Tert-Butylchlorocarbene

A few examples of the formation of chlorocydopropanes via 1,3-insertion of alkylchlorocar-benes into C-H bonds are known (see Section 1,2.1.3.1.2.2.1.). Thus, thermolysis of 1 -fert-butyl-l-chloro-3i/-diazirine (1) at 79 °C leads to the formation of a mixture of l,l-dimethyl-2-chloro-cyclopropane (2) and 2-chloro-3-methyl-2-butene (3), via tert-butylchlorocarbene, which is the common intermediate. ... 

In the absence of pyridine, tert-butylchlorocarbene can undergo two types of intramolecular rearrangements, react with diazirine precursor to form azine or react with solvent. It can also react with an olefinic trap to give a cyclopropane adduct. Analysis of the product mixture by Moss and Liu [25] gives the ratio of rate constants of these processes. As the alkene trapping reaction rate constant is known, the other rate constants of reaction of the invisible species tert-butyl-chlorocarbene can be deduced. 

To obtain k, one measures k, at several pyridine concentrations. To obtain the rate constant of carbene reaction with a quencher, Q, one holds the concentration of pyridine constant and varies the quencher concentration. A plot of k versus [Q] is now linear with slope k. For tert-butylchlorocarbene and trans-3-... 

Jackson, J.E., Soundararajan, N., Platz, M.S., and Liu, M.T.H., Pyridine Ylide Formation by Capture of Phenylchlorocarbene and tert-Butylchlorocarbene. Reaction Rates of an Alkylchlorocarbene by Laser Flash Photolysis,/. Am. Chem. Soc., 110, 5595,1988. 

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See also in sourсe #XX -- [ ]

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