Benzils chloride

C14H 20, 76-93-7) see Flutropium bromide Mepenzolate bromide Pipenzolate bromide Pipoxolan Propiverine benzilic chloride... 

Recently, Koitai et al. (17) have shown that 5,5-diphenyl-2,4-thiazolidinedithione (15) with aluminum chloride in refluxing toluene gives 4,5-diphenyl-A-4-thia2oline-2-thione (16) (Scheme 7). 3-Methyl-4,5-diphenyl (17) and 4,5-diphenyl-A-4-thia2oline-2-thiones (16) are obtained in very low yields (1 to 5%) as by-products of the reaction between deoxybenzoin. benzoin. l,2-diphenyl-1.2-ethanediol. 1.2-diphenylethanol, or benzil, and Sg in hexamethylphosphoamide (18), The transformation of A-4-thiazoline-2-ones to the corresponding thiones by P2S5 (19) is of little synthetic value since the latter are more easily prepared. 

Diphenylcinnoline can be prepared from benzil monophenylhydrazone in the presence of about 80% sulfuric acid (49MI21200). Synthetically more important, however, is the cyclization of mesoxalyl chloride phenylhydrazones under Frledel-Crafts -conditions (61JCS2828). As outlined in Scheme 67, the starting mesoxalate phenylhydrazones are obtained by coupling dlazotized aromatic amines with diethyl malonate. After conversion... 

An 80% yield of tetraphenylfuran is obtained by treatment of benzoyl chloride with active titanium generated by lithium aluminum hydride reduction of titanium trichloride (Scheme 84e) (8UOC2407). The reaction nroceeds via benzil and tetraphenylbut-2-ene-l,4-dione, both of which are minor products of the reaction. 

Baeyer-Villager oxidation, 10, 151, 433 Bamford-Stevens reaction, 402 Barton reaction, 253 Beckmann rearrangement, 140 Benzilic acid rearrangement, 418, 435 3 -Benzoyloxy-7-methylenecholest-5-ene, 60 Benzylmagnesium chloride, 64 3-Benzyloxycholesta-3,5-diene, 342... 

The reaction of diketosulfides with 1,2-dicarbonyl compounds other than glyoxal is often not efficient for the direct preparation of thiophenes. For example, the reaction of diketothiophene 24 and benzil or biacetyl reportedly gave only glycols as products. The elimination of water from the P-hydroxy ketones was not as efficient as in the case of the glyoxal series. Fortunately, the mixture of diastereomers of compounds 25 and 26 could be converted to their corresponding thiophenes by an additional dehydration step with thionyl chloride and pyridine. 

The placement of a nitrogen atom directly on the benzilic carbon atom is apparently consistent with antispasmodic activity. Esterification of 2 (iV-piperidyl)ethanol by means of chloroacyl chloride (68) gives the basic ester (69). Displacement of the remaining halogen by piperidine gives dipiproverin (70). ... 

Chloro-benzal, n. benzal chloride, benzylidene chloride. -benzil, n. dichlorobenzil,... 

N-methyl-4-piperidvl benzi/ata and the methiodide An intimate mixture of 0.1 mol of N-methyM-piperidinol hydrochloride and 0.1 mol diphenylchloroacetyl chloride is heated at 160°C to 180°C until the evolution of hydrogen chloride ceases (usually about 4 to 5 hours). The melt is then dissolved in 500 ml of water and the resultant mixture heated on a steam bath for about Vi hour, after which time complete solution is effected. The acid solution is cooled and rendered alkaline with ammonium hydroxide solution whereupon the ester is precipitated.The ester is purified either by removal by filtration and recrystallization from benzene petroleum ether or by extracting the mixture with benzene and precipitating the ester by the addition of petroleum ether. After recrystallization there is obtained about 0.06 mol of N-methyl-4-piperidyl benzilate, melting point 1 62°C to 163°C. 

Benzy 1 2 carbomethoxycyclopentanone from 2 carbomethoxycyclopentanone and benzyl chloride, 45, 8 2 Benzylcyclopentanone, 46, 7 N Benzyloxycarbonylglycine, 46, 49 Benzyltnmethylammonium hydroxide as catalyst for condensation of benzil with dibenzyl ketone, 46,... 

Benzile lassen sich mit Titan(lIl)-chlorid zu Benzoinen reduzieren. Die Ausbeuten sind hoch, liegen aber trotzdem unter denen der entsprechenden Reduktion mit Vana-dium(II)-chlorid4 ... 

Oxo-1,2-bis-[4-isopropy 1-phenylJ- 656 2-Oxo-l,2-bis-f4-methoxy-phenyl]- 628, 656 aus 4.4 -Dimethoxy-benzil und Vanadin(II)-chlorid 504... 

Samarium iodide (Sml2) gives the same reaction. Benzoyl chloride was coupled to give benzil by subjecting it to ultrasound in the presence of Li wire 2 PhCOCl -I-... 

C14H14O 5472-13-9) see Tofenacin 2-methylbenzhydryl chloride (C]4Hi3C1 41870-52-4) see Orphenadrine methyl benzilate... 

The diketo acids were transformed to their methyl esters under the action of diazomethane (5), SOCl2/CH3OH (102), or methanolic hydrogen chloride (117). Like other benzils, JV-methyloxohydrasteine (109) when... 

A mixture of 45.6 g. (0.2 mole) of benzilic acid (Note 1) in 700 ml. of anhydrous thiophene-free benzene, contained in a 2-1. three-necked flask fitted with a reflux condenser (attached to a calcium chloride drying tube) and a motor-driven sealed stirrer, is cooled in an ice bath until a crystalline mass results. To the stirred mixture is added, in one portion, 80 g. (0.6 mole) of anhydrous aluminum chloride. The stirred mixture is heated until refluxing begins and is maintained at this temperature for 3 hours. During this period much hydrogen chloride is evolved, and the initially yellow solution soon becomes deep red. The solution is cooled and decomposed by the cautious addition of small pieces of ice, and then 400 ml. of water is added cautiously, followed by 200 ml. of concentrated hydrochloric acid. The benzene is removed by steam distillation, and the product is separated by filtration from the hot mixture. The lumps of product are crushed and extracted with 400 ml. of boiling 10% sodium carbonate solution. The mixture is filtered, and the extraction is repeated on the undissolved residue with an additional 200 ml. of hot 10% sodium carbonate solution. The basic filtrates are... 

The procedure described is essentially that of Ballard and Dehn.1 Stilbene has also been prepared by reduction of desoxy-benzoin,20 benzaldehyde,23 and benzil 2o-2c by dehydrogenation of ethyl benzene,30 toluene,30- 33- 3, and bibenzyl 33-3alkaline reduction of phenylnitromethane,40 phenylnitroacetonitrile,40 and desoxybenzoin 43 by distillation of benzyl sulfone,50 benzyl sulfide,60-63 calcium cinnamate,5 cinnamic acid,5d phenyl cinna-mate,6e-6/ and diphenyl fumarate ie by dehydrohalogenation of a,a -dichlorobibenzyl60 and benzyl chloride 63 by dehalogenation of a,a,c/,a -tetrachlorobibenzyl70 and benzal chloride 73 by the coupling of cinnamic acid and phenyldiazonium chloride 8 by de-... 

This interesting derivative of ketene is also obtained from benzilic acid by the old process of Staudinger the add is converted, by the action of phosphorus pentachloride, into diphenylchloracetyl chloride from which the two chlorine atoms are removed by means of zinc. (Formulate this equation.) What is carbon suboxide For information about the ketenes see H. Staudinger, Die Ketene, Stuttgart, 1912. 

Reduction of benzoyl chloride at mercury yields an acyl radical that dimerizes to form benzil. As quickly as it forms, benzd accepts an electron to form an anion radical that is acylated by a molecule of benzoyl... 

Nickel prepared by reduction of nickel chloride with sodium borohydride was used for desulfurization of diethyl mercaptole of benzil. Partial desulfurization using 2 mol of nickel per mol of the mercaptole gave 71% yield of ethylthiodesoxybenzoin while treatment with a 10-fold molar excess of nickel over the mercaptole gave 61% yield of desoxybenzoin (benzyl phenyl ketone) 937. ... 

---