The Thermal Isobutylene-Formaldehyde Condensation¹

Abstract

Uncatalyzed thermal condensation of isobutylene with paraformaldehyde in acetic acid-acetic anhydride affords principally 3-methyl-3-butene-l-ol acetate and 3-methylene-l ,5-pentanediol diacetate. The latter is the principal product of a similar condensation of 3-methyl-3-butene-l-ol acetate with paraformaldehyde. The structure of these products was established by standard chemical and physical methods. Accessory products of the condensations which were isolated and characterized included methanol, methyl acetate and isoprene glycol diacetate. Isoprene was obtained on pyrolysis of 3-methyl-3-butene-l-ol acetate.Recent studies of the uncatalyzed thermal condensation of olefins with formaldehyde by Bain,2

Nontemplate-driven polymers: clues to a minimal form of organization closure at the early stages of living systems

“…The isopentenyl units can be obtained industrially by acid catalyzed Prins reaction from isobutene and formaldehyde (Blomquist and Verdol 1955). Isobutene, ethylene and formaldehyde precursors occur in volcanic gases, suggesting a plausible prebiotic synthesis.…”

Search for the Most ‘primitive’ Membranes and Their Reinforcers: A Review of the Polyprenyl Phosphates Theory

“…7 ). Indeed, they (isopentenol and dimethylallyl alcohol) were synthesized by acid catalyzed Prins reaction from formaldehyde and isobutene (Blomquist and Verdol 1955 ). Isobutene itself was obtained by olefin homologation on zeolite, either from methanol (C1) or from ethylene (C2) in high temperature (Cui et al 2008 ; Ilias and Bhan 2013 ; Oikawa et al 2006 ).…”

“…The history of this optimization over millions of years can be traced in cholesterol metabolic pathway, and especially in the successive removal of methyl groups on its alpha face (Fig. 5 ) which lowered its membrane interactions (Bloch 1983 ). Our hypothesis here is that even before eucaryotic cells and cholesterol appeared on earth, at the level of procaryotic cells, this strategy of incorporating in membranes and optimizing membrane reinforcers was already in place.…”

The Thermal Condensation of Isobutylene with Formaldehyde

“…Thermal condensation of isobutylene with formaldehyde has been carried out in a mixture of acetic acid/acetic anhydride (Blomquist and Verdol, 1955), in acetic anhydride alone (Watanabe and Suga, 1963), and in the absence of solvent (Brace, 1955). In each instance, low yields of 3-methyl-3buten-l-ol derivatives were obtained.…”