BENZIDINE (4,4 diaminobiphenyl; n, n-diaminobiphenyl) — connection from ryadya aromatic diamines, possessing cancerogenic action:
The colourless or slightly yellowish crystals in the form of leaflets or scales darkening on light and air. Pier. weight 184,24; t ° pl 127,5 — 128,7 °; t ° kip 400 — 401 °; water solubility 1: 244, on air — 1: 45, it is easily alcohol-soluble.
B. — the major semi-product developed by the anilinocolourful industry for production azoic dyes (see). In the USSR benzidine-sulfate — sulfate salt of benzidine is applied to their receiving, edges is produced in the form of an aqueous slurry. Benzidine-sulfate is water-insoluble, alcohol and ether.
In laboratory practice benzidine basis and its salts are applied to detection of blood in Calais, a gastric juice and urine (see. the Benzidine test ),
B. and its salts possess cancerogenic action. For the first time experimental data about carcinogenic activity were obtained by Spitts (S. Spitz, 1950) et al. in experiences on dogs who at B.'s feeding had tumors of a bladder. Subcutaneous injections of B. or feeding to his rats led to development at them of a sebaeous gland carcinoma, gepaty and adenocarcinomas of a rectum. At the persons occupied on B.'s production and its salts, tumors of a bladder (papillomas and cancer) are observed more often than at the azoic dyes working in production that is explained by various extent of contact. In foreign countries (according to the data published till 1962) 294 cases of occupational diseases tumors of a bladder caused by B. and its salts took place. It is established that by B.'s production the intermediate product — hydrazo-benzene which is also cancerogenic turns out.
B.'s metabolism in a human body and animals is not identical. At B.'s rats it is partially acetylated and hydroxylated. In urine of the dogs receiving B. it was defined 3,3' - dioxybenzidine and sulfate ether 4,4 of a '-diamino-3-diphenyl. In urine of people, commas in the benzidine production, B. and its acetyl derivatives are not found.
Benzidine-sulfate is manufactured in the USSR since 1930. In the beginning there were many manual operations; the product was issued in the form of paste in barrels. The workers servicing Nutsche filters for benzidine-sulfate and hydrazo-benzene had with them big contact. From hands of filtrovalshchik found up to 141 mg of benzidnn-sulfate and 10,75 mg of hydrazo-benzene in washouts. In 1947 production benzidine-sulfate was completely reconstructed and transferred to continuous technological process owing to what decrease in pollution of the production environment is noted in recent years. On production express methods of qualitative test benzidine-sulfate on integuments of hands, on working clothes, on the surfaces of the equipment are entered that gave the chance to establish systematic control of their pollution and to timely take the appropriate measures. Periodic urological inspections of working are performed. However danger of a disease of professional tumors of a bladder is completely not eliminated. Gradual reduction of release benzidine-sulfate and replacement of the benzidine dyes with others, and then and complete cessation of production benzidine-sulfate shall be a radical recreational action.
A number of the aromatic diamines having carcinogenic activity or suspicious in this respect concerns to group B.: 3,3 '-dikhlorbenzidnn, ortho-tolidine, ortho-dianisidine.
3,3 '-dichlorbenzidine (3,3 '-dichlorine-4,4' - diaminobiphenyl):
Powder of grayish color, inodorous, almost water-insoluble and easily soluble in glacial acetic acid; crystallizes from alcohol and benzene in the form of needles with t°pl 133 °.
In our country since 1954 muriatic salt 3,3 '-dichlorbenzidine, difficult water soluble and easily alcohol-soluble was produced. The product was issued in the form of paste 3,3' - dichlorbenzidine, containing in recalculation on the basis not less than 30% of substance. Blastomogenic action 3,3 '-dichlorbenzidine is established on rats and mice. It was the highly active carcinogenic substance causing tumors in different bodies including at rats in a bladder.
Ortho-tolidine (3,3 '-dimethyl-4,4' - diaminobiphenyl, azoamine blue To):
Crystals in the form of colourless leaflets with t°pl 129 °, soluble in alcohol and ether, in hot water solubility 1: 300. In the USSR ortho-tolidine began to be produced since 1933 and was produced in the form of paste of its muriatic salt with contents in recalculation on the basis apprx. 25% of substance.
Blastomogenic effect of ortho-tolidine is established on rats. It was a highly active, polipotentny carcinogenic substance of resorptive action. Carried out a gigabyte. researches showed unfavorable conditions of work in production 3,3 '-dichlorbenzidine and ortho-tolidine in this connection they were laid off.
Ortho-dianisidine (3,3 '-dimetoksi-4,4' - diaminophenyl, azoamine blue C), the ODE:
Crystals in the form of colourless leaflets, easily ether-soluble, benzene, alcohol; t pl it 137 — 138 °, pier. weight 244,3. For the industrial purposes ortho-dianisidine-sulfate in the form of suspension is produced. From it several brands of azoic dyes are produced. Ortho-dianisidine-sulfate is received from ortho-nitroanisole by recovery by zinc dust to a gidrazoanizol with the subsequent regrouping in ortho-dianisidine-sulfate. Carcinogenic activity of ortho-dianisidine (basis) in the form of 37,7% of paste was studied on rats. This substance possesses weak cancerogenic action.
Production of ortho-dianisidine-sulfate exists in the USSR since 1932 and is placed in the same production rooms where produce benzidine-sulfate. Cases of diseases of tumors of a bladder among working in production of ortho-dianisidine-sulfate are not registered.
See also Oncogenous substances .
Bibliography: Harmful substances in the industry, under the editorship of N. V. Lazarev, p.1, page 599, L., 1971; Genin V. A. Express method of detection of Oyenzidyan and dnanizi-dyne giiokhlority sodium, Gigabyte. work and the prof. having got sick., JV * 5, page 59, 1971; Lipki I. L. K N to a question of a deadline of work in the productions dangerous on impact of the cancerogenic amino compounds on health working, in the same place, - 4s 7, page 56, 1963; T e m to and I. S N. The tumors of a bladder caused by cancerogenic aminoazo compounds, M., 1962; Fizerl. and Fizerm. Organic chemistry, the lane with English, t. 2, page 21 «. 217, 235, M., 1970; Bradshaw L. ampere-second 1 and at s about n D. Metabolism of two aromatic amines in the dog. Nature (Lond.), v.& 176, 974, 1955; Engelbertz P. a b e 1 E. Nachweis von Benzidin und seinen Urawandlungsprodukten im Harn und in Organteilen, zbl. ATbcitsmed. Bd 3, S. 161, 1953.
I. L. Lipkin, L. M. Shabad.