Synthesis of 2-amino-4-aryl-3-cyano-5-hydroxyimino-4,5-dihydrothiophenes

The Michael addition of cyanothioacetamide to nitrostyrenes was investigated. Previously unknown 2-amino-4-aryl-3-cyano-5-hydroxyimino-4,5-dihydrothiophenes were obtained. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1472–1477, October, 2007.     

Regioselective conversion of 3-cyano-6-hydroxy-2-pyridones into 3-cyano-6-amino-2-pyridones

The reaction of a tautomeric mixture of 1-butyl-1,2-dihydro-6-hydroxy-4-methyl-2-oxopyridine-3-carbonitrile and its 2-hydroxy-6-oxo analog with phosphorus oxychloride gave 1-butyl-6-chloro-1,2-dihydro-4-methyl-2-oxopyridine-3-carbonitrile (68%) and 1-butyl-2-chloro-1,6-dihydro-4-methyl-6-pyridine-3-car-bonitrile (3%). Both chloropyridones were converted to their corresponding aminopyridones by reaction with liquid ammonia. Strong support for the molecular structure of 6-amino-1-butyl-1,2-dihydro-4-methyl-2-oxopyridine-3-carbonitrile was obtained on the basis of nmr techniques.     

A new stereoselective synthesis of 2-amino-4,5-dihydrothiophene-3-carbonitrile derivatives

A new stereoselective method for the synthesis of trans-isomers of 2-amino-4-aryl-5-benzoyl-4,5-dihydrothiophene-3-carbonitriles was proposed. The method involves base-catalyzed reactions of phenacyl thiocyanate with 3-(het)aryl-2-cyanoprop-2-enethioamides. (4R,5S/4S,5R)-2-Amino-5-benzoyl-4-(2-chlorophenyl)-4,5-ihydrothiophene-3-carbonitrile was structurally characterized by X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1379–1383, July, 2007.     

Synthesis of substituted 2-amino-3-cyano-4-methylpyrroles

A facile route for the synthesis of substituted 2-amino-3-cyano-4-methylpyrroles from N-acetyl-α-amino ketones and malononitrile is reported.     

Synthesis of 2-amino-4,4-bis(trifluoromethyl)-3-cyano-4,5-dihydro-1H-1,5-benzodiazepine

Conclusions The reaction of 1,2-phenylenediamine with 2,2-bis(trifluoromethyl)-1,1-dicyanoethylene leads to the formation of 2-amino-4,4-bis(trifluoromethyl)-3-cyano-4,5-dihydro-lH-l,5-benzodiazepine, whose structure was established by x-ray diffraction analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1920–1922, August, 1988.     

X-ray structural study of 2-amino-5,5-dimethoxy-3-cyano-4-dicyanomethylene-4,5-dihydropyrrole and its sodium salt

According to the XSA data, a conjugation system in which both endo- and exocyclic bonds are included is realized in the molecule of 2-amino-5,5-dimethoxy-3-cyano-4-dicyanomethylene-4,5-dihydropyrrole and the anion of its sodium salt due to the planar structure, and this is reflected in their unusual length. Due to the developed system of intermolecular hydrogen bonds, the molecules in the crystals are joined in infinite three-dimensional motifs.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow 117813, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 510–517, April, 1998.     

K2CO3-catalyzed synthesis of 2-amino-3-cyano-4H-chromene derivatives with different substituents in water

The direct three-component condensation of resorcinol, 1-(2,4-dihydroxyphenyl)ethanone or 2,4-dihydroxybenzophenone with benzaldehydes and malononitrile to generate some novel 2-amino-3-cyano-4H-chromene derivatives has been carried out over K₂CO₃ (25 mol%) with high efficiency in water as a green solvent at 70 °C.     

1-苯基-2-氰基-3-氨基-3a,3b,6,7-四氢化苯并[4,5]茚的合成及晶体结构

标题化合物C_20H_18N_2是由2-氰-3-苯基-3-(1-萘酮-2-基)丙腈在低价钛试剂作用下还原成环而得。结构通过单晶X-射线衍射分析确定,其晶体属于三斜晶系,空间群P, a = 9.169(2), b = 9.520(2), c = 10.276(2) , a = 91.09(1), = 107.95(1), = 111.05(2), V = 787.8(3),Mr = 286.36 ?, Dc = 1.207 g/cm3, Z = 2, m(MoKa) = 0.071 mm-1, F(000) = 304, R = 0.0399, wR = 0.1008。单晶X-射线分析表明,五员环(C(7)~C(11))采用信封式构象,而六员环(C(10)~C(15))则采用半椅式构象,同时,分子间氢键作用形成二聚体。     

New HA 14-1 analogues: synthesis of 2-amino-4-cyano-4H-chromenes

The synthesis of 2-amino-4-cyano-4H-chromene derivatives as new HA 14-1 analogues by a simple and efficient method is reported. In addition, the reaction of 2-amino-2H-chromene-3-carbonitriles, salicylaldehydes and amines results in the formation of new chromeno[2,3-d]pyrimidine derivatives.     

A convenient synthesis of polysubstituted 2-amino-4,5-dihydrofuran-3-nitriles from benzoins or benzaldehydes

A convenient assembly of polysubstituted 2-amino-4,5-dihydrofuran-3-nitriles from a tandem Michael addition/cyclization reaction between benzoins and arylidenemalononitriles is described. The products are also obtained from readily available benzaldehydes via a sequential N-heterocyclic carbene–catalyzed benzoin condensation and Michael addition/cyclization process in a one-pot tandem procedure.     

Imidazole as an efficient catalyst for the synthesis of 2-amino-3-cyano-4H-chromen-4yl-phosphonates

An efficient procedure for the preparation of 2-amino-3-cyano-4H-chromen-4-yl phosphonate derivatives via a three-component reaction of salicylaldehyde, malononitrile and trialkyl phosphites or diethyl phosphite using inexpensive and environmentally friendly imidazole as organocatalyst has been reported. Beside excellent yields and easy workup, the reaction is done in an almost neutral medium.     

Synthesis and Mesomorphic Properties of New 3-Aryl-5-cyano-4,5-dihydroisoxazoles

New 3-aryl-5-cyano-4,5-dihydroisoxazoles possessing liquid crystalline properties were synthesized in two ways. The key stage in both procedures is 1,3-dipolar cycloaddition of nitrile oxides to acrylonitrile.     

The synthesis of annelated 3-cyano-2-pyridones

Annelated tricyclic 3-cyano-2-pyridones were synthesized from cyanoacetamide adducts using a thermal cyclization process which had previously been reported to afford an annelated pyrimidone product.     

Synthesis of substituted 2-amino-3-cyano-7,9-dimethyl-4H-pyrano[2",3":4,5]thieno[2,3-b]pyridines

4,6-Dimethyl-2H-thieno[2,3-b]pyridin-3-one reacts with 2-aryl-1,1-dicyanoethylenes or an aromatic aldehyde/ketone (cyclohexanone and piperidone derivatives) and malononitrile to give substituted 2-amino-3-cyano-7,9-dimethyl-4H-pyrano[2",3":4,5]thieno[2,3-b]pyridines.     

Synthesis and structure of 2-amino- 5-azolyl-3-cyano-4H-pyrans

Previously unknown 5-azolylpyrans were obtained by reactions ofN-acetonyl- andN-phenacylimidazoles, -triazoles, and -tetrazoles with arylmethylenemalononitriles. The structure of 2-amino-3-cyano-6-methyl-5-(5-nitrotetrazol-2-yl)-4-phenyl-4H-pyran was established by X-ray structural analysis.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2050–2055, August, 1996.     

New synthesis of ethyl 6-amino-4-aryl-5-cyano-1,4-dihydropyrano[2,3-c]pyrazole-3-carboxylates

Ethyl 6-amino-4-aryl-5-cyano-1,4-dihydropyrano[2,3-c]pyrazol-3-carboxylates were synthesized by a reaction of diethyloxalacetate sodium salt with aromatic aldehyde, hydrazine hydrate, and malononitrile in the presence of acetic acid.     

Synthesis of 3-amino-4,5-dichloroisothiazole

4,5-Dichloro-1,2-thiazol-3-amine was synthesized starting from accessible 4,5-dichloro-1,2-thiazole-3-carbonyl azide and -3-carboxamide via Curtius and Hofmann rearrangements, respectively. The procedure involving Curtius rearrangement was found to be more advantageous from the preparative viewpoint.