(N,-dimethyl-N-{8 3-methylmetalolycarbamyloxy)-phenyl{9 -urea
United States Patent 1 91 Boroschewski et al.  
 [ Apr. 22, 1975 [54] (N,N-DI1\/[ETHYL-N- [3- METHYLMETALOLYLCARBAMYLOXY)- PHENYL1-UREA [75] Inventors: Gerhard Boroschewski; Frederich Arndt; Reinhard Rusch, all of Berlin, Germany [73] Assignee: Schering AG, Berlin and Bergkamen, Germany 22 Filed: July 10, 1970 [21] App]. No.: $3,988  
 Related US. Application Data [63] Continuation of Ser. No. 663,938, Aug. 29, 1967,  
 abandoned.  
 [30] Foreign Application Priority Data Sept. 5, 1966 Germany 39491 June 7, 1967 Germany 40838 [52] US. Cl 260/471 C; 71/88; 71/94;  
 [51] Int. Cl. C07c 101/18 [58] Field of Search 260/471 C [56] References Cited UNlTED STATES PATENTS 10/1968 Wilson et al. 260/471 C 3/1969 Wilson et al.... 260:71/471 C;l20 X Primary Examiner-Alex Mazel Assistant Examiner-Jose Tovar 57 ABSTRACT Agents having at least one compound of the general formula where R is hydrogen or alkyl,  
 R aryl, aralkyl, or cycloakly possibly monoor poly-substituted by alkyl and/or halogen alkyl and/0r alkoxy and/or alkyl mecapto and/or halogen and/or the nitro group,  
 R hydrogen or alkyl,  
 A and B are different and represent hydrogen or the radical 1 Claim, No Drawings (N ,N-DIMETHYL-N- [3-METHYLMETALOLYLCAR- BAMYLOXY)-PHENYL]-UREA The invention relates to herbicides. It relates in particular to herbicides having a selective herbicidal effect, containing new N-carbamoyloxy-phenylureas.  
 The herbicidal effect of 3-(Nalkylcarbamoyloxy)- phenylureas, e.g. N,N-dimethyl-N-(3-(N&#34;-tertiary butylcarbamoyloxy)-phenyl)urea, is discussed in known Belgian Patent No. 661,399. These compounds, howwhere R, is hydrogen or alkyl,  
 R aryl, aralkyl, or cycloakyl possibly monoor polysubstituted by alkyl and/or halogen alkyl and/or alkoxy and/or alkyl mecapto and/or halogen and/or the nitro group,  
 R hydrogen or alkyl,  
 A and B are different and represent hydrogen or the radical 41f CX N where R, is hydrogen or alkyl, R hydrogen or alkyl,  
 R alkyl or alkoxy,  
 R and R are jointly with the N atom a heterocyclic ring possibly containing additional N and/or 0 atoms,  
 and  
 Name of Compound X is oxygen or sulfur and, if B represents hydrogen,  
  R may also represent alkyl or alkenyl, possess a herbicidal effect and are suitable in particular for weed control in crop cultivations.  
  Thus, with their use, contrary to the above named known active ingredients, delicate dicotyledons, for example, sugar beets and cotton, are surprisingly enough not harmed, This selective effect extends to the use both in the pre-germination process as by spraying on seed, and to the use in the post-germination process, by treatment of the germinated cultures, so that there is present here a true selectivity as to effect. The tolerance of the crop plants toward the agents to be used according to this invention is considerable, as even major quantities up to 5 kg of active ingredient per hectare cause no damage to the crops.  
  Considerable technical progress is therefore connected with the use of the herbicides according to the invention, since because of the great selectivity of these herbicides a reliable control of weeds in beet and cotton cultivations without damage to these crops, is rendered possible.  
 It is obvious that the herbicides according to the invention are suitable not only for selective weed control,  
 but they also can be used in adequate dosages for the destruction of any undesirable plant growth.  
  As active ingredients; suitable for the above indicated purposes compounds within the above stated general formula and sharing the following characteristics: R is phenyl, 2-,3-,4-tolyl, 2,3-dimethylphenyl, 2,4- dimethylphenyl, 2-,3-,4-chlorophenyl, 4-fluorphenyl, 4-bromophenyl, 4-iodophenyl, 3,4-dichlorophenyl, 2,5-dichlorophenyl, 3-chloro-4-methylphenyl, 3-trifluoromethylphenyl, 4-nitrophenyl, 4-methoxyphenyl, 4-methylmercaptophenyl, alpha-naphthyl, benzyl, 4- chlorobenzyl, alkyl radicals with up to 10 carbon atoms, as methyl, ethyl, alkyl, propyl, isopropyl, etc., cycloalkyl, radicals, such as cyclohexyl and others; R R R and R are each in itself, hydrogen or low alkyl, as methyl or ethyl or ethyl, and others; R is a low alkyl or low alkoxy, as methyl, ethyl, methoxy or ethoxy and others; R and R jointly with the N atom are the morpholino, piperidino, or pyrrolidino group and others, and X is oxygen or sulfur.  
  Examples of compounds usable according to the invention are the following (Fp. means melting point):  
 Physical constant N,N-dimethy Fp. 174 l75,5C  
 Fp. 96 97C Fp.= 151 152C Fp.= 129 -c (4&#39;-methylp enyl)-carbarnoyloxy)- phenyl )-urea Fp.= 154- 155C Fp. 96 97C methylphenyl )-carbamoyloxy)- phenyl )-urea Fp. I29 130C (3&#39;-methyl henyl)-carbamoyloxy)- phenyl)-thiourea resinified N&#34;-(2&#39;-methylphenyl )-carbamoyloxy)- phenyl)-urea Fp. 162 163C N&#39;-( 3&#39;-methylphenyl)-carbamoyloxy)- phenyl)urea Fp. l62,5 l63,5C  
 carbamoyloxy)-phenyl)-urea Fp. 167 168C The new active ingredients to be used according to the invention may be produced, for example, accordingto the following illustrative processes:  
  By reaction of hydroxyphenyl ureas or thioureas of the general formula possibly in the form of the alkali, e.g. of the solium or potassium salt, (a) with isocyanates of the general formula advantageously in an organic solvent, as for example, tetrahydrofurane or dimethyl formamide, and possibly with addition of a catalyst, preferably an organic base, as for example, triethylamine, or (b) with carbamoyl chlorides of the general formula advantageously in an organic solvent, e.g. pyridine, and possibly with addition of an organic or inorganic base, e.g. triethylamine, or (c) with phosgene, advantageously with the use of an organic solvent, e.g. tetrahydrofurane, acetic ester or ethylene chloride, and possibly with addition of an inorganic or organic base, e.g. soda lye or N,N-dimethyl aniline, to the corresponding chloroformic acid ester, which is then reacted with a compound of the general formula advantageously at temperatures between 5 C and room temperature in water or in an organic solvent, e.g. acetic ester or tetrahydrofurane, if desired with addition of an acid-binding agent, as for example, the above-named bases, or alkali or alkaline earth oxides, hydroxides, or carbonates, R R R A, B, and X having the above mentioned meaning in the stated general formulas.  
  The following examples illustrate the production of the new active substances, without limitation thereto.  
  1. Preparation of N,N-dimethyl-N&#39;-(3-(3-methy1phenyl)-carbamoyloxy)-phenyl)-urea 18.0 g (0.1 mole) of N,N-dimethyl-N&#39;-(3- hydroxyphenyl) urea are dissolved in a mixture of 25 ml ofdimethyl&#39;formamide and 50 ml of tetrahydrofurane and the solution is added with 0.5 ml of triethylamine and 13.3 g(0.1 mole) of 3- methylphenylisocyanate. After 2 hours at room temperature, the solution is added with 400 ml of ether, whereupon the carbamate crystallizes out.  
 Yield: 26.3 g 84% of the theory N: calculated 13.42% found 13.34%  
  2. Preparation of N,N-dimethy1-N-( 3-(N&#34;-methyl-N&#34;-(3&#39;- methylphenyl)-carbamoyloxyphenyl)-urea The sodium salt produced from 9.0 g of N,N- dimethyl-N&#39;-(3-hydoxyphenyl)-urea is taken up in 50 ml of acetonitrile. While stirring, 9.2 g of N-methyl-N- (3-methylphenyl)-carbamoylchloride in portions are added at 25 C. Stirring is continued for 30-minutes at 50 C. After cooling to room temperature, the solution is poured into about 20 ml of water, whereupon the carbamate crystallizes out.  
 Yield: 14.3 g 87.5% of the theory m.p.: 126 C i 3. Preparation of N,N-dimethyl-N -(4-( N &#34;-phenylcarbamoyloxy)- phenyl)-urea 12.6 g (0.07 mole) of N,N-dimethyl-N&#39;-4-(hydroxyphenyl)urea are dissolved in ml of tetrahydrofurane and the solution added with 0.5 ml of triethylamine and 8 ml of phenylisocyanate. After several hours at room temperature, the carbamate crystallizes out upon additi&#39;on of light gasoline.  
 Yield: 20.9 g 99.8% of the theory m.p.: 172 174 C 4. Preparation of N,N-dimethyl-N&#39;-(4-(N-methyl-N&#34;-phenylcarbamoyloxy)-phenyl)-urea The sodium salt produced from 18.0 g (0.1 mole) of N,N-dimethyl-N&#39;-(4-hydroxyphenyl) urea was taken up in 50 ml of acetonitrile. While stirring, a solution of 17.0 g of N-methyl-N-phenylcarbamoyl chloride in ml of acetonitrile was added by drops at 20 to 25 C.  
  with ammonia or amines.  
  Some starting products are listed in the following table. (Fp. means melting point) i 137.5 1322.50  
 N-(3-hydroxypheny1)-N-methyl urea Fp N-ethy1N-(3-hydroxyphenyl)-urea Fp.: 135 136C N,Ndimethyl-N&#39;-(3-hydroxyphenyl)-urea Fp.: 190 193C N,N&#39;-dimethyl-N-(3-hydroxyphenyl)-urea Fp.: 123 124C 1 N-( 3-hydroxyphenyl)-N,N&#39;,N-trimethyl)-urea Fp.: 106C N-(3-hydroxyphenyl)-N,N&#39;-tetramethy1ene-urea Fp.: 138 139C Morpholine-N-carboxylic acid-3-hydroxyanilid Fp.: 180 181C N-( 3-hydroxyphenyl )-N&#39;-methylthio-urea F p.: 164C N-eth l-N&#39;-(4-hydroxyphenyl)-urea Fp.: 196 197C N-(4- ydroxyphenyl)-N,N&#39;,N&#39;-trimethyl-urea Fp.: 133 C N,N-dimethyl-N-(4-hydroxy-Z-methyl-phenyl)-urea Fp.: 225 227C EXAMPLE 2 In loamy soil, monogram seeds of sugar beets as well as Stellaria media, Galisoga parviflora and Senecio vuI-&#39; garis were seeded. The active ingredients were sprayed on the seed in a quantity of 5 kg of active ingredient per hectare, suspended in 600 liters of water per hectare. Then the seeds were covered with earth and allowed to germinate. The plants came up after days. Even after 4 weeks, no growth damage was observed on the sugar beets treated with the agents according to the invention, while the weeds were destroyed. The known agent, on the contrary, showed no selectivity for sugar beets.  
 Sugar solid carriers there enter into consideration for example, lime, kaolin, chalk, talcum, attaclay and other clays. As surface-active substances are suitable, among others, salts of the lignin sulfonic acids, salts of alkylated benzenesulfonic acids, sulfonated acid amides and their salts, polyethoxylated amines and alcohols.  
 The production of the various preparations can be 3 effected in a manner known in the art such as, by grinding or mixing processes.  
  The herbicidal effect of the agents according to the invention is evident from the following test examples.  
 Sugar beets, Slellaria media, Galinsoga parviflora, and.  
 Senecio vulgaris were treated with the agents referred to, after the plants had produced their first foliage leaves and were in the young stage. The quantity used was 5 kg of active substance per hectare, suspended in 600 liters of water per hectare. With this treatment in the post-germination process the agent of the invention destroyed only the weeds, while the sugar beets showed no impairment of the growth even four weeks after the treatment. The known agent, on the contrary, de-  
  stroyed also the crop plants.  
  Stellaria Galinsoga Senecio Sugar Active Ingredient media parviflora vulgaris beets N,N-dimethyl-N&#39;-(3-(N&#34;- (3&#39;-methylphenyl)-carbamoyloxy-phenyl) urea 0 0 l0 N,N-dimethyl-N-(3-(N&#34;- tert. butycarbamoyloxy)- phenyl) urea 0 0 0 0 Untreated l0 l0 l0 l0 0 totally destroyed I0 not damaged EXAMPLE 4 EXAMPLE 1 With a quantity used of 5 kg of active ingredient per hectare, suspended in 600 liters of water per hectare, the following selectivity was obtained with sugar beets:  
  Sprayed on seed in Active ingredient pre-germination process N,N-dimethyl-N&#39;-(3-(N&#34;- (3&#39;-methylphenyl)-car- In loamy soil seeds of peas as well as Stellaria media, Galinsoga parviflora, and Senecio vulgaris were seeded. The active ingredients were sprayed in a quantity of 3 In post-germmatron process bamoyloxy)-phenyl) urea 100% N,N-dimethyl-N&#39;-(3-(N&#34;- tert. butylcarbamoyloxy)- phenyl) urea 12 EXAMPLE 6 At a quantity used of 5 kg of active ingredient per hectare, suspended in 600 liters of water per hectare,  
 5 the following selectivity was obtained for sugar beets known agent showed no selectivity. and cotton.  
  Stellaria Galinsoga Senecio Peas Active ingredient media parviflora vulgaris N,N-dimethyl-N&#39;-(3-(N&#34;- methyl-N 3&#39;-methy1- phenyl )-carbamoy1oxy phenyl) urea 0 0 0 10 F: 126 deg. C  
 N,N-dimethyl-N&#39;-(3- (N&#34;-tert. butyl-carbamoyloxy)-phenyl) urea 0 0 0 0 Untreated 10 10 10 10 0 totally destroyed 10 not damaged Sprayed on seed in pre- 1n post-germ- Active ingredient germination process ination process Sugar beet Sugar beet cotton N,N-dimethyl-N -(4-(N&#34;- pheny1carbamoyloxy)- phenyl) urea 100% 100% 100% N,N-dimethyl-N&#39;-(3-(N&#34;- tert. butylcarbamoyloxy)- phenyl) urea 0% 0% 0% EXAMPLE 5 EXAMPLE 7 In loamy soil seeds of sugar beet (Beta vulgaris) as well as of Sinapis ssp. and Solarium ssp. were seeded.  
 35 On the seeds the active ingredients&#39;were sprayed in a quantity of 5 kg of active ingredient per hectare, suspended in 600 liters of water per hectare. Then the seeds were covered with earth and set up for germination. The plants germinated after 10 days. Even after 4 40 weeks, no or no considerable growth damage was noted on the sugar beets treated with the agent according to Slellaria Galinsaga Senecio Peas Active ingredient media parviflora vulgaris N,N-dimethyl-N&#39;-(3-(N&#34;- methyl-N 3 &#39;-methylphenyl )-carbamoyloxy)- phenyl) urea 0 0 0 10 m.p.: 126 deg. C  
 N,N-dimethyl-N&#39;-(3-(N- tert. buty1-carbamoy1oxy)- phenyl) urea 0 0 0 0 Untreated 10 10 10 10 0 totally destroyed 10 not damaged Compound Sinapis ssp. Solarium .rsp. Sugar beets N,N-dimethy1-N&#39;-(4-(N&#34;-phenyl- 0 0 10 carbamoyloxy )-phenyl) urea N,N-dimethyl-N&#39;-(4-(N&#34;-(3&#39;- methylphenyl)-carhamoyloxy)- phenyl) urea 0 0 l0 N,N-dimethy1-N-(4-(N&#34;-methyl- N&#34;-phenylcarbamoyloxy)-phenyl) urea 0 0 8 N,N-dimethyl-N-(4-(N&#34;-hexylcarbamoyloxy)-phenyl) urea 0 0 10 N,N-dimethyl-N-(3-(N&#34;-tert. butylcarbamoyloxy)-phenyl urea 0 0 0 totally destroyed 10 no damage 13 the invention, while Sinapis and Solanum were destroyed. The known agent, on the contrary, showed no selectivity for sugar beets.  
 EXAMPLE 8 Sugar beets (Beta vulgaris), cotton (Gossypium ssp.), Sinapis ssp. and Solanum ssp. were treated with the agents referred to after the plants had produced the first foliage leaves and were in the young stage. The quantity used was 5 kg of active ingredient per hectare, suspended in 600 liters of water per hectare. With this treatment in the post-germination process the agents of EXAMPLE 9 Sugar beets (Beta vulgaris), cotton (Gossypium ssp.) and Sinapis ssp. were treated with the agents referred to after the plants had formed the first foliage leaves and were in the young stage. The quantity used was 5 kg of active ingredient per hectare, suspended in 600 liters of water per hectare. With this treatment in the post-germination process the agents according to the invention destroyed only Sinapis. The sugar beets and the cotton showed no or only minor impairment of the growth. The known agent, on the contrary, destroyed everything.  
 Compound Sinapis Sugar beets Cotton 0 totally destroyed I0 no damage the invention destroyed only Sinapis and Solanum. The 35 From the foregoing description of the invention as sugar beets and the cotton showed no or only minor imexemplified and illustrated, it will be noted that we pairment of the growth. The known agent, on the conhave provided herbicides containing N-carbamoyloxytrary, destroyed everything. phenylureas either alone or in conjunction with other Compound Sinapis Solarium Sugar Beets Cotton ssp. ssp.  
 N,N-dimethyl-N&#39;-(4-(N&#34;-phenyl) carbamoyloxy)-phenyl) urea 0 0 l0 l0 N,N-dimethyl-N&#39;-(4-(N&#34;-(3&#39;- methylphenyl)-carbamoyloxy)- phenyl) urea 0 0 l0 l0 N,N-dimethyl-N-(4-(N&#34;-tert. butylcarbamoyloxy)-phenyl)- urea 0 0 8 l0 N,N-dimethyl-N-4-allylcarbamoyloxy)-phenyl) urea 0 0 l0 l0 N,N-dimethyl-N&#39;-(4-(N&#34;-ethylcarbamoyloxy)phenyl) urea l0 l0 N,N-dimethyl-N&#39;-(4-(N&#34;-isobutylcarbamoyloxy)-phenyl)- urea 2 2 l0 l0 N,N-dimethyl-N&#39;-(4-(N&#34;-propylcarbamoyIoxy)-phenyl) urea 0 0 8 l0 N,N-dimethyl-N-(4-(N&#34;-butylcarbamoyloxy)-phenyl) urea 0 O 9 l0 N,N-dimethyl-N&#39;-(4-(N&#34;-p-tolylcarbamoyloxy)-phenyl) urea l l l0 l0 N,N-dimethyl-N&#39;-(4-(N&#34;-methyl- N&#34;-phenylcarbamoyloxy)-phenyl) urea 0 0 l0 l0 N,N-dimethylN-(4-(N&#34;-dimethyl propylcarbamoyloxy)-phenyl) urea 0 0 l0 N,N-dimethyl-N&#39;-(4-(N&#34;-hexylcarbamoyloxy)-phenyl) urea 0 0 10 N,N-dimethyl-N&#39;-(4-(N&#34;-octylcarbamoyloxy)-phenyl) urea l 0 l0 l0 N,N-dimethyl-N-(4-(N&#34;-cyclohexylcarbamoyloxy)-phenyl) urea 0 0 8 l0 N,N-dimethyl-N&#39;-(4-(N&#34;-2,3-di methylphenyl )-carbamoyloxy )urea 0 0 l0 l0 N,N-dimethyl-N&#39;-(3(N&#34;-tert. butylcarbamoyloxy)-phenyl) urea 0 0 0 0 0 totally destroyed I0 no damage herbicides for synergistic effect which are suitable for weed control in the cultivation of crops.  
 We claim: