ChemInform Abstract: STUDIES ON THE AMIDO-CLAISEN REARRANGEMENT. IX. SUBSTITUENT EFFECT ON THE ALLYL GROUP IN THE THERMAL REARRANGEMENT OF N-ALLYL-N-TOSYL-1-NAPHTHYLAMINES

1978 ◽  
Vol 9 (36) ◽  
Author(s):  
S. INADA ◽  
R. KURATA ◽  
T. ISHIDA ◽  
T. UDA ◽  
M. OKAZAKI
Keyword(s):  
Substituent Effect ◽  
Claisen Rearrangement ◽  
Thermal Rearrangement

scholarly journals Substituent Effect on Claisen Rearrangement of 1-Substituted 2-Cinnamyloxybenzenes.

2002 ◽  
Vol 51 (5) ◽  
pp. 359-364 ◽  
Author(s):  
Yutaka OKADA ◽  
Motoyuki ADACHI ◽  
Takatoshi HAYASHI
Keyword(s):  
Substituent Effect ◽  
Claisen Rearrangement

ChemInform Abstract: Substituent Effect on the Claisen Rearrangement.

ChemInform ◽  
1990 ◽  
Vol 21 (31) ◽  
Author(s):  
G. DESIMONI ◽  
G. FAITA ◽  
A. GAMBA ◽  
P. P. RIGHETTI ◽  
G. TACCONI ◽  
...  
Keyword(s):  
Substituent Effect ◽  
Claisen Rearrangement

HALOGEN MIGRATION AND ELIMINATION IN THE CLAISEN REARRANGEMENT OF ALLYL 2,6-DIHALOPHENYL ETHERS

1963 ◽  
Vol 41 (12) ◽  
pp. 2917-2930 ◽  
Author(s):  
E. Piers ◽  
R. K. Brown
Keyword(s):  
Dielectric Constant ◽  
Lewis Acids ◽  
Claisen Rearrangement ◽  
Stannous Chloride ◽  
Ionic Species ◽  
Thermal Rearrangement ◽  
Polar Solvents ◽  
Factors Affecting ◽  
Competitive Reduction ◽  
Catalytic Effects

A study has been made of some factors affecting the migration or elimination of halogen in the Claisen rearrangement of allyl 2,6-dihalophenyl ethers.In the thermal rearrangement of allyl 2,6-dichlorophenyl ether, carried out in a number of solvents of different dielectric constant, halogen migration proceeds somewhat better in highly polar solvents. However, a competitive reduction to the monohalogenated allylphenol occurs in the presence of oxidizable solvents and/or products. The reaction is also complicated by the catalytic effects of certain solvents and the phenolic products, which give results similar to those obtained with Lewis acids. Stannous chloride acts as a Lewis acid and catalyzes the rearrangement of allyl 2,6-dichlorophenyl ether with simultaneous halogen rearrangement. As well, a competitive reductive removal of the halogen takes place. Results from the rearrangement of allyl 2,6-dibromophenyl ether with zinc chloride and of allyl 2,6-dichlorophenyl ether with zinc bromide, as well as those from the stannous chloride reactions indicate that the halogen migration takes place not only by an allylic shift but also via a competitive halogen substitution probably occurring by an Sn2′ pathway possibly assisted by a zinc halide bridge mechanism and/or an ionic species such as [Formula: see text].

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