Acetals of lactams and acid amides. 35. Synthesis of condensed two- and three-ring pyridine systems on the basis of enamino amides

The synthesis of 2,3,5,6-tetrahydropyrrolo[3,2-c]pyrid-6-one was accomplished by rearrangement of 8H,1-cyano-8-dimethylaminomethylene-2,5,6,7-tetrahydropyrrolo[1, 2-c]pyrimidine. Pyrrolo[3,2-c]pyrimidine, 1,6-naphthyridine, and pyrimido[4,3-b]-azepine derivatives were synthesized on the basis of enamino dinitriles. The hydrolysis of 8H,1-cyano-8-dimethylaminomethylene-2,5,6,7-tetrahydropyrrolo[1,2-c]-pyrimidine in 50% CH₃COOH leads to a pyrrolo[1,2-c]pyrido[4,3-d]pyrimidine derivative. A similar dipyrido[4,3-d-1,2-c]pyrimidine derivative was obtained from 1-cyano-9-dimethylaminomethylene-2,5,6,7,8,9-hexahydropyrido[1,2-c]pyrimidine under these conditions, and 3,4-dioxo-3,4,7,8,9,10-hexahydropyrido[1,2-c]pyrano[4,3-d]-pyrimidine was synthesized bytreatment with a 1 N solution of HCl.See [1] for Communication 34.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 518–522, April, 1982.     

Acetals of lactams and acid amides. 48. Reaction of enamino diketones with amide crystals. Synthesis of derivatives of coumarin and carbostyril

It was established that the reaction of derivatives of 2-aminomethylenecyclohexane-1,3-dione with N,N-dimethyl-diethylacetal gives dienediamines, heating of which in aqueous hydrochloric acid leads, depending on the structure, to derivatives of carbostyril and/or coumarin. This unusual reaction is based on initial attack at the position of the enamino diketone by the ketone acetal, which exists in equilibrium with the starting amide acetal.See [1] for Communication 47.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1470–1476, November, 1987.     

Acetals of lactams and acid amides

It is shown that acetals of acid amides and lactams undergo condensation at the -CH₃ (or CH₂) groups of enamino esters to give dienediamines, the cyclization of which led to benzene, pyridine, indole, quinoline, and benzazepine derivatives.See [1] for communication XXI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1518–1522, November, 1977.     

Acetals of lactams and acid amides. 47. Investigation of the behavior of substituted 6-(Β-dimethylamino) vinyl-4-pyrimidinones in acidic media. Synthesis of 3-cyano-4-anilino-5-formyl-2-pyridone and 3-chloro-4-cyanobenzo[b] [1,6]-naphthyridine

The hydrolysis of 1-substituted 5-cyano-6-(-dimethylamino)vinyl-4-pyrimidinones in acidic media was studied. It was shown that the 1-benzyl derivative is converted to a mixture of -cyano--benzylamino-crotonamide and 3-cyano- and 3-carbamido-4-benzyl-amino-2-pyridones. The principal product in the hydrolysis of the 1-phenyl derivative is 3-cyano-4-anilino-5-formyl-2-pyridone. Cyclization of the latter by heating in phosphorus oxychloride leads to 3-chloro-4-cyanobenzo[b] [1, 6]naphthyr idine.See [1] for Communication 46.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1118–1123, August, 1986.     

Acetals of lactams and acid amides

The reaction of -cyano--dimethylaminocrotonic acid amide with acetals of dimethyl acetamide and N-methylbutyro-, -valero-, and -caprolactams gave enaminoacrylamidines, cyclization of which gave 3-cyano-6-dimethylamino-2-pyridone and the corresponding pyrrolo-,pyrido-, and azepino[2,3-b]pyridine derivatives.See [1] for communication XVIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1106–1109, August, 1977.     

Acetals of lactams and acid amides

The reaction of dimethylformamide diethylacetal with -cyano--dimethylaminoacrylamide proceeds at the NH₂ amide group to give the corresponding acylformamidine, from which 3-cyano-4-dimethylamino-2-pyridone was obtained by thermal cyclization. Pyrrolo-, pyrido-, and azepino-[3,2-c]pyridine derivatives were similarly synthesized from 1-methyl-2-(2-cyano-2-carbamido)-methylenepyrrolidine and the homologous six- and seven-membered enaminoamides.See [1] for communication XVII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1509–1512, November, 1976.     

Bromination of δ-keto amides

It is demonstrated that 3,5-dibromo-3,4-dihydropyridones are formed in the bromination of derivatives of -keto amides. The course of the bromination was investigated in the case of N-substituted and N-unsubstituted -keto amides. Dibromo-3,4-dihydropyridones were converted to the corresponding monobromopyridones. The stabilities of the compounds obtained were studied by subjecting them to thermal analysis. The structures of the compounds obtained were confirmed by their PMR, IR, and UV spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 783–788, June, 1981.     

Acetals of lactams and acid amides. 49. Reaction of N-methyl-2-pyrrolidone and N-methyl-2-piperidone acetals with enamino diketones

It was established that acetals of lactams react with enamino diketones to give cyclic dienediamines. The dienediamines obtained in the reaction of N-methyl-2-pyrrolidone diethylacetal with 2-aminomethylenedimedone and 2-N,N-dimethyl-aminomethylenedimedone are converted to 3-(-methylamino)ethyl-6,6-dimethyl-5,6, 7,8-tetrahydro-5-coumarinone hydrochloride when they are heated in dilute hydrochloric acid.See [1] for Communication 48.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1477–1482, November, 1987.     

Acetals of lactams and acid amides. 41. Enamino amides in the synthesis of pyrimidine derivatives

The reaction of -cyano--dimethylaminomethyleneacrylamide with arylamines was used to synthesize -cyano--arylaminoacrylamides, which react readily with dimethylformamide diethylacetal to give the corresponding N-dimethylaminomethylene derivatives. The latter undergo cyclization to 1-aryl-5-cyano-4-pyrimidinones when they are heated in dimethylformamide or acetic anhydride and to pyrimido-[5,4-c]quinolone derivatives when they are heated in glacial acetic acid.See [1] for communication 40.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 538–542, April, 1984.     

Synthesis and rotatory dispersion of cisoid bicyclic enamino ketones

Optically active cisoid, bicyclic, enamino ketones — N-(-phenylethyl)-4-keto-^9,10-octa-hydroquinoline and N-(-phenylethyl)-4-keto-^8,9-hexahydropyridine — were synthesized by the condensation of ethyl -[N-(-phenylethyl)amino]propionate with cyclohexanone and cyclopentanone, while ethyl -(N-benzylamino)propionate and cyclohexanone gave N-benzyl-4-keto-^9,10-octahydroquinoline. A study of the rotatory dispersion of the compounds obtained demonstrated that a strong positive Cotton effect at 330–350 nm, which is associated with the presence of a cis-enamino ketone chromophore, is characteristic for them.Communication XXVIII of the series Stereochemical Investigations. See [1] for communication XXVII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 541–545, April, 1972.     

Conformational study of chiral cisoid enamino ketones

A study of a number of chiral cisoid cyclic enamino ketones by the circular dichroism method showed that they contain an inner disymmetric chromophore. The presence of homoconjugation of the phenyl and enamino ketone chromophores as a result of the drawing together of their orbitals in space was also established.Communication XXXVI from the series Stereochemical Studies; see [1] for communication XXXVTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 511–515, April, 1976.     

Conformational study of chiral heterocyclic enamino ketones

An assumption regarding the existence of a homoconjugation effect involving enaminoketo and phenyl groups as a result of the drawing together in space of their orbitals was made on the basis of circular dichroism (CD) data and an examination of the preferred conformations of two-ring enamino ketones with -phenylethyl and -benzylethyl substituents. A study of enamino ketones with a chiral alkyl substituent attached to the nitrogen atom made it possible to confirm this assumption.Communication XLIX from the series Stereochemical Studies. See [1] for communication XLVIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1230–1233, September, 1978.     

Acetals of lactams and acid amides. 51. Cyclization of α-cyano-Β-phenylamino-N-dimethylaminomethyleneacrylamide to pyrimido[5,4-c]quinol-4-one

Cyclization of -cyano--phenylamino-N-dimethylaminomethyleneacrylamide to pyrimido[5,4-c]quinol-4-one proceeds via the intermediate formation of 1-phenyl-5-cyano-1,4-dihydropyrimidin-4-one and -cyano--phenyl-amino-N-formylacrylamide.For Communication 50, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 88–90, January, 1988.     

Simultaneous capillary GC-MS determination of triazines and amides in water

Summary A simultaneous capillary Gas Chromatographic-Mass Spectrometric (GC-MS) method is described for the determination of thirteen pesticides belonging to the triazine and amide families in water. The sample is extracted in liquid-liquid mode (dichloromethane) and then the determination of the residues is carried out by capillary gas chromatography with mass spectrometric detection in the Selected-Ion Monitoring mode (SIM). The average recoveries of spiked compounds are in the 78.4–135.4% range between the relative low level (0.100 g L^–1) and the relative high level (10.0 g L^–1). The limits of detection (LOD) are in the 0.009–0.128 g L^–1 range.     

Research on benzimidazole derivatives

The acylation of 2-amino derivatives of benzimidazole and pyridine with-aryl-, -unsaturated carboxylic acid chlorides gave the corresponding amides, which were converted to 2-oxo derivatives of pyrimido [1,2-a]benzimidazole and pyridine by the action of bases.See [1] for communication XLI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 90–93, January, 1978.     

Acetals of lactams and acid amides. 53. Eamidines in the synthesis of pyridine and pyrimidine

The reaction of -cyano--aminocrotonic ester with DMFA diethylacetal gives 1-ethoxycarbonyl-1-cyano-2-(N-dimethylaminomethylene)-amino-4-dimethylaminobutadiene, the reaction of which with ammonium acetate and amines leads to 4-methylenepyrimidine derivatives. Condensation of -cyano--aminocrotonic ester with dimethylacetamide dieethylacetal gave 2-(ethoxycarbonylcyano)methylene-4-dimethylamino-6-methylpyridine. It was found that in an alkaline medium, 1-benzyl-4-(ethoxycarbonylcyano) methylenepyrimidine recyclizes into 1-benzyl-3-cyano-4-amino-2-pyridone.For Communication 52, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1109–1114, August, 1988.     

Glycosides of marine invertebrates. XIII. New holothurinogenins of holothurin B1 fromHolothuria floridana

We have isolated for the first time the native aglycone of a triterpene glycoside of the holoturin series — holothurin B₁ — and have established its structure as holost-9-ene-3,12,17-triol. The structures of two new holostane derivatives have been established — holosta-8,11-diene-3,17-diol and 3,17-dihydroxyholost-9-en-12-one. A scheme of transformation of the native genin of holothurin B₁ under the conditions of the acid splitting of the glycoside has been put forward.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 323–327, May–June, 1982.     

Phytoecdysteroids ofSilene nutans. III. Nusilsterone

A new ecdysteroid — nusilsterone — has been insolated from the whole plantSilene nutans L. It has been shown that it is 1,2,3,14,20R,22R,24,25-octahydroxy-5--cholest-7-en-6-one.Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii. No. 4, pp. 522–525, July–August, 1985.     

Reactions of α-HALO-α,β-unsaturated aldehydes with second amines —novel method for the preparation of N-disubstituted α-aminocrotonaldehydes

Conclusions -Halocrotonaldehydes react with secondary amines to give N-disubstituted -aminocrotonaldehyde derivatives, N,N-tetrasubstituted 1,2-diaminoethenes, and N-formyl derivatives of the amine starting materials.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1801–1805, August, 1987.     

Steroids of the spirostan and furostan series from plants of the genus Allium. XXV. Structure of anzurogenin B from Allium suvorovii and Allium Stipitatum

A new genin of the spirostan series — anzurogenin B having the structure of 2,5-epoxy-(25R)-spirostan-3,6-diol — has been isolated form the collective fruit of the cocultivatedAllium suvorovii Rgl. andAllium stipitatum Rgl. (family Liliaceae).Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 218–221, March–April, 1988.