, and the precipitated solid was separated by filtration. The crude product was dissolved in ethyl acetate and purified by silica gel column chromatography (developing sol~~ent: ethyl acetate) to give 5.55 g of 2-cyano-4(5)-phenylimidazole having a melting point of from 203 to 205°C.
[4] In 88 ml of acetone was dissolved 1.7 g of 2-cyano-4(5)-phenylimidazole as obtained in [3] above, and 1.7 g of anhydrous potassium carbonate was added to the solution. The mixture was heated at the refluxing temperature for 2 hours.
After cooling, 6 ml of an acetone solution containing 1.7 c3 of dimethylsulfamoyl chloride was added '~ 3 4~ ~ 9 ~ ~
1 dropwise to the mixture. After completion of the dropwise addition, the mixture was heated at the refluxing temperature for 2 hours to complete the reaction.
After c:omplet:ion of the reaction, the reaction mixture was cooled, and solid substances were removed by filtration. After the solvent was removed by distillation under reduced pressure, the residue was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. The solvent was _ removed by distillation under reduced pressure to give 2 g of 2-cyano-1-dimethylsulfamoyl-4(5)-phenylimidazole (Compound No. ~E) having a melting point of from 101 to 102°C.
S'tnthesis Example 5 Synthesis of 4(5)-ch7.oro-2-cyano-1-dimethylsulfamoyl-5(4)-phenylimidazole (Compound No. 17) and 4-chloro-2-cyano-1-dimethylsulfamo:yl-5-phenylimidazole (Compound No. 17-b) [1] In 100 ml of chloroform was dissolved 1.352 g of 2-cyano-4(5)-phenylimidazole, and 1.175 g of N-chloro succinimide was added to the solution. The mixture was reacted upon heating at the refluxing temperature for 4 hours.
After completion of the reaction, the reaction mixture was poured into water and extracted with chloro-form. After washing with water, the extracted layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was - ~9 -'3409 49 1 purified by silica gel column chromatography (developing solvent: methylene chloride) to_. give 1.28 g of 4(5)-chloro-2-cyano-5(4)-phenylimidazole (Intermediate No. 15) having a melting point: of from 149 to 151°C.
[2] In 6 ml of acetone was dissolved 0.43 g of 4(5)-chloro-2-cyano-5I;4)-phenylimidazole as obtained in [1] above, and 0.29 g of anhydrous potassium carbonate and 0.36 g of dimethylsulfamoyl chloride were added to the solution. ' The mixture was reacted upon heating at the . refluxing temperature for 30 minutes.
After c:omple~:.ion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. After washing with water, the extracted layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was then purified by silica gel column chromatography ( developing solvent : methylene chloride ) to give 0 . 5 g of 4(5)-chloro-2-cyano-1-dimethylsulfamoyl-5(4) phenylimidazole (Compound No. 17) having a melting point of from 106 to :109°C.
As a result of analysis by means of NMR spectra, the compound dE~scribE~d above was an isomer mixture of 4-chloro-2-cyano-1-dimE:thylsulfamoyl-5-phenylimidazole and 5-chloro-2-cyan~o-1-dimethylsulfamoyl-4-phenylimidazole in almost equal ratios.

'3409 49 1 ~ [3] After allowing to stand for 24 hours at room temperature, 2.9~ g of the mixture of these isomers as obtained in a manner :similar to [ 2 ] above was purified by silica gel column chromatography (developing solvent:
methylene chloride) to give 1.15 g of 4-chloro-2-cyano-1 dimethylsulfamoy:l-5-ph~enylimidazole (Compound No. 17-b) having a melting point of from 109 to 112°C. Further, by purification of ;end isolation from this compound, 0.7 g of 4(5)-chloro-2-cyano-5(4)-phenylimidazole (Intermediate No.
. 15) was also obtained.
~zthesis Example 6 Synthesis of 4(5)-c:hloro-2-cyano-1-dimethylsulfamoyl-5(4)-(4-methylphenyl)imidazole (Compound No. 18) and 4-chloro-2-cyano--1-dimethylsulfamoyl-5-(4-methylphenyl)-imidazole (Compound No. 18-b) An isomer mixture (Compound No. 18), having a melting point of from 101 to 108°C, of 4-chloro-2-cyano-1-dimethylsulfamoyl-5-(4-methylphenyl)imidazole and 5-chloro-2-cyano-1~-dimet~hylsulfamoyl-4-(4-methylphenyl)imid-azole was obtair~ed~from 4(5)-(4-methylphenyl)imidazole in a ratio of 6:4 i:n a manner similar to Synthesis Examples 4 and 5 described above. After 0.75 g of the isomer mixture was reacted at 40°C for 8 hours, the reaction mixture was purified by silica gel column chromatography (developing solvent: methylene chloride) to give 0.45 g of 4-chloro-2-cyano-1-dimethylsulf,amoyl-5~(4-methylphenyl)imidazole (Compound No. 18-b) having a melting point of from 133 to 134°C. Further, by purification of and isolation from 1 this compound, 0.15 g of 4(5)-chloro-2-cyano-5(4)-(4-methylphenyl)imidazole (Intermediate No. 12) having a melting point of from 124 to 129°C was also obtained.
~zthesis Example 7 Synthesis of 4(5)-chloro-5(4)-(4-chlorophenyl)-2-cyano-1-dimethylsulfamoylimidazole (Compound No. 23), 4-chloro-5-(~4-chlorophenyl)-2-cyano-1-dimethyl-sulfamoylimidazole (Compound No. 23-b) and 5-chloro-4-(4-chlorophE~nyl)-2-cyano-1-dimethylsulfamoylimid-azole (Compound No. 23-a) In a manner similar to Synthesis Examples 4 and 5 described above, 0.80 g of an isomer mixture (Compound No.
23)~, having a melting point of 108°C, of 4-chloro-5-(4-chlorophenyl)-2-c:yano-:1-dimethylsulfamoylimidazole and 5-chloro-4-(4-chlorophen.yl)-2-cyano-1-dimethylsulfamoylimid-azole was obtained from 4(5)-(4-chlorophenyl)imidazole.
The isomer mixture was purified by silica gel column chromatography (developing solvent: methylene chloride).
The eluate of the second fraction was concentrated and recrystallized from me~thylene chloride to give 0.16 g of 4-chloro-5-(4--chlorophenyl)-2-cyano-1-dimethyl-sulfamoylimidazol.e (Compound No. 23-b) having a melting point of from 11.7 to 120°C. Further, the eluate of the first fraction was likewise concentrated and recrystalliz-ed from methylene chloride to give 0.50 g of 5-chloro-4-(4-chlorophenyl)-2-cyano-1-dimethylsulfamoylimidazole (Compound No. 23--a) having a melting point of from 133 to 138°C.
w 1~3~09 49 1 ~nthesis Example 8 Synthesis of 1-~dimethylsulfamoyl-4(5)-phenyl-imidazole-2-carbothioamide (Compound No. 49) In 30 ml of dioxane was dissolved 1.0 g of 2 cyano-1-dimethylsulfamoyl-4(5)-phenylimidazole (Compound No. 4), and 0.:36 g of triethylamine was added to the solution. The mixture was heated to 40 to 50°C while stirring, and .a hydrogen sulfide gas was introduced thereinto for one hour and 25 minutes. Thereafter, the m-fixture was reacted at 40 to 50°C for an additional 50 minutes.
After completion of the reaction, the reaction mixture was cooled, poured into water, and extracted with ethyl acetate. After washing with water, the extracted layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: a. 1:3 mixture of ethyl acetate and n-hexane) to give 0.8 g of 1-dimethylsulfamoyl-4(5)-phenyl-imidazole-2-carbothioamide (Compound No. 49) having a melting point o:E from 155 to 175°C. Crystals of 4(5)-phenylimidazole-2-carbothioamide were also obtained in a small quantity.
~nthesis Example 9 Synthesis of 2-cyano-1-isopropylsulfonyl-4(5)-phenylimidazole (C:ompound No. 101) ~3~09 49~
1 One gram of 2-cyano-4(5)-phenylimidazole, 0.98 g of anhydrous potassium carbonate, and 30 ml of aceto-nitrile were mi:Ked at: room temperature. After reacting for 2 hours at the refluxing temperature, the reaction mixture was cooled, and a solution of 1.0 g of isopropylsulfonyl chloride in 5 ml of acetonitrile was added thereto. The mixture was reacted again at the refluxing temperature for 1.5 hours.
After completion of the reaction, the reaction . mixture was poured invto water. Extraction with methylene chloride was carried out. After washing with water, the extract was dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, and t:he rE~sidue was purified by silica gel column chromatography (developing solvent: methylene chloride) to give 1.4 g of 2-cyano-1-isopropylsulfonyl-4(5)-phenylimidazole (Compound No. 101) having a melting point of from 80 to 83°C.
S~~thesis Example 10 Synthesis of 9E(5)-(2-thienyl)-2-cyano-1-di-methylsult:amoyl:imidazole (Compound No. 6) [ 1 ] To 150 ml of formamide was added 25 g of 2-(bromoacetyl)thiophene. The mixture was reacted at 180 to 190°C for 2 hours.
After completion of the reaction, the reaction mixture was poured into water, and concentrated hydrochloric acid was added thereto to render the system 1 3 ~4 ~9 49 acidic. Then, washing with methylene chloride was carried out. After neut:raliz:ing with ammonia water, the aqueous phase was extracted with methylene chloride. After washing with water, the extract was dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressures to give 11 g of 4(5)-(2-thienyl)-imidazole.
[2] To 200 ml. of acetonitrile were added 11.6 g of dimethylsulf.amoyl chloride, 11.1 g of anhydrous _ potassium carbonate, and 11 g of 4(5)-(2-thienyl)imidazole as obtained in [1] above. The mixture was reacted for 2 hours while stirring.
After completion of the reaction, the reaction mixture was poured into water. Extraction with ethyl acetate was carried Out. After washing with water, the extract was driE~d ovE:r anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure to give 14.5 g of 4(5)-(2-thienyl)-1-dimethylsulfamoyl-imidazole.
[3] In 120 m:L of anhydrous tetrahydrofuran was dissolved 9.5 g of 4(5)-(2-thienyl)-1-dimethylsulfamoyl-imidazole as obtained in [2] above. In a nitrogen flow, 26.2 ml of a 1.6 M n-butyl lithium hexane solution was added dropwise to the solution at -78°C, and the mixture was stirred at the same' temperature for 15 minutes. Then, 20 ml of a tetrahydrofuran solution having dissolved ~3~09 49 therein 5.4 g of N,N-dimethylformamide was added dropwise to the mixture. After completion of the dropwise addition, the te~mperat:ure was gradually reverted to room temperature to complete the reaction.
After completion of the reaction, the reaction mixture was poured into water. Extraction with ethyl acetate was carried out. After washing with water, the extract was dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure _ to give 5.4 g of 4(5)-(2-thienyl)-2-formyl-1-dimethyl-sulfamoylimidazole.
[ 4 ] In '54 ml of pyridine were dissolved 2. 6 g of hydroxylamine hydrochloride and 5.4 g of 4(5)-(2-thienyl)-2-formyl-1-dimethylsulfamoylimiazole as obtained in [3]
above. The solution was stirred at room temperature for 15 minutes. Then, 10 ml of acetic anhydride was gradually added to the solution, followed by reacting at 60 to 70°C
for 2 hours.
After completion of the reaction, the reaction mixture was poured into water. Extraction with ethyl acetate was carried out. After washing with water, the extract was dried ovE~r anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: a 2:1 mixture of ethyl acetate and n-hexane) to give 1.2 g of 4(5)-(2-1 thienyl)-2-cyanoimiazole (Intermediate No. 47) having a melting point of from 195 to 203°C.
[5j To 50 ml of acetonitrile were added 1.1 g of dimethylsulfamoyl chloride, 1.0 g of anhydrous potassium carbonate, and ?L.2 g of 4(5)-(2-thienyl)-2-cyanoimidazole as obtained in [4] above. The mixture was reacted at the refluxing temperature for 2 hours.
After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl . acetate. After drying the extract' over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and t:he residue was purified by silica gel column chromatography (developing solvent: methylene chloride) to give 1.3 g of 4(5)-(2-thienyl)-2-cyano-1-dimethylsulfamoylimidazole (Compound No. 6) having a melting point of from 145 to 15d°C
ythesis Example 11 Synthesis of 4(5)-chloro-2-cyano-1-dimethyl-sulfamoyl-5(4)-iso~propylimidazole (Compound No.
125) and 4--chloro-2-cyano-1-dimethylsulfamoyl-5 isopropylimidazole (Compound No. 125-b) [lj 360 g of formamide was heated to 180°C, and 102 g of 1-hydroxy-3-methyl-2-butanone (prepared in a manner as described in Lipshutz and Morey, J. Orq. Chem., 48, 3745 (1983)) ways added dropwise thereto over 30 minutes. After completion of the dropwise addition, the mixture was reacted at 180°C for one hour.

~~4 09 49 1 After completion of the reaction, the reaction mixture was cooled ;end poured =into ice water. The resulting mixture ways adjusted at a pH of 1 with hydrochloric acid and washed with methylene chloride. The aqueous layer was adjusted at a pH of 4 to 5 with ammonia water. 5 g of activated charcoal was added thereto, and the mixture was stirred for one hour. The activated charcoal wa.s removed by filtration, and the filtrate was adjusted at a pH of 8 with ammonia water.
. Then, extraction with methylene chloride was carried out, and the extract was dried over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure to give 13 g of 4(5)-isopropylimidazole.
[ 2 J In :300 ml of acetonitrile was dissolved 11. 8 g of 4(5)-isopropylimiiiazole as obtained in [1) above, and 18 g of anhydrous potassium carbonate was added to the solution. The rnixture~ was refluxed for 30 minutes, and after cooling, :L7 g of dimethylsulfamoyl chloride was added dropwise thereto. After completion of the dropwise addition, the mixture was refluxed to complete the reaction.
After completion of the reaction, the reaction mixture was cooled, poured into water, and then extracted with ethyl acetat:e. T'he extracted layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the ~3~~9 ~~
1 residue was purified by silica gel column chromatography (developing solvent: methylene chloride) to give 13 g of 1-dimethylsulfamoyl-4(5)-isopropylimidazole.
[3] In 200 ml. of tetrahydrofuran was dissolved 13 g of 1-dimeth;ylsulf'amoyl-4(5)-isopropylimidazole as obtained in [2] above. The solution was cooled to -70°C
in a nitrogen flow, and 38 ml of a 1.6 M n-butyl lithium hexane solution was added dropwise thereto over 15 minutes. After completion of the dropwise addition, the . mixture was stirred at -70°C for 30 minutes. After dropwise addition of 5.6 g of N,N-dimethylformamide, the mixture was reacted with stirring for 15 hours while slowly elevating the temperature to room temperature.
After completion of the reaction, the reaction mixture was poured into ice water and extracted with ethyl acetate. The extracted layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off uncter reduced pressure to obtain 8.6 g of 1 dimethylsulfamoyl.-2-formyl-4(5)-isopropylimidazole.
[4] In 7L00 ml of pyridine were dissolved 8.5 g of 1-dimethylsulfamoyl-2-formyl-4(5)-isopropylimidazole as obtained in [3] above and 4.8 g of hydroxylamine hydrochloride, and 10 ml of acetic anhydride was added dropwise to the solution at room temperature. After completion of the dropwise addition, the temperature was ~~~409 49 1 gradually elevated, and the mixture was reacted at 80 to 90°C for 5 hours.
After cc>mplet~~.on of the reaction, the solvent in the reaction mixture was distilled off under reduced pressure. To the residue was added water, and the mixture was extracted with ethyl acetate. The extracted layer was washed with dilute hydrochloric acid and then with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to give 2.35 g of 2-, cyano-4(5)-isopropylim:idazole (Intermediate No. 61) having a melting point of from 88 to 91°C.
[ 5 ) In .BO ml of methanol was dissolved 2 g of 2-cyano-4(5)-isopropylimidazole as obtained in [4] above, and 2.1 g of N-chlorosuccinimide was added to the solution. The m~.xture was stirred at room temperature for hours and then reacted at 40°C for 8 hours.
After completion of the reaction, the methanol in the reaction mixture was distilled off under reduced pressure. To the residue was added water, and the mixture 20 was extracted with ethyl acetate. The extracted layer was washed with water and dried over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure, and the residue w,as purified by silica gel column chromatography (developing solvent: methylene chloride) to give 1.67 g of 4(5)-ch:loro-2-cyano-5(4)-isopropylimidazole ~~~09 ~9 1 (Intermediate No. 62) having a melting point of from 84 to 87°C.
[ 6 ] In 30 ml of acetonitrile was dissolved 1.6 g of 4(5)-chloro-2-cyano-5(4)-isopropylimidazole as obtained in [5] above, and l.SEi g of anhydrous potassium carbonate was added to the solution. The mixture was refluxed for 30 minutes. After cooling, 1.49 g of dimethylsulfamoyl chloride was added dropwise thereto. After completion of the dropwise addition, the mixture was refluxed for 15 _ minutes to complete the reaction.
After completion of the reaction, the reaction mixture was cooled, poured into water, and then extracted with ethyl acetate. The extracted layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: methylene chloride) to give 2.1 g of 4(5)-chloro-2-cyano-1--dimethylsulfamoyl-5(4)-isopropyl-imidazole (Compound No. 125).
As a result of analysis by means of NMR spectra, the compound described above 'was an isomer mixture of 4-chloro-2-cyano-1-dimet:hylsulfamoyl-5-isopropylimidazole and 5-chloro-2-c.yano-1-dimethylsulfamoyl-4-isopropylimid-azole in a proportion of about 2:1.
[7] After allowing to stand for 5 days at room temperature, 2.1 g of the isomer mixture as obtained in 'l 3 ~ 09 49 1 [6] above was purified by silica gel column chromatography (developing solvent: methylene chloride) to give 1 g of 4-chloro-2-cyano-:L-dimethylsulfamoyl-5-isopropylimidazole (Compound-No. 125-b) having a melting point of from 75 to 82°C (decomposed). Further, by purification of and isolation from this compound, 4(5)-chloro-2-cyano-5(4)-isopropylimidazole (Intermediate No. 62) was also obtained.
Synithesis Example 12 . Synthesis of ~E-chloro-1-dimethylsulfamoyl-5-n-propyl-imidazole-2-ca:rbothi~oamide (Compound No. 185-b) [lJ In a four-necked flask were charged 6.0 g of 2-cyano-4,5-dichloro-1-~dimethylsulfamoylimidazole having a melting point of from 100 to 103°C and 180 ml of dry tetrahydrofuran in a nitrogen flow. While maintaining the mixture at -75°C or below with dry ice-acetone, 15.3 ml of a 1.6 M n-butyl lithium hexane solution (manufactured by Aldrich) was gradually added dropwise to the mixture.
After completion of thEa dropwise addition, the system was kept at the same' temperature for 15 minutes. Then, a solution of 5.7 g of n-propyl iodide in 15 ml of tetrahydrofuran w.as added dropwise to the mixture at -70°C
or below. While stirring overnight, the temperature was gradually reverted to room temperature.
After completion of the reaction, the reaction mixture was poured into water. Extraction with 500 ml of methylene chloride was carried out. After washing with °

~3~09 49 1 water, the extract was dried over anhydrous sodium sulfate. The methylene chloride was removed by distillation, and the residue was purified by silica gel column chromatc>graph:y (developing solvent: methylene chloride) and then again purified by silica gel column chromatography (developing solvent: a mixture of ethyl acetate and n-hexane) to give 2.8 g of 4-chloro-2-cyano-1-dimethylsulfamoy:l-5-n-propylimidazole (Compound No. 16-b) having a melting point of from 66 to 68°C.
. [ 2 ] In a four-necked flask were charged 2 . 7 g of 4-chloro-2-cyano-1-dimethylsulfamoyl-5-n-propylimidazole as obtained in [1] above, 40 ml of dioxane, 1.0 g of triethylamine, and 0.8 g of pyridine. Into this mixture was introduced a hydrogen sulfide gas at 20 to 25°C for about 30 minutes until the starting materials had disappeared.
After completion of the reaction, the reaction mixture was poured into water, and precipitated crystals were filtered by means of a Nutsche and dried. The resulting crystals wE~re purified by silica gel column chromatography (;developing solvent: methylene chloride) and separated to give 2.3 g of 4-chloro-1-di methylsulfamoyl.-5-n-propylimidazole-2-carbothioamide (Compound No. 18!5-b) having a melting point of from 160 to 162°C.

X3409 4~
1 Synthesis Example 13 Synthesis of N-~propionyl-4-chloro-1-dimethylsulfamoyl-5-n-propylimidazole-2-carbothioamide (Compound No. 187-b) Into a four-necked flask were charged 2.0 g of 4-_5 chloro-1-dimethylsu,lfamoyl-5-n-propylimidazole-2-carbothioamide (C:ompound No. 185-b), 24 ml of acetone, and 1.12 g of pyridine. 1.19 g of propionyl chloride was added dropwise to the mixture at 0 to 5°C. After completion of t:he dropwise addition, the reaction was carried out at 30 to 35°C for one hour and at the refluxing temperature for an additional 30 minutes with stirring.
After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The ex:tractE~d layer was washed with water and dried over anhydrous sodium sulfate. Thereafter, the ethyl acetate was removed by distillation, and the residue was purified by silica gel column chromatography (developing solvent: methylene chloride) and separated to give 1.02 g of N--propionyl-4-chloro-1-dimethylsulfamoyl-5-n-propylimidazole-2-carbothioamide (Compound. No. 187-b) having a melting point of from 150 to 152°C.
Synt=hesis Example 14 Synthesis of 2-cyano-1-dimethylsulfamoyl-4,5-diphenyl-thioimidazole (Compound No. 141) [1] 8.0 g of 2-cyano-1-dimethylsulfamoyl-5-phenylthioimidazole (Compound No. 10-b) as obtained in a ~~09 49 1 similar manner to Synthesis Example 2 described above, 60 ml of methanol, and 60 ml of ,a 7% hydrochloric acid aqueous solution were charged, and the mixture was reacted with stirring at 40 to 50°C for 2 hours. After completion of the reaction, the reaction mixture was rendered weakly alkaline with ammonia, and precipitated crystals were separated by filtration and dried to give 4.2 g of 2-cyano-4(5)-phenylthioimidazole (Intermediate No. 26) having a melting point of from 166 to 169°C.
l0 - [2] To a mixture of 4.2 g of 2-cyano-4(5)-phenylthioimidazole as, obtained in [1) above, 80 ml of acetonitrile, and 3.1 g of anhydrous potassium carbonate, was added 3.4 g of dimethylsulfamoyl chloride. The resulting mixture' was reacted at the refluxing temperature for one hour. After completion of the reaction, the reaction mixture was cooled, and solid substances were filtered. The solvent in the filtrate was removed by distillation, and the residue was purified by silica gel column chromatography (developing solvent: methylene chloride) and separated to give 5.8 g of 2-cyano-1-dimethylsulfamoyl.-4(5)--phenylthioimidazole (Compound No.
10).
[3] In a four-necked flask were charged 5.8 g of 2-cyano-1-dimeth;ylsulfamoyl-4(5)-phenylthioimidazole as obtained in [2] above and 150 ml of dry tetrahydrofuran in a nitrogen atmo:;phere,, and 12.9 ml of a 1.6 M n-butyl 1 lithium hexane solution (manufactured by Kanto Kagaku) was added dropwise to the mixture; while maintaining the temperature at -75°C or below with dry ice-acetone. After completion of the dropwise addition, the mixture was kept at the same temperature for 15 minutes, and 20 ml of a solution of 5.2 ~g of diphenyl disulfide in tetrahydrofuran was added dropwise thereto at -70°C or below. Thereafter, the mixture was returned to room temperature. After completion of t:he rE~action, the reaction mixture was _ extracted with ei:hyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. The solvent was removed by distillation, and the residue was purified by silica ge:l column chromatography (developing solvent: methylene chloride) and separated to give 1.7 g of 2-cyano-1-dirnethyl;sulfamoyl-4,5-diphenylthioimidazole (Compound No. 141) having a melting point of from 98 to 101°C.
Synthesis Example 15 Synthesis of 9:-bromo-2-cyano-1-dimethylsulfamoyl-5-n-propylimidazole (Compound No. 157-b) [1] 2 - C y a n o - 4 , 5 - d i b r o m o - 1 -dimethylsulfamoylimidazole having a melting point of from 118 to 120°C wa.s synthesized from 2-cyano-4,5-dibromo-imidazole having a melting point of from 200 to 203°C in a similar manner to Synthesis Example 1 described above.
[2] In a, 200 ml four-necked flask were charged 5 g of 2-cyano-4,5-dibromo-1-dimethylsulfamoylimidazole as ~ 3.4 49 49 1 obtained in [1) above and 120 ml of dry tetrahydrofuran in a nitrogen flow. While maintain~.ng the mixture at -75°C
or below with dry ice-acetone, 9.6 ml of a 1.6 M n-butyl lithium hexane solution (manufactured by Aldrich) was gradually added dropwise to the mixture. After completion of the dropwise addition, the system was kept at the same temperature for 15 minutes. Then, a solution of 3.6 g of n-propyl iodide in 1:5 ml of tetrahydrofuran was added dropwise to the mixture at -75°C or below. While _ stirring, the temperature was gradually reverted to room temperature.
After completion of the reaction, the reaction mixture was extracted with ethyl acetate. After washing with water, the extract was dried over anhydrous sodium sulfate. The ethyl acetate was removed by distillation, and the residue' was purified by silica gel column chromatography (developing solvent: methylene chloride) to give 2.1 g of 4-bromo-2-cyano-1-dimethylsulfamoyl-5-n propylimidazole (Compound No. 157-b) having a melting point of from 93 to 94°'C.

Typical examples of the imidazole compounds (general formula (I)) of the present invention are shown in Table 2.
Table 2 R1 I (I) Compound Melting No. Rl _ RZ R3 R4 Point (C) 1 CN H H -N(CH3)2 74-76 2 " CH3 " " 78-83 3 " n-C H " "

4 " phenyl " " 101-102 " 4-chlorophenyl " " 148-149 6 " 2-thienyl " " 145-150 7 " 5-chloro-2- " " 145-148 thienyl 8 " 5-bromo-2- " " 138-140 thienyl 9 " SCH " "

" phe:nylthio " "

11 " 2-c'.hlorophenyl " " 118-121 12 " 4-nitrophenyl " " 107-108 13 " 4-trifluoro- " "

me tlhylphenyl 14 " H C1 "

Table 2 ( cont' d ) Compound Melting No. R1 _ RZ R3 Rg Point (°C) 15 CN CH3 C1 -N(CH3)2 16 " n-C H " "

17 " phenyl " " 106-109 18 " 4-methylphenyl " " 101-108 19 " 3-methylphenyl " " 90-95 20 " 2-methylphenyl " "

21 " 3,4-dimethyl- " " 95-105 phenyl 22 " 4-methoxyphenyl " " 102-107 23 " 4-chlorophenyl " " 108 24 " 2-c:hlorophenyl " "

25 " 3,4-dichloro- " " 99-105 phenyl 26 " 4-f.luorophenyl " " 105-107 2 " SCH. " "
7 .3 28 " phenylthio " "

29 " H Br "

30 " CH " "

31 " ter't-C4H9 " " 88-90 32 " phenyl " "

33 " 4-methylphenyl " " 106-108 34 " 4-tort-butyl- " " 105-110 phenyl 35 " 4-methoxyphenyl " " 96-99 Table 2 (co nt'd) Compound Melting No. Rl _ R2 R3 R4 Point (C) 36 CN 4-f~luorophenyl Br -N(CH3)2 87-93 37 " 4-c:hlorophenyl " "

38 " 1,2-dibromo- C1 "

ethyl 39 " C2H5 Br "

40 " -CH2CH=CH2 " "

41 " 4-b~romophenyl C1 " 110-116 42 " 4-isopropyl- " "

phenyl 43 " 2-naphthyl " 124-126 44 " CH3 CH3 " 52-54 45 " phenyl " " 101-105 46 " " SCH "

47 " " phenyl" 148-149 48 " " CN " 124-129 49 phenyl H " 155-175 -CSNH:Z

50 " 4-chlorophenyl " " 197-201 51 " phenyl C1 " 110-130 52 " H Br " 140-144 53 " phenyl " "

54 CN 3,4-dimethoxy- H "

phenyl 55 " 3-methyl-4- C1 "

met:hoxyphenyl ~~409 49 Table 2 (cont'd) Compound Melting No. R1 _ RZ R3 Rg Point (°C) 56 CN 4-ethylphenyl C1 -N(CH3)2 57 " phenylthio Br "

58 " benzyl " "

59 " 3-chloropropyl H "

60 " -SO C H " "

61 " 3-fluoropropyl C1 "

62 " 4-methylthio- H "

phenyl 63 " vinyl C1 "

64 " 5-methyl-2- H "

thienyl 65 " 2-chlorophenyl Br "

66 " 3,4-dichloro- H " 139-142 phenyl 67 " 4-(2',2',2'- C1 "

trifluoroethoxy )-phenyl 68 ~~ ~~ Br 69 " -CH20H H "

70 " 3-chlorophenyl C1 "

71 " 3-fluorophenyl " "

72 " 2-fluorophenyl " " 96-101 7 " -SC:HZCH=CH2 H "

74 " CH3 N02 " 110-117 ~34~9 49 Table 2 (cont'd) Compound Melting No. R1 _ R2 R3 Rg Point (°C) 75 CN I ~ H -N(CH3)2 -(:H -(1,2-diphenylethyl) OH
7 6 " -CH -O
(a-hydroxybenzyl) OH
77 " -CH-~ C1 " "
(4-chloro-a-hydroxybenzyl) O
7 8 " -CI'.-~- C l (4-chlorobenzoyl) 79 " acetyl " "
S O
80 -CI NHICCH3 phenyl " "
(N-acetylthio-carbamoyl) S O
81 -CI NHICCH2CH2C1 " " "
(N-(3-chloro-propionyl)-thiocarbamoyl]
_ 72 -'3409 49 Table 2 (cont'd) Compound Melting No. R1 _ R2 R3 R4 Point (°C) 82 N-acetyl-- CH3 H -N(CH3)2 thiocarba-moyl S O

8 -yNHC -C

(N-benzoyl thio-carbamoyl) 84 CN 5-methyl-2- " " 120-124 furyl 85 " C2H;5 C1 1-piperid-inyl 86 " " " phenyl 87 " 4-(chloro- H -N(CH3)2 142-146 methylthio)-phenyl 88 " CH3 CN " 80-84 89 " cyclohexyl H "

9 " -S0 CH " "

91 " 4-clhloro- " "

ben:zenesulfonyl 92 " phenyl C1 C2H5 93 " " " cyclo-hexyl 94 " " " CF

95 " " " 2-thienyl ~H3 96 ~~ ~~ ~~ _N

~ 3 4 09 49 Table 2 (cont'd) Compound Melting No. R1 _ R2 R3 Rg Point (°C) 97 CN phenyl C1 -N

~H3 9 8 ~~ ~~ ~~ -N

CH2CH=CH2 99 " " " 1-pyrrol-idinyl 100 " 4-methylphenyl " morpholino 101 " phenyl H isopropyl 80-83 102 " " C1 "

103 " " " -N(C2H5)2 70-80 104 " " Br " 55-76 105 " " C1 morpho- 106-110 lino 106 " " Br " 70-83 107 " " C1 thio-morpholino 108 " 4-(2'-chloro- " -N(CH3)2 ethyl)phenyl 109 " 4-chlorobenzyl Br "

110 " benzyl H "

111 " 4-chloro- C1 "

phenylthio 112 " 3-chloropropyl " "

113 " C H " "

114 " 2-furyl 2-furyl " 118-123 115 " 4-pyridyl H " 138-142 Table 2 (cont'd) Compound Melting No. R1 _ R2 R3 Rg Point (oC) 116 CN 2-thienyl C1 -N(CH3)2 117 " 4-fluoro-n-butyl " "

118 " 5-fluoropentyl " "

119 " n-C4H9 "

120 "
n-C5H11 n n 121 "
n-C6H13 122 " n-C~HiS " "

123 "
n-C$Hl~

124 "
n-C12H25 125 " iso-C3H~ "

126 " iso-CQH9 " "

127 " tert-CqH9 128 " cyclopropyl 129 " cyclohexyl " "

130 " -CH:2CH=CH2 " "

131 " geranyl (CloHl~) "

132 " gC2H5 " "

133 " g-n,-C3H~ "

134 " S-n~-CqH9 " " 36-38 135 " benzylthio " "

136 " 3-t.rifluoro- " "

methyl-2-pyridylthio 137 " " H

_ 75 _ gable 2 (cont'd) Compound Melting No. R1 _ R2 R3 Rg Point (oC) 138 CN 4-clhlorophenyl- H -N(CH3)2 thio 139 ~~ g_n._C3H~

140 " SCZH5 141 " phe:nylthio phenylthio " 98-101 142 " "

143 " benzene- H "

sulfonyl 144 " 2-fluoro- " "

benzenesulfon-yl 145 " 4-c:hlorobutyl C1 "

146 " 5-c:hloropentyl " "

147 " CH2(~CH3 "

148 " CH2QC2H5 " "

149 " 1-h;ydroxypropyl " "

150 " 1-h:ydroxybutyl " "

151 " benzyl " " 94-97 152 " 4-m~ethylbenzyl " "

153 " 3-methylbenzyl " "

154 " 2-methylbenzyl " "

155 " 2-fluorobenzyl " "

156 " phenethyl " "

157 " n-C3H~ gr 158 " n-C4H9 13409 ~9 Table 2 (cont'd) Compound Melting No. R1 _ R2 R3 RQ Point (°C) 159 CN n-C:5H11 Br -N(CH3)2 160 " n-C: H " "

161 " iso-C3H~ " "

162 " isc>-C4H9 " "

163 " cyclopropyl " "

164 " cyclohexyl " "

165 " 4-c:hloro- " "

phenylthio 166 " OCH2CF3 " " 77-79 167 " S-n-C3H~

168 " S-n-C4H9 169 " S-i.so-C4H9 " "

170 " CH2,OCH3 "

171 " CH2,OC2H5 " "

172 " me t:hoxycarbonyl" "

173 " N-(4-chloro- " "

phenyl)carbamoyl 174 " N-phenyl- " "

ca r bamoyl 175 " N-ethyl- " "

ca r' bamoyl 176 -CSNH2 C2H5 C1 "

177 N-acety l- " "

thiocarba-moyl 178 -CSNH2 n-C:4H9 "

_ 77 _ Table 2 (cont'd) Compound Melting No. R1 _ RZ R3 Rg Point (°C) 179 N-acetyl- n-C4H9 C1 -N(CH3)2 thiocarba-moyl 180 CN H I " 101-105 181 n n-C H n n 182 " " -COCF3 "

183 -CSNH2 " Br "

184 N-acetyl- " " "

thio-carbamoyl 185 -CSNHZ " C1 "

186 N-acetyl- " " "

thiocarba-moyl 187 N-propion- " " "

ylthio-carbamoyl 188 N-methyl- phenyl " "

thio-carbamoyl 189 N-acetyl- " "

thio-carbamoyl 190 CN -S02N(CH3)2 H " 142-149 191 " -Si(CH3)3 C1 "

n-CloH2i 193 " C2H5 H

194 " n-CqH9 195 " g-n-C4H9 n n _ 78 _ 13409 ~9 Table 2 (cont'd) Compound Melting No. R1 _ R2 R3 R4 Point (°C) 196 CN 1-hydroxy-3- C1 -N(CH3)2 phe~nylpropyl 197 " 1-hydroxypropyl H "

198 " a-hydroxybenzyl C1 "

199 " a-a,cetoxybenzyl " "

200 " 1-hydroxy-3- " "

met.hylbutyl 201 " 4-methyl-3- " "

chl.orophenyl 202 " " Br 203 " 4-methoxy-3- C1 chl.orophenyl 204 " " Br 205 " 2,?.-dichloro- C1 "

phenyl 206 " 4-e~thoxyphenyl " "

207 " '~ . Br 208 " 3.9:-methylene- C1 "

dioxyphenyl 209 " ~~ Br 210 " 4-c:yanophenyl Cl "

211 " " Br 212 " 4-nitrophenyl C1 " 140-145 213 " 2-t>utenyl " "

214 " iso-CSHli '~ "

_ 79 _ Table 2 (cont'd) Compound Melting No. Ri _ R2 R3 Rg Point (°C) 215 -CSNH2 H Cl -N(CH3)2 216 " CH3 217 '~ C5H11 "

218 " benzyl " "

219 N-acetylthio- H "

carbamoy7_ 220 " CH3 221 " C5 222 " benzyl " "

223 N-propionyl- "

thiocabamoyl 224 -CSNH2 C2H5 Br "

225 N-acetylth_LO-"

carbamoyl 226 N-propionyl- " "

thiocarbamoyl 227 CN 3-chlorobutyl C1 "

228 " -CF2CF=CF2 H "

229 " sec-CqH9 C1 "

230 " -CH2CH=C(CH3)2 " "

Table 2 (cont'd) Compound Melting No. R1 _ R2 R3 Rg Point (oC) 3-b CN n-C3H~ H -N(CH3)2 51-52 9-b " SCH.3 " " 114-115 10-b " phenylthio " " 106-107 14-b " H C1 " 111-114 15-b " CH3 " " 90-95 16-b " n-C3H~ " " 64-66 17-b " phenyl " " 109-112 18-b " 4-m.ethylphenyl " " 133-134 19-b " 3-m.ethylphenyl " "

20-b " 2-m.ethylphenyl " " 93-96 21-b " 3,4-dimethyl- " "

phenyl 22-b " 4-m.ethoxyphenyl " "

23-a " 4-chlorophenyl " " 133-138 23-b " " " " 117-120 24-b " 2-chlorophenyl " " 113-117 25-b " 3,4-dichloro- " "

phenyl 26-b " 4-fluorophenyl " " 120-122 27-b " SCH:3 " " 101-103 28-b " phenylthio " " 107-108 29-b " H Br " 100-103 30-b " CH3 " " 107-110 31-b " tert-C4H9 " "

~340g 4~9 Table 2 (cont'd Compound Melting R2 Rg Rg Point No. R1 - (oC) 32-b CN phenyl Br -N(CH3)2 122-124 33-b " 4-methylphenyl " " 136-137 34-b " 4-t.ert-butyl- "

phenyl 35-b " 4-methoxyphenyl " "

36-b " 4-f~luorophenyl " "

37-b " 4-c:hlorophenyl " "

C ~~ ~~ " 112-115 39-b " 2 s 40-b " -CFi2CH=CH2 " " 92-94 41-b " 4-bromophenyl C1 "

42-a " 4-isopropyl- " " 110-114 phf_nyl 42-b " " " " 135-138 43-b " 2-naphthyl "

46-b " phenyl SCH3 " 99-101 49-b -CSNH2 " H

50-b " 4-chlorophenyl " "

51-b " phenyl C1 " 115-128 52-b .. H Br "

hen 1 " " 110-118 53-b " P y 55-b CN 3-methyl-4- C1 " 115-118 methoxyphenyl 56-b " 4-ethylphenyl " " 110-112 57-b " phenylthio Br " 94-97 _ 82 -Table 2 (cont'd Compound Melting No. R1 R2 R3 R4 Point (°C) 58-b CN benzyl Br -N(CH3)2 87-89 59-b " 3-c:hloropropyl H "

-SC> C H " " 121-12 60-b " 2 2 5 4 61-b " 3-fluoropropyl C1 " 75-79 65-b " 2-c:hlorophenyl Br " 119-123 67-b " 4-(2',2',2'- C1 " 111-113 trifluoro-ethoxy ) phenyl 68-b " " Br " 115-118 69-b " -CH20H H " 106-107 70-b " 3-chlorophenyl Cl " 96-99 71-b " 3-~Eluorophenyl "

72-b " 2-:Eluorophenyl "

73-b " -S~~H2CH=CH2 H " 20-30 75-b " 1,2-diphenyl- " " 101-103 ethyl 76-b " a-:hydroxybenzyl " " 98-100 103-b " phenyl C1 -N(C2H5)2 99-101 104-b " " Hr "

105-b " " C1 morpholino 106-b " " Br " 126-130 111-b " 4-chlorophenyl- C1 -N(CH3)2 92-94 thio 112-b " 3-chloropropyl " " 102-105 113-b " C2H5 119-b " n-~C4H9 13 ~ 09 49 Table 2 lcont'd Compound Melting No. R1 _ R2 R3 Rg Point (C) 120-b CN n-C5H11 C1 -N(CH 3)2 37-39 121-b " n-C~~H13 " " nD 3. 51.

122-b " n-C.~H15 " " nD 3.51.

123-b " n-C~gHl~ " " nD3.61.4981 124-b " n-Ca2H25 " " 34-36 125-b " iso-C3H~ " " 75-82 (decomposed) 126-b " iso-CqH9 " " 73-76 127-b " tert-C9H9 " " 74-80 128-b " cyc:lopropyl " " 76-79 129-b " cyc:lohexyl " " 107-111 130-b " -CH,,CH=CH2 " " 67-72 131-b " geranyl ( CloHl~ "
) 132-b " SC2H5 " " 107-110 133-b " S-n--C3H~ " " 70-74 134-b " S-n--C4H9 " "

135-b " benrylthio " " 149-152 136-b " 3-trifluoro- " " 126-127 methyl-2-pyridylthio 137-b " " H " 109-111 138-b " 4-chlorophenyl- " " 110-112 thic>

140-a " SC2H5 " " 36-40 Table 2 lcont'd Compound Melting No. R1 _ R2 R3 R4 Point CC) 140-b CN SC.,HS H -N
( ) 142-a " phE~nylthio C2H5 " 86-89 145-b " 4-c:hlorobutyl C1 " nD2.i 1,5382 146-b " 5-c:hloropentyl " " nD4.81.5328 147-b " CH~,OCH3 " " 64-66 148-b " CH~,OC2H5 " " 82-84 149-b " 1-hydroxypropyl " " 70-73 24.2 150-b " 1-hydroxybutyl " " nD 1.5097 151-b " benzyl " " 92-100 152-b " 4-methylbenzyl " " 125-129 153-b " 3-methylbenzyl " " 93-96 154-b " 2-methylbenzyl " " 119-123 155-b " 2-fluorobenzyl " " 105-109 156-b " phe~nethyl " " 106-110 157-b " n-C'.3H~ Br " 93-94 158-b " n-C'.4H9 " "

159-b " n-C'5Hii ' "

160-b " n-G6H13 " " 99-101 161-b " iso-C3H~ " "

162-b " iso-C4H9 " "

163-b " cyclopropyl " "

164-b " cyclohexyl " "

Table 2 (cont'd) Compound Melting No. R1 - R2 R3 Rg Point (oC) 165-b CN 4-c:hlorophenyl- Br -N(CH3)2 94-95 thio 167-b " S-n-C3H~ " " 76-78 168-b " S-n-C4H9 " " 48-50 169-b " S-iso-C4H9 " " 77-79 170-b " CH2,OCH3 " " 65-67 171-b " CH2OC2H5 " " 100-101 172-b " met:hoxycarbonyl " " 98-101 173-b " N-(4-chloro- " " 106-109 phe~nyl)carbamoyl 174-b " N-phenyl- " " 105-107 carbamoyl 175-b " N-ethyl- " " 98-101 carbamoyl 181-a " n-C3H~ I " 76-79 181-b " " " " 99-103 182-a " " -COCF3 " 90-92 185-b -CSNH2 " C1 " 160-162 186-b N-acetyl- " " " 119-123 thio-carbamoyl 187-b N-propion- " " " 150-152 ylthio-carbamoyl 188-b N-methyl- phenyl " " 67-72 thio-carbamoyl Table 2 (cont'd Compound Melting No. R1 _ R2 Rg Rg Point (C) 189-b N-acetyl-- phenyl C1 -N
( ) thio-carbamoy7_ 191-b CN -Si(CH3)3 " " 116-119 192-b " n-C1pH21 " " nD3 ~ 6 1.

193-b " C2H5 H " 69-71 194-b " n-C'qH9 " " 52-53 195-b " S-n-CQH9 " " 50-51 196-b " 1-:hydroxy-3- C1 " nDq'~ 1.5512 ph~enylpropyl 197-b " 1-hydroxypropyl H " 94-97 198-b " a-hydroxybenzyl C1 " 102-104 199-b " a-acetoxybenzyl " " 82-86 200-b " 1-hydroxy-3- " " 71-74 methylbutyl 201-b " 4-methyl-3- " " 99-103 chlorophenyl 202-b " " Br " 103-106 203-b " 4-methoxy-3- C1 " 97-101 chlorophenyl 204-b " " Br " 105-110 205-b " 2,3-dichloro- C1 " 103-107 phenyl 206-b " 4-ethoxyphenyl " " 122-124 207-b " " Br " 110-113 208-b " 3,4-methylene- C1 " 150-153 dio.xyphenyl _ 87 _ ~3~09 4~9 Table 2 (cont'd Compound Melting No. R1 _ R2 R3 Rg Point (C) 209-b CN 3,4-methylene- Br -N(CH3)2 95-98 dioxyphenyl 210-b " 4-cyanophenyl C1 " 182-185 211-b " " Br " 175-178 212-b " 4-nitrophenyl C1 " ~ 144-146 213-b " 2-butenyl " " 87-90 214-b " iso-C5H11 " " 45-47 218-b -CSNH2 benzyl " " 118-121 222-b N-acetyl-- " " " 163-165 thiocarbamoyl 223-b N-propionyl- " " " 149-152 thiocarbamoyl 227-b CN 3-clalorobutyl " " 54-57 230-b " -CH;ZCH=C(CH3)2" " 75-78 1 Among the imidazole compounds of the present invention describe=_d in Table 2 above, the compounds having a mark "a" in their compound numbers are ones falling within the general formula (I-a) in the general formula (I) described hereinabove and the compounds having a mark "b" in their compound numbers are ones falling within the general formula (I-b) in the general formula (I) described hereinabove.
The imidazole compounds of the present invention are useful as biocides for controlling harmful organisms in the agricultural and horticultural areas.
_ 88 _ 13 ~ 09 49 1 As agricultural and horticultural fungicides, the compounds exhibit an excellent effect of controlling diseases of crop plants such as rice blast caused by Pyricularia ory~zae, rice sheath blight caused by Rhizoctonia solani, oat crown rust caused by Puccinia coronata, cucumber anthracnose caused by Colletotrichum lagenarium, cucumber powdery mildew caused by Sphaerotheca fuliginea, cucumber downy mildew caused by Pseudoperonospora. cubensis, tomato late blight caused by Phytophthora infestane;, tomato early blight caused by Alternaria solani, citrus melanose caused by Diaporthe citri, citrus common green mold caused by Penicillium digitatum, pear scab caused by Venturia nashicola, apple alternaria blotch caused by Alternaria mali, grape downy mildew caused by Pla~~mopara viticola, and further gray mold caused by Bo_ trytis cinerea and sclerotinia rot caused by Sclerotinia sclerotiorum of various crops, etc.;
or soil diseases caused by phytopathogenic fungi such as Fusarium, Pythium, Rhizoctonia, Verticillium, Plasmodiophora, A. hp anoniyces, etc.
In particular, the compounds exhibit an excellent effect of preventing deseases such as potato or tomato late blight caused by Phytophthora infestans, cucumber downy mildew caused b;~ Pseudoperonospora cubensis, grape downy mildew caused b:y Plasmopara viticola, and tobacco blue mold caused by Peronospora tabacina; and soil _ 89 _ 1309 ~9 1 diseases caused by phycomycetes such as Plasmodiophora, Aphanomyces, Pyth:ium, etc.
The compounds of the present invention have a prolonged residual ei°fect so that they exhibit an excellent preventing effect, and further exhibit an excellent curative effect as well. Therefore, it is possible to control deseases by treatment after infection.
The compounds of the present invention are appropriate to be applied to crop plaints by foliar treatment. Further, the compounds po~.sess a systemic activity so that it is also possible to control deseases of the stem and leaf by soil treatment. :fin addition, the compounds of the present invention show an excellent controlling effect against agriculturally and horticulturally harmful insects such as various planthoppers, diamondback moth (Plutella xylostella), green rice leafhopper (Nephotettix cincticeps), a~izuki bean weevil (Callosobruchus .chinensis), common cui~worm (Spodoptera litura), green peach aphid (MVzus pe~~sicae), etc.; mites such as two-spotted spider mite (Tetranychus urticae), carmine spider mite (Tetranychus c:innabarinus), citrus red mite (Panonychus citri), etc.; and nematodes such as southern root-knot nematodes (Meloidogyne incognita), etc.
Upon use, the .compounds of the present invention can be prepared into a variety of forms of biocidal compositions such as emulsifiable concentrates, suspension concentrates, dusts, wettable powders. aqueous solutions, granules, etc., together with adjuvants, as in conventional formulations. Upon actual use of these formulations, they can be used as such or by diluting with a diluent such ass water or the like to a predetermined concentration.
As the agriculturally acceptable adjuvants used herein, mention may be made of carriers, emulsifying agents, suspending agents, dispersing agents, spreaders, penetrating agents, wetting agents, thickeners, stabilizers, etc.
The carriers are classified into solid carriers and liquid carrif~rs. As the solid carriers, mention may be made of animal and vegetable powders such as starch, sugar, cellulo=>e powders, cyclodextrin, activated charcoal, soybean powders, wheat powders, chaff powders, wood powders, fish powders, powdery milk, etc.; and mineral powders such as talc, kaolin, bentonite, bento-nite-alkylamine comp7Lex, calcium carbonate, calcium sulfate, sodium bicarbonate, zealite, diatomaceous earth, white carbon, clay, al~umina, silica, sulfur powders, etc.
As the liquid c<~rriers, mention may be made of water;
animal and vegetable oils such as corn oil, soybean oil, cotton seed oil, etc.; alcohols such as ethyl alcohol, ethylene glycol, etc.; ketones such as acetone, methyl ethyl ketone, etc.; ethers such as dioxane, tetrahydro-1 furan, etc.; aliphatic hydrocarbons such as kerosene, lamp oil, liquid paraffin, etc.; aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane, solvent naphtha, etc.; halogenated hydro-carbons such as chloroform, chlorobenzene, etc.; acid amides such as dimethylformamide, etc.; esters such as ethyl acetate, fatty acid glycerine esters, ete.;
nitriles such as. acetonitrile, etc.; sulfur-containing compounds such ass dime~thyl sulfoxide, etc.; and N-methyl pyrrolidone, etc.
The adjuvants other than the carriers described hereinabove, such as emulsifying agents, suspending agents, dispersing agents, spreaders, penetrating agents, wetting agents, thickeners, stabilizers, etc. are exemplified more specifically as following surfactants.
PolyoxyethylenE~ alkylarylether, polyoxyethylene glycol nonyl phenylether, polyoxyethylene laurylether, polyoxyethylene caster- oil, polyoxyethylene alkylaryl sulfate (polyoxyethyle ne alkylphenyl ether sulfate), polyoxyethylene fatty acid ester (polyoxyethylene stearate), polyoxyethylene sorbitan fatty acid ester, lower alcohol phosphate, sodium alkylsulfate, sodium lignin sulfonate, calcium lignin sulfonate, alkylaryl sulfonate, sodium alltylbenzene sulfonate, sodium naphthalene sulfonate-formaldehyde condensate, dialkyl-sulfosuccinate.

1309 ~9 1 The compound~of the present invention is uniformly mixed with at least one kind of adjuvants described hereinabove to form a biocidal composition.
A weight ratio of the compound of the present invention to the adjuvants to be formulated is generally from 0.05:99.95 to 90:10, preferably from 0.2:99.8 to 80:20.
Since a concentration of the compound of the present invention to be applied may vary depending upon crop to be applied, method for application, preparation form, dose to be applied, etc., it is difficult to define a specific concentration range. However, if it is forced to define specifically,, the concentration of the compound is generally from 0.1 to 10,000 ppm, desirably from 1 to 2,000 ppm in the case of foliar treatment, and is generally from 10 to 1.00, 000 g/ha, desirably from 200 to 20,000 g/ha in the cases of soil treatment.
Further, if necessary and desired, the compound of the present inver.,tion can be used as admixture with or in combination with other agricultural chemicals, for example, insecticides, acaricides, nematocides, fungi-cides, antiviral ageni~s, attractants, herbicides, plant growth regulators, etc. In this case, more excellent effects can sometimes be exhibited.
As the insecticides, acaricides or nematocides, mention may be made of, for example, organic phosphrous l~~~g ~9 1 compounds, car:bamate compounds, organic chlorine compounds, organic metal compounds, pyrethroid compounds, benzoyl urea compounds, juvenile hormone-like compounds, dinitro compounds, organic sulfur compounds, urea compounds, triazi.ne compounds, etc. The compound of the present invention can also be used as admixture with or in combination with biological pesticides such as BT agents, insect pathogenic viral. agents, etc.
As the fungicides, mention may be made of, for example, organic phosphorus compounds, organic chlorine compounds, dithiocarbamate compounds, N-halogenothioalkyl compounds, dicarbox:Lmide compounds, benzimidazole compounds, azole compounds, carbinol compounds, benz anilide compounds, acylalanine compounds, pyridinamine compounds, piperazine compounds, morpholine compounds, anthraquinone cornpound;s, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, urea compounds, antibiotics, etc.
Hereafter, test:. examples of the biocidal composi tions for controlling harmful organisms in the agri cultural and horticultural areas in accordance with the present invention are dlescribed below.
Standards. for evaluation of the agricultural and horticultural fungicides follow the following criteria for evaluation, unless otherwise indicated.

~~4~09 49 1 Standards for Evaluation The controlling effect was determined by visually observing a degree of desease of a test plant and expressed by thE~ fol7.owing 5 grades of th e index of control.

[Index of Control] [D<~gree of Desease]

5: No lesion is noted at all.

4: ArEea, number or length of lesions is less than 10~ as compared to the non-trE~ated plot.

3: Area, number or length of lesions is leas than 40~ as compared to the non-trE~ated plot.

2: Area, number or length of lesions is less than 70~ as compared to the non-tre~ated plot.

1: Area, number or length of lesions is more than 70% as compared to the non-treated plot.

Test Example 1 Test on preventive effect against cucumber powdery mildew Cucumber (cult:ivars: Suyo) was culti vated in a polyethylene pot having a diameter of 7.5 cm. When cucumber reached the one-leaf stage, 10 ml of a solution obtained from each o1. test compounds adju sted to a predetermined concentration was sprayed ove r cucumber ~~409 49 1 using a spray gun. After keeping the pots in a constant temperature chamber of 22 to 24°C over one day and one night, conidia o:E fungi of powdery mildew (Sphaerotheca fuliginea) were inoculated. Ten days after the inoculation, an area of lesion on the first leaf was investigated; and an index of control was determined by the standards for evaluation described above. The results shown in Table 3 were obtained.
Table 3 Index of Control Compound No. 500 ppm 15-b 4 23-a 4 59-b 4 106~-b 3 13 3'.-b 4 167-b 3 169-b 3 171-b 5 Test Example 2 Test on preventive ef:Eect against cucumber anthracnose Cucumber (culti.vars: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When cucumber reached 'the two-leaf stage, 10 ml of a solution obtained from each of: test compounds adjusted to a predetermined concentration was sprayed over cucumber using a spray gun. After keeping the pots in a constant temperature chamber of 22 to 24°C over one day and one night, a spore suspension of fungi of anthracnose (Colletotrichum 1_aqena.rium) was inoculated. Seven days after the inoculation, an area of lesion on the first leaf was investigated, and an index of control was determined by the standards for evaluation described above. The results shown in Table 4 were obtained.
Table 4 Index of Control Co_ mpound No. 500 ppm 3-lb 3 17-lb 3 28-lb 3 51-lb 3 59-lb 3 69-lb 3 70-lb 4 73-lb 3 75-ib 3 Test Example 3 Test on preventive effect against cucumber downy mildew _ 97 _ 1 Cucumber (cultivars: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When cucumber reached the two-leaf stage, 10 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration was sprayed over cucumber using a spray gun. After keeping the pots in a constant temperature chamber of 22 to 24°C over one day and one night, a spore suspension of fungi of downy mildew (Pseudoperonospor.a cubensis) was inoculated. Six days after the inoculation, an area of lesion on the first leaf was investigated, and an index of control was determined by the standards. for evaluation described above. The results shown in Table 5 were obtained.
Table 5 Index of Control Index of Control Compound No. 125 perm 31 ppm Compound No. 125 ppm 31 ppm 4 'S 5 29-b 5 5 5 5 5 30-b 5 5 'S 4 31 4 3 7 '5 5 32-b 5 5 g 5 3 33 - 5 14-b 5 3 34 5 5 15-b 5 5 36 - 5 16-b ~- 5 37 5 5 17-b ~- 5 47 5 5 Table 5 (cont'd) Index: of Control Index of Control Compound No. 125 1?~ 3:L ppm Compound No. 125 ppm 31 ppm 49 'i 4 101 5 4 52 'i 5 105 4 -53-b 5 5 106 5 5 Test Example 4 1 Test on curative effE~ct against cucumber downy mildew Cucumber (cultivars: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When cucumber reached the two-leaf stage, a spore suspension of fungi of downy mildew (Pseudoperonospora cubensis) was inoculated. Six hours after the inoculation, 10 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration was sprayed over cucumber using a spray gun. After keeping the pots in a constant temperature chamber of 22 to 24°C for 6 days. an area of lesion on the first leaf was investigated, and an index of control was determined by the standards for evaluation described above. They results shown in Table 6 were obtained.
Table 6 Index: of Control Index of Control Compound No . 1-2 5 tam 3:L ppm Compound No . 12 5 ppm 3_ 1 ppm 3-b 5 - 8 5 Table 6(cont'd Index of Control Index of Control Compound No. 125 ppm ~l ppm Compound No. 125 ppm 31 ppm 9-b 5 - 32-b 5 -10-b 5 - 33 5 -12 5 - 33-b 5 -14-b 5 - 36 5 -15-b 5 - 37 5 -16-b 5 - 39-b - 5 17 5 - 40-b - 5 17-b 5 - 41 - 5 18 - 5 46-a 5 -18-b 5 - 48 4 -20-b 5 - 51-b 5 -23 5 - 53-b 5 -23-a 5 - 56-b 5 -23-b 5 - 57-b - 5 24-b - 5 58-b - 5 25 - 4 59-b - 5 26 - 5 60-b - 5 26-b 5 - 61-b - 5 27-b 5 - 65-b 5 -28-b 5 - 67-b 5 -29-b 5 - 68-b - 4 30-b 5 - 69-b 4 -Table 6 l cont' d Inde:c of Control Index of Control Compound No. 125 ppm 31 ppm Compound No. 125 ppm 31 ppm 70-b 5 - 138-b - 5 72 ~- 5 141 4 -74 ~- 4 142-a 5 5 76-b '~ - 145-b - 5 88 ~- 5 146-b - 5 101 4 - 147-b 5 5 103-b 5 - 148-b 5 5 106-b !i - 149-b - 5 111-b -- 5 150-b 5 -112-b !i 5 151 - 5 113-b !i 5 151-b 5 5 119-b 5 5 152-b - 3 120-b 5 5 153-b - 5 121-b .'i 5 154-b - 5 125-b -- 5 155-b - 5 126-b -- 5 156-b - 5 128-b -- 5 157-b - 5 129-b -- 5 160-b 5 5 130-b 5 5 166 5 3 132-b -- 5 167-b 5 5 133-b 5 4 169-b 5 5 134 5 5 170-b 5 5 135-b 4 - 171-b 5 5 136-b -- 3 173-b 4 -1~~09 49 Table 6 (cont'd Inde:~c of Control Index of Control Compound No. 125 perm31 ppm Compound No. 125 ppm 31 ppm 180 5 - 201-b 4 -181-a - 5 203-b 3 -181-b - 5 208-b 4 3 185-b - 5 209-b 5 -186-b - 5 210-b 4 -187-b - 5 212-b 5 5 189-b 5 5 213-b - 5 190 5 4 214-b - 5 1 Test Example 5 Test on :~_ystem:ic effect against cucumber downy mildew Cucumber (cultivars: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When cucumber reached the two-leaf stage, 15 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration was drenched on the surface of soil using a pipette" After keeping the pots in a constant temperature chamber of 22 to 24°C for 2 days, a spore suspension of fungi of downy mildew (Pseudoperonospor,a cubensis) was inoculated. Six days after the inoculation, an area of lesion on the first leaf was investigated, and .an index of control was determined ~~~os ~~
1 by the standard~~ for evaluation described above. The results shown in Table 7 were obtained.
Table 7 Index of Control (:o-mpound No. 500 ppm 125 ppm 14-b 5 5 15-b - 5 29-b 5 5 30-b 5 5 53-b 5 5 -Test Example 6 Test on preventive effect against tomato late blight Tomato (c:ultivars: Ponderosa) was cultivated in a polyethylene pot having, a diameter of 7.5 cm. When tomato reached the four-leaf :stage, 10 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration way, spra:yed over tomato using a spray gun.
After keeping thE~ pots in a constant temperature chamber of 22 to 24°C over one day and one night, a zoosporangium suspension of fungi of late blight (Phytophthora infestans) was inoculated. Five days after the inoculation, an area of lesion on the leaves was investigated, and an index of control was determined by the standards for' evaluation described above. The results shown in Table 8 were obtained.
Table 8 Index of Control Compound No. 125 ppm 31 ppm 8 ppm 3 ~-b - 5 -9--b - 5 ---b - - 5 14--b - 5 ---b - 4 -16--b - 5 4 17 --b 5 5 -18--b - 5 -2 0 --b - 5 -13409 4g Table 8 ( cont' d ) Index of Control Compound No. 125 ppm 31 ppm 8 ppm 2 3 --a - 5 -23--b - 5 -2 4 --b - 5 5 26--b - 5 -27--b - 5 -28--b - 5 -29--b 5 5 -30--b - 5 -32-~b 5 5 -33-~b - 5 -39-b - - 5 40-b - 5 5 42-a - 5 -42-b - 5 -Table 8 (cont'd) Index of Control C- ompound N~o. 125 ppm 31 ppm 8 ppm 46-a 5 5 -51--b 5 5 -53--b 5 5 -5 5--b - 4 5 56--b - 5 -57--b - - 5 58--b - 5 5 59--b - - 5 60--b - 5 -61--b - 5 5 6 5--b - 5 -6 7--b - - 5 6 8--b - - 5 7 0 --b - - 5 7 3--b - 4 -Table 8 (cont'd) Index of Control Compound No. 125 ppm 31 ppm 8 ppm 75-~b - 5 -76-b - 5 -106-b 5 4 -111-b - - 4 112-b - 5 5 113-b - - 5 119-b - 5 5 120-b - 5 5 121-b - 5 5 122-b - 5 5 123-b - 5 5 124-b - 5 5 125-b - - 5 126-b - - 5 128-b - 5 4 129-b - 5 5 130-b - 5 5 ~3~09 49 Table 8 (cont'd) Index of Control C- ompound No 12 5 ppm 31 ppm 8 ppm .

132--b - 5 5 133--b - - 5 135--b - 5 5 136--b - - 5 137--b - - 5 138--b - _ 4 142--a - 5 5 14 5--b - - 4 146--b - 5 5 147--b - 4 3 148--b - 4 -149--b - - 5 151--b - 5 5 152--b - - 5 153--b - - 5 154--b - - 5 15 5--b - - 5 156--b _ _ 5 157--b - - 5 ~3~Og 49 Table 8 (cont'd) Index of Control Compound No. 125 ppm 31 ppm 8 ppm 160-~b - 5 5 167-b - 5 5 169-b - 5 5 170-b - 5 3 171-b - 5 -173-b - 4 3 174-b - 4 -181-b - 5 5 182-b - 5 5 185-b - - 5 186-b - - 5 187-b - - 5 189-b - 5 4 201-b - 5 5 202-b - 5 5 203-b - 4 5 2 0 5-.b - - 5 206-b - 5 5 207-b - 5 -208-b - 5 5 ~~~o~ ~s Table 8 (cont'd Index of Control Compcmnd No. 125 ppm 31 ppm 8 ppm 209--b - 4 -210-~b - 4 3 211-~b - 4 -212-~b - 5 3 213-~b - 5 5 214-~b - 5 5 1 Test Example 7 Test on systemic effect against tomato late blight Tomato (cultivars: Ponderosa) was cultivated in a polyethylene pot laaving a diameter of 7.5 cm. When tomato reached the four-leaf ~~tage, 15 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration was drenched on the surface of soil using a pipette. After keeping the pots in a constant temperature chamber of 22 i:o 24°C for 2 days, a zoosporangium suspension of :Fungi of late blight (Phytophthora infestans) was inoculated. Five days after the inoculation, an area of lesion on the leaves was investigated, and an index of control was determined by the standards for evaluation described above. The results shown in Table 9 cvere olbtained.

13~~9 4~
Table 9 Index of Control Compound No. 500 ppm 125 ppm 3-b - 4 10-b 5 5 16-b - 4 17-b 5 4 20-b 5 4 27-b 5 5 :28-b 5 -~4 0 -b 5 5 !i l 5 5 !51-b 5 5 !i 7 -b - 4 !i 8-b 5 3 !i9-b - 4 ',7 6 -b - 5 Test Example 8 Test on prcsventive effect against rice blast Rice plant (cultivars: Chukyo Asahi) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When rice plant reached the four-leaf stage, 20 ml of a solution obtained from each of test compounds adjusted to a predeterminE~d concentration was sprayed over rice plant using a spray gun. After keeping the pots in a 13 ~ ~~ ~9 1 constant temperai:ure chamber of 22 to 24°C over one day and one night, a spore suspension of fungi of blast (Pyricularia ory~;ae) was inoculated. Five days after the inoculation, a number of lesion was investigated, and an index of control was determined by the standards for evaluation described above. The results shown in Table 10 were obtained.
Table 10 Index of Control (:ompound No. 500 ppm 27-b 4 53-b 3 55-b 4 167-b 3 2'01-b 4 2 ~0 2-b 4 Test Example 9 Test on preventive effect against rice sheath blight Rice plant (cultivars: Chukyo Asahi) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When rice plant reached the five-leaf stage, 20 ml of a solution obtair.~ed from each of test compounds adjusted to a predetermined concentration was sprayed over rice plant using a spray gun. After keeping the pots in a constant temperature chamber of 22 to 24°C over one day ~! 3 4 09 49 1 and one night, rice straw in which fungi of sheath blight (Rhizoctonia solani) had been previously incubated was set between leaf sheath portions to inoculate. After keeping the pots in an inoculation room having a temperature of 28°C and a humidity of 100 for 5 days, a length of lesion was investigated, and an index of control was determined by the standards for evaluation described above. The results shown in Table 11 were obtained.
Tahla 11 Index of Control C'.ompound No. 500 ppm :21 3 27-b 3 :34 3 !51-b 3 !i 3 -b 3 Test Example 10 Test on preventive effect against oat crown rust Oats (cultivars: Zenshin) were cultivated in a polyethylene pot having a diameter of 7.5 cm. When oats reached the two-leaf stage, 10 ml of a solution obtained from each of test comb>ounds adjusted to a predetermined concentration was sprayed over oats using a spray gun.
After keeping the pots in a constant temperature chamber of 22 to 24°C over' one day and one night, conidia of fungi 1 of crown rust (I?uccinia coronata) were inoculated. Ten days after the inocu:Lation, an area of lesion on the second leaf was investigated, and an index of control was determined by the standards for evaluation described above. The results shown in Table 12 were obtained.
Index of Control Compound No. 500 ppm 14-b 3 59-b 3 172-b 4 1 !~ 0 3 Test Example 11 Test on preventive effect against turnip clubroot Soil contaminated with fungi of clubroot (Plasmodiophora brassicae) was filled in a 1/14,000 a (1/140 m2) pot, and 20 ml of a solution obtained from each of test compounds adjusted to 4 kg/10 a and 1 kg/10 a calculated as the active ingredient was drenched on the surface of the soil using a pipette. One day after treatment, the soil was mixed over the whole layers, and turnip (cultivars: Kanamachi Kokabu) was seeded. The - 114 - ' turnip was grown in a greenhouse. Thirty days after the seeding, a degree of clubroot formation was investigated, and an index of control was determined by the standards for evaluation described below. The results shown in Table 13 were obtained.
Standards for evaluation [Index of Control] [Degree of Occurrence of Clubroot]
5: formation of clubroot . none 4: " . slight 3; " . medium 2: " . many 1: " . abundant Index of Control Compound No. 4 kq/10 a 1 kg/10 a 9-b 5 4 10-b - 5 14-b 5 5 15-b - 5 16-b 5 5 Table 13 ( cont' d) Index of Control C'om ound 4 kq/10 a 1 kg/10 No. a 17-b - 5 18-b - 5 20-b 5 4 23 5 ~ 5 23-a - 4 23-b - 4 24-b - 5 26-lb - 5 27-lb 5 5 29-b - 5 3 0-b - 5 32-b - 5 33-b - 5 39-t> - 5 ' 3 4~ 0 9 4 9, Table 13 (cont'd Index of Control !~ompound No. 4 kq/10 a 1 kq/10 a 40-b - 5 42-a - 5 42-b - 5 46-a 5 -51--b 5 5 53--b 5 4 55--b - 5 56--b - 5 58--b - 5 59--b 5 5 65--b - 5 67--b - 5 6 8--b - 5 7 3--b 4 -201--b - 5 202--b - 5 °

Table 13 ( cont' d ) Index of Control Compound No. 4 kq~l0 a 1 kg/10 a 206-b - 5 207-b - 5 1 Vest Example 12 Antimicrobial test (phytopathoqenic fungi) Mycelial disc (agar punching) of preincubated Pythium aphanidermatum was transplanted on potato-dextrose agar medium (PDA medium) containing 100 ppm of streptomycin and 100 ppm of each of test compounds. After incubation at 22°C for 48 hours, a diameter of mycelium was measured. Inhibition of hyphal growth (~) was determined by the following equation. The results shown in Table 14 were obtained.
Diameter of mycelium in treated plot inhibition of hyphal growth (%) _=100 - X 100 Diameterofmycelium in non-treated plot Inhibition of Compound No. Hyphal Growth 3--b 10 0 9 --b 10 0 10--b 100 14-~b 100 15-~b 100 ~~409 ~9 Table 14 (cont'd) Inhibition of Compour.~d No. Hyphal Growth 16-b 100 17-b 100 27-b 100 28-b 100 29-:b 100 30-ib 100 33 100 ($) 53-ti 100 ~3~09 ~9 Table 14 (cont'd) Inhibition of Compound No. Hyphal Growth TEest Example 13 Miticidal test on adults of two-spotted spider mites Kidney bean (cultivars: Edogawa Saito) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When kidney bean reached the primary leaf stage, one primary leaf was left" and other leaves were cut out.
After infesting about 30 adults of two-spotted spider mite (Tetranychus urti.cae: resistant to Dicofol and organic phosphorus insecticides), the seedlings were immersed in 20 ml of a solut_~on obtained from each of test compounds adjusted to a pi:edetermined concentration for about 10 seconds. After drying, the seedlings were allowed to stand in a constant temperature chamber of 26°C with lighting. Two days after releasing the mites, numbers of dead mites were investigated, and a mortality (%) was determined by the following equation. The results shown in Table 15 were obtained.
Numberofdead mites Mortality (%)= X 100 Number of released mites x'3409 49 Table 15 Mortalit y ($) !~ompound No. 800 ppm 200 ppm 9-b 100 100 10-b 100 100 14-b 100 100 15~-b 100 100 23-a 100 -23-b 91 -26-b 100 -29--b 100 100 40--b 100 100 57--b 100 -58--b 100 -112--b 100 -113--b 100 100 119--b 100 100 Table 15 (cont'd) Mortality (~) !~ompound No. 800 ppm 200 ppm 133-b 100 90 151-b 100 -167-b 100 87 169-b 100 100 172-b 100 -205-b 100 -1 Test Example 14 Ovicidal test on two-spotted spider mites Kidney bean with only one primary leaf was transplanted on a polyethylene pot. After infesting adults of two-spotted spider mite (Tetranychus urticae) and ovipositing for 24 hours, the adults were removed.
Then, the kidney bean described above was immersed in 20 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration for about 10 seconds. After drying, the kidney bean was kept in a constant temperature chamber of 26°C with lighting. Five to seven days after thEa treatment, a state of hatching was investigated, and an c'vicidal rate ($) was determined by the following equation. The results shown in Table 16 were obtained. Death immediately after hatching was regarded to be ovicidal..

~1~~~9 h9 Number of killed eggs Ovicidal Rate I;%)= X 100 Numberofoviposited eggs Table 16 Ovicidal Rate C:o- mpound 800 ppm No.

10-b 100 15-b 100 26-b 100 29-b 100 30-b 70 40-b 100 57-b 90 gg 100 113-b 100 119-b 100 133-b 100 167-b 100 169-b 100 1 Test Example 15 Insecticidal test on small brown planthoppers Young seE~dlings of rice plant were immersed in 20 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration for about 10 seconds. After drying, the root was wrapped with wet 1309 ~9 1 absorbent cotton and put in a test tube. Then, 10 larvae of second to third instar of small brown planthoppers (Laodelphax striatellu:>) were released in the test tube, and the opening of the test tube was covered with gauze.
The test tube was kept in a constant temperature chamber of 26°C with lighting. Five days after the release of the larvae, numbers of dead insects were investigated, and a mortality rate (~) was determined by the following equation. The results shown in Table 17 were obtained.
Numberofdead insects Mortality (%)= X 100 Numberofreleased insects Table 17 Mortality C'.o_ mpound 800 ppm 200 ppm No.

14-~b 100 100 15-~b 100 80 40-~b 100 -113-~b 100 -119-~b 100 -133-~b 100 -151-~b 100 -1309 ~g 1 Test Example 16 Insecticidal test on green peach aphids A piece of cabbage leaf was immersed in 20 ml of a solution obtained. from each of test compounds adjusted to a predetermined concentration for about 10 seconds, followed by drying. wet filter paper was put on a petri dish having a diameter of 9 cm, and the air-dried leaf piece was put thereon. Apterous viviparous females of green peach aphids (Myzus persicae) were released on the leaf. The petri dish was covered and kept in a constant temperature chamber of 26°C with lighting. Two days after release of the insects, numbers of dead insects were investigated, an~i a mortality ($) was determined in the same manner as Test Example 15 described above. The results shown in Table 18 were obtained.
Table 18 Mortality (~) (.o_ mpou:nd No. 800 ppm 7. 7 0 32-b 70 Test Example 17 Insecticidal_ test on common cutworms A piece of cabbage leaf was immersed in 20 ml of a solution obtained from each of test compounds adjusted to a predetermined concentration for about 10 seconds followed by drying. Wet filter paper was put on a petri 1 dish having a diameter of 9 cm, and the air-dried leaf piece was put thereon. Second to third instar larvae of common cutworms (SpodC>ptera litura) were released on the leaf. The petri dish was covered and kept in a constant temperature chamber of 26°C with lighting. Five days after release of the larvae, numbers of dead insects were investigated, and a mortality ($) was determined in the same manner as Test Example 15 described above. The results shown in Table 19 were obtained.
Table 19 Mortality (~) Co. mpou.nd No. 800 ppm 2~6-b 100 40-b 100 6'7-b 10 0 6.B-b 100 Formula tion examples of the present invention are described below, but t:he compounds, dose in formulations, type of formulations, etc. in the present invention are not deemed to be limited to those described below.
Formulation Example 1 ~Wettable powder) (a) Compound No. 5 50 parts by weight (b) Kaolin 40 "
(c) Sodium lignin sulfonate 7 "

?3~~949 1 (d) Dialkylsulfosuccinate 3 "

The above components are uniformly mixed.

Formulation owder) Example 2 (Wettable p (a) Compound No. 17-b 20 parts by weight (b) Kaolin 72 (c) Sodium lignin sulfonate 4 "

(d) Polyoxyethylene alkylaryl 4 "

ether The above components are uniformly mixed.

Formulation owder) Example 3 (Wettable p (a) Compound No. 18-b 6 parts by weight (b) Diatomaceous earth 88 "

(c) Dialkylsulfosuccinate 2 "

(d) Polyoxyethylene alkylaryl 4 "

sulfate The above components are uniformly mixed.

Formulation owder) Examp:l_e 4 (Wettable p (a) Kaolin 78 parts by weight (b) Sodium S-naphthalene- 2 "

sulfonate-formaldehyde condensate (c) Polyoxyethylene alkylaryl 5 "

sulfate (d) Fine silica 15 "

A mixture of the above components Compound and No.

22 are mixed in a weight ratio 4:1.
of Formulation owder) Example 5 Wettable p (a) Compound No. 16-b 10 parts by weight (b) Diatomaceous earth 69 "

~3~~9 49 1 (c) Calcium carbonate powder 15 "

(d) Dialkylsulfosuccinate 1 "

(e) Polyoxyethylene~ alkylaryl3 "

sulfate (f) Sodium S-naphthalene- 2 "

sulfonate-formaldehyde condensate The above compc>nents are uniformly mixed.

Formulation Example 6 (Wettable powder) (a) Compound No. 1T-b 20 parts by weight (b) Kaolin 62.4 "

(c) Fine silica 12.8 "

(d) Alkylaryl sulfonate 1.6 "

(e) Polyoxyethylene alkylaryl 2.4 "

sulfate (f) Polyoxyethylene alkylaryl 0.8 "

ether The above components are uniformly mixed.

Formulation Example 7 Dust (a) Compound No. 2:3 5 parts by weight (b) Talc 94.5 "

( c ) Lower alcohol phosphate 0 . 5 "

The above components are uniformly mixed.

Formulation Example 8 (Dust (a) Compound No. lEi-b 0.2 parts by weight (b) Calcium c:arbon<~te powder98.8 "

(c) Lower alc;ohol phosphate 1.0 "
The above components are uniformly mixed.
Formulation Example 9 i;Emulsifiable concentrate) 1 (a) Compound No. 2Ei 20 parts by weight (b) Xylene 60 "
(c) Polyoxyet:hylenE~ alkylaryl 20 "
ether The abovE~ components are mixed and dissolved.
Formulation Exam~~le 10 ('Suspension concentrate) (a) Compound No. 151 10 parts by weight (b) Corn oil (c) Polyoxyet:hylene caster oil 12 "
(d) Bentonite-alkylamine 1 "
complex The above components are uniformly mixed and pulverized.
Formulation Example 11 (Granule) (a) Compound No. 33-b 1 parts by weight (b) Bentonite 61 "
(c) Kaolin 33 "
(d) Sodium lignin ;sulfonate 5 "
A suitable amount of water required is added to the above componE~nts, followed by mixing and granulating.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (5)

1. A compound as an intermediate represented by the following general formula (II'):
wherein R2 and R3 each represents a hydrogen atom; a halogen atom; a nitro group; a cyano group; a trimethylsilyl group; a C3-6 cycloalkyl group; a naphthyl group; an unsubstituted alkyl group or a substituted C1-12 alkyl group which substituent is selected from the group consisting of one or more halogen atoms, hydroxyl groups, acetoxy groups, C1-4 alkoxy groups, halogenated C1-4 alkoxy groups, phenyl groups, halogenated phenyl groups, or C1-4 alkylated phenyl groups; an unsubstituted C2-10 alkenyl group or a substituted C2-10 alkenyl group which substituent is selected from the group consisting of one or more halogen atoms; an unsubstituted C1-6 alkoxy group or a substituted C1-6 alkoxy group which substituent is selected from the group consisting of one or more halogen atoms; an unsubstituted phenyl group or a substituted phenyl group which substituent is selected from the group consisting of one or more halogen atoms, C1-4 alkyl groups, halogenated C1-4 alkyl groups, C1-4 alkoxy groups, halogenated C1-4 alkoxy groups, C1-4 alkylthio groups, halogenated C1-4 alkylthio groups, nitro groups, cyano groups, or 3,4-methylenedioxy groups; an unsubstituted furyl group or a substituted furyl group which substituent is selected from the group consisting of one or more halogen atoms or C1-4 alkyl groups; an unsubstituted thienyl group or a substituted thienyl group which substituent is selected from the group consisting or one or more halogen atoms or C1-4 alkyl groups; an unsubstituted pyridyl group or a substituted pyridyl group which substituent is selected from the group consisting of one or more halogen atoms or C1-4 alkyl groups; an -SO n R7 group, wherein R7 represents a C1-6 alkyl group, a C2-6 alkenyl group, an unsubstituted phenyl group or a substituted phenyl group which substituent is selected from the group consisting of one or more halogen atoms, a benzyl group, an unsubstituted pyridyl group or a substituted pyridyl group which substituent is selected from the group consisting of one or more halogen atoms, C1-4 alkyl groups, or halogenated C1-4 alkyl groups, or an -NR8R9 group, wherein R8 and R9 each represents a C1-4 alkyl group, and n is 0, 1 or 2; or a -CO(NH)m R10 group, wherein R10 represents an unsubstituted C1-4 alkyl group or a substituted C1-4 alkyl group which substituent is selected from the group consisting of one or more halogen atoms, an unsubstituted C1-4 alkoxy group or a substituted alkoxy group which substituent is selected from the group consisting of one or more halogen atoms, or an unsubstituted phenyl group or a substituted phenyl group which substituent is selected from the group consisting of one or more halogen atoms; and m is 0 or 1; provided that compounds represented by the general formula (II"):

wherein R2' and R3' are simultaneously a hydrogen atom, an unsubstituted phenyl group or a phenyl group which substituent is selected from the group consisting of the same or different C1-2 alkoxy group or C1-2 alkylthio group at the para-position, an unsubstituted C1-4 alkyl group or a substituted C1-4 alkyl group which substituent is selected from the group consisting of one or more halogen atoms, hydroxyl groups, acetoxy groups, C1-4 alkoxy groups, halogenated C1-4 alkoxy groups, phenyl groups, halogenated phenyl groups, or C1-4 alkylated phenyl groups, wherein R2' and R3' are each independently selected from the group consisting of a halogen atom, a cyano group, or a nitro group; and wherein one of R2' and R3' is a hydrogen atom and the other is a halogen atom, a methyl group or a phenyl group, are excluded.

2. The compound according to claim 1, wherein R2 represents a halogen atom; R3 represents an unsubstituted phenyl group or a substituted phenyl group which substituent is selected from the group consisting of one or more halogen atoms, C1-C4 alkyl groups, halogenated C1-C4 alkyl groups, C1-C4 alkoxy groups, halogenated C1-C4 alkoxy groups, C1-C4 alkylthio groups, halogenated C1-C4 alkylthio groups, nitro groups, cyano groups, or 3,4-methylenedioxy groups.

3. The compound according to claim 1, wherein R2 represents a halogen atom; R3 represents an unsubstituted phenyl group or a substituted phenyl group which substituent is selected from the group consisting of one or more C1-C4 alkyl groups, or alkoxy groups.

4. The compound according to claim 1 wherein R2 represents a chlorine atom; R3 represents a phenyl group, a 4-methyl phenyl group, a 4-ethyl phenyl group, or a 4-methoxy phenyl group.

5. A compound as an intermediate represented by the following general formula (II'):
wherein R2 and R3 each represents a hydrogen atom; a halogen atom; a nitro group; a cyano group; a C3-6 cycloalkyl group;
a naphthyl group; an unsubstituted C1-12 alkyl group or a substituted C1-12 alkyl group which substituent is selected from the group consisting of one or more halogen atoms, acetoxy group:, phenyl groups; an unsubstituted phenyl group or a substituted phenyl group which substituent is selected from the group consisting of one or more halogen atoms, C1-C4 alkyl groups, halogenated C1-C4 alkyl groups, C1-C4 alkoxy groups, halogenated C1-C4 alkoxy groups, C1-C4 alkylthio groups, halogenated C1-C4 alkylthio groups, nitro groups, cyano groups, or 3,4-methylenedioxy groups; a substituted furyl group which substituent is selected from the group consisting of one or more C1-C4 alkyl groups; an unsubstituted thienyl group or a substituted thienyl group which substituent is selected from the group consisting of one or more halogen atoms or C1-C4 alkyl groups; an -SO n R7 group, wherein R~ represents a C1-6 alkyl group, an unsubstituted phenyl group or an -NR8R9 group, wherein R8 and R9 each represents a C1-C4 alkyl group, and n is 0, 1 or 2; provided that compounds represented by the general formula (II"):
wherein R2' and R3' are simultaneously a hydrogen atom, an unsubstituted phenyl group or a phenyl group which substituent is selected from the group consisting of the same or different C1-2 alkoxy group or C1-2 alkylthio group at the para-position, an unsubstituted C1-4 alkyl group or a substituted C1-4 alkyl group which substituent is selected from the group consisting of one or more halogen atoms, acetoxy groups, phenyl groups, wherein R2' and R3' are each independently selected from the group consisting of a halogen atom, a cyano group, or a nitro group; and wherein one of R2' and R3' is a hydrogen atom and the other is a halogen atom, a methyl group or a phenyl group, are excluded.