2-Chloro-1,3-didehydronaphthalene was generated as a reactive intermediate in both the open (diradical) and closed (bicyclo{3.1.0}-hexatriene) forms by treating either 1-bromo-3,4-benzo-6,6-dichlorobicyclo{3.1.0}hexane or 3,4-benzo-1,6,6-trichlorobicyclo{3.1.0}hexane with potassium tert-butoxide in tetrahydrofuran at 0(DEGREES)C. The open form reacts with solvent to produce 2-chloronaphthalene, 2-chloro-1-(2'-tetrahydrofurfuranyl)naphthalene, and 2-chloro-3-(2'-tetrahydro-furfuranyl)naphthalene. The closed form reacts with nucleophiles to produce 2,3-dichloronaphthalene, 2-bromo-3-chloronaphthalene, 1,2-dichloronaphthalene, 1-bromo-2-chloronaphthalene, 1,3-di(tert-butoxy)naphthalene, 1-tert-butoxy-2-chloronaphthalene, and 2-tert-butoxy-3-chloronaphthalene.
Naphtho{a}cyclopropene was generated in low yield by treating 1-bromo-2-(p-boluenesulfonatomethyl)naphthalene with n-butyl lithium in tetrahydrofuran at -15(DEGREES)C. This compound was characterized by both low temperature nuclear magnetic resonance spectroscopy and by its reaction with tert-butyl alcohol in the presence of silver tetrafluoroborate to produce a mixture of 1 and 2-(tert-butoxymethyl)-naphthalene.
The reactions of 2,2-dichloro-1-methylenecyclopropane with potassium tert-butoxide were studied. The products of this reaction were cis and trans-1-tert-butoxybut-1-ene-3-yne. 2-Chloro-1-methylene-cyclopropene is proposed as a reactive intermediate in these reactions.
| Identifer | oai:union.ndltd.org:RICE/oai:scholarship.rice.edu:1911/15534 |
| Date | January 1980 |
| Creators | BUYNAK, JOHN DAVID |
| Source Sets | Rice University |
| Language | English |
| Detected Language | English |
| Type | Thesis, Text |
| Format | application/pdf |
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