Oxidation of N-(1-Hydroxypolychloroethyl)sulfonamides

N-(2,2,2-Trichloro-1-hydroxyethyl)- and N-(2,2-dichloro-1-hydroxy-2-phenylethyl)arenesulfonamides are oxidized with chromium(VI) oxide to give, respectively, N-(arylsulfonyl)trichloroacetamides and N-(arylsulfonyl)dichloro(phenyl)acetamides. Under analogous conditions N-(2,2,2-trichloro-1-hydroxyethyl)trifluoromethanesulfonamide is converted into 1,1,1-trichloro-2,2-bis(trifluoromethylsulfonylamino)ethane.     

Alkylation of Phenols with N-(2,2,2-Trichloroethylidene)- and N-(2,2,2-Trichloroethyl)arenesulfonamides

N-(2,2,2-Trichloroethylidene)- and N-(2,2,2-trichloroethyl)arenesulfonamides react with phenol, 2-chlorophenol, and 2-methylphenol in the presence of oleum or sulfuric acid to give the corresponding 4-(2,2,2-trichloro-1-arylsulfonylaminoethyl)phenols in good yields.     

N-(2,2,2-Trichloroethylidene)- and N-(1-Hydroxy-2,2,2-trichloroethyl)amides in C-Amidoalkylation Reaction of Functionally-substituted Aromatic Compounds

A reaction with phenol and pyrocatechol of N-(2,2,2-trichloroethylidene)arenesulfonyl-, ethoxycarbonylamides and 1-hydroxy-substituted N-(2,2,2-trichloroethyl)amides of arenesulfonic, carbamic, and acetic acids in the presence of oleum or in sulfuric acid provided the corresponding (1-amido-2,2,2-trichloroethyl)-substituted phenols. N-(2,2,2-Trichloroethylidene)-4-chlorobenzenesulfonamide reacted with salicylamide in the presence of oleum to afford 3-aminocarbonyl-4-[2,2,2-trichloro-1-(4-chlorobenzenesulfonamido)ethyl]benzene whereas the 1-hydroxy-2,2,2-trichloroethylamides of the acetic, carbamic, and arenesulfonic acids did not enter into such reactions.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-Arylsulfonyl-α-thienylglycines from <Emphasis Type="Italic">N</Emphasis>-(2,2,2-Trichloro-1-thienylethyl)arenesulfonamides

Reactions of N-(2,2,2-trichloroethylidene)arenesulfonamides with thiophene, 2-chlorothiophene, and 2,5-dichlorothiophene, as well as of N-(2,2,2-trichloro-1-hydroxyethyl)arenesulfonamides with 2-chlorothiophene, lead to formation of the corresponding N-(2,2,2-trichloro-1-thienylethyl)arenesulfonamides. Alkaline hydrolysis of the latter occurs selectively at the trichloromethyl group to give N-arylsulfonyl-α-thienylglycines.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 93–96.Original Russian Text Copyright © 2005 by Aizina, Rozentsveig, Ushakova, Levkovskaya, Mirskova.     

Synthesis of N-arylsulfonyl-2-aryl(hetaryl)aminoacetic acids

Hydrolytic transformations of 4-[2,2,2-trichloro-1-(arylsulfonylamino)-and-(ethoxycarbonylamino)ethyl]phenyloxy(or sulfanyl)acetic acids under microwave irradiation in alkaline medium involve both trichloromethyl group and ester fragment to give N-arylsulfonyl-2-[4-carboxymethyloxy(or sulfanyl)phenyl]-2-aminoacetic acids in good yields. Hydrolysis of methyl 4-[2,2,2-trichloro-1-(arylsulfonylamino)ethyl]phenyloxy(or sulfanyl)acetates without microwave activation occurs only at the ester group with quantitative formation of 4-[2,2,2-trichloro-1-(arylsulfonylamino)ethyl]phenyloxy(or sulfanyl) acetic acids. N-[2,2,2-Trichloro-1-(1-naphthyl, 2-furyl, and 1-methylindol-3-yl)ethyl]-4-chlorobenzenesulfonamides in alkaline medium under microwave irradiation were converted in 10–15 min into the corresponding N-(4-chlorophenylsulfonyl)-2-aryl-2-aminoacetic acids in preparative yields.     

Synthesis and reactions with <Emphasis Type="Italic">N</Emphasis>-nucleophiles of 1-(thien-2-yl)- and 1-(4-hydroxyphenyl)-3,4,4-trichloro-3-buten-1-ones

Acylation of thiophene and phenol with 3,4,4-trichloro-3-butenoyl chloride afforded the corresponding 1-(thien-2-yl)- and 1-(4-hydroxyphenyl)-3,4,4-trichloro-3-buten-1-ones, whose reaction with amines led to the formation of 3-amino-1-(thien-2-yl, 4-hydroxyphenyl)-4,4-dichloro-2-buten-1-ones The heterocyclization of the initial ketones into pyrazole structure was not observed, and the reaction with hydrazine hydrate provided bispyrazole products, N,N′-bis(5-thien-2-yl)- and N,N′-bis[5-(4-hydroxyphenyl)-1H-pyrazol-3-ylmethylene]hydrazines.     

Reactions of Aroxy- and Arylsulfanylacetic Acids and Their Esters with N-(2,2,2-Trichloro-1-hydroxyethyl)sulfonamides and -carboxamides

C-Amidoalkylation of aroxy- and arylsulfanylacetic acids and their methyl esters was effected by reaction with N-(2,2,2-trichloro-1-hydroxyethyl)sulfonamides and -carboxamides in the presence of methane- or trifluoromethanesulfonic acids as catalyst and solvent. The process is regioselective, and the substitution occurs at the para-position with respect to the heteroelement-containing group.     

Unusual Cyclization of N-(1-Aryl-1-chloro-2,2,2-trifluoroethyl)-N'-(p-tolyl)-carbodiimides in the Presence of Triethylamine

1-Aryl-1-chloro-2,2,2-trifluoroethyl)-N'-(p-tolyl)carbodiimides treated with triethylamine undergo intramolecular cyclization into 4-aryl-6-methyl-2-triethylammonio-4-trifluoromethyl-4-dihydroquinazolidines.     

Synthesis and Properties of N-(2,2,2-Trichloroethylidene)trifluoromethanesulfonamide and Its Derivatives

The reaction of N,N-dichloromethanesulfonamide with trichloroethylene gave N-(2,2,2-trichloro- ethylidene)trifluoromethanesulfonamide which showed high reactivity toward oxygen- and nitrogen-centered nucleophiles, as well as in C-alkylation of aromatic compounds.     

New approach to the preparation of <Emphasis Type="Italic">p</Emphasis>-(1-cyanoethyl)arenesulfonamides by reaction of arylsulfonyl imines of polychloroacetaldehydes with acetone cyanohydrin

Reaction of N-(2,2,2-trichloroethylidene)- or N-(1-phenyl-2,2-dichloroethylidene)arenesulfonamides with acetone cyanohydrin in acetone in the presence of potassium carbonate led to the formation of N- (2,2,2-trichloro-1-cyanoethyl)- or N-(2-phenyl-2,2-dichloro-1-cyanoethyl)arenesulfonamides.     

Chemical transformations of reaction products of 2-methyl-3-(4-tolyl)-4(3<Emphasis Type="Italic">H</Emphasis>)-quinazolone with benzil and its 4,4′-derivatives

The reaction of 2-methyl-3-(4-tolyl)-4(3H)-quinazolone with benzil produces 2-[(Z)-3-oxo-2,3-diphenylprop-1-enyl]-3-(4-tolyl)-4(3H)-quinazolone, which is readily transformed into 2-(3,3-diphenylsuccinimido)-N-(4-tolyl)benzamide on dissolution in organic water-containing solvents. The rearrangement mechanism was suggested and investigated by the quantum chemical PM3 method. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 146–151, January, 2007.     

Regioselectivity in the reactions of <Emphasis Type="Italic">N</Emphasis>-(polychloroethylidene)-sulfonamides with 1<Emphasis Type="Italic">H</Emphasis>-pyrrole and 1-methyl-1<Emphasis Type="Italic">H</Emphasis>-pyrrole

N-(2,2,2-Trichloroethylidene)arenesulfonamides react with 1H-pyrrole and 1-methyl-1H-pyrrole to give the corresponding N-[2,2,2-trichloro-1-(1H-pyrrol-2-yl)ethyl]arenesulfonamides. The reaction of N-(2,2,2-trichloroethylidene)trifluoromethanesulfonamide with pyrrole leads to a mixture of 2-mono-and 2,5-disubstituted pyrroles, whereas in the reaction with 1-methyl-1H-pyrrole only the 2-substituted compound is formed. N-(2,2-Dichloro-2-phenylethylidene)-4-methylbenzenesulfonamide reacts with 1H-pyrrole to form N-[2,2-dichloro-2-phenyl-1-(1H-pyrrol-2-yl)ethyl]-4-methylbenzenesulfonamide, and its reaction with 1-methyl-1H-pyrrole gives a mixture of 2-and 3-monosubstituted derivatives. The results of quantum-chemical calculations of the initial reactants and products indicate that the process is orbital-controlled. A good agreement is observed between the experimental data and theoretical conclusions concerning the dependence of the reaction regioselectivity on the nature of substituents in the electrophile molecule.     

Reaction of trihalo(phenylenedioxy)phosphoranes with acetylenes: X. specific features of the reactions of substituted 2,2,2-trichloro-1,3,2λ5-benzodioxaphospholes with 3-chloro(bromo, iodo)propynes

It was shown for the first time that 3-chloro-, 3-bromo-, and 3-iodopropynes can react with 2,2,2-trichloro-, 2,2,2-trichloro-5-methyl-, and 5,6-dibromo-2,2,2-trichloro-1,3,2λ⁵-benzodioxaphospholes to give derivatives of 4-(halomethyl)-2-chloro-2H-1,2λ⁵-benzoxaphosphinin-2-ones. The reaction involves nonselective chlorination of the phenylene substituent in different positions, and the resulting isomer ratio is temperature-dependent. In the reactions of 3-bromo-and 3-iodopropynes with 2,2,2-trichloro-1,3,2λ⁵-benzo-dioxaphosphole, a side process takes place, viz. nucleophilic substitution of bromine and iodine with chlorine. The structure of some of the prepared 4-(chloromethyl)-1,2-benzoxaphosphinines was studied by means of X-ray diffraction.     

Hydroxymethylation and cyanoethylation of nitroimidazoles

A series of nitroimidazoles were subjected to hydroxymethylations under a variety of conditions. Hydroxymethylation of 1-(2-hydroxyethyl), 1-(2-acetoxyethyl), and 1-(2-chloroethyl) substituted 5-nitroimidazoles with paraformaldehyde in dimethyl sulfoxide yielded the respective 2-hydroxymethyl analogs (5–7). However, attempts to hydroxymethylate 1-(2-hydroxyethyl), 1-(2-acetoxyethyl), 1-(2-cyanoethyl) substituted 4-nitroimidazoles and 1-(2-hydroxyethyl)-2-nitroimidazole were unsuccessful. Treatment of 1-(2-acetoxyethyl)-5-nitro-2-imidazolecar-baldehyde(10) with hydroxylamine-O-sulfonic acid afforded a mixture of corresponding 2-carbonitrile (12) and 2-(N-hydroxy)carboximidamide (13). Hydrolysis of 10 with ethanolic hydrochloric acid yielded 8-ethoxy-5,6-dihydro-3-nitro-8H-imidazo[2,1-c] [1,4]oxazine (11) which, on subsequent reaction with hydroxylamine-O-sulfonic acid, afforded 1-(2-hydroxyethyl)-5-nitroimidazole-2-(N-hydroxy)carboximidamide (15). Reaction of 4(5)-nitroimidazole with chloropropionitrile produced a mixture of the isomeric 1-(2-cyanoethyl) substituted 4- and 5-nitroimidazoles. Treatment of 2,4(5)-dinitroímidazole with chloropropionitrile afforded a mixture of 4(5)-chloro-5(4)-nitroimidazole and 1-(2-cyanoethyl)-4-nitro-5-chloroimidazoIe. Reaction of nitroimidazoles with acrylonitrile in the presence of Triton B yielded the corresponding 1-(2-cyanoethyl) substituted derivatives.     

Synthesis of N-(5-Pyrazolyl) Schiff Bases Derived from Aryl Trifluoromethyl Ketones

5-Amino-1-aryl-4-methylpyrazoles readily add to methyl 1-aryl-2,2,2-trifluoroethylidenecarbamates to give the corresponding methyl 1-aryl-2,2,2-trifluoro-1-(5-pyrazolylamino)ethylcarbamates which undergo fragmentation at elevated temperature in the presence of an organic base to afford N-(5-pyrazolyl)-1-aryl-2,2,2-trifluoroethanimines.     

A new method for the synthesis of N-substituted (4-oxo-4,5,6,7-tetrahydroindol-3-yl)acetic acids

A new method for the synthesis of N-substituted 2-(4-oxo-4,5,6,7-tetrahydroindol-3-yl)acetic acids was developed. Alkylation of cyclic 1,3-diketones with 3,5,5,5-tetrachloropentan-2-one affords 1,4-diketones, which undergo cyclization with different primary amines into N-substituted 3-(2,2,2-trichloroethyl)-4,5,6,7-tetrahydroindol-4-ones. Acid hydrolysis of the latter gives the corresponding indol-3-ylacetic acids. The structures of the compounds obtained were confirmed by ¹H and ¹³C NMR data.     

Derivatives of 5-(Dimethylamino)-4-tosyl-1,3-oxazole-2-carbaldehyde and Its Analogs

Treatment of N-(2,2,2-trichloro-1-tosylethyl)dichloroacetamide with excess dimethylamine, piperidine, or morpholine gave substituted aminals of the oxazole series, whose facile acid hydrolysis provided 5-(dimethylamino)-4-tosyl-1,3-oxazol-2-carbaldehyde and its analogs having the piperidino and morpholino group in the 5 position of the oxazole ring. The resulting aldehydes and their aminals were condensed with phenylhydrazine, thiosemicarbazide, N-alkylrhodanines, and 1,3-dimethylbarbituric acid to obtain 2,5-disubstituted derivatives of 4-tosyl-1,3-oxazole.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 1002–1006.Original Russian Text Copyright © 2005 by Vyzhdak, Danielova, Kiselev, Drach.     

Synthesis of heterocyclic compounds from the products of addition of polyhaloalkanes to unsaturated systems 4. Synthesis of substituted furo[2,3-d]pyrimidines

2-Amino-5-methyl-4-(2,2,2-trichloroethyl)-3-furonitrile was synthesized from 3,5,5,5-tetrachloropentan-2-one, a product of the radical addition of CCl₄ to methyl vinyl ketone, according to a scheme known for -haloketones. The product was converted via the corresponding imino-ether into N²-substituted N¹ [5-methyl-4-(2,2,2-trichloroethyl)-3-cyano-2-furyl]formamidines. Cyclization of these formamidines gave 2-methyl-3-(2,2,2-trichloroethyl)-5-R-4-imino-4,5-dihydrofuro[2,3-d]pyrimidines, which readily regroup according to Dimroth into 2-methyl-3-(2,2,2-trichloroethyl)-4-R-aminofuro[2,3-d]pyrimidines.For communication 3, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 124–129, January, 1993.     

Reduction of <Emphasis Type="Italic">N</Emphasis>-(polychloroethylidene)- and <Emphasis Type="Italic">N</Emphasis>-(1-hydroxypolychloroethyl) arenesulfonamides with adamantane in the presence of superacids

N-(2,2,2-Trichloroethylidene)-, N-(2,2-dichloro-2-phenylethylidene)-, and N-(1-hydroxy-2-polychloroethyl) arenesulfonamides reacted with adamantane in carbon tetrachloride in the presence of oleum or concd. H₂SO₄-P₄O₁₀ mixture to give the corresponding N-(2-polychloroethyl)arenesulfonamides as a result of reduc-tion of the azomethine and OH group, respectively.     

Interaction of 2-diethoxyphosphoryl-1,3,2-dithiaphosphorinane with chloral in the presence of water

Conclusion 2-Oxo-2-(2,2,2-trichloro-1-hydroxyethyl)-1,3,2-dithiaphosphorinane was formed on interaction of 2-diethoxyphosphoryl-1,3,2-dithiaphosphorinane with chloral in the presence of water.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 427–429, February, 1986.