Patent GB-774802-A (GB)
Title: Improvements relating to derivatives of diphenyl urea and their use
IPC: C07C275/30
Filed: 1954-06-16
Abstract: The invention comprises compounds of the general formula <FORM:0774802/IV(b)/1> wherein one X represents a trifluoromethyl group, the other X represents hydrogen or halogen, one Y represents halogen, the trifluoromethyl or the nitro group, the other Y represents hydrogen, halogen or an alkoxy group and Z represents hydrogen or halogen.  The compounds of the invention may be prepared by reacting one mol. of a halide, a diester, a halide monoester or the diamide of carbonic acid with two mols. of suitably substituted aminobenzene compounds, the components being chosen so that compounds of the above general formula are obtained.  In a modification of the above process 1 mol. of a halide or halide mono-ester of carbonic acid is reacted first with one mol. of a suitably substituted aminobenzene compound to form the corresponding phenyl carbamic acid halide or ester which is then converted with a second mol. of an identical or another suitably substituted aminobenzene compound into the diphenyl urea derivative.  In a further modification the reaction product from one mol. of phosgene with one mol. of a suitably substituted aminobenzene compound is converted into the corresponding phenyl isocyanate by heating in an inert organic solvent boiling at over 100 DEG  C. while splitting off hydrogen halide and then 1 mol. of a suitably substituted aminobenzene compound is added to the isocyanate to produce a diphenyl urea compound having the above general formula.  Substituted amino-benzene compounds containing a trifluoromethyl group include 4-trifluoromethyl - 2 - chloro -, 4 - trifluoromethyl - 3 - chloro -, 4 - trifluoromethyl - 2,5 - dichloro -, 3 - trifluoromethyl -, 5 - trifluoromethyl - 2 - chloroand 3 - trifluoromethyl - 4 - chloro - 1 - aminobenzene. To form unsymmetrically substituted diphenyl urea derivatives 4-chloro-, 4-bromo-, 4-fluoro- or 4-nitro-1-amino-benzenes, 3,4-dichloro or dibromo, 3-chloro-4-bromo, 2,3,4- or 2,4,5- or 3,4,5-trichloro-1-aminobenzenes, 3-chloro - 4 - methoxy - or 3 - chloro - 4 - ethoxy - or 3 - nitro - 4 - chloro - 1 - aminobenzenes may be employed.  Reactive derivatives of carbonic acid which may be employed include phosgene, chloro-carbonic acid phenyl ester and urea.  Solvents mentioned include nitrobenzene, o-dichlorobenzene and acetone.  Substituted diphenyl ureas of the above general formula are obtained when in examples: the isocyanate formed by reacting 4-chloro-3-trifluoromethyl-1-aniline with phosgene, is heated with 1-amino-4-chloro-3-benzo-trifluoride in chlorobenzene (1); the isocyanate formed by reacting 3,4-dichlor-aniline with phosgene is heated with 1-amino-4-chloro - 3 - benzotrifluoride in chlorobenzene (4); the isocyanate formed by reacting 1-amino-3-benzo-trifluoride with phosgene is heated with 1 - amino - 3 - benzotrifluoride (6); the isocyanate formed by reacting 1-amino-2-chloro-5-benzotrifluoride with phosgene is heated with 1 - amino - 2 - chloro - 5 - benzotrifluoride in chlorobenzene (7); the isocyanate formed by reacting 1-amino-2,5-dichloro-4-benzotrifluoride with phosgene is heated with 1-amino-2,5-dichloro - 4 - benzotrifluoride in chlorobenzene; 1 - amino - 4 - chloro - 3 - benzotrifluoride, dissolved in acetone, is treated with phosgene and aqueous sodium acetate (2); 1-amino-4-chloro-3-benzotrifluoride chlorohydrate and urea are boiled in water, the precipitate formed is filtered off, treated with sodium carbonate and steam distilled (3); 4-chloro-3-trifluoromethyl-phenyl-isocyanate is heated with 3,4-dibromo-1-aniline in chlorobenzene (5) and additional products are obtained in a manner corresponding to that described in Example (1) from 4-chloro-3-trifluoromethyl phenyl isocyanate and 2 - chloro - 5 - trifluoromethyl -, 5 - trifluoromethyl-, 2,5 - dichloro - 4 - trifluoromethyl-, 2 - chloro - 4 - trifluoromethyl-, 4 - bromo - 5 - chloro-, 3,4,5 - trichloro-, 4 - ethoxy - 5 - trifluoromethyl-, 2,5 - dichloro -, 4 - chloro -, 2,4-dibromo-, and 4-bromo- and 4-ethoxy-5-chloro-anilines, from 4-nitrophenylisocyanate and 3-trifluoromethyl - 4 - chloraniline, from 2-chloro-5 - trifluoromethylphenylisocyanate and 5 - trifluoromethyl-, 2,5 - dichloro - 4 - trifluoromethyl, 4,5 - dichloro -, 4 - bromo - 5 - chloro -, 4,5 - dibromo - and 3,4,5 - trichloroanilines and from 2,5 - dichloro - 4 - trifluoromethylphenylisocyanate and 4,5-dichloroaniline.  The products are employed in insecticidal and fungicidal compositions (see Group VI) and in proofing keratin fibres against insect attack (see Group VIII).  1 - Amino - 2,5 - dichloro - 4 - benzotrifluoride is obtained by acetylating and nitrating 1-amino - 4 - chloro - 3 - benzotrifluoride, saponifying the acetylamine group and diazotizing and replacing the amino group by chlorine in a Sandmeyer reaction and reducing the nitro group.ALSO:Insecticidal and fungicidal compositions comprise as active ingredients diphenyl urea compounds of the general formula <FORM:0774802/VI/1> wherein one X represents a trifluoromethyl group, the other X represents hydrogen or halogen, one Y represents halogen, the trifluoromethyl group or the nitro group the other Y represents hydrogen, halogen or an alkoxy group and Z represents halogen or hydrogen (see Group IV(b)) and as carriers dialkyl ketones, chlorobenzenes, nitrobenzene, ethylene glycol monoalkyl ethers, pyridine bases are mentioned or the active ingredients may be employed as aqueous dispersions of the finely ground powder or of organic solvent solutions.  Dispersing agents such as condensation products formed from formaldehyde and naphthalene sulphonic acid or alkylene polyglycol ethers of phenols containing higher aliphatic or alicyclic hydrocarbon ring substituents are specified.  The use of the products of the invention in aqueous media to treat keratin fibres is referred to.  In example (9) wool is treated with a dispersion comprising N,N1 - bis(3-trifluoromethyl - 4 - chlorophenyl)- urea, glycol monomethyl - ether, sulphonated castor oil and water to which sulphuric acid is subsequently added.