Bromination of cyclohexa-1,3-diene and (R,S)-cyclohexa-3,5-diene-1,2- diol

Journal of Organic Chemistry

Volumn 64, Issue 14, 1999, Pages 5245-5250

  Han, Xinghua ^a   Khedekar, Rajashree N ^a   Masnovi, John ^a   Baker, Ronald J ^a  

^a CLEVELAND STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BROMINE DERIVATIVE; CYCLOHEXA 1,3 DIENE; CYCLOHEXA 3,5 DIENE 1,2 DIOL; CYCLOHEXANE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; BROMINATION; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL STRUCTURE; ISOMER; PROTON NUCLEAR MAGNETIC RESONANCE; STOICHIOMETRY; X RAY CRYSTALLOGRAPHY;

EID: 0342353230     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo990473s     Document Type: Article

References (20)

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10. Taken in part from: Khedekar, R. N. M.S. Thesis, Cleveland State University, 1997.
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13. -.
14. Hammett, L. P. Physical Organic Chemistry, 2nd ed.; McGraw-Hill: New York, 1970; p 119.
15. The presence of the hydroxyl groups slightly inhibits this rearrangement, which has a half-life of about 3 h. This is reflected in the similar product distributions of isomers 6 observed at -70 °C and at 20 °C (Table 1).
16. The structure of 7a has two bromines and the hydroxyl group equatorial, and the other two bromines and benzoate group are axial. Benzoate is sterically bulkier than hydroxyl, and the unusual preference is for bulkier groups to be situated equatorial. The axial orientation of benzoate in crystalline 7a is supported by extensive hydrogen bonding, both inter- and intramolecular, which is evident in this structure. For example, the nonbonded contacts of the hydroxyl hydrogen with O1 of the same molecule is 2.197 Å and with O7 of an adjacent molecule is 1.998 Å.
17. The structure for 6c in Scheme 3 was proposed as the 3,4c,5t,6c-tetrabromo-1t, 2t-diol with this in mind; however, the alternative 3,4c,5t,6c-tetrabromo-1c, 2c-diol cannot be ruled out.
18. 20 in brominations. However, we note that bromination of 1 with or without pyridine proceeds similarly.
19. McElvain, S. M.; Morris, L. R. J. Am. Chem. Soc. 1951, 73, 206.
20. Han, H.; Baker, R. J.; Masnovi, J. M. Acta Crystallogr. 1999, C55, in press.