Synthesis of some derivatives of bis-2-chloroethyl 2,2,2-trichloro-1-hydroxyethylphosphonate

Conclusions A number of derivatives of bis-2-chloroethyl 2,2,2-trichloro-1-hydroxyethylphosphonate was synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1373–1377, August, 1966.     

Synthesis and Characterization of O,O-Dimethyl-N-(2,2,2-trichloro-1-arylaminoethyl) Phosphoramidothioates

Several novel trichloromethyl-containing O,O-dimethyl phosphoramidothioate derivatives have been synthesized by the reaction of O,O-dimethyl phosphoramidothioate with chloral imines. The latter were prepared in good yields by refluxing the dichloroethane solution of chloral and substituted anilines using 3 Å molecular sieves as dehydrating agent. Structures of title compounds were confirmed by IR, ¹H NMR, ³¹P NMR, and FT-MS studies.     

Synthesis of some 1-methyl-3-alkoxy-5-arylpyrrolecarboxylic acids and derivatives

By a combination of hydrolysis, decarboxylation, and methylation diethyl 1-methyl-3-hydroxy-5-phenylpyrrole-2,4-dicarboxylate was converted into 1-methyl-3-methoxy-5-phenyl-pyrrole-2,4-dicarboxylic acid (5) and into the isomeric compounds ethyl 1-methyl-2-phenyl-4-methoxypyrrole-3-carboxylate (4a) and ethyl 1-methyl-3-methoxy-5-phenylpyrrole-2-carboxylate (9a). 1-Methyl-2-phenyl-4-methoxypyrrole-3-carboxylic acid was synthesized both by the selective decarboxylation of 5 and by the hydrolysis of 4a. Hydrolysis of 9a, however, did not give the corresponding acid, but rather an oxidation product, 1-methyl-3-methoxy-5-hydroxy-5-phenyl-3-pyrrolin-2-onc (10a). Compound 10a was shown to arise from the air oxidation of the completely decarboxylated product, 1-methyl-2-phenyl-4-methoxypyrrole. Reduction of 9a with lithium aluminum hydride gave 1-methyl-3-methoxy-5-phenylpyrrole-2-methanol, which yielded 10a upon oxidation with silver oxide.     

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.     

Synthesis and some properties of 2,2,2-trimethoxy-3-isopropyl-4-bromo-5-oxo-1, 5,2 -oxazaphosphol-4-ene

Conclusions 2,2,2-Trimethoxy-3-isopropyl-4-bromo-5-oxo-1,5,2-oxazaphosphol-4-ene was isolated when trimethyl phosphite is reacted with 1-bromo-1-nitro-3-methyl-1-butene, and some of its transformations were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 462–465, February, 1978.The authors wish to thank É. I. Gol'dfarb for taking the³¹P-¹H} NMDR spectra.     

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%).     

Reaction of 2-chlorophenylacetylene with 2,2,2-trichloro-1,3,2λ5-benzodioxaphosphole

According to the ¹³C and ¹H NMR data (one-and two-dimensional spectra), o-chlorophenylacetylene reacts with 2,2,2-trichloro-1,3,2λ⁵-benzodioxaphosphole under mild conditions to give a mixture of diastereoisomeric 2,6-dichloro-4-(2-chlorophenyl)-1,2λ⁵-benzoxaphosphinin-2-ones differing in the configuration of the phosphorus atom and rotation of the o-chlorophenyl group about the C⁴-C_arom bond. Hydrolysis of that mixture leads to 6-chloro-4-(2-chlorophenyl)-2-hydroxy-1,2λ⁵-benzoxaphosphinin-2-one as a single stereoisomer.     

Synthesis of exo- and endobrevicomines from 1,1,5-trichloro-1-pentene

Conclusions A synthesis was described for exo- and endobrevicomies from 1,1,5-trichloro-1-pentene through the ethyleneketal of 6-nonyn-2-one.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2633–2635, November, 1984.     

Synthesis and some properties of 1-amino-3-nitroindazole

By treating 3-nitroindazole with hydroxylamine-O-sulfonic acid in basis medium, we have obtained its 1-amino derivative. We have observed that in chloroform solution in the presence of triethylamine, it is slowly converted to 1-ethylideneamino-3-nitroindazole. We discuss a possible mechanism for this unexpected reaction.Scientific-Research Institute of Physical and Organic Chemistry, Rostov State University. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1343–1346, October, 1996.     

Synthesis and some properties of 1H-1-benzazepines

1H-1-Benzazepines were synthesized by thermal ring opening of 2a,7b-dihydrocyclobut[b]indoles. The thermal and photochemical behavior of the 1H-1-benzazepines is also described.     

Synthesis and properties of 1-aminoalkyl-dibenzo(b,e)bicyclo(2,2,2) octadienes

The syntheses of dibenzo [b, e] bicyclo [2.2.2] octadienes substituted at the bridgehead by aminomethyl, aminoethyl or aminopropyl groups are described. The influence of this substitution on the fragmentation upon electron impact and on the nmr spectra of the new compounds is discussed.     

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 and NMR spectra of 2,2,2-trideuterioethylarsine and 2,2,2-trideuterioethylcyclopentaarsine

Pentakis(2,2,2-trideuterioethyl)cyclopentaarsine (PDECA) was synthesized by the reaction of 2,2,2-trideuterioethylarsine with dibenzylmercury. Variable temperature NMR spectra in C₆D₆ are interpreted in terms of fast pseudorotation. NMR and mass spectra and synthesis of 2,2,2-trideuterioethylarsine are also described.