Rearrangement in the homogeneous elimination kinetics of 3-chloro-2,2-dimethylpropan-1-ol in the gas phase

✍ Scribed by Gabriel Chuchani; Rosa M. Dominguez

• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 299 KB
• Volume: 9
• Category: Article
• ISSN: 0894-3230
• DOI: 10.1002/(sici)1099-1395(199608)9:8<583::aid-poc818>3.0.co;2-z

✦ Synopsis

3-Chloro-2,2-dimethyIpropan-l-ol was pyrolysed in a static system at 410.0-459-1 "C and 62-179 Torr. The reaction, in a seasoned vessel and in the presence of the free radical suppressor propene, is homogeneous, unimolecular, and follows a first-order rate law. The rate coefficient follows the Arrhenius equation: log k , (s-') = (13-14*0*15) -(218-8i2.1) W mol-' (2.303RT)-'. The products are isobutene, formaldehyde and HCI gas. The exclusive intramolecular migration of the CH,OH group to the positively charged carbon atom, from the C-CI bond polarisation, appears to proceed by way of an intimate ion-pair type of mechanism. The intermediate 3-methylbut-3-en-1-01, under the reaction conditions, undergoes a six-centered decomposition characteristic of 1-hydroxyalkenes to produce isobutene, formaldehyde and HCI. The pyrolysis of the deuterated substrate, 3-chlor0-2,2-dimethyIpropan-l-[~H]01, serves to support the mechanistic consideration assumed above.