Umlagerungen bizyklischer 2-Vinyl-aziridine
Addition of phthalimidonitrene to cyclopentadiene (5), 1,3-cyclohexadiene (6) as well as cyclooctatetraene (7) led to the bicyclic 2-vinyl-aziridines: N-phthalimido-6-aza-bicyclo[3.1.0]hex-2-ene (8a), N-phthalimido-7-aza-bicyclo[4.1.0]hept-2-ene (9a) and N-phthalimido-9-aza-bicyclo[6.1.0]nona-2,4,6...
Saved in:
| Main Authors: | , |
|---|---|
| Format: | Article |
| Language: | deu |
| Published: |
Swiss Chemical Society
1972-12-01
|
| Series: | CHIMIA |
| Online Access: | https://www.chimia.ch/chimia/article/view/9046 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1849311269827379200 |
|---|---|
| author | Lienhard Hoesch André S. Dreiding |
| author_facet | Lienhard Hoesch André S. Dreiding |
| author_sort | Lienhard Hoesch |
| collection | DOAJ |
| description |
Addition of phthalimidonitrene to cyclopentadiene (5), 1,3-cyclohexadiene (6) as well as cyclooctatetraene (7) led to the bicyclic 2-vinyl-aziridines: N-phthalimido-6-aza-bicyclo[3.1.0]hex-2-ene (8a), N-phthalimido-7-aza-bicyclo[4.1.0]hept-2-ene (9a) and N-phthalimido-9-aza-bicyclo[6.1.0]nona-2,4,6-triene (10a), respectively. Thermolysis of 8a gave pyridine (16) and phthalimide (17), whereas from the thermolysis of 9a and of 10a the products of a 2-vinylaziridine-rearrangement were isolated, namely N-phthalimido-7-aza-bicyclo[2.2.1]hept-2-ene (11) and N-phthalimido-9-aza-bicyclo[4.2.1]nona-2,4,7-triene (23), respectively. 11 was found to be thermally labile under the conditions of its formation and decomposed into N-phthalimido-pyrrole (12) and, presumably, ethylene. N-Phthalimido-indole (24) was isolated as a by-product from the thermolysis of 10a.
Hydrazinolysis of 8a and of 9a gave the corresponding N-amino-aziridines 8b and 9b, respectively. NMR-Monitoring of the CDCl3-solutions of 8b and of 9b suggested the formation of N-amino-5-aza-bicyclo[2.1.1]hex-2-ene (22) along with cyclopentadiene (5), and of N-amino-7-aza-bicyclo[2.2.1]hept- 2-ene (13) along with 1,3-cyclohexadiene (6), respectively, as well as of hydrazine (14). In the presence of catalytic amounts of 14, 8b and 9b decomposed into cyclopentene (21) and cyclohexene (15), respectively.
Interpretations are suggested for these highly diversified reactions.
|
| format | Article |
| id | doaj-art-c89ee951e01a40ffa4af400d3ecbcc9d |
| institution | Kabale University |
| issn | 0009-4293 2673-2424 |
| language | deu |
| publishDate | 1972-12-01 |
| publisher | Swiss Chemical Society |
| record_format | Article |
| series | CHIMIA |
| spelling | doaj-art-c89ee951e01a40ffa4af400d3ecbcc9d2025-08-20T03:53:27ZdeuSwiss Chemical SocietyCHIMIA0009-42932673-24241972-12-01261210.2533/chimia.1972.629Umlagerungen bizyklischer 2-Vinyl-aziridineLienhard Hoesch0André S. Dreiding1Organisch-Chemisches Institut, Universität Zürich Rämistraße 76, 8001 ZürichOrganisch-Chemisches Institut, Universität Zürich Rämistraße 76, 8001 Zürich Addition of phthalimidonitrene to cyclopentadiene (5), 1,3-cyclohexadiene (6) as well as cyclooctatetraene (7) led to the bicyclic 2-vinyl-aziridines: N-phthalimido-6-aza-bicyclo[3.1.0]hex-2-ene (8a), N-phthalimido-7-aza-bicyclo[4.1.0]hept-2-ene (9a) and N-phthalimido-9-aza-bicyclo[6.1.0]nona-2,4,6-triene (10a), respectively. Thermolysis of 8a gave pyridine (16) and phthalimide (17), whereas from the thermolysis of 9a and of 10a the products of a 2-vinylaziridine-rearrangement were isolated, namely N-phthalimido-7-aza-bicyclo[2.2.1]hept-2-ene (11) and N-phthalimido-9-aza-bicyclo[4.2.1]nona-2,4,7-triene (23), respectively. 11 was found to be thermally labile under the conditions of its formation and decomposed into N-phthalimido-pyrrole (12) and, presumably, ethylene. N-Phthalimido-indole (24) was isolated as a by-product from the thermolysis of 10a. Hydrazinolysis of 8a and of 9a gave the corresponding N-amino-aziridines 8b and 9b, respectively. NMR-Monitoring of the CDCl3-solutions of 8b and of 9b suggested the formation of N-amino-5-aza-bicyclo[2.1.1]hex-2-ene (22) along with cyclopentadiene (5), and of N-amino-7-aza-bicyclo[2.2.1]hept- 2-ene (13) along with 1,3-cyclohexadiene (6), respectively, as well as of hydrazine (14). In the presence of catalytic amounts of 14, 8b and 9b decomposed into cyclopentene (21) and cyclohexene (15), respectively. Interpretations are suggested for these highly diversified reactions. https://www.chimia.ch/chimia/article/view/9046 |
| spellingShingle | Lienhard Hoesch André S. Dreiding Umlagerungen bizyklischer 2-Vinyl-aziridine CHIMIA |
| title | Umlagerungen bizyklischer 2-Vinyl-aziridine |
| title_full | Umlagerungen bizyklischer 2-Vinyl-aziridine |
| title_fullStr | Umlagerungen bizyklischer 2-Vinyl-aziridine |
| title_full_unstemmed | Umlagerungen bizyklischer 2-Vinyl-aziridine |
| title_short | Umlagerungen bizyklischer 2-Vinyl-aziridine |
| title_sort | umlagerungen bizyklischer 2 vinyl aziridine |
| url | https://www.chimia.ch/chimia/article/view/9046 |
| work_keys_str_mv | AT lienhardhoesch umlagerungenbizyklischer2vinylaziridine AT andresdreiding umlagerungenbizyklischer2vinylaziridine |