Patent GB-1268085-A (GB)
Title: Organic polyazo compounds and their use as polymerisation initiators
Inventor: SHEPPARD CHESTER STEPHEN
IPC: C09B43/00
Filed: 1969-08-13
Abstract: 1,268,085. Bis- and poly-azo compounds. PENNWALT CORP. 13 Aug., 1969 [15 Aug., 1968], No. 40533/69. Headings C2C and C2P. [Also in Division C3] Bis- and poly-azo compounds of the formulµ (I) Q-N = N-A-B-A<SP>1</SP>-N = N-Q<SP>1</SP> (II) Q-N=N-A-B-A<SP>1</SP>-N=N-A<SP>1</SP>-BA-N=N-Q (wherein (i) Q and Q<SP>1</SP> are each (R<SP>2</SP>O) 2 P(O)-, R 2 NC(O)-, NH 2 C(NH.HX)-, R<SP>2</SP>SC(O)-, R<SP>2</SP>OC(O)-, R<SP>1</SP>C(O)-, R<SP>1</SP>R<SP>2</SP>ZC-, aryl of 6-14 carbon atoms, or (ii) A and A<SP>1</SP> are each (iii) B is -C(O)O-, -OC(O)O-, -C(O)NH-, -OC(O)NH-, -SC(O)-, -O-, -S- or a direct bond between A and A<SP>1</SP>; (iv) X is an inorganic anion; (v) Z is -CN, -Cl, -Br, -N 3 , -OCN, -SCN, -OOH, -R<SP>1</SP>, -NO 2,  -NO 3 , -C#C-R, -OR, -SR<SP>1,</SP> -OOR<SP>4</SP>, -C(O)NH 2 , -C(O)OR<SP>2</SP>, -C(NH)NH 2 , -C(NH)OR<SP>2</SP>, -C(NOH)NH 2 , -OC(O)R, -OC(O)OR<SP>1</SP>, -SC(O)R<SP>1</SP>, -SC(O)OR<SP>1</SP>, -SC(S)OR<SP>1</SP>, -OOC(O)R<SP>1</SP>, -NR 2 , -NHNHR<SP>1</SP>, -NHNHC(O)OR<SP>2</SP>, -N(COR<SP>1</SP>) 2 , -ONR 2 , -ON(O) =CR<SP>1</SP> 2 , -ON=CR<SP>1</SP> 2 , -C(R)(COOR<SP>2</SP>) 2 , (vi) R is hydrogen, C 1 -C 6  alkyl or C 6 -C 14  aryl; (vii) R<SP>1</SP> is C 1 -C 6  alkyl or C 6 -C 14  aryl; (viii) R<SP>2</SP> is C 1 -C 6  alkyl; (ix) R<SP>4</SP> is C 4 -C 8  tertiary alkyl; (x) R<SP>5</SP> is C 1 -C 6  alkylene; with the provisos that: (xi) Q and Q<SP>1</SP> are different, but may be the same when A and A<SP>1</SP> are different; (xii) A and A<SP>1</SP> are different, but may be the same when Q and Q<SP>1</SP> are different in Formula I and when A in Formula II is a divalent radical other than a divalent radical corresponding to the monovalent radical Q; and (xiii) in the definitions of A and A<SP>1</SP>, in the radical R<SP>5</SP> and R<SP>2</SP> can be joined to form a cyclic group of from 5-8 ring carbon atoms) are prepared by standard techniques, e.g. (when B is -C(O)O-) by condensation of Q-N=N-A-C(O)Cl with HO-A<SP>1</SP>-N=N-Q<SP>1</SP> or condensation of Q-N = N-A-COONa with Cl-A<SP>1</SP>-N = N-A<SP>1</SP>-Cl, or by oxidation of the corresponding hydrazo derivatives. The preparation of 13 compounds is detailed and over 40 compounds are listed. The compounds yield free radicals upon decomposition and are useful as sequential polymerization initiators (see Division C3). 2 - Ethoxycarbonylhydrazo - 2 - cyano - 5- hydroxypentane (A) is prepared from ethyl carbazate, NaCN, and 3-acetyl-1-propanol, and reacted with 4-t-butylazo-4-cyanovaleryl chloride to give 4-ethoxycarbonylhydrazo-4-cyanopentyl 4 - t - butylazo - 4 - cyanovalerate. Oxidation of A with chlorine water gives 2-ethoxycarbonylazo - 2 - cyano - 5 - hydroxypentane, which with NH 3  at 5‹ C. gives 2-carbamylazo- 2 - cyano - 5 - hydroxypentane. 2 - Hydroxyethyl t-butylhydrazocarboxylate is prepared from tbutylhydrazine and ethylene carbonate; N-2- hydroxyethyl - t - butylazoformamide from isopropyl t - butylazocarboxylate and ethanolamine; and 2 - phenylazo - 2 - cyano - 5 - hydroxypentane from HCN and 3-acetyl-1-propanol phenylhydrazone.