Laszlo Urogdi

N-Triphenylphosphorylidene-1-(benzotriazol-1-yl)methylamine, a novel synthon equivalent to +CH2NH2: the preparation of primary amines

Abstract Primary amines are readily prepared by reaction of the title compound with organolithiums or Grignard reagents.

Benzotriazole-assisted synthesis of monoacyl α-aminoglycines

Adducts (8,12), derived from benzotriazole (7), glyoxylic ester (6) or acid (11), and an amide (5), react with ammonia in a novel, convenient route to monoacylated α-aminoglycines (9,13) useful for the synthesis of peptide analogues.

Benzotriazole-assisted synthesis of α-acylaminonitriles and a conceptually novel method for peptide elongation

A general method for the synthesis of α-acylamino nitriles is reported. Initially, the adducts resulting from Mannich-type condensation of benzotriazole with an aldehyde and an amide are prepared. These undergo elimination of benzotriazole with cyanide to give α-arylamino nitriles in high yields. Subsequent hydrolysis of the nitrile function to the di-amides, followed by a repetition of the cyanoalkylation sequence, constitutes a novel method for the elongation of peptides.

Mono-N-alkylation of α-aminoacetonitriles. A novel route to unsymmetrical secondary amines

Mannich-type condensation products of an aldehyde with an α-aminoacetonitrile and benzotriazole are treated with sodium borohydride or with a Grignard reagent to give unsymmetrical N,N-dialkylaminoacetonitriles, which, on decyanomethylation, provide unsymmetrical secondary amines.

The chemistry of N-substituted benzotriazoles. Part 14. Novel routes to secondary and tertiary amines and to N, N-disubstituted hydroxylamines

Tertiary amines of types R4R3CHNR1R2(2), (R2CH2)2NR1(10) and (11), or (R2CH2)3N (12), secondary amines of type (R2CH2)2NH (8), and N, N-disubstituted hydroxylamines of type (R2CH2)2NOH (9), are prepared in high yield by the action of Grignard reagents or sodium borohydride on easily available N, N-dialkyl-N-[benzotriazolylalkyl-(or arylalkyl-)]amines (1) or tris(benzotriazolylmethyl)amine (7), on bis(benzotriazolylmethyl)amines (3), (5), and (6), and on N, N-bis(benzotriazolylmethyl)hydroxylamine (4), respectively.

Reactions of benzotriazole with formaldehyde and aliphatic primary amines: selective formation of 1 : 1 : 1, of 2 : 2 : 1, and of 2 : 3 : 2 adducts and a study of their reactions with nucleophiles

Benzotriazole (BtH) reacts easily with aliphatic primary amines and formaldehyde in aqueous media to give one or more of three types of product: (i)(BtCH2)2NR (5), (ii)(BtCH2NR)2CH2(6), and/or (iii) BtCH2NHR (7). The product formed depends on the molar ratio of the substrates, and on the degree of steric hindrance in the amine, and is also influenced by the nature of the solvent. Primary aliphatic 1,2- or 1,3-diamines yield cyclic aminals which are imidazolidine (8a) and hexahydropyrimidine (8b) derivatives. Reactions of these aminals with Grignard reagents, and with cyanide anion as nucleophiles, are also described.

The chemistry of some bicyclic pyridinium anhydrobases

The anhydrobase from 5,6,7,8-tetrahydro-2,4-Biphenyl-1-p-tolylquinolinium reacts with C-, N-, and S-electrophiles to form adducts and new anhydrobases. The tautomeric structures of the adducts are deduced from spectral evidence.

Benzotriazol-1-ylalkyl isocyanides: versatile synthons for preparation of unsymmetrical formamidines

Adducts from benzotriazole, an aldehyde, and formamide are dehydrated to α-(benzotriazol-1 -yl)alkyl isocyanides which readily add to secondary amines to form N′-(benzotriazol-1-ylalkyl)-N,N-dialkylformamidines. The benzotriazolyl group in the latter is displaced by Grignard reagents to yield the corresponding unsymmetrical formamidines.