Indole derivatives

7-Nitroindole, 5-methoxyindole, and 6-methoxyindole were synthesized by oxidation of 2-naphthol derivatives with hydrogen peroxide to the corresponding o-carboxycinnamic acids and cyclization of their amides under the conditions of the Hofmann reaction.See [1] for communication LXXXIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 207–210, February, 1974.     

Morpholine derivatives

The β-oxide ring of 3-alkyl-3-(N-morpholinomethyl)oxacyclobutanes is opened to give methiodides or hydrohalide salts, respectively, of 2-alkyl-2-(N-morpholinomethyl)-3-halopropanol when they are heated with methyl iodide in methanol under pressure or heated with hydrohalic acids. When two morpholinomethyl groups are present in the 3 position of the oxacyclobutane ring, it is not opened.     

Differential thermal analysis of hydrazinium derivatives

A thermobalance with two symmetrical pans was constructed in order to avoid thermogravimetry errors under pressure. The balance functions at 1000°C under 50 atm of hydrogen. The influence of parameters such as pressure, temperature and gas flow rate on the baseline deviation was studied. An example is given of the application of this balance to the hydrogenation of lignite char.     

Regioselective cyclization of chloroacylaminobenzenesulfonamide derivatives

Chloroacylaminobenzensulfonamides regioselectively thermally cyclize under solvent free conditions to 1,2,4-benzothiadiazines with five- and six-membered rings fused on face b.     

Vinyl derivatives of thiocaprolactam

A study is made of the reaction of N-vinylcaprolactam with phosphorus pentasulfide. When the reaction is run in xylene, thiocaprolactam is isolated, when Na₂CO₃ is present, or pyridine, a dimer of N-vinylcaprolactam is formed. As a result of a study of the reaction of thiocaprolactam with acetylene under various conditions, a method is devloped for synthesizing new sulfur- and nitrogen-containing monomers of N-vinylthiocaprolactam and S-vinylthiocaprolactam.     

Synthesis of substituted 1,3,4-oxadiazole derivatives

Monosubstituted oxadiazoles were synthesized by the reaction of hydrazides with triethyl orthoformate. Their reactions with benzoyl chloride gave benzoylcarbohydrazides, which under the action of thionyl chloride were cyclized to the respective 2,5-disubstituted oxadiazoles. 1-Aryl-4-(5-thioxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)-pyrrolidin-2-ones were synthesized from acid hydrazides using carbon disulfide under basic conditions. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 269-272, February, 2009.     

Tetrazole derivatives

1-(5-Tetrazolyl)-3,5-diphenylverdazylium betaine was obtained by oxidation of the leuco base of 1-(5-tetrazolyl)-3,5-diphenylverdazyl under the influence of PbO₂ in acetone, whereas verdazylium nitrate, which is capable of undergoing conversion to the betaine, was obtained by oxidation with nitric acid. Both oxidation products in concentrated NaOH form the sodium salt of verdazyl, and the betaine adds perchloric acid to give verdazylium perchlorate.     

Invisible photochromism of diarylethene derivatives

Diarylethene derivatives with oxidized thiophene rings shift their absorption band to a shorter wavelength in the UV region upon photocyclization; no color change was observed during the photochromic reaction, and the invisible photochromism is advantageous for devices used under room light.     

Some papaverine derivatives

Heating papaverine with chloral hydrate and benzoyl chloride formed products of the replacement of the hydrogen at the 15-C atom of papaverine: 15-(β-trichloro-α-hydroxyethyl)papaverine and 15-benzoylpapaverine. In reactions with monochloro- and trichloroacetic acids under mild conditions in the cold, salts at the nitrogen atom were formed: the monochloroacetate and the trichloroacetate. The products were characterized by the results of TLC (type KSK silica gel fixed with gypsum), elementary analyses, and IR and PMR spectroscopy.     

Synthesis of 2-indolylacetic acid derivatives

2-Indolylacetic acid derivatives were synthesized by condensation of diethyl acetonedicarboxylate with α-substituted arylhydrazines under the conditions of the Fischer reaction, and their transformations were studied.     

The cyclization reaction of ortho-ethynylbenzaldehyde derivatives into isoquinoline derivatives

In order to elucidate the reaction mechanism of the cyclization between an ethynyl group and an imino group at the ortho-position on an aromatic ring to afford isoquinolines, reaction of 2-ethynylbenzaldehydes under various conditions was examined. It is concluded that reaction proceeds via an ionic process and the isoquinoline 4-hydrogen atom derives from the solvent. In addition, it was found that 2-ethynylbenzaldehyde O-methyloximes underwent cyclization in the presence of primary and secondary alcohols to give 3-substituted isoquinolines.     

Azaindole derivatives

The polarographic oxidation of a series of 5-azaindoline, 7-azaindoline, and 5,7-diazaindoline derivatives (22 compounds) was studied, and the results are compared with the ease of dehydrogenation of these substances under the influence of quinones. It is shown that E_1/2 increases on passing from 7-azaindolines to 5-azaindolines and then to 5,7-diazaindolines. The effect of substituents is satisfactorily described by cross-correlation equations, while the deviations from the correlation are associated with the peculiarities of the lactam-lactim tautomeric equilibrium in a number of 6-hydroxy-5- and 7-azaindolines.See [1] for communication XLI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 773–776, June, 1973.     

Synthesis of 1,3-dioxolane derivatives

Chloral cyanomethylhemiacetal is converted to 2-trichloromethyl-4-imino-1,3-dioxolane under the influence of hydrogen chloride or pyridine. Acetone cyanohydrin reacts with chloral to give 2-trichloromethyl-4-imino-5,5-dimethyl-1,3-dioxolane, the hydrochloride of which in water gives 2-trichloromethyl-4-oxo-5,5-dimethyl-1,3-dioxolane.     

Indole derivatives

The Wittig reaction with indole-3-aldehyde and its N-acetyl derivative has been studied. Data are presented on the influence of various factors on the formation of the unsaturated compound. Some hypotheses are put forward concerning the reactivity of indole-3-aldehydes under the conditions of this reaction. The previously unknown -(indol-3-yl)--phenylethylene has been obtained with a yield of 54%.For part XXXIV, see [15].     

Investigation of benzimidazole derivatives

A number of bis(1-benzimidazolyl)alkanes (I) were synthesized, and their behavior toward sodium amide and potassium hydroxide was studied. While compounds with n=3-5 (Ic-Ie) are aminated by NaNH₂ and hydroxylated by KOH to give diamines (II) and bisbenzimidazolones (III), Ia,b with n=1, 2 decomposed under the influence of these reagents. Considerations regarding the possible reasons for this phenomenon are stated.See [1] for communication XXVIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1418–1421, October, 1972.     

Azaindole derivatives

A comparative study of the dehydrogenation of azaindoles by chemical (under the action of quinones) and electrochemical (anode polarography at a rotating platinum disc electrode) methods has been made. The influence of substituents in positions 1 and 6 of the azaindole molecule on the ease of oxidation of the compounds has been investigated. The results are discussed using the method of correlation equations.For part XXVII, see [16].     

Monolayers of reactive cellulose derivatives

Functional cellulose derivatives are very versatile materials for the creation of mono- and multilayer systems. Hydrophobic alkyl and trimethylsilyl celluloses form highly ordered Langmuir-Blodgett multilayers on hydrophobic substrates. Cellulose thiosulfates and methyl thio ethers were self-assembled on gold and silver surfaces to form hydrophilic monolayers. Cellulose layer systems are capable for chemical transformations under conservation of the structural order. They are suitable platforms for the investigation of molecular recognition at surfaces and the construction of sensor devices. Both biological ligands, e.g. biotin, and enzymes, e.g. horse radish peroxidase, could be attached to cellulose under conservation of their biological function.     

2-Carboazetidine derivatives

A reaction sequence is reported for converting methyl 7-bromocrotonate to 1-alkyl-2-carbo-methoxyazetidines thus confirming our earlier structural assignments of these compounds obtained by a more direct route. Methods are described for obtaining azetidinyl alcohols, acids, amides, amines and ketones. 1-t-Butyl-2-carbomethoxyazetidine was observed to undergo ring opening to an acyclic γ-aminohydrazide derivative when treated with hydrazine hydrate. On the other hand, the corresponding N-benzylazetidine under similar conditions rearranged to 1-benzyl-2-pyrrolidinone.     

Reactions of hydrazine derivatives

On the basis of a combined study of chemical properties and UV, IR, PMR, and mass spectra, it has been shown that the product of the transformation of 3,4-tetramethylene-5, 5-pentamethylenepyrazoline under the action of sulfur has the structure of 3-pentyl-4,5,6,7-tetrahydroindazole.For part XLIV, see [1].     

Cubane derivatives

The reduction of 1-bromo-9,9-ethylenedioxypentacyclo[4.3.0.0^2,5.0^3,8.0^4,7]nonane-4-carboxylic acid (2) with lithium aluminum hydride and aluminum hydride in THF was studied. A new effective method for preparing 1-bromo-9,9-ethylenedioxypentacyclo[4.3.0.0^2,5.0^3,8.0^4,7]-non-4-ylcarbinol (1) based on reduction of2 with AlH₃ under mild conditions was developed.