Addition, of acetylene to cyclohexanone

An attractive alternative procedure for the preparation of 1-ethynylcyclohcxanol which gives yields of 80-90% employs the potassium salt of ferf.-amyl alcohol to effect the addition of acetylene to cyclohexanone. This condensation has been brought about by a suspension of sodium amide in ether 7.8.9.10.11 and by potassium hydroxide in ether. 1-Ethynylcylclohexanol has also been prepared by the action of acetylene on the sodium enolate of cyclohexanone. The procedure described here is essentially that of Campbell, Campbell, and Kby. ... 

The addition of HOOH to 2 1 pyridine/acetic acid solutions that contain FeIRPA)2 (PA = picolinate ion) and cyclohexane (C-C6H12) results in the catalyzed transformation of C-C6H12 to cyclohexanone [c-CgHioCO)]. Table 4-5 summarizes the conversion efficiencies and product yields for the oxygenation by the HOOH/Fe(PA)2 combination of several organic substrates (hydrocarbons with methylenic carbons, acetylenes, and aryl olefins). Catalyst turnovers (moles of product per mole of catalyst) are also tabulated. The relative reaction efficiencies for cyclohexane, n-hexane, cyclohexene, and 1,4-cyclohexadiene are roughly... 

A rapid stream of dry acetylene is passed into approximately 1 1. of liquid ammonia in a 2-1. three-necked flask equipped with a gas inlet tube and a mechanical stirrer while 23 g. (1 gram atom) of sodium is added over a period of 30 minutes (Notes 1 and 2). The flow of acetylene is then reduced (Note 3), and 98 g. (1 mole) of cyclohexanone is added dropwise. When this addition, which requires about an hour, is completed, the reaction mixture is allowed to stand for about 20 hours to permit the evaporation of nearly all the ammonia (Note 4). 

An interesting reaction is the addition of l-phenyl-2-TMS-acetylene to carbonyl compounds, e.g. cyclohexanone (113) in the presence of catalytic amounts of tetrabutyl-ammoniumfluoride to form, for instance, [l-(phenylethynyl)cyclohex-l-yloxy]tri-methylsilane (569) (equation 287)324. However, if 4-t-butylcyclohexanone (570) reacts... 

The synthesis of 4,5,6,7-tetrahydroindoles from cyclohexanone oxime and 1,2-dihaloethanes has been disclosed [303], The best overall yields (52%-61%) of NH- and N-vinyl-4,5,6,7-tetrahydroindoles are reached when molar ratio of cyclohexanone oxime-dichloroethane-KOH-DMSO is 1 1-2 7 10. For the successful synthesis of 4,5,6,7-tetrahydroindoles, it is important to add the alkali and dihaloethane to the solution of the ketoxime in DMSO in portions. Otherwise, the reaction of diether formation becomes appreciable. At the sacrifice of decreasing the yield to -30%, one can attain 94%-95% selectivity relative to the major product, 4,5,6,7-tetrahydro-indole. Like in the reaction with free acetylene, this is achieved mainly due to the addition of small amounts of water (10%-20%) to the reaction mixture. In this case, the water can be conveniently fed into the mixture by dissolving alkali in it, which simultaneously also facilitates the dispensing of both components. Somewhat poorer results are obtained with 1,2-dibromoethane under comparable conditions [303]. 

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