JPS5815962A - Novel sulfonylureide derivative - Google Patents

Abstract

NEW MATERIAL:The sulfonylureide derivative of formulaI[X is H, halogen, lower alkyl, lower alkoxy, nitro, carboxyl, lower alkoxycarbonyl, phenoxycarbonyl, or di-(lower alkyl)-substituted amino; Y is H, halogen, or trifluoromethyl; R is group of formula II or formula III; R1 is methoxy or methyl; R2 is halogen, methyl, etc.; R3 is halogen, methyl, etc.; R4 is methyl or lower alkoxy; Z is O, S, or imino]. USE:Agent for controlling noxious life. It efficiently controls the harmful agricultural weeds, especially broad-leave weeds such as morning-glory in the plowed land. It has also fungicidal activity against rice blast, gray mold, etc. PROCESS:The compound of formulaIcan be prepared by reacting (A) chlorosulfonyl isocyanate, (B) a heterocyclic compound of formula IV or formula V, and (C) the compound of formula IV (A is OH, NH2, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION The present study relates to a novel sulfonylureido derivative, a method for producing the same, and a pest control agent containing a temporary binding compound.

For details, refer to the general formula [1] [wherein X is a hydrogen atom, a halogen atom, a lower alkyl group,
A nitro group, a carboxyl group, a lower alkoxysulfonyl group, a fenoquine carbonyl group, or a di-lower alkyl-substituted amino group, Y represents a hydrogen atom, a halogen atom, or trifluoromethyl, represents methoxy water or a methyl group, R2 represents a halogen atom, methyl group, or methoxy group) or a general formula (wherein, R3 represents a halogen atom, methyl group, or methoxy group, and R4 represents a methyl group or a lower alkoxy group) )
and Z represents an oxygen atom, a sulfur atom or an imino group]
This invention relates to a novel sulfonylureido derivative represented by:

The object of the present invention is to obtain the sulfonylureido derivative represented by the general formula (1) and its compounds industrially advantageously, and to provide a simple and reliable agricultural chemical.

The present inventors studied the production of a number of novel compounds having sulfonylureido groups while keeping the above object in mind, and found that the compound represented by the above general formula (1) can be obtained industrially advantageously and that it can be easily used in agriculture. The compound of the present invention represented by the general formula m, which has been found to have excellent effects and has completed the present invention, can be prepared by the following method. That is, a pyrimidine or triazine visiting conductor known in the literature represented by the general formula (IV) or the general formula [v] (wherein R□, R2, R3, and R4 are the same as above) is reacted with chlorosulfonyl isocyanate, The corresponding ureidosulfonyl chloride is obtained (reaction formula-1).

Reaction Formula-1 Reaction Formula-1 is preferably carried out at room temperature and pressure in an inert aprotic organic solvent such as methylene chloride, tetrahydrofuran or acetonitrile. The method of addition is not critical, but it is advantageous to suspend the pyrimidine or triazine visiting conductor in a solvent and add dropwise a dilute solution of chlorosulfonyl isocyanate in the solvent, the reaction being generally exothermic. . The thus obtained ureidosulfonyl chloride may be purified, or may be left unpurified with a substituted aniline derivative as shown in the following reaction formula-2, or may be treated with a deoxidizing agent such as triethylamine, dimethylaniline, pyridine or potassium carbonate. By reacting with a ureidosulfonyl chloride derivative in the presence of , a sulfonylureido derivative in which 2 in the general formula [1] is coated with an imino group can be obtained. In reaction formula-2, 2 of general formula [1] is 0 using phenol or thiophenol derivative in the same manner as A.
It is still possible to synthesize S compounds.

Further, when reacted with Reaction Formula 3 anate as shown in Reaction Formula 6, one chlorosulfonyl carbamate derivative is produced, but a rearrangement reaction to phenoxysulfonyl isocyanate occurs while further producing HCA. This rearrangement reaction proceeds favorably when heated under reflux in a solvent such as toluene or quinolene. Since phenoxysulfonyl isocyanate is normally a liquid, it is easy to add these substances! You can control lJ. General formula [
[■] or the pyrimidine or triazine derivative represented by the general formula [■] is dissolved in an inert non-phnilotonic organic solvent such as methylene chloride, tetrahydrofuran or acetonitrile, and the above phenoxysulfonyl isocyanate derivative is added. It can be manufactured by

The method for synthesizing the heterocyclic amine derivative used in the production method of the present invention is described in Interscience Publ New Year.
f published by k and London
, - Book 1 of The Chemistry of Heterocyclic Compounds (The Chemistry of Heterocyclic Compounds)
(Heterocyclic compounds)
Pyrimidine derivatives have been reviewed in J.
, Brown, the above first category, Ra, pOpOr
Same L4F (7) Volume XI I s -Triaz-in
es and Derivatives) can be synthesized according to the method described in J.

The compounds of the invention having the general formula 1'1 are distinguished by an extremely good herbicidal action.

Agriculturally harmful weeds can be efficiently controlled by applying these compounds to soil or foliage. It exhibits excellent herbicidal activity against a wide range of broad-leaved weeds, especially broad-leaved weeds in field crops, such as Japanese sagebrush, Japanese sagebrush, Japanese mustard, and other broad-leaved weeds, and is highly safe for crops, as well as paddy field weeds such as Japanese cypress, Japanese cypress, and bulrush. It also shows excellent herbicidal activity.

The compound represented by the general formula (1) according to the present invention also has excellent bactericidal activity. For example, rice blast disease (
Pyricura, JM oryzae), ii.
Botrytis ci4ere), Botrytis ci4ere
a), Powde-ry mild
ew), and is also partially effective against potato late blight and apple leaf spot fungus.

Next, representative examples of the compound proboscis represented by the general formula (1) and their physical properties are classified by compound number and shown in Section 1S above.

The effective component compounds and test compounds of the following synthesis examples, examples, tests, and test examples are indicated by compound numbers in Table 1.

Synthesis Example-1 (Synthesis of Compound No.-5) 2-amino-4-methoxy-6-methylpyrimidine 43
．． 9 ft (0.1 mol) were dissolved in 200 m/d of dry tetrahydrofuran and chlorsulfonyl iso/anate 14.1 ? (0.1 mol) was dropped by 500 ml under cooling at 1°C to 15°C, and further stirred at the same temperature for 30 minutes. Add 16.1 y of m-trifluoromethylaniline to this solution.
(o, 1 mol), triethylamine 715.2 f
((1,15 mol) and 50 m dry tetrahydrofuran
/ was added dropwise while stirring while cooling at 1°C to 15°C, and the mixture was further stirred for 1 hour. The produced triethylamine HCt salt was used to obtain 1~, and the oral fluid was concentrated. The residue was recrystallized from ethyl acetate, m, p, 141-143°C.
21.59 of white crystals (yield: 600 cm) of the target substance were obtained.

Synthesis Example-2 (Synthesis of Compound No.-9) 2-amino-4,6-simethoxy s-triazine is
, 6r (o, i mol) in dry acetonitrile 300
m/, chlorosulfonylincyane-14,1
? A solution of (0, i mol) dissolved in 50 mA' of dry acetonitrile was added dropwise while cooling at 10 to 15°C, and the mixture was further stirred at the same temperature for 1 hour. This 1NfKO-chlorophenol 15.4 f (0.12 mol), pyridine 1
1.99 (0.15 mol) and dry acetonitrile 5
The mixture consisting of 0m was added dropwise while stirring while cooling at 10 to 15°C, and the mixture was further stirred for 2 hours. The produced pyridine/HCt salt was used to concentrate the oral fluid. the residue
Recrystallized with j'l-m ethyl, m, p, 149-15
White crystals of the target substance at 1°C 23. Of (59,0chi)
I got it.

Synthesis Example-6 (Synthesis of Compound No.-12) 0-Methoxyphenol 6.21 (005 mol) Totally dry toluene 50 m
7.1
? (0.05 mol) was added, and the mixture was heated under reflux on an oil bath for 6 hours.

After cooling, toluene was distilled off under reduced pressure to obtain crude O-methoxyphenoxysulfonyl isocyanate. 2-amino-
4-methquin-6-methylpyrimidine 6, Of'(
0.05 mol) was suspended in 100 ml of dry acetonitrile, and while stirring at 20°C, the crude O-methoxyphenoxysulfonyl iso/anate prepared previously was added, and the mixture was further stirred for 1 hour. The solvent was distilled off and the residue was subjected to licage gel column chromatography (developing solvent: ethyl acetate).
10 filters of semi-solid target substance (58,
Article 5) was obtained.

Synthesis Example-4 (Synthesis of Compound No.-23) 2-chloro-4
-trifluoromethylphenol 9.8 f (0,0
5) was dissolved in 50 trtl of dry toluene, 7.12 (005 mol) of chlorosulfonyl isocyanate was added,
The mixture was heated under reflux on an oil bath for 6 hours to obtain a 2-chloro-4-trifluoromethylphenoxysulfonyl iso/anatotoluene solution. 2-amino-4,6-dimethoxy-S
- triazine 7,8 r (0,05 mol) was suspended in dry tetrahydrofuran and the previously prepared 2-chloro-4
A solution of -triful-1-methylphenoxysulfonyl isocyanate in toluene was added at 20° C. with stirring, and the mixture was further stirred for 1 hour.

The solvent was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate to give white crystals of the target substance 1 with m, p, 129-130°C.
tsf (yield 50.2%) was obtained.

The other compounds shown in Table 1 above can also be synthesized according to any of the synthesis methods of Synthesis Examples 1 to 4.

In order to use the compound of the present invention as a herbicide or fungicide, the active ingredient compound represented by the above general formula (1) may be used as is, but in general, depending on the purpose of use, the active ingredient compound may be used as is. is dissolved or dispersed in a suitable liquid carrier (eg, an organic solvent) or mixed or adsorbed on a suitable solid carrier (eg, diluent, filler). At that time, by adding various auxiliary agents (e.g. emulsifiers, stabilizers, dispersants, suspending agents, spreading agents, wetting agents, penetrating agents) as necessary, emulsions, irrigation agents, granules, powders can be prepared. It can be used in various dosage forms such as.

When the compound of the present invention is used as a herbicide or fungicide, one or more other herbicides or fungicides, pesticides, pesticides such as plant growth regulators, soil conditioners, or fertilizers may be used. Not only can it be used in combination with sexual substances, but also mixed preparations with these substances are possible, and in some cases, a synergistic effect can be expected.

The content of the active ingredient of the compound of the present invention is 1 to 10 in the case of granules.
%, 1 to 10% for powders, 3 to 20 to 80 for wettable powders,
In emulsions, 10 to 50% (all of which represent 1fi, i, and 4'chi) is desirable.

Next, formulation examples and physiological activity test examples of a male paleonticide containing the compound of the present invention as an active ingredient will be shown, but the present invention is of course not limited to these. In the Examples, the active ingredient compound represented by the general formula (1) is represented by the compound number in Table 1, and Dish-1 represents "parts by weight."

Example 1. Mix 25 parts of the granule compound, 72 parts of bentonite, 20 parts of talc, 2 parts of dobuflubenzenesulfone aqueous soda, and 1 part of sodium ligninsulfonate, add an appropriate amount of water, form an electric wire, and then use an extrusion granulator to process the mixture. It was granulated by the method described above to obtain 100 parts of granules.

Example 2 85 parts of a powder compound, 94 parts of talc, and 1 part of polyoxy/ethylcine alkyl allyl ether were mixed and ground to give -100 parts of a powder.
I got the department.

Example 3 Wettable powder compound 13 soi, 40 parts of diatomaceous powder, and 10 parts of dodecylbenzenesulfone kuma soda were mixed and ground to obtain a wettable powder ion part.

Example 4 1950 parts of an emulsion compound, 55 parts of solvent naphtha, 30 parts of dimethylformamide, and 7 parts of polyoxyethylene alkyl allyl ether were mixed to obtain 100 parts of an emulsion.

Next, regarding the herbicidal activity and fungicidal activity of the compound of the present invention,
This will be explained in detail using test examples.

Test Example 1 Pre-emergence weed killing test in a paddy field Filled with soil in a 4ooo Wagner Ponot, seeds of Japanese millet, other broad-leaved weeds (Japanese grasshopper, Japanese aphrodisiac, Japanese azalea), firefly, and Helaomodaka were sown and flooded. Two cultivated paddy rice seedlings (2-6 leaf stage) were used as one plant, and the two plants were transplanted and grown in a greenhouse.

Five days after transplanting paddy rice, at the beginning of weed emergence, a predetermined amount of the test compound was treated under flooding using a granule according to the method described in Example 1 above. Fifty days after the treatment, the occurrence of tuna grass and the chemical damage to paddy rice were investigated, and the results shown in Table 2 were obtained.

In this table, the degree of chemical damage to crops and the herbicidal effect on weeds are expressed by comparing the appearance and growth of weeds on the edges of the crops with those of the air-dried type in the untreated plot, according to the evaluation criteria below.

The test compounds are indicated by compound numbers in Table 1 above.

Evaluation criteria 0: Survival rate expressed as air dry weight ratio vs. untreated area 91~i
00'%1
71~9o%2
41-70%3
11~4o%4
6-10%5
0 to 5 chloride x 2,4-dichlorochloride, metquine, 4'-nitrophe, JL-chill Test Example 2 Weed killing test during paddy growing season a<ooo Fill a Wagner pot with soil,
Other broad-leaved weeds (Konagagi, Kikashigusa, Azena nato),
Seeds of Firefly and Helaomodaka were sown. Tubers of Urikawa were transplanted to this to make it flooded. Two paddy rice seedlings (2-6 leaf stage) that have been raised in advance are used as one plant.
The two plants were transplanted and grown in a greenhouse. Paddy rice transplant 12
Example 1 A predetermined amount of the test compound was added during the weed growth period after 1 day.
The treatment was carried out using a granule according to the method described in . 60 days after the treatment, weed growth conditions and chemical damage to paddy rice were investigated, and the results are shown in Table 3.

In this table, the degree of chemical damage to crops and the herbicidal effect on weeds are expressed by the method shown in Test Example 1.

Seeds of blueberry, 70 za, wild mustard, mulva asakao, Japanese fir tree, and crabgrass were sown.

Six days after sowing, the test compound was added to Example 5 (using an irrigation agent according to the method described, the prescribed amount was 10% per are.
It was diluted with the equivalent of a liter of water and sprayed with a micro-pressure sprayer. This was grown in a greenhouse, and 60 days after the treatment, the appearance and growth of crops and weeds was investigated, and the results shown in Table 4 were obtained.

In this table, the degree of chemical damage to crops and the herbicidal effect on weeds were expressed using the method shown in Test Example 1.

Test Example 4 Upland cultivation period kidney grass trial Mosquito a/1ooo Planters were filled with soil, and seeds of wheat, blueberry, whiteweed, wild mustard, red cabbage, Japanese fir, chickweed, and Japanese knotweed were sown.
It was grown in room A.

When the test plant has grown to the 15th to 25th leaf stage, a predetermined amount of the test compound is added to water equivalent to 10 liters per area using an emulsion according to the method described in Example 4.
and sprayed with a micro-pressure sprayer. Sixty days after the treatment, the growth status of crops and weeds was checked to obtain the fifth results. In this table, the degree of chemical damage to crops and the herbicidal effect on weeds are expressed by the method shown in Test Example 1.

Test 1 Test Example 5 Blast disease control test (chemical soil application)”/
10. . . . Paddy rice (variety: Ko/Hikari, plant height: 30 cm) grown in a color pot was submerged in water to a depth of 1 cm, and a specified needle of the test compound was prepared according to the method described in Example 1 on the left above. The treatment was carried out using the granules prepared in the following manner.

Five days after treatment, rice was inoculated into a box (humidity 95 degrees or higher, 24 degrees Celsius).
After inoculating the rice blast fungus spores by gravity for 213 days, the rice was placed in a high humidity room (humidity 95 degrees or higher, 26 to 60 degrees).
℃) for 8 days to induce blast disease. The formation of lesions 61 was investigated, and the control value was determined using the following formula.

The results are shown in Table 6 below.

The test compounds are indicated by compound numbers in Table 1 above.

Table 6 Patent Applicant Mitsui Toatsu Kagaku Co., Ltd. Procedural Amendment Written by Haruki Shimada, Commissioner of the Japan Patent Office, July 1982, Haruki Shimada 1. Display of the case 1982 Patent Application No. 112986 2. Name of the invention New sulfonylureido Derivative 3, Person making the amendment 4 Date of amendment order Voluntary action 5, Number of inventions increased by the amendment 06 Subject of amendment 1, The scope of claims in the specification is corrected as shown in the attached sheet.

2 Detailed description of the invention column a) Page 7, line 10 (sixth line from the bottom) “Kill group,
"Nitro group" is corrected to "Kyl group, lower alkoxy group, nitro group."

Attachment 2 Claim 1 General formula [1] [In the formula,
A halogen atom or a trifluoromethyl group, R is a general formula (in the formula, R+u represents a methoxy group or a methyl group, R2 represents a halogen atom, a methyl group, or a methoxy group) or a general formula (in the formula, R3 is a halogen atom) , a methyl group, or a methoxy group, R4 represents a methyl group or a lower alkoxy group, and Z represents an oxygen atom, a sulfur atom, or an imino group.

2. The compound according to claim 1, wherein in the general formula [■], 2 is an oxygen atom.

3. The compound according to claim 1, wherein in general formula [1)], 2 is an imino group.

4 In general formula CII, R is general formula [II] p.

(In the formula, Rr HR1 is the same as above.) The compound according to claim 1.

5. The compound according to claim 1, which has the general formula [in I'3, R is a general formula] 3 4 (in the formula, R3 and R1 are the same as above).

6 chlorosulfonyl isocyanate, general formula (wherein,
R1 represents a methoxy group or a methyl group, R2 represents a halogen atom, a methyl group, or a methoxy group, respectively) or a general formula (in the formula, R represents a halogen atom, a methyl group, or a methoxy group, and R4 represents a methyl group or a lower alkoxy group) any one of the heterocyclic compounds represented by the general formula (in the formula, X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a carboxyl group, a lower alkoxycarbonyl group, phenoxycarbonyl group or di-lower alkyl substituted amine group, Y is hydrogen atom, halogen atom or trifluoromethyl group, A is OH group, NH
2 groups or SH groups, respectively) [wherein X and Y are the same as above. R is the general formula p.

2 (wherein Rr and R2 are the same as above) or the general formula R.

(wherein R3 and R4 are the same as above), and Z represents an oxygen atom, a sulfur atom, or an imino group, respectively.

7 General formula [I] [wherein, represents a hydrogen atom, a halogen atom, or a trifluoromethyl group; Among them, R3 represents a halogen atom, a methyl group or a methoxy group, R4 represents a methyl group or a lower alkoxy group), and Z represents an oxygen atom, a sulfur atom or an imino group). A pest control agent characterized by containing it as an ingredient.

Claims (1)

[Scope of Claims] 1. General formula fin [wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a nitro group, a carboxyl group, a lower alkyl group]
sulfonyl group, phenoxycarbonyl group or (1-lower alkyl-substituted amino group, Y is a hydrogen atom, halogen atom or trifluoromethyl), R is a general formula (wherein R1 represents a methoxy group or a methyl group) , R2 represents a halogen atom, a methyl group, or a
) or general formula (wherein R3 represents a rogen atom, methyl group, or methoxy group, R4 represents a methyl group or a lower alkoxy group), and Z represents an oxygen atom, a sulfur atom, or an imino group. ] A novel sulfonylureido derivative. 2. The compound according to claim 1, wherein in the general formula [■], Z is an oxygen atom: a proboscis. 6. The compound according to claim 1, wherein in general formula (1), Z is an imino group. 4 In the general formula (1), R is the general formula [11] (in the formula 2.
R1 and R2 are the same as above. ) is the first claim
Compounds described in Section. 5. The compound according to claim 1, wherein in general formula [1], R is general formula (III) pa4 (wherein R3 and R4 are the same as above). (In the formula, R1 represents a methoxy group or a methyl group, R3 represents a halogen atom, a methyl group, or a methoxy group, respectively) or the general formula (In the formula, R3 represents a halogen atom, a methyl group, or a methoxy group, and R4 represents a methyl group. or a lower alkoxy group), and any one of the heterocyclic compounds represented by the general formula (wherein, X is a hydrogen atom, A compound represented by an alkoxycarbonyl group, a fenoquinecarbonyl group, or a di-lower alkyl-substituted amine group, Y represents a hydrogen atom, a halogen atom, or a trifluoromethyl group, and A represents an OH group, an NF2 group, or a SH group, respectively. [wherein, X and Y are the same as above]. R represents a general formula (in the formula, R and R2 are the same as above) or a general formula (in the formula, R3 and R4 are the same as above), and Z represents an oxygen atom, a sulfur atom, or an imino group, respectively. A method for producing the represented sulfonylureido derivative. Z general formula [I] (wherein, atom, )・rogen atom or trifluoromethyl group, R represents the general formula (1.Ro represents a methoxy group or a methyl group, R2
represents a halogen atom, a methyl group, or a general formula (wherein R3 represents a methoxy group), a halogen atom, a methyl group, or a methoxy group, and R4 represents a methyl group or a lower alkoxy group. ), and Z represents an oxygen atom, a sulfur atom, or an imino group.