ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The crystal structures of (1R,4R,5S,8S)-9,10-dimethylidentricyclo[6.2.1.02,7]undec2(7)-ene-4,5-dicarboxylic anhydride (3), (1R,4R,5S,8S)11-isopropylidene-9,10-dimethylidenetricyclo[6.2.1.m2,7]undec-2(7)-ene-4,5-dicarboxylic anhydride (6), (1R,4R,5S8S)-9,10-dimethylidenetricyclo[6.2.2.02,7]dodec-2(7)-ene-4,5-dicarboxylic anhydride (9), (1R4R5S8S)-TRICYCLO[6.2.2.02,7]dodeca-2(7), 9-diene-4,5-dicarboxylic anhydride (12) and (4R,5S)-tricyclo[6.1.1.02.7]dec-2(7)-ene-4,5-dicarboxylic acid (16) were established by X-ray diffraction. The alkyl substituents onto the endocyclic bicyclo[2.2.1]hept-2-ene double bond deviate from the C(1), C(2), C(3), C(4), plane by 13.5°4 in 3 and by 13.9° in 6, leaning toward the endo-face. No such out-of-plane deformations were observed with the bicyclo[2.2.2]oct-2-ene derivatives 9 and 12. The exocyclic s-cis-butadiene moieties in 3, 6 and 9 do not deviate significantly from planarity. The deviation from planarity of the double bond n bicyclo[2.2.1]hept-2-ene derivatives and planarity in bicyclo[2.2.2]oct-2-ene analogues is shown to be general by analysis of all known structures in the Cambridge Crystallographic Data File. The non-planarity of the bicyclo[2.2.1]hept-2-ene double bond cannot be attributed only to bond-angle deformations which would favour rehybridizatoin of the olefinic C-atoms since the double bond in the more strained bicyclo[2.1.1]hex-2-ene drivative 16 deviates from planarity by less than 4°.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19840670428
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