GB1572542A - Herbicidally active diurethanes process for their manufacture and their use - Google Patents

Description

(54) HERBICIDALLY ACTIVE DIURETHANES, PROCESS FOR THEIR MANUFACTURE AND THEIR USE (71) We, SCHERING AKTIENGESELLSCHAFT, a Body Corporate organised according to the laws of Germany, of Berlin and Bergkamen, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statesmen The present invention is concerned with new herbicidally active diurethanes, a process for the manufacture of these compounds and their use.

The selective-herbicidal action of diurethanes has already been known (German Patent Specification No. 1,567,151). A satisfactory herbicidal action against weeds that are especially difficult to combat, for example Amarantus sp., Galium aparine and Poa annua, and a sufficient selectivity towards cereals and potatoes has not hitherto been established for these urethanes.

The problem upon which the present invention is based has therefore been to provide a herbicide which, as compared with the known diurethanes, combines a better action against weeds with a better tolerability towards cereals and potatoes.

This problem has now been solved by the herbicidally active diurethanes of the present invention.

The present invention accordingly provides diurethanes of the general formula

in which R, represents a halogenoalkyl group, R2 represents a phenyl, methylphenyl, halogenophenyl, trifluoromethylphenyl or methoxyphenyl group, and R3 represents an alkyl, alkenyl or alkynyl group, or Rl represents a hydrogen atom or an alkyl, alkenyl, alkynyl or halogenoalkyl group, R2 represents an alkyl, halogenoalkyl, alkenyl, cycloalkyl, alkynylcycloalkyl, benzyl, phenylethyl, phenyl, methylphenyl, ethylphenyl, halogenophenyl, trifluoromethylphenyl or methoxyphenyl group, and R3 represents a methoxyethyl group, and X represents an oxygen or sulphur atom.

The compounds of the present invention are distinguished by a surprisingly high tolerability towards potatoes, cereals, maize and rice.

As weeds difficult to combat and which can be combated by the active compounds of the present invention, there may be mentioned, for example, Amarantus sp. Galium aparine, Poa annua, Echinochloa crus galli, Setaria, Digitaria sangutnalls and A vena jatua.

The most favourable action is exhibited by the new compounds when thay are used in the post-emergence stage. In this connection the herbicidal action extends to many types of plants,for example Stellaria media, Senecio vulgaris, Lamium amplexicaule. Centaurea cyanus, A marantus retroflexus, Chrysanthemum segetum, Ipomea sp. Polygonum lapathifolium, Galium aparine, Setaria italica, Poa annua, Echinocloa crus gaul, Digitaria sanguinalis, Avenafatua and Alopecurus myosuroiaes.

The amount required of the new compounds for combating weeds selectively is approximately 0.5 to 5 kg of active substance per hectare; when two or more compounds of the present invention are used the range of approximately 0.5 to 5 kg refers of course to the total amount applied of these compounds.

The present invention accordingly also provides a herbicidal preparation which comprises a compound of the general formula I, in 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 in the vicinity of a living plant is 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 is treated with a compound of the general formula I.

The present invention further provides a pack which comprises a compound of the general formula I together with instructions for its use as a herbicide.

The halogenalkyl groups represented by R1 and R2 are advantageously bromalkyl or chloralkyl groups, for example a bromethyl or chlorethyl group.

The alkyl, alkenyl and alkynyl groups represented by R1 adantageously contain up to 5 carbon atoms.

The halogenophenyl group represented by R2 is advantageously a chlorophenyl group.

The alkyl and alkenyl groups represented by R2 and the alkyl, alkenyl and alkynyl groups represented by R, advantageously contain up to 4 carbon atoms.

Preferred compounds of the present invention are the following: N - (2 - Bromethyl)- carbanilic acid [3 - (methoxycarbonylamino) - phenyl] ester, N - (2 - Bromethyl) - carbanilic acid [3 - (ethoxycarbonylamino) - phenyl] ester, N - (2 - Bromethyl) - carbanilic acid [3 - (methylthiocarbonylamino) - phenyl ester, N - (2 - Bromethyl) - carbanilic acid [3 - (ethylthiocarbonylamino) - phenyl] ester, N - (2 - Chlorethyl)- carbanilic acid [3 - (methoxycarbonylamino) - phenyl] ester, N - (2 - Chlorethyl) - carbanilic acid [3 - (ethoxycarbonylamino) - phenyl] ester, N - (2 - Chlorethyl) - carbanilic acid [3 - (methylthiocarbonylamino) - phenyl] ester, N - (2 - Chlorethyl) - carbanilic acid [3 - (ethylthiocarbonylamino) - phenyl] ester, N - (2 - Bromethyl) - carbanilic acid [3 - (allyloxycarbonylamino) - phenyl] ester, N - (2 - Chlorethyl) - carbanilic acid [3 - (1 - methylpropynyloxycarbonylamino) phenyl] ester N - (2 - Bromethyl)- carbanilic acid [3 - (2 - propynyloxycarbonylamino) phenyll ester N - (2 - Chiorethyl) - carbanilic acid [3 - (2 - propynyloxycarbonylamino) phenyl] ester N - (2 - Bromethyl) - 2 - methylcarbanilic acid [3 - (methoxycarbonylamino) phenyl] ester N - (2 - Bromethyl) - 3 - chlorocarbanilic acid [3 - (methoxycarbonylamino) phenyl] ester N - (2 - Bromethyl) - 2 - methylcarbanilic acid [3 - (ethoxycarbonylamino) phenyl] ester N - (2 - Brom'ethyl) - 3 - chlorocarbanilic acid [3 - (I - methylethoxycarbonylamino) - phenyl] ester, N - (2 - Bromethyl) - carbanilic acid [3 - (2 - methylpropoxycarbonylamino) phenyl] ester, N - (2 - Bromethyl) - 3 - chlorocarbanilic acid 13 - (2 - methylpropoxycarbonyl- amino) - phenyll ester, N - (2 - Chlorethyl) - 3 - methoxycarbanilic acid 13 - (methoxycarbonylamino) phenyll ester, N - (2 - Chlorethyl) - 3 - trifluoromethylcarbanilic acid 13 - (methoxycarbonyl- amino) - phenyll ester and N - (2 - Bromethyl) - 3 - trifluoromethylcarbanilic acid 13 - (methoxycarbonyl- amino) - phenyl] ester.

The compounds of the present invention may either be used alone, in admixture with one another or with other active substances. If desired, other defoliating, plant protecting or pest combating agents may be added depending on the purpose desired.

The action and speed of action can be increased, for example, by actionincreasing additions, for example organice solvents, wetting agents and oils. This enables the quantities applied of the active substance itself to be reduced.

Advantageously, the active compounds of the general formula I or mixtures containing them are used in the form of herbicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid vehicles or diluents and, if desired, of surface-active agents, for example wetting agents, adherent agents, emulsifying agents and/or dispersing agents.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide, and also mineral oil fractions.

As solid carriers there are suitable, for example, mineral earths, for example tonsil, silica gel, talcum, kaolin, attaclay, limestone and silicic acid, and vegetable products, for example meals.

As surface-active agents there may be mentioned, for example, calcium lignin sulphonate, polyoxyethylene alkyl-phenol ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, formaldehyde condensates, fatty alcohol sulphates and also substituted benzene sulphonic acids and salts thereof.

The total amount of the active compound or compounds of the general formula I in the various herbicidal preparations may vary within wide limits. For example, the preparations may contain approximately 10 to 80% by weight of active compound(s), approximately 90 to 20,ó by weight of liquid or solid carrier and also, if desired, up to 209d by weight of surface-active agent(s).

The active compounds of the present invention may be applied in the usual manner, for example, with water as carrier in quantities of spray liquor of about 100 to 1000 litres per hectare. It is also possible to use the active compounds in the socalled "Low Volume-" and "Ultra-low-Volume-Method ' as well as to apply them in the form of so-cailed microgranules.

The production of these preparations may be carried out in 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 is carried out in practice by the so-called tank-mix method.

The new compounds of the present invention may be prepared by methods known per se for the manufacture of similar compounds, for example by one of the methods defined below.

The present invention accordingly further provides a process for the manufacture of the compounds of the general formula I, wherein (a) a compound of the general formula II

in which R3 and X have the meanings given above, is reacted with an amine of the general formula III

in which Rl and R2 have the meanings given above, in the presence of an acid acceptor, for example with the addition of an excess of the amine of the general formula III or an inorganic base, for example a sodium hydroxide solution, sodium carbonate or potassium carbonate, or a tertiary organic base, for example triethylamine, or (b) a compound of the general formula IV

in which R3 and X have the meanings given above, is reacted in the presence of a tertiary organic base, for example triethylamine or pyridine, or is reacted in the form of an alkali salt thereof with a carbamoyl chloride of the general formula V

in which Rl. and R2 have the meanings given above, each reaction being carried out at a temperature within the range of from 0 to 1000 C, or, if desired, when Rl represents a hydrogen atom, is reacted in the presence of a catalyst, advantageously an organic base, with an isocyanate of the general formula VI R2-N=C=O (VI), in which R2 has the meaning given above, or (C) a nitro compound of the general formula VII

in which R, and R2 have the meanings given above (provided that they do not represent groups that are capable of being easily hydrogenated), is catalytically hydrogenated, for example by means of nickel in methanol, to form the corresponding amine which is then reacted in the presence of an acid acceptor, for example an inorganic base, for example a sodium hydroxide solution, sodium carbonate or potassium carbonate, or a tertiary organic base, for example triethylamine, with a compound of the general formula VIII Cl-CO-X-R3 (VIII), in which R3 and X have the meanings given above.

The starting compounds for the process of the present invention are known or may be prepared by methods known per se.

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

TABLE I Compound of the invention Physical constant 1. N-(2-Chlorethyl)-carbanilic acid [3-(methoxycarbonylamino)-phenyll ester M.P.: 98-100 C 2. N-(2-Bromethyl)-carbanilic acid [3-(methoxycarbonylamino)-phenyll ester M.p.: 88-900C 3. N-(2-Bromethyl)-carbanilic acid [3-(ethoxycarbonylamino)-phenyll ester M.p: 80-82 C 4. N-(2-Bromethyl)-carbanilic acid [3-(methylthiocarbonylamino)-phenyl] ester M.p.: 118-120 C 5. N-(2-Bromethyl)-carbanilic acid [3-(ethylthiocarbonylamino)-phenyll ester M.p.: 78-800C 6. N-(2-Chlorethyl)-carbanilic acid [3-(ethoxycarbonylamino)-phenyl] ester M.p.: 71-73 C 7. N-(2-Chlorethyl)-carbanilic acid [3-(methylthiocarboriylamino)-phenyl] ester M.p.: 122-124 C 8. N-(2-Chlorethyl)-carbanilic acid [3-(ethylthiocarbonylamino)-phenyl] ester M.p.: 75-76 C 9.N-(2-Bromethyl)-carbanilic acid [3-(allyloxycarbonylamino)-phenyl] ester M.p.: 88 I 0C 10. N-(2-Chlorethyl)-carbanilic acid [3-(1-methyl- propynyloxycarbonylamino)-phenyl] ester M.p.: 96-980C II. N-(2-Bromethyl)-carbanilic acid [3-(2-propynyl oxycarbonylamino)-phenyll ester M.p.: 105-106 C 12. N-(2-Chlorethyl)-carbanilic acid [3 (2-propynyloxycarbonylamino)-phenyl] ester M.p.: 121-123 C 13. N-(2-Bromethyl)-3-chlorocarbanilic acid [3 (1-methylethoxycarbonylamino)-phenyl] ester M.p.: 102-104 C 14. N-(2-B romethyl)-2-methylcarbanilic acid [3-(methoxycarbonylamino)-phenyl] ester M.p.: 108-110 C 15. N-(2-Bromethyl)-2-methylcarbanilic acid [3-(ethoxycarbonylamino)-phenyl] ester M.p.: 104-106 C 16.N-(2-Bromethyl)-3-chlorocarbanilic acid [3-(methosycarbonylamino)-phenyl] ester M.p.: 100-102 C 17. Carbanilic acid [3-(2-methoxyethoxy carbonylamino)-phenyl] ester M.p.: 117-118 C 18. N-Methylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 70-72 C 19. N-Ethylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 82-84 C 20. N-Butylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester n20 = 1.5502 TABLE I - Continued Compound of the invention Physical constant 21. N-Ethyl-2-methylcarbanilic acid [3-(2 methoxyethoxycarbonylamino)-phenyl] ester M.p.: 117-119 C 22. N-Ethyl-3-methylcarbanilic acid [3-(2 methoxyethoxycarbonylamino)-phenyl] ester M.p.: 89-91 C 23.N-Ethyl-4-methylcarbanilic acid [3-(2 methoxyethoxycarbonylamino)-phenyl] ester M .p.:96-970 C 24. 3-Methylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 89-900C 25. 3-Chlorocarbanilic acid [3-(2-methoxy .ethoxycarbonylamino)-phenyl] ester Mp.: 87-88 C 26. N-Allylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 66-68 C 27. N,N-Dimethylcarbamic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 113-115 C 28. N,N-Diethyiethyicarbamic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 69-71 C 29. N,N-Bis-(2-chlorethyl)-carbamic acid [3-(2 methoxyethoxycarbonylamino)-phenyl] ester M.p.: 79-81 C 30. N-Ethyl-N-butylcarbamic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester nD20 = 1.5164 31.N,N-Dipropylcarbamic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester n2g= 1.5157 32. N,N-Dibutylcarbamic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester nD20 = 1.5098 33. N-Butylcarbamic acid [3-(2-methoxy ethoxycarbonylamino)-phenyll ester M .p.:84-85 C 34. N-Propyl-3-methoxycarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 86-87 C 35. N-Methyl-3-methylcarbanilic acid [3-(2-methoxy- ethoxycarbonylamino)-phenyl] ester n2g= 1.5620 36. N-Cyclohexyl-N-propylcarbamic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 86-87 C 37. N-(l -Ethynylcyclohexyl)-carbamic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 128-130 C 38. N.N-Diallylcarbamic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester nD20 = 1.5302 39. N-Methyl-N-(1-methyl-2-propynyl)-carbamic acid [3-(2-methoxyethoxycarbonylamino) phenyl] ester nD20 = 1.5164 40. 2-Methyl-N-propylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 63-67 C TABLE I - Continued Compound of the invention Physical constant 41. 4-Methyl-N-propylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester nD20 = 1.5273 42. N,N-Bis-(2-bromethyl)-carbamic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 81 -840C 43. N-Pentylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyll ester n2,0 1.5166 44.N.N-Bis-(1-chloro-1-methylethyl) carbamic acid [3-(2-methoxyethoxy carbonylamino)-phenyl] ester n2g= 1.5136 45. N-Butyl-3-methoxycarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester nD20 = 1.5349 46. N-Butyl-2-methoxycarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester nD20 = 1.5290 47. N-Butyl-4-methylcarbanilic acid [3-(2-methoxy- = 1.5340 ethoxycarbonylamino)-phenyl] ester 48. N-isobutyl-2-methylcarbanilic acid [3-(2 methoxyethoxycarbonylamino)-phenyl] ester nD20 = 1.5374 49. N-Isobutyl-3-methylcarbanilic acid [3-(2 methoxyethoxycarbonylamino)-phenyl] ester n2D = I .5379 50. N-Isobutyl-4-methylcarbanilic acid [3-(2 methoxyethoxycarbonylamino)-phenyl] ester nD20 = 1.5372 51.N-Isobutylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester n2g= 1.5346 52. 2-Chloro-N-methylcarbanilic acid [3-(2-methoxy- M.p.: 104-106 C ethoxycarbonylamino)-phenyl] ester 53. 3-Chloro-N-methylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester M.p.: 62-64 C 54. 4-Chloro-N-methylcarbanilic acid [3-(2-methoxy ethoxycarbonylamino)-phenyl] ester n2g= 1.5586 55. N-(2-Chlorethyl)-carbanilic acid [3-(2-methyl propoxycarbonylamino)-phenyl] ester M.p.: 95-96 C 56. N-(2-Bromethyl)-2-methylcarbanilic acid [3-(1 methylethoxycarbonylamino)-phenyl] ester M.p.: 126-128 C 57. N-(2-Chlorethyl)-3-chlorocarbanilic acid [3-(2-methoxycarbonylamino)-phenyl] ester M.p.: 97-99 C 58.N-(2-Bromethyl)-4-methylcarbanilic acid [3-(methoxycarbonylamino)-phenyl] ester M.p.: 101-103 C 59. N-(2-B romethyl)-3-chlorocarbanilic acid [3-(1 methylethoxycarbonylamino)-phenyl] ester M.p.: 102-104 C 60. N-('-B romethyl)-2-methylcarbanilic acid [3-(methoxycarbonylamino)-phenyl] ester M.p.: 108-I l00C TABLE I - Continued Compound of the invention Physical constant 61. N-(2-Bromethyl)-2-methylcarbanilic acid [3-(ethoxycarbonylamino)-phenyl] ester M.p.: 104-106 C 62. N-(2-Bromethyl)-3-chlorocarbanilic acid [3-(methoxycarbonylamino)-phenyl] ester M.p: 100-102 C 63. N-(2-Bromethyl)-carbanilic acid [3-(2-methyl propoxycarbonylamino)-phenyl] ester M.p.: 82--83"C 64.N-(2-Bromethyl)-3-chlorocarbanilic acid [3-(2 methylpropoxycarbonylamino)-phenyl] ester M.p.: 60630C 65. N-(2-Chlorethyl)-3-chlorocarbanilic acid [3-(2-methoxycarbonylamino)-phenyl] ester M.p.: 97--99"C 66. N-(2-Bromethyl)-4-methylcarbanilic acid [3-(2-methoxycarbonylamino)-phenyl] ester M.p.: 101-103 C 67.N-(2-Bromethyl)-3-chlorocarbanilic acid [3-(methylthiocarbonylamino)-phenyl] ester M.p.: 152-154 C 68. N-(2-Bromethyl)-2-methylcarbanilic acid [3-(methylthiocarbonylamino)-phenyl] ester M.p.: 1 120C 69. 3-Chloro-N-(2-chlorethyl)-carbanilic acid [3-(ethoxycarbonylamino)-phenyl] ester M.p.: 89--91"C .70. 3-Chloro-N-(2-chlorethyl)-carbanilic acid [3-(1 methylethoxycarbonylamino)-phenyl] ester M.p.: 103-105 C 71. N-(2-Bromethyl)-4-methylcarbanilic acid [3-(ethoxycarbonylamino)-phenyl] ester M.p.: 88-900C 72. 3-Chloro-N-(2-chlorethyl)-carbanilic acid [3-(methylthiocarbonylamino)-phenyl] ester M.p.: 140-142 C 73.N-(2-Chloroethyl)-carbanilic acid [3-(1-methyl- 2-propenyloxycarbonylamino)-phenyl] ester M.p.: 82-84 C 74. 3-Chloro-N-(2-chlorethyl)-carbanilic acid [3-(2 methylpropoxycarbonylamino)-phenyl] ester nD20 = 1.5514 75. N-(2-Bromethyl)-3-trifluoromethylcarbanilic acid [3-(ethoxycarbonylamino)-phenyl] ester M.p.: 73-75 C 76. N-(2-Bromethyl)-4-methylcarbanilic acid [3-(1 methylethoxycarbonylamino)-phenyl] ester M.p.: 79-81 C 77. N-(2-Bromethyl)-3-trifluoromethylcarbanilic acid [3-(methoxycarbonylamino)-phenyl] ester M.p.:86-880C 78 N-(2-Bromethyl)-3-trifluoromethylcarbanilic acid [3-(methylthiocarbonylamino)-phenyl] ester M.p.: 125-126 C 79.N-(2-Bromethyl)-3-trifluoromethyl carbanilic acid [3-(1-methylethoxy carbonylamino)-phenyl] ester M.p.: 85-870C 80. N-(2-Bromethyl)-3-methylcarbanilic acid [3-(methoxycarbonylamino)-phenyl] ester M.p.: 106-108 C TABLE I - Continued Compound of the invention Physical constant 81. N-(2-Bromethyl)-4-chlorocarbanilic acid [3-(methoxycarbonylamino)-phenyl] ester M.p.:99-101 C 82. N-(2-Bromethyl)-3-methylcarbanilic acid [3-(ethoxycarbonylamino)-phenyl] ester M.p.: 91--93"C 83. N-(2-Bromethyl)-4-chlorocarbanilic acid [3-(ethoxycarbonylamino)-phenyl] ester M.p.: 80--820C 84. N-(2-Bromethyl)-4-chlorocarbanilic acid [3-(1 methylethoxycarbonylamino)-phenyl] ester M.p.: 83--85"C 85.N-(2-Bromethyl)-4-chlorocarbanilic acid [3-(allyloxycarbonylamino)-phenyl] ester M.p.: 9W92 C 86. N-(2-Bromethyl)-3-methylcarbanilic acid [3-(1 methylethoxycarbonylamino)-phenyl] ester M.p.: 127-129 C 87. N-(2-Bromethyl)-3-chlorocarbanilic acid [3-(2 propynyloxycarbonylamino)-phenyl] ester M.p: 115-117 C 88. N-(2-Chlorethyl)-3-methoxycarbanilic acid [3-(methoxycarbonylamino)-phenyl] ester n2g= 1.5289 89. N-(2-Chlorethyl)-3-trifluoromethylcarbanilic acid [3-(methoxycarbonylamino)-phenyl] ester n2D= 1.5345 These compounds are soluble in acetone, cyclohexanone, ethyl acetate, isophorone, ether, tetrahydrofuran and dimethylformamide and are practically insoluble in water and light gasoline.

The following Examples illustrate the invention. Example I illustrates the process of the present invention for the manufacture of the compounds of the general formula I and Example 2 illustrates the herbicidal activity of the compounds of the general formula I.

Example 1.

N-(2-Chlorethyl)-carbanilic acid [3-(methoxycarbonylamino)-phenyll ester.

Into a solution of 23 grams of N-(2-chlorethyl)-aniline hydrochloride in 50 ml of water and 50 ml of ethyl acetate were introduced dropwise, while stirring, a solution of 22.9 grams of chloroformic acid 3 - methoxycarbonylamino-phenyl ester in 50 ml of ethyl acetate and simultaneously a solution of 30.5 grams of potassium carbonate in 150 ml of water at 10 to 15 C. The mixture was further stirred for 30 minutes at 15 C, and then the organic phase was separated and diluted with about 100 ml of ethyl acetate, and washed at 0 C in succession with dilute sodium hydroxide solution, water, dilute hydrochloric acid and water. After being dried with magnesium sulphate, the mixture was evaporated under reduced pressure. The initially oily residue so obtained soon crystallized throughout and was recrystallized from ethyl acetate/pentane. Yield: 30 grams = 86% of the theoretical yield. Melting point: 98--1000C.

The other compounds listed in Table I above may be prepared in an analogous manner.

Example 2.

In a series of tests carried out in a greenhouse the plants listed in the Table below were treated at the post-emergence stage with preparations used in such amounts that 3 kg of the active compound being tested were applied per hectare.

As the agents used for comparison there were used the known compounds (1) 3-Methoxycarbonylaminophenyl-N-(3-methylphenyl)-carbamate and (2) 2,4-Dichloro-phenoxyacetic acid.

The plants were in the young stage: The active compounds being tested were applied in the form of aqueous emulsions using quantities of liquid corresponding to 500 litres per hectare. After 14 days the results of the treatment were evaluated and expressed by a numerical scale extending from 0 to 10, the value 0 representing total destruction and the value 10 representing no damage.

The values listed in the following Table illustrate the good tolerability towards crops of the compounds of the present invention, whereas the known agents used for comparison caused considerable damage to the crop plants.

ur snAn3atlolp I I I In. N f auan p N I I Cy C\1 'S B!AD3!8a O m I O m N 8 o]Y30lllli3I O C) O 0 0 '1) 110d O m v, rc, m O 7 D!1DlaS o o o o o o 't tUnf7 O 0 O N O ' urnuogClo 'd nautodl o o o s urnuraylus.iry3 o o o o o 1 SnylUDIDU( C n N DamDJua > ) O O O O o O Compounds ofthe invention O 0 n O N-(2-B o?Jaus5 acid c o o o o o 'ur tAtllldrS 3 10 10 10 10 10 0 0 0 0 0 0 0 0 0 0 0 0 0 I 2 N-(2-Bromethyl)-carbanilic acid aalM ester 3 10 10 10 10 10 o o o o o 0 0 0 0 0 3 0 3 2 Aape E: El acid o o o sarlM ester 3 8 10 10 | X az!C 4: 4: acid Q\ I SaoEod ester 3 10 o 10 10 10 O o 0 0 0 0 0 0 2 0 3 0 0 - ey acid [3-(methoxy asueXsqns apt Jo 9 - gy m m m m m m N-(2-Chlorethyl)-carbanilic acid [3 o o c $ c c c ; -r r C n u r O r rt c Y S ct O cd O Y C 3 . ra Q ~ * ~ C Q t) C D = D E D 0* D D C D C e C zD;;O .S d > , 5C ; C r C C g C C > C C + C D C .N D D9 o eS es D t1 Ú z < D z o) z S z S z Y Z O

ul smnJad /V ss DU9A V I I I I I t S Is,tlD a t ~ N o o O 30 poly00g??t9S N m N t t7 d e I I I N ? D?2t71as O o O O O o 'D Ul.llDD o 0 zunuof;;fl d o o o 'd aurodl o o o o t o C S N C Compounds ofthe invention s urnluayluasniy3 o o o o acid o 'A SnYJU13A17Ulp O 3 o 10 s O 10 0 0 0 0 0 'J I7amolua33 o o o o o o D Uln?tUD7 ester o o 10 10 10 10 O O O 0 0 0 0 0 0 0 - 5 1 - n otauag o o o o acid 6 uc Illrt7lldlS 3 10 10 10 10 10 0 0 0 0 0 0 0 0 1 0 - 2 2 - N-(2-Chlorethyl)-carbanilic acid t3-(l -methyl a3!I ester 3 10 10 10 10 KallPS I O O O acid E3 WaM | ester 3 o 10 9 0 az!tl o o o o o o saopod ester 3 - 10 9 10 10 0 2 0 0 0 0 0 0 0 0 3 - 0 4 aoueXsqns aA!l3 J M < e n 3 &commat; CO ç Ç Q Yç = Yc s ec W .çe So ec c C D A ~O m n v .9 D gN w9 C S S Y g rC C wC Zt S ÚS C C rÇ 0 0 0 C o0 0 o X Ço O O C E C D D D D = C ; D S D

uu s-mnsad /V S Du9A F s t7!1Dl!3!a N t t 3 J D0/yJou!tt)7 n t?Og &verbar; N o '! aralaS o o o I o o k nmle I C J usnuofflod o o o i o o C C. C S . . C C C C C Dauuodl o N | o o o - C C o S . - C C s of the invention S o o o I o o 1 SnYUtlAt7UIP O 0 0 I acid '3 DaAnoiua3 ester o 10 o 10 10 10 O o O 0 0 0 0 0 - 0 5 - 2 - N-(2-B UUXtUlD7 O O C O O acid A O?J9UaS | | ester 3 10 o o o N(2BromoetIiyl)3-chlorocarbanilic acid uu D!12711alS o o 10 o 10 10 10 I o o 0 0 0 2 0 - 0 - - 4 - Carbanilic acid 3 A311B ester 3 o O 10 10 10 o O O m N-M ethylcarbanilic acid o o o o oo azreyV ester 3 10 10 10 o o o azIey oo acid 13-(2-methoxy saolzXod ester 3 10 10 8 8 10 o o o 0 0 0 0 0 0 0 0 3 - - BIO lad asuelsqns aA!loe J BD1 m t > w ^s a Y t > d S X D C D C = E > c > c > c C S = S O 5 Q > C: :1 C 7 C S eS C ' C ~ C C Y t) W c E > ' E E c o D Q D D o m ms m c < > s > > 9 C e D O 2 sQ > , sQ U Zm Z m Z ' Ú Z 0D Z O

uu snmJadolv S DUSA V s o?lt71!X!a XOJ D0IYD0U!YJX eD 270d ! D?lx7las q C uumlDD C m . C) '-'C C C C S 0 uunuofXlod .'-' o o m o cs o C C) C C S N C C 'd Daurodl o invention t e o N-Butylcarbanilic acid o o I r snyutiraurp ester o 10 10 10 10 10 O O I O J saml7lua,,) o N o o tlarnDlud3 o m o o o 'S7 uun?uuD7 o o ester o o e o o o N-Ethyl-3-methylcarbanilic acid t3-(2-methoxy on ester 3 o 10 10 10 I I ~ o o I I o I 'Ul DJJD//a}S O O O O acid o a3!I ester o o 10 o 10 10 O o O 0 0 0 2 0 1 0 A^3llPg O o O O acid o 1BaylM ester 3 10 10 10 10 10 0 0 0 0 - - 1 2 4 XB3U, O o acid O o azleyg ester 3 10 10 10 o o o o o saoezod o o o o o Bl IOd asusxsqns aA!lrJB Jo S31 e ;Y xz x > 8 x o o w Q o x O ,C ra ra a ra w ra w a 3c '5 c; c m ~s ~ O,4 v > ~ o 5 > o n o n o U O c) O C Q C ; C ; C W C Y C Y C .~ Q C ~ C Q C Q C ~ C ~ C C ~ s s s = C r ~ C z W > H > I > O ed C ç C o C s) C s C D C ra wD 'C C O C O l~ O W O O = X c X s X < X o X xz Q m ;;s r;; 6;S Ss Us U Z O Z Q Z O Z o

U S uu smnsadolv w / DUaA V s 17?lt7l!3!d m XJ nolysOU??.7 t ! I m D DOg I DllDJ S O t7 UUXllDD O L: uunuofSl d O I m O C C U t7auwodl I m o w o 0 - C C o s N s uunulayluDstly,) o N-Allylcarbanilic acid [3-(2-methoxy- ','-'S I o C C , > ~ '3 t7arntl3ua3 ester 3 8 10 9 9 10 0 0 0 0 0 0 0 0 0 0 3 4 5 - 4 N,N-Dimethylcarbamic acid l3-(2-methoxy D UU7t?lUD7 O | ester o o 10 10 10 10 N,N-Diethylcarbamic acid I I UU D?lD//d1S ester I O 10 m o m aalX o o o o acid E:: AalE ester 3 10 10 10 10 10 b o o o o O N-Ethyl-N-butylcarbamic acid [3-(2-methoxy waqNt ester 3 10 10 10 10 o o ~ o azleyg o o o o acid o Sa010d ester 3 O0 10 10 o o o o o eq lad aouelsqns aA!;ae*po Ba . , s > xz X > o t1 a eO X X t) ,C gL) Q Q Q O N o cC Q a eS r ç a Y tÇ Z ra 9 a Ç > > t ~ > , C o r > h m~ C C r C ~C Q C r C *3o ~s ,Ys ts ; W s ) = C ir) co X,c C s > , .C Cct.co ,C < ;Ç n C oC lÇ 9 wC r C 5 > C Q C S OX = C > } C w 3xz ;xh x > 8 m; s xz x > 8 Eo < , Z s Z s Z ,O > c Z-s U Z O Z^s Z O ZE Z O Z O

uu snmoadolv SDuaY S D?lD}?3?a I I O &verbar; m t J-J 270l?JOU?YJ,] &verbar; &verbar; ~ O D DOg U ! D!lS7waS l l es o os w 'D urn I I I I I s uunuo3Sl d I es 0 0 0 'd Daurodl o o o C' C C C U C C C o S . V V C C) C "-' C C C s. uunuwaylUrsSlyJ t" ~ o es N C,C '1 S8ylUDlDUUt ^. O O acid v, ;7 raxnnIua,) I ester o o ~ N-Butylcarbamic acid o cr {l o};7auaS ester I 8 I o I I N-Propyl-3-methoxycarbanilic acid [3-(2-methoxy 'ur tnAalla3S ester 3 o 10 10 10 10 O I a3!I O Q El acid or IcaIlea ester O O 9 8 8 10 O 0 0 0 0 0 0 0 1 0 - 0 - - Baq, 0 o o acid o o az!sW ester 3 10 10 10 1 2 0 5 2 0 0 - 2 - - 5 - saolelod I -Ethynylcyclohexyl)-carbamic acid oo I X ey iad aousXsqns aAIXJB s0 st &verbar; xz xz z s 4. o N E o Q x ev r L) ' Y 3o na = eS ,C Y s C s Y s t) s > - = r 3 > = X v 3 X o s e YE CEd s < ^ YE , YE EY ,wo < c c c c É c > > c O c ra > , O ~O O &verbar; < ~; X > ) S So cX ,cd U Z O Z v Z s Z u Z O Z o

U uu smnnadolv [S7ua.zV s t7!li7l!3!a &verbar; i I I N BJ t7o/tto0a?YJ7 | ~ i i I o 'D t70d 7 9razzs . C)' 'D C)' C) C U C C'' C V C C C 0 V ''-' , C C C Z C C ' C 'V ' C' C C 'V J Uln1108XIOd O O O O I m d Daurodl o o "-' 'V v 'V C "-'C C '-' 'V C N,N-Diallylcarbamic I o t I o '1 SIIYUDIDUlp ester 3 - 10 10 10 10 0 - 0 2 3 - 0 0 - 3 N- M ethyl-N-( I -methyl-2-propynyl)-carbamic acid DamUlua) o 9 N I O 17 urn!uroir o o 9 0 - 0 1 i O 0 0 - 0 - 1 1 - 'A o?oauaS [ i i i | acid [3-(2 'UU D!lD/]alS ester 3 8 10 10 10 10 O I O 2 3 3 4 0 - 5 4-M ethyl-N-propylcarbanilic acid 13-(2-methoxy a3!tr ester 3 10 10 10 ~ ~ ~ ~ ÁalJeXd o is-(2-bromethyl)-carbamic acid l3-(2 lsaq ester 3 10 10 10 10 10 azleyV o o o o acid o saolelod ester I 10 10 I 9 00 o o o eq lad aaUB;SqnS aAIlae Jo BM xb .E cs ,J ZD s o E m C ^ O D ,C Q E O c > cx r v > c X e~ c E c m c so ce Q c .O c Y c es c . r c ;; > , c CEd c c cd C ,c c E-E E; E E C Q ~ ,c X c Q z X > Q 5 - C 2 C , ó) &verbar; C U z z Y F t X Z; Z O

V U Du hnJnz7ado/v SJ t7uatl V s t7?1Dl!X!a &commat;3 J POIYJOU!YJO7 &verbar; A, O D --'-' . nOd V 27!1DI9S . . C C' C C) C U CC 'V C' -"C' C a urnrlo I I I I 0 V C C C ,'-' C' C uunuoEl d t I o o | o d ofthe invention I I 'V'-' C 'V '-' C "-' "-' C I 'V C s tunuuaywursSly,) I I Aq I N o acid snyaumt7uuV I ", tAQ O I ~ phenyl] ester 3 - 10 10 10 10 10 - - 5 - - - - 4 - - - - 3 - 7 DamDJU9k) j | | acid [3-(2-methoxy D urn!uut77 Q o ester 3 10 10 10 10 10 3 - N N-B utyl-2-methylcarbanilic acid I j I I v, UU 17?1D]lalS I m 10 10 10 o N-Butyl-4-methyicarbanilic acid [3-(2-methoxy as!I ester 3 10 10 10 10 10 narJt3 8 53 41 3 acid X l?aYnn ester 3 10 10 o o o o aZ!Byç o o o o acid I saoXsXod ester 3 8 o 9 8 9 1 5 2 I I 0 - 0 - 1 - 05 Bq J aJUB}SqllS JA!}JB JO Xz ' I 0 > 0 > D.~ f9 ,E ,E c,s > , &verbar; > r rn a r ca X z c > Y t O o C ev C Q C E D Y Ô D Ô D c > , C X c w o c o c O c c cz Ec > , O C Q IC C D sC O o1 0 D C I f O &verbar; ~ c ^ x x x o O o x U Z Y ^o Z O Z s) Z Q Z u Z o

uu snm7ado/V i m i I n S Du9A F S D?lD}?3!a \^l O N O O sz RJ DOIYJ U?Y)7 ~ o N O ~ D DOd U a ? D!lD}Ss O O O O V UUttilD;9. C) 7 UlnUOBilIO O O I 'V C U ' C V 'V C' C C 0 V C C d aaurodl C o 'V o C' m C s urnuraylut7slCly3 o I "-"V o o 'V'-' o "-"C o "-''-' "-' C'0 N-Isobutyl-4-methylcarbanilic acid O O 7 DalD;;tUR, ester o 10 o 10 10 10 m o O O N-lsobutylcarbanilic acid 13-(2-methoxy 'D UlnlUlt77 ester 3 - - O O 10 0 N 0 0 0 n o3auaS I I I I acid [3-(2-methoxy ur rtirolaiS ester o I o o o 10 - - 2 5 3 - 2 2 - a3!E acid 6aI"B8 ester 3 - - - - 10 0 - 0 0 0 0 0 1 - 0 - 0 0 - 4-Chloro-N-methylcarbanilic acid l3-(2-methoxy aZ!ByÇ ester 00 1 1 1 00 b az!t?y oo I I I oo acid [3-(2-methyl saoxszod ester 3 10 7 10 8 10 I 1 - I I I I Bq J3d m asuslsqnS JA!}OB S0 Ba z O X X O E , E E E É , ev ,E ev 8 t e i O x O x x x x , o

V U ssnsadolv J nua^V S D!JD}?2 O]ç70U!p, I o o .D flOd I u N I I 7 artiiag I o o - - o D tUNZlDD I o U C' C J UNUo3{(/og o o o o t O d taurodl I o o ~ o 's urnurayluosllry3 o o o 'V'-' o co "'-'C o C 'A SnYIUtllDUIP O 0 0 0 O O 7 DamD14a,) c9 0 0 ester 3 10 10 10 10 10 3 o N-(2-Chlorethyl)-3-chlorocarbanilic acid D uun?uun7 ester o 10 o o 6 o A 0?7auas t O O acid ur t?!lalldlS ester 3 10 6 8 9 8 0 0 0 0 0 0 1 0 - 0 2 0 0 - as!E t l acid [3-(2-methyl ÁallB ester o a, a, O O o Aape 8 o o acid o D XB2qM ester O 10 oo 10 O 3 8 1 viz aZ!Byg o > W^ 00 acid S30}B}Od ester 3 O s l l l Bq lad 3::)UB],S4nS 3A!;OB JO iibl U ' c l o e E

V U uu snJn7adolV DuaAv t S D?JD}.ss3?a J-J DO/yJOU?y7, D t70g ? D?JDI9S ~ D UUNZlD;f) C). I o urnuoB1Clod U C C 'd DauvodI [ > > x o - N V C C) C 'V ' C' C 'V s zunuwaylursSlyD o o o "-'C' o o 1 snyluDlD2V O O O O acid 7 DamDJuaD tlarntl3up3 o o 'r, urnluroir acid o {t 0?7avaS o o - 10 10 10 m o N-(2-Bromethyl)-2-methylcarbanilic acid 'ur ttAola3S ester o o 8 10 10 o 0 2 0 0 0 0 7 10 - 0 aII I I I 1 acid Á3llBa ester 3 - 10 10 10 o o 5 x 0 0 0 8 10 - 1 ]B3qjLi X O O O acid az!EJIV ester 3 - 7 8 8 - 0 0 0 0 0 0 0 0 - 0 - - - - - saolelod Bq lad 2OuBlSqNs JAll:)B 30 3 Q > C V ~ C C 0 0 C n S m e c E O E = E o E > E x Ú ^ F es F t 4 E

IU SiNJ9d0l F J t7ua^V s t7?2171?3!a o o o o o BJ DOlySo4!yJv ~ o ~ G U 17 170g 7 D?1DI9S o o o o C) C 17 tU4.llDD I m I V C C " V "-'C) C 'V tunuoXXl d o o o o N o d osusod/ C s umuvaylut7gily,,) acid o o 'A SIIYIUDADUIP ester 3 10 10 8 8 8 0 0 0 0 0 N(2Bromethyl)-2-methyl-carbaniIic acid J Dal8DIUaJ ester 3 10 10 8 10 9 0 0 0 0 0 'r) utn!uct7? o o o o acid 'n 413auaS o o 10 10 10 10 10 o o o o 0 0 0 0 1 0 - 1 0 - UU D?lD/]alS o o o o o o a31I ester 3 10 10 10 10 10 o o o ce N-(2-B romethyl)-4-methylcarbanilic acid ÁXllB ester 3 10 10 10 10 10 x o o o o IfaqM oc oo El acid a aZ!ByV ester 3 10 10 10 o o o o o saolelod o o o o o o Bq lad aDuBaSqnS JA[lOB S0 BM n m Q ~ Q ~ C D C A Y C C: C D C C%; C c o ~ ;E E , o ; > E > 8 c c c C E C 4 F w E É C E X S = S O N D CS X ZD ( > l D E = z =' E s O s E N o s s

uz snms9dolv [l7uaAV I I m I o s n?l17l?X?a ^ N ~ ~ 3 J DOlyJou?yJg D 170g ? D?1171aS w N o o U D lUNllDO l l 0 c9 0 J urnuo8njod o o o o d 17aulodl o o o C) C C' C 'V C k' us uunuvaylul7sSly,) o o '-"-' o o o of SnylUDlDUUt O O '- '-"'V O O O 0 Compounds "V C "V "-' C '-'e "V C J D9ml71U9,) O acid o O O tl utnlurt7ir ester o 10 10 10 10 10 O O O 0 0 0 0 0 - 4 - - 3 - A o!J9U9S O o acid O O UU D.tl1711alS ester o 10 10 10 10 10 O O O I 0 0 0 0 - 2 - - 2 - N-(2-B romethyl)-3-trifluoromethylcarbanilic acid as!I O 1Cape 8 0- acid O O O ?aylM S! 0 N-(2- o romethyl )-3-trifluoromethylcarbanilic acid saoplod ooooo Bq lad e n avuslsqns aA!1os Jo 3 r r S, s m C : C gL} ;Y cJ,c Y ,c O~ C r C C ~ C C > (S CL Cn C O C Y r C o > o c ' U 50 > m, +, m, Q m E > ) E N s N E n~ U Zo Zm Z ~ Z n

V uu ss?mJ9dolF S DUaAF &verbar; m N m s D!iDI!X!a t g J D < OIY70U!Y7 D UOg t st | O ! D!1DI9S ~ t D um?lDD C' C 'V t C C" C'' C J uunuofXl d "o o o o S C V "-' -" C C C C' C "V 'd aautodl o Dauuodl t o CC' bi) V s umuwaylunsS o o invention 1 snyiuaiautb o o I o acid J t7amDlua) ester o 10 10 10 10 10 t o O N-(2-Bromethyl)-3-trifluoromethyl D uun?lun7 o o o o o A o?Javas o 10 10 o 10 10 o O 0 0 0 0 0 0' 0 4 4 - 4 5 N-(2-Bromethyl)-3-methylcarbanilic acid ur a!At7lalS ester o 10 o 10 - - 1 2 0 4 - 0 4 0 5 0 - 5 - 2 4 a3!M I > acid Aapea I m m lB3qNç o X o oc oo az!ely ester 3 10 10 10 o X X o saolelod o o o o o Bq lad m m n n avuslsqns aA!XDs Jo Ba r ct u ~ d.} r r o r; 77 s o. U Ê o Ê o Ê > o m o m c C m Q m o =,c z c! . Y O e e H u zn ze Y ze ze ze

uu ssnsadolv > DuaA V s D?lDl?ss?a U a '8'3 DOY30U!Y3 I I I I m D DOg o C) ? D?1DIaS C' | I ~ 6 U C 'V C C '-" C V C C C 'V C C ' C C) C C) C C C ' C C 'V S N V V "-' o o m "-' "-' o m Compoundsoftheinvention O o "-',C' o C'C o o d taourodl o o o o acid s utnutayJuos,Cly3 o o 10 10 10 10 10 o o o o 0 0 0 0 0 0 0 - - - '1 snylusls7uuV o o o o acid o 7 D91nD}U7J ester o 0 61 10 10 10 0 0 o o N-(2-B romethyl)4-chlorocarbanilic acid a utniutair ester o 10 10 10 10 10 O s O O 0 0 0 0 3 n oauaS o o o .o acid 'UX D?lD7/a}S ester o 10 10 10 10 10 o o O O a3!I x ÁXllB a o o o o I x aylM 3 8 O O 8 0 '0 I X az!ey acid o o 10 o 8 I 5 1 saolsXod o o o o X X 'I?rI lad asuslsqnS aA!lOB S0 BM O ' uz c e; ' c CC i 2 E s E X E U &verbar; O r ' C c Ú 9 C e S r S m 0 0

Claims (81)

WHAT WE CLAIM IS:

1. A compound of the general formula I

in which R, represents a halogenoalkyl group, R2 represents a phenyl, methylphenyl, halogenophenyl, trifluoromethylphenyl or methoxyphenyl group, and R3 represents an alkyl, alkenyl or alkynyl group, or R, represents a hydrogen atom or an alkyl, alkenyl, alkynyl or halogenoalkyl group, R2 represents an alkyl, halogenoalkyl, alkenyl, cycloalkyl, alkynylcycloalkyl, benzyl, phenylethyl, phenyl, methylphenyl, ethylphenyl, halogenophenyl, trifluoromethylphenyl or methoxyphenyl group, and R3 represents a methoxyethyl group, and X represents an oxygen or sulphur atom.

2. A compound as claimed in claim 1, wherein R1 represents a bromalkyl or chloralkyl group.

3. A compound as claimed in claim 2, wherein R, represents a bromethyl or chlorethyl group.

4. A compound as claimed in any one of claims 1 to 3, wherein R2 represents a chlorophenyl group.

5. A compound as claimed in any one of claims 1 to 4, wherein the alkyl, alkenyl or alkynyl group represented by R3 contains up to 4 carbon atoms.

6. A compound as claimed in claim 1 or 4, wherein the alkyl, alkenyl or alkynyl group represented by R1 contains up to 5 carbon atoms.

7. A compound as claimed in any one of claims I to 3 and 6, wherein the halogenalkyl group represented by R2 is a bromalkyl or chloralkyl group.

8. A compound as claimed in any one of claims I to 3 and 6, wherein the alkyl or alkenyl group represented by R2 contains up to 4 carbon atoms.

9. N - (2 - Bromethyl) - carbanilic acid [3 - (methoxycarbonylamino) phenyl] ester.

10. N - (2 - Bromethyl)- carbanilic acid [3 - (ethoxycarbonylamino) phenyl] ester.

II. N - (2 - Bromethyl) - carbanilic acid [3 - (methylthiocarbonylamino) phenyll ester.

12. N - (2 - Bromethyl) - carbanilic acid [3 - (ethylthiocarbonylamino) phenyl] ester.

13. N - (2 - Chlorethyl) - carbanilic acid [3 - (methoxycarbonylamino) phenyl] ester.

14. N - (2 - Chlorethyl)- carbanilic acid [3 - (ethoxycarbonylamino) phenyl] ester.

15. N - (2 - Chlorethyl) - carbanilic acid [3 - (methylthiocarbonylamino) phenyll ester.

16. N - (2 - Chlorethyl) - carbanilic acid L3 - (ethylthiocarbonylamino) phenyl] ester.

17. N - (2 - Bromethyl)- carbanilic acid [3 - (allyloxycarbonylamino) - phensl] ester.

18. N - (2 - Chlorethyl) - carbanilic acid [3 - (1 - methylpropynyloxycarbonylamino) - phenyl] ester.

19. N - (2 - Bromethyl) - carbanilic acid [3 - (2 - propynyloxycarbonylamino) - phenyl] ester.

20. N - (2 - Chlorethyl) - carbanilic acid [3 - (2 - propynyloxycarbonylamino) - phenyl] ester.

21. N - (2 - Bromethyl) - 2 - methylcarbanilic acid [3 - (methoxycarbonylamino) - phenyl] ester.

22. N - (2 - Bromethyl) - 3 - chlorocarbanilic acid [3 - (methoxycarbonylamino) - phenyl] ester.

23. N - (2 - Bromethyl) - 2 - methylcarbanilic acid [3 - (ethoxycarbonylamino) - phenyl] ester.

24. N - (2 - Bromethvl) - 3 - chlorocarbanilic acid [3 - (I - methylethdxycarbonylamino) - phenyl] ester.

25. N - (2 - Bromethyl) - carbanilic acid [3 - (2 - methylpropoxycarbonylamino) - phenyl] ester.

26. N - (2 - Bromethyl) - 3 - chlorocarbanilic acid [3 - (2 - methylpropoxycarbonylamino) - phenyl] ester.

27. N - (2 - Chlorethyl) - 3 - methoxycarbanilic acid [3 - (methoxycarbonylamino) - phenyl] ester.

28. N - (2 - Chlorethyl) - 3 - trifluoromethylcarbanilic acid [3 - (methoxycarbonylamino) - phenyl] ester.

29. N - (2 - Bromethyl) - 3 - trifluoromethylcarbanilic acid [3 - (methoxycarbonylamino) - phenyl] ester.

30. Any one of the compounds numbered as 17 to 54 in Table I herein.

31. Any one of the compounds numbered as 55 to 62, 65 to 76 and 78 to 87 in Table I herein.

32. A herbicidal preparation which comprises a compound of the general formula I given in claim 1, in which R1, R2, R3 and X have the meanings given in claim 1, in admixture or conjunction with a suitable carrier.

33. A herbicidal preparation which comprises a compound claimed in any one of claims 2 to 8, in admixture or conjunction with a suitable carrier.

34. A herbicidal preparation which comprises the compound claimed in any one of claims 9 to 24, in admixture or conjunction with a suitable carrier.

35. A herbicidal preparation which comprises the compound claimed in any one of claims 25 to 29, in admixture or conjunction with a suitable carrier.

36. A herbicidal preparation which comprises a compound as claimed in claim 30, in admixture or conjunction with a suitable carrier.

37. A herbicidal preparation which comprises a compound as claimed in claim 31, in admixture or conjunction with a suitable carrier.

38. A preparation as claimed in any one of claims 32 to 37, which is in the form of a powder, a strewable preparation, granules, a solution, an emulsion or a suspension.

39. A preparation as claimed in any one of claims 32 to 38, containing a single compound of the general formula I in an amount of approximately 10 to 80% by weight.

40. A preparation as claimed in any one of claims 32 to 38, containing two or more compounds of the general formula I in a total amount of approximately 10 to 800o/ by weight.

41. A preparation as claimed in any one of claims 32 to 40, containing a single surface-active agent in an amount of up to 20% by weight.

42. A preparation as claimed in any one of claims 32 to 40, containing two or more surface-active agents in a total amount of up to 20% by weight.

43. Any one of the herbicidal preparations as claimed in claim 32 and substantially as described in Example 2 herein.

44. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound of the general formula I given in claim 1, in which R1, R2, R3 and X have the meanings given in claim 1.

45. A method as claimed in claim 44, wherein the area is treated with a compound as -claimed in any one of claims 2 to 8.

46. A method as claimed in claim 44, wherein the area is treated with the compound claimed in any one of claims 9 to 24.

47. A method as claimed in claim 44, wherein the area is treated with the compound claimed in any one of claims 25 to 29.

48. A method as claimed in claim 44, wherein the area is treated with a compound as claimed in claim 30.

49. A method as claimed in claim 44, wherein the area is treated with a compound as claimed in claim 31.

50. A method as claimed in claim 44, wherein the area is treated with a herbicidal preparation as claimed in any one of claims 32 to 43.

51. A method as claimed in any one of claims 44 to 50, wherein a single compound of the general formula I is used for the treatment in an amount of approximately 0.5 to 5 kg per hectare.

52. A method as claimed in any one of claims 44 to 0, wherein two or more compounds of the general formula I are used for the treatment in a total amount of approximately 0.5 to 5 kg per hectare.

53. A method as claimed in claim 44, conducted substantially as described in Example ' herein.

54. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound of the general formula I given in claim I, in which R1, R2, R and X have the meanings given in claim 1.

55. A method as claimed in claim 54, wherein the crop area is treated with a compound as claimed in any one of claims 2 to 8.

56. A method as claimed in claim 54, wherein the crop area is treated with the compound claimed in any one of claims 9 to 24.

57. A method as claimed in claim 54, wherein the crop area is treated with the compound claimed in any one of claims 25 to 29.

58. A method as claimed in claim 54, wherein the crop area is treated with a compound as claimed in claim 30.

59. A method as claimed in claim 54, wherein the crop area is treated with a compound as claimed in claim 31.

60. A method as claimed in claim 54, wherein the crop area is treated with a herbicidal preparation as claimed in any one of the claims 32 to 43.

61. A method as claimed in any one of claims 54 to 60, wherein a single compound of the general formula I is used for the treatment in an amount of approximately 0.5 to 5 kg per hectare.

62. A method as claimed in any one of claims 54 to 60, wherein two or more compounds of the general formula I are used for the treatment in a total amount of approximately 0.5 to 5 kg per hectare.

63. A method as claimed in any one of claims 54 to 62, wherein the crop is a cereal crop or a potato crop.

64. A method as claimed in any one of claims 54 to 62, wherein the crop is a maize, wheat, barley or rice crop.

65. a pack which comprises a compound as claimed in claim I together with instructions for its use as a herbicide.

66. A pack which comprises a compound as claimed in any one of claims 2 to 8 together with instructions for its use as a herbicide.

67. A pack which comprises the compound claimed in any one of claims 9 to 24 together with instructions for its use as a herbicide.

68. A pack which comprises the compound claimed in any one of claims 25 to 29 together with instructions for its use as a herbicide.

69. A pack which comprises a compound as claimed in claim 30 together with instructions for its use as a herbicide.

70. A pack which comprises a compound as claimed in claim 31 together with instructions for its use as a herbicide.

71. A process for the manufacture of a compound of the general formula I given in claim 1, in which R1, R2, R3 and X have the meanings given in claim 1, wherein (a) a compound of the general formula II

in which R3 and X have the meanings given above, is reacted in the presence of an acid acceptor with an amine of the general formula Ill

in which R1 and R2 have the meanings given above, or (b) a compound of the general formula IV

in which R3 and X have the meanings given above, is reacted in the presence of a tertiary organic base or is reacted in the form of an alkali salt thereof with a carbamoyl chloride of the general formula V

in which R, and R2 have the meanings given above, each reaction being carried out at a temperature within the range of from 0" to 1000C, or, when R, represents a hydrogen atom, is reacted in the presence of a catalyst with an isocyanate of the general formula VI R2-N=C=O (V1), in which R2 has the meaning given above, or (c) a nitro compound of the general formula VII

in which R, and R2 have the meanings given above (provided that they do not represent groups that are capable of being easily hydrogenated), is catalytically hydrogenated to form the corresponding amine which is then reacted in the presence of an acid acceptor with a compound of the general formula VIII CI-CO-X-R3 (VIII), in which R3 and X have the meanings given above.

72. A process as claimed in claim 71, wherein the acid acceptor used for the reaction with the amine of the general formula III is an excess of the amine of the general formula III, an inorganic base or a tertiary organic base.

73. A process as claimed in claim 72, wherein the inorganic base is a sodium hydroxide solution, sodium carbonate or potassium carbonate.

74. A process as claimed in claim 72, wherein the tertiary organic base is triethylamine.

75. A process as claimed in claim 71, wherein the tertiary organic base used for the reaction of the free compound of the general formula IV is triethylamine or pyridine.

76. A process as claimed in claim 71, wherein the catalyst used for the reaction with the isocyanate of the general formula VI is an organic base.

77. A process as claimed in claim 71, wherein the catalytic hydrogenation is carried out by means of nickel in methanol.

78. A process as claimed in claim 71 or 77, wherein the acid acceptor used for the reaction with the compound of the general formula VIII is an inorganic base or a tertiary organic base.

79. A process as claimed in claim 78, wherein the inorganic base is a sodium hydroxide solution, sodium carbonate or potassium carbonate.

80. A process as claimed in claim 78, wherein the tertiary organic base is triethylamine.

81. A process as claimed in claim 71, conducted substantiall@ as described in Example 1 herein.