The Reaction of Diethyl Malonate with Styrene Oxide

Abstract

l,l,7,7,tetrasiloxane.-To a solution of 0.390 g. (1.33 mmole.) of the tetrol in 40 ml. of ether was added 4.0 ml. (31.6 mmoles.) of trimethylchlorosilane and 2.0 ml. of pyridine. Work-up as above yielded 0.422 g. (57%) of distillate which mostly solidified to a waxy solid. Vapor phase chromatography showed this to be about 95% pure; a specimen collected by v.p.c. melted at 85-90°and had an infrared spectrum identical with that of a sample prepared by Simmler's2 procedure. This spectrum (in CS2) showed a very strong raSiOSi band near 1062 cm.-1 [probably a 1065 (s), 1052 (m) doublet] with a medium shoulder near 1105 cm.-1, but no bands of SiOH groups.

Reaction of 1-(p-Chlorophenyloxycarbonyl)-azetidine with Aromatic Amines

“…II 0-Phenyl-7-butyrolactone (Ila), mp 46-47°, was isolated from the reaction of styrene oxide with sodiomalonic ester, as described earlier. [1][2][3] Its pmr spectrum corresponded with that described by DePuy and coworkers,1 and we therefore agree1,2 that a attack by diethyl malonate anion on styrene oxide is of greater importance than ß attack. 7-Phenyl-7-butyrolactone (la), mp 37°, was prepared5 by catalytic reduction of /3-benzoylpropionic acid.…”

Functionalization of Poly(styryl)lithium with Styrene Oxide

“…Investigations into the behavior of styrene oxide in the presence of nucleophiles indicated that a mixture of products may be expected due to the electronic contributions of the benzene ring. 11,12 Oligomerization of the epoxide at the chain end is also possible, as has been observed for ethylene oxide under certain conditions. [4][5][6] A variety of analytical tools were utilized to determine the functionality, regiochemistry, and degree of oligomerization, including 1 H and 13 C NMR spectroscopy and MALDI-TOF MS.…”

“…11,12 The reaction of styrene oxide with sodium diethyl malonate resulted in the formation of two lactones. 11 The major product (60%) resulted from nucleophilic attack at the more hindered carbon, while the minor product resulted from attack at the least hindered carbon. Subsequent work on the ring opening of para-substituted styrene oxides indicated that the substituent had a dramatic effect on the regiochemistry of the reaction.…”

Structural modifications of strigol analogs. Influence of the B and C rings on the bioactivity of the germination stimulant GR24

“…Methyl 2indanylacetate (21) was prepared by hydrogenolysis and subsequent esterification of the tricyclic lactone 20 (ABC part of GR24), as depicted in Scheme IV. ß• and 7-phenyl-7-butyrolactone were obtained as a mixture from styrene oxide and diethyl malonate (De Puy et al, 1964) and subsequently separated by chromatography. (7-Phenyl-7-butyrolactone is also commercially available.)…”