CA1108133A

CA1108133A - Isoxazolylmethylthiol carbamates

Info

Publication number: CA1108133A
Application number: CA282,229A
Authority: CA
Inventors: Karl Eicken; Hans Theobald; Hanspeter Hansen; Bruno Wuerzer; Kurt Fett
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1976-07-28
Filing date: 1977-07-07
Publication date: 1981-09-01
Also published as: FR2359833B1; IL52365A0; BE857260A; IE45532B1; CH629080A5; DK145717B; DE2633790A1; AU511197B2; IL52365A; AU2633377A; DK338577A; AT355862B; ZA774535B; DK145717C; PL102149B1; ATA543077A; PL199854A1; FR2359833A1; IT1079363B; NL7707697A

Abstract

ABSTRACT OF THE DISCLOSURE:
The present invention is concerned with new and valuable isoxazolylmethylthiol carbamates of the general formula (I) :

I

where R1 denotes hydrogen, alkyl, unsubstituted or alkyl-substituted cycloalkyl, aralkyl, unsubstituted or halogen-substituted phenyl, R2 denotes hydrogen, alkyl, aryl, or halogen, R3 denotes hydrogen or alkyl, R4 denotes hydrogen or alkyl, and R5 and R6 are identical or different and each denotes alkyl, alkenyl, unsubstituted or alkyl-substituted cycloalkyl, alkoxyalkyl or haloalkyl, and additionally R5 and R6 together with the nitrogen atom denote an unsubstituted or a lower alkyl-substituted azetidine, pyrrolidine, piperidine, hexahydroazepine, heptamethyleneimine, bicyclo-(3,2,2)-3-azanonane or morpholine radical.

Description

~8~3~
OOZo ~2~106 ISOXAZOLYLMETHYLTHIOL CARBAMATES

The present invention relates to new and valuable isoxazolylmethylthiol carbamates, herbicides containing these compounds, and methods of controlling the growth of unwanted plants with these compounds.
It is known from French 2~205,514 that the thiolcarbamic acid esters of imidazole have a herbicidal action.
There is no disclosure of the type of herbicidal activity, e.g., selectivity in and tolerance by crop plants, and application rates. The herbicidal action of the active ingredients is only slight.
Numerous thiol carbamates are known as herbicides. Some of them have achieved considerable importance in agriculture and horticulture for controlling the growth of unwanted plants.
A characteristic common to these compounds is the good action on unwanted grasses. However, this action varies from species to species of this family. For instance, N,N-dipropylthiol-ethyl carbamate controls wild oats (German Published Appli-cation DAS 1,031,571), but this species is not listed in the manufacturer's recommendations for N,N-dipropylthiolpropyl carbamate (German Published Application DAS 1,031,571). It is reported that N,N-dipropylthiolethyl carbamate has a good ; action on Setaria spp., whereas the action Or N,N-diisopropyl-thiol-2,3-dichloroallyl carbamate (German Published Appli-.~

~a 0 Z. 32,106 cation DAS 1,142,464) was inferior here. In addition to con-trolling unwanted grasses, some compounds of this class also destroy Cyperaceae and some broadleaved weedsO For instance, N,N-dipropylthiolpropyl carbamate has an extremely reliable action on Cyperus spp., whereas N,N-diisopropylthiol-2,3-dichl~oallyl carbamate has practically no effect on these species An essential criterion for the use of these agents is the difference in selectivity from crop plant to crop plant. Thus, N-ethyl-N-cyclohexylthiolethyl carbamate (British 995,316) i!s used predominantly in Beta beets. Tne most important crop plant for N,N-diisobutylthiolethyl carbamate (German Published Application DAS 1,031,571) is Indian corn. This difference is particularly surprising in the case of N,N-diisopropylthiol-2,3-dichloroallyl carbamate and N,N-diisopropylthiol-2,3,3-trichloroallyl carbamate (German Published Application DAS 1,142,464). Both products can be employed without diff;culty in broadleaved crops such as beet and rape. For cereals, the manu~acturers and distributors only recommend N,N-diisopropylthiol-2,3,3-tri-chloroallyl carbamate, as it i8 less aggressive in these crops.
Prior art thiol carbamates have in general a high vapor pressure, as the following list shows:
Active ingredient vapor pressure mm Hg at C

N,N-dipropylthiolethyl carbamate 34 x 10 3 25 N,N-diisobutylthiolethyl carbamate - 2 - x 10 3 25 , ' ~

11`~8133 O.Z. 32,106 N,N-dipropylthiolproDyl carbamate 10.4 x 10 3 25 N-ethyl-N-cyclohexylthiol-ethyl carbamate 6.2 x 10 3 2 N,N-diisopropylthiol~2,3-dichloroallyl carbamate 1.5 x 10 4 25 N,N-diisopropylthiol-2,3,3-trichloroallyl carbamate 1.2 x 10 4 25 hexahydro-lH-azepine-1-carbamic acid thiolethyl ester 5.6 x 10 3 25 (German 1,300,947) All these compounds have to be incorporated into the soil to prevent loss through evaporationO In the case of the last compound, the submerging of rice paddies probably has the same effect as incorporation.
Although generally speaking the incorporation of herbi-cides is positive for a number of reasons, this method of application does have considerable disadvantages, e.g., the - work burden is increased, and special incorporation equipment has to be acquired. This makes itself felt particularly at farms having a low degree of mechanization. The seedbed is excessively lo~sened, and as a consequence certain seeds have emergence difficulties in dry weatherO In areas where heavy rainfalls occur, this additional soil treatment increases the risk of erosion, particularly on sloping ground.
Similarly, loosening of the soil assists wind erosion in arid wind-swept tracts. For these reasons, attempts are made under the abovementioned conditions to move the soil as little as , possible during cultivation ("reduced tillage").

There is therefore a demand for active ingre-dients which offer an alternative to incorporation. In the field of thiol carmamates with their specific properties, such compounds, with the exception of hexahydro-lH-azepine-l-carba-mic acid thiolethyl ester and S-(4-chlorobenzyl)-N,N-diethyl-thiol carbamate - which are used in rice -, have hitherto not been available. Attempts have recently been made in this di-rection with the manufacture of thiol carbamate sulfoxides. :

lGWe have now found that isoxazolylmethylthiol carbamates of the formula N ~ -S-C-N /
R4 ~ \ R6 .~
where R1 denotes hydrogen, alkyl, unsubstituted or alkyl-sub~ .
stituted cycloalkyl, aralkyl, unsubstituted or halogen-sub-stituted phenyl, R2 denotes hydrogen, alkyl, aryl, or halogen, R3 denotes hydrogen or alkyl, R4 denotes hydrogen or alk.yl, and R5 and R6 are identical or different and each denotes alkyl, alkenyl, unsubstituted or alkyl-substituted cycloalkyl, al-koxyalkyl or haloalkyl, and additionally R5 and R6 together with the nitrogen atom denote an unsubstituted or a lower alkyl-substituted azetidine, pyrrolidine, piperidine, hexahydroazepine, heptamethyleneimine, bicyclo-(3,2,2)-3-azanonane or morpholine : radical,have a strong herbicidal and selective action.

These active ingredients offer, in addition to the wider spectrum of action, a flexibility in the method of application hitherto unknown in this class of compounds.

"'~

O O Z D 32,106 The radicals R contained in the isoxazolylmethylthiol carbamates of the formula I have for instance the following meanings:
R = hydrogen; lower alkyl of a maximum of 6 carbon atoms, eOgO, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butylg n-pentyl, 2-pentyl, 3-pentyl, n-hexyl; cycloalkyl of a maximum of 8 carbon atoms optionally substituted by lower alkyl, e.g., cyclo-propyl, cyclopentyl, cyclohexyl, cyclooctyl; aralkyl, e.g., benzyl9 1-phenylethyl, 2-phenylethyl; and optionally substituted aryl, e~gO, phenyl, chlorophenyl, fluorophenyl, dichlorophenyl, trifluoromethylphenyl;
; R2 = hydrogen; optionally substituted lower alkyl of a maximum of 6 carbon atoms, e.g., methyl, ethyl, isopropyl, chloromethyl; aryl, eOgO, phenyl; and halogen, e.g., chloro, bromo, iodo;
R3 and R4 = hydrogen, and lower alkyl, especially methyl;
; R5 and R6 = lower alkyl of a maximum of 6 carbon atoms, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, n-hexyl; lower alkenyl of a maximum of 4 carbon atoms, eOg., allyl, methallyl, but-2-en-1-yl, but-4-en-1-yl; cycloalkyl of a maximum of 8 carbon atoms optionally substituted by lower alkyl, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,

2-methylcyclopentyl; alkoxyalkyl of a maximum of 6 carbon atoms, eOgO, 2-methoxyethyl, 2-ethoxy-ethyl, 1-methoxy-2-propyl, 3-methoxypropyl; halo-Bi33 O~ZO 32,106 alkyl of a maxlmum of 4 carbon atoms, eOg., 2-chloroethyl, 1-chloro~2-propyl~ 3-chloropropyl, R5 and R6 together with the nitrogen atom may also denote a heterocyclic ring of a maximum of 10 car-bon atoms optionally substituted by one or more ; lower alkyl groups, eOg~, azetidine, 2-methyl-azetidine, 2,4-dimethylazetidine, 2,4,4-trimethyl-azetidine, pyrrolidine, 2-methylpyrrolidine, 2-ethylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 2-methylpiperidine, 2-ethylpiperidine, 2-methyl 5-ethylpiperidine, hexahydroazepine, 2-methylhexahydroazepine, 2,3-dimethylhexahydro-azepine, heptamethylenimine, bicyclo- C3,2,2~ -3-azanonane, morpholine, 2,6-dimethylmorpholine,

3,5-dimethylmorpholineO
The compounds according to the invention of the formula I
may be prepared in accordance with the equation below by :
; reaction of an isoxazolyl methyl halide or isoxazolyl methyl-alkane sulfonate with a salt of a thiol carbamate.
: 20 Process A:

~ N~ ~ - X + M-S-C N ~' R
-~ R4 \ R6 II III
Rl ,R2 N~ ~ R3 0 / R5 0 C -S-C-N \ + M-X

11~8133 OOZo 32,106 R1 to R6 ha~e the abovementioned meanings; X denotes halogen or alkane sulfonate and M an alkali metal atom or ammonium optionally substituted by 2 or 3 alkylsO The starting materials of the formula II employed in process A are known or may be prepared by reaction of nitrile oxides with acetylene : halidesO Examples of such compounds are 5-chloromethyl-3-methylisoxazole, 5-bromomethyl-3-ethylisoxazole, 5-chloro-methyl-3-isopropylisoxazole, 5-bromomethyl-3-tert-butyl-isoxazole, 5-chloromethyl-3,4-dimethylisoxazole, 5-(1'-chloro-ethyl)-3-methylisoxazole, 5-bromomethyl-3-phenylisoxazole, 5-chloromethyl-3-(3',4'-dichlorophenyl)-isoxazole, and 5-bromomethyl-3-cyclohexylisoxazoleO The compounds 5-chloro-methylisoxazole and 5-bromomethyl-3-methyl-4-chloro (or

4-bromo)-isoxazole are known from the literature (Kochetkow . and coworkers, Chemical Abstracts, 47, 2167, 1953; Khim.
GeterotsiklO SoedinO, 1974, 602)o The corresponding isoxazolyl methylalkane sulfonates may be prepared from prior art isoxazolyl methanols (Gazz~ chimO italO, 69, 536, 1939) in con-ventional manner by reaction with alkanesulfonic acid chlorides in the presence of agents which bind hydrogen chloride, eOgO, pyridineO The isoxazolyl methyl halides may ~or instance be prepared as follows:
Specification A1 . FH2-Br ., CH3 N~0 '.1 238 g (parts by weight) of propargyl bromide, 476 g ;

~8133 0.Z. 32,106 (parts by weight) of phenyl isocyanate and 158 g (parts by weight) of nitroethane are dissolved in 1500 ml of toluene;
at 15 to 20C, 1 ml of triethylamine (to activate the phenyl isocyanate) is added. The temperature is kept at from 15 to 30C for 3 hours, and 1 ml of triethylamine (4 ml in all) is added each hour. The mixture is then stirred for 1 hour at 70C and then cooled~ The precipitate is suction filtered and the residue rinsed with 1 l of toluene. The combined filtrates are concentrated and the residue is distilled under an oil pump vacuum. At 59 to 61C/002 mm Hg, 310 g (~ 88% of theory) of 3-bromomethyl-5-methylisoxazole distils over (n25: 1.5168).
C5H6BrN0 (176) C H N Br CalcO: 34~2 3O4 7.9 45.5 Found: 34Oo 3.4 8.o 45O4 60 MHz nmr spectrum (CDC13; ~ values) 2.3 (3H, s), 4.44 (2H,s), 6015 (lH, s) 13C nmr spectrum (CDCl3, ppm values relative to TMS):
167.2 (C), 16001 (C), 10405 (CH), 18.8 (CH2), 11.3 tCH3).

Specirication A2 3 ~ CH3 N~

93.5 g (parts by weight) of acetohydroximoyl chloride (Ber. dtsch. chemO Ges., 40, 1677~ 1907) and 90 g (parts by weight) of isobutynyl chloride are stirred in 1500 ml of ; - 8 -~8~

OoZo 32~106 benzene; at 15 to 20 C, 105 g ~parts by weight) of triethyl-amine is added dropwise~ The mixture is then stirred for 1 hour at from 20 to 25C and for 1 hour at 70Co After the mixture has been allowed to cool it is filtered and the fil-trate concentratedO The distillate wh;ch remains is distilled under an oil pump vacuumO There is obtained 133 g (92% of theory), bopo 48 to 50C/0005 mm Hg; n25- 1047400 C6HgNOCl (14505) C H N Cl Calc.: 4906 505 907 2405 Found: 49~5 507 lOoO 2400 60 MHz nmr spectrum (CDCl3, ~ values) 1078 (d, 3H), 2.3 (s, 3H), 5~05 (9~ lH), 6009 (s~ lH)o 3C nmr spectrum (CDCl3, ppm values relative to TMS):
171~5 (C)~ 15908 (C)~ 10205 (CH)~ 4704 (CH), 23.3 (CH3), 11~ 5 (CH3)o Sepcification A3 N~O~CH2-Br 119 g (parts by weight) of propargyl bromide, 95 g (parts by weight) of nitropropane and 440 g (parts by weigh) of tri-ethylamine are dissolved in 1200 ml of chloroform; at 0C, 155 g (parts by weight) of phosphoroxy chloride is added drop-wiseO The mixture is kept at 20C for 30 minutes and refluxed for 2 hours. After the mixture has been cooled, filtration ; and concentration are carried out 3 and the residue is taken _ g _ -li'~8~33 0,Z. 32,106 up in water. The water phase is extracted several times with toluene and the combined toluene phases are washed with water and subsequently dried over sodium sulfate. The sodium sulfate is then separated and the filtrate concentrated; the residue is distilled under an oil pump vacuumc At 78 to 79C/0.1 mm Hg, 150 g (79% of theory) distil off; nD5 : 1.5108.

C6H8BrNO ( 190 ) C H N Br Calc.: 3709 407 704 4200 Found: 3800 406 7.6 41.7 The following compounds are obtained analogously:

3 ~ n25 = 104806 CH3 ~ CH2-~ nDS : 1.5500 C 2H5 ~

i-C3H7-S-cH2~c~H3 CH-Br i-C3H7~clH3 CH-Cl . .

~8133 OOZo ~2,106 CH3-0-CH2 ~3~
C~12 Cl The compounds designated w;th formula III are salts of thiolcarbamic acidsc Typical representatives, which may be pre-pared in conventional manner, are the sodium salts or the ammonium salts - optionally substituted by 2 or 3 alkyls - of N,N-dimethylthiolcarbamic acid~ N,N-diethylthiolcarbamic acid, N,N-diisopropylthiolcarbamic acid, N,N-di-n-propylthiolcar-bamic acid, N,N-di-n-butylthiolcarbamic acid, N,N-diisobutyl-thiolcarbamic acid, N-ethyl-N~n-butylthiolcarbamic acid, N-ethyl-N-isopropylthiolcarbamic acid, N-ethyl-N-cyclohexyl-thiolcarbamic acid, ~,N-diallylthiolcarbamic acid, further N-azetidine-, N-pyrrolidine-, N-piperidine- and N-hexahydro-azepinethiolcarbamic acid and their derivatives substituted in the ring by 1 to 3 methyl and/or ethyl groups.
Process A may be carried out in the presence of any inert organic solvents, for instance hydrocarbons, e.g., cyclo-hexane, benzene, toluene; halogenated hydrocarbons, e.g., methylene chloride, chloroform, carbon tetrachloride, chloro-benzene; ethers, e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether; lower alco-hols and ketones, e.gO, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, cyclohexanone; nitriles9 eOg., acetonitrile; and water. Mixture of these solvents may also be usedO
For the preparation of the new active ingredients, pro-cess A is preferredO

8~3 O.Z. 32,106 If desired, the isoxazolylmethylthiol carbamates of theformula I according to the invention may also be prepared in accordance with process B by reaction of isoxazolylmethyl mer-captans or their salts with carbamic acid chlorides Process B

R3 ~, / R5 N ~ R ~ R5 C-S-Y + Cl-C-N - ~ C-S-CO-N ~ + Y-Cl R4 \ R6 R4 R6 IV V

In the formulae, R1 to R6 have the above meanings and Y
denotes hydrogen, an alkali metal atom, or ammonium optionally substituted by 2 or 3 alkyls. -~
Formula IV represents starting materials which may be prepared by conventional methods from the isoxazolyl methyl halides of the formula II by reaction with hydrogen sulfide or salts thereof (e.g., Houben-Weyl, Methoden der Organischen Chemie, IX, 1-18)o The following are examples of mercaptan5 of the formula IV: 3-methylisoxazoly1-5-methyl~ercaptan, 3-ethylisoxazolyl-5-methylmercaptan, 3-phenylisoxazolyl-5-methylmercaptan, 3-methylisoxazolyl-5-(1'-ethyl)-mercaptan.
Examples of carbamoyl chlorides of the formula V are those of dimethylamine, diethylethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, N-ethyl-n-butylamine, N-ethyl-n-isopropylamine, azetidine, pyrrolidine, piperidine, hexahydroazepine and derivatives thereof substituted on the ring by 1 to 3 methyl and/or ethyl groups.

'' . .

~.Z0 32,106 Process B is expediently carried out in the presence of a hydrogen chloride acceptorg Suitable for this purpose are any inorganic bases, eOg., alkali metal bicarbonates,car-bonates and hydroxides; organic bases, such as alkali metal alcoholates, e.g~, sodium methylate; tertiary amines, e.g., triethylamine and N,N-dimethylcyclohexylamine; and saturated or unsaturated nitrogen heterocycles, eOg., N-methylpiperidine, pyridine and quinoline. The process is advantageously carried out using one of the solvents (or mixtures thereof) listed at process Ao The isoxazolylmethylthiol carbamates of the invention of the formula I may also be prepared by reaction of an isoxa-zolylmethylthiochlorocarbonic acid ester with a secondary amine.
Process Co , R ~ R1 2 N ~ R3 0 / R5 N ~ ~ " / + HCl C-S-C-Cl + HN ~ C-S-0-N
R4 ~ R6 R4 ~ R6 VI VII

In the formulae, R1 to R6 have the abovementioned meanings.
The thiochlorocarbonic acid esters of the formula VI may be prepared in conventional manner from the isoxazolylmethyl-mercaptans Or the formula IV (Y = hydrogen) and phosgene.
Examples of compounds of the formula VI are 3-methylisoxa-zolyl-5-methylthiocarbvn~l chloride, 3-ethylisoxazolyl-5-.

OOZo 32,106 methylthiocarbonyl chloride3 and 3-phenylisoxazolyl-5-methyl-thiocarbonyl chloride. Suitable secondary amines of the for-mula VII are particularly those listed at process B as compo-nents of the carbamic acid chloridesO Process C may be carried out using the inert solvents mentioned in process A - less advantageously in alcohols or water - and with or without the addition of one of the hydrogen chloride acceptors mentioned in process Bo In detail, process A may for instance be carried out as follows.
At from -20 to ~50C, 1 mole of an isoxazolylmethyl halide or alkane sulfonate of the formula II, optionally in one of the above solvents, is dripped into a solution or sus-pension of at least 1 mole of a thiol carbamate of the for-mula III~ To complete the reaction, the mixture is stirred for from 3 to 12 hours at from 0 to to 80Co Upon completion of the reaction, the mixture is poured into water and the pro-duct is extracted, if desired with an inorganic solvent immiscible with water, and subsequently isolated by distil-lation or crystallization, Process B may for instance be carried out in the follo-wing manner.
A solution of 1 mole of isoxazolylmethylmercaptan of the formula IV in a solvent is reacted with at least one mole of a carbamic acid chloride of the formula V in the presence of at leat 1 mole of one of the abvementioned inorganic or organic bases at from -10 to +80C and for from 1 to 12 hours The thiol carbamates according to the invention of the formula I

O.Z. 32,106 are isolated as described aboveO
Process C is for instance carried out as follows~
A solution Or 1 mole of a thiochlorocarbonic acid ester of the formula VI in an inert organic sol~ent is reacted with at least 1 mole of an amine of the formula VII; the acid-binding agent may be at least 1 mole of the inorganic or organic bases mentioned in process Bo The reaction temperature is from -10 to +80 C and the reaction time from 1 to 12 hours, as in process B, depending on the reactants, the base and the solvent employed. The thiol carbamates are isolated as described above~
The following examples, in which the parts are by weight, illustrate the processes for preparing the isoxazolylmethyl-thiol carbamates according to the in~ention of the formula I.

EXAMPLE
At 0C, 60.0 parts of carbonyl sulfide was gassed into a mixture of 102 parts of N-ethylcyclohexylamine, 80.8 parts of triethylamine and 700 parts of methylene chloride, and the whole was stirred for 2 hours at room temperature. Subsequent-ly, 105.3 parts of 3-methyl-5-chloromethylisoxazole was dripped in over a period of 1 hour at 0C, and the mixture stirred for 10 hours at room temperature. The salt which had formed was filtered off and the filtrate was washed successively with water, lN hydrochloric acid and again with water, and dried. After removal Or the solvent, distillation of the residue gave 194.2 parts of 3-methyl-5-isoxazolyl-methyl-N-ethyl-N-cyclohexylthiol carbamate, b.p. (0.2 mm Hg) 176-179C (m.p. 60-62C) O.Z0 32~106 At 0C~ 8.0 parts of carbonyl sulfide was gassed into a mixture of 2102 parts of diisopropylamine in 100 parts of toluene, and the whole stirred for 30 minutes at 0C and for 1 hour at room temperature. Subsequently, 19.0 parts of 3-ethyl-5-bromomethylisoxazole was dripped in over a period of 15 minutes and the whole stirred for 3 hours at room tempera-ture. After working up as in Example 1, there was obtained 21.8 parts of 3-ethyl-5-isoxazolylmethyl-N,N-diisopropylthiol carbamate having a boiling point at 0.3 mm Hg of 154-156C
(nD5: 105089).

While cooling, 2908 parts of N,N-diethylcarbamic acid chloride was dripped into a mixture of 2508 parts of 3-methyl-isoxazolyl-5-methylmercaptan in 100 parts of ether and 50 parts of pyridine; the whole was then refluxed for 3 hours.
After working up as in Example 1, there was obtained 35.8 parts of 3-methyl-5-isoxazolylmethyl-N,N-diethylthiol carbamate having a boiling point at 0.05 mm Hg of 136-138C.
; The following isoxazolylmethylthiol carbamates according to the invention may be prepared by one of the abovementioned processes.

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- a -0 Zq 32,106 Examples demonstrating the herbicidal action of the new isoxazolylmethylthiol carbamates A series of experiments, divided in the main into the follo~ing three groups, was carried out to provide evidence in support of the statements made in the introduction about these active ingredientsO
I Greenhouse experiments .

The vessels employed were paraffined paper cups having a volume of 200 cm3, and the substrate was a sandy loam con-taining about lo 5% (wt%) humusO The seeds of the test plantswere sown shallow and separated according to speciesO The active ingredients were applied immediately (preemergence treatment), suspended or emulsified in water as the distribution medium and sprayed onto the soil surface by means of finely distributing nozzles. Prior to the chemical treat-ment, the cups were lightly sprinkler-irrigated; the agents therefore came into contact with moist soilO After application of the agents the vessels were covered with transparent plastic hoods until the plants had taken root. This cover pre-vented the evaporation of water and readily volatile sub-stances. Another effect was the more uniform emergence of the test plants, to the extent that they were not impaired by chemicals. When postemergence treatment was employed, the plants were first grown in the vessels to a height of from 3 to 10 cm~ depending on the form of growth, and then treated~
A cover was not used~ Depending on the temperature require-ments of the plants, the experiments were set up either in the cooler (10-20C) or warmer (18-30C) portion of the green-: .
. , .

~iU~1~33 O.Z0 32,106 house. The experiments lasted for from 2 1/2 to 6 weeks.
During this period, the plants were tended and their reaction to the individual treatment was evaluated. The substances examined, the dose rates employed (in kg/ha of active ingredient) and the types of plant used in the experiments are given in the following tables. A 0 - 100 scale was used for assessment, 0 denoting no damage or normal emergence, and 100 denoting complete destruction or non-emergence.

IIo Experiments in the open These experiments were carried out on small plots of various sizesO The soil was a sandy loam having a pH of 5-6 and 1 - lo 5% humusO The compounds were applied from early to late fall and from early to late spring, corresponding to the sowing period for the crop plantsO The compounds were emulsi-fied or suspended in water as carrier and distribution medium, and applied by means of a motor-driven plot spray mounted on a hitcho The application methods most frequently employed were preplant incorporation and preemergence surface application.
In individual experiments, the action of the agents when sprayed during emergence of the crop plants and weeds, and postemergence after formation of a few genuine leaves was examined. All the experiments were run for several months;
during this period assessments were made at certain intervals employing the 0 to 100 scaleO
IIIo Herbic_dal action via the vapor phase The remarkable herbicidal action of isoxazolylmethyl-thiol carbamates, even when not incorporated into the soil as is necessary with prior art thiol carbamates, suggested that 3~

0uZO 32,106 the losses of active ingredient through evaporation were low.
To examine this, the following experiment was carried out in the greenhouse~ Seeds of a sensitive oat crop were sown as described in Section I (greenhouse experiments) and treated with the herbicidal active ingredients at various rates. The vessels were not however covered with a plastic hood, but placed in pairs in 5 liter glass cylindersO The pairs were made up Or a treated and an untreated vesselO ~or comparison purposes, control cylinders containing only untreated pots were usedO To prevent gas exchange with the atmosphere, the rims of the cylinders were coated with Vaseline and the opening was covered with a glass plateO Readily evaporating substances were thus able to escape from the surface of the soil in the vessels into the cylinder space and possibly influence the germination and development of the test plants in the parallel vessels originally free from active ingredient. The temperature in the glass cylinders varied from 11C in the morning to 30C in the afternoon in sunlight.
After 14 days, the plants in the control cylinders had reached a height of from 13 to 15 cm and the differences be-tween the various treatments were readily perceptible. In addition to a visual assessment~ the green weight of the oat shoots was determined for each vesselO This is given in Table llo Results The individual results from the various experiments and tables combine to give the following pictureO
1) The introduction of the isoxazolylmethyl radical into the 8~33 00%0 32,106 thiol carbamates resulted in a shirt in action, parti-cularly in a broadening of the range Of action compared with prior art thiol carbamatesc Thus, for instance~ some compounds developed an actlvity embracing that Of N,~-di-isopropylthiol-2,3-dichloroallyl carbamate or N,N diiso-propylthiol-2,333-trichloroallyl carbamate and of N,N-dipropylthiolethyl carbamate (cfo Tables 2, 3 and 5)0 In other instances, a similar, at times somewhat poorer, her-bicidal performance to that N-ethyl-N-cyclohexylthiolethyl carbamate was found~ However~ the selectivity range in crop plants was incomparably greater (cfo Table 6) It should be pointed out at this juncture that the prior art thiol carbamates were only employed in the experiments because Of their action as herbicidesO Compounds having a structure similar to that of the compounds of the invention are hitherto unknown. A thiol carbamate having a heterocyclic ; ring and known as a herbicide had insignificant activity (Table 3) The corresponding dithiol carbamate was com-pletely inef~ective. Table 4 contains a further example of the herbicidal action of the new isoxazolylmethylthiol carbamatesO
2) Whereas prior art thiol carbamates can only be used in specific crop plants or groups thereof (eOg., broadleaved species) because of (a) their phytotoxicity, (b), incor-poration necessary ~or herbicidal action~ and (c) the weed spectrum combatted, some of the new compounds have an im-proved and wider selectivity (Tables ~, 5, 6 and 7)~ Plant physiology may provide an explanatio~ for the selectivity .~

B~;~3 OOZ~ 32,106 of the compounds of the invention; the selectivity may also be attributable in part to the application method employed.
Immobile substances distributed on the surface of the soil do not come into contact in phytotoxic amounts with the seeds and roots of the crop plants lying somewhat deeper.
This selectivity is apparent in the case of compounds which can be left on the surface of the soil after application, but does not exist when the active ingredients have to be incorporated into the soil because of their high vapor pressure or for other reasons, in order to avoid eva-poration lossesO
3) The new compounds according to the invention had, when incorporated before sowing, an action similar to that of prior art compoundsO When applied without incorporation they were superior to the prior art thiol carbamates suit-able for the crop in question (Table 8)o Remarkable in this connection is the fact that for instance the compound 3-methyl-5-isoxazolylmethyl-N,N-diisopropylthiol carbamate, when applied preemergence to the surface, combatted un-wanted plants in Indian corn just as well as significant ; prior art preemergence herbicides of different structure (Table 9)O Successful control was also obtained during and after emergence of the unwanted plants; the crop plants remained unaffected (Tables 8~ lC)o 4) The phytotoxicity of the vapors of N,N-diisopropylthiol-2,3,3-trichloroallyl carbamate for wild oats is known. This was confirmed in model experiments. Of the new compounds, ' . .

0OZo 32,106 it was f`ound that for instance the substance 3-methyl-5-isoxaæoly]methyl-N,N~diisopropylthiol carbamate had just as aggressive an action on the crop plant oats in the directly treated vessels as N,N-diisopropylthiol-2,3-dichloroallyl carbamate ~r N,N-diisopropylthiol-2,3,3-trichloroallyl carbamateO The plants in the untreated pots located in the same glass cylinder remained undamaged by this new com-pound, whereas plant growth in the case o~ the comparative compound had suffered (Table ll)o Consequently, not enough active ingredient had escaped from the directly treated pots to cause damage, via the gas phase, to the neigh-boring test plantsO The actual vapor pressure of 3-methyl-; 5-isoxazolylmethyl-N,N-diisopropylthiol carbamate was 1.3 x 10 5 mbar at 20C, whereas that Or N,N-diisopropyl-thiol-2,3-dichloroallyl carbamate at the same temperature was 3.7 x 10 4 mbar.
It goes without saying that the experimental results dis-cussed here are only examples of the reaction of numerous un-wanted and crop plants from a wide variety of botanical families. The application rates too can be varied beyond the examples; they depend on the end to which they are applied and on local conditions (site, plant size), and may for instance vary from 0O1 to 10 kg of active ingredient per hectareO
The particular advantage of this new group of isoxa~olyl-methylthiol carbamates over prior art thiol carbamates is the range of possible application methods.

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26 3.0 PRE - 90 90 3,0 POST 90 90 9 _ 3.0 POST 90 90 90 -- -- -- _ _ _ ~ 29 3.0 PRE - 90 90 ; 3.0 POST 70 90 50 , . -- -- _ _ _' 33 3.0 PRE - o O
.~ 3.0 POST O 90 50 38 3.0 PRE - go 30 3.0 POST 90 90 90 _ PRE = preemergence treatment POST = postemergence treatment O = no damage ~ 100 = complete destruction :~ `
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O.Z. 32,106 Table 5 - Selective control of grassy weeds in beet with various thiol carbamates in the open; preplant incorporation Basic molecule 2 / "

Substituents in the Compound Appl. Test plants and compounds examined NoO rate % damage kg~ha Beta Al.opecurus R1 R2 R3 vulgaris myosuroides _ 16 2.0 0 75 3 2.0 5 80 13 4.0 0 5 ~ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ 9 4,0 50 70 _ ~ 14 400 50 90 -- -- _ _ _ _ C3H7i C3H7i ClCl 2~0 0 30 CH2-C = C-Cl 400 0 80 prior art C3H7nC3H7n C2H5 prior art 200 10 80 4.0 30 95 ' 0 - no damage 100 - complete destruction _ 34 _ O.Z. 32,106 ~ l l o ~ ~ o U~ o Lr) I o o "~ ~ l'co ~ .,.
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8~33 0,Z 32,106 In view of the methods of application possible with thecompounds of the invention, they, or compositions containing - them, may be used not only in the crops listed in the tables : but also in a wide variety of other crops for combatting unwanted plant growthO Application rates may be from 0.1 to 15 kg/ha and more, depending on the object to be combatted.
; Individual crop plants are listed below:

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~1~8~33 O.Z. 32,106 The new isoxazolylalkylthiol carbamates of the invention may be mixed with numerous respresentatives Or other groups ; of herbicidal active ingredientsO Such combinations broaden the spectrum of action and have in some cases synergistic effects. The following compounds are examples of those which can be mixed with the compounds of the invention:

.

0, ~ . 32, 106 R

~N-C-C132Cl R 0 ~ -R Rl P PY

~3 CH- C -. CH .
CH3 ~H3 ~_ , 2 3 C2~15 ~_ - CH -C-OC H

~H 3 -~ ~

CH3 CH2-CH2-0CH3 ~;
C~3 .
.

~8~33 O.Z. ~2 106 CH2-CH-CH2 CH2=CH-CH2-Rl~ CH3 N-C-N

' R Rl R2 CH
~HC~ H CH3.

H3CO~ H CH3 Cl ~ H CH

;~ H3C~ H CH3 C~3 :
C 14~ H C H- C- CH

Cl-~9-0~ H CH3 .

~N/>-- CH3 ` . H

~--N
/`S~ CH3 H

Br~3- H OCH3 C'- ~ H OCH3 .

' - 45 - .

O. Z, 32 106 R Rl R2 C l-Ç3 - H OCH 3 Cl H 3co-~3 - H OCH 3 Cl o R~ N_ ~ N;~ 2 R R~ R2 tert. CIlH9 IIH2 SCH3 ~CH3 tert . C 4Hg -N - CH- CH SCH;

~9- NH2 3 O CH

" [~3 R

-CH~ . :

-N ~

-N~
C-CH
" 3 O

B:~33 O.Z. 32 106 Rl ~ N ~ 4 R Rl R2 R3 R4 CF3 H n.C3H7n.C3 7 CF3 H n.C3H7 CH2cH

H S2NH2 H n.C3H7 3 7 H CF~ H n.C3H7 CH2~ -H CF3 NH2 n.C3H7n.C3H7 X
. ~
NHRl R-HN

' ` R Rl X

tert.C4H9 C2H5 C2H5 Cl i-C3H7 ~ Cl C2~5 C2H5 Cl : CH3 C2H5 -C-CN Cl - .
' .

llU~3133 O. Z, ~52 lC6 R Rl X
C~l 3 -4 -C-CN Cl C2H5 CH CH2 C 3 Cl R

- CH3 CH3 ~ anion R

H

CH3-CC12~,C~-ONa CCl 3-- C-ONa C l-Ç3 -N~ C~- C- O- C 2~ 5 C=O O
~Cl ~

N- C'H- C-O- CH \
Cl 1= CH3 ,, ~ .

o~ z~ 32 106 Bo~ and salts Br NC ~ OH and salts I

Br 02N ~3-o-N-~H~ OH and salts r I /CH 3 HN~N-C-NH-CH2-CH~

O
Cl ~NJ~o, N~
.H3C H

., .
O

H

Q

C4Hg sec 02N-~-OH and salts CI~H9 sec .

ilS~8133 0, Z, 32 106 ~3 N ~__ NH2 0 Cl ~ N}~CH 3 CF3 0 Cl ~-CII~ lmd sslts H

-CH.~ and salts 3 :

~N ' 2 ~N-CH~ and salts H

~3 / 3 ~NH-C--CH2-C-c C'~2 Cl C~ B13;~ o z ,2 o6 C 1 - ~ - CH2 - CH- C- O- CH .~
O ' .

" 3 C l~ o _ ~3 - O C H C - O- C H ~ - C

3 ~3 ~ 3 ' 3 C~ Cl - .. ..
CH3 ~ Cl OR C 3H ~n ' ~1~, C-NH-O-CH2-CH=CH~ :~

3 ~ land salts C-OCH
" 3 O

R - H or Na Cl ~Cl Cl ~Cl : - 55 -' ~8~33 ' O,Z, ~2 106 CO~H
Cl ~1 1 and scllts Cl NHz Cl~ O~CH?-C-OH and sa.lts or. esters ~
Cl -O-CII2~C-OH and salts or esters CJ.~O-(CH2)3-C-OH and salts or esters O
Cl O
N~C-CX2-0-S- NHCH
~ ,- 3 ~ O O
. -H3~
As-ONa ~0 0 Cl Cl-~-0~~ 0-C~I- C-O-Na O

Cl COOH

F3C ~~ ~-~2 :- ~ 56 ~ .
~' .~, .

~)8 13;~
O.Z. 32,106 ~ ,, N-C-CH2-0-S-I~H ~ i-propyl ,, O O

~N-C-CH2-0-S-NH i-propy 1 O O

It is also useful to be able to apply the new compounds according to the invention9 either alone or in combination with other herbicides, in admixture with other crop protection --agents, e.gO, agents for combatting pests and phytopathogenic fungi, and growth regulatorsO The new compounds may also be mixed with mineral fertilizer solutions used to overcome nutritional or trace element deficienciesO
Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), disper-sions, emulsions, oil dispersion, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broad-casting or wateringO The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etcO and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as ` benzene, toluene, xylene, paraffin, tetrahydronaphthalene, i~)813~

OOZ. 32,106 alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohe~anone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, di-methyl sulfoxide, N-methylpyrrolidone, water, etc. are suit-ableO
Aqueous formulations may be prepared from emulsion con-centrates, pastes, oil dispersions or wettable powders by adding waterO To prepare emulsions, pastes and oil dispersions : 10 the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiersO Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, ~ alkyl sulfates, and alkyl sulfonates, alkali metal and : 20 alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal : and alkaline earth metal salts of fatty acids, salts of sul-fated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers,condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphtha-lene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers,ethoxylated isooctylphenol, - ' ~D18133 OOZ. 32,106 ethoxylated octylphenol and ethoxylated nonylphenol, alkyl-phenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcoholsa isotridecyl alcohols, ratty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carriers~ Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, amrnonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell rneal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably ` 0.5 to 90, % by weight of active ingredient.
There may be added to the compositions or individual active ingredients (if desired, immediately before use (tank-mix)) oils of various types, wetting agents or adherents, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoams (e.g., silicones), growth regulators, antidotes and other ~ 59 -O~ZO 32,106 herbicidally effective compounds~ The last-mentioned herbici-dal compounds may also be applied before or after the individual active ingredients according to the invention or compositions thereof.
These agents may be added to the herbicides according to the invention in a ratio by weight of from 1:10 to 10:1. The same applies to oils, wetting agents and adherents, fungi-cides, nematocides, insecticides, bactericides, antidotes and growth regulatorsO

90 parts by weight of compound 1 is mixed with 10 parts by weight of N-methyl-~-pyrrolidoneO A mixture is obtained which is suitable for application in the form of very fine dropsO
: EXAMPLE 5 20 parts by weight of compound 2 is dissolved in a mix-: ture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles o~ ethylene oxide to 1 mole of oleic acid-N-monoethanolamide~ 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oilO ~y pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0~02% by weight of the active ingredient.

; 20 parts by weight of compound 3 is dissolved in a mix-` ture consisting of 40 parts by weight of cyclohexanone, : - 60 -.

O~ZO 32,106 30 parts by weight of ;sobutanol, 20 parts by weight of the adduct of 7 moles Or ethylene oxide to 1 mole of isooctyl-phenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oilO By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0002% by weight of the active ingredientO

20 parts by weight of compound 4 is dissolved in a mix-ture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil.
By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
` EXAMPLE 8 20 parts by weight of compound 4 i.s well mixed with 3 parts by weight of the sodi.um salt of diisobutylnaphthalene-~-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill~ By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.
. EXAMPLE 9 3 parts by weight of compound 4 is intimately mixed with -` llV8i33 O.Z. 32,106 97 parts by weight of particulare kaolin. A dust is obtained containing 3% by weight of the active ingredient.
EXAMPL,E 10 30 parts by weight of compound 4 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gelO A
formulation of the active ingredient is obtained having good adherence 40 parts by weight of compound 5 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of waterO Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0004 wt% of active ingredientO

; 20 parts of compound 6 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

.;

. ' - : ~ ~ . '

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. Isoxazolylmethylthiol carbamates of the formula :

(I) where R1 denotes hydrogen, alkyl, unsubstituted or alkyl-sub-stituted cycloalkyl, aralkyl, unsubstituted or halogen-sub-stituted phenyl, R2 denotes hydrogen, alkyl, or halogen, R3 denotes hydrogen or alkyl, R4 denotes hydrogen or alkyl, and R5 and R6 are identical or different and each denotes alkyl, al-kenyl, unsubstituted or alkyl-substituted cycloalkyl, alkoxy-alkyl or haloalkyl, and additionally R5 and R6 together with the nitrogen atom denote an unsubstituted or a lower alkyl-sub-stituted azetidine, pyrrolidine, piperidine, hexahydroazepine, heptamethyleneimine, bicyclo-(3,2,2)-3-azanonane or morpho-line radical.

2. A process for controlling the growth of un-wanted plants wherein the soil or the plants are treated with an isoxazolylmethylthio carbamate of the formula (I) where R1 denotes hydrogen, alkyl, unsubstituted or alkyl-sub-stituted cycloalkyl, aralkyl, unsubstituted or halogen-sub-stituted phenyl, R2 denotes hydrogen, alkyl, aryl, or halogen, R3 denotes hydrogen or alkyl, R4 denotes hydrogen or alkyl, and R5 and R6 are identical or different and each denotes alkyl, alkenyl, unsubstituted or alkyl-substituted cycloalkyl, alkoxyalkyl or haloalkyl, and additionally R5 and R6 together with the nitrogen atom denote an unsubstituted or a lower alkyl-substituted azetidine, pyrrolidine, piperidine, hexahy-droazepine, heptamethyleneimine, bicyclo-(3,2,2)-3-azanonane or morpholine radical.

3. Compound according to claim 1 which is the 3-methyl-5-isoxazolylmethyl-N-ethyl-N-cyclohexylthio carbamate.

4. Compound according to claim 1 which is the 3 ethyl-5-isoxazolylmethyl-N,N-diisopropylthio carbamate.

5. Compound according to claim 1 which is the 3-methyl-5-isoxazolylmethyl-N,N-diethylthio carbamate.