Cyclic Acetals. Structural Analysis of 1,3‐Dioxepine and Related Compounds

Flemming S. Jørgensen; Michael Gajhede; Bruno Frei

doi:10.1002/hlca.19850680809

Cyclic Acetals. Structural Analysis of 1,3‐Dioxepine and Related Compounds

Flemming S. Jørgensen^*, Michael Gajhede, Bruno Frei

^*Corresponding author for this work

Abstract

The He(I) PE spectra of 1,3‐dioxepine (1) and the related bicyclic acetals 1,3,7,7‐tetramethyl‐2,11‐dioxabicyclo[4.41]undeca‐3,5‐dien‐10‐one (2) and 1,3,7,7‐tetramethyl‐10‐methylidene‐2,11‐dioxabicyclo[4.4.1]undeca‐3,5‐diene (3) have been recorded and analyzed. Interpretation of the PE data indicate strong orbital interactions between the diene and acetal moieties in 1. Different conformations have been evaluated by a joint MMP2 molecular mechanics and ab initio molecular orbital analysis, which shows 1 to prefer a slightly boat‐shaped conformation with the diene part being planar and the CH₂ group placed considerably out‐of‐plane. The bicyclic acetals 2 and 3 show a frontier orbital picture similar to 1 superimposed with the characteristics of the CO and CC groups, respectively. The crystal structure of the keto‐acetal 2 was determined by an X‐ray analysis.

Original language	English
Journal	Helvetica Chimica Acta
Volume	68
Issue number	8
Pages (from-to)	2148-2157
Number of pages	10
ISSN	0018-019X
DOIs	https://doi.org/10.1002/hlca.19850680809
Publication status	Published - 1 Jan 1985

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title = "Cyclic Acetals. Structural Analysis of 1,3‐Dioxepine and Related Compounds",

abstract = "The He(I) PE spectra of 1,3‐dioxepine (1) and the related bicyclic acetals 1,3,7,7‐tetramethyl‐2,11‐dioxabicyclo[4.41]undeca‐3,5‐dien‐10‐one (2) and 1,3,7,7‐tetramethyl‐10‐methylidene‐2,11‐dioxabicyclo[4.4.1]undeca‐3,5‐diene (3) have been recorded and analyzed. Interpretation of the PE data indicate strong orbital interactions between the diene and acetal moieties in 1. Different conformations have been evaluated by a joint MMP2 molecular mechanics and ab initio molecular orbital analysis, which shows 1 to prefer a slightly boat‐shaped conformation with the diene part being planar and the CH2 group placed considerably out‐of‐plane. The bicyclic acetals 2 and 3 show a frontier orbital picture similar to 1 superimposed with the characteristics of the CO and CC groups, respectively. The crystal structure of the keto‐acetal 2 was determined by an X‐ray analysis.",

author = "J{\o}rgensen, {Flemming S.} and Michael Gajhede and Bruno Frei",

year = "1985",

month = jan,

day = "1",

doi = "10.1002/hlca.19850680809",

language = "English",

volume = "68",

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journal = "Helvetica Chimica Acta",

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T1 - Cyclic Acetals. Structural Analysis of 1,3‐Dioxepine and Related Compounds

AU - Jørgensen, Flemming S.

AU - Gajhede, Michael

AU - Frei, Bruno

PY - 1985/1/1

Y1 - 1985/1/1

N2 - The He(I) PE spectra of 1,3‐dioxepine (1) and the related bicyclic acetals 1,3,7,7‐tetramethyl‐2,11‐dioxabicyclo[4.41]undeca‐3,5‐dien‐10‐one (2) and 1,3,7,7‐tetramethyl‐10‐methylidene‐2,11‐dioxabicyclo[4.4.1]undeca‐3,5‐diene (3) have been recorded and analyzed. Interpretation of the PE data indicate strong orbital interactions between the diene and acetal moieties in 1. Different conformations have been evaluated by a joint MMP2 molecular mechanics and ab initio molecular orbital analysis, which shows 1 to prefer a slightly boat‐shaped conformation with the diene part being planar and the CH2 group placed considerably out‐of‐plane. The bicyclic acetals 2 and 3 show a frontier orbital picture similar to 1 superimposed with the characteristics of the CO and CC groups, respectively. The crystal structure of the keto‐acetal 2 was determined by an X‐ray analysis.

AB - The He(I) PE spectra of 1,3‐dioxepine (1) and the related bicyclic acetals 1,3,7,7‐tetramethyl‐2,11‐dioxabicyclo[4.41]undeca‐3,5‐dien‐10‐one (2) and 1,3,7,7‐tetramethyl‐10‐methylidene‐2,11‐dioxabicyclo[4.4.1]undeca‐3,5‐diene (3) have been recorded and analyzed. Interpretation of the PE data indicate strong orbital interactions between the diene and acetal moieties in 1. Different conformations have been evaluated by a joint MMP2 molecular mechanics and ab initio molecular orbital analysis, which shows 1 to prefer a slightly boat‐shaped conformation with the diene part being planar and the CH2 group placed considerably out‐of‐plane. The bicyclic acetals 2 and 3 show a frontier orbital picture similar to 1 superimposed with the characteristics of the CO and CC groups, respectively. The crystal structure of the keto‐acetal 2 was determined by an X‐ray analysis.

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U2 - 10.1002/hlca.19850680809

DO - 10.1002/hlca.19850680809

M3 - Journal article

AN - SCOPUS:84987493226

SN - 0018-019X

VL - 68

SP - 2148

EP - 2157

JO - Helvetica Chimica Acta

JF - Helvetica Chimica Acta

IS - 8

ER -

Cyclic Acetals. Structural Analysis of 1,3‐Dioxepine and Related Compounds

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