Patent GB-1417019-A (GB)
Title: Stiblene derivatives
IPC: D06L3/12
Filed: 1972-12-22
Abstract: 1417019 Stilbene derivatives; quaternary phosphonium compounds SANDOZ Ltd 22 Dec 1972 [24 Dec 1971 26 Jan 1972] 59306/72 Headings C2C and C2P [Also in Division C3] The invention comprises compounds of the formula where R 1  and R 5  are H, nitrile or linear alkyl of 1 to 4 carbon atoms, R 2 , R 4 , R 6  and R 8  are H, one of the following first-order substituents: halogen, alkyl or alkoxy of 1 to 8 carbon atoms, alkenyl of 3 to 8 carbon atoms, or one of the following second-order substituents: -CN, -COOR<SP>1</SP>, -CONR<SP>1</SP>R<SP>11</SP>, -SO 3 R<SP>111</SP>, -SO 2 NR<SP>1</SP>R<SP>11</SP> or SO 2 R<SP>1111</SP>, in which R<SP>1</SP> is H, alkyl of 1-22 carbon atoms, hydroxyalkyl of 2 to 4 carbon atoms, phenyl or methyl- or chlorine-substituted phenyl, R<SP>11</SP> is H, alkyl of 1 to 8 carbon atoms or hydroxyalkyl of 2 to 4 carbon atoms, or R<SP>1</SP> and R<SP>11</SP> together with the vicinal nitrogen atom form a pyrrolidine, piperidine, piperazine or morpholine ring, R<SP>111</SP> is phenyl or methyl- or chlorinesubstituted phenyl, R<SP>1111</SP> is alkyl of 1 to 4 carbon atoms, phenyl or methyl- or chlorine-substituted phenyl, R 3  and R 7  are hydrogen, a first-order or second-order substituent as defined above or a heterocycle of the formula where X is -O-, -S-, -NH- or -NR<SP>11111</SP>-, R<SP>11111</SP> is alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 2 to 4 carbon atoms, A 1  and A 2  each signifies, if X is -O-, phenyl or phenyl substituted by chlrine or alkyl or alkoxy of 1 to 4 carbon atoms, or if X is -O-, -S-, -NH- or -NR<SP>11111</SP>-, they together form the atoms of a condensed naphthalene nucleus, a condensed benzene ring or a condensed benzene ring substituted by F, Cl, CN, alkyl of 1 to 8 carbon atoms and/or alkoxy of 1 to 8 carbon atoms, and A 3  is phenyl or phenyl substituted by one of the named first-order substituents or by a second order substituent which does not contain a heterocyclic radical, A 4  is H or methyl, p and q are 1 to 3, with the proviso (i) that the total of p and q is at least 3, (ii) the total of p and q and the number of second-order substituents in the molecule is at least 5, the heterocycle significances (a), (b) and (c) for R 3  and R, and the -CN significance for R 1  or R 5  being considered as second-order substituents, and (iii) except where p is 1, R 3  is a heterocycle (c), A 3  is unsubstituted phenyl, A 4  is methyl, R 1  is cyano, R 2  and R 4  are both H, q is 2, R 5  is H and either R 6 , R 7  and R 8  are all H or R 6  and R 7  are both chlorine and R 8  is H, then if only one of the substituents R 3  and R 7  is a heterocycle (a), (b) or (c), either the total of p and q is at least 4 and/or at least 2 further non-heterocyclic second order substituents are present in the molecule. The compounds may be prepared (a) by reacting together compounds of the formula where Y is -CHO or a functional derivative thereof or -CO-COOH and Z is a substituent which activates the vicinal methylene group, or H if Y is an anile derivative of the aldehyde group and no equally active or more active methyl is present, and if a substituent Z with a significance other than hydrogen remains in the reaction product, replacing this with hydrogen, (b) cleavage of two of the substituents Y 1  and Z 1  with simultaneous reduction or oxidation if necessary of compounds of the formula where Y 1  and Z 1  are H, halogen, hydroxy or acyloxy or (Y 1 ) 2  and/or (Z 1 ) 2  are oxo, and if Y 1  and/or Z 1  have a significance other than H in the reaction product, replacement of such substituent by H, (c) replacing a halogen atom by a nitrile group in a compound of the formula where at least one of R 1 <SP>1</SP> to R 8 <SP>1</SP> is halogen and the remaining symbols are as R 1  to R 8 , (d) converting a compound of Formula I in which at least one of R 2 , R 3 , R 4 , R 6 , R 7  and R 8  is CN by conversion of the CN into a compound of Formula I having a corresponding carboxylic acid or carboxylic amide or ester, (e) converting a compound of Formula I in which at least one o R 3  and R 7  is a carboxylic acid, amide or ester into a compound of Formula I having the corresponding heterocycle (a) substituent, if necessary after reaction to the corresponding carboxylic halide group, (f) reacting in alkaline medium and/or under oxidative conditions a compound of the formula where W is H, halogen or -p<SP>(+)</SP>(aryl) 3  anion<SP>(-)</SP>, for which reaction the medium must be alkaline if W is halogen and must be carried out in the presence of a proton acceptor and an oxidizing agent if W is p<SP>(+)</SP>(aryl) 3  anion<SP>(-)</SP> to form a compound of Formula I in which R 5 , R 6 , R 7 , R 8  and q are identical to R 1 , R 2 , R 3 , R 4  and p in Formula VI or (g) by thermal treatment to split off CO 2  or N 2  in an inert gas atmosphere of compounds of the formulµ The invention further comprises compounds of Formula V, which may be produced by methods analogous to those used for producing compounds of Formula I. The intermediates 4 - (4<SP>1 </SP>- cyanophenyl)- benzyl triphenyl phosphonium bromide and periodate are prepared by reacting 4-cyano-4<SP>1</SP>- bromomethylbiphenyl with triphenyl phosphine and optionally reacting the product with sodium periodate.