Diphenyl acetic acid

Diphenylacetic acid Acetic acid, diphenyl- (8) Benzeneacetic acid, Diphenyl- (9) (117-34-0)... 

When heated in palladium acetate-containing acetic acid, diphenyl ether, diphenylamine, benzophenone, and benzanilide gave high yields of cyclized products (eq 69). A large number of ring substituents were tolerated in the cyclization. ... 

Acetamide, N-(p-hydroxybenzyl)-, 41 Acetanilide, 58 Acetic acid, diphenyl-, 50 Acetoacetic acid, 31 Acetoin, 37 Acetone, acetyl-, 39 dichloro-, 39 dihydroxy-, 31 Acetophenone, 52, 54 o-amino-, 55... 

Diphenyl. Reflux a mixture of 1 g, of diphenyl, 2 ml. of glacial acetic acid and 0 -5 ml. of fuming nitric acid for 10 minutes. Pour into 20 ml. of cold water, filter oflF the precipitate, wash it with cold water imtil free from acid, and recrystallise from alcohol. The product is 4-nitrodiphenyl, m.p. 114°,... 

Diphenic acid. Phenanthrene upon oxidation in acetic acid solution at 85° with 30 per cent, hydrogen peroxide gives diphenic acid (diphenyl-2 2 -di-carboxyHc acid) no phenanthraquinone is formed under these experimental conditions. The reaction is essentially an oxidation of phenanthrene with peracetic acid. (For another method of preparation, see Section I V,74.)... 

Place 125 ml. of glacial acetic acid, 7 -5 g. of purifled red phosphorus (Section II,50,d) and 2 5 g. of iodine in a 500 ml, round-bottomed flask fitted with a reflux condenser. Allow the mixture to stand for 15-20 minutes with occasional shaking until aU the iodine has reacted, then add 2 5 ml. of water and 50 g, of benzilic acid (Section IV,127). Boil the mixture under reflux for 3 hours, and filter the hot mixture at the pump through a sintered glass funnel to remove the excess of red phosphorus. Pour the hot filtrate into a cold, weU-stirred solution of 12 g. of sodium bisulphite in 500 ml, of water the latter should be acid to litmus, pro duced, if necessary, by passing sulphur dioxide through the solution. This procedure removes the excess of iodine and precipitates the diphenyl-acetic acid as a fine white or pale yellow powder. Filter the solid with suction and dry in the air upon filter paper. The yield is 45 g., m.p. 

The spectra and halochromism of thiophene analogs of triphenyl and diphenyl carbinol, " the spectra of anilides of 2- and 3-thenoyl-acetic acid, " and the fluorescence of some thiophene compounds have been investigated. 

The cyclization of 1,3,5-triketones to pyrones will not be discussed here, although this is a related reaction, because pyrones are not true pyrylium salts. Mention will be made, however, of the formation of 2,6-diphenyl-4-pyrone from 1,3-dibenzoylallene this ketone adds secondary amines leading to 3-dialkylamino-l,5-diphenyl-4-penten-l,5-diones, which arc cyclized by hydrogen chloride in acetic acid to 2,6-diphenyl-4-dialkylaminopyrylium chlorides (R = Me and/or Ph) (see Scheme. 5). 

Tlie smallest compounds among the azafulvalenes described to date are the azacalicenes, which are formed by combining a cyclopropenylidene moiety with a nitrogen-containing cyclopentadienylidene. Tlius, heating di-or triphenylpyrroles with diphenyl-methylsulfanyl-cyclopropenylium perchlorate in acetic acid gives the aza-triafulvalenium salts 33 and 34... 

Using different mono- and diketones in acetic acid (at room temperature) afforded the following products from benzophenone, 2,2-diphenyl-2//-imid-azo[4,5-/]quinoline from dibenzylketone, the 2-benzyl-imidazo[4,5-/]quino-line and from 2,4-pentanedione, 2-methyl-imidazo[4,5-/]quinoline. Cyclohexanone under reflux gave 2-n-pentyl-, whereas at room temperature it afforded the. s pira[cyclohexane-l,2 ]-(2//)-imidazo[4,5-/]quinoline 108 (R R =(CFl2)5) (86UC527). 

In a recent communication, the parent system 2 has been obtained in poor yields (16% and 10%, respectively) from the double cyclization of N-diphenyl-1,3-phenylenediamine either by using two equivalents of palladium acetate in refluxing acetic acid or by irradiation in methanol in the presence of a catalytic amount of iodine (00SC3651). All the available approaches sununarized so far were marred by harsh reactioi conditions or troublesome-to-prepare starting materials, leading to low overall yields of the desired products and difficulty in introducing sensitive substituents. 

Diketones 1 can be converted into the salt of an a-hydroxy carboxylic acid upon treatment with alkali hydroxide after acidic workup the free a-hydroxy carboxylic acid 2 is obtained. A well-known example is the rearrangement of benzil (R, R = phenyl) into benzilic acid (2-hydroxy-2,2-diphenyl acetic acid). The substituents should not bear hydrogens a to the carbonyl group, in order to avoid competitive reactions, e.g. the aldol reaction. 

Esters of diphenylacetic acids with derivatives of ethanol-amine show mainly the antispasmodic component of the atropine complex of biologic activities. As such they find use in treatment of the resolution of various spastic conditions such as, for example, gastrointestinal spasms. The prototype in this series, adiphenine (47), is obtained by treatment of diphenyl acetyl chloride with diethylaminoethanol. A somewhat more complex basic side chain is accessible by an interesting rearrangement. Reductive amination of furfural (42) results in reduction of the heterocyclic ring as well and formation of the aminomethyltetrahydro-furan (43). Treatment of this ether with hydrogen bromide in acetic acid leads to the hydroxypiperidine (45), possibly by the intermediacy of a carbonium ion such as 44. Acylation of the alcohol with diphenylacetyl chloride gives piperidolate (46). ... 

Preparation of 4,4 -Dioxy-Diphenyl-(2-Pyridyl)-Methane 100 g of 3,3 -dichloro-4,4 -dioxy-diphenyl-(2-pyridyl)-methane, obtained as above described, are dissolved in 660 ml of 10% sodium hydroxide and 49 g of Raney-nickel alloy are added to the solution with vigorous stirring, at room temperature and during 4 hours. The mixture is stirred overnight at room temperature, then it is filtered and brought to pH 5 with 10% acetic acid. The precipitate obtained, filtered, washed and dried is then dissolved in 1,500 ml of 95°C boiling alcohol to eliminate the insoluble salts. The residue obtained after the evaporation of the alcoholic solution weighs 74 g (yield 92%). The yield in respect to 2-pyridinaldehyde is 63.5%. 

The (diazoacetyl)dihydropyrazole 4a is converted into the 1 //-l, 2-diazepin-6(7//)-one 5a in hot acetic acid 73 a somewhat similar reaction affords the diphenyl analog 5b.74... 

Aminobenzylamine (1, R1 = H) reacts with benzil in refluxing acetic acid for 24 hours to give the yellow 2,3-diphenyl-5//-l,4-benzodiazepine (2) in 47% yield, but the reaction is not general. However, 2-chloro-2//-azirines function as diketone equivalents, yielding the benzodiazepines 3, when treated with equivalent amounts of the diamines 1 in pyridine at 20 C. Further details were not reported.192... 

B. l,l-Diphenyl-2-bromo-Z-acetoxy- -j>ropene. A 250-ml. flask equipped with a condenser is charged with 17.6 g. (0.050 mole) of 1,1-dibromo-2,2-diphenylcyclopropane, 12.5g. (0.075 mole) of silver acetate [Acetic acid, silver(l +) salt] (Note 4), and 50 ml. of glacial acetic acid, then immersed in an oil bath at 100-120° for 24 hours (Note 5). After cooling, the mixture is diluted with 200 ml. of ether and filtered. The ethereal filtrate is washed with two 100-ml. portions of water, two 100-ml. portions of aqueous saturated sodium carbonate, and finally with two 100-ml. portions of water. After drying over anhydrous sodium sulfate, the ether is removed on a rotary evaporator. Distillation of the resulting residue under reduced pressure yields 12.0 g. (72%) of the product, b.p. 142-145° (0.15 mm.), 1.6020-1.6023 (Note 6). 

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