Synthesis and properties of 1-methyl-2-phenyl-5-(2-furyl)- and 1-methyl-2-phenyl-5-(2-thienyl)imidazoles

2-Phenyl-5-(2-furyl)- and 2-phenyl-5-(2-thienyl)imidazoles were synthesized by condensation of 2-furoylmethyl and 2-thenoylmethyl acetates with benzaldehyde under the conditions of Weidenhagen reaction. The products were converted to N-methyl derivatives in the KOH-acetone system. The electrophilic substitution reactions of the products (acylation, bromination, nitration, sulfonation, hydroxymethylation) were studied.     

1-甲基-2-苯基-5-溴1H-苯并咪唑的合成研究

1-甲基-2-苯基-5-溴-1H-苯并咪唑是制备抗癌药物和有机电场致发光器件的中间体。以N-甲基-2-硝基苯胺为原料,经过苯环的溴代、N-苯甲酰化反应得到N-(2-硝基-4-溴苯基)-N-甲基苯甲酰胺;再经硝基还原和分子内脱水闭环反应合成了1-甲基-2-苯基-5-溴-1H-苯并咪唑。化合物结构用1H-NMR、13C-NMR、IR表征,纯度用HPLC确定。     

Nuclear-substituted 1-phenyl-1-methyl-1-silacyclobutane derivatives

Conclusions The synthesis of some nuclear-substituted derivatives of 1-phenyl-1-methyl-1-silacyclobutane by the reaction of 1-methyl-1-chloro-1-silacyclobutane with the appropriate arylmagnesium bromides was described.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1686–1688, July, 1978.     

Sulfur derivatives of 3-methyl-5-phenyl-1,2,4,3-triazaphosphole

The triazaphosphole 1 adds sulfur along with HCl or H₂S to yield, respectively, the dihydrotriazaphosphole thiochloride 4 and sesquisulfide 5 (two diastereomers). In pyridine solution, 1 adds sulfur alone to yield the trimer of a triazaphosphole monosulfide 7 . Its central cyclotriphosphazane trisulfide ring has a trans structure and a boat conformation.     

Synthesis of substituted indolizines from 1-phenacyl-5-methyl-4-phenyl-2-phenacylidene-1,2-dihydropyridine

1-Phenacyl-5-methyl-4-phenyl-2-phenacylidene-1,2-dihydropyridine was obtained, and its cyclization to substituted indolizines was examined.     

Synthesis,halogenation, and nitration of 6-methyl-3-phenyl-2-pyrone derivatives

Simple methods for the synthesis of 3-aryl-6-methyl-2-pyrones and 3-aryl-5-carbalkoxy-6-methyl-2-pyrones by the reaction of ethyl -formylarylacetates with acetone and acetoacetic acid esters, respectively, are proposed. Some electrophilic substitution reactions of 6-methyl-3-phenyl-2-pyrone and 5-carbethoxy-6-methyl-3-phenyl-2-pyrone were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1477–1480, November, 1985.     

Synthesis of 1,4-dihydro-4-methyl-1-phenyl-5H-1,3,4-benzotriazepin-5-ones

The synthesis of 1,4-dihydro-4-methyl-1-phenyl-5H-1,3,4-benzotriazepin-5-one ( 4a ) and its 8-chloro analog ( 4b ) is described. Attempted synthesis of the 2-methyl analog of 4a from 2-(phenylamino)benzoic acid 1-methylhydrazide ( 10 ) and triethyl orthoaeetate led only to the Schiff base intermediate, 2-(phenylamino)benzoic acid 2-(1-ethoxyethylidene)-1-methylhydrazide ( 11 ). Cyclization of 11 was attempted unsuccessfully with a variety of reagents. The intere?ting reaction products from the treatment of 11 with trifluoroacetic acid are described.     

Synthesis of unnatural 1-methyl-2-quinolone derivatives

Unnatural 1-methyl-2-quinolone derivatives were synthesized by regioselective C-C bond formation. When 1-methyl-3,6,8-trinitro-2-quinolone (TNQ) was treated with enamines, nucleophilic addition readily occurred at the 4-position, and succeeding hydrolysis of enamine moiety followed by elimination of nitrous acid furnished 4-acylmethyl-1-methyl-6,8-dinitro-2-quinolones. The same products could be prepared by the reaction of TNQ with ketones in the presence of triethylamine. The present reaction enabled the introduction of various kinds of acylmethyl groups substituted with alkyl, aryl or hetaryl groups.     

Capillary electrochromatography of 1-phenyl-3-methyl-5-pyrazolone derivatives of some mono-and disaccharides

Summary A packing procedure was adopted for capillary electrochromatography (CEC) that produces capillary columns with high separation efficiencies. The columns were fully packed, 50 cm long, with UV detection being performed through the packed section 30 cm from the inlet end. The CEC experiments were run at ambient pressure, with no additional pressure applied to the ends of the column. The stationary phase (octadecyl silica (ODS), 5 μm) promoted a high velocity electroosmotic flow (EOF), enabling rapid and efficient separation of a hydrocarbon test mixture. Some 1-phenyl-3-methyl-5-pyrazolone (PMP) derivatives of mono- and disaccharides were baseline separated, using a 5 mM NaH₂PO₄ in 80% acetonitrile and 20% water (v/v) buffer solution. CEC shows promise for future applications in carbohydrate analysis. Presented at Balaton Symposium on High Performance Separation Methods, Siófok, Hungary, September 1–3, 1999     

Spirobutyrolactone derived from 1-phenyl-3-methyl-2-pyrazolin-5-one

X-ray diffraction and NMR spectral examination have shown that 1-phenyl-3-methyl-2-pyrazolin-5-one reacts with methyl acrylate in methanol to give spiro[(1-phenyl-3-methyl-2-pyrazolin-5-one)-4,5-butyrolactone]. The conformation has been shown to be the same in the crystal and in solution, the pyrazoline ring has been found to be nonplanar, the reasons for the acoplanarity established, stabilizing and destabilizing interactions studied, and the orientation of the phenyl substituent relative to the pyrazolin-5-one ring determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 909–913, July, 1988.     

Interaction of 1-Benzyl-4-benzoyl-5-phenyl-2,3-dihydro-2,3-pyrroledione with Ketene Diethylacetal: Synthesis and Crystal and Molecular Structure of 1-Benzyl-4-benzoyl-3-hydroxy-5-phenyl-5-ethoxycarbonylmethyl-2,5-dihydro-2-pyrrolone

1-Benzyl-4-benzoyl-5-phenyl-2,3-dihydro-2,3-pyrroledione reacts with ketene diethylacetal, forming 1-benzyl-4-benzoyl-3-hydroxy-5-phenyl-5-ethoxycarbonylmethyl-2,5-dihydro-2-pyrrolone, whose crystal and molecular structure was studied by XRD.     

Formylation of 2-phenyl- and 3-phenyl-5-hydroxybenzofuran derivatives

The Vilsmeier formylation of 2-phenyl- and 3-phenyl-5-hydroxybenzofuran derivatives was studied. It is shown that 2-phenyl-5-methoxybenzofuran is formylated in the 4 position, whereas 3-phenyl-5-methoxybenzofuran is formylated in the 2 position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1023–1024, August, 1976.     

Synthesis of pyridin-2(1H)-one derivatives via enamine cyclization

The nucleophilic vinylic substitution reaction of the aliphatic enaminone 3-dimethylamino-2-formyl acrylonitrile 1 with the nucleophiles malononitrile and ethyl cyanoacetate produced the two unusual reaction adducts 3a and 3b in good to moderate yield under milder reaction conditions. Upon reaction with aromatic amines, these adducts yielded enamines 4 and 5, which eventually cyclized in the presence of base to produce the novel pyridin-2(1H)-one derivatives 8 and 9.     

Preparation of 3(5)-phenyl-1-hydroxypyrazole 2-oxide and 4-methyl-3(5)-phenyl-1-hydroxypyrazole 2-oxide

Nitrosation of acrylophenone oxime or of methacrylophenone oxime with n-butyl nitrite in the presence of pyridine and copper(II) sulfate gives the copper complexes of the title compounds. The free 1-hydroxypyrazole 2 -oxides are isolated by treating the copper complexes with dilute sodium hydroxide, filtration, and acidification of the basic filtrates. The title compounds are the first examples of 1-hydroxypyrazole 2 -oxides in which the C3(5) ring position is unsubstituted.     

Convenient synthesis of trifluoromethylated 2-pyrrolidone and 2-pyrrolone derivatives

The reaction of a set of enamines with methyl trifluoropyruvate and its imine was investigated. As a result, a simple procedure for synthesis of trifluoromethylated 2-pyrrolidone and 2-pyrrolone derivatives has been developed.     

Synthesis of some 1-methyl-3-alkoxy-5-arylpyrrolecarboxylic acids and derivatives

By a combination of hydrolysis, decarboxylation, and methylation diethyl 1-methyl-3-hydroxy-5-phenylpyrrole-2,4-dicarboxylate was converted into 1-methyl-3-methoxy-5-phenyl-pyrrole-2,4-dicarboxylic acid (5) and into the isomeric compounds ethyl 1-methyl-2-phenyl-4-methoxypyrrole-3-carboxylate (4a) and ethyl 1-methyl-3-methoxy-5-phenylpyrrole-2-carboxylate (9a). 1-Methyl-2-phenyl-4-methoxypyrrole-3-carboxylic acid was synthesized both by the selective decarboxylation of 5 and by the hydrolysis of 4a. Hydrolysis of 9a, however, did not give the corresponding acid, but rather an oxidation product, 1-methyl-3-methoxy-5-hydroxy-5-phenyl-3-pyrrolin-2-onc (10a). Compound 10a was shown to arise from the air oxidation of the completely decarboxylated product, 1-methyl-2-phenyl-4-methoxypyrrole. Reduction of 9a with lithium aluminum hydride gave 1-methyl-3-methoxy-5-phenylpyrrole-2-methanol, which yielded 10a upon oxidation with silver oxide.     

Synthesis of derivatives of α-phenyldinicotinic acid and 2-phenyl-3,5-bis(5-phenyl-2-oxazolyl)-pyridine

The dichloride, diethylamide, and amide were obtained from -phenyldinicotinic acid. 2-Phenyl-3,5-diamino- and 3,5-dicyanopyridine were synthesized from the amide. 2-Phenyl-3,5-bis(5-phenyl-2-oxazolyl)pyridine and 2-phenyl-3-carboxy-5-(5-phenyl-2-oxazolyl)pyridine were obtained. The luminescence properties of the synthesized compounds were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 405–411, March, 1990.The authors thank A. A. Ustenko and E. N. Smirnova for their assistance in calculation of the spectral data.