Molecular rearrangements. VII. Neat, thermal rearrangement of optically active 2-chloronorbornene exo-oxide

1969 ◽  
Vol 91 (3) ◽  
pp. 782-784 ◽  
Author(s):  
Richard N. McDonald ◽  
Richard N. Steppel
Keyword(s):  
Optically Active ◽  
Thermal Rearrangement ◽  
Molecular Rearrangements

Molecular Rearrangements. Part IV. Aryl (Alkyl) Amines (1), Thermal Rearrangement of N-Benzyl-N-Methylaniline

1974 ◽  
Vol 52 (2) ◽  
pp. 293-298 ◽  
Author(s):  
M. Zarif A. Badr ◽  
M. M. Aly
Keyword(s):  
Free Radicals ◽  
Reaction Mechanism ◽  
Tertiary Amine ◽  
Thermal Rearrangement ◽  
Molecular Rearrangements ◽  
Intermediate Products ◽  
Alkyl Amines ◽  
Rearrangement Process ◽  
Homolytic Fission

Heating N-benzyl-N-methylaniline under reflux or heating at ∼315° in sealed tubes, in the absence of any promotor for 100 h, resulted in its rearrangement, producing methylamine, diphenylmethane, and dibenzyl together with o-toluidine and 4-methylacridine. Heating N-methylaniline in a sealed tube under the same conditions, in absence of any promotor, resulted in its rearrangement, producing methylamine and o-toluidine together with unidentified neutral products.When pyrolysis of the tertiary amine was carried out with quinoline as a solvent, the normal products of rearrangement were obtained together with 2-and 4-benzylquinolines and 2,2′-biquinolyl.The reaction mechanism is discussed on the basis of the products separated, from which it is concluded that the tertiary amine undergoes homolytic fission to benzyl and N-methylphenylamino free radicals, followed by a series of homolytic fissions of initially separated intermediate products, during the rearrangement process. Throughout the whole mechanism, the C—N bonds are the only ones to suffer homolytic fission.

MOLECULAR REARRANGEMENTS OF OPTICALLY ACTIVE RADICALS

1934 ◽  
Vol 56 (2) ◽  
pp. 491-491
Author(s):  
Everett S. Wallis ◽  
P. I. Bowman
Keyword(s):  
Optically Active ◽  
Molecular Rearrangements

Thermal rearrangement of optically active tetradeuterated 2-methoxymethyl-methylenecyclopropane and the bent bond/antiperiplanar hypothesis

2019 ◽  
Vol 17 (29) ◽  
pp. 7007-7012 ◽  
Author(s):  
Ghislain Deslongchamps ◽  
Pierre Deslongchamps
Keyword(s):  
Mechanistic Model ◽  
Optically Active ◽  
Thermal Rearrangement ◽  
First Time

The bent bond/antiperiplanar hypothesis (BBAH) provides, for the first time, a mechanistic model that rationalizes methylenecyclopropane rearrangements.

MOLECULAR REARRANGEMENTS INVOLVING OPTICALLY ACTIVE RADICALS. VIII. THE WOLFF REARRANGEMENT OF OPTICALLY ACTIVE DIAZOKETONES

1940 ◽  
Vol 05 (3) ◽  
pp. 276-285 ◽  
Author(s):  
JOHN F. LANE ◽  
JULIUS WILLENZ ◽  
A. WEISSBERGER ◽  
EVERETT S. WALLIS
Keyword(s):  
Optically Active ◽  
Wolff Rearrangement ◽  
Molecular Rearrangements

Thermal rearrangement of optically active α-hydroxy-imines to α-amino-ketones

1967 ◽  
Vol 0 (20) ◽  
pp. 1058-1060
Author(s):  
Shun-ichi Yamada ◽  
Hatsuhiko Mizuno ◽  
Shiro Terashima
Keyword(s):  
Optically Active ◽  
Thermal Rearrangement

Molecular Rearrangements. Part VI. Aryl(alkyl)amines (II) Thermal Rearrangement of N-Benzylaniline

1975 ◽  
Vol 53 (24) ◽  
pp. 3831-3836 ◽  
Author(s):  
M. Z. A. Badr ◽  
H. A. H. El-Sherief
Keyword(s):  
Free Radicals ◽  
Secondary Amine ◽  
Thermal Rearrangement ◽  
Molecular Rearrangements ◽  
Alkyl Amines ◽  
Trans Stilbene ◽  
Homolytic Fission

Heating N-benzylaniline resulted in migration of the benzyl group to the ortho- and para-positions of the aniline nucleus. Ammonia, toluene, biphenyl, diphenylmethane, dibenzyl, trans-stilbene, aniline, together with 9-phenylacridine, and 2,3-diphenylindole, were also formed.When phenol, quinoline, or isoquinoline were used as solvents, the normal rearrangement products were accompanied by 2- and 4-benzylphenols, 3-benzylquinoline, 2- and 4-(aminophenyl)quinoline, 4-benzylisoquinoline, and 1-(aminophenyl)isoquinolines.It is concluded that the pyrolysis of the secondary amine depends on its homolytic fission to benzyl and phenylamine free radicals. Homolysis of some initially separated products was also observed.

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