Synthesis of 1-alkoxy-5-alkyluracils

1-Alkoxy-5-alkyluracils 2a-f have been prepared by the reaction of 2-alkyl-3-methoxyacryloyl isocyanates 8a-b with alkoxyamines 9a-c followed by cyclization of the resulting N-alkoxy-N'-(2-alkyl-3-methoxyacryloyl)ureas 10a-f. The isocyanates 8a-b were prepared from ethyl 2-alkylacrylates 3a-b in 5 steps.     

The 1-alkoxy-1,2,3-benzotriazole system

The 1-alkoxy-1,2,3-benzotriazole system has been synthesized and defined on the basis of its physical and spectral properties. Bond orders and charge densities of the parent compound in the series 1-methoxy-1,2,3-benzotriazole have been calculated. All-valence-electron calculations with configuration interaction give a reasonable account of the observed absorption spectrum.     

Reduction of 1-alkoxy- and 1-aryloxy-2,2-dichlorocyclopropanes

Conclusions The possibility of obtaining alkyl and aryl cyclopropyl ethers (yields 48–64%) by the reduction with sodium in liquid ammonia of the corresponding 1-alkoxy- and 1-aryloxy-2,2-dichlorocyclopropanes has been shown for the first time.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 413–414, February, 1967.     

The 1-alkoxy-6-nitro-1,2,3-benzotriazole system

The 1-alkoxy-6-nitro-1,2,3-benzotriazole system has been synthesized and characterized via its physical and chemical properties. INDO/molecular orbital calculations provide a good account of the major bands in its ultraviolet absorption spectrum.     

Synthesis of 6-substituted 1-alkoxy-5-alkyluracils

Synthesis of 6-substituted 1-alkoxy-5-alkyluracils 2a-c have been achieved from readily accessible 2-alkyl-3,3-di(methylthio)acryloyl chlorides 4a,b in high overall yields. Treatment of 4a,b with silver cyanate followed by reaction of the resulting isocyanates 5a,b with an appropriate alkoxyamine afforded N-alkoxy-N′-[2-alkyl-3,3-di(methylthio)acryloyl]ureas 6a,b in 85–88% yields. Cyclization of 6a,b in acetic acid containing methanesulfonic acid followed by oxidation with 3-chloroperoxybenzoic acid gave high yields of 1-alkoxy-5-alkyl-6-(methylsulfonyl)uracils 9a,b. Nucleophillic addition-elimination reaction of 9a,b with sodium azide, phenylthiol, or phenylselenol produced 6-azido-1-butoxythymine ( 2a , 98%), 5-ethyl-1-(2-phenoxyethoxy)-6-(phenylthio)uracil ( 2b , 95%), or 5-ethyl-1-(2-phenoxyethoxy)-6-(phenylselenenyl)uracil ( 2c , 91%).     

The 5-chloro-1-alkoxy-1,2,3-benzotriazole system

The 5-chloro-1-alkoxy-1,2,3-benzotriazole system has been synthesized and characterized via its physical and chemical properties. HMO calculations predict the most reactive sites on the molecule.     

Alcoholysis of 3-alkoxy-2-cyclohexene-1-thiones

Russian Journal of Organic Chemistry -     

The 1-alkoxy-4,5-dichloro-1,2,3-benzotriazole system

The 1-alkoxy-4,5-dichloro-1,2,3-benzotriazole system has been synthesized and characterized via its physical and chemical properties. INDO/S MO calculations provide a good account of the ultraviolet absorption spectrum.     

The 1-alkoxy-4-nitro-1,2,3-benzotriazole system

The 1-alkoxy-4-nitro-1,2,3-benzotriazole system was prepared using a phase transfer catalysis procedure. The physical and spectral properties of the system are reported. Molecular orbital calculations on the 1-methoxy derivative are used to explain the spectroscopic and electronic properties of the system.     

Synthesis and some properties of 2,2,2-trichloro-1-alkoxy-1-nitroxyethanes

Conclusions A number of 2,2,2-trichloro-1-alkoxy-1-nitroxyethanes were synthesized and some of their properties were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 676–677, March, 1973.     

Convenient synthesis of 1-alkoxy-1,2-dihydrophosphinine 1-oxides by ring enlargement

The addition of dichlorocarbene to the double bond of 1-alkoxy-dihydrophosphole oxides and subsequent thermolysis of the adduct so obtained affords mixtures of the two double bond isomers of alkoxy-dihydrophosphinine oxides, if the latter step is carried out in the presence of triethylamine. Experimental data support the involvement of a cationic intermediate during the opening of the cyclopropane ring. A simplified procedure for the preparation of the starting dihydrophospholes is also presented.     

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.     

Synthesis of glycidyl ethers of tertiary 1-alkoxy-1-en-3-ynols

Conclusions New unsaturated glycidyl ethers have been prepared by reaction of tert-1-alkoxy-1-en-3-ynols with epichlorohydrin in alkaline solution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2792–2795, December, 1975.     

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.     

Acetylenic condensation of 1-alkoxy- and 1-alkylthio-1-buten-3-ynes with substituted iodobenzenes

Conclusions New -arylenyne ethers and thioethers were prepared by the acetylenic condensation of 1-alkoxy-(1-ethylthio)-1-buten-3-ynes with a series of substituted iodobenzenes in the presence of CuI.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 692–693, March, 1976.     

Synthesis of new 5-substituted hydantoins from 2-alkoxy-1-cyano-1-trimethylsiloxypropenes

Synthetic procedures for preparing previously unknown 5-(1′-alkoxyethylidene)hydantoins from 2-alkoxy-1-cyano-1-trimethylsiloxy-1-(or -2-)propenes by one-pot successive reactions with ethanol and (NH₄)₂CO₃ are developed. Some intermediates, reaction mechanism, and parameters determining the optimal yields are considered. Acid hydrolysis of ethylidenehydantoins occurs at the vinyloxy group and gives 5-acetylhydantoin in 64% yield.