GB1280887A - New isothiocyano-diphenylamines their production and compositions containing same - Google Patents

Abstract

1280887 Isothiocyano-diphenylamines AGRIPAT SA 11 July 1969 [12 July 1968] 34956/69 Heading C2C Novel compounds I where R is H or alkyl or alkenyl of at most 3C, R 1 and R 3 are H, halogen, CN, OH, NO 2 , CO 2 H, CF 3 , or alkyl, alkenyl, alkoxy, alkenyloxy, alkylthio or alkenylthio of at most 5C, or alkanoylamino, alkanoyl, alkanoyloxy or alkoxycarbonyl of at most 6C, or dialkylamino having a total of at most 5C, or groups of the formulµ -D-N(R<SP>1</SP>) 2 or -X-D-N(R<SP>1</SP>) 2 where D is alkylene of 2 or 3 C, R<SP>1</SP> is C 1-3 alkyl, the sum of the carbons of D and the two R<SP>1</SP> groups not exceeding 6, and X is O or S and R 2 is H, halogen, NO 2 , NCS or C 1-5 alkyl (an isothiocyano group must be in m- or p-position to any OH or CO 2 H in the phenyl nuclei or to the -NR- bridge when R is H, and when R, R 1 and R 3 are H, the group -NCS at ring B is in m- or p-position and an isothiocyano group R 2 is in m-position) are made: (a) by reacting II with Halogen.CS.Y (Halogen is Cl or Br, Y is Cl, Br or dialkylamino and R<SP>1</SP> 2 is H, halogen, NO 2 , NH 2 or C 1-5 alkyl) ; (b) by reacting II with III (m is 1 or 2 and alkyl has at most 4 C); (c) by reacting II with a pentathio-dipercarbonic acid-bis-(trihalogeno-alkyl)-ester ; or (d) by reacting II (R, R 1 , R<SP>1</SP> 2 and R 3 may not be NO 2 , CF 3 or carboxy) with ammonium thiocyanate in the presence of excess hydrogen chloride, or with benzoyl isothiocyanate to afford the corresponding thiourea which is subsequently decomposed to give I. The invention also comprises a process for making IV (also novel; R 4 is alkyl or alkenyl of at most 5 C or dialkylaminoalkyl of at most 6 C, Y is O or S, n is 0 or 1, R 5 is H, -NCS, halogen, NO 2 , CF 3 , or alkyl or alkenyl of at most 5 C, R 6 is H, halogen, NO 2 , CF 3 , alkyl or alkenyl of at most 5 C or is the group -YR 4 , the -NCS group at ring B and an isothiocyano group R 5 being in m- or pposition to the -NR- bridge in the case where R is H, or to a R 4 -Y group, and in those cases where n is 0, R 6 signifies the group -Y-R 4 ) by reacting V with a compound R 4 .Z (Z is C1, Br or I and R<SP>1</SP> 6 is H halogen, NO 2 , CF 3 , alkyl or alkenyl of at most 5 C or is the group -Y-H). Products I and IV, can, if desired, be converted into their quaternary ammonium or acid addition salts. The following compounds are also prepared: 1 - N - (41 - methylthiophenyl) - 4- amino - phenyl - thiourea, N - allyl - 4 - methoxy- 4<SP>1</SP> - nitro - diphenylamine, N - n - propyl - 4- methoxy - 41 - amino - diphenylamine and N- methyl - 4 - methoxy - 4<SP>1 </SP>- (nitro - and - amino)- diphenylamines. Pharmaceutical preparations active against parasitic helminths contain I and/or salts thereof as active ingredient; administration is preferably orally.