Gas-phase thermolysis of allyl propargyl amine, allyl cyanomethyl propargyl amine, allyl propargyl 2-thiapropyl amine, and allyl methanesulfonyl propargyl amine

✍ Scribed by Gonzalo Martin; Julian Ascanio; Jesus Rodriguez

• Publisher: John Wiley and Sons
• Year: 1994
• Tongue: English
• Weight: 543 KB
• Volume: 26
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550260409

✦ Synopsis

Abstract

The title amines have been pyrolyzed in a stirred‐flow reactor, at temperatures of 360–500°C, pressures of 7–16 torr, and residence times of 0.5–2.9 s, using toluene as carrier gas. The reaction products were allene, propene, and the corresponding imines. The ratio allene:propene varied in the range 6.7–1.6. The amines with CH~2~CN and SO~2~CH~3~ substituents also formed HCN and SO~2~. These appear to arise from complex free radical decomposition of the imine product. The first‐order rate coefficients for the production of allene plus propene followed the Arrhenius equations: Allyl propargl amine:
Allyl cyanomethyl propargyl amine:
Allyl propargyl 2‐thiapropyl amine:
Allyl methanesulfonyl propargyl amine:
Nonconcerted mechanisms, involving polar six center cyclic transition states, are suggested for the elimination of allene and propene. © 1994 John Wiley & Sons, Inc.