Roberts, John D. and Johnson, Frederick O. and Carboni, Rudolph A. (1954) Some Chlorine Derivatives of Norbornane (Bicyclo[2.2.1]heptane). Journal of the American Chemical Society, 76 (22). pp. 5692-5699. ISSN 0002-7863. doi:10.1021/ja01651a027. https://resolver.caltech.edu/CaltechAUTHORS:20151021-142339039
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Abstract
The endo-cis and trans-5,6-dichloronorbornenes were prepared by the respective additions of cis- and trans-dichlorocthylene to cyclopentadiene. The sterochemical assigments were confirmed by dipole moment studies. The cis-dichloride was inert to hydrolysis while the trans isomer was hydrolyzed to 3,5-dihydroxynortricyclene. Hydrogenation of the dichloride isomers gave the endo-cis- and trans-2,3-dichloronorbornanes. Contrary to expectations based on preferential trans-elimination of hydrogen halide, the saturated cis-dichloride appeared to dehydrohalogenate somewhat less readily than the trans isomer, although the reaction was slow in both cases. Both isomers gave the same dehydrohalogenation product, 2-chloronorbornene, the structure of which was confirmed by oxidation to cis-cyclopentane-1,3-dicarboxylica cid and hydrolysis to norcamphor. Chlorination of norbornene at - 75º gave nortricyclyl chloride and syn-7-exo-2-dichloronorbornane. The structure of the latter was assigned (in preference to exo-cis-2,3-dichloronorbornane)because of the compound's relative inertness to dehydrohalogenating reagents. endo-cis-2,3-Dichloronorbornane was not readily hydrolyzed, but trans-2,3-dichloronorbornane and syn-7-exo-2-dichloronorbornane hydrolyzed to anti- and syn-7-exo-Z-norborneol, respectively. The syn-isomer also was obtained by addition of hypochlorous acid to norbornene. The structures of the chloro alcohols were inferred from their modes of formation and oxidation to chlorine-containing dicarboxylic acids which were presumed to be, respectively, trans- and cis-2-chloro-cis-cyclopentane-1,3-dicarboxylic acids. These acids were different from trans-and cis-4-chloro-cis-cyclopentane-1,3-dicarboxylic acids obtained by oxidation of exo- and endo-dehydronorbornyl chlorides, respectively. The assignments of the syn and anti configurations to the ketones were confirmed by dipole moment measurements. The syn and anti-chlorohydrins were converted by pyrolysis of their carboxylic acid esters in low yield to syn- and anti-7-chlorotiorbornenes. Each of the latter substances on hydrogenation gave the same compound, 7-chloronorbornane.
Item Type: | Article | |||||||||
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Additional Information: | © 1954 American Chemical Society. Received April 23, 1954. | |||||||||
Issue or Number: | 22 | |||||||||
DOI: | 10.1021/ja01651a027 | |||||||||
Record Number: | CaltechAUTHORS:20151021-142339039 | |||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20151021-142339039 | |||||||||
Official Citation: | Some Chlorine Derivatives of Norbornane (Bicyclo[2.2.1]heptane) John D. Roberts, Frederick O. Johnson, and Rudolph A. Carboni Journal of the American Chemical Society 1954 76 (22), 5692-5699 DOI: 10.1021/ja01651a027 | |||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
ID Code: | 61395 | |||||||||
Collection: | CaltechAUTHORS | |||||||||
Deposited By: | Ruth Sustaita | |||||||||
Deposited On: | 22 Oct 2015 18:13 | |||||||||
Last Modified: | 10 Nov 2021 22:48 |
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