Ethyl 3-chlorovinyl ketone

Acetylene was passed into a stirred solution of 3.05 grams (0.44 mol) of lithium in 300 ml of liquid ammonia until the blue color exhibited by the mixture had disappeared. Ethyl /3-chlorovinyl ketone (47.4 grams 0.40 mol) dissolved in 50 ml dry ether was then added to the resulting solution of lithium acetylide over a period of 20 minutes, during which the color deepened through yellow to reddish-brown. The mixture was stirred under reflux maintained with a Dry Ice condenser for 2 hours. Thereafter, dry ether (200 ml) was added and the ammonia was permitted to evaporate with stirring overnight. 

N-Ethyl-3Pipenzolate bromide 1-Ethyl-3-chloropyrrolidine Doxapram HCI Ethyl /3-chlorovinyl ketone Ethchlorvynol Ethyl cyanoacetate Ethosuximide Piprozolln TInorldIne... 

At higher temperatures the mixture of 10 and methyl vinyl ketone yields the 1,4-carbocyclic compound as described previously. Methyl isopropenyl ketone (5), ethyl acetylacrylate (d), 2-cyclohexenone (21), and 1-acetyl-1-cyclohexene (22) also undergo this type of cyclization reaction with enamines at higher temperatures. This cycloalkylation reaction occurs with enamines made of strongly basic amines such as pyrrolidine, but the less reactive morpholine enamine combines with methyl vinyl ketone to give only a simple alkylated product (7). Chlorovinyl ketones yield pyrans when allowed to react with the enamines of either alicyclic ketones or aldehydes (23). 

Carbethoxy-4-cyano-l,4-diphenyl-2-butene-l-one (XII-S3), from ethyl a-cyano-0(-phenylacetate and phenyl -chlorovinyl ketone, is cyclized in 86% sulfuric acid to 3,6-diphenyl-2-pyridone. ... 

E)-2-Chlorovinyl phenyl ketone (1.83 g, 11 mmol) and triisopropyl phosphite (2.08 g, 10 mmol) were heated under an argon atmosphere for 1 h at 120 to 130°C. When all of the isopropyl chloride formed had distilled, the residue was chromatographed on a column of silica gel (18 g) being eluted with a 1 1 mixture of methylene chloride-ethyl acetate. The eluent was evaporated of solvent and the residue vacuum distilled to give pure diisopropyl (E)-2-benzoylvinylphosphonate (1.33 g, 45%). 

The Peterson reaction of the chlorovinyl-complex with ethyl trimethylsilylacetate provided the 11Z isomer preferentially (77%), and the 1 IE isomer as a secondary product (15%). The ester was transformed into the C 8 ketone (PhsSnCfy, BuLi, Et20, 79%). Reaction with (/Pr0)2P(0)CH2CN afforded the 1 lZ-retinonitrile in 73% yield. The complex was removed by CuC (72%) and DIBAL-H reduction led quantitatively to 1 lZ-retinal, Fig. (24). 

ETHYL ETHER, 34, 16, 49 Chlorourea, see Monochlorourea (3-ChloroviNYL isoamyl ketone, 32, 27, 79... 

The Vilsmeier-Haack reaction of ketones forms chlorovinyl aldehydes, which can add thiols readily. The reaction with a-tetralone gave the chlorovinyl aldehyde (230), and reaction with ethyl thioglycolate in ethanolic ethoxide solution formed the dihydro derivative (231), easily dehydrogenated to naphtho[l,2-6]thiophene-2-carboxylate (73JCS(P1)2956). 

Chlorovinyl ethyl ether, 140, 613 d-Chlorovinyl isoamyl ketone, 11,29 Cholane-24-al, 305 Cholane-12a-ol, 919 Cholane-24-ol, 305 A -Cholene, 919 A -Cholene-24-ol tosylate, 965 A 3-Cholcstadiene, 73, 313, 919 A -Cholestadiaie-3/8-ol, 645 A ,>M3iolestadien-3 yl acetate, 586, 793 Cholestane, 799 Oholestan6-2i3,3a-diol, 304 Cholestane-2/3,3/8-diol, 1003 Cholestane-3i8,5 -diol, 579 Cholestane-3,9,6/J-diol 3-acetate, 658 Cholestane-3, 6o -diol, 579 diacetate, 204... 

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