GB1414841A - 2,5-anhydro-dalloses derivatives thereof and c-glycosylnucleosides derived therefrom - Google Patents

2,5-anhydro-dalloses derivatives thereof and c-glycosylnucleosides derived therefrom

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Publication number
GB1414841A
GB1414841A GB585873A GB585873A GB1414841A GB 1414841 A GB1414841 A GB 1414841A GB 585873 A GB585873 A GB 585873A GB 585873 A GB585873 A GB 585873A GB 1414841 A GB1414841 A GB 1414841A
Authority
GB
United Kingdom
Prior art keywords
compounds
compound
yield
groups
benzoyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB585873A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syntex USA LLC
Original Assignee
Syntex USA LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syntex USA LLC filed Critical Syntex USA LLC
Publication of GB1414841A publication Critical patent/GB1414841A/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/08—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/18—Acyclic radicals, substituted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/20—Carbocyclic rings
    • C07H15/203—Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
    • C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
    • C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
    • C07H19/052—Imidazole radicals

Abstract

1414841 2,5-anhydro-D-alloses and their nucleosides SYNTEX (USA) Inc 6 Feb 1973 [11 Feb 1972] 5858/73 Heading C2C Novel compounds I in which OR<SP>3</SP> is a hydrolyazble C 1-12 acyloxy group, t-butoxy, tetrahydropyran-2<SP>1</SP>-yloxy, 4<SP>1</SP>- methoxytetrahydropyran-2<SP>1</SP>-yloxy, benzyloxy (optionally substituted by nitro, halo, C 1-6 alkyl or C 1-6 alkoxy) and OR<SP>1</SP> and OR<SP>2</SP> are the same and are selected from the groups for OR<SP>3</SP> or together form an alkylenedioxy or cycloalkylidenedioxy group of up to 10 C atoms and R is phenyl optionally substituted by nitro, halo, C 1-6 alkyl or C 1-6 alkoxy are prepared from compound A in which R 9 is benzoyl (optionally substituted). Compound A is heated with dry halogen bromide in benzene and the product formed reacted with mercuric cyanide is nitromethane, to form a compound B in which R 10 is benzoyl. The free hydroxy (R 10 =H) compound is formed by reaction with sodium methoxide and neutralization. This is treated with isobutylene in concentrated sulphuric acid, or with dehydropyran or 4-methoxy 5,6-dihydro-2H-pyran in the presence of toluenesulphonic acid to yield the respective ether groups (R 10 =t-butyl, tetrahydropyran-2-yl or 4-methoxy-tetrahydropyran-4-yl). Compounds B are reacted with sodium hypophosphite and Raney nickel in pyridine/water/acetic acid and with an N,N<SP>1</SP>-diphenylethylenediamine to form a compound I in which R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP> are benzoyl, butyl or the above pyranyl groups. Compounds I (R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>=benzoyl) are hydrolysed and treated with (a) sodium hydride in dimethyl sulphoxide followed by benzyl chloride to form compounds I in which R<SP>1</SP>, R<SP>2</SP> and R<SP>3</SP> are benzyl or (b) a carboxylic acid anhydride in pyridene to form compounds I in which R<SP>1</SP> R<SP>2</SP> and R<SP>3</SP> are acyl. Treatment of compounds I (R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>= benzoyl) with methanolic ammonia gives the 2,3- dehydroxy compound which is reacted with a ketone and the corresponding acetal in the presence of perchloric acid to yield compounds I in which R 2 and R 3 are alkylidene or cycloalkylidene. Novel compounds III in which R<SP>4</SP> is 3(5)-carboxy-4-pyrazolyl, 3,5- dicarboxy-4-pyrazolyl, 5-carboxy-3-isoxazolyl, 4,5-dicarboxy-3-isoxazolyl or a hydrolysable ester containing up to 12 C atoms or the amide thereof, OR<SP>7</SP> is hydroxy, C 1-12 hydrolysable acyloxy group, t-butoxy tetrahydropyran-2- yloxy, 4-methoxytetrahydropyran-4-yloxy benzyloxy (optionally substituted by nitro, halo, C 1-6 alkyl or C 1-6 alkoxy) and OR<SP>5</SP> and OR<SP>6</SP> are the same and are selected from the groups OR<SP>7</SP> or are together alkylidene or cycloalkylidene of up to 10C atoms are obtained from compounds I Thus Compound VIII is prepared by reacting a novel Compound II (prepared from Compounds I by method claimed in 50993/74 (Specification 1,414,842) with carbomethoxymethylene triphenyl phosphorane to form a compound IV which upon reaction with diazomethane yields the corresponding 2-pyrazoline which is halogenated and dehydrohalogenated with chlorine in CCl 4 to yield a Compound V which yields the methyl ester of Compound VIII by one of the following treatments: (1) when OR<SP>1</SP>, OR<SP>2</SP> and OR<SP>3</SP> are ester groups with a sodium methoxide and a cation exchange resin in hydrogen form (2) when OR<SP>1</SP>, OR<SP>2</SP> and OR<SP>3</SP> are benzyloxy, with ethanol containing 10% of (10% Pd on BaSO 4 ) and hydrogen with vigorous stirring, (3) when OR<SP>1</SP>, OR<SP>2</SP> and OR<SP>3</SP> are the remaining groups with 90% trifluoroacetic acid at room temperature. Treatment of compound (V) or the methyl ester of compound VIII with methanolic ammonia yields the amide of compound VIII. Treatment of the methyl ester with sodium hydroxide gives the free carboxylic acid VIII. Compounds (IX) in which R 12 is carboxy, a C 1-12 acyloxy group or carboxamido are prepared by reacting compounds IV with ethyl diazoacetate to yield a 2-pyrazolidine which undergo a similar set of reactions as above to yield compounds IX. Compounds XIII and XV in which R 13 and R 14 are carboxy. C 1-12 acyloxy or carboxamido are prepared by reacting aldehyde II with hydroxylamine hydrochloride and the resulting oxime is chlorinated in a diethyl ether solution to give an oximino chloride which upon reaction with (a) ethyl propiolate in the presence of triethylamine gives a 5-carbethoxy-3-isoxazole derivative or with (b) dimethylacetylene dicarboxylate in the presence of triethylamine forms the 4,5-dicarbmethoxy-3- isoxazole derivative. These derivatives undergo reactions as described above to yield the various compounds XIII and XIV. Compounds III are anti-metabolic, antibacterial and anti-viral agents and form with an excipient a pharmaceutical composition.
GB585873A 1972-02-11 1973-02-06 2,5-anhydro-dalloses derivatives thereof and c-glycosylnucleosides derived therefrom Expired GB1414841A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US22561372A 1972-02-11 1972-02-11

Publications (1)

Publication Number Publication Date
GB1414841A true GB1414841A (en) 1975-11-19

Family

ID=22845555

Family Applications (2)

Application Number Title Priority Date Filing Date
GB585873A Expired GB1414841A (en) 1972-02-11 1973-02-06 2,5-anhydro-dalloses derivatives thereof and c-glycosylnucleosides derived therefrom
GB5099374A Expired GB1414842A (en) 1972-02-11 1973-02-06 2,5-anhydro-d-alloses

Family Applications After (1)

Application Number Title Priority Date Filing Date
GB5099374A Expired GB1414842A (en) 1972-02-11 1973-02-06 2,5-anhydro-d-alloses

Country Status (5)

Country Link
JP (1) JPS4891053A (en)
DE (1) DE2305894A1 (en)
ES (1) ES411472A1 (en)
FR (1) FR2181721B1 (en)
GB (2) GB1414841A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004084796A2 (en) * 2003-03-28 2004-10-07 Pharmasset Ltd. Compounds for the treatment of flaviviridae infections

Also Published As

Publication number Publication date
FR2181721A1 (en) 1973-12-07
GB1414842A (en) 1975-11-19
DE2305894A1 (en) 1973-09-06
JPS4891053A (en) 1973-11-27
FR2181721B1 (en) 1977-07-01
ES411472A1 (en) 1976-03-16

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