Reaction of nucleosides with thionyl chloride; Preparation of the deoxy derivatives of cytidine and adenosine

Hřebabecký, Hubert; Brokeš, J.; Beránek, Jaroslav

doi:10.1135/cccc19800599

Cited by 17 publications

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“…Nucleosidation reaction of silylated 5-benzyluracil with 1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose in 1, 2-dichloroethane, catalyzed with tin tetrachloride, afforded 2′,3′,5′-tri-O-benzoyl-5-benzyluridine (10) which was subsequently converted into 2′,3′,5′-tri-O-benzoyl-5-benzyl-4-thiouridine (11) by reaction with Lawesson reagent. The 4-thio derivative 11 was debenzoylated with methanolic ammonia to give free 5-benzyl-4-thiouridine (12).…”

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confidence: 99%

Preparation of 5-Benzyluracil and 5-Benzylcytosine Nucleosides as Potential Inhibitors of Uridine Phosphorylase

Krečmerová

Hřebabecký

Holý

1996

Collect. Czech. Chem. Commun.

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Reaction of 3,4,6-tri-O-acetyl-2-deoxyglucopyranosyl bromide (1) with silylated 5-benzyluracil and subsequent ammonolysis afforded α- and β-anomers of 5-benzyl-1-(2-deoxy-D-glucopyranosyl)uracil (2 and 3). Under catalysis with tin tetrachloride, silylated 5-benzyluracil reacted with 1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose to give 2',3',5'-tri-O-benzoyl-5-benzyluridine (10), which was converted into the 4-thio derivative 11 by reaction with Lawesson reagent. Debenzoylation of compound 11 afforded 5-benzyl-4-thiouridine (12), whereas its reaction with methyl iodide and deblocking gave 4-methylthiopyrimidine nucleoside 14. Amonolysis of derivative 12 at elevated temperature afforded 5-benzylcytidine (15). This reacted with thionyl chloride at room temperature to give cyclic sulfite 16 which on heating at 100 °C in dimethylformamide was converted into 5-benzyl-2,2'-cyclocytidine (17). Mild alkaline hydrolysis of compound 17 afforded 1-(β-D-arabinofuranosyl)-5-benzylcytosine (18). With boiling thionyl chloride, compound 15 formed 2',3'-cyclic sulfite 19 which on alkaline hydrolysis gave 5-benzyl-5'-chloro-5'-deoxycytidine (20). Compound 20 was reduced with tributylstannane to 5-benzyl-5'-deoxycytidine (21). Reaction of silylated 5-benzyluracil with 2-deoxy-3,5-bis(O-p-toluoyl)-D-ribofuranosyl chloride, catalyzed with mercury(II) bromide, afforded 5-benzyl-2'-deoxy-3',5'-bis(O-p-toluoyl)uridine (22) and its α-anomer 23. With Lawesson reagent, compound 22 gave 5-benzyl-4-thiouracil derivative 24 which was ammonolyzed to give 5-benzyl-2'-deoxycytidine (25). Analogously, compound 23 was converted into 5-benzyl-2-deoxy-α-cytidine (27). 5'-O-Benzoyl-5-benzyluridine (29) was converted into the 2,2'-anhydro derivative 30 which on reaction with hydrogen chloride afforded 3'-chloro-3'-deoxynucleoside 31. This compound was reduced with tributylstannane and the obtained 2'-deoxynucleoside 32 on treatment with thionyl chloride gave a mixture of erythro- and threo-3'-chloro-2',3'-dideoxynucleosides (33 and 34, respectively) which were reduced to 5'-O-benzoyl-5-benzyl-2',3'-dideoxyuridine (35). Compound 35 reacted with Lawesson reagent under formation of 4-thiouracil derivative 36 and this was deblocked to 5-benzyl-4-thio-2',3'-dideoxyuridine (37). On heating with ammonia, compound 37 was converted into 5-benzyl-2',3'-dideoxycytidine (38). Reaction of 4-thiouracil derivative with methyl iodide and subsequent hydrazinolysis afforded 4-hydrazino derivative 40 which was heated with silver oxide in ethanol to give a mixture of anomeric 5-benzyl-1-(2,3-dideoxyribofuranosyl)-2(1H)-pyrimidinones (42).

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confidence: 99%

Preparation of 5-Benzyluracil and 5-Benzylcytosine Nucleosides as Potential Inhibitors of Uridine Phosphorylase

Krečmerová

Hřebabecký

Holý

1996

Collect. Czech. Chem. Commun.

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“…ErwartungsgemaB haben wir bei der Synthese von 5'-0-TritylJ-ethyl-2'-desoxyuridin (2)') eine hohe Ausbeute (74,9 %) erhalten. (2) 7,68 g (30mmol) 5-Ethyl-2'-desoxyuridin (1) werden in IOOml trockenem Pyridin gelost und mit 9,20g (33mmol) Chlortriphenylmethan versetzt und im c)lbad von 100" 3h unter Riickflua und Feuchtigkeitsausschlua erhitzt. Die abgekiihlte Lasung wird in ein Gemisch aus 500ml Wasser und 100 ml Dichlormethan gegossen und 5 min bei Raumtemp.…”

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Bequeme Synthese von Bis‐3′‐0‐(5‐ethyl‐2′‐desoxyuridin)‐sulfoxid (KK‐Ro 258)

Keppeler

Kiefer

1983

Archiv der Pharmazie

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Die Titelverbindung 4 wurde durch Umsetzung von 5'-O-Trityl-5-ethyl-2'-desoxyundin mit Thionylchlorid in einer Mischung von Dichlormethan und Pyridin hergestellt. Die Tritylschutzgruppe wurde nach bekannten Verfahren abgespalten. Convenient Synthesis of Bis-3'-&(5-ethyl-2'-deoxyaridine) Sulfoxide (KK-Ro 258)The title compound 4 was prepared by treating 5'-O-trityld-ethyl-2'-deoxyuridine with thionyl chloride in a mixture of dichloromethane and pyridine. The trityl group was removed by standard procedures.

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“…In order to study structure-activity relationships (1)(2)(3)(4)(5), various derivatives of deoxynucleosides were recently synthesized, in particular those incorporating the cancerostatic agents 5-fluorouracil (1,6) and arabinosylcytosine (2,7). Attention was focussed on 5'-deoxy derivatives which are unable to form 5'-phosphate esters, the proposed active forms of both agents (8)(9)(10).…”

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Structure and conformation of 2′,5′-anhydroarabinosylcytosine: X-ray, ¹H nmr and ¹³C nmr analyses

Birnbaum¹,

Budêšínský²,

Beránek³

1987

Can. J. Chem.

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Crystals of 2',5'-anhydroarabinosylcytosine hemihydrate belong to the monoclinic space group P21. The cell dimensions are a = 9.643(2), b = 10.328(1), c = 10.544(2) A, P = 94.55!1)". X-ray intensity data were measured on a diffractometer and the structure was determined by direct methods. Least-squares refinement, which included all nucleoside hydrogen atoms, converged at R = 0.041 for 2298 observed reflections. The asymmetric unit contains two molecules of the nucleoside and one molecule of water. In both nucleoside molecules, the conformation about the glycosyl bond is anti, with XCN values of 15.5(3) and 26.3(3)", respectively. In the bicyclic sugar moiety, the arabinofuranose rings adopt a C(3')exo/C(2')endo conformation and are highly puckered (7, = 57"). The solution conformation was studied by 'H and I3C nmr spectroscopy. A difference nOe proton nmr spectrum and 3~(~,~) coupling constants reveal an anti conformation in solution, with torsion angles very similar to those obtained from X-ray analysis. A comparison of observed 3J(H,H) coupling constants with those calculated on the basis of a modified Kitrplus equation shows significant differences, probably due to the presence of the bicyclic system. Une comparaison des constantes de couplage 3~( H ,~) observkes avec celles calculCes en se basant sur une Cquation de Karplus modifiee prksente des differences notables qui sont probablement dues i la presence du systkme bicyclique.[Traduit par la revue]

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Reaction of nucleosides with thionyl chloride; Preparation of the deoxy derivatives of cytidine and adenosine

Cited by 17 publications

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Preparation of 5-Benzyluracil and 5-Benzylcytosine Nucleosides as Potential Inhibitors of Uridine Phosphorylase

Preparation of 5-Benzyluracil and 5-Benzylcytosine Nucleosides as Potential Inhibitors of Uridine Phosphorylase

Bequeme Synthese von Bis‐3′‐0‐(5‐ethyl‐2′‐desoxyuridin)‐sulfoxid (KK‐Ro 258)

Structure and conformation of 2′,5′-anhydroarabinosylcytosine: X-ray, ¹H nmr and ¹³C nmr analyses

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Reaction of nucleosides with thionyl chloride; Preparation of the deoxy derivatives of cytidine and adenosine

Cited by 17 publications

References 0 publications

Preparation of 5-Benzyluracil and 5-Benzylcytosine Nucleosides as Potential Inhibitors of Uridine Phosphorylase

Preparation of 5-Benzyluracil and 5-Benzylcytosine Nucleosides as Potential Inhibitors of Uridine Phosphorylase

Bequeme Synthese von Bis‐3′‐0‐(5‐ethyl‐2′‐desoxyuridin)‐sulfoxid (KK‐Ro 258)

Structure and conformation of 2′,5′-anhydroarabinosylcytosine: X-ray, 1H nmr and 13C nmr analyses

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Structure and conformation of 2′,5′-anhydroarabinosylcytosine: X-ray, ¹H nmr and ¹³C nmr analyses