Cyclohexyl magnesium chloride

An intramolecular Kulinkovich cyclopropanation of an oxa-tu-alkenoic ester 433 occurs upon treatment with cyclohexyl magnesium chloride to furnish the cyclopropanochroman-3-ol 434 in moderate yield (Equation 179) <20030BC3600>. 

Cyclohexene 1.2 dicarboximide tetramethrin Cyclohexene oxide propargite Cyclohexyl aldehyde triapenthenol Cyclohexyl amine hexazinone, hexythiazox Cyclohexyl hydroxylamine furmecyclox Cyclohexyl magnesium bromide cyhexatin Cyclohexyl magnesium chloride cyhexatin Cyclohexyl urea lenacil... 

Tricyclohexyltin hydroxide can be prepared via the Grignard reaction, by reaction of cyclohexyl magnesium halide with stannic chloride. 

In a i-l. three-necked, round-bottom flask fitted with a mechanical stirrer through a mercury seal, a separatory funnel and an efficient reflux condenser to which a calcium chloride tube is attached, are placed 25 g. (1.03 moles) of magnesium turnings 140 cc. of dry ether, and a small crystal of iodine. The stirrei is started and a small portion (about 10 cc.) of a solution of 118.5 g. (i mole) of cyclohexyl bromide (Note i) in 120 cc. of dry ether is added through the separatory funnel. After the reaction starts, the remainder of the solution is run in at such a rate that the whole is added at the end of forty-five minutes. The mixture is stirred and refluxed for an additional thirty to forty-five minutes. 

A) Preparation of p-Hydroxy-p -Methoxybemhydrylidenecyclohexane To a Grignard solution prepared from 110 g of magnesium (4.5 mols) and 840 g of p-bromoanisole (4.5 mols) in one liter of anhydrous ether, there was added dropwise with vigorous agitation 307 g of p-hydroxyphenyl cyclohexyl ketone (1.5 mols) dissolved in one liter of anhydrous ether. Upon completion of the addition the reaction mixture was refluxed for 2.5 hours with agitation, and was then cooled. Thereupon 15 mols of ammonium chloride dissolved in 3 liters of water were added. The ethereal layer was separated, washed with water, dried over anhydrous sodium sulfate and distilled. Yield 370 g. BP 180° to 190°C at 0.1 mm. The substance was recrystallized from a mixture of carbon tetrachloride and petroleum ether. MP 145° to 146°C. 

The manufacture of the cyclohexyl analog is as follows. Phenyl magnesium bromide was prepared from 48.5 g (0.308 mol) of bromobenzene, 7 g (0,29 mol) of magnesium, and 125 ml of dry ether. To it was added at 5°C over a period of A hour 40 g (0.18 mol) of cyclohexyl (3-(N-piperidyl)-ethyl ketone (BP 115° to 117°C/1 mm) in 125 ml of dry ether. The mixture was allowed slowly to come to room temperature, refluxed for one hour, and then poured into ice containing 80 ml of concentrated hydrochloric acid. Ammonium chloride (100 g) and 200 ml of concentrated ammonium hydroxide were added and the organic layer was separated. After drying and removing the solvent, the residue was distilled under reduced pressure. The base distilled at 158° to 170°C (1 mm) and solidified. Upon recrystallization from methanol it melted at 112° to 113°C. 

Cyanoguanidine, 3 43 Cyanuric chloride, formation of, from cyanogen chloride, 2 94 1-Cyclohexyl-l, 1-diethylhydra-zonium chloride, 6 92 Cyclopentadiene, magnesium and other metal derivatives of, 6 11, 15... 

Tin triphenyl cyclohexyl is obtained from tin triphenyl chloride and an excess of magnesium cyclohexyl bromide. It forms bushy, colourless... 

In the case of a still less reactive halide, or one with a tendency to undergo dehydrohalogenation, it is advantageous to add a reactive halide such as 1-bromo-naphthalene or n-butyl bromide for entrainment. Thus the reaction of 0.05 mole of eyclohexyl chloride and 0.05 mole of 1-bromonaphthalene with 0.33 g. atom of magnesium and isopropanol (0.3 mole) in 50 + 20 ml. of decalin afforded a mixture of 83% of cyclohexane and 10% of cyclohexene (removable with sulfuric acid). By this procedure cyclohexyl fluoride gives cyclohexane (33%) and benzotrifluoride gives toluene (10%). Fluorobenzene is inert. 

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