Substituted 2-methyl- and 2-methyleneindolines. 3. Nitroamino-5,6-disubstituted 2-methyl- and 2-methyleneindolines

A method is developed for the synthesis of 5,6-disubstituted nitroamino- and nitromethylamino-2-methyl- and-2-methyleneindolines. These are starting compounds for the synthesis of 2-methyleneindolines condensed with some heterocycle.See [1] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1495–1499, November, 1990.     

Substituted 2-methyl-and 2-methyleneindolines 4. Hetaryl-condensed 2-methyl- and 2-methyleneindolines with a linear structure

Methods have been developed for the synthesis from amino-substituted indolines of first linear trinuclear hetaryl-condensed2-methyleneindolines having quinolone, quinoline, quinoxaline, and benzmidazole fragments. The structure of the obtained compounds was confirmed by ¹H and ¹³C NMR spectra.For communication 3, see [1]Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1331–1335, October, 1992.     

Substituted 2-methyl- and 2-methyleneindolines. 6. Adducts of dialkylphosphites with 1,3,3-trimethyl-2-methyleneindoline. Reagents for synthesizing 5-substituted 2-methyl- and 2-methyleneindolines

The readily formed addition products of dialkylphosphites and 1,3,3-trimethyl-2-methyleneindoline have been used to synthesize 1,2,3,3-tetramethyl-3H-indolium salts and their derivatives substituted in the benzene ring. In most cases the protecting phosphorus group can be readily removed by adding mineral acids.For Communication 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1049–1054, August, 1993.     

Nitro- and amino-substituted 10,10-dimethyl-10-sila-2-azaanthrones

Under conditions of the Mencke reaction, 10,10-dimethyl-9,10-dihydro-10-sila-2-azaanthracene is nitrated on the benzene fragment of the molecule, but the corresponding ketone is nitrated on the pyridine fragment. Dihydrosilaazaanthrone is nitrated by nitrating mixture in positions 5, 7, and 8 of the benzene fragment of the molecule. The nitro-substituted dihydrosilazaanthrones have been reduced to the corresponding amino derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1528–1531, November, 1985.     

5-Benzopyridyl-substituted 2-methyl- and 2-methyleneindolines

A method of synthesis of 5-(isoquinol-l-yl)- and 5-(quinol-2-yl)-1,3,3-trimethyl-2-methyleneindolines has been developed consisting of hetarylation of 1,2,3,3-tetra-methylindoline with isoquinoline and quinoline in the presence of benzoyl chloride, followed by oxidation and aromatization of N-benzoyl-1,2-dihydrobenzopyridine derivatives of 1,2,3,3-tetramethylindoline formed at the first stage to 5-benzopyridyl-substituted 2-methylene-indolines.For a preliminary communication on this subject, see [15].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1367–1372, October, 1989.     

5-Substituted 2-methyl- and 2-methyleneindolines

A method for the synthesis of 5-substituted 1,3,3-trimethyl-2-methyleneindolines has been developed, in which the substituents are introduced into the benzene ring of 1,2,3,3-tetramethylindolines, followed by oxidation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1474–1477, November, 1986.     

Substituted 2-methyl- and 2-methylenindolines

Methods were developed to convert 1,2,3,3-tetramethyl-6-hydroxyindoline into coumarin dyes, in which the amino group is in the indoline system. The structure of the products was indicated by ¹H and ¹³C NMR spectroscopy.Communication 4, see ref. [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1614–1616, December 1992.     

Synthesis and Stereochemistry of Substituted 1,3-Dioxa-2-silacyclohexanes: VII. Synthesis and Stereochemistry of Substituted 2-Vinyl-2-methyl-1,3-dioxa-2-silacyclohexanes

The stereochemistry of substituted 2-vinyl-2-methyl-1,3-dioxa-2-silacyclohexanes was studied by ^1Hand ^13C NMR spectroscopy. The configurational and conformational assignment of a mixture of 2-vinyl-2,4-dimethyl-1,3-dioxa-2-silacyclohexane diastereomers with various ratios of the cis and trans forms was made. The molecules of both conformers occur chiefly in the chair conformartion with equatorial location of the methyl group at the C⁴ atom. The experimental data were confirmed by AM1 and MM+ optimization of the molecular geometry.     

Nitropyridines. 2. Hantzsch Synthesis of Nitro- and Dinitropyridines

The interaction of α, β-unsaturated nitro ketones and various enamines leads to the synthesis of 5-nitro-1,4-dihydropyridines containing acetyl, amide, benzoyl, ester, and cyano groups in position 3, and also unsymmetrical 3,5-dinitro-1,4-dihydropyridines. Aromatization of the nitrodihydropyridines was carried out with sodium nitrite in acetic acid. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 858–863, June, 2005.     

5-Hetaryl-substituted 2-methyleneindolines and polymethine dyes based on them

2-Methyleneindolines containing benzazole residues at the 5-position were synthesized and polymethine dyes were obtained from them. The bathochromic shifts induced by the introduction of heterocyclic residues into indocyanines exceed the similar shifts induced by the same heterocycles in thio and quinocyanines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1050–1054, August, 1990.     

INDO Calculation of Spin Densities in Radical Cations of a Series of Substituted Nitro- and m-Dinitrobenzenes

The spin densities in radical cations of 22 substituted nitro- and m-dinitrobenzenes were calculated by the INDO method. For radical anions of substituted nitrobenzenes, a good linear correlation was obtained between the spin densities s_Ns_N and experimental hyperfine coupling constants with the nitrogen atoms of the NO₂ groups (a ^N): a ^N = K _N s _N s _N, where K _N = 428.58 (R ² = 0.96). For radical anions of substi- tuted m-dinitrobenzenes, no satisfactory agreement between the calculated and experimental a ^N constants was attained.     

Substituted pyridines 5-methyl-4-benzyl-2-styryl(phenylethynyl)pyridines

5-Methyl-4-benzyl-2-styrylpyridine (II), its p-dimethylaminostyryl analog IV, and 5-methyl-4-benzyl-2-(1,3-dioxo-2-hydrindenyl)pyridine (V) have been prepared. II has been converted into 5-methyl-4-benzyl-2-phenylethynylpyridine (VII), 5-methyl-4-benzylpyridine-2-carboxylic acid (VIII), and 3-styryl-6, 7-benzoisoquinoline (X).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1228–1231, September, 1970.     

Tetracyclische 1,2,4-Benzothiadiazine, 2. Mitt.: Nitro- und Cl-Derivate

Zusammenfassung Es wurden neue Derivate des 11-Oxo-11H-isoindolo[1,2-c] (1,2,4)-benzothiadiazin-5,5-dioxids (I) dargestellt, über dessen Synthese in unserer 1. Mitt.¹ berichtet worden war. Ausgehend von o-Aminobenzolsulfonamid und substituierten Phthalsäuren wurden das 8-Cl- und das 9-Nitroderivat des Ringsystems erhalten. Weiters wurde bei der NaBH₄-Hydrierung neben dem Hauptprodukt II eine bisher unbekannte Verbindung III erhalten, bei der die CO-Gruppe des Ringsystems zur CHOH-Gruppe reduziert wurde.

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New derivatives of 11-Oxo-11H-isoindolo[1,2-c] (1,2,4)-benzothiadiazine-5,5-dioxide (I), the synthesis of which had been reported in the preceding paper¹, have been prepared. Starting from orthanilamide and subsituted phthalic acids, the 8-chloro- and 9-nitro-derivatives of the ring system were obtained. Further, NaBH₄-hydrogenation yielded, in addition to the main product II, a so far unknown byproduct III, the CO-group of which was reduced to the CHOH-group.

     

2-Substituted imidazoles. 3. Metallation of 1-methyl-2-phenyl- and 1-methyl-2-(furyl-2)imidazoles

1-Methyl-2-phenylimidazole reacts with butyllithium to give 5-lithium substituted products. On the other hand, 1-methyl-2-(furyl-2)imidazole is metallated under the same conditions exclusively on the furan ring and primarily in the 3 position. The introduction of triethylamine into the reaction mixture, or replacement of butyllithium by lithium 2,2,6,6-tetramethylpiperidide leads to the formation of a lithium derivative substituted at the 5-position of the furan ring exclusively.For Communication 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 61–66, January, 1992.     

Nitroimidazoles. V . Synthesis of 1-methyl-2-(2-methyl-4-thiazolyl)nitroimidazoles

Reaction of readily available 2-methyl-4-formylthiazole ( 1 ) with glyoxal and ammonia gave 2-(2-methyl-4-thiazolyl)imidazole ( 2 ). Nitration of 2 with a mixture of nitric acid-sulfuric acid at 100° yielded 2-(2-methyl-4-thiazolyl)-4,5-dinitroimidazole ( 3 ) as the sole reaction product, while nitration at 65° afforded 2-(2-methyl-4-thiazolyl)-4-(or 5)-nitroimidazole ( 4 ). N-Methylation of compound 4 in the presence of base gave 1-methyl-2-(2-methyl-4-thiazolyl)4-nitroimidazole ( 6 ), whereas N-methylation with diazomethane afforded 1-methyl-2-(2-methyl-4-thiazolyl)-5-nitroimidazole ( 5 ). N-Methylation of compound 3 yielded 1-methyl-2-(2-methyl-4-thiazolyl)-3,5-dinitroimidazole ( 7 ) in high yield.     

The i.r. spectra of 3-methyl-2-butenenitrile and 3-methyl-3-butenenitrile

A commercial sample of supposedly 3-methyl-3-butenenitrile was separated by gas chromatography into two components. Analysis of the i.r. and NMR spectra of these two components showed that the original mixture contained 25% 3-methyl-3-butenenitrile and 75% 3-methyl-2-butenenitrile, and that an i.r. spectrum recently reported in this journal [1] for 3-methyl-3-butenenitrile was actually that of 3-methyl-2-butenenitrile. Thus, the spectral data reported for 3-methyl-3-butenenitrile [1] and the resulting conclusions regarding the nature of the conformational equilibrium in this molecule should be disregarded.     

Synthesis and structure of azido-and amino-substituted dibenzoxazepinones

1,3-Dinitro[b, f][1,4]dibenzoxazepin-11(10H)-one enters nucleophilic substitution reactions with N-nucleophiles, azide ion preferably replacing the nitro group in position 3, whereas amines the one in position 1. Structures of the substitution products were confirmed by X-ray diffraction and ¹H NMR NOE spectroscopy. The selectivity observed in the reaction with amines was supposed to be caused by the stabilization of the intermediate σ-complex with the NH…O intramolecular hydrogen bond. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2018–2022, October, 2007.     

Polyethers. I. Polymerization of 2-methyl-2-butene oxide

2-Methyl-2-butene oxide (2,3-epoxy-2-methylbutane) was polymerized with modified alkylaluminum initiators a t low temperatures to a high-melting, crystalline, film-forming polymer. High yields and comparatively high molecular weights were obtained with Al(i-Bu)₃?xH₂O initiators in inert diluents. When such initiators were modified with acetylacetone they became ineffective. Ammonia could be substituted for water in formulating an active initiator. Attempts to prepare an active initiator in the presence of the monomer were unsuccessful indicsting competition with the water for Al(i-Bu)₃. Thermal decomposition of the polymer produced methyl isopropyl ketone with some pivaldehyde.