Synthesis of 2'(3')-phosphates and 2'(3')-phosphorothioates of 5'-O-carboxymethylinosine and related compounds

1980 ◽  
Vol 45 (10) ◽  
pp. 2817-2829 ◽  
Author(s):  
Antonín Holý ◽  
Pavol Kois
Keyword(s):  
Acid Hydrolysis ◽  
Alkaline Hydrolysis ◽  
Phosphorus Oxychloride ◽  
Triethyl Phosphite ◽  
Subsequent Treatment ◽  
Disodium Salt ◽  
Ethyl Chloroformate ◽  
Streptomyces Aureofaciens ◽  
Derivatives Of ◽  
Related Compounds

5'-O-Carboxymethylinosine (IX) was prepared from disodium salt of 2',3'-O-isopropylideneinosine (VIII) by treatment with sodium chloroacetate, followed by acid hydrolysis. 5'-O-(2-Aminoethylamidocarbonylmethyl)inosine (XIII) was obtained by reaction of IX with p-nitrophenol and subsequent treatment with ethylenediamine. Action of triethyl phosphite on the compounds IX and XIII afforded the corresponding 5'-O-substituted 2'(3')-phosphites X and XIV which on reaction with trimethylsilyl chloride and sulfur gave the 2'(3')-phosphorothioates XI and XV. The compound IX was transformed by phosphorus oxychloride in 5'-O-carboxymethylinosine 2'(3')-phosphate (XII). Uridine, adenosine and inosine 2'(3')-phosphorothioates (Ia-Ic) were obtained from 2',3'-O-di-n-butylstannylene derivatives of the nucleosides IV by treatment with thiophosphoryl chloride followed by alkaline hydrolysis; inosine and guanosine 2'(3')-phosphorothioates (Ic,Id) were prepared by reaction of the corresponding 2'(3')-phosphites VIc, VId with trimethylsilyl chloride and sulfur. Cyclization of Ic and Id with ethyl chloroformate in the presence of tri-n-butylamine afforded inosine 2',3'-O,O-cyclophosphorothioate (VIIc) and the corresponding guanosine derivative VIId. Compounds VIIc and VIId are not cleaved by Streptomyces aureofaciens ribonuclease.

C-Lactam Derivatives of Oleanolic Acid. Hydrolysis and Further Acylation of Methyl Acetyloleanolate C-Lactam and C-Thiolactam

2014 ◽  
Vol 9 (3) ◽  
pp. 1934578X1400900
Author(s):  
Barbara Bednarczyk–Cwynar ◽  
Lucjusz Zaprutko
Keyword(s):  
Acetic Anhydride ◽  
Acid Hydrolysis ◽  
Oleanolic Acid ◽  
Alkaline Hydrolysis ◽  
Beckmann Rearrangement ◽  
Mass Spectrometric ◽  
Hydroxyl Group ◽  
Mass Spectrometric Data ◽  
Spectrometric Data ◽  
Derivatives Of

Acetyl methyl oleanolate was transformed into a seven-membered C-lactam derivative (2) using Beckmann rearrangement of the corresponding C-oxime during the last step of the synthesis. The C=O group of the lactam system was transformed into a C=S group by Lavesson's reagent. The resulting acetylthiolactam 3 and initial acetyllactam 2 were subjected to alkaline hydrolysis to obtain lactam 4 and thiolactam 5 with an unsubstituted C-3 hydroxyl group. Subsequently, compounds 4 and 5 were acylated with either succinic or acetic anhydride in pyridine. Various acylating conditions were tested for hydroxythiolactam 5. The structures of the newly obtained compounds were supported by spectral and mass spectrometric data.

Preparation of aliphatic analogues of S-adenosyl-L-homocysteine and related compounds

1981 ◽  
Vol 46 (12) ◽  
pp. 3134-3144 ◽  
Author(s):  
Antonín Holý
Keyword(s):  
Hydrogen Sulfide ◽  
Acid Hydrolysis ◽  
Sodium Salt ◽  
Liquid Ammonia ◽  
Disodium Salt ◽  
Sodium Hydrogen ◽  
Benzylidene Derivative ◽  
Polymeric Compounds ◽  
Related Compounds

Reaction of 9-((RS)-2,3-dihydroxypropyl)adenine (I) with p-toluenesulfonyl chloride afforded the 3-O-p-toluenesulfonyl derivative II which on treatment with 2,3-dihydropyran was transformed into the 3-O-p-toluenesulfonyl-2-O-tetrahydropyranyl derivative III. Reaction of II with sodium isobutyl mercaptide in liquid ammonia gave 9-((RS)-3-isobutylthio-2-hydroxypropyl)adenine (IV). Analogously, compound III and disodium salt of L-homocysteine after acid hydrolysis afforded S-((RS)-3-(adenin-9-yl)-2-hydroxypropyl)-L-homocysteine (V). 9-((2S,3S)-threo-2,3-O-Isopropylidene-4-O-p-toluenesulfonyl-2,3,4-trihydroxybutyl)adenine (VIII) was transformed in a similar way into the 4-isobutylthio derivative IX and the L-homocysteine derivative X. 9-Allyladenine (XII) on treatment with bromine in dioxane afforded 9-((RS)-2,3-dibromopropyl)adenine (XIII) and probably 3,9-(2-bromotrimethylene)adeninium bromide (XIV). Reaction of compounds XIII, XIV and 9-((RS)-2,3-bis-p-toluenesulfonyloxypropyl)adenine (XI) with sodium hydrogen sulfide or sodium thioacetate led invariably to polymeric compounds. 4-p-Toluenesulfonyloxymethyl-2,2-dimethyl-1,3-dithiolane (XVa) reacted with sodium salt of adenine to give 9-(X)-2,2-dimethyl-1,3-dithiolane-4-ylmethyl)adenine (XVIa); analogously, 4-p-toluenesulfonyloxymethyl-2-phenyl-1,3-dithiolane (XVb) afforded the 2,3-S-benzylidene derivative XVIb and 1-p-toluenesulfonyloxy-2,3-bis(benzylthio)propane (XIXb) gave 9-((RS)-2,3-bis(benzylthio)propyl)adenine (XIXc). Acetolysis of XVIa or reduction of XVIb with sodium in liquid ammonia led to 9-((RS)-2,3-dimercaptopropyl)adenine (XVIII) and the corresponding episulfide XVII.

Synthesis of N4-Amino and N4-Hydroxy Derivatives of 5-Azacytidine. A Facile Rearrangement of the N4-Amino Derivative to 5-(3-β-D-Ribofuranosylureido)-1H-1,2,4-triazole

2004 ◽  
Vol 69 (4) ◽  
pp. 905-917 ◽  
Author(s):  
Alois Pískala ◽  
Naeem B. Hanna ◽  
Milena Masojídková ◽  
Pavel Fiedler ◽  
Ivan Votruba
Keyword(s):  
Acid Hydrolysis ◽  
Alkaline Hydrolysis ◽  
Hydroxylamine Hydrochloride ◽  
Amino Derivative ◽  
Cytostatic Activity ◽  
Thermal Rearrangement ◽  
Water Solutions ◽  
Hydrolysis Of ◽  
Derivatives Of

Treatment of methoxyribosyltriazinone 4 with hydrazine in methanol afforded crude 4-hydrazino-1-β-D-ribofuranosyl-1,3,5-triazin-2(1H)-one (N4-amino-5-azacytidine) (2), which rearranged rapidly to isomeric 5-ribosylureidotriazole 6. The rearrangement proceeds easily also in water solutions of 2. Alkaline hydrolysis of 6 gave a mixture of 5-ureidotriazole 7 and 5-aminotriazole 8. Acid hydrolysis of 6 afforded only 7. This compound was also prepared by thermal rearrangement of 5-amino-1-carbamoyltriazole 9 or on reaction of cyano(formyl)guanidine 10 with hydrazine hydrochloride. Treatment of benzoylated methoxyribosyltriazinone 4a with hydrazine in methanol gave only the rearranged product 6a. Reaction of tribenzoylribosyl isocyanate 12 with aminotriazole 8 gave 1-triazolecarboxamidotribenzoylribose 13, which afforded by methanolysis oxazoloribofuranose 14 and aminotriazole 8. Compound 14 was also obtained by methanolysis of blocked ribosylcarbamate 16. Reaction of methoxyribosyltriazinone 4 with hydroxylamine in methanol afforded 4-hydroxylamino-1-β-D-ribofuranosyl-1,3,5-triazin-2(1H)-one (N4-hydroxy-5-azacytidine) (3), which on the action of excess hydroxylamine yielded 1-cyano-1-hydroxy-5-β-D-ribofuranosylisobiuret (19). Treatment of methoxy-1,3,5-triazinone 18 with a solution of hydroxylamine in methanol gave 4-hydroxylamino-1-methyl-1,3,5-triazin-2(1H)-one (N4-hydroxy-1-methyl-5-azacytosine) (17). Heating of cyano(formyl)guanidine 10 with hydroxylamine hydrochloride in water lead to the formation of triuret (21). The mechanisms of the reactions of methoxyribosyltriazinone 4 with hydrazine and hydroxylamine are discussed. Compounds 2, 6 and 19 exhibited no significant antibacterial or cytostatic activity.

1-[3-(2-Alkoxyphenoxy)-3-phenylpropyl]piperazines and some related compounds

1981 ◽  
Vol 46 (5) ◽  
pp. 1280-1287 ◽  
Author(s):  
Vladimír Valenta ◽  
Marie Bartošová ◽  
Miroslav Protiva
Keyword(s):  
Thionyl Chloride ◽  
Alkaline Hydrolysis ◽  
Mannich Bases ◽  
Ethyl Chloroformate ◽  
Substitution Reactions ◽  
Sodium Salts ◽  
Specific Effects ◽  
Chloro Derivatives ◽  
High Doses ◽  
Related Compounds

Amino alcohols VIIIa-c, prepared by reduction of the Mannich bases VIa-c, were transformed by treatment with thionyl chloride to the chloro derivatives IXa-c which were subjected to substitution reactions with the sodium salts of guaiacol, 2-ethoxyphenol and 2-benzyloxyphenol giving the title compounds IIIb,c, IVb,c and Va-c. N,N-Dimethyl-3-(2-benzyloxyphenoxy)-3-phenylpropylamine (Va) was partially demethylated by treatment with ethyl chloroformate and by the following alkaline hydrolysis to the secondary amine XI. Amines III-V and XI in high doses exhibit central excitation but do not show antireserpine activity; they have several structurally less specific effects (hypotensive, local anaesthetic, spasmolytic).

Synthesis of 5,7-dihydroxynaphthoquinone derivatives and their reactions with nucleophiles: Nitration of 2,3-dimethylnaphthalene and subsequent transformations

1976 ◽  
Vol 29 (10) ◽  
pp. 2247 ◽  
Author(s):  
HJ Banks ◽  
DW Cameron ◽  
MJ Crossley ◽  
EL Samuel
Keyword(s):  
Unusual Reaction ◽  
Nitro Derivatives ◽  
Reactions With Nucleophiles ◽  
Derivatives Of ◽  
Related Compounds ◽  
Benzenoid Ring

5,7-Dihydroxy-2,3-dimethyl-l,4-naphthoquinone (5) and related compounds have been synthesized. The quinone affords an accessible substrate for studying an unusual reaction with nucleophiles, which involves attack at the 8-position, i.e. at the benzenoid ring. An unsuccessful approach to (5) has led to tri- and tetra-nitro derivatives of 2,3-dimethylnaphthalene. Reduction of the former and subsequent conversions have given aminonaphthoquinone and perimidinone derivatives.

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