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Studies in aryne chemistry
The principal methods for the generation of arynes, and the Diels–Alder reactions of steroidal dienes are briefly reviewed. Tetrafluorobenzyne (generated from pentafluorophenyl-lithium and pentafluorophenyl magnesium chloride) reacts with simple models for steroidal diene systems to give mainly 1,4-...
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| Format: | Default Thesis |
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1969
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| Online Access: | https://hdl.handle.net/2134/36144 |
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| _version_ | 1818169046839853056 |
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| author | Ian F. Eckhard |
| author_facet | Ian F. Eckhard |
| author_sort | Ian F. Eckhard (7165949) |
| collection | Figshare |
| description | The principal methods for the generation of arynes, and the Diels–Alder reactions of steroidal dienes are briefly reviewed. Tetrafluorobenzyne (generated from pentafluorophenyl-lithium and pentafluorophenyl magnesium chloride) reacts with simple models for steroidal diene systems to give mainly 1,4-addition products. Benzyne (generated from o-bromofluorobenzene and anthranilic acid), tetrachlorobenzyne (from tetrachloroanthranilic acid) and tetrafluorobenzyne react with steroidal-5,7-dienes to give products of the ene-reaction. In addition, tetrafluorobenzyne forms a 5,8-adduct with a 5,7-diene and with a 5,7,9(11)-triene. Cholesta-2,4-diene gives 1,4-adducts with benzyne and tetrafluorobenzyne which undergo retro-Diels–Alder reactions on pyrolysis. Steroidal-1(10),9(11)-dienes also give 1,11-adducts with benzyne and tetrachlorobenzyne. The adducts of tetrafluorobenzyne with models for the oestrogen steroids, and with oestradiol dimethyl ether are reported. An unsuccessful attempt to synthesise an adduct from a steroidal styrene is described. Finally the photoisomerisation of 5,6,7,8-tetrafluoro-1,4-dihydro-1,4-ethanonaphthalene is reported and a mechanism proposed. |
| format | Default Thesis |
| id | rr-article-9396251 |
| institution | Loughborough University |
| publishDate | 1969 |
| record_format | Figshare |
| spelling | rr-article-93962511969-01-01T00:00:00Z Studies in aryne chemistry Ian F. Eckhard (7165949) Other chemical sciences not elsewhere classified untagged Chemical Sciences not elsewhere classified The principal methods for the generation of arynes, and the Diels–Alder reactions of steroidal dienes are briefly reviewed. Tetrafluorobenzyne (generated from pentafluorophenyl-lithium and pentafluorophenyl magnesium chloride) reacts with simple models for steroidal diene systems to give mainly 1,4-addition products. Benzyne (generated from o-bromofluorobenzene and anthranilic acid), tetrachlorobenzyne (from tetrachloroanthranilic acid) and tetrafluorobenzyne react with steroidal-5,7-dienes to give products of the ene-reaction. In addition, tetrafluorobenzyne forms a 5,8-adduct with a 5,7-diene and with a 5,7,9(11)-triene. Cholesta-2,4-diene gives 1,4-adducts with benzyne and tetrafluorobenzyne which undergo retro-Diels–Alder reactions on pyrolysis. Steroidal-1(10),9(11)-dienes also give 1,11-adducts with benzyne and tetrachlorobenzyne. The adducts of tetrafluorobenzyne with models for the oestrogen steroids, and with oestradiol dimethyl ether are reported. An unsuccessful attempt to synthesise an adduct from a steroidal styrene is described. Finally the photoisomerisation of 5,6,7,8-tetrafluoro-1,4-dihydro-1,4-ethanonaphthalene is reported and a mechanism proposed. 1969-01-01T00:00:00Z Text Thesis 2134/36144 https://figshare.com/articles/thesis/Studies_in_aryne_chemistry/9396251 CC BY-NC-ND 4.0 |
| spellingShingle | Other chemical sciences not elsewhere classified untagged Chemical Sciences not elsewhere classified Ian F. Eckhard Studies in aryne chemistry |
| title | Studies in aryne chemistry |
| title_full | Studies in aryne chemistry |
| title_fullStr | Studies in aryne chemistry |
| title_full_unstemmed | Studies in aryne chemistry |
| title_short | Studies in aryne chemistry |
| title_sort | studies in aryne chemistry |
| topic | Other chemical sciences not elsewhere classified untagged Chemical Sciences not elsewhere classified |
| url | https://hdl.handle.net/2134/36144 |