ChemInform Abstract: HIGHLY STEREOSELECTIVE CLAISEN REARRANGEMENT OF VINYL ETHER OF 1-(1-HYDROXYETHYL)-2-METHYL-3-ALKYLCYCLOPENTENE. A ROUTE TO CIS- AND TRANS(1E)-ETHYLIDENE-8-METHYLHYDRINDAN-5-ONE

1982 ◽  
Vol 13 (20) ◽  
Author(s):  
T. TAKAHASHI ◽  
H. YAMADA ◽  
J. TSUJI
Keyword(s):  
Vinyl Ether ◽  
Claisen Rearrangement ◽  
Cis And Trans

Carbanion Rearrangements in the Gas Phase: The Unusual Claisen Rearrangement of Deprotonated Allyl Vinyl Ether

1990 ◽  
Vol 43 (9) ◽  
pp. 1479 ◽  
Author(s):  
PCH Eichinger ◽  
JH Bowie
Keyword(s):  
Gas Phase ◽  
Vinyl Ether ◽  
Condensed Phase ◽  
Claisen Rearrangement ◽  
Negative Ions ◽  
Marked Contrast ◽  
Wittig Rearrangement ◽  
Major Reaction

Allyl vinyl ether is reported to undergo a facile Wittig rearrangement to yield penta-1,4-dien-3-ol under base- catalysed conditions in the condensed phase. In marked contrast, the Wittig rearrangement is not a major reaction in the gas phase. Instead, initial rearrangement occurs by a Claisen process and subsequent fragmentations involve some of the most complex interconversions yet proposed for negative ions.

scholarly journals 1H- und C-NMR-Spektren von Methoxy-substituierten Äthylenen / 1H and 13C NMR Spectra of Methoxy-substituted Ethylenes

1976 ◽  
Vol 31 (1) ◽  
pp. 35-38 ◽  
Author(s):  
M. Herberhold ◽  
G. O. Wiedersatz ◽  
C. G. Kreiter
Keyword(s):  
Charge Distribution ◽  
Vinyl Ether ◽  
13C Nmr ◽  
Nmr Spectra ◽  
13C Nmr Spectra ◽  
1H And 13C Nmr ◽  
Methyl Vinyl ◽  
Methyl Vinyl Ether ◽  
Cis And Trans ◽  
C Nmr

The charge distribution in the methoxy -substituted olefins of the series ethylene, methyl vinyl ether, 1,1-dimethoxyethylene, cis- and trans-dimethoxyethylene, tetramethoxyethylene, is discussed on the basis of the 1H and 13C NMR spectra

Investigation of quantitative structure–reactivity relationships in the aliphatic Claisen rearrangement of bis-vinyl ethers reveals a dipolar, dissociative mechanism

2014 ◽  
Vol 12 (8) ◽  
pp. 1292-1308 ◽  
Author(s):  
Natasha F. O'Rourke ◽  
Jeremy E. Wulff
Keyword(s):  
Vinyl Ether ◽  
Claisen Rearrangement ◽  
Substituent Effects ◽  
Quantitative Structure ◽  
Vinyl Ethers ◽  
Dissociative Mechanism ◽  
Mechanism Of Reaction ◽  
Kinetic Investigations

Kinetic investigations of substituent effects in the Claisen rearrangement of bis-vinyl ether substrates suggest a dissociative mechanism of reaction.

ChemInform Abstract: One-Pot Claisen Rearrangement with n-Butyl Vinyl Ether.

ChemInform ◽  
2010 ◽  
Vol 33 (34) ◽  
pp. no-no
Author(s):  
Hidetoshi Tokuyama ◽  
Takaki Makido ◽  
Toshihiro Ueda ◽  
Tohru Fukuyama
Keyword(s):  
Vinyl Ether ◽  
Claisen Rearrangement ◽  
One Pot

Vinyl ether hydrolysis. XXIX. 1-Methoxy-1,3-butadiene: reaction mechanism and implication for hydrolysis of the mutagen fecapentaene-12

1994 ◽  
Vol 72 (7) ◽  
pp. 1632-1636 ◽  
Author(s):  
Yvonne Chiang ◽  
Robert Eliason ◽  
Gary H.-X. Guo ◽  
A. Jerry Kresge
Keyword(s):  
Vinyl Ether ◽  
Trans Isomer ◽  
Acid Catalysis ◽  
Isotope Effects ◽  
Hydronium Ion ◽  
Rapid Formation ◽  
Methyl Vinyl Ether ◽  
Cis And Trans ◽  
Hydrolysis Of ◽  
Cis Isomer

The hydrolysis of cis- and trans-1-methoxy-1,3-butadiene in aqueous solution occurs by hydron transfer to the δ-carbon atom with little or no β-hydronation to give crotonaldehyde as essentially the sole aldehyde product. The reaction gives appreciable hydronium-ion isotope effects in the normal direction [Formula: see text] and shows general acid catalysis; five carboxylic acid catalytic coefficients for hydrolysis of the trans isomer give a good Brønsted relation with the exponent α = 0.59. This is taken as evidence that these reactions occur by the conventional mechanism for vinyl ether hydrolysis involving rate-determining hydron transfer to substrate carbon followed by rapid formation and decomposition of a hemiacetal intermediate. Comparison of the reactivity of the present dienyl ethers with that of their monoenyl analog, methyl vinyl ether, shows that introduction of the second double bond decreases reactivity considerably: the hydronium-ion catalytic coefficient is reduced by a factor of 8.3 for the trans isomer and by a factor of 160 for the cis isomer. This reduction supports a hypothesis advanced to explain the occurrence of reaction by a different mechanism recently discovered in the hydrolysis of the strongly mutagenic polyenyl ether, fecapentaene-12.

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