ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A new interpretation - based on a reevaluation of the spectroscopic properties of products 16 to 27 - is proposed for the reaction of diphenyl-cyclopropen-one 14 and -thione 15 with ketene-A, N-diacetals 8 to 13 (A = R2N, RO and RS) originally reported by Sauer & Krapf. It is concluded that the previous structural assignments (see the a-structures), made on the assumption of a prevailing “C,C-insertion” reaction, must be rcplaced as follows: (1) All the “secondary adducts” are, in fact, derivatives (amides and lactams) of 2,3-diphenyl-penta-2, 4-dienoic acid and thioacid (structures 16b to 24b); (2) the “isomerization products”, differ from the latter only in the configuration of the α,β-double bond (structures 25b and 26b); (3) the common “hydrolysisproduct” is α,β-diphenyl-γ-methyl-γ-hydroxy-Δα-butenolide (27b), The above cyclopropenone-ketcneacetal reactions represent, therefore, cases of “C, N-insertion”.This is rationalized with a reaction scheme, in which the “acylide” structure of the “primary adducts” plays a role.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19720550536
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