JPH0356469A - Herbicide sulfoneamide derivative - Google Patents

Abstract

NEW MATERIAL: A compd. represented by formula I [wherein Q is groups represented by formulae II, III (wherein W¹ is O or S; R₁ and R₂ are each H, halogen, alkyl, arylthio, aryloxy, alkoxy, etc.; R₃ is H, alkyl, alkenyl, aryl, etc.; and R₄-R₆ are each H, halogen, alkoxy, alkyl, etc.), W is O or S; A is groups represented by formulae IV, V (wherein X is CH₃, OCH₃, halogen, etc.; Y is H, CH₃, OCH₃, NH₂, etc.; Z is CH, N, OCH₃, etc.; and X₁ is CH₃, OCH₃, etc.); and R is alkyl, alkenyl, alkynyl aryl, etc.].

EXAMPLE: N-[(4,6-dimethoxypyridin-2-yl)aminocarbonyl]3-methyl-4-oxo-(3H) quinazoline-5-sulfonamide.

USE: A herbicide.

PROCESS: A sulfonyliso(thio)cyanate represented by formula VI is reacted with a heterocyclic amine represented by formula VII to obtain the compd. represented by formula I.

COPYRIGHT: (C)1991,JPO

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to organic compounds having biological activity, particularly organic compounds having herbicidal activity and plant growth regulating activity, methods for preparing such compounds, and methods for preparing such compounds. Intermediates useful in the preparation, as well as herbicidal compositions and methods using such compounds. [Prior Art] The use of certain sulfonylureas as herbicides is known in the art. For example, '''Pesti-ci
de Manual' (C.RJorthingW
, The British Crop Protecti
on Council, 7th edition, 1983), chlorsulfuron (1-(2-chlorophenylsulfonyl)-3-(4-methoxy-6-methyl-1.3.5-
describes a sulfonylurea commercially known as }Ryazin-2-yl)urea and its use as a broadleaf weed herbicide in cereals. Australian Patent Application No. 23.771/88 is
Novel bicyclic heterocyclic sulfonylureas and related prior art are described. SUMMARY OF THE INVENTION It has been discovered that a new group of bicyclic heterocyclic sulfonylurea derivatives exhibits particularly useful herbicidal activity. They have both pre- and post-emergence applications and exhibit selective herbicidal activity against broadleaf and grass weeds in important cereal crops such as corn, rice, wheat, barley, sugar beet, cotton and soybean. ．． Accordingly, the present invention provides compounds of formula I: 111 RoSO! N}IcNA (1) R Q is the next Q. ~Q. W. W. and W, are independently 0 or S; R, and R2 are independently hydrogen, halogen, CI-C4
Alkyl, C+ -Ca haloalkyl, arylthio, aryloxy, nitro, C+ -Ca alkoxy, CI
-C4 haloalkoxy, cyano, carboxy, carbamoyl, N- (c.-C4 alkyl)carbamoyl, N
, N-diCC+-Ca alkyl)carbamoyl, CI-
04 alkoxycarbonyl, C, -C. alkylthio,
C+C4alkylsulfinyl, CI C4
Alkylsulfonyl, sulfamoyl, C.I. -C. Alkylsulfamoyl, di(C.-04alkyl)sulfamoyl, amino, CI-04alkyl, di(C.
+ Cm alkyl) acylamino or, Cl104 acylamino; R and R, each independently hydrogen, Ct Ca alkyl, Ct C4 alkenyl, C which may be substituted
z Ca alkynyl, or optionally substituted aryl or arylalkyl; R3 is hydrogen, optionally substituted Cr Ca alkyl, C. -C. alkenyl, Cz-Ca alkynyl,
optionally substituted aryl or arylalkyl, or Ct Cs alkoxyalkyl; R4 , Rs and R. each independently hydrogen, halogen, CI-C4 alkoxy, haloalkoxyaryloxy, optionally substituted C. -C alkyl, Cm
"-Ca alkynyl or optionally substituted aryl or arylalkyl ξno, CI104 alkylamino or di(Ct1C4 alkyl)aξno, arylaξnoalkylthio, haloalkylthio or arylthio: A is any one of the following A-1 to A-7; A-2 , l λ・4 ? is CII, OCR.OCIIzCHz+ Cl+
F* Br+ L OCPJ. CItF or CF!
and: Y is H, CH3, OCHz, OCtHs,
CLOCII1 NH■ NHCII3IN (CH3)
■ CJs, CFs. SCH1? (OCHs) Cll1
0CHtCH-CH■ OCHzC=CI,OCI{
zCF1 cycloprovir, OCH zcH gOcH
s , elf zsc}I s , (Cﾊ0)R
■? Rs(OCHgCH!)■OCFJ,SCFJ.
C = co or CECCH3 (where Q is O or S and RI is H or CHs i”)
;z is CI. N. ccos. CCJs. CCj!
or CBr: Y1 is O or Cut;
1 is C old, OCH. OCJs or ocpzn;
Y Mayuzumi is H or CB. and Xt is cod. cans
or CHtCFs; Y, is OCII■OCJs
, SCHs, SC Snow Hs, CHs or CHtCHs
; X, is C}13 or ocus; Y4 is Cl■OCII! IOCHxCHs or Cj! and X4 is CHs. OCHs. OCHzCHs
．． CHzOCHs or Cl. The present invention also relates to salts in which the compound of 2 can be formed with anion, an alkali metal base and an alkaline earth metal base or with a quaternary ammonium base. In the above definitions, the term "alkyl" used alone or in compound terms such as "alkylthio" or "haloalkyl" refers to straight or branched chain alkyl, such as methyl, ethyl, n-probyl, isoprobyl or Refers to various butyl isomers. The term "aryl" used alone or in the compound "arylalkyl" includes halogen, methoxy,
means an aromatic ring such as phenyl or pyridyl, which may be substituted by a methyl, trifluoromethyl or nitro group. "Alkoxy" means methoxy, ethoxy, n-proboxy, isopropoxy or the various butoxy isomers. "Alkenyl" refers to straight or branched chain alkenyl, such as vinyl, 1-propenyl, 2-propenyl, 3-propenyl and the various butenyl isomers. "Alkylsulfonyl" means methylsulfonyl, ethylsulfonyl or the various probylsulfonyl isomers. "Alkylthio", "alkylsulfinyl", "alkylamino", etc. are similarly defined. Preferred compounds of the invention include: 1) Compounds of formula I, where W is O and A is A-1. 2) R is hydrogen; and R8 is independently hydrogen,
fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, methoxycarbonyl or methylthio;
and preferred compounds of l), wherein Y is methyl, methoxy, ethoxy, methoxymethyl, trifluoromethyl, 2.2.2-}lifluoroethoxy, dimethoxymethyl or difluoromethoxy. Examples of basic types of fused saturated heterocyclic ring systems attached to the sulfonyl end of a sulfonylurea linkage are: 5-Sulfonyl-4-oxo3,4-dihydroquinazoline (Bl): 8-sulfonyl-4-oxo3,4-dihydroquinazoline (B2)i 5-sulfonyl-1.2.3.4-tetrahydroquinazoline- 2.4-dione (B3); 8-sulfonyl-1.
2.3.4-Tetrahydroquinazoline-2,4-dione (B4)i5-sulfonylquinazoline (B5)i8-sulfonylquinazoline (B6).

B2 B3 B4 Specific examples of compounds of the invention are: Listed in Table 1 Contains compounds such as

In the first Nihy expression, M is M. Table 11 (Continued) Compound Nα RR 23 Table 21 (continued) 86 SC H 65 H OCH30C}+3 CH E-2 Table 1 In the formula, M is M2. 0 Compound magnetism R I R 2 Nα R IR 2 In the formula, M is M. 0 Compound R Ha 1 R 2 R 3 R 4 X Y 2 First ΣL table (continued) Compound R1 Nα R2R3R4 X Y 2 Yuichi; In the above formula, M is M. 8 C1 H ■ H CH30CH3 N Yi 12 L 1 table (continued) Compound R1 Nα R RR 2 3 4 X Y 2 l6 H 8r H H CH30CH3 N 20 H Co2C83H H CH30CH3 H Yi 12 L 1 barley (continued) Compound R1 Nα R2R3R4 Compound Nα R 2 R s R s X Y 2 l0 CO2CH3 H H H CM30CH3C}l Table 5 (continued) Compound NIL R RR 2 5 6 H30CH3N CH3C}l3CH H II H }IH}l OCH3C}l QC}I3N 29 H ■ H C FI3 C H 3 C H 3CH Compound Nu Man-5 Table 1 (continued) R RR 2 5 6 X Y 2 Chemical substance NIL 1st "L Table 1 (continued) R RR 2 5 6 X Y 2 Compound Nn Table 5 (continued) R RR 2 5 6 X Y 2 Table 5 (continued) Compound NIL R 2 R s R 6 Co2C }13H COC}IH 23 CO2CH3H CH3C}l OCH3C}l OCH3CH Br OCH30CH3CH30CH3N Yuichi 5 Table (continued) Compound R1 Nα RR R 2 5 6 X Y 2 127 H C1 C1 Q C}I3QC}l3C}l 134 H C1 C] CH3QC}l3C}l Yuichi 5 Table (continued) Compound R1 No. R2R5R6 It is. Compound no. RIR2 R5R6 X Y 2 l0 ■ Co2CH3H H CH30C83CH Compound NIL R 2 R s R 6 (continued) jlLl (continued) Compound, NcL1 R 2 R s R s X Y 2 Table 1 (continued) Compound R1 Nα R 2 R s R 6
{OCH30CH3C}l3C}l3C}IOCII3
QC}l3CM30CH3CHQC}l3QC}l3Q
C}+30CH3CH115 H H C1 C1 QC}+30CH3C}I 1st L table (continued) Compound 8 Nα 1 RR R 2 5 6 Co2CH3H Co2CM3H CI CI CI Cl OCH3CH OCH3CH 1st L table (continued) Compound R1 Nα R2R5R6 X Y 2 140 H 8r C1 C1 CI130CH3N Table 1 (continued) Compound R No. 1 R2R5R6 X Y 2 As the compounds of the invention can be prepared in a variety of ways, in a further aspect the invention provides methods for preparing compounds of formula I. Conveniently, the preparation of the compounds of the invention can be considered in three parts. Part A relates to the preparation of fused phenyl sulfonamides of formula (1).

QSOJHg (II) where Q is as defined for formula ■, and R, ~R.
．． W. and W2 are as defined for Formula I. The sulfonate ξ-do of formula ■ can be prepared in a variety of ways, including the general methods outlined below.

The required sulfonate compound (■) can be synthesized from the corresponding sulfonyl chloride (■) as summarized in Scheme 1. (III) (n) where Q is as defined above.

The reaction shown in Formula I involves adding an excess of either anhydrous ammonia or concentrated ammonium hydroxide to a solution of the sulfonyl chloride in a suitable solvent such as tetrahydrofuran or diethyl ether at -30°C to 0°C. This is most conveniently done by: The sulfonyl chloride in Part 2 has the following chemical reaction formula 2.3.
Alternatively, it can be prepared by one or more of the methods shown in 4. Chemical reaction scheme 2 represents the oxidative iodination of a thiol or thioether of formula (1).

(IV) (III) where R,
is hydrogen or benzyl. The reaction shown in Scheme 2 is best carried out in a suitable solvent such as chloroform or methylene chloride; in some cases it is advantageous to use acetic acid as the solvent. The reaction is carried out in the presence of at least 2.5 equivalents of water and 3 equivalents of chlorine gas at a temperature of 0° C. to 30° C. for 1 to 5 hours. The living precepts are
It is most conveniently isolated by filtration and is usually used in the next step without purification.

Another method for the preparation of sulfonyl chloride Ⅰ is summarized in Scheme 3 and involves the reaction of an unsubstituted compound of formula V with chlorosulfonic acid. (V) (III) The reaction of equation 3 is best carried out by addition of compound ① to excess chlorosulfonic acid. The reaction mixture is then heated typically to 100-150°C for 1-5 hours,
Cool to 25°C and carefully pour onto crushed ice. The desired sulfonyl chloride (■) is usually isolated by filtration. A third method for the synthesis of sulfonyl chlorides of formula (2) involves diazotization of the aniline derivative (2) and coupling with sulfur dioxide in the presence of cupric chloride as shown in Scheme 4. 1824 (1960)). (J.Qrg.Chem.. (Vl) (III)
The required aniline derivatives of formula (1) can be prepared in a simple manner by reduction of the corresponding nitro compounds of formula (5) as shown in Scheme 5. (■) (Vl) Various methods exist to carry out the reduction of aromatic nitro derivatives to the corresponding anilines. One of the more common methods
First, the nitro compound of formula
It involves processing at a temperature of 80°C. Or Haz
let and Dornfeld. J. Aa+. Chem
．． Soc. ．． 66. 178H1944), the reduction can be carried out using iron powder in glacial acetic acid solution. For a general overview, see Grag
gins et al., “Unit Processes in
Organic Synthe-sis”. McGr
aw-11i11 Book Co. , New Wo
R.K., 1947. pp. See 73-128. Suitable nitro intermediates (2) can also be obtained from appropriately substituted nitroanthranilic acids (6)a as summarized in Scheme 6(a) or by nitration of the parent quinazoline V.

Kita 1' self-mobilization (i (a) (■a) R..=H, alkyl or aryl (■a) (■b) (Va) Many of the above necessary intermediates are known in the literature or or by methods known to those skilled in the art. The reaction summarized in Equation 6 is often cited in the literature. Quinazoline is described by Baker, B.R. et al.
J. Or. Chem. (1952) 164 and Le
onard, N, J, et al., left JLLS Ishi Ritsuyo (197
5) Average. It can be prepared from the appropriate anthranilic acid derivative ① according to the method of 363. Synthesis and functionalization of quinazoline
), a comprehensive compilation of references related to, for example, W.
．． L. F. Ar+sarego 'Heteroc c
lic false 肚 Animal ■” Medium, Part 1 Quinazoline, DJ Br
own g, John Wiley and Sons
(Interscience), New York, 19
See 1967.

Another approach to the desired thioether ■ involves nucleophilic displacement of the leaving group L from ■ as summarized in Scheme 7.

(IX) (IV) Examples of sulfonade 2 can be prepared from Ila as summarized in chemical reaction 28 (for Q=Q5 and Q6) using methodologies well known in the literature. ). North 140 [(4 (■d) (I.) In reaction 28, the group R. is hydrogen or a tertiary butyl protecting group; the latter protecting group can be easily removed with an acid, e.g. trifluoroacetic acid. Part B of the preparation of compounds of the invention relates to the preparation of various nitrogen-containing heterocycles A-1-A-7.
can be prepared by methods well known to those skilled in the art in the literature or by simple variations thereof. 2-Amino and 2-methylagonopyridine (X
, A=A- 1 , Z=CH) and an overview of the reactions, see The Chsu++istro
f Hetero-c clic Cos+'ound
s Vol. 16+ Wiley-Intersci
ence, New York (1962). For an overview of the combinations and reactions of 2-amino and 2-methylamino-s-triazines (X, A=A-1 .Z=N), see The Che+sistro
f }leteroc click Cow ounds
Vol. 13. Wiley-1interscience
E., New York (1959) and F.E., New York (1959). C. S
chaefer and K. R. Huffman. lyu''ΣOtsu1e average. , Hammer. See 1812 (1963), I! P-A No. 84.224 and -. B
Raker et al., J. Aser. Che*. Soc. +
Deaf, 3072 (1947) describes a method for preparing triazines and anonymous ξdines substituted with acetal groups such as dialkoxymethyl or 1,3-dioxolan-2-yl. U.S. Patent No. 4,515.
No. 626 describes a process for the synthesis of cyclopropyl-pyrimidines and triazines substituted by groups such as alkyl, haloalkyl, alkoxy, haloalkoxy, alkylano, dialkylamino or alkoxyalkyl. 5.6-dihydrofuro (2.3-d)
pyrimidine-2-amine, cyclopenta[d]pyrimidine-2-amine (formula X where A is A-2) and 6.7
-dihydro-5H-vilano(2.3-d)pyridξdine-2-anξone (formula X where A is A-3) as taught in U.S. Pat. It can be prepared by Furo(2.3-d)-2-amines (formula X, where A is A-4) are described in U.S. Pat. No. 4,487,626. Compounds of formula X where A is A-5 are E
P-A-0 073 562.
Compounds of formula X where A is A-6 are disclosed in U.S. Patent No. 4.496
．． It is described in No. 392. Compounds of formula X where A is A-7 are BP-A-0 12
5 864 (published November 21, 1984) or by suitable modifications that will be apparent to those skilled in the art. Part C of the preparation of compounds of the invention (formula 1) involves the coupling of a sulfonamide of formula 1 with a heterocyclic amine of formula X. Compounds of formula (■) are represented by a) to d) as described below.
It can be prepared by one or more of the following methods. a) A number of compounds of formula I can be prepared by reacting a sulfonylisocyanate or sulfonylisothiocyanate of formula XI with a heterocyclic amine of formula X. 10(XI) (X) (1) Here, Q is as defined for formula ■, and W, Wi
．． W! , R , R I'''Re and A are as previously defined. 0.5 at 25°C to 100°C in protic solvent
It will be held for ~24 hours. intermediates sulfonylisocyanates} (compounds of formula XI where W is O) and sulfonylisothiocyanates (
Compounds of formula XI in which W is S) are well known in the art and, for example, II! It can be prepared by various methods described in P-A-0 212 779 Patent Application No. 212.779 and the references cited therein. b) A number of compounds of formula I in which w is oxygen can be prepared by reacting a phenyl carbamate of formula X■ with a suitable amine of formula X. (XI[)
(X) (Ia) This reaction is carried out in a solvent such as dioxane or N,N-dimethylformamide at 0°C to 100°C for 0.5 to 24 hours.
The required carbamate X■ is the corresponding sulfonamide■
It is prepared by reacting with diphenyl carbonate in the presence of a strong base. C) Compounds of formula 1a can also be prepared by reacting a heterocyclic carbamate of formula X■ with a suitable sulfonate ξ of II. (If) (XIII
) (Ia) This reaction is carried out in a solvent such as acetonitrile, dioxane or N,N-dimethylformamide in the presence of a non-nucleophilic base such as DBU at temperatures ranging from 0.2 to 100 °C. It is held for 24 hours. The required phenylcarbame}XII[ is prepared by reacting the corresponding heterocyclic amine X with diphenyl carbonate or phenyl chloroformate in the presence of a strong base. Alternatively, a methyl carbamate derivative of the heterocyclic amine X may be used. d) Some of the compounds of formula 1b according to the invention can be prepared by reacting the sulfonate ξ do with a heterocyclic isocyanate or isothiocyanate of formula XIV. Ga II Q-SOJH*+Ichitomi C Snow N-A・-・-→QSOJH
CNH A(II) (XIV)
(Ib) This reaction is carried out at 25°C to 80°C in an inert aprotic solvent such as acetone or acetonitrile in the presence of a base such as potassium carbonate. 5
It will be held for ~24 hours. The required heterocyclic isocyanate and isothiocyanate XIV are BP-A-0 03
5 893 from the corresponding amine H*NA which would be known to those skilled in the art. In each of b), c) and d) above, the group Q. W,
A and R are as defined above.

2n. m, ■. v. Since some of the intermediate compounds of vi, ■ and ■ are novel compounds, in a further aspect the invention provides m. ■、v. vt. The novel compounds of (1) and (2) and their preparation methods are provided. Agriculturally suitable salts of compounds of Formula I are also useful as herbicides and can be prepared by a number of methods known in the art. For example, metal salts are prepared by contacting a compound of formula 1 with a solution of an alkali or alkaline earth metal salt (e.g. hydroxide, alkoxide, carbonate) with a sufficiently basic anion. be able to.

Quaternary amine salts can also be prepared using similar techniques. Salts of compounds of formula I can also be prepared by exchanging one cation for another. Cation exchange can be carried out by directly treating an aqueous solution of a salt (eg an alkali metal salt or a quaternary amine salt) of a compound of formula I with a solution containing the cation to be exchanged. This method requires that the desired salt containing the exchanged cation is insoluble in water;
For example, it is a copper salt and is most effective when it can be separated by filtration. Exchange can also be carried out by passing an aqueous solution of a salt (for example an alkali metal salt or a quaternary amine salt) of the compound of formula (1) through a column packed with a cation exchange resin containing the cation to be exchanged. In this method, the cations of the resin are exchanged with the cations of the original salt, and the desired raw material is eluted from the column. This method is particularly useful when the desired salt is a water-soluble salt, such as a potassium, sodium or calcium salt. Acid addition salts useful in the present invention can be obtained by reacting a compound of Formula I with a suitable acid, such as P-}luenesulfonic acid, trichloroacetic acid, and the like. The compounds of formula (1) are active as herbicides and therefore, in a further aspect, the present invention provides a method for killing or severely damaging unwanted plants. The method comprises applying an effective amount of a compound of formula (1) as defined above to the plant or to the growth medium of the plant. The compound of formula ■ can be applied directly to the plant (post-emergence application) or to the soil before emergence (pre-emergence application). Although the compounds of formula I can be used alone to regulate plant growth, compositions containing the compounds of the invention generally preferably include a solid or liquid diluent and in admixture with a carrier. It is used in the form of Accordingly, in a further aspect, the present invention provides a plant growth regulating composition comprising a compound of formula I as defined above and a carrier inert thereto. The composition according to the invention comprises a ready-to-use diluted composition,
and concentrated formulations that usually require dilution with water before use. The diluted composition is preferably 1 ppm
Contains ~2% active fraction, while concentrated compositions contain 20-99%
% of the active ingredient, but usually 20 to 70% is preferred. The solid composition can be in the form of a granule or a dusting powder;
In this case, the active ingredient is mixed with finely divided solid diluents, such as kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, magnesium powder, Fuller's earth or gypsum. They may also be in the form of certain dispersible powders or grits containing wetting agents to facilitate dispersion of the powder or grits in the liquid. Solid compositions in powder form can be applied as foliar sprays. The liquid composition may comprise a solution or suspension of the active substance in water, optionally containing a surfactant, or a solution or suspension of the active substance in a water-immiscible organic solvent dispersed as droplets in water. It can be used to contain a solution or suspension of active precepts. The amount of a compound of the invention to be applied depends on a number of factors including, for example, the compound used, the identity of the plant to be treated, the formulation used and whether the compound is to be applied by foliar or root absorption. It will depend. However, as a general rule, an application rate of 0.001 to 10 kilograms (kg) per hectare (ha) may be appropriate, with 0.01 to 5 kg/ha being preferred. Compositions of the invention may include, in addition to one or more assemblies of the invention, one or more compounds that are biologically active but not of the invention. In some applications, it may be preferable to use certain herbicidal combinations comprising a mixture of at least one herbicidal compound of formula II as defined above and at least one other herbicide. .

The compounds of the invention and their preparation are further illustrated by the following examples. 6-chloro-5-nitro-4 in acetone (100d)
(3H) Monoquinazolinone (9.5g, 4.2X10-
A suspension of methyl iodide (6.0 g) and potassium carbonate (6.2 g, 4.2 x 10-" moles) was boiled for 3 hours. The solvent was then evaporated, water (IOM) was added and the suspension was stirred at room temperature for 30 minutes. Filtration yielded the desired methylquinazolinone (8.2
g, 82%) was obtained.

δ'H (db-DMSO): 8.46 (s.IH)
; 8.06 (d, J 9H, z. IH); 7.88
(d.J 9Hz, IH); 3.59 (s.3H).

Lithium hydroxide hydrate (11.1g, 1.7xlO
-'mol) of dry N. N-dimethylformamide (I
Nitroquinazolinone and pendylmercabutane of Example 1 in OM) (19.5 ad!, 1.7 XIO
-'-F-ru) in portions over 15 minutes at water bath temperature under a nitrogen atmosphere. The water bath was then removed and the reaction was stirred at room temperature overnight. Water (500a+dl
) and stirring for a further 30 minutes at room temperature,
The resulting suspension was filtered, washed with water, then ethanol, and dried to yield the desired pendyl thioether (38 g. 78%) as a colorless solid. δ'11(
da-DMSO): 8.41 (s.IH); 7
．． 82 (d.J 9Hz.IH); 7.53 (d.J
9Hz. IH);7.1? (brs, 541): 4
．． 20 (s. 2H) i3.50 (s, 3H).

1104 While maintaining the internal temperature below 5°C, acetic acid/water (1:
1. Chlorine gas was gently bubbled into a stirred suspension of the pendyl thioether of Example 2 (7.5 g, 2.5 x lO-3 moles) in 100 Jd) for 30 minutes'. Water (100 m ) was added and the resulting suspension was filtered, washed well with water and dried to give the desired sulfonyl chloride (6.7 g.93
%) was obtained. δ'H (di-DMSO): 9.20 (s.IH)
; 7.85 (d, J 9Hz.IH); 7.65 (
d, J 90! , IH): 3.51 (3.3H). 0℃
The sulfonyl chloride of Example 3 (19.Og, 6.5X) in dry acetonitrile (300m) cooled to
Dry ammonia gas was bubbled gently into the stirred suspension of IO-"mol) for 1 hour. The solvent was then evaporated and water (300 d) was added. The resulting suspension was filtered and diluted with water. and drying yielded the desired sulfonate as a colorless solid (16.0 g, 90%).
I got it. δ'H (di-DMSO): 8.52 (s.LH)
; 7.95 (d, J 9Hz.IH): 7.80 (
d. J 9Hz. IH): 7.64 (brs.2H).
3.53 (s.3H). N. Chlorosulfonate ξ-de prepared in Example 4 (12.0 g, 4.4 XIO-” moles) in N-dimethylformamide (400 m ),
10% pd-c (4.0 g), ammonium formate (3.0 g, 4.8 XIO-” moles)
and sodium acetate (4.0 g, 4.8 x lO
-” mol) suspension was stirred for 3 hours under a hydrogen atmosphere at 50 psi. The reaction mixture was then filtered and the solvent was evaporated to give a viscous oil. Water (200 m ) was added and The resulting suspension was filtered to yield the desired dechlorinated sulfonate as a colorless solid (9.2 g.
8%). δ'H (dh-DMSO): 8.54 (s.IH)
3 8.30-8.10 (s, 1B): 17.98
-7.93 (m.2H); 7.44 (brs.2H)
．． 3.56 (s.3H). Sulfonate prepared in Example 5 (1.5g, 6.3X10-3 mol) and O-phenyl-N-(4.6-dimethoxypyrimidin-2-yl) in dry acetonitrile (75ag) at 0°C. 1,8-diazabicyclo(5.4.0)undec-7-ene (lm, 6.9 XIG-' mol) to a stirred suspension of carbamate (1.8 g, 6.9 X 10-' mol)
was added. The cooling bath was removed and the resulting solution was stirred at room temperature overnight. Evaporate the solvent to obtain a viscous oil,
This was dissolved in water (50ml). The stirred solution was acidified (pll 4-5) with aqueous citric acid (60 g/l). The resulting suspension was filtered, washed with water then ether and dried to give the desired sulfonylurea as a colorless solid. (2.
6 g, quantitative) was obtained.

δ'H(da-D)150): 12.58(brs
．． IH): 10.42 (brs.1tl): 8.4
7(s,11): 8.44-8.33(s.lH);
8.05-8.00 (m.211): 5.96 (s.
IH); 4.01 (s.6H); 3.76 (s.
．． 3H). 6-chloro-3-methyl-4-oxo(3H)quinazoline- in dimethylformamide (5M1)
A mixture of 5-sulfonamide (0.5 g, 1.8 mmol) and diethylamine (0.4 ad, 3.8 mmol) was heated at 60° C. for 1.5 hours. The solvent was distilled off, and water was added to the residue. The resulting suspension was filtered, and the solid was washed with water and air-dried to form a colorless solid.
0.2g. 36%). Prepared from 6-chloro3-methyl-4-oxo(3H) quinazoline-5-sulfonade ξ following a procedure similar to that described in Example 7. Nal 8 of 1st volume 4th table 1. 19. 22. 23,
24. 63. Compounds 85 and 86 and Na6 and 7 of Table 4 were prepared according to the conditions described in Example 6 by reaction of the appropriate 2-anobilimidine O-phenyl carbamate with the required sulfonamide quinazoline. The compounds were characterized by proton nuclear magnetic resonance spectroscopy. The results are described in Example IO. Real JLf Kodan compound Hiromu (Table 1) 22 Chemical shift of proton nuclear magnetic resonance spectrum δ(1)P-) (d, [lMSO)9.62(brs, IH); 8
．． 37 (s.IH): 7.96 (d, J 8Hz.
IH); 7.72 (d, J 8Hz.lH);
6.39 (s, IH); 3.36 (s.3H):
3.33 (s.3H); 2.35 (s.3H).

(di-DMSO) 12.71 (brs, IH):
10.53(bra.LH) s 8.48(a.IH
) s 8.02 (d, J 8Hz.lH); 7.
8? (d.J 8Hz.IH) :6.00(s.IB
): 3.99(s.3H); 3.33(s.3H)
H). (da-D?ISO) 12.58 (brs.IH);
10.42 (brs.IH); 8.47 (s.I
B): 8.44-8.33 (s, LH) s 8.
05-8.00(s.211)'; 5.96(s, 1
B): 4.01 (s, 61): 3.76 (s.
3H). (da-DHSG)13.18(brs.lH
): 10.39(brs.IH); 8.47(
s. IR) s 8.43-8.33 (Proverb. IH);
8.03-7.98 (m.2H): 6.53 (s.I
H): 4.0G (s.3H): 3.42 (s.
3H): 3.35 (s.311). (di-DMSO)? -86 (dsJ 81g 11)
: 7.37 (s.IH); 7.29 (d.J
8Hz. IO): 3.81 (a.311);3.
346 (s.3B): 2.21 (s.3B). 63 21 85 (da-DMSO) 12.78 (brs.IH):
10.48 (brs. IH); 8.52 (s. IH
) s 8.00-7.93 (s.2H); 5.98
(s.IH): 5.23(s.IH): 3.97(s.IH): 5.23(s.IH): 3.97(s.IH)
．． 6H): 3.1? (a.3B), (da-DMS
O) 11.10 (brs.IH) s 9. T? (br
s. IH): 8.3g (s.IH): 7.86
(d, J8Hz.IH): 7.43 (d.J8H
z. IH) ; 6.65 (s.IH) s 3. T.O.
(s.3H) s 2.23 (a.6H). (da-D
MSO) 11.10 (brs.IH); 9.83 (
brs, IH); 8.38 (s.IH); 7.
6G (s.21) 3 5.91 (s.lH); 3
．． 91 (a.3H) s3.11-3.05 (■.41
1) f 1.28-1.13 (s+, 61). This non-limiting example illustrates a method for preparing formulations of compounds of the invention. a) 7% (v/v) “Teric” N13 and 3% (v/v)
V) @KesIsat''Toluene/D containing SC15B
Compound Nal8 (Table 1) was dissolved in MSO to obtain an emulsifiable concentrate, which was diluted with water to the desired concentration to obtain an aqueous emulsion, which was applied by spraying. ('Taric' is a trademark and 'Teric' N1
3 is the raw material of ethoxylation of nonylphenol; "Kea+ma.t" is a trademark, 1κemmat
'sc15B is a calcium dodecylbenzenesulfonate preparation. ) b) Compounds Nal8 (5 parts by weight) and “Dyap” of Table 1
ol”PT (1 part by weight) to “Teric’N 8
A suitable aqueous suspension was prepared by milling the mixture in a ball mill. This suspension can be diluted with water to the desired concentration to obtain an aqueous suspension, which can be applied by spraying. (′
"Dyapol" is a trademark and "Dyapol" PT
is an anionic suspending agent; "Teric" N8 is a raw material of ethoxylation of nonylphenol. )C)
Compound Nl118 (10 parts by weight) of Table 1, "Te
rtc”N13 (5 parts by weight) and “Kemsat”S
C15B (5 parts by weight) was added to “So1vesso”150
(80 parts by weight) to obtain an emulsifiable concentrate. This emulsifiable concentrate can be diluted with water to the desired concentration to obtain an aqueous emulsion, which can be applied by spraying. (“So1vesso” is a trademark and “Solvesso” is a trademark.
so''150 is a high-boiling aromatic petroleum fraction.) d) Compound Nal8 (10 parts by weight) in Table 1, '''Mat
exil”D^/AC (3 parts by weight), “Aerosol
"OT/B (1 part by weight) and China Clay 298 (86 parts by weight) were blended, then finely pulverized, and
A powder composite material having a particle size of 0 microns or less was obtained. (“Matexil” is a trademark and “Matexil” is a trademark.
” DA/AC is naphthalene sulfonic acid disodium salt/formaldehyde condensate: “Aerosol”
is a trademark and "Aerosol" OT/B is a dioctyl ester formulation of sodium sulfosuccinate. ) e) LL! ! Compounds 11kL18 (10 parts by weight) of Table 1, attabulgite (10 parts by weight) and birophyllite (8 parts by weight)
0 parts by weight) were thoroughly mixed and then ground in a hammer mill to produce a powder with a particle size of less than 200ξ croons. Essentially a) above. Emulsifiable concentrates and/or suspensions of the compounds of the invention are prepared as described under b) or c) and optionally contain surfactants and/or
or diluted with water containing oil to obtain an aqueous suspension of the desired concentration, which is used as described in Examples 12 and 13 in the evaluation of herbicidal activity of compounds of the invention before and after emergence. did. The pre-emergence herbicidal activity of the compound of the present invention formulated as described in Example 1l was evaluated by the following procedure. Seeds of the test plant species were placed in 2 ml of soil in a sowing box.
The seeds were sown in rows at a depth of . Monocots and dicots were sown in separate boxes, and after sowing the two boxes were sprayed with the required amount of a compound of the invention. Two more identical seeding boxes were prepared in a similar manner, but were not sprayed with the Kumikaimono of the present invention, and were used for comparison purposes. All boxes were placed in a glass chamber and lightly irrigated with overhead spray to initiate germination, followed by supplemental watering as needed for optimal plant growth. After 3 weeks, the boxes were removed from the glass chamber and the effects of the treatment were visually evaluated. The results are given in Table 7. Damage to plants is rated on a scale of 0 to 5. 0 represents 0-1O% damage, 1 represents 11-3
0% damage, 2 represents 3l~60% damage, 3
indicates 61-80% damage, 4 indicates 81-99% damage, and 5 indicates 100% death. dash(
-) means no experiment was performed. The names of the test plants are as follows.

wh Wheat 01 Oat Rg Rye h Barnyard grass B Barley P Pea ip Sweet potato Ms Mustard Sf Sunflower Daiichi 1 Table Pre-emergence herbicidal activity Application amount in Table 1 18 0.4 0 0 0
0 0 0 019 0.4
4 0 0 1 1 0
222 0.4 0 0
0 0 0 0 523 0
．． 4 0 0 0 0 0
0 024 0.4 - 3
3 4 0 0 063
0.4 3 0 0 0
4 3 2゛The post-emergence herbicidal activity of the compounds of the present invention formulated as described in Example 11 was evaluated by the following procedure. Seeds of the test plant species were placed 2 cm into the soil in a sowing box.
The seeds were sown in rows at a depth of . Monocots and dicots were sown in separate boxes, and duplicates of each were prepared. Four boxes were placed in a glass chamber and lightly watered with overhead spray to initiate germination, followed by supplemental watering as needed for optimal plant growth. Plants are approximately 10-12.5C1
After growing to 1 plant height, 1 each of monocots and dicots.
Two boxes were removed from the glass chamber and sprayed with the required amount of the composition of the invention. After spraying, the boxes were returned to the glass chamber for 3 weeks and the effects of the treatment were visually evaluated by comparison with untreated controls. The results are given in Table 8.
Evaluate damage to plants on a scale of 0 to 5. O is 0-
1 represents 10% damage, 1 represents 11-30% damage,
2 represents 31-60% damage, 3 represents 6-80% damage, 4 represents 81-99% damage, and 5 represents 100% withering. A dash (-) means no experiment was performed.

The names of the test plants are as follows. wh wheat 01 Oat R. Rye J seaweed millet barley pea sweet potato Callan Sun Flower Tsuta-JL first table Post-emergence herbicidal activity Application amount in Table 1

Claims (1)

[Claims] 1. The following formula I: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the above formula, Q is any one of the following Q_1 to Q_6; ▲ Numerical formula, chemical formula , tables, etc.▼Q_1 ▲There are mathematical formulas, chemical formulas, tables, etc.▼Q_2 ▲There are mathematical formulas, chemical formulas, tables, etc.▼Q_3 ▲There are mathematical formulas, chemical formulas, tables, etc.▼Q_4 ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Q_5 ▲There are mathematical formulas, chemical formulas, tables, etc.▼Q_6 W, W_1 and W_2 are independently O or S; R_1 and R_2 are independently hydrogen, halogen, C_1
-C_4 alkyl, C_1-C_4 haloalkyl, arylthio, aryloxy, nitro, C_1-C_4 alkoxy, C_1-C_4 haloalkoxy, cyano, carboxy, carbamoyl, N-(C_1-C_4 alkyl)carbamoyl, N,N-di(C_1 -C_4 alkyl)carbamoyl, C_1-C_4 alkoxycarbonyl, C_1-C_4 alkylthio, C_1-C_4 alkylsulfinyl, C_1-C_4 alkylsulfonyl, sulfamoyl, C_1-C_4 alkylsulfamoyl, di(C_1-C_4 alkyl)sulfamoyl,
Amino, C_1-C_4 alkylamino, di(C_1-
C_4 alkyl) amino or C_1-C_4 acylamino, and R and R_7 are each independently hydrogen, unsubstituted or substituted C_1-C_4 alkyl, C_2-C_4 alkenyl, C_2-C_4 alkynyl, or unsubstituted or substituted selected from aryl or arylalkyl; R_3 is hydrogen, unsubstituted or substituted C_1-C_
4 alkyl, C_2-C_4 alkenyl, C_2-C_
4 alkynyl, unsubstituted or substituted aryl or arylalkyl, or C_2-C_5 alkoxyalkyl; R_4, R_5 and R_6 each independently hydrogen, halogen, C_1-C_4 alkoxy, haloalkoxy, aryloxy, non- Substituted or substituted C_1-C_
4 alkyl, C_2-C_4 alkynyl or unsubstituted or substituted aryl or arylalkyl,
Amino, C_1-C_4 alkylamino or di(C
_1-C_4 alkyl) selected from amino, arylamino, alkylthio, haloalkylthio, or arylthio; A is any of the following A-1 to A-7; ▲ Numerical formula, chemical formula, table, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Here, X is CH_3, OCH_3, OCH_2CH_3
, Cl, F, Br, I, OCF_2H, CH_2F or CF_3; Y is H, CH_3, OCH_3, O
C_2H_5, CH_2OCH_3, NH_2, NHC
H_3, N(CH_3)_2, C_2H_5, CF_3
, SCH_3, N(OCH_3) CH_3, OCH_2
CH=CH_2, OCH_2C≡CH, OCH_2CF
_3, cyclopropyl, OCH_2CH_2OCH_3
, CH_2SCH_3, (C=0)R_8, CR_8(
OCH_3)_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
▲There are mathematical formulas, chemical formulas, tables, etc.▼, CR_8 (OCH
_2CH_3)_2, OCF_2H, SCF_2H, C
≡CH or C≡CCH_3 (where Q is O or S and R_8 is H or CH_3) Z
is CH, N, CCH_3, CC_2H_5, CCl or CBr; Y_1 is O or CH_2;
_1 is CH_3, OCH_3OC_2H_5 or OC
F_2H; Y_2 is H or CH_3;
_2 is CH_3, C_2H_5 or CH_2CF_3
and Y_3 is OCH_3, OC_2H_5, SCH_
3, SC_2H_5, CH_3 or CH_2CH_3
and X_3 is CH_3 or OCH_3; Y
_4 is CH_3, OCH_3, OCH_2CH_3 or Cl; and X_4 is CH_3, OCH_3,
OCH_2CH_3, CH_2OCH_3 or Cl] and salts thereof. 2. Claim 1, wherein W is oxygen and A is A-1.
Compounds described in. 3, R is hydrogen; R_1 and R_2 are independently hydrogen, fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, methoxycarbonyl or methylthio; and Y is methyl, methoxy, ethoxy, methoxymethyl, 2. A compound according to claim 1, which is trifluoromethyl, 2,2,2-trifluoroethoxy, dimethoxymethyl or difluoromethoxy. 4. Q is Q1, and a) in Q1, (i) R_1 is selected from the group consisting of hydrogen, chlorine, bromine, methoxycarbonyl, nitro, methoxy, methylthio, diethylamino and phenylthio; (ii) R_2 is hydrogen; and (ii) R_3 is selected from the group consisting of hydrogen, methyl, ethyl and methoxymethyl; and b) in A-1, (i) X and Y are independently selected from the group consisting of methyl and methoxy. and (ii) Z is selected from the group consisting of nitrogen and CH. 5. Process for preparing the compound according to claim 1 by reacting a compound of formula X I with a compound of formula X ▲ Numerical formulas, chemical formulas, tables, etc. Q, W, R and A are as defined in claim 1). 6. The compound according to claim 1, wherein W is oxygen, by reacting the compound of formula XII with the compound of formula X (I a
) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (XII) (X) (I a) (where Q, R and A are as defined in claim 1). 7. A compound according to claim 1, wherein W is oxygen, by reacting a compound of formula II with a compound of formula XIII (I
Preparation method of a) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (XIII) (I a) (where Q, R and A are as defined in claim 1). 8. A compound according to claim 1, wherein R is hydrogen, by reacting a compound of formula II with a compound of formula XIV (I b
) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (XIV) (I b) (where Q, W and A are as defined in claim 1). 9. A herbicidal composition comprising the compound according to claim 1. 10. A method of killing or severely injuring unwanted plants, the method comprising applying an effective amount of a compound according to claim 1 to the plants or the growth medium of the plants.