Synthesis and absorption spectra of polymethine dyes — Derivatives of substituted thieno- and indolothiazoles

Cyanine, merocyanine, and styryl dyes that are derivatives of halo-, alkyl-, alkylene-, and arylthieno[2,3-d]thiazoles and halo- and alkylindolo[3,2-d]thiazoles were synthesized. It is shown that both electron-donor and electron-acceptor substituents in the 5 and 5 positions of the heteroresidues of thienothiazolocarbocyanines lead to a more uniform distribution of the electron density in their chromophore than in the unsubstituted dye and to a bathochromic shift of the absorption maximum. Methyl groups in the heteroresidues of indolothiazolocarbocyanines give rise to a small bathochromic effect.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1278–1283, September, 1988.     

Synthesis and properties of indolo-3,3′-trimethinecyanines substituted in the polymethine chain and heterorings

New 8-chloro-, 9-cyano-, and 8-methyl-9-carboxy-substituted (in the outer polymethine chain), indolo-3,3-trimethinecyanines containing substituents in the 2, 5, or 7 position of the indole heteroresidues were synthesized, and their spectral, polarographic, and photographic properties were studied. It is shown that electron-acceptor substituents in the 2 and 2 positions of the indole heteroresidues and the 8 and/or 9 positions of the polymethine chain of the dye molecules that do not have steric hindrance give rise to a bathochromic shift of their absorption maxima. 8-Chloro-, 9-cyano- and 8-methyl-9-carbethoxyindolo-3,3-trimethinecyanines with electron-acceptor groups in the 2 and 2 positions are ineffective sensitizers of direct positive silver halide emulsions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 897–901, July, 1988.     

Synthesis of substituted 1-isopropenyl- and 1-alkylbenzimidazolones

1-Isopropenylbenzimidazolones, the alkylation of which with alkyl halides and γ-butyrolactone proceeds in the 3 position, were obtained by reaction of o-phenylenediamine and its aromatic ring-substituted derivatives with acetoacetic ester.     

Luminescence spectroscopic studies of trimethinecyanines substituted in polymethine chain with nucleic acids and proteins

The series of symmetrical beta-substituted and alpha,gamma-substituted trimethinecyanine dyes were studied for their absorption and fluorescent characteristics in unbound state and in the presence of nucleic acids and proteins. It was shown that beta-substituted and alpha,gamma-bridged trimethinecyanines containing extended heterocyclic systems or N-phenyl as well as N-cyclohexyl substituents demonstrate increased affinity to proteins. At the same time the presence of both N-phenyl and N-cyclohexyl substituents leads to the decrease of the dye fluorescence intensity in complexes with nucleic acids. For trimethinecyanines similarly to unsymmetrical monomethines the presence of N-omega-hydroxy alkyl substituents results in the increase of fluorescence intensity of dye-DNA complex and the emission decrease of dye-RNA complex.     

Synthesis of some substituted 3-alkenyl-1-phenylpyrazoles

The regioselective synthesis of new 3-alkenyl-1-phenylpyrazoles 4 from the reaction of phenylhydrazine with 2,3-dihydro-4H-pyran-4-ones 1 is described.     

Synthesis of 1-hydrocarbon substituted cyclopropyl silyl ketones

The synthesis of cyclopropyl silyl ketones possessing a hydrocarbon group at 1-position of three-membered ring was investigated. The reaction of sulfoxonium ylide with α,β-unsaturated acylsilanes derived from α,β-unsaturated aldehydes did not afford the desired acylsilane derivatives. Instead, the corresponding silyl enol ethers were yielded exclusively. On the other hand, the Corey-Chaykovsky cyclopropanation of α-substituted α,β-unsaturated aldehydes proceeded well to give 1-substituted cyclopropyl aldehydes. The silyl substitution of formyl proton in the obtained aldehydes via umpolung of carbonyl group afforded the target acylsilanes.     

Synthesis of substituted 1H-indazoles from arynes and hydrazones

The 1H-indazole skeleton can be constructed by a [3 + 2] annulation approach from arynes and hydrazones. Under different reaction conditions, both N-tosylhydrazones and N-aryl/alkylhydrazones can be used to afford a variety of indazoles. The former reaction affords 3-substituted indazoles either via in situ generated diazo compounds or through an annulation/elimination process. The latter reaction leads to 1,3-disubstituted indazoles likely through an annulation/oxidation process. The reactions operate under mild conditions and can accommodate aryl, vinyl, and less satisfactorily, alkyl groups.     

Synthesis of substituted pteridines

Conclusions The cyclocondensation of 2,5,6-triamino-4-oxo-3,4-dihydropyrimidine and tetraaminopyrimidine with butylthioacetone and 2-butylthiopropanal gives 7-methylpteridines, while the reaction of these pyrimidine derivatives with 2-phthalimidopropanal, 1,1-dibutoxyacetone, 1,1-dichloroacetone, and 1,1-dibromoacetone gives mixtures of 6- and 7-methylpteridines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 452–455, February, 1986.     

Synthesis of some trifluoromethyl substituted 1‐methylpyrazoles

The major products from the reaction of β‐alkoxyvinyl trifluoromethyl ketones 1a‐c with methylhydrazine ( 2 ) in absolute ethanol are the 3‐(trifluoromethyl)‐substituted‐1‐methylpyrazoles 3a‐3c with lesser amounts of the 5‐(trifluoromethyl)‐substituted products 4a‐4c and 5a‐5c. Carrying out the reaction in non‐polar, aprotic solvents can further enhance the regioselectivity favoring the 3‐ (trifluoromethyl) ‐substituted isomers.     

Synthesis of substituted 1H-pyrrolo[3,2-c]quinolines

1H-2-Phenylpyrrolo[3,2-c]quinoline (1a) is made by thermal cyclization of quinol-4-yl hydrazone. Subsequent substitution of the C-3 hydrogen atom of the pyrrole ring of 1a with chlorine and a formyl group is easily achieved by reacting 1a with trichloroacetyl chloride and phosphorus oxychloride in DMF, respectively.     

Synthesis of substituted hydroxypyrazines

Conclusions A new method was developed for the synthesis of substituted hydroxypyrazine derivatives by reacting the hydrochlorides of-amino ketones with the acid chlorides of N-phthaloyl--amino acids in acetone in the presence of diethylaniline, and subsequent treatment of the intermediate N-(N-phthaloyl--aminoacyl)--amino ketones with aqueous sodium acetate solution at 100°.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2417–2421, October, 1978.     

取代邻苯二腈的合成

在室温条件下合成了一系列芳氧基邻苯二腈化合物,应用无素分析、1HNMR、IR确定了它们的结构,讨论了不同取代基对反应的影响.结果表明,酚的芳环上有推电子基时反应容易进行;酚的芳环上有拉电子基时反应慢或不反应.     

Synthesis of substituted thienothiazoles

The action of sulfur monochloride on 2-amino-3-carboxy-5-phenylthiophene or 2-amino5-phenylthiophene hydrochloride gave 5-phenylthieno[2,3-d]-2-thioniathiazole chloride, which is converted to the corresponding hydrate on treatment with water. Heating of the thionium salt or its hydrate with carbon disulfide in an aqueous alcohol solution of aklaki gave 2-mercapto-5-phenylthieno[2,3-d]thiazole, which under the influence of dialkyl sulfates or on oxidation with potassium permanganate in alkaline media is converted, respectively, to S-alkyl derivatives or a 5-phenylthieno[2,3-d]thiazole-2-sulfonic acid salt. 2-Sulfo-3-alkylthieno[2,3-d]thiazolium betaines are obtained by heating the latter with alkylating agents. 2-Hydroxy-thieno[2,3-d]thiazoles were synthesized by hydrolysis of thienothiazole-2-sulfonic acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 477–480, April, 1979.     

Synthesis of substituted N-aminoisomaleinimides

,-Disubstituted monohydrazides of maleic acid form stable aminoisomaleinimides on treatment with acetic anhydride in the presence of anhydrous sodium acetate. The structure of the products was confirmed by IR and PMR spectroscopy and by chemical methods.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 443–445, April, 1973.     

Synthesis of substituted thiabicyclanes

A simple preparative method for the synthesis of cis-1-thiahydrindan and cis-2-thiabicyclo[3, 3, 1]nonane has been developed. The method can be used to obtain substituted thiabicyclanes by a general method starting from 3-chloromethylcyclohexene. In the cyclization of 3 (-mercaptoethyl)cyclohexane both by an ionic and by a radical mechanism, a mixture of cis-1-thiahydrindan and cis-2-thiabicyclo [3,3,1] nonane in approximately equal amounts is formed.