IE45532B1 - Isoxazolymethylthiol carbamates and their use as herbicides - Google Patents

Abstract

Novel isoxazolylmethyl thiocarbamates of the formula I are used for controlling undesired plant growth either by themselves or together with a carrier. The symbols in formula I have the meaning given in Patent Claim 1.

Description

The present invention relates to new and valuable isoxazolylmqthylthiol carbamates, herbicides containing these compounds, and methods of controllihg the growth of unwanted plants with these compounds.

It is known from French Patent Specification 2,205,514 that the thiolcarbamic acid esters of imidazole have a herbicidal action. However, 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-dipropylthiolethyl carbamate controls wild oats (German Published Application DAS 1,031,571), but this species is not listed in the manufacturer's recommendations for Ν,Ν-dipropylthiolpropyl carbamate (German Published Application DAS 1,031,571)· It is reported that Ν,Ν-dipropylthiolethyl carbamate has a good action on Setaria spp., whereas the action of Ν,Ν-diisopropylthiol-2,3-dichloroallyl carbamate (German Published Appli2 ϊ ΰ 5 3 2 cation DAS 1,142,464) was inferior here. In addition to controlling unwanted grasses, some compounds of this class also destroy Cyperaceae and some broadleaved weeds. For instance, Ν,Ν-dipropylthiolpropyl carbamate has an extremely reliable action on Cyperus spp., whereas N,N-diisopropylthiol-2,3dicblcroallyl 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-athyl-N-cyclohexylthiolethyl carbamate ( British Patent Specification 935,316) is used predominantly in Beta beets. The 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-2,3,5-trichloroallyl carbamate (German Published Application DAS 1,142,464). Both products can be employed without difficulty in broadleaved crops such as beet and rape. For cereals, the manufacturers and distributors only recommend N,N-diisopropylthiol-2,3,3-tri20 chloroallyl carbamate, as it is 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 i:,N-dipropylthiolefchyl carbamate 34 x 10-^ 25 N,N-diisobutylthiolethyl carbamate 13 x 10 2 25 N,N-dipropylthiolpropyl carbamate 10.4 x. IO3 25 N-ethyl-N-cycIohexylthiolethyl carbamate 6.2 x IO’3 25 5 N,N-diisopropylthiol-2,3dichloroallyl carbamate 1.5 x 10“4 25 N,N-diisopropylthiol-2,3,3trichloroallyl carbamate 1.2 x 10“ 4 25 10 hexahydro-IH-azepine-1carbamic acid thiolethyl ester 5.6 x io“3 25 (German Patent Specification 1,300,947) All these compounds have to be incorporated into the soil 15 to prevent loss through evaporation. 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 herbicides 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 loosened, and as a consequence certain seeds have emergence difficulties in dry weather. 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 -ib5 3:i possible during cultivation (reduced tillage).

There is therefore a demand for active ingredients which offer an alternative to incoi-poratior,. In the field of thiol carbamates with their specific properties, such compounds, with the exception of hexahydro-lH-azepine-l-carbamie acid thiolethyl ester and S-(4-chlorobenzyl)-N,N-diethylthiol carbamate - which are used in riee -, have hitherto not been available. Attempts have recently been made in this direction with the manufacture of thiol carbamate sulfoxides.

We have now found that isoxazolylmethylthiol carbamates of the formula where R1 denotes hydrogen, alkyl, alkyl interrupted by oxygen or sulfur (i. e. alkoxyalkyl or nikylncrcaptoalkyl), unsubstituted or alkyl-substituted cyeloalkyl, aralkyl, or optionally substituted aryl, p R denotes hydrogen, optionally substituted alkyl, aryl, or X ll halogen, R denotes hydrogen or alkyl, R denotes hydrogen or c β alkyl, and ic and R are identical or different and each denotes alkyl, alkenyl, unsubstituted or alkyl-substituted cyeloalkyl, alkoxyalkyl or haloalkyl, and additionally R and together with the nitrogen atom denote an unsubstituted or lower alkyl-substituted heterocyclic ring having up to 10 ring carbon atoms, preferably 4,5,6 or 7 ring marbers, have a strong herbicidal and selective adicn.

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.

The radicals R contained in the isoxazolylmethylthiol carbamates of the formula I have for instance the following meanings: R = hydrogen; lower alkyl qf a maximum of 6 carbon atans optionally interrupted fay 0 or S, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, • n-hexyl, isopropylmercaptaiethyl methoxymethyl; cyeloalkyl of a maximum of 8 carbon atoms optionally substituted by lower alkyl,e.g. cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl; aralkyl, e.g. benzyl, 1-phenylethyl, 2-phenylethyl; and optionally substituted aryl, e.g. phenyl, chlorophenyl, fluorophenyl, dichlorophenyl, trifluoromethylphenyl; R = hydrogen; optionally substituted lower alkyl of a maximum of 6 carbon atoms, e.g., methyl, ethyl, isopropyl, chloromethyl; aryl, e.g. phenyl; and halogen, e.g. chloro, bromo, iodo; 4 R and R = hydrogen, and lower alkyl of a maximum of 6 carbon atoms, especially methyl; R^ and R° = lower alkyl of a maximum of 6 carbon atoms, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, n-hexyl; lower alkenyl of a maximum of 4 carbon atoms, e.g. allyl, methallyl, but-2-en-l-yl, but4-en-l-yl; cyeloalkyl 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, e.g. 2-methoxyethyl, 2-ethoxyethyl, l-methoxy-2-propyl, 3-methoxypropyl; halo6 ia 5533 alkyl of a maximum of 4 carbon atoms, e.g., 2-ehloroethyl, 1-chloro-2-propyl, 3-chloropropyl; R? ana R' together with the nitrogen atom may also denote a heterocyclic ring of a maximum of 10 carbon atoms, preferably 4-7 ring members, optionally substituted by one or more lower alkyl groups, e.g. azetidine, 2-methylazetidine, 2,4-dimethylazetidine, 2,4,4-trimethylazetidine, pyrrolidine, 2-methylpyrrolidine, 2ethylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 2-methylpiperidine, 2-ethylpiperidine, 2-methyl-5-ethylpiperidine, hexahydroazepine, 2-methylhexahydroazepine, 2,3-dimethylhexahydroazepine, heptamethylenimine, bicyclo-[3,2,2]-3azanonane, morpholine, 2,6-dimethylmorpholine, 3,5-dimethylmorpholine.

The compounds according to the invention of the formula I may be prepared in accordance with the process A equation below by reaction of an isoxazolyl methyl halide or isoxazolyl methylalkane sulfonate with a salt of a thiol carbamate.

Process A: RR6Ν'·ΟΖ>- X R* M-S-C-fi + i»l-X 3 2 In the above formulae’ to R6 have the abovementioned meanings, X denotes halogen or alkane sulfonate and M denotes an alkali metal atari or amrcnium optionally substituted ty 2 or 3 alkyls. The starting materials of the formula II employed in process A are known or may be prepared by reaction of nitrile oxides with acetylene halides. Examples of such compounds are 5-chloromethyl-3“ methylisoxazole, 5-bromomethy1-3-ethylisoxazole, 5-chloromethyl-3-isopropylisoxazole, 5-bromomethy1-3-tert-butylisoxazole, 5-chloromethyl-3,4-dimethyiisoxazole, 5-(l’-chloro10 ethyl)-3-methylisoxazole, 5-bromomethyl-3“phenylisoxazole, -chloromethyl-3-(3,,1l,-dichlorophenyl)-isoxazole, and 5bromomethyl-3-cyclohexylisoxazole. The compounds 5-chloromethylisoxazole 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.

Geterotsikl. Soedin., 1971¼ 602). The corresponding isoxazolyl methylalkane sulfonates may be prepared from prior art isoxazolyl methanols (Gazz. chim. ital., 69, 536, 1939) in con· ventional manner by reaction with alkanesulfonic acid chlorides in the presence of agents which bind hydrogen chloride, e.g., pyridine. The isoxazolyl methyl halides may for instance be prepared as follows: Specification Al 238 g (parts by weight) of propargyl bromide, 476 g ίϊ 3 3 3 £2 (parts by weight) of phenyl isocyanate and 15θ g (parts by weight) of nitroethane are dissolved in 1500 ml of toluene; at 15° to 20°C, 1 ml of triethylamine (to activate the phenyl isocyanate) is added. The temperature is kept at from 15° to °G 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 70°C and then cooled. The precipitate is suction filtered and the residue rinsed with 1 1 of toluene. The combined filtrates are concentrated and the residue is distilled under an oil 10 pump vacuum. At 59° to 6l°C/0,2 mm Hg, 310 g (9 88% of theory) of 5-bromomethyl-3-methylisoxazole distils over (n^: 1.5168).

C^HgBrNO (176) C Η N Br Calc.: 34,2 3.4 7.9 45.5 15 Pound: 34.0 3.4 8.0 45.4 60 MHz nmr spectrum (CDC13; cf values) 2.3 (3H, s), 4.44 (2H,s), 6.15 (1H, s) 15C nmr spectrum (CDCl^, ppm values relative to TMS): 167.2 (C), 160.1 (C), 104.5 (CH), 18.8 (CH2), 11.3 (CHj).

Specification A2 CH CH.

I > CH-C 93.5 g (parts by weight) of acetohydroximoyl chloride (Ber. dtsch. chem, Ges., 40, 1677, 1907) and 90 g (parts by weight) of isobutynyl chloride are stirred in 1500 ml of 45533 benzene; at 15° to 20°C, 105 g (parts by weight) of triethylamine is added dropwise. The mixture is then stirred for 1 hour at from 20° to 25°C and for 1 hour at 70°C, After the mixture has been allowed to cool it is filtered and the fil5 trate concentrated. The distillate which remains is distilled under an oil pump vacuum. There is obtained 133 g (92% of theory), b.p. 48° to 5O°C/O.O5 mm Hg; n^5: 1.4740,, CgHgNOCl (145.5) C H N Cl 10 Calc.: 49.6 5.5 9.7 24.5 Found: 49.5 5.7 10.0 24.0 60 MHz nmr spectrum (CDCl^, & values): 1,78 (d, 3H), 2.3 (s, 3H), 5.05 (9, IH), 6.09 (s, , IH).

^C nmr spectrum (CDCl^, ppm values relative to TMS): 171.5 (C), 159.8 (C), 102.5 (CH), 47.4 (CH), 23.3 (CHj), 11.5 (CH3).

Specification A3 C2H5T^ ^(ZCHg-Br 119 g (parts by weight) of propargyl bromide, 95 g (parts 20 by weight) of nitropropane and 440 g (parts by weigh) of triethylamine are dissolved in 1200 ml of chloroform; at 0°C, 155 g (parts by weight) of phosphoroxy chloride is added dropwise. The mixture is kept at 20°C for 30 minutes and refluxed for 2 hours. After the mixture has been cooled, filtration and concentration are carried out, and the residue is taken ro S3 32 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 vacuum. At 78° to 79°C/O.l mm Hg, 150 g (79% of theory) distil off; n· I.5IO8.

CgHgBrNO (190) £ Η N Br Calc.: 37.9 4.7 7.4 42.0 10 Found: 38,0 4.6 7.6 41.7 The following compounds are obtained analogously CH,—-- 1 Νχ0. n?3 s 1.4806 CH2-C1 CH, λ n^5 = 1.5500 ch2-i c2h5ν' !l CHx Ν\θ\· 3 CH-Br i-C,H 3 7 Jjc Hr CH-Cl CH-Br i-C,H7· 3 7 CH-Cl 3B CH2-C1 The compounds designated with formula III are salts of thiolcarbamic acids. Typical representatives, which may be prepared in conventional manner, are the sodium salts or the ammonium salts - optionally substituted by 2 or 3 alkyls - of N,N-dimethylthiolcarbamic acid, Ν,Ν-diethylthiolcarbamic acid, Ν,Ν-diisopropylthiolcarbamic acid, N,N-di-n-propylthiolcarbamic acid, N,N-di-n-butylthiolcarbamic acid, N,N-diisobutylthiolcarbamic acid, N-ethyl-N-n-butylthiolcarbamic acid, N-ethyl-N-isopropylthiolcarbamic acid, N-ethyl-N-cyclohexylthiolcarbamic acid and Ν,Ν-diallythiolcaxbamio acid. Also, salts of Ν-azetidine-, Ν-pyrrolidine-, N-piperidine- and N-hexahydroazepinethiolcarbamic acid and their derivatives substituted in the ring by 1 to 3 methyl and/or ethyl groups nay be used.

Process A may be carried out in the presence of an inert organic solvent , for instance hydrocarbons, e.g. cyclohexane, benzene, toluene; halogenated hydrocarbons, e.g. methylene chloride, chloroform, carbon tetrachloride, chlorobenzene; ethers, e.g. diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether; lower alcohols, and ketones, e.g. methanol, ethanol, isopropanel, acetone, methyl ethyl ketone, cyclohexanone; nitriles, e.g. acetonitrile; and water. Mixtures of these solvents may also be used.

For the preparation of the new active ingredients, process A is preferred.

If desired, hcwever the isoxazolylmethylthiol carbamates of the formula I according to the invention may be prepared in accordance with process B by reaction of isoxazolyImethyl mercaptans or their salts with carbamic acid chlorides.

Process B ί + Cl-C-NL V VttK3 5 c-s-co-nC + Y-Cl 14 \ fi IT R° IV V I In these formulae, R to R 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). The following are examples of mercaptans of the formula IV: 3-methylisoxazolyl-5-methylmercaptan, 3ethylisoxazolyl-5-methylmereaptan, 3-phenylisoxazolyl-5methylmereaptan, 3-methylisoxazolyl-5-(l'-ethyl)-mercaptan.

Examples of carbamoyl chlorides of the formula V are those of dimethylamine, diethylamine, 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. 43033 Process B is expediently carried out in the presence of a hydrogen chloride acceptor. Suitable for this purpose are are inorganic bases, e.g. alkali metal bicarbonates,carbonates and hydroxides; organic bases, such as alkali metal alcoholates, e.g. sodium methylate; tertiary amines, e.g. triethylamine and Ν,Ν-dimethylcyclohexylamine; and saturated or unsaturated nitrogen heterocycles, e.g., N-methylpiperidine, pyridine and quinoline. The process is advantageously carried out using one of the solvents (or mixtures thereof) listed under process A.

The isoxazolylmethylthiol carbamates of the invention of the formula I may also be prepared 'in accordance with process C by reaction of an isoxazolylmethylthiochlorocarbonic acid ester with a secondary amine.

Process C: + HN XR6 C-S-O-N . ’il Rq + HCl VII I In these formulae, R1 to R^ have the abovementioned meanings.

The thiochlorocarbonic acid esters of the formula VI may be prepared in conventional manner from the isoxazolylmethylmercaptans of the formula IV (Y = hydrogen) and phosgene. Examples of compounds of the formula VI are 3-methylisoxazolyl-5-methylthiocarbonyi chloride, 3-ethylisoxazolyl-514 j ό 5 3:2 methylthiocarbonyl chloride, and 3-phenylisoxazolyl-5-methylthiocarbonyl chloride. Suitable secondary amines of the formula VII are particularly those listed at process B as components of the carbamic acid chlorides. Process C may be carried out using the inert solvents mentioned under process A~less advantageously in alcohols or water - and with or without the addition of one of the hydrogen chloride acceptors mentioned under process B.

In detail, process A may for instance be carried out as 10 follows: At fi’om -20° to +50°C, 1 mole of an isoxazolyImethyl halide or alkane sulfonate of the formula II, optionally in one of the above solvents, is dripped into a solution or suspension of at least 1 mole of a thiol carbamate of the for15 mula III, To complete the reaction, the mixture is stirred for from 3 to 12 hours at from 0° to to 80°C. Upon completion of the reaction, the mixture is poured into water and the product is extracted, if desired with an inorganic solvent immiscible with water, and subsequently isolated by distil20 lation or crystallization.

Process B may for instance be carried out in the following manner. Λ 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 least 1 mole of one of the abovementioned inorganic or organic bases at from -10° to +80°C and for from 1 to 12 hours. The thiol carbamate according to the invention of the formula I 53 2 is isolated as described above.

Process C is for instance carried out as follows.

A solution of 1 mole of a thiochlorocarbonic acid ester of the formula VI in an inert organic solvent is reacted with 5 at least 1 mole of an amine of the formula VII; the acidbinding agent may be at least 1 mole of the inorganic or organic bases mentioned in process B. The reaction temperature is from -10° to +80°C and the reaotion time from 1 to 12 hours, as in process B, depending on the reactants, the base and the solvent employed. The thiol carbamate is isolated as described above.

The following examples, in which the parts are by weight, illustrate the processes for preparing the isoxazolylmethylthiol carbamates according to the invention of the formula I.

EXAMPLE 1 At 0°C, 60.0 parts of carbonyl sulfide was gassed into a mixture of 102 parts of N-ethyleyclohexylamine, 80.8 parts of triethylamine and 700 parts of methylene chloride, and the whole was stirred for 2 hours at room temperature. Subsequent20 ly, 105.3 parts of 3-methyl-5-chloromethylisoxazole was dripped in over a period of 1 hour at 0°C, 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, IN hydrochloric acid and again with water, and dried. After removal of the solvent, distillation of the residue gave 194,2 parts of 3-methyl-5-isoxazolylmethyl-N-ethyl-N-cyclohexylthiol carbamate, b.p. (0.2 mm Hg) 176°-179°C (m.p. 6O°-62°C).

EXAMPLE 2 At 0°C, 8.0 parts of carbonyl sulfide was gassed into a mixture of 21.2 parts of diisopropylamine in 100 parts of toluene, and the whole stirred for 30 minutes at 0°C and for 1 hour at room temperature. Subsequently, ld.O parts of 3ethyl-5-bromomethylisoxazole was dripped in over a period of 15 minutes and the whole stirred for 3 hours at room temperature. 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 154-156°C (n^5: 1.5989).

EXAMPLE 3 While cooling, 29.8 parts of Μ,Ν-diethylcarbamie acid chloride was dripped into a mixture of 25.8 parts of 3-methyl15 isoxazolyl-5-methylmercaptan in 100 parts of ether and parts of pyridine; fche 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°-138°C.

EXAMPLE 4-75 The following isoxazolylmethvlthiol carbamates according to the invention may be prepared by one of the abovementioned processes. tiO □ J << h£)zrt tnn, «Ρ wc rt g fi Ό B Q o oo vo W 0, 0« b> · ♦ Λί S At*-* VO X tn κ tn (fi °ifi tn CM rl in in in in in o m O o CM o Φ o CM CM Φ • • * • • • Η ι • • ’ ;· rt o 'rl o o O σ ‘ ; ft' o O o a •V. ''s. •s.1 s V. **. ε tn tn CM o O\ rt tn j* CT' rt -sr CM ft CM tn VO tn κ =r VO κ rl c rl rl rl rl ω rl rl rl cfi O **·» CM z·»» rl tn CM rl X X X o υ VO It o b- b- b- X as X I c x w X X o X o 0 X_ tn m tn tn tn 1 •=r 1 rt o X o Q o CM Q CM o o I CM I 1 1 X | X >s I •rt O •rt fi •rt o fi o O c vc z*» CM S3 O bw tn O I •rt CM g Cx m tn X φ CM I ϋ *rt b- bx x »n tn ϋ O I I fi *rt S3 iB S3 S3 m tn m S3 S3 a _ Ο Ο O S3 o o tn bi CM b0« tn X co or Λ . ω «taZ s 1 CM I z**. tn tn tn CM z“\ z“\ X X CM CM o u X X II o o X cn X V *w* o X o 1 =r 1 in in 1 1 CM o CM X X X I X CM CM o c υ ϋ O S3 S3 S3 S3 S3 S3 S S3 SB S3 S3 SB tn X O *—* o I CM tc o I X“x tn X o SB υ S3 S3 S3 S3 K SB S3 tn tn tn tn tn tn m X tn tn tn tn tn tn tn tn tn X X X X X X CM X X X X X X X X X o o o a υ a O o o o o o o o o o in vo ή» co 0\ CM O rl CM rl tn £3 in VO b- rl rt rl rl rl rl rl rt $ 5 5 3 2 X ΛΓ X tn X CM X fc X ο ο ο σ· co co Ρ. ε ιη X CM Ο **CM ϋ ο ο fc ο fc I CT θ' Ρ« έ ίχ m α ι 'Η ε*χ ιη ο ι •Η tn X CM ϋ fc ο fc CM tn m CM fc in C fc fc CM fc fc St o • • * « • • « <* • A o o o O O o O O o © o o •x. V. **> •v. **x '-s •v. CM o XT o CC o AT o in \P © xr in CC X cr kO tn in t- kD kC CC CM fc fc fc fc fc fc fc fc fc fc fc ιη +r« ο b- cr. cr X 1 X X tn XT -=r o XT O o ι 1 1 1 c CM C c 1 X CM S- X X XX σ\ fc I ko CM X ϋ a Z—» in v-z K* ι , I X I 1 CM o £f X tn *-z XT m o X o OJ z-s Z—«. ϋ I X CM CM I CM ϋ X X z—k X X ϋ ϋ m o o 1 o X I 1 Z—' 1 1 ϋ Z—» in Z—« z—» m m X tn tn X X X CM X ϋ o o ϋ o o *-z σ\ •ν' | X HM X X X X ϋ ~χτ a in a o o S- X X X χ in tn X X CM CM ϋ ϋ Ο fc CM CM cm tn λγ in w CJ CM CM CM CM fc fc X kC ο I ο ο Ο ιη X CM ϋ ίΧ Kk ϋ ι «Η ιη CM ϋ in in in in in in w W X X X X CM CM CM CM CM CM Ο ϋ ϋ Ο Ο Ο in in in in X X X X tn CM CM CM CM X O O O O ϋ S- CO CM OJ σ\ O fc cm cm m tn tn « u? «J U ti bO -P CM £ *1 * •α ε o o vo b» o. ft · · J2& € Ch*VO CC in tt tt tn S3 CM rl O tt a* o o to CM CM CM • • a • a· • • • O o O O b- O O O X. X. X. • X. x. X» O vo ti b- & CM · co co o tn vo in • IT XT ΖΪ CM Vt V< vl ε vi rl Ή S3 O 1 tn o tt CM ΛΓ o CM CM 32 1 z—» ι z-s z’*·» O CM CM tn tn CM CM X X X X X Ζ·Χ o o o o o tn S-*1 1 ι tn Sz W 1 1 W X tt X o ζ*·*» CM 0-0 o o sz in tn Z*> o r> X CM | CM o X CM tt o X O X \»Z O o I CM 1 1 8 o tn ζ-'S 1 tn X tn tn m CM tt o X X X z* o CM CM o o o o CM z*s rs CM *®Z o tt X tn tn tt tt X tt o o * X X o O o o S-* | o o CM CM kZ ^taZ X I I s 1 X X tt O ! o o o S3 as S3 tn tn tn Β Β B se ο ο o a as tt tt tt tt tt tt o tt tn tn tn tn tn tn tn CM z·*· tn tt o s-z tt tt tt tt x tt tt a o o o o o o o o tn -sr tn tn in ‘ vo tn tn b~ tn eo tn CM *- z—«. T· HS V“ T“ w w to w. VO o CM VO VO o z~s o 1 o w KS N os 1 o o to o z-s to 0 rt I o rt KS xt rt O OJ O to o O ►» w to >> o 1 s 0 o o 0 *»> o G 0 Gl W o hs to CM o to cm CM o Ζ·> z-v to ll KS KS O to w to 1 o o o in US tn CM SbX w w to W w to to CM CM CJ o O O O O o Χί- CM hT o S-z CM to a CM z-s KS w o <_z CM T· V- w o'0 CM /*, wf* to o \zZ OS CM CM t* W to OS to I OS to to z—·» K to o o W_ o w O to o χι- KS ks t xt 1 o rt χί- t ό w O CM CM 0 CM S-z 0 Ο • cm I o z·** 1 to to 1 to to >» 1 to C *_z MS β o o β o o o β o o to o CM s-z to to o O Z~M /A ns ks CM to to x*> CM o o KS to 'w' « o CM CM Gl to w o tl z*S z-s O o t— KZ w KS KS KS I 1 W to o to to to tn KS o 1 in o 0 US US o to o CM CM to s-z to W , \-Z CM 1 to to CM w to CM CM to O β o o O o O O o o WWW W to to M w W w w W to WWW κ\ ks ks WWW ooo KS ΗΊ w w o o WWW wwwwwwww w *s MS KS KS KS KS US US W W to w ο o CM CU *-✓ S-* o o o o KS K\ KS K to to to w Ο Ο Ο o m m us tn m\ ks w to to w w W CM CM CM CM ο ο ο ο ο o ¢0 C\ CD O * • o O σι vr V CD <-> ο· Ο ΜΤ Ο Ο W os * , <τS ο° \0, KS Γ' c*·. < ο σι ο t- VO τ· $*>· Ο\ σι ΙΛ σι R US ο ft Η Ο σι η υ I ΗΪ* Μ υ W V0 Ο I ο W >ι Ο ms ns to to Ο ϋ W MS Ο to I ΙΛ ϋ σι to ν-* MS to ο &Γ υ σι Ι'·'* MS *Λ δ \£> ο os J5s » w to ο Ο Ο p I ι is OHO «· σι ν* to ts ο bP ο US 1, ϋ 8. to* ο US US ΙΛ I ts to to σι σι σι σι η ο ο ο ο ο ι &?* ο I Ν g σι I ο ’σι σι » to ο σι σι ι to tow &Ρ ϊ oom I **-* Ο ΐ ’ to I MS MS g~tsN ww I I I ttWWW-WWWWWWWWHW HS MS MS MS MS MS MS MS MS MS MS MS MS w w w w ^wtowwwwwww O O O o noooooouoo totototoHMWHtoto bP US ϋ to σι to o o MS w υ 8 s 8 8 8 o to* o & o K_y O V-# O MS MS to u ο ο MS LNS to , MS to σι to OOO to o hP -1822 Examples demonstrating the herbicidal action of the new isoxazolyImethylthiol carbamates A series of experiments, divided in the main into the following three groups, was carried out to provide evidence in support of the statements made in the introduction about these active ingredients.

I. Greenhouse experiments The vessels employed were paraffined paper cups having a volume of 200 cm^, and the substrate was a sandy loam containing about 1,5% (wt%) humuso The seeds of the test plants were sown shallow and separated according to species. 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 treatment, the cups were lightly sprinkler-irrigated; the agents therefore came into contact with moist soil. After application of the agents the vessels were covered with transparent plastic hoods until the plants had taken root. This cover prevented the evaporation of water and readily volatile substances. 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 requirements of the plants, the experiments were set up either in the cooler (10°-20°C) or warmer (18°-3O°C) portion of the green23 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.

II. Experiments in the open These experiments were carried out on small plots of various sizes. The soil was a sandy loam having a pH of 5-6 and i - 1.5$ humus. The compounds were applied from early to late fall and from early to late spring, corresponding to the sowing period for the crop plants. The compounds were emulsi15 fied or suspended in water as carrier and distribution medium, and applied by means of a motor-driven plot spray mounted on a hitch. 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 scale.

III. Herbicidal action via the vapor phase The remarkable herbicidal action of isoxazolylmethylthiol carbamates, even when not incorporated into the soil as is necessary with prior art thiol carbamates, suggested that •i ΰ 5 3 2 the losses of active ingredient through evaporation were low.

To examine this, the rollowinr 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 cylinders. The pairs were made up of a treated and an untreated vessel. For comparison purposes, control cylinders containing only untreated pots were used. To prevent gas exchange with the atmosphere, the rims of the cylinders were coated with Vaseline (Registered Trade Mark) and the opening was covered with a glass plate. 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 ll°C in the morning to 30°C 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 between the various treatments were readily perceptible. In addition to a visual assessment, the green weight of the oat shoots was determined for each vessel. This is given in Table 11.

Results The individual results from the various experiments and tables combine to give the following picture. 1) The introduction of the isoxazolyImethyl radical into the 2) Whereas prior art thiol carbamates can only be used in specific crop plants or groups thereof (e.g., broadleaved species) because of (a) their phytotoxicity, (b), incor25 poration necessary for herbicidal action, and (c) the weed spectrum combatted, some of the new compounds have an improved and wider selectivity (Tables 3, 5, 6 and 7). Plant physiology may provide an explanation for the selectivity 532 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 evaporation losses, 3) The new compounds according to the invention had, when incorporated before sowing, an action similar to that of prior art compounds. When applied without incorporation they were superior to the prior art thiol carbamates suitable for the crop in question (Table 8). Remarkable in this connection is the fact that for instance fehe compound 3-methyl-5-isoxazolylmethyl-N,N-diisopropylfchiol carbamate, when applied preemergence to the surface, combatted unwanted plants in Indian corn just as well as significant prior art preemergence herbicides of different structure (Table 9). Successful control was also obtained during and after emergence of the unwanted plants; the crop plants remained unaffected (Tables 8, 10). 4) The phytotoxicity of the vapors of N,N-diisopropylthiol2,3,3-trichloroallyl carbamate for wild oats is known. This was confirmed in model experiments. Of the new compounds, 5 3 2 it was found that for instance the substance 3-methyl-5isoxazolyImethyl-N,N-=-diisopropylthio1 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 or N,N-diisopropylthiol-2,3,3-trichloroallyl carbamate. The plants in the untreated pots located in the same glass cylinder remained undamaged by this new compound, whereas plant growth in the case of the comparative compound had suffered (Table 11). Consequently, not enough active ingredient had escaped from the directly treated pots to cause damage, via the gas phase, to the neighboring test plants. The actual vapor pressure of 3~methyl5-isoxazolylmethyl-N,N-diisopropylthiol carbamate was 1.3 x 10“5 mbar at 20°C, whereas that of Ν,Ν-diisopropyl15 thiol-2,3-dichloroallyl carbamate at the same temperature -l) was 3.7 x 10 mbar.

It goes without saying that the experimental results discussed here are only examples of the reaction of numerous unwanted 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 0.1 to 10 kg of active ingredient per hectare, 25 The particular advantage of this new group of isoxazolylmethylthiol carbamates over prior art thiol carbamates is the range of possible application methods.

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OOO rt rf mmm m:—t- ooo FA-1 rf 000 σ»σιθ 888 j < » OOm m c~ Si ooo rf rf Ol ooo ca rtj a CiOiO 100 IOC 100 0 0 0 m O u aas 883 838 O 0 ci S CiO RoS 000 0 0 0 0 0 0 rf . , . OOO O O Ifl rt u 0 0 ra •J Q rt :y f'j lArti rtj rt rt O C- rti 0 cj m S St 5 OOO m t- c.< rt CJ m 0 m O t-t- OOO 0 0 in 0 0 m mmm rtj 0 mm rt FA mmm 7J OOO OOO OOO OOO OOO , I ooo ooo OOO OOO OOO OOO OOO OOO ooo 0 0 0 ooo '* r** rt G] -rf -· CJ rf rt OJrf rt v'J J rt CJ rf rt Cjrf rt c3rf* f— m. g Sfi a a r ε - F 0-0 u =£ uN c x'’ —< 0-0 g·' sf rt) Q 0 υ rt ϋ af- JJ a? 0 aT* C 0J c a£'‘ d* V O •rf* 0 g rt V3 Φ T3 O Φ >1 ft O 5 3 2 Table 4 - Herbicidal action of new isoxazolylalkylthiol carbamates in the greenhouse; pre- and postemergence application Compound Appl.rate Method Test plants and % damage no. kg/ha Cyperus escul. Echinochloa crus galli Lolium multif1. 26 3.0 PRE - 90 90 3.0 POST 90 90 90 28 3.0 PRE - 90 70 3.0 POST 90 90 90 29 3.0 PRE - 90 90 3.0 POST 70 90 50 33 3.0 PRE - 0 0 3.0 POST 0 90 50 38 3.0 PRE - 90 30 3.0 POST 90 90 90 PRE = preemergence treatment POST = postemergence treatment = no damage 100 = complete destruction - 5 S 3 2 Table 5 - Selective control of grassy weeds in beet with various thiol carbamates in the open; preplant incorporation C-S-R3 II 0 Test plants and ί damage Basic molecule?> iv Appl. rate kg/ha Substituents in the compounds examined Compound No. R1 R2 R3 Beta vulgaris Alopecurus myosuroides 2 2,0 5 95 16 2.0 0 75 3 2.0 5 80 10 4.0 0 65 13 4.0 0 50 9 4.0 50 70 14 4.0 50 90 C3H?i C3H 71 Cl Cl 2.0 0 30 ch2-6 = C-Cl 4.0 0 80 prior art Cjti7ri CjHyn ^2^5 Pri°r art 2,0 10 80 4.0 30 95 = no damage 100 = complete destruction 5 3 2 Φ to d <υ ω ο G G φ φ G to φ G Ρ C •rt Φ Ο *0 G d co P P co Φ EH ¢4 Φ rt Ο Ρ Ρ § rt a α ο G ο ε: ο Ή •d ρ c d G ο •rt |Λ ϋ Φ Φ ϋ rt G d Φ Ό bO •rt G ο •rt Ρ G Φ Φ rt d Eh KS W ί co t OsO I Λ I CM (β φ rt O Φ rt O S O •rt W Φ CQ • d rt Φ xj ap*^ a d to < G^i *0 G O O' ♦ o o O G G •rt (0 V) Ό P G G 3 Φ O ατ3 p •rt O G Ρ Ο·Η co S χι Φ d 3X5 X CO Ρ Φ 0 si B o· W) V K n 5 0 λ σ»0\ SS h m e ss o 0 men 0 0 co os 4 h 5ά S» Ο ΙΛ m<0 ss o?cn c 2 ώ a« ss ss SS M PS ss 1 1 fc h Π S8 ss ss 4! M «4 4» *» ή n 00 88 »4 0 0 *4 a. h tf\O OO0 2 O J3 g 0 § £s 0 0 Ο O rx-3· 0 0 β ώ ίϊ Ο ό 0 0 0 0 oo0 Ό» 00 nV nV P G d G O •rt G a r. na £w« ¢) aP lc uw Φ to d E d τί o G G o •rt P ϋ G P co Φ Ό Φ P Φ rt a e o o o o rt Δ a 5 3 2 + 4· W w 0 ti Ό tirt Table 7 - Tolerance of sone thiol carbamates by rape and spring wheat in the open; preplant incorporation ti o 0 n bo £ 0 5 Ej 0< *o Ό efe· css «1 o > ω rt rt ,: rt rt to ι:,:, o «0 a rt ω H O •r-l (0 to ti ίύ rt ti a c rt x: a^ Ol ω > *0 ti ti O o: a t ε · w 1 o c o c OcO rt ti o 0 rt 0 O χ: ό £ rt 0 o ti ti •ri •ri rt E to 0 0 W X ω rt 0 ti 0 W tird rt ti •rl ti rt o Vi a xt E ti O w c PA oi Cd ti cm m i ko o co ch ι co o cr Cj mo CM 00 O tA I in OJ m r- ι cm oc ir cm I cj cc rtco i rtco o o rt t ! 3 1 1 1 ο O 1 O O 1 o o 1 1 1 1 f 1 1 s I 1 I 1 ι mo ι me ♦ > i • 4 i · 4 I · * 1 4 · CMi a cj^r i ojrt 1 rt PA 1 I I vi m « i 41 rt 1 41 3 rt 1 ti l·, ! Ϊ ti 1 | 0 ί I I 0 1 ti ! ti ! * ! tt -5Γ 1 0 o0 0 1 •ri I *ri •h •ri 1 ti ti ti ti 1 J ! 1 ti, J Pl a t 1 1 1 a rt O rt *E 1 >ri I 1 1 0*0 o *o 1 j It II 1 rt rt 1 O *O O-o m 1 in 1 1 :c 1 tc CMl CM CM 1 CM W 32 O 3 o O o 1 •rt i· •ri ►Ή >47a o •ri Ch X ^r o ti t►H **pa o ti O •ri rt o '0 •ri ϋ •rl X> ti x: X! rt Ch O ti O rt o •ri cfcti tA o rt c* w tA ϋ •ri Ch X xr ϋ ti h32 fA o rt ti ti 0 •ri rt rt ti o 0 ti ti V) rt 0 ta rt 0 0 TJ Ό 0 0 0 5 0 bO 0 £ 0 rt E Φ hO Pi 0 rt c wr0 0, •ri co E ti 0 0 0 a ti ti o n ω II II II II *5532 v ω cd E cd ♦d Table 8 - Action of some thiol carbamates when applied by different methods in cereals in the open fc/ x (X w rc. ο o 'S < cd co o +> »ri · fi P 43 Cd »ri W fc fc a>z-s a fc cd tn -p w CD fc Ε & & Φ cd Ό fcD fc fc o 3 — X > CM τ> a O fc.fi XP < £ Φ cd fc n X * cd fc.fi a>ft a ω «3.14 ( T3 ω fi t 3 OSO o 1 E · o o o fi 0) fc Φ fc O o •ri V) CD X5*d 43 CD c fi »ri to tt 43 CD 3 CD W 3 Ό 43 C •ri 3 P O SO Ά ,Q S 3 O co o tn • X CM X fc X σ\xt ino vo tno tn Ο o tnvo lAkO CM CM CM tnko CO lAtn CM o fc cm tn t-js· tno\ kpco Okb- t—Lnxr ko Lnkokc in (M tn O *O 1 »O O 1 ο O tn i fc CM in tn • A cm Ο Ο O OOO I CMO Ο» fc fc’ fc . fc κί> fc fc t» fc fc fc» fc fc fc w fc fc H fc fcfcfcfc o o o o o o o O OOOO 0 A A A • A * A ΑΑΑ» CM CM CM CM OJ X CM CM X CM CM CM P • k 43 cd Fl XT fc cd 0 •H fc 0 fc •ri a fc a fc »-i fc O Q «-Ο «-Ο i tl fc 0-0 t u 1 X 8 CM X X o O •ri ί- in Χ X, K\ CM o O •ri ¢- in X X ΐ tn X 1 O O to P § bO fi •ri ω fc Φ g Φ O O 43 ( 0 Φ < fi 0 fi S •ri C O ( Φ·Η t bOP f ~ fc Cd < cd Φ ο t fc E *ri < 0i φ fc 4 Φ Φ ft C fc fc cut X X < p fi H fcfc> fcfcfcfc 100 = complete destruction >5 Φ 43 fc cd fc o φ cd X! to £) fc cd g fc fc cd Φ Φ T3 43 P fi fi o •rl •ri fi fc & n o CM tn O 455 33 Ό rt •rl rl P 04 fi 04 (tf (tf fi fi rt 0 -rt P •rl T3 (tf fi o fi 04 01 (tf o X) XI rt c fi P bi) (D ctf •rt (tf n r·; fi 0 O •rt W XI τι P rt rt >> P< ft G o o fi o & o (ft •rt •rt T5 IA Ό * g.n m 'i'l £ 3« « 2 ω rt ., -Λ IT o (MVO ir. in rt tn o CM o brt >5 rt o P «rt rt »* 0 04 ,»n x: •rl t> P P w (tf to fi rt O 04 fi o o to fi •rt b (tf G P fi (ti o rt λ: b: p O m co o\ OO fi w rt •rt 04 I o IA I rt rt .fi >» P x: ρ fi Φ ·Η G I tn rt P rt fi rt <3J o o • * CMiJ ΟΜΠ sr oo in in vo σ\ in in O ¢¢-( o fi o •rt P o o o fi a) to bO »d U fi rt & rt £ Μ O 0. O Xi rt E“! fi fi o fi o o m X X> OJ X Ο I co O so I X •rl fi P fi rt •rt Ό rt fi ω fi •rt o o 1 1 o o 1 1 o o « « 1 • ·· I * « oj^t 1 1 1 c. 1 CM it 1 +> ! fi 1 (M ir P fi ! « ! (tf 1 I fi (tf ρ { fi o fi rt X •π ί •rl | 0 Ο -o 11 fi j 04 [ tn X rt fi 1 04 I 1 rt •rt fi 04 rt 1 o o 1 o O -O I 1 1 1 1 fi o •rt P o fi fi P to rt rt P rt rt o H o o •rt > . X \ λΟ I OJ X o I co I OSO X •rt / ’rt %/\ΐ o 'o 1 tn X 1 X o 1 o 1 co 1 1 o 1 X I 1 ο- -2 if* 1 ι 1 X 1 m OJ 1 X O 3 1 o Ctf fi ctf 'd fi II 48833 • · Ρ X2 Φ rt mo co in £*n 0 3*rt Q) Ό rrt c WH 0 CM VC inm intn r+in β •rt · x: be co co o · b-btt 0 in CO 'able 10 - Herbicidal action and crop plant tolerance of some thiol carbamates in the greenhouse; postemergence treatment m tt t ω ι 0=0 I tt S K Φ jrt β O ω rH O E •rt « rt tt Φ . . g £3 S &3 in tr. vcvo OO τ-i tn tA β «ί «Ρ rrt «X «Ρ <0 $ nJ c ® rt 1*4 a · 0 0 «ί E a a w .8.*5 α β ΗΛ ft-x p*&0 «5 .* rt bO P irt Ο β tt > •tf β O' · O O Ο β tn tt CM tt rl tt in co 00 8 1 I I Ο O t—CO b-b- 1 1 I CM VC 0 0 co os OO in o\ s 1 ί ί 1 I Ϊ 1 1 1 Ο O I 1 1 1 1 1 1 8 0 m o 0 Λ «I rt CM p β rt β o •rt β Or »rt X 0*0 rrt 0*0 I CM X C O Λ ·» rl CM P β rt β O •rt β Or rrt O I CM X o •rt 1 8 b» 1 in X « X tn 8 CM 0 ί O 1 •rt 8 1 b- 1 in X 1 X tn ί CM Ci ί o no damage 100 = complete destruction il toP p, Φ β co •ri CO Φ rt > •ri rri Ρ Φ rt p CO P rt rt q o β rt q Φ P. o φ < β •ri β fe P 0 o P P β <0 ω φ •ri P φ Φ rt P > Φ rt Fi E β P rt Φ £ Φ >> q q η rt o P o p rri φ q o •ri •ri Ό β P Φ Φ E P o rt co q fe • rt rl β O Φ m Pa to (0 Prt rt 1 β w Q, 1 XJ Oto β q P o X Ο P. rt β’ / \ Ε · / \ Ο Ο P' CM ‘ Ο β Φ fe fe β P ¢4 0 r'J Φ rri P P •H O O 0 Φ •rl p rri x rt 0 o o E P ια O P o fe ρ q •ri rt co β r~f rt o< a PQ I rH CJ Ρ Μ Φ rri β rt Ρ Η κ 1 1 1 1 1 I 1 1 1 Φ A 1 i P ω ι 1 a q Ο 1 fe fe 1 •ri ο Ο ϋ. Ο I opw 1 cn CC P ΪΗ ίχ- ίχΐ cn ι fe ο η 1X00 X P I 1 β £ 1 1 ‘ E φ 1 h-O\P 1 t'-LT't'- 1 | t-KO lf\ c- S X . Α Α Α | A A A 1 A A A A Φ η (Μ r-i Ρ 1 CM Ρ P 1 iAIAfA fA β 0 1 1 ϋ 1 1 0 •Η 1 1 Ρ I 1 β W 1 1 rt •Η 1 1 o Ρ 1 1 β rt 1 f β 4-5 ! 1 G W 1 1 ί fe G ( G fe Μ Ο 1 fe G O ί fe o _ P ο ο cn cn ι fe O fe 1 G fe CQ β Ο < < I G fe) < I O < < Φ 0 1 1 * q φ 1 I Φ q 1 CM 1 fe β KUO CM I CO OCO ι moo cm fe •υ A a a I AAA I a a A ♦ri φ Ρ Ο Ο 1 P P o 1 P o o τί ο 1 1 ο 1 1 >5 q 1 1 iri fe 1 1 P 1 1 β Ό 1 t rt β ί 1 I ϋ rt ο ο O 1 o o o 1 ooo •rl fe 0 A A A | AAA •ri φ P CM-=T 1 p (M«=r I p CM-=r β Ρ t 1 to a i 1 •ri ♦ri 1 1 0 o 1 1 β 1 1 P •ri I 1 o q 1 1 β fe 1 1 1 1 «SJ· 1 Φ q 1 1 1 i 1 rt X 1 1 β • 1 1 1 1 o 1 1 Ap 1 ί 0 φΟΟ 1 1 o •iri-xr Ρ X 1 rri rri 1 q 0-0 1 0-0-0 1 β q ♦ 1 1 •ri 0 p, Ii I II 1 k*'- r ·» a r-i I P 1 q ia 0-0 1 o -o t Φ o Ό - 1 1 1 1 r~» P · β o CM 1 CM 1 •d P o rtko a: ι x 1 Φ Φ σ\ ο 1 O 1 P rri rri • P 1 i rt Φ G 1 1 Φ rt > • β 1 1 q o 0 1 1 P tow • Ό •ri I «ri 1 β β fe β K- 1 t- I β •ri a o a: « X 1 > P •O ια ι fA 1 rt ω P ο 1 O 1 rri β φ φ a 1 1 0 +3 Φ o I 1 q 0 P •ri 1 •ri i P φ φ W β K~ 1 b- 1 β β ω 0 x ι X i 0 Ρ β • Γη K\ I fA 1 o rt rt CM 0 o i O 1 ί> q cm e-i Φ CO O G c 0) 0) G bQ Φ G P G •rt G O •rt P d o •rt rt a d* ο o G Φ to G Φ ε φ φ G a Φ to d B d τ, d •rt G d · p a φ a OT W G G O Ort Ό >» O P G ϋ >» d Ο Ό CJ CM fc- OS in in c* os φ o •rt G G •rl G O •rt P O d rt d Ό •rt o •rt X) G Φ g o > •rt P υ Φ rt Φ OT G d co P G d rt a P co Φ Φ r-t G d d * o •rt rt rt G rt O d O to c •rt co G 3 O G w O >»P g d o « Ό G O t · o o o c os VO fr- CO OT Ch in o o * OT to G •rt G Φ G P •rt o o G o Φ o G Φ to G Φ E Φ G O G Φ to d II A3532 In view of the methods of application possibJe with the compounds of the invention, they, or comnositionn 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 growth. 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: tfc o U ε rt β β (0 •rt Η faO β ω Ρ x*x Φ co Φ P β β β τ) Ό φ β β β co ο co β* 01 Ρ β Ρ Φ Φ β to co φ Ρ co Ρ Φ rt Φ οι Ρ φ φ Ρ β •rt β trt Η β φ β φ β φ β Ρ a β O. 01 &D φ β co rt & β Φ CO Or Ρ rt β β a rrt ο co a φ φ « β c rt β β β φ φ •rt a «Η β φ ω φ β £ o Φ β cd 01 rt •ϋ Η φ β a 0 a β a 0 β •rt β rt a Ρ ω Ό β a β rt a £ rt rt a irt ο β •rt φ 01 rt β Ο rt rt β φ rt Φ β β ο Φ β 0 Or a rt ο co a Ρ β Ρ Ρ co rrt bO ο ο £ ο rt rt rt ο •rt β rt Ρ ο ω rt rt CO •rt a £ P rt β rt •rt β β P β CO Φ co β CO rt co rt β 0 rt Φ 0 •rt rt β a a a > P a 0 rt rt rt H rt co rt rt CO β β β •rt φ •rt rt β Φ 01 to a irt • • • β a rt • • 6 β β β • •rt rt o β a a a rt rt rt β co β o rt •rt a a a > > b rt •rt 0 ρ v_z z-x Φ 0 CO co CO > 01 P rt CO rt co 01 rt •rt 01 01 01 c 0 rt irt ♦rt rt o 3 β bO a co (0 co β β β rt Φ c β CO 0 «rt > co Ο a rt •rt •rt •rt a a a a β •rt β £ 0 β •rt β 0 ♦rt rt ο a o > β β β rt rt rt rt •rt P ο •rt •rt Φ β Φ irt P a £ •rt rt 3 bO 0 c β β β CO £ N P c rt β Φ rt φ Ο β co P to bO 01 •rt rt Φ •rt β *rt £ 01 ο ϋ β rt irt rt rt rt rt rt rt rt β irt £ β 01 rt Η (0 hO co β β β 0 0 0 0 •rt £ co co ε 01 •rt rt > > > •ri •rt •rt •rt irt rt CO co CO CO rt rt •rt •rt <3 rt β β rt CO CO CO co irt β 3 β 3 3 Φ φ g g •rt β Ο rt β rt rt rt CO to CO co Φ P β β β β a a 3 3 •rt rt rt a Φ P P P rt rt rt rt £ β P Ρ P P a a 0 0 rrt β β co ► Φ φ φ β β β β rt rt •rt •rt •rt •rt o o 3 3 < < < tt tt tt tt tt tt tt o υ ω Ο O O O Q ϋ O Cynodon dactylon Bermudagrass in turf and lawns A 3 5 3 2 Φ £ co X ra ♦ri fc bO fi W CO ra Φ CO P o Φ C P CO •rl co td cd E fc fi fc P «—I fc co Φ a 0 cd Φ fi s a Q- p cd fi o fi >» Φ O ι—1 Φ Φ P cd X) P fit X fc to Φ fc fi >3 P fi X fi a φ •ri P o 0 3 3 cd o fc O co co 0 co fi X X co Φ P P Φ co fc •rl P C Φ r-i tt CO fc ς-ι to Φ P cd E p Φ Φ fc p cd Φ cd fc to a ω c, cd cd o φ ε cd fi fc cd ο •ri fi cd P o CQ w ε s _ e 3·η e y mn co 3 0 0 0 •ri P £. 0) CO 3 Ο Λ-Η C w ρ £ι P Φ 0 £, j. qj.H Φ to •rl « x; > fi Φ tt •C _ _ „ •ri 3 > 3 £ E 3 § § bO cd 3 «ri -ri *ri •ri Φ •ri a a a co fc fi a ?>» >3 >» •ri cd •ri >i CO CO CO Φ bi 0 to CO to to cd cd >3 » o o o fc fc fc OOOO ω a O O'— <0 CO CO co 0 •ri 3 fc ra 3 Φ C Φ ra ra fi X Φ fc 3 3 fi 3 •ri 3 fc P 3 P r| bO 3 3 •ri fc a P CO co CO 3 3 3 3 3 3 > fc X X X fc P P X ε co 3 fi fi 3 3 Φ 3 3 3 φ fc 0 •ri •ri Φ Td 3 ε rl fc > fc S O Φ Φ Φ 0 3 a X X X X X κ cd •rl P cd CO cd fc CO C Φ fc •ri CO CO •ri P cd P •ri CO fc •ri to fc Φ a o 3 0 P >» fi fc Φ fi fc 3 0 0 0 • CO •ri a Φ CO a fc ra P Φ o a co X 0 3 •ri 0 fc C >3 3 3 E Medieago sativa alfalfa (lucerne) Mentha piperita peppermint Musa spp. banana plants Nicotiana tabacum tobacco (N. rustica) «£ V 4F ra C Ε ti X ra •π rri bO ti W •ri § rt o ra ti rt •ri r—i o a o ti rt O 0 X C 0 0 ti 0 to 0 ra ra ti 0 0 ra ra * ti to 0 0 ra 0 ra rt ra ra ra ra Ol 0 a ti 0 0 0 c C ti ti ti ra 0 rt 0 ti 0 0 0 0 0 0 >5 ti X ti rt ti ti 0 0 0 0 0 >3 rt ra >> rt rt ti X X X X rt 0 •ri ti X 3 0 bO a ra S 0 rt ti £ 0 ti 0 E β 0 >> ti ti ti ti tO 0 3 0 0 Ό •ri ti ti ti 0 Ο ·Η •ri C X rt 0 0 0 rt E w Ό O« Ol ω 0 Ol Ol Ol ti ra E ra •ri £ 3 3 ti 3 0 rt o 0 0 0 0 to to 0 0 £ c rt rt •ri 3 3 3 bO rt rt E > •ri § E ra ra ra 3 3 3 3 rt £ rt rt rt 0 3 O O O ra 0 0 0 0 •ri •ri ra ra ra £ c 0 0 0 £ 0 X X X 0 til P4 til til til O< ra ra 3 O ra > £ ti 0 0 e •ri •ri 0 •ri X Ol rt rt x X rt Ol 0 0 3 0 0 ra ra ra rt 0 0 ra ra E ti « 0 0 3 3 rt Oi 0 •ri £ ra 0 0. ♦ri X •ri •ri ti· ra til tti til B ti ra ti C ti ti til 0 0 ra 0 0 Ol •ri •ri 0 ra ti ra £ rt 0 •ri rt •ri 3 ra •ri c ra ti E 0 ra 3 0 0 g E ti 0 o 0 0 g rt a Ό Ol O >3 > 0 ra 3 ra ra ra 3 3 3 ra ra ra £ a £ 3 0 0 •ri 3 3 ti X X 0 ti ti >3 •ri •ri •ri til til til Οί a: « officinarum sugar cane ti x o a co ti CO ti •ri ε ti E ra co 3 2 o o P Φ Botanical name English Φ o ε fi co Λ P p P to co fi cd fco C fi Φ Φ co fi P fi cd rt •rt •rt C o o 0 r-l ·> fi fi Λ to o ft co X ft O fi fi Φ o rrt Φ Φ P Φ co fi x: fi cd o O P X) P X 04 Φ cd φ ω •rt C cd cd o c ft •rl N •rt cd •rt o Ό Φ fi cd o £ cd •0 »rt fi fi ft cd Φ p rrt fi •rt 0 fi fi cd H ω CO o fi £ P o P o hO w ε (ti P (ti Φ rrt fi fi cd o bO •rt (rt fi fi hO cd fi ε Φ 3 • 3 co Φ co β £ cd CO ε o •rl ί> fi Φ C □ P 1 co fi o 0 Φ ε CO o o cd cd cd P •rt >> •rt CO cd fi rrt fi fi o cd P fi P •rt fi Φ 0 P φ (ti fi co o •rt CO Φ X) O o rrt rt ft Φ rt > fi ¢-1 fi •rt o o cd cd Φ •rl p P *3 cd e ε ε P fi fi cd ε 3 ε fi fi cd •rt •rt ε E ε •rt 0 •rt fi •rt •rl Ch CO > fi fi 3 O fi rrt rt fi fi fi p P cd P 0 •rl •rl •rt cd cd CO cd hO to fi 0 fit P o o •rt fi •rt rrt fi fi •rt Φ •rt •rt o o rt bO P o 0 o ft P fi fi cd cd •rt •rt •rt w w w CO Eh E4 Eh > > > > g iti φ tq to >> co The new isoxazolylalkylthiol carbamates of the invention may be mixed with numerous respresentatives of other groups of herbicidal active ingredients. 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: ... ΰ r> 3 :ϊ :n-c-ch„ci II CH, isopropyl CH? -CH-C=CH CHj -CH-CH2OCH3 c2h5C2H5 -ch2-och3C2H5 c2h5 CH,-C-OC,H^ 2 it 2 5 c2h5 0CH, CH, ch2-ch2-och3 K2 sir·»·' CH2=CH-CH2ch2=ch-ch2R CHj H-C-N.

R 0 XR Br· Cl-Q CHj · H CHj H H OCHj H OCH, R Cl och3 OCHy II ή R-^ Ij-R1 R tert. C,|Hg tert. CjjHg NH, -N=CH-CJI ZH3 '•CH, csch3 SCH, j CH3 -CHj /CH3 -N -N χοη3 /CH3 C-CH, II 3 II R-SO NH, CH, HCH3 'oc2h5 .,5532 Ζ R1 _ZJ_ RZ 'NO- R R1 R2 R3 R1* H CFj H Il < C jHy n.CjH? H CFj H n.CjHy ch2ch2ci H SO2NH2 H n.CjHy n.CjH? H CFj H n.CjHy M /A CHj CHj H Η ΟΗχ. c2h5 H CFj nh2 n.CjHy n.CjHy NHR R-HN fcerfc.CjjHjjC2H5 SCH. 1« CjHyC2H5 Cl l.CjHy 4 Cl c2h5C2H5 CH, • > Cl CA -C-CH • Cl C2H5 H CH, R' CH, -C-CN CHj -CH-CH,-O-CH, , 2 3 CH, N_S-N CH, CH, 3 3 X Cl Cl anion CH,-CCl--C-OHa 5 ii CCl,-C-ONa J II ClCH5 ^-N-CH-C-O-C2H5 C=O 0 Cl CH, CH, F-^^-N-CH-C-O-CH·^ ci ?θ θ CH3 45! / y-NH-C-O-CH /CH3 CH, NH-C-O-CH2-C=C-CH2C1 Cl 1 4 5 5 4 Cl· Cl e y-CHg-CH-C-O-CHj 0 ci-fy-o-/ y-o-cH -c-och, ci CHj 0 J ^CH3 Cl-C '>-OCH -C-O-CH.-CH^.

CH3 δ C»3 FjCy-O-CH -C-O-Na CHj 0 HCBC· CH, J •ONH CHj Cl Cl iand salts R = H or Na COOH Λ Cl NH. and saltsCl-/ V-O“CH.-C-OH and salts or esters ti Cl N-C-CH.-O-S-NHCH, It II 0 0 H,C .-As-ONa < it HO 0 Cl-/ Cl '^-O-Z'Vo-CH-C-O-Na 0 Cl COOH 5 3 2 i-propyl N-C-CHo-0-S-NH /If d !! If ft i-propyl It is also useful to be able to apply the new compounds according to the invention, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g,, agents for combatting pests and phytopathogenic fungi, and growth regulators. The new compounds may also be mixed with mineral fertilizer solutions used to overcome nutritional or trace element deficiencies.

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersion, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. 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, and oils of Vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, <4 alkylated naphthalenes hydrocarbon derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene and isophorone, and strongly polar solvents such as dimethylformamide, di5 methyl sulfoxide, N-methylpyrrolidone and water may be used.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions 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 emulsifiers. 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, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and 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 sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers,condensation products of sulfonated naphthalene and naphthalene derivatives tilth formaldehyde, condensation products of naphthalene or naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers,ethoxylated isooctylphenol, 5532 ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, trihutylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty 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 granules, 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, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal and cellulosic powders.

The formulations generally contain frcm 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 (tankmix)) oils of various types, wetting agents or adherents, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilisers, antifoams (e.g., silicones), growth regulators, antidotes and other > Ό 5 ,'J herbicidally effective compounds, The last-mentioned herbicidal 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, fungicides, nematocides, insecticides, bactericides, antidotes and growth regulators, EXAMPLE 76 parts by weight of compound 1 is mixed with 10 parts by weight of Ν-methyl-oC-pyrrolidone» A mixture is obtained which is suitable for application in the form of very fine drops,, EXAMPLE 77 parts by weight of compound 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of 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 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 78 parts by weight of compound 3 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, *j» kJ if »'* parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, 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 79 parts by weight of compound 4 is dissolved in a mix10 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 280°C, 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 80 parts by weight of compound 4 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene tfL-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 ,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 81 parts by weight of compound 4 is intimately mixed with parts by weight of particulare kaolin. A dust is obtained containing yi by weight of the active ingredient.

EXAMPLE 82 parts by weight of compound 4 is intimately mixed 5 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 gel. A formulation of tho active ingredient is obtained having good adherence.

EXAMPLE S3 parts by weight of compound 5 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acidurea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.0M wt of active ingredient.

EXAMPLE 84 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 (27)

1. CLAIMS:1. An isoxazolylmethylthiol carbamate of the formula where R 1 denotes hydrogen, alkyl, alkyl interrupted by oxygen or sulfur, unsubstituted or alkyl-substituted cycloalkyl, aralkyl, or optionally substituted aryl, R denotes hydrogen, optionally substituted alkyl, aryl, or halogen, R 3 denotes hydrogen or alkyl, 7 denotes hydrogen or alkyl, and R 3 and R& are identical or different and each denotes alkyl, alkenyl, unsubstituted or alkyl-substituted cyeloalkyl, 5 6 alkoxyalkyl or haloalkyl, and additionally R and R together witn the linking nitrogen atom may denote an unsubstituted or lower alkyl-substituted heterocyclic ring having up to 10 ring carbon atoms.

2. An isoxazolylmethylthiol carbamate as claimed in claim 1 wherein any alkyl radical has a maximum of 6 carbon atoms, and cyeloalkyl radical has a maximum of 8 carbon atoms, any aryl radical contains a single benzene ring and any alkenyl radical has a maximum of 4 carbon atoms.

3. An isoxazolylmethylthiol carbamate as claimed in claim 1 wherein R^ denotes alkyl of 1 to

4. Carbon atoms or optionally ο halogen-substituted phenyl, R denotes hydrogen or chlorine, R 3 denotes hydrogen or methyl, R^ denotes hydrogen, and and R^ independently denote alkyl or alkenyl (other than 1-alkenyl) of 2 to 4 carbon atoms, cyclohexyl, cr alkoxyalkyl of at least two carbon atoms in the alkyl moiety and a maximum of 6 carbon atoms, 5. 6 or R and R together with the linking nitrogen atom denote an unsubstituted or methyl substituted saturated N-heterocyclic ring of 4 to 7 ring members optionally including an oxygen atom in addition to the nitrogen atom. £ ΰ 5 3 2 A. An isoxazolylmethylthiol carbamate identified, herein as any of compounds Nos. 1 to 75.

5. 3-Methyl-5-isoxazolylmethy1-N,N-diisopropylthiol carbamate.

6. 3-Methyl-5-isoxazolylmethyl-N-ethyl-N~cyclohexylthiol 5 carbamate.

7. 3-Methyl-5-isoxazolylmethyl-N,N~diethylthiol carbamate. S. A process for the production of an isoxazolylmethylthiol carbamate claimed in claim 1, wherein an isoxazolyl methyl halide or methyl alkane sulfonate of the formula :-x li. IC 1 4· where R to R have the above meanings and X denotes halogen or alkane sulfonate, is reacted vzith a thiol carbamate of the formula K M-S-S-N· Rr 5 6 where R and R have the above meanings and M denotes an alkali metal atom or ammonium optionally substituted by 2 or 3 alkyls.

8. 9. A process for the production of an isoxazolylmethylthiol carbamate as claimed in claim 1, wherein an isoxazolylmethylmercaptan of the formula where R 1 to R /+ have the above meanings and Y denotes hydrogen, an alkali metal atom or ammonium optionally subsituted by 2 or 3 alkyls, is reacted vzith a carbamic acid chloride of the formula .5 c £ where fr and R have the-.above meanings.

9. 10. A process as claimed in claim 8 or 9 carried out substantially as hereinbefore described or illustrated in any of Examples 1 to 3. 5

10. 11. Isoxazolylmethylthiol carbamates when prepared by a process as claimed in any of claims 8 to IQ.

11. 12» The use of an isoxazolylmethylthiol carbamate claimed in any of claims 1 to 7 or 11 as a herbicide.

12. 13. A herbicidal composition comprising an isoxazolylmethyllo thiol carbamate claimed in any of claims 1 to 7 or 11 and a solid; or liquid carrier,

13. 14. A herbicidal composition as claimed in claim 13 in the form of a wettable powder or a dust or. granules.

14. 15» A herbicidal composition as claimed in claim 13 in the form 15 of a solution paste, emulsion concentrate, suspension or dispersion in an oily liquid.

15. 16. A herbicidal composition as claimed in claim 13 in the form of an aqueous suspension or dispersion containing a wetting or dispersing agent, adherent or emulsifier. 20

16. 17. A herbicidal composition as claimed in any of claims 13 to 16, containing a further biologically active Ingredient.

17. 18. A herbicidal composition as claimed in claim 17 wherein the further biologically active ingredient is a herbicide.

18. 19. A herbicidal composition as claimed in claim 18 wherein 25 the further herbicide is one depicted hereinbefore.

19. 20» A herbicidal composition as claimed in claim 13 and substantially as hereinbefore described or exemplified in any of Examples 76 to 84.

20. 21 A process for producing a herbicidal composition wherein an 30 isoxaaolylmethylthiol carbamate as claimed in any of claims 1 to 7 er 11 is admixed with a solid or liquid carrier.

21. 22. A process for controlling the growth of unwanted plants '» u 5 3 3 wherein a phytotoxic amount of an isoxazolylmethylthiol carbamate as claimed in any of claims 1 to 7 or II is applied to the locus where the growth is to be controlled.

22. 23. A process for selectively controlling the growth of weeds 5 in a crop wherein a selectively phytotoxic amount of an isoxazolylmethylthiol carbamate as claimed in any of claims 1 to 7 or 11 is applied to the crop area.

23. 24. A process as claimed in claim 22 or 23 wherein the herbicide is applied preemergence of the unwanted plants or weeds. 10

24. 25. A process as claimed in any of claims 22 to 25 wherein the herbicide is applied without incorporation into the soil.

25. 26. A process as claimed in any of claims 23 to 25 wherein the crop is rape, cotton, maize, beet, soyabean, barley, wheat or oats.

26.

27. A process as claimed in claim 22 or 23 carried out 15 substantially as hereinbefore described.