Synthesis of 2-methyl-3-nitro-4-phenyl-1,4-dihydroquinoline

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, p. 1696, December, 1989.     

Synthesis of 3-nitro-4-amino- and 3,4-diaminothiocoumarins

Nitration of 4-hydroxythiocoumarin gave 3-nitro-4-hydroxythiocoumarin, which was converted to 3-nitro-4-chlorothiocoumarin by the action of phosphorus oxychloride in dimethylformamide. The corresponding 3-nitro-4-aminothiocoumarins were synthesized by reaction of 3-nitro-4-chlorothiocoumarin with ammonia or amines. The 3-nitro-4-aminothiocoumarins were hydrogenated in alcohol over Raney nickel to give 3,4-diaminothiocoumarins. The-aminovinylcarbonyl form of the 4-substituted 3-aminothiocoumarins was established on the basis of the UV, IR, and PMR spectra.See [1] for our preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 43–47, January, 1978.     

Synthesis of 3-alkoxycarbonylaminomethylcarbonylamino-4-benzoyl-1,2-dihydropyridines and their cyclization to 5-phenyl-1,3,8,9-tetrahydro-2H-pyrido[3,4-e]-1,4-diazepin-2-ones

The regiospecific reaction of 3-benzyloxycarbonylaminomethylcarbonylamino-4-benzoylpyridine (6a) , or 3-t-butoxycarbonylaminomethylcarbonylamino-4-benzoylpyridine (6b) , with either acetyl chloride or ethyl chloroformate, and either n-butylmagnesium chloride or phenylmagnesium bromide afforded the respective 1-acetyl (or ethoxycarbonyl)-2-n-butyl (or phenyl)-3-benzyloxy (or t-butoxy) carbonylaminomethylcarbonylami-no-4-benzoyl-1,2-dihydropyridines 7 in 60-75% yield. Reaction of 1-acetyl (or ethoxycarbonyl)-2-n-butyl (or phenyl)-3-t-butoxycarbonylaminomethylcarbonyl-4-benzoyl-1,2-dihydropyridines 7b, 7f, 7d, 7h with trifluoroacetic acid gave the corresponding 5-phenyl-8-acetyl (or ethoxycarbonyl)-9-n-butyl (or phenyl)-1,3,8,9-tetrahydro-2H-pyrido[3,4-e]-1,4-diazepin-2-ones 8a, 8b, 8c, 8d respectively in 45–63% yield. N¹-Methylation of 5-phenyl-8-acetyl-9-n-butyl (or phenyl)-1,3,8,9-tetrahydro-2H-pyrido[3,4-e]-1,4-diazepin-2-ones 8a, 8b using sodium hydride and iodomethane yielded the corresponding N¹-methyl derivatives 9a (48%) and 9b (54%). Oxidation of 5,9-diphenyl-8-ethoxycarbonyl-1,3,8,9-tetrahydro-2H-pyrido[3,4-e]-1,4-diazepin-2-one (8d) using p-chloranil afforded 1,3-dihydro-5,9-diphenyl-2H-pyrido[3,4-e]-1,4-diazepin-2-one (10) . 5-Phenyl-8-acetyl-9-n-butyl-1,3,8,9-tetrahydro-2H-pyrido[3,4-e]-1,4-diazepin-2-one (8a) and the corresponding 8-ethoxycarbonyl analog 8c exhibited weak anticonvulsant activity indicating that 8a and 8c may be acting at the same site as the 7-halo-1,4-benzodiazepin-2-one class of compounds.     

5-Endo-dig electrophilic cyclization of 1,4-disubstituted but-3-yn-1-ones: regiocontrolled synthesis of 2,5-disubstituted 3-bromo- and 3-iodofurans

[reaction: see text] 5-Endo-dig electrophilic cyclization of 1,4-diaryl but-3-yn-1-ones with N-bromosuccinimide or N-iodosuccinimide/acetone and iodine monochloride/CH(2)Cl(2), at room temperature, in the absence of base, provides 3-halo-2,5-diarylfurans with excellent regiocontrol and high yields (81-94%).     

Synthesis and properties of azoles and their derivatives. 10. Synthesis of 3,5-diaryl-4-nitroisoxazoles

A method was proposed for the synthesis of 3,5-diaryl-4-nitroisoxazoles entailing the brominatian of potassium salts of the corresponding 3,5-diaryl-²-isoxazolinyl-4-nitronic acids. The method may be used for the conversions of both the trans and cis isomers of 3,5-disubstituted 4-nitro-²-isoxazolines.Communication 9, See [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 189–192, February, 1985.     

Absence of the Nitrone Form among the Refined Crystal Structures of 1-Methoxy- and 1-(2-Chloro-ethyl)oxy-2-hydroximino-3-methyl-4-nitro-3-phospholene-1-oxides

Crystal structure refinement has been performed by XRD for 1-methoxy- and 1-(2-chloroethyl)oxy-2-hydroximino-3-methyl-4-nitro-3-phospholene-1-oxides (I) C₆H₉N₂O₅P, Z=8, space group P2₁/c, and (II) C₇H₁₀ClN₂O₅P, Z=4, space group P2₁/c. Disordering of independent molecules I and I' in the crystal structure of I and of molecule II in the crystal structure of II has been found. Full-matrix least-squares refinement of I and II was performed anisotropically (isotropically for H) to R=0.052 (I) and 0.034 (II) for all 4377 (I) and 2533 (II) independent reflections (CAD-4 automatic diffractometer, MoK). The authors of the first XRD analysis of crystals I and II made the wrong conclusion that compounds I and II exist in crystal in NH-nitrone form; i.e., that they contain an ON(H)=C nitrone isomer group instead of an H–O–N=C oxime group. As shown in this study, compounds I and II exist in ordinary oxime form. The authors of the first XRD analysis failed to notice the disordering of molecules I, I', and II, and they erroneously took the second, low-occupied oxygen sites of the disordered oxime groups for the H atoms at N atoms.     

Synthesis of phenyl-substituted 2H-3,4-dihydro-3-aminomethyl-1,4-benzoxazines. Intermediates for 1H-2,3,3a,4-tetrahydroimidazo[5,1-c][1,4]benzoxazin-1-one derivatives. Part II

The synthesis of 2H-3, 4-dihydro-3-aminomethyl-1, 4-benzoxazines substituted by one phenyl group in the 2, 3 or α-position is reported. The two diastereoisomers of the 2-phenyl-derivative were independently synthesized from ethyl trans-3-phenylglycidate by a stereospecific route. A previous attempt at the synthesis of these same compounds gave rise to an unexpected aliphatic-aromatic ketone rearrangement.     

Synthesis of 4,6-disubstituted 2-methylpyridines and their 3-carboxamides

A new one-pot synthesis of title compounds by the reactions of α,β-unsaturated carbonyl compounds with β-aminocrotononitrile in the presence of sodium hydroxide is described.     

Synthesis and investigation of some 1,4-disubstituted 2-pyrrolidinones

A series of condensation products of 1-aryl-4-hydrazinecarbonyl-2-pyrrolidinones with acetone, 2,4-pentanedione, and aromatic aldehydes was obtained and identified by the combination of IR, mass and ¹H, ¹³C NMR spectroscopy. The results of their structural studies by NMR spectroscopy are provided. It was ascertained that the presence of the NH group determines the existence of the mixtures of the Z/E-isomers of compounds under study. The availability of Z-isomer as a sterically favorable one was also verified by computer molecular modeling. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1336–1345, September, 2006.     

Interaction of Hydroxylamine with Esters of 2-Oxobutenoic Acids. Synthesis of 1-Hydroxy-3-hydroximino-2-pyrrolidinones

New 3-hydroximino-1-hydroxy-2-pyrrolidinones have been synthesized by the interaction of NH₂OH and NH₂OBn with the methyl esters of 2-oxo-3-butenoic acid derivatives. Some intermediate compounds have been isolated and identified and the reaction mechanism is discussed.     

Reactions of 3-nitro-2-trihalomethyl-2H-chromenes with C-nucleophiles. Synthesis of 3-nitro-4-(pyrazol-4-yl)-2-trihalomethylchromanes

The nucleophilic addition of acetylacetone and ethyl acetoacetate at the double bond of 3-nitro-2-trihalomethyl-2H-chromenes in the presence of NaH affords 2,3,4-trisubstituted chromanes containing the β-dicarbonyl fragment at position 4. The trans-trans configuration and the enol structure of the reaction products were confirmed by ¹H NMR spectroscopy and X-ray diffraction. Treatment of these compounds with hydrazine gives the corresponding 3-nitro-4-(pyrazol-4-yl)-2-trihalomethylchromanes. The reactions of 3-nitro-2-trihalomethyl-2H-chromenes with nitromethane and nitroethane in the presence of K₂CO₃ produce 1,3-dinitro derivatives of the chromane series. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1945–1955, November, 2006.     

Synthesis of 2-amino-5-nitro-4H-pyran-3-carbonitriles

Reaction of 2-carbomethoxy-ω-nitroacetophenone with arylmethylenemalononitriles gives the previously unknown 2-amino-4-aryl-5-nitro-6-(2-carbomethoxyphenyl)-4H-pyran-3-carbonitriles. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. E-mail: muskat@cacr.ioc.ac.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1661–1663, December, 1998.     

Reactions of 2,4-disubstituted 5-nitro-1,2,3-triazole 1-oxides. 2. Oxidation of 2-substituted 4-amino(alkylamino)-5-nitro-1,2,3-triazole 1-oxides

The oxidation of substituted aminonitrotriazole oxides to the corresponding dinitro derivatives of triazole and azotriazole oxides has been studied. Communication 1, see ref. [1]. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow, Russia; e-mail: cheminst@mail.psu.ru. Institute of Chemical Physics at Chernogolovka, Russian Academy of Sciences, 124432 Chernogolovka, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1356–1362, October, 1999.     

Synthesis of chalcogeno lactones. II. 3, 4-dihydro-1 H-2-benzothiin-3-one, 3,4-dihydro-1H-2-benzoselenin-3-one and 3,4-dihydro-1H-2-benzotellurin-3-one

The synthesis of 3, 4-dihydro-1H-benzothiin-3-one and its selenium and tellurium analogs is reported from o-bromomethylphenylacetyl chloride and sodium hydrogen chalcogenates, via phase-transfer catalysis.     

Synthesis of 3-methyl-4-cyano-3-butenoic acid amides and their cyclization into 6-amino-2-pyridones

Two groups of amides, derivatives of 3-methyl-4-cyano- and 3-methyl-4-cyano-4-carbethoxy-3 acids were obtained from acetoacetamides in the form of mixtures of Z, E-isomers and the pure E-isomers were isolated. It was shown that amides from the first group are cyclized by bases into the corresponding 6-amino-4-methyl-2-pyridones and amides from the second group are cyclized into 6-hydroxy-5-cyano-4-methyl-2-pyridones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1636–1640, December 1992.     

Construction of Highly Substituted Nitroaromatic Systems by Cyclocondensation. Part I. Synthesis of 4-nitro-3-oxobutyrate

Methyl 4-nitro-3-oxobutyrate ( 1 ) is prepared by substitution of 4-bromo- and 4-iodo-3-oxobutyrate enol ether or enol acetate derivatives with nitrite and deprotection of the keto function (Schemes 2 and 3). A much more convenient access to 1 is, however, the nitration of acetoacetate dianion with alkyl nitrates (Scheme 4). Compound 1 is stable and storable, and can be handled safely. Its use in cyclocondensations is established by the reaction with acetylacetone (Scheme 5), affording 4,6-dimethyl-3-nitrosalicylate 48 in 70% yield. The halogen-substitution method for the synthesis of 1 gives also access to the crystalline (E)-enol ether 18 of 1 , as well as to its dimethyl acetal 25 , (Z)-enol acetate 32 , and (E)-enol acetate 33 . The 3-substituted 4-bromobutenoates 15, 16 and 26 have been prepared from 4-bromo-3-oxobutyrate 12 , a useful alternative to existing methods applying N-bromo-succinimide.