IL44276A - Carbamoyloxyphenyl-carbamic acid esters and herbicidal compositions containing the same - Google Patents

Description

Carbamoyloxy phenyl carbamic add esters and herblcldal compositions containing the same m»oanp msain o»mon The present Invention 1s concerned with new dlurethanes having selective herblddal properties, which herbicides are especially suitable for combating weeds, 1n cotton crops, with processes for their manufacture, with herblddal preparations containing them and with their use.

The herblddal action of dlurethanes has been known (cf. German Of enl egungsschrl f ten Nos. 1,567,151 and 1,568,621). These specifications are, however, preponderantly concerned with selective herbicides for use in beet crops. These herbicides do not possess a selectivity towards cotton plants.

The problem upon which the present Invention 1s based has been to provide a weed combating agent that can be used especially 1n cotton crops, which problem has now been solved by the present Invention.

The present Invention provides compounds of the general formula I represents an ally! group, an unsubstl tuted alkyl group containing 1 to 4 carbon atoms or a halogen-substituted ethyl group, represents an ally! group, an unsubstl tuted alkyl group containing 3 to 4 carbon atoms, a halogen-substituted ethyl group, or a cyclohexyl, benzyl or phenylethyl group. represents a methyl or ethyl group, and represents an oxygen or sulphur atom.

The compounds of the present Invention are dlstln- Ί gulshed by a surprisingly high tolerablHty towards cotton In all stages of development, the crop plants not being damaged by the use of the compounds even 1n the embryo stage. The surprisingly good tolerablHty towards crops represents an extraordinary technical advance, because weeds can be combated 1n these crops Indpendently of the crops' stage of development at any time when an optimum attack by the weeds present can be expected. This 1s not possible with the herbicides based on phenyl-ureas hitherto used for combating weeds 1n cotton, which can be used only 1n a stage of growth of the cotton at which the weeds have also strongly developed and are therefore difficult to combat.

German Application 21 08 975 (corres. to Israel Patent 38738) describes herblddal N-acyl -b1 scarbamates and their mixtures with other b1 scarbamates which are selective towards beet plants. German Application 20 20 729 (corres. to Israel Patent 36 647) describes herblddal preparations containing at least two carbamoyl oxyphenyl carbamates which show a selectivity towards sugar beet plants. Israel Patent 28516 «-described algiddes containing substituted phenyl carbamates , and Israel Patent 28661 describes a process for the manufacture of N-carbamoyloxyphenyl-carbamates.

None of the compounds specifically described 1n said references however 1s within the scope of the present Invention and said patents neither teach nor suggest the unexpected superior selectivity towards cotton plants exhibited by the compounds of the present Invention as shown 1n comparative example 6 hereinafter.

The compounds of the present Invention exhibit the most favourable action when they are applied by the post-emergence method. In this case the compounds do not act only against the weeds that have sprouted, but, owing to their residual action 1n the soil, attach germinating weed plants, so that a long lasting / attack Is ensured.

Apart from their use 1n cotton crops, the compounds of the present Invention can also be used for combating weeds 1n carrot crops, ground-nut crops and rice crops, 1n which they also have an extraordinary selective action.

The herb1c1dal action of the compounds of the general formula I extends to many kinds of weeds, among which, for example, there may be mentioned the following: Setarla vertld 11 ata , Amarantus sp1 nosus , Datura stramonium, Portulaca oleracea , Xanthl urn pensyl vanlcum, Eleuslne 1nd1ca, Rottboel 11a exal tata . S1nap1s sp., Sol anum sp. , Stellarla media , Senedo vulgaris , Lamlum amplexlcaule , Centaurea cyanus , Amarantus retrof lexus , Gal 1 urn aparl ne , Chrysanthemum segetum, Echlnochloa crus gall 1 , Setarla 1 tal 1ca , Ipomoea purpurea , Polygonum lapathlfoHum, D1g1 tarla sangul nal 1 s and Setarla faberl .

The rates of application for a selective weed control are approximately 1 to 3 kg of active substance per hectare; when two or more compounds of the general formula I are used the range of approximately 1 to 3 kg refers of course to the total amount applied of these compounds. These rates of application may even be Increased to 10 kg of active substance per hectare substantially without Injuriously affecting the crop plants.

The present Invention accordingly also provides a herblddal preparation which comprises a compound of the general formula I, 1n admixture or conjunction with a suitable carrier. The preparation may of course contain one or more compounds of the general formula I.

The present Invention further provides a method of protecting a living plant against weeds, wherein the area 1n the vicinity of a living plant 1s treated with a compound of the general formula I.

The present Invention further provides a method of protecting a crop area against weeds, wherein a crop area nd ene al formula I.

The compounds of the present Invention can be used either singly as the sole active substance, or 1n admixture with one another or 1n admixture with other active substances. If desired, there may be added other plant protecting agents or pest combating agents, for example fungicides, nematlddes or other agents, depending on the purpose desired. Fertilizers may also be added.

When 1t 1s Intended to widen the spectrum of action there may also be added other herbicides, but, of course, the selectivity 1s not always maintained. As herblddally active co-components of such mixtures there are suitable, for example, active substances belonging to the groups of carbamic add esters and th1ocarbam1c add esters, substituted anilines and anlUdes, trlazlnes, ami no-tr1 azoles , d1az1nes, for example uracils, for example 3-cyclohexyl -5 ,6-tr1methylene-urac1l , l-phenyl-4-am1no-5-chloropyr1dazone-(6) , aliphatic carboxyllc adds and hal ogencarboxyl 1c adds, halogenated benzoic adds and phenyl -acetl c adds, aryloxy-carboxyllc adds, hydrazldes, amides, nltrlles, halogen-carboxyl 1c adds, for example 2,2-d1chloroprop1on1c add or salts thereof and tetrafluoro-prop1on1c add or salts thereof, esters of such carboxyllc adds, ureas, N-phenyl -ureas , 2 ,3 ,6-tr1chlorobenzyloxy-propanol , agents containing thlpcyanogen and other compounds.

Depending on the purpose of use other substances may be added, among which there are also to be understood, for example, non-phytotox1c additions, which 1n combination with herbicides may give a synergistic Increase 1n action, for example wetting agents, emuls1f1ers, solvents and oily additions.

The active compounds of the present Invention are advanta eousl used 1n the form'of herblddal re arations for example powders, spraying or dusting agents, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid vehicles or diluents, and, 1f desired, of surface-active agents, for example wetting, adherent, emulsifying and/or dispersing agents.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, for example benzene, toluene, xylene, cycl ohexanone and Isophorbne, and also mineral oil fractions.

As solid carriers there are suitable mineral earths, for example tonsil , silica gel, talcum, kaolin, attaclay, limestone and s 111 c 1 c add, and vegetable products, for example meals.

As surface-active agents there may be mentioned, for example, calcium I1gn1n sulphonate, polyoxyethylene-octyl -phenol ethers, naphthalene' sulphonlc adds, phenol sulphonlc adds, formaldehyde condensates, fatty alcohol sulphates and alkali metal and alkaline earth metal salts of fatty adds.

It has been surprisingly found that the herblddal action and the selectivity of the preparations can be Increased, when they contain the surface-active agents 1n proportions that exceed the usual quantities.

The total amount of the active compound or compounds of the present nvention 1n the various herblddal preparations may vary within wide limits. The preparations may contain, for example, approximately 20 to 80 per cent by weight of active compound(s), approximately 80 to 20 per cent by weight of liquid or solid carrier, and also, 1f desired, up to 30 per cent by eelght of surface-active agent(s).

The active compounds may be applied 1n the usual manner, for example, with water as carrier 1n quantities of spray e F r t e a destruction of weeds 1t may be necessary 1n some cases to apply quantities of spray Hquor exceeding 1,000 litres per hectare. It 1s also possible to use the active compounds 1n the so-called "U1 tra-low-Volume method", and also to apply them 1n the form of the so-called m crogranules.

These preparations may be prepared 1n a manner known per se, for example, by mixing or grinding methods. If desired, the Individual components may be mixed together only shortly before being used, such, for example, as 1n the so-called tank mix method carried out 1n practice.

The new compounds of the present Invention may be prepared by methods known per se, for example by one of the following processes which are also Included within the scope of the present Invention.

The present Invention accordingly further provides a process for the manufacture of a compound of the general formula I, wherein a) a compound of the general formula 1n which 3 and X have the meanings given above, or an alkali metal salt thereof 1s reacted with a carbamoyl chloride of the general formula 1n which -j and R2 have the meanings given above, 1f desired 1n the presence of a tertiary organic base, for example tr1ethylam1ne or pyridine, at a temperature of 0°C to 100°C, or a compound of the general formula 1n which and X have the meanings given above, 1s reacted 1n the presence of an add-b1nd1ng agent, for example an Inorganic base, for example sodium hydroxide solution, sodium carbonate or potassium carbonate, or a tertiary organic base, for example tr1ethylam1ne, with ar: 3m1ne of the general formula n which Rj and R2 have the meanings given above, nltro compound of the general formula 1n which Rj and R2 have the meanings given above, 1s catalytlcally hydrogenated , for example, with the use of nickel 1n methanol, to form the corresponding amine which 1s then reacted 1n the presence of an ac1d-b1nd1ng agent, for example an inorganic base, for example sodium hydroxide solution, sodium carbonate or potassium car R3 - X - CO - CI in which R3 and X have the meanings given above.

The products of the process of the present i nventi on isolated in the usual manner.

Some compounds of the present invention are listed the following Table.

Table I Compound Name of the compound Physical No. constant 1 Ethyl -N-[3- (N-ethyl -N-isopropyl - carbamo l ox ) -phenyl ] -carbamate M.p.: 65 - 66°C 2 Ethyl -N- [3- ( , N-di propyl -carbamoyl oxy ) - phenyl] -carbamate M.p.: 82 - 84°C 3 Methyl -N- [3- (N-ethyl -N-benzyl - carbamoyl oxy ) -phenyl ] -carbamate M.p.: 97 - 98°C 4 S-Methyl -N-[3- (N-ethyl -N-benzyl - carbamoyl oxy ) -phenyl ] - thi ocarbamate M.p.: 108 - Ill 5 Ethyl -N-[3- (N-ethyl -N-benzyl - carbamoyl oxy ) -phenyl ] -carbamate M.p.: 93 - 94°C 6:-. ' Methyl -N-{3- [N-methy 1 -N- (2-phenyl ethyl ) - carbamoyl oxy ]-phenyl } -carbamate M.p.: 88 - 90°C 7 S-Methyl -N- [3- (N-butyl -N-benzyl *- carbamoyloxy)-phenyl J-thi ocarbamate M.p.: 82 - 84°C 8 Ethyl -N-[3- (N-methy 1 -N-benzyl - carbamoyloxy)-phenyl]-carbamate M.p.: 83 - 85*C 9 S-Methyl -N- [3- (N-methy 1 -N-benzyl - carbamoyl oxy ) -phenyl ] - thi ocarbamate M.p.: 83 - 85°C 10 Methyl -N-[3- (N-butyl -N-benzyl - carbamoyl oxy ) -phenyl ] -carbamate M.p.: 57 - 61 °C 11 Methyl -N-[3- (N-methyl -N-benzyl - carbamoyl oxy )-phenyl]-carbamate M.p.: 79 - 82°C 12 Ethyl -N-{3-[N-methyl -N- (2-phenyl ethyl )- carbamoyl oxy]-phenyl}-carbamate M.p.: 101 ■ - 103 13 S-Methyl-N-{3-[N-methyl-N-(2-phenylethyl)- carbamoyloxy]-phenyl}-thi ocarbamate M.p.: 69 - 72°C 14 Methyl -N-{3-[N,N-bis-(2-chloroethyl )- carbamoyl oxy]-phenyl}-carbamate M.p.: 58 - 61 °C 15 Ethyl -N-{3-[N,N-bi s-(2-chlorethyl ) - carbamoyl oxy] -phenyl} -carbamate M.p.: 69 - 72°C 16 S-Methyl -N-[3-(N,N-d1 propyl - carbamoyl oxy) ?-phenyl ]-th1 ocarbamate M.p. : 92 - 93°C 17 S-Methyi r-N-[3- (N-ethyl rN-butyl ¾ carbamoyl oxy ) -phenyl ] -thi ocarbamate M.p . : 98 - 100°C 18 S-Methyl -N-[3r (N,N-d1-1sobutyl - carbamoyl oxy ) -phenyl ] -th1 ocarbamate M.p. : 117 - 118°C 19 S-Methyl -N-[3- ( ,N-di butyl - carbamoyl oxy ) -phenyl ]-th1 ocarbamate M.p. : 57 - 58°G 20 S-Methyl -N- [3- (N-ethyl -N-1 sopropyl - carbamoyl oxy ) -phenyl J - th1 ocarbamate M.p, : 124 - 126°C 21 S-Methyl -N-C3- (N-methyl -N-cycl ohexyl - carbamoyl oxy) -phenyl ]-th1 ocarbamate M.p. : no - 113°C 22 S-Methyl -N-[3- (N-ethyl -N-cycl ohexyl - ' carbamoyl oxy ) -phenyl ]- thi ocarbamate M.p. : 155 - 156PC 23 . S-Methyl -N-{3-[N,N-bis-(2-chlorethyl )- carbamoylox ]-phenyl } -thi ocarbamate Mf p. : 104 - 106°C 24 S-Methyl -N-[3- ( ,N-d1 al lyl -carbamoyl oxy ) - phenyl ] '-thi ocarbamate M.p. : 67 - 70°C 25 S-Methyl -N-[3- ( ,N-d1 -1 sopropyl carbamoyl oxy) -phenyl ]-th1 ocarbamate M.p. : 1 7 - m 26 Methyl -N-[3-(N-propyl -N-cycl ohexyl -? carbamoyl oxy j -phenyl ]-carbamate M.p. : 102 - 103,5eC 27 Methyl -N- [3- (N-1 sobuty 1 -N-cycl ohexyl - carbamoyioxyj-phenyl ]-carbamate Μ,ρ, : 105.5 - 107°C 8 Methyl -N-[3-(N,N-d1 propyl Carbamoyl oxy) - phenyl ] -carbamate Μ,ρ, : 68 - 69°C 9 Methyl -N-[3- (N-ethyl -N-butyl - carbamoyioxyj-phenyl ]-carbamate M.P, : 69 - 71 °C 0 Methyl -N- [3- (N-ethyl -N-1 sopropyl - carbamoyioxyj-phenyl ] -carbamate Μ,ρ, : 93 - 95°C 1 Methyl -N-[3- ( ,N-d1 al lyl -carbamoyl oxy ) - phenyl ]-carbamate Μ,ρ, : 46 - 48°C 2 Ethyl -N-[3- (N-ethyl -N-butyl carbamoyl oxy ) - phenyl ]- carbamate M.p. : 57 - 59eC 3 Ethyl -N-[3- (Ν ,Ν-dtal lyl -carbamoyl oxy )- phenyl ] -carbamate nD 1 ,5250 4 Methyl -N-[3- (N-methyl -N-cycl ohexyl - carbamoyl oxy j-phenyl^l-carbamate .p, : 120 121°C 5 Ethyl -N-[3- (N-methyl -N-cycl ohexyl - carbamoyl oxy ) -phenyl ]v¾arbamate M.p. : 77 - 79°C 6 Methyl - ^- [3- (N-cycl ohexyl -N-isobutyl - carbamoyloxyj-pheny j-carbamate Μ,ρ, : 105,7 - 107°C 7 Ethyl -N-[3- (N-cycl ohexyl -N-propyl - carbamoyl oxy) -phenyl ]-carbamate M.p. : 91 - 95°C 8 Ethyl -N- [3- (N-cycl ohexyl -N-1 sopropyl - carbamoy loxy) -phenyl ]-carbamate M.p, ,: 134 - 137°C Compound Name of the compound Physical constant No. 39 Methyl -N- [3- ( N-cycl ohexyl -N- Isopropyl -carbamoyl oxy) -phenyl ] -carbamate M.p. : 128 - 130°C 40 S-Methyl -N-[3- (N-cycl ohexyl -N-propyl - carbamoyl oxy ) -phenyl ] -ch1 ocarbamate M.p. : 116 - 119eC 41 Ethyl -N-[3-(N-butyl -N-cyclohexyl- ! carbamoyl oxy) -phenyl ]-carbamate Mip. : 89 - 93°C 42 Methyl -N-[3-(N-n-butyl -N-cycl ohexyl - carbamoyl oxy) -phenyl J-carbamate n20 a nD 1 .5140 43 S-Methyl -N- [3- (N-cycl ohexyl -N-1 sobuty 1 - carbmaoyl oxy) -phenyl ]-thi ocarbamate M.p. : 117 :- 119°C 44 Ethyl -N-[3- (N-cycl ohexyl -N-sec, -butyl - carbamoyl oxy) -phBnyl ]-carbamate M.p. : 98 - 100°C 45 Methyl -N-[3- (N-cycl ohexyl -N-sec . -butyl - carbamoyl oxy) -phenyl ]-carbamate M.p. : 106 - 107°C 46 Methyl -N-{ 3- [N- ( 1 -methyl -2-propyny 1 ) - N-methyl -carbamoyloxy]-phenyl}-carbamate M.p. : 115 - 117°C 47 Ethyl -N-[3- (N-1 sobuty 1 -N-cycl ohexyl - 20_ carbamoyloxy) -phenyl j-carbamate nD s 1 .5210 48 S-Ethyl -N-[3- (N-ethyl -N-benzyl carbamoyl - oxy ) -phenyl ]-th1 ocarbamate M.p. : 86 - 89°C 49 S-Ethyl -N- C3- (N-cycl ohexyl -N-methyl - carbamoyloxy) -phenyl ]-th1 ocarbamate M.p. : 144 - 146°C 50 S»Ethyl -N- [3- ( ,Ν-dl al lyl -carbamoyl oxy ) - phenyl ]-th1 ocarbamate M.p. : 48 - 52°C 51 S-Ethyl -N- C3- (N-ethyl -N-1 sopropyl - , carbamoyl oxy ) -phenyl ]- th1 ocarbamate M.p. : 95 - 96°C 102°C 124°C 55 S-Eth l -N-[3- (N-cycl ohexyl -N- sobutyl - carbamo 1 oxy ]-phenyl ] - thi ocarbamate M.p. : 140 - 142°C 56 S-Ethyl -N-[3- (N-sec. -butyl -N-cycl ohexyl - carbamoyl oxy) -phenyl ] -thi ocarbamate M.p. : 130 - 132°C 57 Methyl -N-{3-[N-ethyl -N-(2-chl orethyl ,)- carbamoyl oxy ]-phenyl } -carbamate . M.p. : 100 - 102°C 58 Ethy1 -;N-{3-[N-ethyV-N-(2-chlorethyl )- carbamoyloxy]-phenyl }-carbama$a M.p. : 96 - 986C 59 Ethyl -N-{ 3- [N-methyl -N- ( 2-chl oreth l ) - carbamoyl oxy]-phenyl }-carbamat¾ M.p. : 86 - 88°C 60 S-Ethyl -N-[3- (N-benzyl -N-methyl - carbamoyl oxy) -phenyl ]-th1 ocarbamate M.p. : 68 - 79°C Compound Name of the compound Physical constant No. . 61 S-Ethyl -N-{3-[N-methyl-N- (2- phenylethyl )-carbamoyloxy]- phenyl}-th1ocarbamate M.p.: 84 - 87°C 62 S-Ethyl -N- [3- (N,N-d1 ethyl carbamoyl oxy ) - phenyl ]-th1ocarbamate M.p.: 83 - 84°C 63 S-Methyl-N-{3-[N-methyl-N-(2-chlorethyl )- carbamoyl oxy]-phenyl}-th1ocarbamate M.p.: 80 - 82°C 64 S-Ethyl-N-{3-[N-ethyl-N-(2-chlorethyl)- carbamoyloxy]-phenyl}-th1ocarbamate M.p.: 83 - 85eC 65 S-Ethyl-N-{3-[N-methyl-Nr(2-chlorethyl )- carbamoyl oxy]-phenyl}-th1ocarbamate M.p.: 86 - 88°C 66 S-Ethyl-N-[3-(N,N-d1butyl-carbamoyloxy)- 2Q phenyl 3-th1ocarbamate nQ ° 1.5250 67 Methyl -Nr [3- (N-al lyl -N-cycl ohexyl - carbamoyl oxy) -phenyl ]-carbamate , M.p.: 99 - 101°C 68 Methyl -N-{3-[N-ethyl-N-j8-bromethyl )- carbamoyl oxyJ-phenyl}-carbamate M.p.: 117°C 69 Methyl -N-[3- (N-butyl -N-tert . -butyl - carbamoyloxy)-phenyl]-carbamate M.p.: 59 - 62°C 70 Ethyl -N-{3-[N-ethyl-N-(2-bromethyl )- carbamoyl oxy ]-phenyl}-carbamate M.p.: 110°C 71 S-Methyl-N-{3-[N-ethyl-N-(2-chlorethyl )- carbamoyl oxy]-phenyl}-th1ocarbamate M.p.: 98 - 100°C 72 Methyl-N-{3-[N-methyl-N-(2-chlorethyl)- carbamoyl oxy] -phenyl} -carbamate M.p.: 103 - 104°C 73 S-Ethyl -N- [3- (N,N-d1 propyl -carbamoy 1 ox ) - phenyl ]-th1 oca rbamate M.p.: 73 - 74°C These compounds are readily soluble 1n acetone, cyclo-hexanone, ethyl acetate, Isophorone, ether and tetrahydrof uran and are practically Insoluble 1n water and light gasoline.

Among the compounds of the Invention, the compounds numbered 2, 14, 15, 16, 17, 21, 23, 28, 30 and 34 1n the above Table are especially suitable as selective herbicides In cotton, carrot, ground-nut and rice crops.

The following Examples Illustrate the Invention. Examples 1 and 2 illustrate the manufacture of compounds of the present Invention and Examples 3 to 5 Illustrate the herblddal activity of compounds of the present Invention.

Example 1 Ethyl -N- [3- (N -ethyl -N-1 sopropyl -carbamoyl oxy ) -phenyl ] -carbamate (Compound No. 1 ) Into a mixture of 5.3 grams of N-ethyl -1 sopropyl amine , 50 ml of water and 30 ml of ethyl acetate were Introduced drppwlse, while stirring at 10 to 15°C, a solution of 14.6 grams of chloroformlc ac1d-3-(N-carbethoxyamino)-phenyl ester 1n 30 ml of ethyl acetate and simultaneously a solution of 8.3 grams of potassium carbonate in 30 ml of water. The mixture was further stirred for 30 minutes while cooling with fee, and then the organic phase was separated and washed at 0°C with a small amount of a dilute solution of sodium hydroxide and water.

After drying the organic phase with magnesium sulphate, 1t was concentrated under reduced pressure, pentane was added to the evaporation residue and cooled with 1ce, whereupon the reaction product crystallized out.

Yield: 14.1 grams = 80¾ of the theoretical yield. .p.: 65 - 66°C.

Example 2 Ethyl -N- [3- ( ,N-d1 propyl -carbamoyl oxy ) -phenyl ] -carbamate {Compound No. 2) _j A solution of 16.7 grams of 3-hydroxy-carbani 11 c acid methyl ester and 19.6 grams of Ν,Ν-dipropyl-carbamoyl chloride 1n about 50 ml of dry pyridine was heated for 45 minutes in a water bath at 90°C. After evaporating the solution In. vacuo , the residue was dissolved in ethyl acetate, the solution was washed at 0°C with a small amount of a dilute solution of sodium hydroxide, dilute hydrochloric add and water, and the solution was dried with magnesium sulphate and concentrated under reduced pressure, The evaporation residue was crystallized by the addition of pentane, and was recrystallized from tetrahydrofuran/pentane.

Yield: 21.0 grams ■ 68¾ of the theoretical yie¾a.

M.p. : 82 - 84°C The other compounds listed in Table I above can be prepared 1n an analogous manner.

Example 3 In a greenhouse the plants listed In the following Table were treated by the post-emergence method 1n a series of tests with preparations used In such amounts that 3 kg of the active substance being tested was applied per hectare. The active substances were 1n each case applied 1n the form of an aqueous emulsion using 500 litres of water per hectare at an early stage 1n the development of the plants. Evaluation of the results was carried out 14 days after the treatment by classification according to a scale of values extending from 0 representing "totally destroyed" to 10 representing "not damaged".

The results show the much better selectivity and anti-weed action of the compounds of the present Invention as compared with those of the known agents. ethyl -N-[3- (N-ethyl -N-butyl -carbamoyl oxy )-phenyl ]-carbamate 3 10 10 10 10 ethyl -N-[3-(N-ethyl-N-isopropyl-carbamoyloxy)-phenyl]-carbamate 3 10 10 - -ethyl -N-[3-(N,N-dial lyl-carbamoyloxy)-phenyl]-carbamate 3 - 10 - - · thyl -N-[3- ( ,N-di propyl -carbamoyloxy )-phenyl ]-carbamate 3 10 10 10 10 thyl-N-[3- (N-ethyl -N-butyl -carbamoyloxy)-phenyl]-carbamate 3 10 10 10 10 thy 1 -N- [3- ( » -di all y l-carbamoyl oxy) -phenyl ]-carbama te 3 ; - 10 10 -thyl-N-C3-(N-ethyl-N-isopropylcarbamoyloxy)-phenyl]-carbamate 3 - 10 10 9 ethyl -N-[3- (N-methyl -N-cyclohexyl carbamoyloxy ) -phenyl ] -carbamate 3 - - 10 9 thyl -N- [3- (N-methyl -N-cycl ohexy 1 carbamoyl oxy ) -phenyl ]-carbamate 3 - 9 10 9 ethyl -N- [3- (N-propyl -N-cycl ohexy 1 carbamoyl oxy) -phenyl ]-carbama te 3 - 10 10 - ■ ethyl -N- [3- (N- i sobu tyl -N-cycl ohexy 1 carbamoyl oxy ) -phenyl ]-carbamate 3 10 10 10 10 ethyl -N- [3- ( N-ethyl -N-beniryl carbamoyl oxy ) -phenyl ]-carbamate 3 10 10 0 0 Compound of the present Invention in the preparation S- ethyl-N-[3- (N-ethyl-N-benzylcarbamoyloxy)-phenyl ]-thiocarbaniate 3 10 10 0 0 2 Ethyl-N-[3-(N-ethyl-N-benzylcarbamoyloxy)-phenyl ]-carbamate 3 - " 10 10 - 1 Methyl -N-{ 3- [N-methyl -N-(2-phenyl ethyl ) -carbamoyl oxy]-phenyl}-carbamate 3 -· 10 10 10 0 S-Methyl-N-[3- (N-butyl-N-benzyl-carbamoyloxy)-phenyl]-thiocarbamate 3 - 10 10 10 0 Ethyl-N-[3- (N-methyl-N~benzylcarbamoyloxy)-phenyl ]-carbamate. 3 10 10 10 10 0 S-Methy 1 -N- [3- (N-methyl -N-benzy 1 carbamoyl oxy ) -phen l ] -thiocarbamate 3 - - 10 10 0 MethyT-N-[3- (N-butyl -N-benzyl carbamoyl oxy )rphenyl ]-carbamate 3 10 10 10 10 1 Methyl -N-[3- (N-methyl -N-benzylearbamoyl oxy ):-phenyl 3-carbamate 3 10 10 10 - 0 Ethy 1 -N-{ 3- [N-tne thy 1 -N- ( 2-phenyl ethyl ) -carbamo oxy ]-phen l } -carbamate 3 - 10 10 10 Θ S-Methy 1 -N-{ 3- [N-methyl -N- (2-phenylethy 1 ) -carbamoyl oxy]-phenyl } -thiocarbamate 3 10 10 10 10 0 Methyl-N-{3-[N,N-bis-(2-chTorethyl )-carbamoyloxy]-phenyl}-carbamate 3 10 10 .0 Compound of the present Invention in the preparation Ethyl-Nr 3-[N,N-bis- (2-chlorethyl )-carbamoyloxy]-phenyl -carbamate 3 - 10 10 - . 0 S-Methyl -N-[3- (N,N-di propyl carbamoyl oxy )-phenyl ]-thiocarbamate 3 - 10 10 - 0 S-Methyl-N- [3- (N-ethyl-N-butyl carbamoyl oxy) -phenyl ]-thiocarbamate 3 - 10 10 10 0 S-Methyl-N-[3-( ,N-di-isobutylcarbamoyloxy)-phenyl ]-thiocarbamate 3 - 10 10 0 1 S.-Methyl-N-[3-(N,N-dibutylcarbamoyloxy)-phenyl]-thiocarbamate 3 - 10 10 10 0 Compound of the present invention S-Methyl-N-C3-(N,N-di-isopropy1carbamoyloxy)-phenyl ]-thiocarbamate 3 - - 19 10 Methyl -N- [3- (N-cyclohexyl -N-i sobutyl carbamoyl oxy )-phenyl ]-carbamate 3 - 0 10 10 Ethyl -N- [3- (N-cycl ohexyl -N-propyl carbamoyl oxy ) -phenyl ]-carbamate 3 - - 10 10 Ethyl -N- [3- (N-cycl ohexy -N-ri sopropyl carbamoyl oxy )-phenyl ]-carbamate 3 - - 10 10 Methyl-N-[3- (N-cyclohexyl-N-isopropylcarbamoyloxy)-phenyl ]-carbamate 3 - 10 10 S-Methyl-N-[3- (N-cycl ohexyl -N-propyl carbamoyl oxy ) -phenyl ]-thiocarbamate 3 - - 10 10 Ethyl-N-[3-(N-butyl-N-cyclohexylcarbamoyloxy)-phenyl]-carbamate 3 - 10 10 10 Methyl -N- [3- (N-n-butyl -N-cycl ohexyl carbamoyl oxy )-phenyl ]-carbamate 3 - 10 10 10 S-Methyl-N-CS-iN-cyclohexyl^N-isobutylcarbamoyloxyJ-phenyl ]-thiocarbamate 3 - - 10 10 Ethyl -N- [3- (N-cycl ohexyl -N-sec . -bu tylcarbamoyl oxy ) -phenyl] -carbamate 3 - ■ - 10 4 Methyl-N-[3-(N-cyclohexyl-N-sec.-butyl-carbamoyloxy)-phenyl ]-carbamate 3 10 10 10 Methyl-N-{3-[N-(l-methyl-2-propynyl )-N-methyl -carbamoyl oxy]-pheny 1 }-carbamate 3 9 9 th l-N-[3- (N-ethyl -N-tsopropyl carbamoyl oxy) -phenyl ]-thi ocarbamate 3 10 - 10 10 thyl-N-[3-(N-ethyl-N-butylcarbamoyloxy)-phenyl]-th1ocarbamate 3 10 10 10 10 thy! H- [3- (Ν ,Ν-diethylcarbamoyl oxy) -phenyl ]-thi ocarbamate 3 10 9 10 -ethyl -N-{ 3- [N-methyl -N- (2-chlorethy 1 )-carbamoyl oxy]-phenyl } -ocarbamate 3 - - 9 9 thy1-N-{ 3- [N-ethyl -N-(2-chl orethyl ) -carbamoyl oxy]-phenyl } -ocarbamate 3 10 9 9 8 thy 1-Nr{ 3- (N-methy 1-N- (2-chl orethyl ) -carbamoyl ox 3-phenyl } -ocarbamate 3 9 10 10 10 thyl -N- [3^ (N ,N-dt butyl -carbamoyl oxy) -phenyl ]-thi ocarbamate 3 - 10 10 10 ihyi-N-CS- iN-anyl-N-cyctohexylcarbamoyloxyj-phenyll-carbamate 3 - - 9 9 ;hyi-N-{ 3- [N-ethyl -N-(2-bromethyl )-carbamoyloxy]-phenyl} -carbamate 3 - 8 10 10 ih 1 -N- [3- (N-bu ty 1 -N-tert * pbu ty 1 carbamoyl oxy ) -phenyl ]-carbama te 3 9 10 10 10 iyl-N-{3-[Niethyl-N-(2-bromethyl j-carbaineiyloxyj-phenyl }-carbamate 3 10 10 10 10 Compound of the present Invention in the preparation S-f4ethyl-N-{3-[N-ethyl-N-(2-chlorethyl )-carbamoylo)v]-phenyl }-thi ocarbamate 3 8 10 0 Me thy 1 -N- { 3- [N-methy 1 -N- ( 2- ch 1 orethy 1 ) - carbamoyl ox ]-phenyl }- carbamate 3 - 10 - 0 S-Ethyl-N-[3-(N,N-dipropylcarbamoylo^y)-phenyl ]-thiocarbamate 3 8 10 10 10 0 Compound in preparation used for comparison N- ( 3-Tri f 1 uoromethy 1 phenyl ) - ,N-dimethy 1 -urea 3 0 1 1 0 0 Methyl -N-{3- [N- ( 3-methy 1 phenyl ) -carbamoy lo y ]-pheny 1 }-carbamate 3 5 2 8 2 0 = total ly destroyed 10 = not damaged Example 4 In a greenhouse the plan Table were uniformly sprayed In a emergence (that 1s by the pre-eme used 1n such amounts that 3 kg of was applied per hectare. The acti used 1n the form of an aqueous em hectare. After 14 days, the results were .evaluated according to the scale given 1n Exampl$3.

The results demonstrate the excellent tolerablllty of the compounds of the present Invention towards cotton, carrots, ground-nut, potatoes and rice combined with a very good anti-weed action.

In contrast therew th, the known agent exhibited no action at the corresponding rate of application.

Example 5 In a greenhouse .plants in an early stage of development were sprayed. In a series of tests with preparations used In such amounts .that 2 kg of active substance being tested was applied per hectare, the active substances 1n each case being used 1n the form of an aqueous emulsion using 500 litres of water per hectare.

The evaluation was carried out 14 days after the treatment by a classification as described in Example 3.

Even at this rate of application the compounds of the present .invention still exhibit an excellent herbicide! action* Comparative example 6 In a greenhouse, the plants listed In the following table were treated by the post-emergence method 1n a test with preparations used 1n such amounts that 3 kg of the active substance being tested was applied per hectare.

The active substances were in each case applied 1n the form of an aqueous emulsion using 500 litres of water per hectare at an early stage 1n the development of the plants. Evaluation of the results was carried oiit 14 days after the treatment by classification according to a scale of values extending from 0 representing "totally destroyed" to 10 representing "not damaged" .

The results show the much better selectivity towards cotton plants of the compounds of the present Invention as compared with those of known agents with a very close structure.

Compound of the present Invention 1n the preparation Ethy l-N-( 3- (N,N-d1 propyl -carbamoy 1 oxy ) -phenyl ) -carbamate >θ 0 0 0 0 0 0 Ethyl-N-(3-(N,N-b1s-(2-chl orethyl) -carbamoy -oxy)-phenyl)-carbamate 10 0 0 0 0 0 0 ethyl-N-(3-(N,N-b1s-(2-chl orethyl ) -carbamoy oxy-phenyl )-carbamata 10 0 0 0 0 0 1 V e S. <ø U to -a 3 X 2 Z 0) *-> I— ID (O Compound of the present (O o Invention in the § ¾ £ ¾ϊ *i +3 preparation (II) Specifically described in Israel Patents 28516 and 28661. - 24b -

Claims (9)

1. S claimed 1s: A compound of the general formula I in which R.| represents an ally! group, an unsubs ti tuted alkyl group containing 1 to 4 carbon atoms or a halogen- substituted ethyl group, R2 represents an allyl group, an unsubsti tuted alkyl . group containing 3 to 4 carbon atoms, a halogen- substituted ethyl group, or a cyclohexyl , benzyl or phenylethyl group, R3 represents a methyl or ethyl group, and ¾ X represents an oxygen or sulphur atom.

2. A compound as claimed 1n claim 1, wherein each of the halogen-substituted alkyl groups is a 2-chlorethyl group.

3. Ethy 1 -N- [3- (N ,N-d1 propyl -carbamoyl oxy ) -phenyl ]-carbamate.

4. E thy l-N-{ 3- [N, -bi s- ( ]-ch 1 ore thy 1 ) -carbamoyl oxy ]-phenyl }-carbamate .

5. Methyl-N-{3-[N,N-b1s-(2-chlorethyl ) -carbamoyl oxy ]-phenyl }-carbamate.

6. S-Me thyl -N- [3- ( ,N-d1 propyl -carbamoyl oxy )- phenyl ]-thiocarbamate.

7. S-Methyl-N-[3-(N-ethyl-N-butyl-carbamoyloxy)-phenyl]-thi ocarbamate . 8 t 9 * 1 1 1 c 1 g h w 14. A herblcldai preparation which comprises a compound as claimed In claim 2, 1n admixture or conjunction with a suitable carrier. 15. A herblcldai preparation which comprises the compound claimed In any one of claims 3 to 12, 1n admixture or conjunction with a suitable carrier. 16. A herblcldai preparation which comprises any one of the compounds numbered 1 , 3 to 13, 18 to 20, 22, 24 to 27, 29, 31 to 33 and 35 1n Table I herein, 1n admixture or conjunction with a suitable carrier. 17. A herblcldai preparation which comprises any one of the compounds numbered 36 to 73 1n Table I herein, in admixture or conjunction with a suitable carrier. 1

8. A preparation as claimed 1n any one of claims 13 to 17, which 1s 1n the form of a powder, a spraying or dusting agent, granules, a solution, an emulsion or a suspension. 1

9. A preparation as claimed 1n any one of claims 13 to 18, containing a single compound of the general formula I in an amount of approximately 20 to 80% by weight. 20.. A preparation as claimed 1n any one of claims 13 to l£)j containing two or more compounds of the general formula I 1n a total amount of approximately 20 to 80% by weight. 2,1.. A preparation as claimed 1n any one of claims 13 to 20, containing a single surface-active agent 1n an amount of up to 30% by weight. 22. A preparation as claimed 1n any oneo of claims 13 to 20, containing two or more surface-active agents 1n a total amount of up to 30% by weight. 23. Any one of the herbiddal preparations as claimed 1n claim 13 and substantially as described 1n Example 3 herein. 24. Any one of the herbiddal pceparatlons as claimed 1n claim 13 and substantially as described in Examples 4 and 5 herein. 25. A method of protecting a living plant against weeds, wherein the area 1n the vicinity of a living plant 1s treated with a compound of the general formula I given 1n claim 1, 1n which f*i , R2, R3 and X have the meanings given 1n claim 1. 26. A method as claimed 1n claim 25, wherein the area 1s treated with a compound as claimed 1n claim 2. 27. A method as claimed 1n claim 25, wherein the area 1s treated with the compound claimed 1n any one of claims 3 to 12. 28. A method as claimed 1n claim 25, wherein the area 1s treated with any one of the compounds numbered 1, 3 to 13, 18 to ,20, 22, 24 to 27, 29, 31 to 33 and 35 1n Table I herein. 29. A method as claimed 1n claim 25, wherein the area 1s treated with any one of the compounds numbered 36 to 73 1n Table I herein. .30. , A method as claimed 1n claim 25, wherein the area 1s •t eated with a herbiddal preparation' as .ciafmed 1n any one of claims 13 to 24. 31 ^ A method as claimed 1n any one of claims 25 to 30, wherein 32. A method as claimed 1n any one of claims 25 to 30, wherein two or more compounds of the general formula I are used for the treatment 1n a total amount of approximately 1 to 3 kg per hectare. 33. A method as claimed 1n any one of claims 25 to 32, wherein the treatment 1s carried out at the post-emergence stage of the weeds. 34. A method as claimed 1n claim 25, conducted substantially as described In Example 3 herein. 35. A method as claimed 1n claim 25, conducted substantially as described 1n Example 4 herein. 36. A method of protecting a crop area against weeds, wherein a crop area 1s treated with a compound of the general formula I given 1n claim 1, 1n which , F^* R3.and X have the meanings given 1n claim 1. 37. A method as claimed 1n claim 36, wherein the crop area 1s treated with a compound as claimed 1n claim 2. 38. A method as claimed in claim 36, wherein the crop area 1s treated with the compound claimed 1n any one of claims 3 to 12. 39. A method as claimed in claim 36, wherein the crop area 1s treated with any one of the compounds numbered 1 ,3tto 13, 18 to 20, 22, 24 to 27, 29, 31 to 33 and 35 1n Table I herein. 40. A method as claimed 1n claim 36, wherein the crop area 1s treated with any one of the compounds numbered 36 to 73 In Table I herein. 41. A method as claimed 1n claim 36, wherein the crop area 1s treated with a herblcldal preparation as claimed 1n any one of claims 13 to 24. 42. A method as claimed 1n any one o claims 36 to 41, wherein a single compound of the general formula I 1s used for the treatment in an amount of approximately 1 to 3 kg per hectare. 44276/2 43. A method as claimed in any one of claims 36 to 41 , wherein two or more compounds of the general formula I are used for the treatment In a total amount of approximately 1 to 3 kg per hectare. 44. A method as claimed 1n any one of claims 36 to 43, wherein the treatment 1s carried out at the post-emergence stage of the weeds. 45. A method as claimed in any one of claims 36 to 44, wherein the crop 1s a cotton crop. 46. A method as claimed 1n any one of claims 36 to 44, wherein the crop 1s a carrot, ground-nut or rice crop. 47. A process for the manufacture of a compound of the general formula I 1n which 1*1 represents an ally! group, an unsubstl tuted alkyl group containing 1 to 4 carbon atoms, or a halogen- substituted ethyl group, R2 represents an all 1 group, an unsubstl tuted alkyl group containing 3 to 4 carbon atoms, a halogen- substituted ethyl group, or a cyclohexyl , benzyl or phenylethyl group, represents a methyl or ethyl group, and X represents an oxygen or sulphur atom, wherein - 29 - a compound of the general formula 1n which or an alk carbamoyl 1n which R.j and R| have the meanings given above, or : a compound4 of the general formula 1s with In which R-j and R2 have the meanings given above, 1s catalytlcally hydrogenated to form the corresponding amine which is then reacted 1n the presence of an add- binding agent with a compound of the general formula - X - CO - CI 1n which R3 and X have the meanings given above. 48. A process as claimed 1n claim 47, wherein the reaction with the carbamoyl chloride is carried out in the presence of a tertiary organic base. 49. A process as claimed in claim 47, conducted substantially as described 1n Example J or 2 herein. For the Applicant Wolff, Bregman and Goller