JPS6160667A - 1-(2-alkylthiophenylsulfonyl)-3-heteroarylurea or thioureas - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel 1-(2-alkylthiophenylsulfonyl 13-heteroaryl-(thio)urea), a method for producing the same, and a method for using the same as a herbicide.

1-arylsulfonyl-5- to 7° arylurea of the a species, e.g. 1-(2-methoxy-phenylsulfonyl)-3-(4,6-somethyl-pyrimison-2-yl)
It is known that urea has a herbicidal effect. However, the action of these compounds is not always completely titrated (see U.S. Pat. Nos. 4,169,719 and 4,
12S 405, and European Patent Nos. 35,893, 84°020 and 101,308).

This time, general formula (I) [wherein Q represents oxygen or sulfur, R represents C1-C6 alkyl, R' represents hydrogen, CI-'4 alkyl or benzyl, R''h water IA, halogen , hydroxyl, (', ~
C. 'l~C4 alkylamino or no(C,~C4 alkyl)amine, X represents nitrogen or -〇H- group, Y represents nitrogen or -〇H- group, provided that R8 is hydrogen, halogen, CI-C4 alkyl, (C1-C4 alkoxy)-carbonyl or acetyl, and Z represents nitrogen or a -〇R4- group, with R' being hydrogen,
Halogen, hydroxyl, C tsuta ~ C4 furkyl, C1 ~
C, alkoxy, "I-C4 alkylthio, CI-0
4-alkylamino or no(C, ~C4 alkyl)amino] Novel 1-(2-alkylthiophenylsulfonyl)
-6-heteroarylureas or thioureas, provided that the compound 1-(2-methylthiophenylsulfonyl)-3-(
4-Methoxy-6-methyl-pyrimidin-2-yl)-
Excludes urea. was discovered.

The novel 1-(2-alkylthiophenylsulfonyl)-6-heteroaryl-urea or thiourea of formula (1) has the formula (α) (rI) [wherein Q represents oxygen or sulfur; R is 01~
2-alkylthiophenylsulfonylinocyanate or inthiophanate representing C6 alkyl] is added to 2-alkylthiophenylsulfonylinocyanates or inthiophanates of R', if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst. , R", X, Y and Zh have the meanings given above; or (b) 2-alkylthiophenylsulfo/ An acid amide, if appropriate in the presence of a diluent, and if appropriate an acid acceptor, is added to , and R5 represents C8-C4 alkyl, benzyl or phenyl] (7) React with N-heteroaryl-urethanes, or (C) formula ■ [wherein Q represents oxygen or sulfur, R' f-JC, ~C4 alkyl, benzyl or phenyl, and R represents 01-C alkyl] oN-(2-alkylthio-phenylsulfonyl)-urethanes, if appropriate in the presence of a diluent and If appropriate, in the presence of an acid acceptor, the formula (e) [wherein R', R'',
X, Y and z have the meanings described above] Produced by a method of reacting with a heteroarylamine.

The novel 1-(2-alkylthio-phenylsulfonyl)-3-heteroaryl-(thio)ureas of formula (I) are characterized by a strong herbicidal activity.

Surprisingly, the new compounds of formula (T'') exhibit a significantly better herbicidal action than previously known urea rust conductors of the same type of action.

Preferably, in the present invention, Q represents oxygen, R represents C8-C4 alkyl, R1 represents hydrogen or methyl, and R' is hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, ethoxy, represents sofluoromethoxy, methylthio, ethylthio, amino, methylamino, ethylamino, trimethylamino or damethylamino, X represents nitrogen or a -CH- group, Y represents nitrogen or a -〇R'- group, provided that R3 is hydrogen,
represents fluorine, chlorine, bromine, methyl or acetyl, and 2 represents nitrogen or a -〇R'- group, provided that R4 is hydrogen,
Compound 1- (2-, 'Tylthiophenylsulfonyl), representing fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, propoxy, impropoxy, methylthio, ethylthio, methylamine, ethylamino, damethylamino or damethylamino -5-(4-methoxy-6-methyl-pyrimidine-
Compounds of formula (I) excluding 2-yl)-urea.

The present invention uses %K.

Q represents oxygen, R represents methyl, ethyl, n-7aa pyru or inglovir, R' represents hydrogen, R1 represents methyl, methoxy, ethoxy or trimethylamino, X represents nitrogen, Y represents nitrogen or The compound 1-(2-methylthio -phenylsulfonyl)-
Compounds of formula (I) excluding 5-(4-methoxy-6-methyl-pyrimidin-2-yl)-urea.

For example, as starting materials for process embodiment (α) 2-mekylthiophenylsulfonylthiocyanate and 2-amino-4-ethoxy-6-methyl-B-)
When using 97son, this reaction process can be summarized by the following equation.

Example: 2-ethylthio-benzenesulfonic acid amide and O-phenyl-N-<4-ethylamino-6-methylthio-s-triazin-2-yl)-urethane as starting materials for process embodiment (6). When used, this reaction process can be reduced to the following equation: For example, tba0-phenyl-N-(2-inglobylthiophenylsulfonyl)-urethane and 2-amino-4-chloro-6- When medoxypyrimidine is used as the starting material for process embodiment (C), the reaction process can be represented by the following equation: , -gives the definition of -phenylsulfonyl iso(thio)cyanate.

In formula (n), R and Q preferably and especially represent formula (
O having the same meaning as given above as preferred or particularly preferred in connection with the definition of substances of I) Examples of compounds of formula (2) that may be mentioned are 2-methylthio-1
2-ethylamino, 2-isopropylthio and 2-
W -f lobylthiophenylsulfonylincyanate and 2-methylthio-12-ethylthio-12-isopropylthio- and 2-n-globylthiophenylsulfonylinthiocyanate.

Compound m) of formula (5) has not yet been described in the literature. Compounds of formula (2) in which Q represents oxygen and R represents 01-C8 alkyl are prepared by combining the 2-alkylthio-benzenesulfonic acid amide of formula IV) with thionyl chloride in an amount of 50 to 100
C. and the product is then reacted with phoscene, if appropriate in the presence of a diluent such as toluene and if appropriate in the presence of a catalyst such as pyridino, at a temperature of 50 DEG to 120 DEG C. [Reference, Soei Org Chem (J, Org, Chem, 54 r(1
969), 3200).

Compounds of formula (2) in which Q represents sulfur and R represents C1-C, alkyl are prepared by reacting a 2-alkylthio-benzenesulfonic acid amide of formula dM with K and K in the presence of an acid acceptor such as potassium hydroxide. React with carbon disulphide at a temperature of 0 to 5° C., if appropriate in the presence of a diluent such as trimethylformamide, and then react the product with phosdan or thionyl chloride, if appropriate in the presence of a diluent such as methylene chloride. 0
React at a temperature of ~50°C [see Ark Farm (AdeC5, PnατTake-) 299 (1966)
, 174).

Formula (e) provides a general definition of heteroarylamines that can be used as starting materials for process embodiment (α). In formula (e), RI, R1, has.

Examples which may be mentioned of compounds of formula (e) are 4,6-nomethyl-4-methoxy-6-methyl-14-ethoxy-
6-methyl- and 4,6-dimethoxy-2-aminopyrimison, 4,6-dimethyl-, (4-methoxy-6-
Methyl-14-ethoxy-6-methyl- and 4,6-somethoxy-2-amine-8-trianone, 516-nomethyl-2-amino-1,3,4-)ryanone and 4-methyl-5-7cetyl-2- This is aminovirimison.

The compound of formula (e) is known and can be produced by a known method [see Chem Pharm Pull (Cher
n, pharm, IfhLll,) 11 (19
63) +1682 and U.S. Patent No. 4.299.960
issue〕.

Member 2-alkylthiobenzenesulfonamides which can be used as starting materials for process embodiment (b) have not yet been described in the literature. .

Compounds of the formula tt'l in which R represents C1-C6 alkyl are prepared by adding 2-alkylthio-benzenesulfonic acid chlorides of the formula For example, it is produced by a method of reacting with ammonia at a temperature of 0 to 50°C in the presence of water and/or acetone.

Compounds of formula 6111 have not yet been described in the literature.

A compound of formula (2) in which R represents C1-C, alkyl,
The substituted 2-alkylthio-aniline in which R represents C, -C, alkyl is reacted with sodium nitrite and hydrochloric acid, if appropriate in the presence of a diluent, at a temperature of -20 to +15°C, and then It is prepared by reacting this product with sulfur dioxide, if appropriate in the presence of a catalyst, such as steel chloride (1), and if appropriate, a diluent, such as glacial acetic acid, at a temperature of -20 DEG to +20 DEG C.

2M is N that can be used as a starting material in embodiment (6)
-Gives general definitions of heteroaryl-urethanes.

In 2M, i, R'', X, Y and Z preferably have the same meanings as mentioned above as preferred or particularly preferred in connection with the definition of substituents for formula (I)K. furthermore, Q preferably represents oxygen and R5 is methyl, penzyl or phenyl,
Especially methyl or phenyl.

Examples which may be mentioned of compounds of 2M are N-(4,6-trimethylhyrimison-2-yl)-1#-(4-methoxy-
6-methyl-pyrimidin-2-yl)-1N-(4-ethoxy-6-methyl-pyrimidin-2-yl), y-(
4+6-somethoxypyrimison-2-yl)-1N-
(4,6-somethyl-&-triazon-2-yl)-1
#-(4-methoxy-6-methyl-8-triazine-2
-yl)-1N-(4-ethoxy-6-methyl-8-triazin-2-yl)-1A'-(4,6-dimethoxy-8-triazon-2-yl)-1N-(5,6-nomethyl- 1.3.41rhianon-2-yl)- and N-(
4-Methyl-5-acetyl-pyrimidin-2-yl-O
-methyl-urethane and O-phenyl-urethane.

The compound of 2M is known and can be produced by a known method (see European Patent Publication No. J01,67).
No. 0).

Formula (1) provides a general definition of A'-(2-)lyfluoromethoxyphenylsulfonyl)-urethanes that can be used as starting materials for process embodiment (C). Preferably, in formula (1), Q is oxygen, and R6 is methyl,
Penzyl or phenyl, especially methyl or phenyl.

Examples which may be mentioned for compounds of formula IV) are N-(2-
Methylthio °-12-ethylthio-12-ingropyrthio and 2-? L-propylthiophenylsulfonyl)-□-phenyl-urethane.

Compound 2M is known and can be produced by a known method (Sagochi Kokai Patent No. 101゜670).

The formula gives a general definition of the silaN-<2-alkylthiophenylsulfonyl)-urethane used as starting material for process embodiment (C)K. In the second part, Q preferably represents oxygen, RF'i, methyl, ethyl, inglobil or n-propyl, and R6 is methyl, pencil or 7-enyl, especially methyl or phenyl.

Examples which may be mentioned of compounds of the formula (VD) are A'-(2-methylthio-,2-ethylthio-92-isopropylthio-
and '1-n-globylthiophenylsulfonyl)-
〇-Phenylurethane theal.

Compounds of the formula 1 have not yet been described in the literature. These compounds combine a 2-alkylthio-benzenesulfonamide of the formula 0 with an appropriate 0 receptor such as sodium hydride, potassium tart-butyrate or soaza. In the presence of bicycloundecane (DB(J) and, if appropriate, a diluent such as acetonitrile or dimethylformamide, the formula 1 A-C-0-R' [wherein Q and R8 are as defined above) and representing Ad chlorine or phenoxy] at a temperature of 0 to 50°C (see European Patent Publication No. 101, 407).
issue).

For the compound of formula (I), the production method described in (α) is:
It is preferably carried out in the presence of a diluent. Possible diluents are virtually all inert organic solvents. These include, in particular, aliphatic or aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, benzene,
Petroleum ether, ligroin, cyclohexane, benzene, toluene, xylene, chlorobenzene, methylene chloride, chloroform and carbon tetrachloride, ethers such as soethyl ether, twinpropyl ether, tetrahydro7
Ran, 1,2-nomethoxyethane and sooxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and gropionitrile, ethers such as methyl acetate and ethyl acetate, amides such as trimethylformamide and trimethylacetamide, and Contains methyl sulfoxide.

If appropriate, process (α) is carried out in the presence of a catalyst.

Catalysts are in particular aliphatic, aromatic or heterocyclic amines such as triethylamine, N,N-trimethylaniline, pyridine, 2-methyl-5-ethylvirison, 4-dimethylamino-pyridine, soazabicyclooctane (D A B
CO), soazabicyclononene (DBN) and noazabicycloundecene (13BN).

The reaction temperature can be varied within a substantial range in embodiment (α). Generally the reaction is carried out at a temperature of 0 to 150'C1, preferably 20 to 100C.

To carry out the method (α) of the present invention, 1.0 to 1.5 mol per mol of heteroarylamine of formula (a),
Preferably 1.0 to 1.2 mol of 2-alkylthio-phenylsulfonyliso(thio)sia$-)7>E is used.

The starting materials for the formula surface and α[O, and if appropriate catalyst and diluent, are combined at room temperature or with mild external cooling, and the reaction mixture is heated, if appropriate at an elevated temperature, until the reaction is complete. Stir.

The novel compounds of formula (r) are processed and isolated in conventional manner. When the compound of formula (I) is obtained as a crystal,
It is isolated by suction filtration. Otherwise, suitably after concentration, adding an organic solvent substantially immiscible with ice and water, shaking thoroughly, separating the organic phase, drying, filtering and concentrating the formula ( The product of I) is obtained as a residue.

For compounds of formula (I), the preparation process described above under (b) is preferably carried out in the presence of a diluent. The same organic solvents as mentioned above in connection with the description of embodiment (α) of the invention are also suitable in this case.

Embodiment (b) is preferably carried out in the presence of an acid acceptor. Possible acid acceptors are all common inorganic acid binders and organic bases. These include, for example, alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, sodium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, and aliphatic, aromatic and heterocyclic amines such as triethylamine, N,N'-trimethylaniline, N,N-somethylbenzylamine, pyridine, 2-methyl-5-ethyl-pyridine, 4-dimethylamino-pyridine, soazabicyclo Octane (DAB)
CO), soazabicyclononene (DBN) and soadebicycloundecene (DBII).

The reaction temperature can be varied within a substantial range in embodiment (b). Generally the reaction is carried out at a temperature of -20 to +100°C, preferably 0 to 50°C.

In order to carry out the process (b) of the invention, it is generally necessary to use 1.0 to 1.5 iM per mole of N-heteroaryl-urethane.
moles, preferably 1.0 to 1.2 moles of 2-A
/f obenzene sulfo/acid amide t-use.

The starting materials of M and M, and if appropriate the acid acceptor and diluent, are brought together at room temperature or with mild external cooling, and the reaction mixture is stirred until the reaction is complete, if appropriate at an elevated temperature. do.

The novel compounds of formula (I) are worked up and isolated in conventional manner. Generally, after concentration, if appropriate, the mixture is stirred with water and, if appropriate, acidified by salting.

If the compound of formula (I) is obtained as crystals, it is separated off by suction filtration. Otherwise, the mixture is extracted with a substantially water-immiscible solvent such as ethyl acetate or methylene chloride, the organic phase is separated, dried, filtered,
Concentration gives the product of formula (I) as a residue.

For compounds of formula CI), the preparation process described above under (C) is preferably carried out in the presence of a diluent. Possible diluents are the same organic solvents as mentioned above in connection with the description of embodiment (C) of the invention.

Embodiment (C) is preferably carried out in the presence of an acid acceptor. Possible acid acceptors are the same inorganic acid binders and organic bases as mentioned above in connection with the description of embodiment (6) of the present invention.

The reaction temperature can vary within a substantial range in embodiment (C). Generally the reaction is carried out at a temperature of -20 to +100°C, preferably 0 to 50°C.

To carry out process (c) of the invention, generally 1.0 to 1.5 mol, preferably 1.0 to 1.
2. A heteroarylamine of formula (e) is used.

The method and process in aspect (c) are as described above for aspect (b).

The active compounds according to the invention are defoliants, desiccants.

It can be used as a hardwood destroyer and especially as a weed killer. By weeds we mean, in the broadest sense, all plants that grow where they are not desired. The substances according to the invention act as either total herbicides or selective herbicides depending on the amount used. .

The compounds according to the invention can be used, for example, in connection with the following plants: Siuapis, Leipidium, Galium, Chickweed E. (Stellari
a), Anthemis 7401atricaria), Anthemis, Ga
linsoga), Chenapod rIi (Chenapod
ium), Urtica, Senecio, Amar
anthux), Portulaca 1
, Xantium, Convolvulus (C
onvolvulus), sweet potato FIli (Ip
omoea), Tade JM (Pa 17gonum)
, Sesbania rA, AmbroSia, Cirsium kA
), Carduus, Sonchus, Solanum,
Rorippa, Rorippa (
RoLala), A Zena Jf, (Lindania)
), Laa+ium, Veronica, Abut
i fan), emex! (Emex), Datura Jin (Datura), Viola (Viola)
), Chishimaro:! jd (Galeopsis),
Poppy (Papaver) and Centaurea (Cen)
taurea).

・Cultivation amount: Cotton ji (Goasyp)
ium), soybean B (GI7cine), 7 Danso JilfE (Beta), carrot g (Daucu
s), Phaseo 1us, Pisum, Solanum
, ljnum, Ipomoea (I
pomoea), Vicia (Vicia),
Tobacco ji (Nicotiana), tomato! 1
! (Lycopersrcon), groundnut jl (A
racbjs), Brassica,
Lactuca E, cucumber ij4
(Cucumrs) and Uri Ji (Cucurbita)
).

cy>F-cy>, L5H: Barnyardgrass ff1 (Ecbin
ochloa), x, t Setar
ia), Millet J, i: (Panicum), Digitaria, Phl
eum), Fegtuca) JS (POa), Fegtuca 7, Fegtuca 1 (El
eusine), Brachiaria spp.
ia), Loliua, Bromus, Avena
, Cype rus , Sorghum , Agro
p! ron), Genus Dinoton (CffnodO)
・Monochoria f7, Fiibristylis, Sagittaria, Eleoch
aris), Firefly II: (Scirpus), Pagpalum fi, Platypus E
(Ischaesum), Sphnicrea, 1 (Sp
henoclea), Dactyloctenium (Dact
ylocteniuj+), Agrosti
S), Alopecurus,
and Apara.

I-Culture: Or7za, Maize H (Zea), Tritic Wheat 75
um), barley (Hordeuti), oat (Avena), rye (Sscale),
Sorghum, millet! ! (Pan
icum), Saccharum
, Ananas , Ananas , A
sparagus), and green onion & (Allium)
.

However, the use of the active compounds according to the invention does not limit these l111i1. : It is not limited at all and extends to other plants in the same way.

Depending on the concentration, the compounds are suitable for complete control of weeds, for example on industrial areas and railway lines, on roads and squares with or without trees. Equally, the compounds are useful for perennially cultivated plants, such as silviculture, ornamental trees, orchards, grape groves, citrus groves, walnut orchards, banana plantations, coffee plantations, tea plantations, rubber tree plantations, oil plantations, etc. Palm plantations, cocoa plantations, small fruit tree plantings can be used to control weeds in cultivated plants of hops, and for selective control of weeds in single-pole cultivated plants.

The active compounds can be used in the pre-emergence or post-emergence method for killing monocotyledonous and dicotyledonous weeds.

The active compounds can be used in common compositions such as solutions, emulsions, wettable powders, suspensions, powders, powders, pellets, wettable powders, granules,
It can be converted into aerosols, suspension-emulsion concentrates, natural and synthetic substances impregnated with active compounds, and very fine capsules in polymeric substances.

These compositions can be prepared in known manner8, for example by mixing the active compounds with extenders, i.e. liquid solvents and/or solid carriers, and optionally surfactants, i.e. emulsifiers and/or dispersants and/or blowing agents. Manufactured.

Furthermore, when water is used as an extender, for example, an organic solvent can also be used as an auxiliary solvent. As liquid solvents, mainly aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, salts; modified aromatic or unsalted aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, fatty hydrocarbons e.g. cyclohexane, or paraffin e.g. mineral oil fractions,
Suitable are mineral and vegetable oils, alcohols such as butanol or glycols and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

As solid carriers, e.g. ammonium salts and ground natural drugs such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and ground synthetic minerals such as highly dispersed silicic acid, alumina As solid carriers for the granules, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as inorganic and organic stretched synthetic R-grains and organic materials are suitable. Granules such as sawdust, coconut, corn cob and tobacco stalks are suitable; as emulsifiers and/or blowing agents non-ionic and anionic emulsifiers such as polyoxyethylene fat II/1m ester, polyoxyethylene aliphatic Alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolysis products are suitable.Suitable dispersants are, for example, genin sulfite waste liquor and methylcellulose.

Adhesives such as carboxymethyl cellulose as well as powders,
Particulate or latex natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalin and lecithin, and synthetic phospholipids can be used in the composition.

Furthermore, additives can be oils and vegetable oils.

Colorants such as inorganic pigments such as iron oxides, titanium oxides and Prussian blue and chromatic dyes such as alizarin dyes and metal phthalocyanine dyes, and l1tffi nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc are used. be able to.

Preparations generally contain between 0.1 and 951J1% of active compound;
The content is preferably between 0.5 and 90% by weight.

The active compound according to the invention may also be used as such or in the form of 2 g.
In the form of I products, it can also be used for controlling weeds as a mixture with known herbicides, finished formulations or seed mixtures are possible.

Suitable herbicides for the mixture are known herbicides such as tho(2-benzothiazolyl)-N,N'-dimethyl-urea, 3-(3-chloro-4-methylphenyl)-1,1-
Dimethylurea, 3-(4-isopropylphenyl)-1
゜l-Dimethylurea, 4-7minor 6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4+1)-one, 4-amino-8-(1,1 −
dimethyl-ethyl)-3-ethylthio-1,2,4-)
Riazin-5(4H)-one, l-amino-6-ethylthio 3-(2,2-dimethylpropyl)-1°3.5
-triazine-2,4-(IH,3H)-dione, 4-
Amino-3-methyltophenyl-1,2,4-)lyasia-5(4H)-one, 2-chloro-4-dithylamino-6-imbrobylamino-1,3,5-)lyazine, (trimethylsilyl) )-methyl 2-(4-(3
, 5-dichloro-pyridin-2-yloxy)phenoxy]-propionate, (2-benzyloxy)
-ethyl 2-[4-(3゜5-dichloro-pyrido-2-
R enantiomer of yloxy)-phe/xy]-propionate, 2,4-diclocephe/xyacetic acid, 2-(2,4-dichlorophenoxy)-propionic acid, 4-chloro-2-
Methyl-phenoxy vinegar S, 2-(2-methyl-4-chlorophenoxy)-propionic acid, 3,5-short-
4-hydroxy-benzonitrile, 3.5-sifurome-
4-hydroxy-benzonitrile and diphenyl ether and phenylpyridazines such as pyridate. 1
<In particular, some mixtures also have synergistic effects.

Also other known active compounds, such as fungicides, insecticides (i.e.
nsect ic 1dea), acaricide (acari
cideS), nematicide
Mixtures with , bird repellents, plant nutrients and soil amendments are possible.

The active compounds may be used as such or in the form of their formulations or further diluted from their formulations, such as prepared solutions, suspensions, emulsions.

It can be used in the form of powders, coatings and granules.

These can be applied using conventional methods, such as liquid spraying (wat).
ering), spraying, atomizing (at.

granule scattering) or granule scattering
g).

The active compounds according to the invention can be applied before or after germination of the plants.

The compound can be mixed into the soil before seedlings are sown.

The use of the active compounds can vary within a substantial range. This amount depends on the nature of the desired effect. In general, the application rate is between 0.001 and 15 Kg of active compound per hectare of soil surface, preferably between 0.01 and 10 Kg/ha.

The preparation and use of the active compounds according to the invention can be learned from the following examples.

Production Examples Example 1 (Process Aspect (b)) 2-Methylmercatbenzenesulfonic acid amide 4,1
r (0.02 mol), A'-(4,6-trimethyl-pyrimidin-2-yl)-□-phenyl-urethane: y4. q
2.59 (α
0215 mol) was added in portions at 20-30°C with stirring. This mixture was then pressed at 20-25°C for a period of 15 hours. The reaction mixture was poured into 120ml of water and made soluble with concentrated hydrochloric acid.

The resulting crystalline product was separated by suction.

1-(2-methylthio-phenylsulfonyl)-3-(4,6-nomethyl-hyrimison-2 with an lfi point of 198°C)
-yl)-urea4. tr (58% of theory) was obtained.

The compounds of formula (I) shown in Table 1 below could be produced by the method exemplified in the examples above: Example 10 Ct (Process Embodiment (α)) Ozalyl chloride 7 in toluene 50 .62(0,
0.05 mol) and 2-methylthiobenzenesulfonic acid amide a1F (0.04 mol) was added to a mixture of Noade and cyclo[2.2.2]octane (DAECO) ly.
C. and the reaction mixture was heated under reflux for 5 hours. The mixture was filtered when cold, the P solution was evaporated and the residue was taken up in about 100 methylene chloride. The resulting mixture was filtered again and the filtrate containing 2-methylthio-phenylsulfonyl isocyanate was mixed with 4 fC of 2-amino-4-chloro-6-medoxypyrimison (0,025 mol) of methylene chloride 5
- Added to medium solution. The reaction mixture was stirred for 12 hours at 20° C. and the product obtained in crystalline form was separated by suction filtration. As a result, a melting point of 197°C was obtained. Ta.

The compounds of formula (I) shown in Table 1α below could be produced by the method exemplified in Example 10 above: Preparation Example (IT-1) of Starting Materials of Formula 2-Methylthio-benzenesulfonic acid Amide 42r(0
, 2 mol), soazabicyclo[2.2.2]octane (
Catalyst) Oxalyl chloride 52F (0.4 solu) was added dropwise to a mixture of α2F and toluene 60° at 95°C. The reaction mixture was stirred at 95-100°C for 5 hours and filtered after cooling. Next, the F solution was introduced into the kiln under the vacuum of a water pump. 2-Methylthiophenylsulfonylisocyanate 429 (92% of theory) was obtained in the form of an oily residue with a refractive index np=tsa42.

Example (TV-1) 2-) fruthiobenzenesulfonyl chlorite 60f (
To a mixture of 27 mol of α) and 60 me of acetone, 50 ml of concentrated ammonia was added dropwise at 20 to 50° C. while stirring. The reaction mixture was then stirred for 1 hour at 20° C. and then poured into 60 Otrre of 10% sodium hydroxide solution. The solution was filtered and the filtrate acidified with concentrated hydrochloric acid.

The resulting crystalline product was separated by suction filtration.

2-Methylthio-benzenesulfonic acid amide 19 with M point 149°C? (30% of theory) was obtained.

Compounds of formula (1) shown in Table 2 below could be produced by the method exemplified in the above examples: Table 2 Example No. R@Point ('C) (rV-2) CtHs (TV-3 ) C5Ht-'
Production example (n-1) of starting materials for formula 102 155 ml of concentrated hydrochloric acid, 40 ml of glacial acetic acid and 2-methylthio-
A solution of 68 g (0.55 mol) of sodium nitrite in 70 g of water was added dropwise to a mixture of 70 g (0.5 mol) of aniline at -5 DEG -0.degree. C. while stirring. The mixture was subsequently stirred at -5-0 DEG C. for 3 portions and 0 minutes, and the reaction mixture was then treated with 500 rItl of glacial acetic acid.

Chlorinated steel (I) 10 F (0.1 mol) and sulfur dioxide 200? (3.1 mol) dropwise. The mixture was stirred at 0°C for 3 hours and at 20°C for a further 2 hours. The reaction mixture was then mixed with 1! of toluene! I put it inside.

After washing the toluene solution with ice water, drying, filtering and concentrating, 2-methylthio-benzenesulfonyl chloride was obtained as a non-grade material with a melting point of 60<0>C.

The compounds of formula 6 shown in Table 5 below could be prepared by the methods exemplified in the examples above: Table 3 (Vll-2) C,H.

(ff-3) (1'lll?-i qo℃/1
．． 35 mbar Experimental example A Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of aryl polyglycol ether in alcohol To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the above amounts of solvent and Mixed with the above amount of emulsifier, the concentrate was diluted with water to the desired concentration.

The seeds of the test plants were sown in normal soil and after 24 hours were sprayed with the active compound preparation. The concentration of active compound in the yA product was not important, only the amount of active compound applied per unit area.

After 5 weeks, the degree of plant damage was compared with the growth of an untreated control group and determined as % damage.

The numbers have the following meanings: 0% = ineffective (same as untreated control group) up to 100 = total mortality In this test, the active compounds of the invention showed a very good herbicidal activity. This is particularly true for example in production examples 5 and 8.
．． This was true for compounds 10, 11, 12 and 13.

The compounds of Preparation Examples 5.8, 10, 11.12 and 13 have already shown good activity against monocotyledonous and dicotyledonous weeds in crops such as cotton. A portion of the results are shown in Table A.

Experimental Example B Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the above amount of solvent and the above amount. of emulsifier and the concentrate was diluted with water to the desired concentration.

The preparation of the active compound was applied to test plants 5 to 15 cm high.
Spraying was carried out so that the desired amount of active compound per unit area was applied. The concentration of the spray solution was chosen so that the desired amount of active compound was applied in 2.0001 parts of water/ILα. After 5 weeks, the degree of damage to the plants was compared with the growth of an untreated control group and evaluated as % damage. Values indicate the following meanings: 0% = no effect (same as untreated control group) 100
= total death In this test, the active compounds according to the invention showed very good herbicidal activity. This is especially true for production examples 5 and 8.
10. This was true for compounds '11, 12 and 13.

A portion of the results are shown in Table B.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, Q represents oxygen or sulfur, R represents C_1 to C_8 alkyl, R^1 represents hydrogen, C_1-C_4 alkyl or benzyl, R^2 is hydrogen, halogen, hydroxyl, C_1-C_4 alkyl, C_1-C_4 halogenalkyl, C_1-C_4 alkoxy, C_1-C_4 halogenoalkoxy, C_1-C_4 alkylthio, C_1
~C_4 halogenoalkylthio, amino, C_1~C_
4 alkylamino or di-(C_1-C_4 alkyl)
represents amino, X represents nitrogen or a -CH- group, Y represents nitrogen or a -CR^3- group, provided that R^3 is hydrogen, halogen, C_1-C_4 alkyl, (C_1-C
_4 alkoxy)-represents carbonyl or acetyl,
and Z represents nitrogen or a -CR^4- group, provided that R^4 is hydrogen, halogen, hydroxyl, C_1-C_4 alkyl, C_1-C_4 alkoxy,
1-(2-alkylthiophenylsulfonyl)-3- representing C_1-C_4 alkylthio, C_1-C_4 alkylamino or di-(C_1-C_4 alkyl)amino]
Heteroaryl-ureas or thioureas, provided that compound 1-
(2-Methylthiophenylsulfonyl)-3-(4-methoxy-6-methyl-pyrimidin-2-yl)-urea is excluded. 2. (a) Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, Q represents oxygen or sulfur, and R represents C_1
~ C_8 alkyl] 2-alkylthiophenylsulfonyl isocyanate or isothiocyanates of formula (III) ▲ where the mathematical formula, chemical formula, table etc. ▼(III) [In the formula, R^1, R^2, There are chemical formulas, tables, etc. ▼ (IV) A 2-alkylthiophenylsulfonic acid amide of [in the formula, R has the above-mentioned meaning], if appropriate in the presence of a diluent and if appropriate, in the presence of an acid acceptor. Below is the formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) [In the formula, R^1, R^2, Q, X, Y and Z have the above meanings, and R^ 5 represents C_1 to C_4 alkyl, benzyl or phenyl] or (c) Formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) [In the formula , Q represents oxygen or sulfur, R^6 represents C_1-C_4 alkyl, benzyl or phenyl, and R represents C_1-C_8 alkyl], using suitable Then, in the presence of a diluent and if appropriate in the presence of an acid acceptor, the formula (III) ▲ has a mathematical formula, chemical formula, table, etc. ▼ (III) [where R^1, R^2, X , Y and Z have the above-mentioned meanings] 1-( of the general formula (I) according to claim 1, characterized by reacting with a heteroarylamine)
A method for producing 2-alkylthio-phenylsulfonyl)-3-heteroaryl-urea or thioureas. 3. 1- of general formula (I) described in claim 1
A herbicide containing at least one type of (2-alkylthiophenylsulfonyl)-3-heteroaryl-urea or thioureas. 4. 1- of general formula (I) described in claim 1
The use of (2-alkylthio-phenylsulfonyl)-3-heteroaryl-ureas or thioureas in the control of unwanted plant growth. 5. 1- of general formula (I) described in claim 1
A method for producing a herbicide, which comprises mixing (2-alkylthio-phenylsulfonyl)-3-heteroaryl-urea or thioureas with a filler and/or a surfactant. 6. Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, Q represents oxygen or sulfur, and R represents C_1
~C_8 alkyl] 2-alkylthiophenylsulfonyl isocyanate or isothiocyanate. 7. Formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) [In the formula, R represents C_1 to C_6 alkyl] 2-
The alkylthio-benzenesulfonic acid amide is reacted a) with thionyl chloride when Q represents oxygen at a temperature of 50 to 100°C, and the product is then reacted with thionyl chloride, if appropriate in the presence of a diluent and if appropriate with a catalyst. or b) if Q represents sulfur, with carbon disulfide in the presence of an acid acceptor and if appropriate in the presence of a diluent. The reaction is carried out at a temperature of 50°C and the product is then reacted with phosgene or thionyl chloride, if appropriate in the presence of a diluent, from 0 to 50°C.
A method for producing 2-alkylthiophenylsulfonyl isocyanate or isothiocyanates of the formula (II) according to claim 6, characterized in that the reaction is carried out at a temperature of . 8. Formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) [In the formula, R represents C_1 to C_8 alkyl] 2-
Alkylthio-benzenesulfonic acid amides. 9. Formula (VII) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) [In the formula, R represents C_1 to C_8 alkyl] 2-
Claim 8, characterized in that the alkylthio-benzenesulfonic acid chlorides are reacted with ammonia, if appropriate in the presence of a diluent, at a temperature of 0 to 50°C.
A method for producing a 2-alkylthio-benzenesulfonic acid amide of formula (IV) as described in Section 1. 10. Formula (VII) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VII) [In the formula, R represents C_1 to C_6 alkyl] 2-
Alkylthio-benzenesulfonic acid chlorides. 11. Formula (VIII) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VIII) [In the formula, R represents C_1 to C_6 alkyl] 2-
The alkylthio-anilines are reacted with sodium nitrite and hydrochloric acid, if appropriate in the presence of a diluent, at a temperature of -20 to +15°C, and the product is then reacted, if appropriate in the presence of a catalyst and if appropriate. The 2-alkylthio-benzenesulfonic acid chloride of formula (VII) according to claim 10 is reacted with sulfur dioxide at a temperature of -20 to +20°C in the presence of a diluent. How to manufacture. 12,1-(2-methylthio-phenylsulfonyl)-
3-(4,6-dimethoxy-1,3,5-triazine-
2-yl)-urea, 1-(2-methylthio-phenylsulfonyl)-3-(
4,6-dimethoxy-pyrimidin-2-yl)-urea, 1-(2-methylthio-phenylsulfonyl)-3-(
4-chloro-6-methoxypyrimidin-2-yl)-
Urea, 1-(2-methylthio-phenylsulfonyl)-3-(
4-methoxy-6-methylthio-1,3,5-triazin-2-yl)-urea, 1-(2-methylthio-phenylsulfonyl)-3-(
4-Methyl-6-methylthio-1,3,5-triazin-2-yl)-urea, and 1-(2-methylthio-phenylsulfonyl)-3-(
A compound according to claim 1 selected from the group consisting of 4-dimethylamino-6-methylthio-1,3,5-triazin-2-yl)-urea.