Patent GB-1272284-A (GB)
Title: Unsymmetrical azo and hydrazo compounds
Inventor: MACLEAY RONALD EDWARD
IPC: C08F283/01
Filed: 1969-04-24
Abstract: 1,272,284. Unsymmetrical azo and hydrazo compounds. WALLACE & TIERNAN Inc. 24 April, 1969, No. 21119/69. Heading C2C. [Also in Division C3] Novel compounds I in which R<SP>11</SP> is 1-13 C alkyl, phenyl-1-13 C alkyl, or phenyl, not more than one R<SP>11</SP> being phenyl; A and B are both H or together a further bond; X is a mono-, di- or tri-valent group and n is 1, 2 or 3, wherein (1) when A and B are both H and n is 1, X is -CONR 3 R 4  (R 3  and R 4  are H, 1-20 C aliphatic radicals, or cycloaliphatic radicals or together may form an alkylene biradical); (2) when A and B together form a bond and n is 1, X is (a) -COE where E is NR 3 R 4 , R 5 ,-N(R 3 )-R 13 -N(R 3 )-CO-N= N-C(R<SP>11</SP>) 3 , or -R 13 -CO-N=N-C(R<SP>11</SP>) 3 ; R 5  is a 1-20 C aliphatic, cycloaliphatic or aromatic radical; and R 13  is an aliphatic, cycloaliphatic or aromatic biradical; (b) -C(F)(R 1 )R 2  where R 1  and R 2  are 1-20 C aliphatic or cycloaliphatic radicals and together may be alkylene and R 2  may also be phenyl or substituted phenyl; F is -CN, -CONH 2 , -COOR 6 , -C(NH 2 )=NH, -C(OR 6 )=NH, -C(NH 2 )- NOH, Cl, Br, -OCOH, -OCOR 5 , -OCOOR 5 , -OCOOOR, -SCOR 5 , -SCSR 5 , -SCOOR 5 , -SCSOR 5 , -OR 5 , -SR 5 , -N 3 , -SCN, -OCN, -OOR, -OOCOR 5 , -OOH, -OH, -R 5 , -N(R 10 ) 2 , -NHN(R 5 ) 2 , -NHNHCOOR 6 , -N(COR 1 )COR 2 , -NO 2 , -NO 3 , -C#CR 10 , -O-N=C(R 5 ) 2 , -ON(R 10 ) 2 , -ON(#O) = CR 3 R 4 , -CR 14 (R 15 ) (R 10 ), -Y<SP>11</SP>-C(R 1 ) (R 2 )-N=N-C(R<SP>11</SP>) 3 , or R is -C(R<SP>11</SP>) 3 ; R 6  is 1-13 C alkyl; Y<SP>11</SP> is -S-S-, -NH-NH-, -X<SP>11</SP>-C(=X<SP>11</SP>)-R 13  -C( = X<SP>11</SP>)-X<SP>11</SP>-, X<SP>11</SP>-C( = X<SP>11</SP>)O-R 13 - O-C( = X<SP>11</SP>)-X<SP>11</SP>-, -X<SP>11</SP>-R 13 -X<SP>11</SP>-, -OO-CO-R 13 -CO-OO , -OO-C(R 1 )- (R 2 )-R 13 -C(R 1 ) (R 2 )-OO-,-C(R 14 ) (R 15 )-, or -00-; X<SP>11</SP>is O or S; R 10  is H, or a 1-20 C aliphatic, cycloaliphatic or aromatic radical; R 14  and R 15  are -COOR 10 , -CN, -COR 10 , -NO 2 , -CO-N(R 10 ) 2 , -C(R 10 ) 2 -OCOR 10 , -COOH, -COOM, -CH 3 , -C(R 10 ) 2 OH, -C(R 10 ) 2 -OCOCl, -C(R 10 ) 2 -OCOOR 10 , -C(R 10 ) 2 OCON(R 10 ) 2 , -COCl or -NH 2 ; and R 14  and R 15  can together form -CO-R 13 - CO-, -COOR 13 O-CO-, -CON(R 6 )-R 13 - N(R 6 )-CO-, -C(R 10 ) (OH)-R 13 -C(R 10 ). (OH)-, -C(R 10 )(OCOR 10 )-R 13 -C(R 10 )- (OCOR 10 )-, -C(R 10 ) (O-CO-NR 6 R 6 )-R 13  -C(R 10 ) (O-CO-NR 6 R 6 ), or and M is an alkali metal; (c)-C(R 1 ) (F)-R 13 - C(R 1 ) (F)-N=N-C(R<SP>11</SP>) 3  ; (d) -C(R 6 )= C(R 7 )R 8  where R 7  and R 8  are H or 1-13 C alkyl or together form an alkylene biradical and R 6  and R 8  may together form an alkylene biradical; (e) a radical where Z 1  is the residue of the heterocyclic ring; (3) when A and B together form a bond and n is 2, X is where Z 2  is the monovalent residue of the heterocyclic ring and (4) when A and B together form a bond and n is 3, X is where Z 3  is the divalent residue of the heterocyclic ring; are prepared by procedures given below:- (1) RNHNH 2  is reacted with R 1 COR 2  to give R-NHN = CR 1 R 2  and this is reacted with HCN to give RNHNH-C(R 1 )(R 2 )CN, which on oxidation gives R-N=N-C(R 1 )(R 2 )CN. (2) RNHN = C(R 1 )(R 2 ) is reacted with halogen to give R-N=N-C(R 1 )(R 2 )hal. (3) The product of (2) may be reacted with an appropriate alkaline earth or alkali metal compound M(Y) 1-2  or M 1-2 Y<SP>11</SP> to give R-N= N-C(R 1 )(R 2 )Y or [R-N=N-C(R 1 )(R 2 )] 2 Y<SP>11</SP> where Y is as defined above for F, but is not -CONH 2 , -COOR 6 , -C(NH 2 )=NH, -C(OR 6 )=NH, -(NH 2 )=NOH, Cl, Br or -Y<SP>11</SP>-C(R 1 )(R 2 )-N=N-C(R<SP>11</SP>) 3 . (4) R-N=N-COOR 9  is reacted with HNR 3 R 4  to give R-N=N-CONR 3 R 4  where R 9  is 1-13 C alkyl. (5) R-NHNH 2  is reacted with R 5 COhal to give R-NHNHCOR 5  which may be oxidized to give R-N=N-COR 5 . (6) RNHNH 2  is reacted with a compound where X<SP>1</SP> is halo and Z<SP>1</SP> is Z 1 , Z 2  or Z 3 , to give a compound which on oxidation gives a compound (7) RNHNH 2 .HX<SP>111</SP> is reacted with H 2 NCON(R 11 ) 2  to give R-NHNH-CON(R 11 ) 2  (X<SP>111</SP> is C1-, Br-, I-, SO 4 - or HSO 4 - and R 11  is H or 1-13 C alkyl). (8) R-NHNH 2  is reacted with M<SP>1</SP>CNO to give R-NH-NHCONH 2  (M is H or metal).