Some properties of 2-alkoxy-1-alken-3-ols

Conclusions The reaction of 2-alkoxyacroleins with Grignard reagent gave some new 2-alkoxy-1-alken-3-ols, which in the presence of p-toluenesulfonic acid are cyclodimerized to 2,3,5,6-tetraalkyl-2,5-dialkoxy-1,4-dioxanes, which tend to cleave ethanol to give 2,3,5,6-tetraalkyl-5-alkoxy-1,4-dioxenes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2534–2538, November, 1980.The authors express their gratitude to V. I. Lavrent'ev and V. Yu. Vitkovskii for taking the mass spectra.     

Efficiency of alkoxyl radical product formation from 5-substituted 3-alkoxy-4-methylthiazole-2(3H)-thiones

In a comparative study, reactions between 5-(p-methoxyphenyl)-substituted 3-alkoxy-4-methylthiazole-2(3H)-thiones and appropriate mediators (BrCCl₃, Bu₃SnH) provided higher yields of alkoxyl radical products (δ-bromohydrins, cyclic ethers, carbonyl compounds) than respective transformations of 5-phenyl- and 5-methyl-substituted derivatives. The unusual selectivity of applied thiohydroxamates to furnish products of O-alkylation, even upon treatment with soft carbon electrophiles, and the marked propensity of 3-alkoxy-5-(p-methoxyphenyl)-4-methylthiazole-2(3H)-thiones to crystallize, facilitated preparation and purification of the new family of alkoxyl radical precursors in a noteworthy manner.     

1-Amino-3-alkylbenzimidazoline-2-thiones (selenones)

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1689–1690, December, 1990.     

Photochemical and thermal addition of alcohols to 2-cyanofuran : 1-alkoxy-2-cyanocyclopropane-3-carboxaldehydes; 2-alkoxy-3-cyano-2, 3-dihydrofuran; 1-alkoxy-1-(2-furan)-methylenimine; photochemical ring contraction; cis-trans-isomerization of dihydrofurans

The photolysis of 2-cyanofuran in alcohols yields 1-alkoxy-2-cyanocyclopropane-3-carboxaldehydes as the major products, which rearrange thermally to trans-2-alkoxy-3-cyano-2,3-dihydrofurans and small amounts of cis-isomers. Thermal mutual rearrangements between trans- and cis-2- alkoxy-3-cyano-2, 3-dihydrofurans were studied. Liquid phase thermal addition of alcohols in a temperature range between 100° and 200° yields 1-alkoxy-1-(2-furan)-methylenimines, which rearrange photochemically to 2-furyl-methylamino-ketone in case of the methoxy derivative. 3-Cyano-furan does not yield photoaddition or thermal addition products. The different behaviors of 2- and 3-substituted furans are discussed.     

Synthesis of 2-alkoxy-3-chlorotetrahydrofurans

A simple one-stage method for the synthesis of 2-alkoxy-3-chlorotetrahydrofurans has been developed which is based on the chlorination of tetrahydrofuran with sulfuryl chloride at 55–65 C with the subsequent addition of an alcohol (without the isolation of the dichlorinated tetrahydrofurans). Eight compounds of the type mentioned have been synthesized by this method, six of them being previously unknown.     

Synthesis of 3-alkoxy-2-nitroxypropyl-N-alkylnitramines

It was shown that 3-alkoxy-2-nitroxypropyl-N-alkylnitramines can be prepared by nitration of the corresponding 3-alkoxy-2-hydroxypropyl-N-alkylsulfamates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1987–1989, November, 1997.     

Alkylation of 1-alkoxy-3-methyl-1-triazene 2-oxide sodium salts

1-Alkoxy-3-methyl-1-triazene 2-oxide sodium salts react with chloromethyl methyl sulfide to give a mixture of 1-alkoxy-3-methyl-3-(methylthiomethyl)-1-triazene 2-oxides and 3-alkoxy-1-methyl-3-(methylthiomethyl)-1-triazene 2-oxides. The reaction of these triazene oxide sodium salts with 3,3-dialkyl-1-chloromethoxy-1-triazene 2-oxides produces a complex mixture of product bearing the oxytriazene moieties of the starting alkoxy-1-triazene 2-oxides bonded with the methylene group as a key structural fragment.     

Synthesis of 2-alkoxy-3-chlorotetrahydrofurans

A simple one-stage method for the synthesis of 2-alkoxy-3-chlorotetrahydrofurans has been developed which is based on the chlorination of tetrahydrofuran with sulfuryl chloride at 55–65? C with the subsequent addition of an alcohol (without the isolation of the dichlorinated tetrahydrofurans). Eight compounds of the type mentioned have been synthesized by this method, six of them being previously unknown.     

Reaction of chloroethynylphosphonates with 1-methyl-3H-imidazole-2-thiones

Russian Journal of General Chemistry -     

Synthesis of 1-alkoxy-3-(2-hydroxyethyl)-1-triazene 2-oxides

Synthetic procedure to access the first representatives of a new series of 3-monosubstitued functional derivatives of 1-alkoxy-1-triazene 2-oxides, i.e., 1-alkoxy-3-(2-hydroxyethyl)- and 1-alkoxy-3-(2-acetoxyethyl)-1-triazene 2-oxides, were elaborated. 1-Alkoxy-3,3-bis(2-hydroxyethyl)-1-triazene 2-oxides were used to derive 3-(2-acetoxyethyl)-, 3-(2-bromoethyl)- and 3-(2-cyanoethyl)substituted 1-alkoxy-3-(2-acetoxyethyl)-1-triazene 2-oxides.     

Homopolycondensation of 1-halogenopropane-2-thiones

Homopolycondensation of 1-halogenopropane-2-thiones was studied; the polymers obtained were structurally characterized by ESR, UV, and IR spectroscopy, elemental analysis, and electrochemical methods. Their molecular masses, dark conductivities, and photoconductivities were determined. The capability for film formation on various substrates was investigated. These polymers were found to be new organic metals (Hal=I), semiconductors (Hal=Cl and Br), and photoconductors (Hal=Cl, Br). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 330–333, February, 2000.     

芳亚甲基双(3-羟基-5,5-二甲基-2-环己烯-1-酮)类化合物的合成

在水溶剂中,酸性离子液体[bmim][HSO4]可以有效地催化芳香醛与5,5-二甲基-1,3-环己二酮反应3～5h,得到产率为76%～86%的芳亚甲基双(3-羟基-5,5-二甲基-2-环己烯-1-酮)类化合物.该反应产物后处理简单,催化剂可以回收利用.催化剂在循环使用五次时对产物的收率影响不大,是一种环境友好的绿色合成方法.     

Novel synthesis of 1-aroyl-3-aryl-4-substituted imidazole-2-thiones

[reaction: see text] An efficient route to 1-aroyl-3-aryl-4-substituted imidazole-2-thiones (2, 4-6) has been developed. The methodology involves the cyclization of 1-aroyl-3-arylthioureas with a variety of carbonyl compounds bearing alpha-H in the presence of bromine and triethylamine.     

Synthesis of 1-Benzoyl-3-aryl-4-hydroxy-4-phenylimidazolidin-2-thiones

l-Benzoyl-3-aryl-4-hydroxy-4-phenylimidazolidin-2-thiones can be synthesized readily from the cyclization of 1-benzoyl-3-arylthioureas with bromine-acetophenone in the presence of excess triethylamiqe.     

Spectrophotometric determination of nickel with cyclohexylidine-ammonium 2-aminocyclohexylidene-1-cyclohexene-1-dithiocarboxylate

An (extraction)-spectrophotometric method is reported for the determination of nickel(II) with cyclohexylidineammonium 2-aminocyclohexylidene-l-cyclohexene-l-dithiocarboxylate. The violet 1:2 chelate is soluble in aqueous ethanolic or acetonic media at pH 6–9, or can be extracted into methyl isobutyl ketone. The molar absorptivity of the complex is about 2.5 × 10⁴ l mol^?1 cm^?1 at 550 nm.     

One-pot synthesis of 4-substituted 4-alkoxy-1,4-dihydro-3,1-benzoxazine-2-thiones by the reaction of 2-isothiocyanatobenzoates with organolithiums

An efficient one-pot procedure for the preparation of 4-substituted 4-alkoxy-1,4-dihydro-3,1-benzoxazine-2-thiones from 2-isothiocyanatobenzoates has been developed. Thus, 2-isothiocyanatobenzoates were reacted with organolithiums including lithium enolates of acetates and tertiary acetamides in THF at −78 °C to give the desired products in generally good yields.     

Reaction of 3-cyanopyridine-2(1H)-thiones with N-butyllithium

The reaction of 3-cyanopyridine-2(1 H)-thiones with BuLi in ether was studied. It was found that the metallation proceeds initially at the sulfur atom. The resulting lithium salts add a second equivalent of n-butyllithium at the CN group. The hydrolysis of the dilithium derivatives leads to 3 pentanoylpyridine-2(IH)-thiones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 231–234, February, 1996.