147729-86-0Relevant articles and documents
Base-induced trifluoroethanolysis of acyclic di- and trihalogeno ketones: Favorskii rearrangement and [4+3] cycloaddition
Foehlisch, Baldur,Franz, Thilo,Kreiselmeier, Guenter
, p. 4687 - 4698 (2005)
Reactions of five acyclic dihalogeno- and trihalogeno ketones, representing the αα-, α,α′-, α,α,α- and α,α,α′-di- and trihalogeno substitution pattern, with sodium 2,2,2-trifluoroethoxide in 2,2,2-trifluoroethanol (NaTFE/TFE) in the presence of furan were investigated with the aim of obtaining [4+3] cycloadducts of the corresponding oxyallyl intermediates. Preference of Favorskii rearrangement over cycloaddition was observed with dichloromethyl isobutyl ketone (1a) and 1,3-dibromobutan-2-one (12) that formed mainly the trifluoroethyl esters of 3-chloro-2-isopropylpropanoic acid (9a), and (Z)-but-2-enoic acid (isocrotonic acid) (13), respectively. 9a was dehydrohalogenated to form trifluoroethyl 3-isopropylacrylate (11a). [4+3] Cycloaddition was favored with the 1,1,3-trihalogenobutan-2-ones 24 and 25, leading to 2,4-dihalogenated 8-oxabicyclo[3.2.1]oct-6-en-3-ones (26, 27) as a mixture of endo-exo-stereoisomers. With trichloromethyl isobutyl ketone (30) the isomeric 2,4-dichloro-substituted oxabicycles (34) were formed in lithium perchlorate/diethyl ether/furan/triethylamine, while in NaTFE/TFE solvolytic displacement of one chloro substituent occurred, providing 2-chloro-4- trifluoroethoxy-4-isopropyl-8-oxabicyclo[3.2.1]oct-6-en-3-one (36). By analogy, 27 reacted with sodium methoxide/methanol to form the methoxy-substituted oxabicycles 39a and 39b. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
Novel Rearrangement of 2α-Isopropyl-8-oxabicyclooct-6-ene Producing the Monoterpene 3-Hydroxyphellandral
Barbosa, Luiz Claudio de Almeido,Demuner, Antonio J.,Mann, John,Veloso, Dorila P.
, p. 585 - 588 (2007/10/02)
We describe a five-step synthesis of 2α-isopropyl-8-oxabicyclooct-6-ene from 1,1,3,3-tetrabromo-4-methylpentan-2-one, and its unexpected rearrangement to yield trans-3-hydroxy-4-isopropylcyclohex-1-enecarbaldehyde (3-hydroxyphellandral).