Phenyl methyl nitrosamine

Nitrosamine and para Nitroso Methyl Aniline.—The reaction with nitrous acid is characteristic of secondary amines and yields phenyl methyl nitrosamine, the nitroso group entering the amino radical. This, however, undergoes rearrangement with the transference of the nitroso group to the ring yielding a nitroso benzene compound. 

The rearrangement occurs also when nitro benzene is electrolytically reduced by immersing the cathode in nitro benzene and sulphuric acid and the anode in sulphuric acid. Phenyl hydroxyl amine is first produced and by the above rearrangement is converted into para amino phenol. This rearrangement is analogous to the one occurring when phenyl methyl nitrosamine goes over to para-nitroso methyl aniline (P- S59)-... 

In saurer Losung wird Methyl-phenyl-nitrosamin an Blei zu N-Methyl-N-phenyl-hydra-zin reduziert (80% d.Th.)4. Analog verhalten sich Dialkyl-nitrosamine ( — 0,9 V, bis 82% d.Th.) in alkoholischer Salzsaure5. Zur Hcrstellung von N,N-Dimethyl-hydrazin aus dem N-Nitroso-Derivat s.ds. Handb., Bd. X/2, S. 42 (zuN,N-Dialkyl-hydrazinen s.Lit.6). 

Although 3-amino-l,2,4-thiadiazoles (e.g. the 5-phenyl homolog) fail to yield nitrosamines under the usual conditions,126 5-nitrosamines are well known.81, 5,190,191 Thus, 3-alkoxy-,8 3-alkylthio-,85 3-dialkyl-amino-,87 and 3-alkylsulfonyl-5-amino-86 (243) as well as 3-aryl-5-arylamino-l,2,4-thiadiazoles,74 on treatment with the calculated quantity of sodium nitrite in dilute mineral acid, or concentrated formic acid, yield crystalline nitrosamines (244). Their unusual stability has permitted a close study of their formation and properties. 170 Their positive Liebermann reaction85,87,170 and the results of their methylation (outlined in the reaction scheme) show that nitro-sation occurs in the side-chain and not in the nucleus.170... 

Methyl-phenyl nitrosamine separates as a yellow oil, which solidifies on cooling (M.P. 12°—15°). 2 gms. methyl-phenyl nitrosamine are dissolved in 4 gms. ether and 8 gms. absolute alcohol which have been saturated with hydrochloric acid gas then added. After a time needles separate out which are filtered and washed with a mixture of alcohol and ether. 

Methyl-aryl)- XI/1, 853 N-Nitroso- s.u. Nitrosamin N-Nitro- s.u. Nitramin (2-Phenyl-ethyl)- IV/lc, 119 Silyl- E18, 740 (Imin./Hydrosilylier.) N-Sulfinyl- Ell, 569... 

Nitrosamin (2,3-Dichlor-phenyl-thio)-methyl- E14a/3, 522 (Imin + NOCl/Ar —SH)... 

The parent compound, coumarin, has been found to cause chromosome breakage in animal tissues [207, 336]. The mechanism of this action and the effect on chromosomes by chemical mutagens has not yet been elucidated [337], There is hardly any structural relationship of action between these compounds. Good chromosome breakers of mammalian cells or plants include bromouracil, caffein and derivatives, alkylating agents, phenols, quinones, colchicine, methyl-phenyl-nitrosamine [337-343]. However, there is another plant product, podophyl-lotoxin, related to coumarin, which also causes chemical mutagenesis [338, 344]. 

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