Preparation of Chloro and Sulfanyl Derivatives of 1-(2-Deoxy-4-C-hydroxymethyl-α-L-threo-Pentofuranosyl)uracil

3'-Chloro and 3'-acetylsulfanyl derivatives of 1-(2-deoxy-4-C-hydroxymethyl-α-L-threo-pentofuranosyl)uracil were prepared by reaction of 2,3'-anhydro-1-{5'-O-benzoyl-4'-C-[(benzoyloxy)methyl]-2'-deoxy-α-L-erythro-pentofuranosyl}uracil (3) with hydrogen chloride and thioacetic acid, respectively. The reaction with hydrogen chloride gave a mixture of N-1 and N-3 substituted uracil derivatives 12 and 14. Reaction of 1-{3-O-benzoyl-4-C-[(benzoyloxy)methyl]-2-deoxy-α-L-threo-pentofuranosyl}uracil (7) with thionyl chloride and subsequent debenzoylation afforded 1-(4-C-chloromethyl-2-deoxy-β-D-erythro-pentofuranosyl)uracil (19). Nucleophilic substitution with lithium thioacetate, followed by deacylation, converted 1-{3-O-benzoyl-4-C-[(benzoyloxy)methyl]-2-deoxy-5-O-p-toluenesulfonyl-α-L-threo-pentofuranosyl}uracil (9) into 1-(2-deoxy-4-C-sulfanylmethyl-β-D-erythro-pentofuranosyl)uracil (21). The obtained thiols were oxidized with iodine or air to give 1,1'-[disulfandiylbis(2,3-dideoxy-4-hydroxymethyl-α-L-threo-pentofuranose-3,1-diyl]di(pyrimidine-2,4-(1H,3H)-dione) (17) and 1,1'-[disulfandiylbis(2,5-dideoxy-4-hydroxymethyl-α-L-threo-pentofuranose-5,1-diyl]di(pyrimidine-2,4(1H,3H)-dione) (22). Reaction of 1-{3-acetylsulfanyl-5-O-methanesulfonyl-4-C-[(benzoyloxy)methyl]-2,3-dideoxy-α-L-threo-pentofuranosyl)}uracil (24) with methanolic sodium methoxide afforded 1-(3,5-anhydro-2,3-dideoxy-4-C-hydroxymethyl-3-sulfanyl-α-L-threo-pentofuranosyl)uracil (25). The same reagent was used in the preparation of 1-(3,5-anhydro-2-deoxy-4-C-hydroxymethyl-α-L-threo-pentofuranosyl)uracil (26) from 1-{4-C-[(benzoyloxy)methyl]-2-deoxy-5-O-p-toluenesulfonyl-α-L-threo-pentofuranosyl}uracil (8). From the series of 4'-substituted 2'-deoxyuridine derivatives, synthesized in this study, solely the 4'-chloromethyl derivative 19 and the oxetane derivative 26 exhibited an appreciable activity against HIV-1 and HIV-2.

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Synthetic use of the ribosyl derivatives of 2,4- and 2,5-thiazolidinediones

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19791475 ◽

1979 ◽

Vol 44 (5) ◽

pp. 1475-1482 ◽

Cited By ~ 4

Author(s):

Hubert Hřebabecký ◽

Zdeněk Točík ◽

Jiří Beránek

Keyword(s):

Hydrazine Hydrate ◽

Hydrogen Chloride ◽

Sodium Methoxide ◽

Aqueous Ammonia ◽

Hydroxylamine Hydrochloride ◽

Acetyl Derivative ◽

High Yield ◽

Derivatives Of ◽

Methanolic Ammonia

On ribosidation of 2,4-thiazolidinedione (2,5-thiazolidinedione, respectively), the 3-β-D-ribofuranosyl derivative is formed in high yield, either the benzoyl derivative Ia (IIa) or the acetyl derivative Ib (IIb). The unsubstituted ribosyl derivative Ic is formed from the acetyl derivative Ib by methanolic hydrogen chloride. The benzoylated ribosyl-2,4-thiazolidinedione Ia affords the benzoylated ribosylurea III on reaction with aqueous ammonia, the hydroxyethylurea derivative IVa with 2-aminoethanol, the semicarbazide derivative Va with hydrazine hydrate, the ribosylhydroxyurea derivative VIa on reaction with hydroxylamine hydrochloride and triethylamine, the benzoyl derivative of ribosylbiuret VII with O-methylisourea hydrochloride and triethylamine, and (analogously) ribosylisothiobiuret VIII with S-methylisothiourea. Methanolysis of the benzoyl derivative of hydroxyethylurea IVa with sodium methoxide affords the unprotected riboside IVb. Ribosylhydroxyurea VIb is formed on debenzoylation of compound VIa with methanolic ammonia. Acetylation of compound VIb furnishes the pentaacetyl derivative VIc.

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Synthesis of 6-(alkoxymethyl)- and 6-(alkylsulfanylmethyl)furo[2,3-d]pyrimidin-2(3H)-one analogues

Canadian Journal of Chemistry ◽

10.1139/v06-042 ◽

2006 ◽

Vol 84 (4) ◽

pp. 561-568 ◽

Cited By ~ 2

Author(s):

Zlatko Janeba ◽

Noha Maklad ◽

Morris J Robins

Keyword(s):

Potassium Carbonate ◽

Thionyl Chloride ◽

Sodium Methoxide ◽

Predominant Formation ◽

Alkyl Ether ◽

Potential Inhibitors ◽

Derivatives Of

Treatment of 6-(hydroxymethyl)furo[2,3-d]pyrimidin-2(3H)-one (2) with 1-iodoalkanes and potassium carbonate resulted in predominant formation of N3 (and minor amounts of O2) alkylated regioisomers. Treatment of the 3-alkyl products (3) with thionyl chloride gave highly reactive 6-chloromethyl intermediates (5). Direct solvolysis of 5 in alcohol solutions (~50 °C) produced 3-alkyl-6-(alkoxymethyl)furopyrimidin-2(3H)-ones (6), whereas extensive decomposition of 5 occurred with added base promoters. Sonication of 5 with sodium thioacetate in acetonitrile gave the air-stable 6-(alkylsulfanylmethyl) intermediates (7), which were subjected to deacetylation (methanolic sodium methoxide) and in situ alkylation to give 3-alkyl-6-(alkylsulfanylmethyl)furo[2,3-d]pyrimidin-2(3H)-ones (8). Lipophilic derivatives of furo[2,3-d]pyrimidin-2(3H)-one are of interest as potential inhibitors of viral penetration of cells.Key words: furo[2,3-d]pyrimidin-2(3H)-ones, alkyl, ether and thioether derivatives of furo[2,3-d]pyrimidin-2(3H)-one.

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SELECTIVE NUCLEOPHILIC SUBSTITUTION AND PREFERENTIAL EPOXIDE FORMATION

Canadian Journal of Chemistry ◽

10.1139/v66-013 ◽

1966 ◽

Vol 44 (1) ◽

pp. 79-87 ◽

Cited By ~ 23

Author(s):

A. J. Dick ◽

J. K. N. Jones

Keyword(s):

Nuclear Magnetic Resonance ◽

Magnetic Resonance ◽

Nucleophilic Substitution ◽

Sodium Azide ◽

Sodium Methoxide ◽

Nuclear Magnetic Resonance Analysis ◽

Resonance Analysis ◽

Selective Substitution ◽

Derivatives Of ◽

Epoxide Formation

The tri-O-methanesulfonyl derivatives of methyl β-D-xylopyranoside, methyl β-L-arabinopyranoside, and methyl α-L-arabinopyranoside undergo selective substitution at C-4, when heated with sodium azide in N,N-dimethylformamide, to yield 4-azido derivatives with inversion of configuration at C-4. The resultant 4-azido-2,3-di-O-methanesulfonyl derivatives were converted, by reaction with sodium methoxide, into 2,3-anhydro compounds whose configurations were assigned by nuclear magnetic resonance analysis. The mechanism of epoxide formation is discussed.

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Some 1-substitution derivatives of 4-aryl-2,3-dihalogeno-1-naphthols

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19840110 ◽

1984 ◽

Vol 49 (1) ◽

pp. 110-121 ◽

Cited By ~ 1

Author(s):

Jiří Křepelka ◽

Drahuše Vlčková ◽

Milan Mělka

Keyword(s):

Thionyl Chloride ◽

Oxirane Ring ◽

Secondary Amines ◽

Two Phase ◽

Lytic Effect ◽

Primary And Secondary Amines ◽

Phase Medium ◽

Chloro Derivatives ◽

Derivatives Of

Alkylation of derivatives of 4-aryl-1-naphthols (I-V) by 2,3-epoxypropyl chloride in methanolic sodium hydroxide gave epoxy derivatives VI, VIII, IX, XI and XII, apart from products of cleavage of the oxirane ring, VII and X. Analogous alkylation of compounds I, IV and V by 2-(N,N-diethylamino)ethyl chloride hydrochloride in a two-phase medium afforded basic ethers XIII to XV. The cleavage of the oxirane ring in compound VI by the action of primary and secondary amines, piperidine and substituted piperazines led to compounds XVI-XXIV. Reaction of thionyl chloride with compounds XXI, XXII and XXIV gave chloro derivatives XXV-XXVII.Exposure of compound XXII to 4-methylbenzenesulfonyl chloride produced compound XXVIII, retaining the secondary alcoholic group. In an antineoplastic screening in vivo none of the compounds prepared had an appreciable activity. Compound XVII, being an analogue of propranolol, was used in the test of isoproterenolic tachycardia, and showed a beta-lytic effect comparable with that of propranol.

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Reactions of 3-cyano-1-methylquinolinium methyl sulphate with some C-acids and with p-nitroaniline

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19810503 ◽

1981 ◽

Vol 46 (2) ◽

pp. 503-505 ◽

Cited By ~ 6

Author(s):

Oldřich Kocián ◽

Miloslav Ferles

Keyword(s):

Sodium Methoxide ◽

Ethyl Cyanoacetate ◽

Derivatives Of

The action of malononitrile, ethyl cyanoacetate, dibenzoylmethane and/or p-nitroaniline on compound I in the presence of sodium methoxide gives rise to derivatives of 3-cyano-1-methyl-1,4-dihydroquinoline, II and III

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