Loading…
Photorearrangement of 2-cyanobicyclo[2.2.1]hept-2-ene. Observation of 1,2- and 1,3-sigmatropic shifts
Irradiation of 2-cyanobicyclo[2.2.1]hept-2-ene (2-cyanonorbornene, 4 ) in hexane, with the full arc of a mercury vapour lamp, gives the rearrangement products 1-cyanobicyclo[4.1.0]hept-2-ene 5 and 7-cyanotricyclo[4.1.0.0 3.7 ]heptane 6 in the ratio 20:1. These products were separated by preparative...
Saved in:
| Published in: | Canadian journal of chemistry 1982-07, Vol.60 (13), p.1657-1663 |
|---|---|
| Main Authors: | , , , , |
| Format: | Article |
| Language: | eng ; fre |
| Citations: | Items that cite this one |
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| cited_by | cdi_FETCH-LOGICAL-c136f-61f91065007977bfc932ebdc1e910bbca6ee5b9b5460fcbfa9cf4a1d143c31803 |
|---|---|
| cites | |
| container_end_page | 1663 |
| container_issue | 13 |
| container_start_page | 1657 |
| container_title | Canadian journal of chemistry |
| container_volume | 60 |
| creator | Akhtar, Ikbal A McCullough, John J Vaitekunas, Susan Faggiani, Romolo Lock, Colin J. L |
| description | Irradiation of 2-cyanobicyclo[2.2.1]hept-2-ene (2-cyanonorbornene,
4
) in hexane, with the full arc of a mercury vapour lamp, gives the rearrangement products 1-cyanobicyclo[4.1.0]hept-2-ene
5
and 7-cyanotricyclo[4.1.0.0
3.7
]heptane
6
in the ratio 20:1. These products were separated by preparative vpc. The structure of the major product
5
was determined by single crystal X-ray analysis. Reduction of
5
with lithium aluminum hydride gave the corresponding primary amine, which was converted to the p-bromobenzenesulfonamide
9
, mp 150-151 °C, which gave single crystals from ethanol-water. The crystal and molecular structures are described. The minor product
6
was hydrogenated to give 7-cyanobicyclo[2.2. 1]heptane. Formation of
5
and
6
may involve concerted σ
2s
+ π
2s
and σ
2a
+ π
2a
processes respectively, which are photochemically allowed. |
| doi_str_mv | 10.1139/v82-226 |
| format | article |
| fullrecord | <record><control><sourceid>crossref_nrcre</sourceid><recordid>TN_cdi_nrcresearch_primary_10_1139_v82_226</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>10_1139_v82_226</sourcerecordid><originalsourceid>FETCH-LOGICAL-c136f-61f91065007977bfc932ebdc1e910bbca6ee5b9b5460fcbfa9cf4a1d143c31803</originalsourceid><addsrcrecordid>eNp1kF1LwzAUhoMoOKf4F3qlIKbmJG3XXIr4BYN5oVciJUlP1sqWlKQM9u_N2PBC8Op88PByzkPIJbAcQMi7Tc0p59URmUBRMyq4hGMyYYzVtGAFPyVnMX6nccZ4OSH41vnRB1QhKLfENbox8zbj1GyV87o3W7PynzznOXx1OIyUU3SYZwsdMWzU2Hu34-GW00y5NjWCxn65VmPwQ2-y2PV2jOfkxKpVxItDnZKPp8f3hxc6Xzy_PtzPqQFRWVqBlcCqMh0nZzNtjRQcdWsA01proyrEUktdFhWzRlsljS0UtFAII6BmYkqu97km-BgD2mYI_VqFbQOs2dlpkp0m2Unk1Z50wQSM6X_T_cIHqBlam8Cb_8G_qT8bZXIm</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Photorearrangement of 2-cyanobicyclo[2.2.1]hept-2-ene. Observation of 1,2- and 1,3-sigmatropic shifts</title><source>EZB Electronic Journals Library</source><creator>Akhtar, Ikbal A ; McCullough, John J ; Vaitekunas, Susan ; Faggiani, Romolo ; Lock, Colin J. L</creator><creatorcontrib>Akhtar, Ikbal A ; McCullough, John J ; Vaitekunas, Susan ; Faggiani, Romolo ; Lock, Colin J. L</creatorcontrib><description>Irradiation of 2-cyanobicyclo[2.2.1]hept-2-ene (2-cyanonorbornene,
4
) in hexane, with the full arc of a mercury vapour lamp, gives the rearrangement products 1-cyanobicyclo[4.1.0]hept-2-ene
5
and 7-cyanotricyclo[4.1.0.0
3.7
]heptane
6
in the ratio 20:1. These products were separated by preparative vpc. The structure of the major product
5
was determined by single crystal X-ray analysis. Reduction of
5
with lithium aluminum hydride gave the corresponding primary amine, which was converted to the p-bromobenzenesulfonamide
9
, mp 150-151 °C, which gave single crystals from ethanol-water. The crystal and molecular structures are described. The minor product
6
was hydrogenated to give 7-cyanobicyclo[2.2. 1]heptane. Formation of
5
and
6
may involve concerted σ
2s
+ π
2s
and σ
2a
+ π
2a
processes respectively, which are photochemically allowed.</description><identifier>ISSN: 0008-4042</identifier><identifier>EISSN: 1480-3291</identifier><identifier>DOI: 10.1139/v82-226</identifier><language>eng ; fre</language><publisher>Ottawa, Canada: NRC Research Press</publisher><ispartof>Canadian journal of chemistry, 1982-07, Vol.60 (13), p.1657-1663</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c136f-61f91065007977bfc932ebdc1e910bbca6ee5b9b5460fcbfa9cf4a1d143c31803</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Akhtar, Ikbal A</creatorcontrib><creatorcontrib>McCullough, John J</creatorcontrib><creatorcontrib>Vaitekunas, Susan</creatorcontrib><creatorcontrib>Faggiani, Romolo</creatorcontrib><creatorcontrib>Lock, Colin J. L</creatorcontrib><title>Photorearrangement of 2-cyanobicyclo[2.2.1]hept-2-ene. Observation of 1,2- and 1,3-sigmatropic shifts</title><title>Canadian journal of chemistry</title><addtitle>Revue canadienne de chimie</addtitle><description>Irradiation of 2-cyanobicyclo[2.2.1]hept-2-ene (2-cyanonorbornene,
4
) in hexane, with the full arc of a mercury vapour lamp, gives the rearrangement products 1-cyanobicyclo[4.1.0]hept-2-ene
5
and 7-cyanotricyclo[4.1.0.0
3.7
]heptane
6
in the ratio 20:1. These products were separated by preparative vpc. The structure of the major product
5
was determined by single crystal X-ray analysis. Reduction of
5
with lithium aluminum hydride gave the corresponding primary amine, which was converted to the p-bromobenzenesulfonamide
9
, mp 150-151 °C, which gave single crystals from ethanol-water. The crystal and molecular structures are described. The minor product
6
was hydrogenated to give 7-cyanobicyclo[2.2. 1]heptane. Formation of
5
and
6
may involve concerted σ
2s
+ π
2s
and σ
2a
+ π
2a
processes respectively, which are photochemically allowed.</description><issn>0008-4042</issn><issn>1480-3291</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1982</creationdate><recordtype>article</recordtype><recordid>eNp1kF1LwzAUhoMoOKf4F3qlIKbmJG3XXIr4BYN5oVciJUlP1sqWlKQM9u_N2PBC8Op88PByzkPIJbAcQMi7Tc0p59URmUBRMyq4hGMyYYzVtGAFPyVnMX6nccZ4OSH41vnRB1QhKLfENbox8zbj1GyV87o3W7PynzznOXx1OIyUU3SYZwsdMWzU2Hu34-GW00y5NjWCxn65VmPwQ2-y2PV2jOfkxKpVxItDnZKPp8f3hxc6Xzy_PtzPqQFRWVqBlcCqMh0nZzNtjRQcdWsA01proyrEUktdFhWzRlsljS0UtFAII6BmYkqu97km-BgD2mYI_VqFbQOs2dlpkp0m2Unk1Z50wQSM6X_T_cIHqBlam8Cb_8G_qT8bZXIm</recordid><startdate>19820701</startdate><enddate>19820701</enddate><creator>Akhtar, Ikbal A</creator><creator>McCullough, John J</creator><creator>Vaitekunas, Susan</creator><creator>Faggiani, Romolo</creator><creator>Lock, Colin J. L</creator><general>NRC Research Press</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19820701</creationdate><title>Photorearrangement of 2-cyanobicyclo[2.2.1]hept-2-ene. Observation of 1,2- and 1,3-sigmatropic shifts</title><author>Akhtar, Ikbal A ; McCullough, John J ; Vaitekunas, Susan ; Faggiani, Romolo ; Lock, Colin J. L</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c136f-61f91065007977bfc932ebdc1e910bbca6ee5b9b5460fcbfa9cf4a1d143c31803</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng ; fre</language><creationdate>1982</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Akhtar, Ikbal A</creatorcontrib><creatorcontrib>McCullough, John J</creatorcontrib><creatorcontrib>Vaitekunas, Susan</creatorcontrib><creatorcontrib>Faggiani, Romolo</creatorcontrib><creatorcontrib>Lock, Colin J. L</creatorcontrib><collection>CrossRef</collection><jtitle>Canadian journal of chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Akhtar, Ikbal A</au><au>McCullough, John J</au><au>Vaitekunas, Susan</au><au>Faggiani, Romolo</au><au>Lock, Colin J. L</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photorearrangement of 2-cyanobicyclo[2.2.1]hept-2-ene. Observation of 1,2- and 1,3-sigmatropic shifts</atitle><jtitle>Canadian journal of chemistry</jtitle><addtitle>Revue canadienne de chimie</addtitle><date>1982-07-01</date><risdate>1982</risdate><volume>60</volume><issue>13</issue><spage>1657</spage><epage>1663</epage><pages>1657-1663</pages><issn>0008-4042</issn><eissn>1480-3291</eissn><abstract>Irradiation of 2-cyanobicyclo[2.2.1]hept-2-ene (2-cyanonorbornene,
4
) in hexane, with the full arc of a mercury vapour lamp, gives the rearrangement products 1-cyanobicyclo[4.1.0]hept-2-ene
5
and 7-cyanotricyclo[4.1.0.0
3.7
]heptane
6
in the ratio 20:1. These products were separated by preparative vpc. The structure of the major product
5
was determined by single crystal X-ray analysis. Reduction of
5
with lithium aluminum hydride gave the corresponding primary amine, which was converted to the p-bromobenzenesulfonamide
9
, mp 150-151 °C, which gave single crystals from ethanol-water. The crystal and molecular structures are described. The minor product
6
was hydrogenated to give 7-cyanobicyclo[2.2. 1]heptane. Formation of
5
and
6
may involve concerted σ
2s
+ π
2s
and σ
2a
+ π
2a
processes respectively, which are photochemically allowed.</abstract><cop>Ottawa, Canada</cop><pub>NRC Research Press</pub><doi>10.1139/v82-226</doi><tpages>7</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0008-4042 |
| ispartof | Canadian journal of chemistry, 1982-07, Vol.60 (13), p.1657-1663 |
| issn | 0008-4042 1480-3291 |
| language | eng ; fre |
| recordid | cdi_nrcresearch_primary_10_1139_v82_226 |
| source | EZB Electronic Journals Library |
| title | Photorearrangement of 2-cyanobicyclo[2.2.1]hept-2-ene. Observation of 1,2- and 1,3-sigmatropic shifts |
| url | http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-01T19%3A27%3A44IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-crossref_nrcre&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Photorearrangement%20of%202-cyanobicyclo%5B2.2.1%5Dhept-2-ene.%20Observation%20of%201,2-%20and%201,3-sigmatropic%20shifts&rft.jtitle=Canadian%20journal%20of%20chemistry&rft.au=Akhtar,%20Ikbal%20A&rft.date=1982-07-01&rft.volume=60&rft.issue=13&rft.spage=1657&rft.epage=1663&rft.pages=1657-1663&rft.issn=0008-4042&rft.eissn=1480-3291&rft_id=info:doi/10.1139/v82-226&rft_dat=%3Ccrossref_nrcre%3E10_1139_v82_226%3C/crossref_nrcre%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-c136f-61f91065007977bfc932ebdc1e910bbca6ee5b9b5460fcbfa9cf4a1d143c31803%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true |