Spectroscopic and X-ray Crystallographic Evidence for Electrostatic Effects in 4-Substituted Cyclohexanone-Derived Hydrazones, Imines, and Corresponding Salts
The axial conformer of several 4-substituted cyclohexanone hydrazone salts was found to predominate in solution. Changes in the charge of the molecule and the polarity of the solvent led to changes in the conformational preference of each molecule that were consistent with electrostatic stabilizatio...
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| Veröffentlicht in: | Journal of organic chemistry 2011-10, Vol.76 (19), p.7706-7719 |
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| container_issue | 19 |
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| container_title | Journal of organic chemistry |
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| creator | Dibble, David J Ziller, Joseph W Woerpel, K. A |
| description | The axial conformer of several 4-substituted cyclohexanone hydrazone salts was found to predominate in solution. Changes in the charge of the molecule and the polarity of the solvent led to changes in the conformational preference of each molecule that were consistent with electrostatic stabilization of the axial conformer. 1H NMR spectroscopic analysis was utilized to determine the structure of cyclohexanone-derived substrates by comparison to conformationally restricted trans-decalone derivatives and computational models. X-ray crystallography demonstrated that the axial configuration of a pendant benzyloxy group is the preferred conformation of an iminium ion in the solid state. The structure of a neutral hydrazone was also determined to favor the axial configuration for a pendant benzyloxy group in the solid state. |
| doi_str_mv | 10.1021/jo200950s |
| format | Article |
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A</creatorcontrib><title>Spectroscopic and X-ray Crystallographic Evidence for Electrostatic Effects in 4-Substituted Cyclohexanone-Derived Hydrazones, Imines, and Corresponding Salts</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>The axial conformer of several 4-substituted cyclohexanone hydrazone salts was found to predominate in solution. Changes in the charge of the molecule and the polarity of the solvent led to changes in the conformational preference of each molecule that were consistent with electrostatic stabilization of the axial conformer. 1H NMR spectroscopic analysis was utilized to determine the structure of cyclohexanone-derived substrates by comparison to conformationally restricted trans-decalone derivatives and computational models. X-ray crystallography demonstrated that the axial configuration of a pendant benzyloxy group is the preferred conformation of an iminium ion in the solid state. The structure of a neutral hydrazone was also determined to favor the axial configuration for a pendant benzyloxy group in the solid state.</description><subject>Alicyclic compounds</subject><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>Chemistry</subject><subject>Crystallography, X-Ray</subject><subject>Cyclohexanones - chemistry</subject><subject>Exact sciences and technology</subject><subject>Hydrazones - chemistry</subject><subject>Imines - chemistry</subject><subject>Models, Molecular</subject><subject>Molecular Conformation</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>Salts - chemistry</subject><subject>Solutions</subject><subject>Spectrum Analysis</subject><subject>Static Electricity</subject><subject>Stereoisomerism</subject><subject>Substrate Specificity</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2011</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkc2O0zAUhS0EYsrAghdA3iCERMC_abJBQqEwI43EorNgF904TuuRawfbqQgPw7Pi0tIBCW-ufM_nc6x7EXpOyVtKGH135xkhtSTxAVpQyUhR1kQ8RAtCGCs4K_kFehLjHclHSvkYXTBakZJIvkA_16NWKfio_GgUBtfjr0WAGTdhjgms9ZsA4zZLq73ptVMaDz7glT2-SpAO0jDka8TGYVGspy4mk6ake9zMyvqt_g7OO1181MHsc_dq7gP8yJ34Bl_vzO96CG58CDqO3vXGbfAabIpP0aMBbNTPTvUS3X5a3TZXxc2Xz9fNh5sCBBepoGUvl1pUPQUpCKiBA-WcEdpVuuyA8aWggi0HpqTs-EA1EYMQnVKiVpopfoneH23HqdvpXmmXAth2DGYHYW49mPZfxZltu_H7ltOacyGywauTQfDfJh1TuzNRaWvBaT_FtqplJSsmWCZfH0mVxxeDHs4plLSHbbbnbWb2xd_fOpN_1peBlycAogI7BHDKxHtOHFIluedAxew_BZeH-Z_AX8a9t7A</recordid><startdate>20111007</startdate><enddate>20111007</enddate><creator>Dibble, David J</creator><creator>Ziller, Joseph W</creator><creator>Woerpel, K. 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A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a434t-16d57e48d1a540acf3a133201b8e6ba23741427f2c55b3f1e04f44bcc49ce2c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2011</creationdate><topic>Alicyclic compounds</topic><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>Chemistry</topic><topic>Crystallography, X-Ray</topic><topic>Cyclohexanones - chemistry</topic><topic>Exact sciences and technology</topic><topic>Hydrazones - chemistry</topic><topic>Imines - chemistry</topic><topic>Models, Molecular</topic><topic>Molecular Conformation</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><topic>Salts - chemistry</topic><topic>Solutions</topic><topic>Spectrum Analysis</topic><topic>Static Electricity</topic><topic>Stereoisomerism</topic><topic>Substrate Specificity</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Dibble, David J</creatorcontrib><creatorcontrib>Ziller, Joseph W</creatorcontrib><creatorcontrib>Woerpel, K. 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Chem</addtitle><date>2011-10-07</date><risdate>2011</risdate><volume>76</volume><issue>19</issue><spage>7706</spage><epage>7719</epage><pages>7706-7719</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>The axial conformer of several 4-substituted cyclohexanone hydrazone salts was found to predominate in solution. Changes in the charge of the molecule and the polarity of the solvent led to changes in the conformational preference of each molecule that were consistent with electrostatic stabilization of the axial conformer. 1H NMR spectroscopic analysis was utilized to determine the structure of cyclohexanone-derived substrates by comparison to conformationally restricted trans-decalone derivatives and computational models. X-ray crystallography demonstrated that the axial configuration of a pendant benzyloxy group is the preferred conformation of an iminium ion in the solid state. The structure of a neutral hydrazone was also determined to favor the axial configuration for a pendant benzyloxy group in the solid state.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>21806053</pmid><doi>10.1021/jo200950s</doi><tpages>14</tpages><oa>free_for_read</oa></addata></record> |
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| ispartof | Journal of organic chemistry, 2011-10, Vol.76 (19), p.7706-7719 |
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| subjects | Alicyclic compounds Alicyclic compounds, terpenoids, prostaglandins, steroids Chemistry Crystallography, X-Ray Cyclohexanones - chemistry Exact sciences and technology Hydrazones - chemistry Imines - chemistry Models, Molecular Molecular Conformation Organic chemistry Preparations and properties Salts - chemistry Solutions Spectrum Analysis Static Electricity Stereoisomerism Substrate Specificity |
| title | Spectroscopic and X-ray Crystallographic Evidence for Electrostatic Effects in 4-Substituted Cyclohexanone-Derived Hydrazones, Imines, and Corresponding Salts |
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