Flow allylic amination reaction

Scheme 7.37 A flow asymmetric allylic amination reaction.

ALLYL CHLORIDE (107-05-1) Forms explosive mixture with air (flash point -20°F/ —29°C). Violent polymerization and explosion may occur from elevated temperatures, light, acid catalysts, ferric chloride, aluminum chloride, Lewis acids, or Ziegler catalysts, finely divided metals. Violent reaction with oxidizers, alkyl aluminum chlorides. Incompatible with strong acids, oleum, amines, aluminum chloride, boron trifluoride, chloro-sulfonic acid, ethylene diamine, ethyleneimine, ferric chloride, sodium hydroxide. Slow decomposition with moisture. Attacks some coatings, plastics, and rubber. Corrosive to steel. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

A closely related 2C-T-X compound was also started quite a while later -this was the allylthio homologue of the methallyl material 2C-T-3 or 2C-T-20. Its place in the flow of things is evident from its numbering, 2C-T-16. A mixture of 2,5-dimethoxythiophenol and KOH and allyl chloride in MeOH gave 2,5-dimethoxyphenyl allyl sulfide as a white oil which boiled at 110-125 °C at 0.25 mm/Hg. This, with POCI3 and N-methylformanilide provided 2,5-dimethoxy-4-(allylthio)benzaldehyde which distilled at 140-160 °C at 0.4 mm/Hg and could be recrystallized from MeOH as a pale yellow solid. Reaction of this aldehyde in nitroethane in the presence of ammonium acetate (steam bath for 2.5 h) provided 2,5-dimethoxy-4-allylthio-beta-nitrostyrene as red crystals from acetonitrile. Its mp was 114-115 °C. Anal. (C13H15N04S) C,H. This has not yet been reduced to the final amine, 2,5-dimethoxy-4-allylthiophenethylamine, 2C-T-16. The corresponding amphetamine would be, of course, ALEPH-16. 

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