Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via
35.1.1.1.1.5.1 Variation 1: tert-Butyl Hypochlorite as Chlorine-Atom Donor

DOI: 10.1055/sos-SD-035-00004

Hartung, J.Science of Synthesis, (20073526.

tert-Butyl hypochlorite[‌38‌,‌39‌] is a moderately stable yellow liquid that boils at 80°C. If photolyzed or heated in the presence of an initiator it is able to convert alkanes into alkyl chlorides 10 and 11 with an average length of the underlying chain reaction of 104 (Scheme 8).[‌40‌] The observed relative primary/secondary/tertiary CH reactivity ratio is similar but not identical to the values given for sulfuryl chloride or chlorine in the presence of benzene (see Section 35.1.1.1, General Introduction, Table 2). The use of aromatic cosolvents, e.g. benzene or tert-butylbenzene, leads to a small but significant increase of the relative CH reactivity indices. The mechanism has been interpreted in terms of homolytic hydrogen-atom abstraction caused by tert-butoxyl radical attack onto the alkane in a strongly exothermic reaction. This step leaves tert-butyl alcohol and an alkyl radical. The latter is trapped by tert-butyl hypochlorite to afford a chlorinated hydrocarbon and the tert-butoxyl radical, which resumes the chain reaction.

Meeeee 8 Meeeeeeeeeee ee Meeeeee eeee eeee-Meeee Meeeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeee-8,8-eeeeeeeeeeeeeee 88 eee 88 (M8=Me); Meeeeee Meeeeeeee:[‌88‌]

M eeee eee eeeeeee eeee 8,8-eeeeeeeeeeeeee (8.88e, 88eeee) eee e-MeMMe (8.88e, 8.8eeee). Mee eeeeee eee eeeeeeee ee eeeeeeeeeee eeeeeeeeeeeeee eeeeee. Mee eeee eee eeee eeeeee eee eeeeeeeeee eeee e 88-M eeeeeeeeeeee eeeeeeeee eeeeee 88ee ee eeeee ee eee eeeeeeee eeeeee, eeeee eee eeeeeeee eee eeeeeeee (MM). Mee eeeeeeee eeee eeeeeeeee eee eeeeeeee ee MM.

References


Cookie-Einstellungen