Aluminum phenyls

Diketene (635) is converted into 3-phenyl-3-butenoic acid (636) by the reaction of phenylzinc, magnesium, and aluminum reagents via C—O bond clea-vage[495j. 

Amides result from the reaction of aromatic hydrocarbons with isocyanates, such as phenyl isocyanate [103-71-9], ia the presence of aluminum chloride. Phenyl isothiocyanate [103-72-0] similarly gives thioanilides (136). 

Acetophenone. Acetophenone [98-86-2] (methyl phenyl ketone) is a colorless Hquid that forms laminar crystals at low temperature (mp 20°C). It has a characteristic sweet orange blossom odor, and is soluble in alcohols and ethers. It is found in nature in oil of casatoreum, obtained from beavers oil of labdanum, recovered from plants and in buds of balsam poplar. It can be prepared by the Friedel-Crafts reaction (qv) of acetyl chloride with benzene in the presence of aluminum chloride however, this route is of Htde commercial significance. 

Propiophenone. Propiophenone [93-55-0] (ethyl phenyl ketone) is a colorless Hquid with a flowery odor. It can be prepared by the Friedel-Crafts reaction of benzene and propionyl chloride in the presence of aluminum chloride (346), or by the catalytic reaction of benzoic acid and propionic acid in the presence of water (347). Propiophenone is commercially available (348), and is sold in Japan at 2700 Y/kg (349). It is used in the production of ephedrine, as a fragrance enhancer, and as a polymerization sensitizer. 

These reactions proceed rapidly and in good yield with primary alkyl and phenyl organotin compounds at ca 200°C. The reactions proceed at lower temperatures if anhydrous aluminum chloride is used as a catalyst. 

Benzanthrone has been prepared by three general methods, the first of which is generally regarded as the best (i) by heating a reduction product of anthraquinone with sulfuric acid and glycerol,1 or with a derivative of glycerol, or with acrolein. The anthraquinone is usually reduced in sulfuric acid solution, just prior to the reaction, by means of aniline sulfate, iron, , or copper. It has also been prepared (2) by the action of aluminum or ferric chloride on phenyl-a-naphthyl ketone, and (3) from i-phenylnaphthalene-2-carboxylic acid. ... 

Sulfuric acid is also a very satisfactory catalyst aluminum alkoxides also are useful, especially when the alcohols would be adversely affected by strong acids. Sodium alkoxides produce undesirable side reactions and give lower yields. When alkaline catalysts are employed, an alkaline polymerization inhibitor, such as j j-phenylenediamine or phenyl-d-naphthylamine, should be used instead of hydroquinone. 

Vinyl and phenyl mfluoromethyl groups are reactive in the presence of aluminum chloride [10] Replacement of fluorine by chlorine often occurs Polyfluori-nated trifluoromethylbenzenes form reactive a,a-difluorobenzyl cations in antimony pentafluoride [11] 1 Phenylperfluoropropene cyclizes in aluminum chloride to afford 1,1,3-trichloro 2 fluoroindene [10] (equation 10) The reaction IS hypothesized to proceed via an allylic carbocation, whose fluoride atoms undergo halogen exchange... 

Modifications of this method, such as the use of the more stable diazonium trifluoroacetates and the decomposition of benzenedia-zonium zincichloride with zinc dust, have been used as sources of aryl radicals, although not in the arylation of heterocyclic compounds. Pyridine, quinoline, and thiophene can be phenylated by treatment with benzenediazonium chloride and aluminum trichloride. ... 

Pyridine has been phenylated with the following free-radical sources benzenediazonium chloride with aluminum trichloride the Gomberg reaction " phenylhydrazine and metal oxides A -nitroso-acetanilide dibenzoyl peroxide phenylazotriphenylmethane di-phenyliodonium hydroxide and electrolysis of benzoic acid. ° Although 2-phenylpyridine usually accounts for over 50% of the total phenylated product, each of the three phenyl derivatives can be obtained from the reaction by fractional recrystallization of the... 

There is an early report that thiophene reacts at the 3-position in phenylation with benzenediazonium chloride and aluminum trichloride, but in the Gomberg reaction thiophene has been found to substitute mainly at the 2-position both with p-tolyl and with p-chloro-phenyl radicals.Bcnzothiazole is phenylated at the 2-position in low yield by dibenzoyl peroxide a small quantity of the 4-isomcr is also obtained. ... 

Preparation of cholesta-5,7-diene-ia,3/3-diol a solution of 500 mg of the 1,4-cyclized adduct of cholesta-5,7-dien-3/3-ol-ia,2a-epoxideand 4-phenyl-1,2,4-triazoline-3,5-dione in 40 ml of tetrahydrofuran is added dropwise under agitation to a solution of 600 mg of lithium aluminum hydride in 30 ml of THF. Then, the reaction mixture liquid Is gently refluxed and boiled for 1 hour and cooled, and a saturated aqueous solution of sodium sulfate is added to the reaction mixture to decompose excessive lithium aluminum hydride. The organic solvent layer is separated and dried, and the solvent Is distilled. The residue Is purified by chromatography using a column packed with silica gel. Fractions eluted with ether-hexane (7 3 v/v) are collected, and recrystallization from the methanol gives 400 mg of cholesta-5,7-diene-la, 3/3-diol. 

N-Chloroacetyl-N-phenyl-2,6-dichloroaniline Aluminum chloride Sodium hydroxide... 

Butyl alcohol in synthesis of phenyl 1-butyl ether, 46, 89 1-Butyl azidoacetate, 46, 47 hydrogenation of, 46, 47 1-Butyl chloroacetate, reaction with sodium azide, 46, 47 lre l-4-i-BUTYLCYCLOHEXANOL, 47,16 4-(-Butylcyclohexanonc, reduction with lithium aluminum hydride and aluminum chloride, 47, 17 1-Butyl hypochlorite, reaction with cy-clohexylamine, 46,17 l-Butylthiourea, 46, 72... 

Dibenzothiazepinones 6 are formed in almost quantitative yield by the aluminum trichloride induced ring closure of 2-isocyanatophenyl phenyl sulfides, exactly as described for the dibenzo-oxazepinone analog (see Section 4.1.1.3.2.4.) (Method C). Exact yields were not reported.40... 

Reduction of the 1//-1,2-benzodiazepines 6 with lithium aluminum hydride results in the dihydro compounds 8, which are dehydrogenated to the 3H-1,2-benzodiazepines 9 by 4-phenyl-4//-l,2,4-triazole-3,5-dione.123 The products readily revert to the 1//-tautomers in the presence of sodium methoxide. 3//-1,2-Benzodiazepines react with 3-chloroperoxybenzoic acid to give mixtures of 1- and 2-oxides, 10 and 11, in which the latter predominate. Treatment of the 2-oxides 11 with nucleophiles provides 3-substituted H- 1.2-benzodiazepines 12. Selected examples are given.124... 

The condensed l//-l,2-diazepines 12 are transformed into the 3//-tautomers 24 by reduction with lithium aluminum hydride to give 23, followed by dehydrogenation with 4-phenyl-4//-1,2,4-triazole-3,5-dione.146... 

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