Reactions of primary amines with tetracyanoethylene

Primary amines, 3-triethoxysilylpropylamine, 3-silatranylpropylamine, and cyclohexylamine, react with tetracyanoethylene in acetonitrile at room temperature via addition at the cyano group to afford the corresponding amidines. N-Cyclohexyltricyanoacrylamidine exists as a mixture of two of the three possible isomers, while N-(3-triethoxysilylpropyl)tricyanoacrylamidine and N-(3-silatranylpropyl)tricyanoacrylamidine exist mainly as a single isomer containing NH₂ group. N-(3-Triethoxysilylpropyl)tricyanoacrylamidine was used to prepare gels and films.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004, pp. 1308–1314.Original Russian Text Copyright © 2004 by Ladilina, Semenov, Kurskii, Khorshev, Domrachev.     

Reactions of o-bromoacetylacylphenones with several primary amines

o-Monobromoacetylacylphenones, 3a and 3b reacted with hydroxylamine or hydrazine hydrate to produce heterocycles, 2,3-benzoxazine or phthalazine derivatives. The reaction of bromoacetyl group of 3a and 3b with several thioamides afforded thiazole derivatives in high yields. Whereas o-dibromoacetyl-benzophenoe 2a reacted with aniline or cyclohexylamine to produce non-heterocycles, 2-substituted-iminophenylindanones and the mechanism for the formation of these non-heterocycles is proposed.     

Reactions of 4-dicyanomethylenepyrans with hindered primary amines

The reaction of 2,6-dimethyl- and 2,6-diphenyl-4-dicyanomethylene-4H-pyran with hindered primary amines such as isopropylamine and cyclohexylamine gave 1-alkyl-2-amino-3-cyano-6-rnethyl(or phenyl)-4-acetonylidene (or phenacylidene)-1,4-dihydropyridine derivatives. The 6-methyl-4-acetonylidene examples underwent a facile thermal rearrangement to give 1-alkyl-2,6-dimethyl-4-dicy anomethy lene-1,4-dihydropy ridines. Several reactions of the acylidene derivatives are described.     

Reactions of tetracyanocyclopropyl ketones with ammonia and primary amines

Reactions of aliphatic 2,2,3,3-tetracyanocyclopropyl ketones with aqueous ammonia afforded 4-alkyl- 4-amino-2-oxo-3-azabicyclo[3.1.0]hexane-1,6,6-tricarbonitriles with conservation of the three-membered ring. Reactions of the same compounds with primary amines were accompanied by opening of the cyclopropane ring, and they led to the formation of 5-amino-6,6a-dimethyl-2-oxo-1,2,6,6a-tetrahydropyrrolo[2,3-b]-pyrrole-3,4-dicarbonitriles as a result of successive heterocyclizations.     

Reactions of 4-chloro-3-formyl-coumarin with primary amines

The reaction of 4-chloro-3-formylcoumarin with primary amines in the presence of triethylamine was studied. The reaction with aliphatic and aromatic amines leads to N-substituted 4-amino-3-formylcoumarins, whereas hetarylamines react primarily with the formyl group to form a mixture of the Z-and E-isomers of N-substituted 3-aminomethylenechroman-2,4-diones. Replacement of the triethylamine by anhydrous sodium acetate in the reaction of chlorocoumarin with 2-aminopyridines leads to the formation of the condensed benzopyranopyridopyrimidine system as a result of nucleophilic attack of the amino group by the chlorine atom at position 4. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 660–668, May, 2006.     

Reactions of 2‐Pentynyl trimethylsilylethynyl selenides with primary amines via allenyl selenoketene

Reactions of 2‐pentynyl trimethylsilylethynyl selenide 3 with primary amines 5 via allenyl selenoketene 4 afforded the corresponding selenine 6 , selenophene 7 and β,γ‐unsaturated selenoamide 8 , respectively.     

Reactions of 3-cyanochromones with primary amines: structures of the products

Reactions of 3-cyanochromones with primary aromatic amines in boiling benzene gave mixtures of Z- and E-3-arylamino-2-(2-hydroxyaroyl)acrylonitriles and 2-amino-3-(aryl-iminomethyl)chromones. The latter can easily be obtained in the individual state when the reaction is carried out in the presence of triethylamine. In the case of primary aliphatic amines, the open-chain reaction product immediately undergoes cyclization into 3-alkyliminomethyl-2-aminochromones. The structures of the products were examined by 1D and 2D ¹H, ¹³C, and ¹⁵N NMR spectroscopy in DMSO-d₆ and CDCl₃.     

Reactions of triethylborate with amines

Russian Chemical Bulletin -     

Reactions of chloroalkyl-gem-dichlorocyclopropanes with amines

N-Alkylation of primary and secondary amines with monochloroalkyl-gem-dichlorocyclopropanes under conditions of thermal and microwave heating results in the corresponding amino-gem-dichlorocyclopropanes. With microwave irradiation heating, the reaction time has been decreased to 1 h, the yields of the amines containing gem-dichlorocyclopropane moiety being the same. Formation of the bicyclic amine in reaction of cis-2,3-dichloromethyl-gem-dichlorocyclopropane with primary amines under conditions of phasetransfer catalysis has been studied.     

Reactions of some 4-methylene-4H-pyran derivatives with primary and secondary amines

4-Dicyanomethylene-4H-pyrans react with secondary amines to give 2-aminopyridine and 2-pyridone derivatives which, in turn, have been used to prepare copyrine derivatives. These pyrans and primary amines gave copyrine and iminopyridone derivatives in addition to the dicyanomethylene-1,4-dihydropyridines, which had been reported previously. Reaction of cyanocarbamoylmethylene-4H-pyrans with secondary amines gave 2-pyrones, and with primary amines, gave copyrines and 1,4-dihydropyridine derivatives.     

Reactions of 4-ethoxycarbonylbenzo-[c]pyrylium with ammonia and primary amines

We have studied the reactions of 4-ethoxycarbonylbenzo[c]pyrylium perchlorates with ammonia and primary amines. We have obtained previously unknown derivatives of isoquinoline and 1-naphthylamine.Institute of Physical Organic Chemistry and Coal Chemistry, National Academy of Sciences of Ukraine, Donetsk 340114. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1222–1224, September, 1994. Original article submitted September 5, 1994.     

Reactions of sulfites with secondary amines

The interaction of diethylamine and morpholine with diphenyl, methyl phenyl, ethyl phenyl, and isopropyl phenyl sulfites was studied. It was established that two reactions, substitution and alkylation, can occur in parallel. Diphenyl sulfites react with amines to give only substitution products, while other sulfites react with substitution at the sulfur atom and with alkylation of the amines. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1395–1397, July, 1998.     

Reactions of Me2Al-i-Bu and Me2AlCCMe with primary and secondary amines

The elimination reaction which takes place in complexes of dimethylisobutylaluminium or dimethylpropynylaluminium and N-methylaniline, di-n-butylamine or octylamine was investigated. The abilities of methyl, isobutyl and propynyl groups to take part in elimination reactions were different. A radical exchange reaction was observed.     

Reactions of 4-pyrones with primary amines. A new class of ionic associates

Primary aliphatic amines react with 2,6-dimethyl-4-pyrone to give 2,6-dialkylamino-2,5-heptadien-4-one derivatives. When the alkyl group was methyl, the diamino derivative cyclized on warming to give 1,2,6-trimethyl-4-pyridone. The corresponding butylamino derivative did not thermally cyclize, but did give a pyridone on treatment with acid. The isopropylaminoketone did not cyclize. Several examples of 1,2,6-trisubstituted-4-pyridones formed “ionic associates” consisting of two parts of the pyridone and one part of perchloric acid. These associates are useful primary standards for nonaqueous titrations.     

Reactions of boryloxymethyl- and hydroxymethylphosphines with amines

Conclusions 5-(Hydroxymethyl)-2,2,5-triphenyl-1,3,2,5-dioxaborataphosphoniarinane reacts with diphenylamine and o-aminobenzoic acid with the formation of 5-(aminomethyl)-2,2,5-triphenyl-1,3,2,5-dioxaborataphosphoniarinanes, whereas 1,5,3,7-diammoniadiphosphacyclooctanes are formed with m- and p-aminobenzoic acids. With o-aminobenzoic acid, hydroxymethylphosphines and hydroxymethylphosphonium salts give the corresponding aminomethylphosphines and aminomethylphosphonium salts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1340–1343, June, 1989.Deceased.