Gy. Simig

Hydantoins, thiohydantoins, glycocyamidines—36: 1,5,5- and 3,5,5-triphenyl derivatives

Abstract In contrast to the α-chloroamides 1a-c which, when reacted with potassium N-cyanoanilide, furnish anomalous substitution products ( 2a-c ), the related nitrile and ester yields normal substitution products ( 3a and b ) under the same conditions. 1,5,5-Triphenylhydantoin ( 4a ) and a series ( 5a-8a, 13 and 14 ) of its derivatives have been prepared starting with 3a and b . Acid hydrolysis of 3a yields, in addition to the normal products ( 4a and 5a ) considerable quantities of the rearranged product 4b . An authentic sample of the latter, as well as a series of its derivatives ( 5b-8b and 11 ) have been prepared starting with α,α-diphenylglycinonitrile and 2-methylthio-1,4,4-triphenyl-2-imidazolin-5-one ( 9 ). When reacted with ammonia and ammonium iodide, 9 gave, in addition to the normal ammonolysis product 7b , the Dimroth rearrangement product 16 , as well as 5,5-diphenylglycocyamidine, by apparent dephenylation of 16 . The mass spectra of the imidazole derivatives 4–8, a and b, 9, 11, 13 and 14 are discussed.

The reaction of N-cyanoamines with 1-(t-butyl)-3,3-diphenylaziridinone: A general method for the synthesis of 1-alkyl-, 1-aralkyl- and 1-aryl-5,5-diphenylhydantoins and -glycocyamidines

Abstract N-Cyanomanines react with aziridinone 1 to yield the amides 2 . Base catalysed ring closure of the latter furnished the glycocyamidines 3 . Acid catalysed de-t-butylation, and deimination combined with de-t-butylation of the compounds 3 leads to 1-substituted 5,5-diphenylglycocyamidines ( 4 ) and -hydantoins ( 5 ), respectively. Part of the hydantoins 5 were also directly obtained by hydrochloric acid treatment of amides 2 . Selective de-t-butylation in position 3 of the glycocyamidine 3 (R = t-Bu) was brought about by heating with methanolic NH 3 in the presence of NH 4 I. Reaction of 1 with the un substituted N-cyanoamine furnished carbodiimide 7 which was cyclized to the glycocyamidine 8 . The mass spectra of some glycocyamidines 4 and hydantoins 5 , as well as of compounds 7 and 8 are discussed.

The reaction of α-chloro-α,α-diphenylacetamides with potassium n-cyanoanilide: A novel type of cine substitution☆

Abstract Three types of products are formed in the reactions of α-chloro-α,α-diphenylacetamides (1a–c with potassium N-cyanoanilide: cine substitution products of type 2 as the main products, and two types of normal products (4a and b, and 3, 6 and 7a, respectively) whose formation reflects the ambident reactivity of the N-cyanoanilide anion.

On the mechanism of formation of dimeric and reduced products from an α-halo amide with sodium methoxide

Abstract Treatment of 2-bromo-N,N-dimethyl-2,2-diphenylacetamide 1 with sodium methoxide in 2,2-dimethoxypropane furnishes mixtures of the reduced product 2 and the dimer 5 . Crossing experiments have shown that 2 is not a precursor of 5 , supporting thereby the S RN 1 mechanism for the formation of both 5 and 2 .

Anomalous substitutions and reductive dehalogenations of α,α-diaryl-α-halogeno- n,n-dimethylacetamides by methoxide

Bei der Behandlung der a,a-Diaryl-a-halogen-N,N-dimethylacetamide (I) mit einem Uberschus an Natriummethylat werden neben den normalen Substitutionsprodukten durch Halogenaustausch am α-C-Atom zusatzlich anomale Enthalogenierungsprodukte sowie Kemsubstitutionsprodukte erhalten.

SOME PROPIONIC ACIDS AND DERIVATIVES, SUBSTITUTED IN POSITION 2 WITH HETEROCYCLIC GROUPS

Im Hinblick auf die antjphlogistischen Eigenschaften von p-substituierten Phenylessigsauren und 2-Phenyl-propion- Sauren wird eine Anzahl von Propionsauren, Propionsaureestern und -amiden, die in 2-Stellung mit Heterocyclen substituiert sind, synthetisiert.

A novel thermal rearrangement of N-cyano-N-(α-cyanobenzhydryl)-aniline

Abstract The title compound 1 is rearranged, when refluxed with toluene, to the carbodiimide 5 and the cyanoaniline 7 . While rearrangements analogous to the transformation 1→5 have recently been observed, the transformation 1→7 is novel.