Showing papers on "Triazene published in 1969"

Triazene Rearrangement. III. A Kinetic Study of the Rearrangement of N-Methyldiaryltriazenes

Abstract: The rate constants of the hydrochloric acid-catalyzed rearrangement of N-methyldiaryltriazenes were determined in 95% aqueous ethanol in the presence of N-methylaniline. Electrondonating substituents on the diazo-part in triazene promoted the rearrangement. A Hammett plot of the rate constants gave a good straight line. The negative ρ-value (−3.63 at 30.0°C) and the large positive values of the entropy of activation suggested that the rate-determining step in this rearrangement is the dissociation of protonated triazene; this is in contrast with the case of the Friswell-Green mechanism. This theory was suppoted by such a solvent effect as that the rate decreased a little as the polarity of the solvent increased. The kinetic behavior of triazenes in the absence of N-methylaniline, and the incorporation of N-methyl-o-toluidine into the product in the rearrangement of 1-p-chlorophenyl-3-methyl-3-phenyltriazene (Id), were also discussed in connection with the above mechanism.

New triazene derivatives and pharmaceutical compositions thereof

Abstract: 1282757 Triazene derivatives FARBENFABRIKEN BAYER AG 25 July 1969 [3 Aug 1968] 37614/69 Heading C2C Novel triazene derivatives of the general formula wherein R 1 , R 2 , R 3 , R 4 and R 5 are each a hydrogen or halogen atom or an alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl group which may be substituted, or a nitro, cyano, -O(CH 2 ) n -COOY, -(CH 2 ) n COOY, -O(CH 2 ) n -CON(R 1 ) 2 or -(CH 2 ) n CON(R 1 ) 2 group (in which Y is a hydrogen atom or an optionally substituted alkyl group, or a cation such that the salt is pharmaceutically acceptable, n is 0 or an integer from 1 to 5 and R 1 is an aliphatic (two aliphatic R 1 groups together optionally completing a heterocyclic ring system) or cyclo-aliphatic radical; an SO 3 Y 1 or -O(CH 2 ) m N(R 11 ) 2 group (in which Y 1 is a hydrogen atom or a cation such that the salt is pharmaceutically acceptable, m is 2, 3 or 4 and R 11 is a C 1-4 aliphatic radical) or an esterified carboxy (other than COOY), esterified sulpho, sulphamoyl, N - alkylsulphamoyl, N,N - dialkylsulphamoyl (the two alkyl groups optionally together completing a heterocyclic ring) or acyl group; R 1 also possibly being a group of the formula -N=N-NR 6 R 7 in the p-position with respect to X; R 6 and R 7 are each an alkyl or alkenyl group optionally substituted by a halogen atom; and X is a direct bond, an oxygen or sulphur atom, a carbonyl, sulphonyl sulphoxide, or azo group, an optionally substituted methylene, ethylene or vinylene group, or an ethynylene group; and pharmaceutically acceptable acid addition salts of those derivatives having basic groups are prepared by diazotization of an amine of the general formula and reaction of the product with a secondary amine of the general formula R 6 R 7 NH, followed optionally by salification of the product. Pharmaceutical compositions having a selective cell-damaging effect against malignant tumour cells comprise, as active ingredient, at least one triazine derivative of the first general formula above or acid addition salt as defined above, in admixture with a pharmaceutically acceptable diluent or carrier, and may be administered orally, parenterally or rectally.