Synthesis of 3-acetamidoindole derivatives

2-Carbethoxy-3-phenylazoindoles, which are reduced to 2-carbethoxy-3-acetamidoindoles, were obtained by diazo coupling of 2-carbethoxyindoles with benzene diazonium chloride. Some transformations of these compounds were studied.     

Nitro derivatives of 3-hydroxyquinoline

The nitration of 3-hydroxyquinoline with concentrated nitric acid in sulfuric acid at ?30 to +30°C gives 5-nitro-3-hydroxyquinoline (85–92%) and 7-nitro-3-hydroxyquinoline (7–12%). 4-Nitro-3-hydroxyquinoline is formed in 70% yield by nitration in acetic acid. 4,5-Dinitro-3-hydroxyquinoline is formed by further nitration of 4- and 5-nitro-3-hydroxyquinolines.     

Amide derivatives of 3-aminopropylsilatrane

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Synthesis of 3-ketothiophane derivatives

Conclusions 3-Keto-5-alkylthiophane-4-carboxylic acid esters were synthesized by acylation of Meldrum acid with S acetylthioglycolic acid chloride, followed by alcoholysis of 2,2-dimethyl-4,6-dioxo-5-acetylthiomethyl-1,3-dioxane to -(acetylthio)acetoacetic acid esters. These were treated by aldehydes and the crotonic condensation products were cyclized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2042–2045, September, 1986.     

Alkylation of 3-aminoisocarbostyryl derivatives

The alkylation of derivatives of 3-aminoisoquinolin-1(2H)-one in the presence of NaH may proceed in three directions: 1) at the carbonyl group oxygen atom, 2) at the nitrogen atom N-2, and 3) at the 3-amino group. The reaction of equivalent amounts of the reagents gives predominantly products of substitution at the 3-amino group. Repeated alkylation proceeds at the lactam fragment to give a mixture of O-alkyl and N-alkyl derivatives. Acylation of 3-dialkylamino- and 3-alkylanilinoisoquinolin- 1(2H)-ones in the presence of NaH gave derivatives of 3-amino-1-isoquinolinyl 4-ethoxybenzoate.     

The alkylation of 3H-phenoxazin-3-one derivatives

2-Alkyl-, 4-alkyl-, and 2,4-dialkyl-3H-phenoxazin-3-ones were prepared by reacting 3H-phenoxazin-3-one with alkyl radicals in aqueous acetonitrile at 70–75°. The alkyl radicals were generated from the silver catalysed oxidative decarboxylation of acids with peroxydisulphate.     

Synthesis of derivatives of 3-amino- and 3-aminomethylquinuclidine

Various methods of preparing 3-aminoquinuclidine from quinuclid-3-one oxime and hydrazone are developed. Quinuclidine derivatives with a substituted amino group at position 3 are synthesized.     

New synthesis of 3-fluoropyridine derivatives

The reaction of 2,2-bis(dimethylamino)-3,3-difluoro-1-methylcyclobutane-carbonitrile with alkyl lithiums leads to the formation of 6-alkyl-2-(dimethylamino)-3-fluoro-5-methylpyridines in moderate to good yields.     

Some pyrazolid-3-one derivatives

In order to study their photographic properties, a number of 3-amino-1-(p-aminophenyl)-2-pyrazolines have been synthesized from the corresponding amines.For part II, see [4].     

3-疏基香豆素及其衍生物的研究

研究了3-疏基香豆素(8)、3,3'-二硫代双香豆素的合成及8与一系列Michael受体的反应.按受体结构不同,除都能发生分子间的加成反应外,有些还可进一步发生第二次分子内的加成反应,关环后得到一系列四氢噻吩并[2,3-C][1]苯并吡喃-4(H)-酮的衍生物.对这些化合物的立体化学及结构进行了鉴定.8分别和烯丙基溴、肉桂基溴缩合,前者在N,N-二甲苯胺内发生正常的Claisen重排,得到1,2-二氢-2-甲基噻吩并[2,3-C][1]苯并吡喃-4-(H)-酮及1,2,3,5-四氢硫代吡喃并[2,3-C][1]苯并吡喃-5-酮,但后者的反应产物是3-(ρ-N,N-二甲氨基)苄硫基香豆素.     

3-Thiolcoumarin and its derivatives

3-Thiolcoumarin (8) and 3,3′-dithio-biscoumarin (9) were prepared. When compound (8) reacted with various Michael acceptors, some of the intermolecular primary addition products were followed by a sequential intramolecular Michael addition with ring closure forming a series of tetrahydro-thieno [2,3-c][1]benzopyran-4(H)-one derivatives (e.g. 16), the formation of which depends upon the structures of the acceptors. The stereochemistry of the tricyclic compounds was determined and discussed. The allyl thioethers of compound (8) were prepared. 3-Allyl coumarin thioether (26) was subjected to Claisen rearrangement in N, N-dimethylaniline, the expected rearranged products (27) and (28) being obtained. However, 3-cinnamyl coumarin thioether (29) under the same condition gave 3-(p-N,N-dimethylamino) thiobenzyl-coumarin (32) and other products. Phenyl cinnamyl thioether reacted similarly giving p-(N,N-dimethylamino)benzyl phenyl thioether (35).     

Some pyrazolid-3-one derivatives

In order to study their photographic properties, starting from the corresponding aromatic diamines the first representatives of a number of dipyrazolidonylarylenes have been synthesized: di[4-(pyrazolid-3-on-1-yl) phenyl] oxide and 1,2-di[4-(pyrazolid-3-on-1-yl)phenyl]ethane.For part IV, see [14].     

Synthesis of carbonyl derivatives of 3-phenylthiophene

3-Phenyl-2-acetylthiophene was synthesized by the acetylation of 3-phenylthiophene with acetic anhydride in the presence of 56% perchloric acid. Previously undescribed , -unsaturated ketones were synthesized by the crotonic condensation of 3-phenyl-2-acetylthiophene with several aromatic and heterocyclic aldehydes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1365–1367, October, 1971.     

Conformational behaviour of 3-phenyl- and 3-carbomethoxy-substituted cyclopropene derivatives

According to MNDO calculated heats of formation for various 3-substituted cyclopropenes the π-acceptor methoxycarbonyl as well as the π-donor group phenyl both prefer a non-bisected orientation with respect to the three-membered ring. Temperature dependent NMR chemical shifts seem to confirm this behaviour for the free molecules. In the crystalline state, however, 1,2,3-triphenylcyclopropene (3e) and 3-isopropyl-1,2,3-triphenylcyclopropene (3f) both adopt a conformation with a bisected orientation of the 3-phenyl groups.