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CA2798383A1 - Process for the preparation of bimosiamose - Google Patents

Process for the preparation of bimosiamose Download PDF

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Publication number
CA2798383A1
CA2798383A1 CA2798383A CA2798383A CA2798383A1 CA 2798383 A1 CA2798383 A1 CA 2798383A1 CA 2798383 A CA2798383 A CA 2798383A CA 2798383 A CA2798383 A CA 2798383A CA 2798383 A1 CA2798383 A1 CA 2798383A1
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CA
Canada
Prior art keywords
bis
hexane
phenyl
alpha
carboethoxymethylphenyl
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Abandoned
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CA2798383A
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French (fr)
Inventor
Remo Kranich
Daniel Bock
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Revotar Biopharmaceuticals AG
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Revotar Biopharmaceuticals AG
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Filing date
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Application filed by Revotar Biopharmaceuticals AG filed Critical Revotar Biopharmaceuticals AG
Publication of CA2798383A1 publication Critical patent/CA2798383A1/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/20Carbocyclic rings
    • C07H15/203Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/70Carbohydrates; Sugars; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00Drugs for disorders of the alimentary tract or the digestive system
    • A61P1/02Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00Drugs for disorders of the alimentary tract or the digestive system
    • A61P1/04Drugs for disorders of the alimentary tract or the digestive system for ulcers, gastritis or reflux esophagitis, e.g. antacids, inhibitors of acid secretion, mucosal protectants
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P11/00Drugs for disorders of the respiratory system
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P27/00Drugs for disorders of the senses
    • A61P27/02Ophthalmic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P27/00Drugs for disorders of the senses
    • A61P27/16Otologicals
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P29/00Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/55Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Engineering & Computer Science (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Molecular Biology (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • Genetics & Genomics (AREA)
  • Ophthalmology & Optometry (AREA)
  • Pulmonology (AREA)
  • Pain & Pain Management (AREA)
  • Rheumatology (AREA)
  • Epidemiology (AREA)
  • Saccharide Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for the preparation of 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-a-D-mannopyranosyloxy)-phenyl] hexane (I) which comprises the steps of converting the compound (2'-Methoxy-biphenyl-3-yl)-acetic acid (A) into the (2'-Methoxy-biphenyl-3-yl)-acetic acid ethyl ester, which is reacted with adipoyl chloride to 1,4-Bis-[3-(3-carboethoxymethylphenyl)-4-methoxybenzoyl]-butane (B) which is catalytically reduced to 1,6-Bis-[3-(3-carboethoxy-methylphenyl)-4-methoxy- phenyl] -hexane (C), which is reacted with boron tribromide in a solvent to 1,6-Bis-[3-(3- carboethoxy-methylphenyl)-4-hydroxyphenyl]-hexane (D), which is reacted with a mannopyranosyl derivative to obtain 1,6-Bis-[3-(3-carboethoxy-methylphenyl)-4-(tetra-0- pivaloyl-a-D-mannopyranosyloxy)-phenyl]-hexane (E), which is reacted to form 1,6-Bis- [3-(3-carboxymethyl-phenyl)-4-(2-a-D-mannopyranosyloxy)-phenyl] hexane, which is re- crystallized, leads to the product (I) with high purity.

Claims (15)

1. A process for the preparation of 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl] hexane, compound of formula (I) which comprises the steps of converting the compound (2'-Methoxy-biphenyl-3-yl)-acetic acid (A) into the (2'-Methoxy-biphenyl-3-yl)-acetic acid ethyl ester, which is reacted with adipoyl chloride to obtain 1,4-Bis-[3-(3-carboethoxymethylphenyl)-4-methoxybenzoyl]-butane (B) which then is catalytically reduced to form 1,6-Bis-[3-(3-carboethoxy-methylphenyl)-4-methoxyphenyl]-hexane (C), which is reacted with boron tribromide in a solvent to obtain 1,6-Bis-[3-(3-carboethoxy-methylphenyl)-4-hydroxyphenyl]-hexane (D), which is reacted with a protected mannopyranosyl derivative to obtain the 1,6-Bis-[3-(3-carbo-ethoxy-methylphenyl)-4-(tetra-O-protected-.alpha.-D-mannopyranosyloxy)-phenyl]-hexane-derivative, which then is reacted under basic reaction conditions to form 1,6-Bis-[3-(3-carboxymethyl-phenyl)-4-(2-.alpha..alpha.-D-mannopyranosyloxy)-phenyl]-hexane, which optionally is recrystallized from one, two or several organic solvents and/or water to obtain the product Bimosiamose of formula (I).
2. Process for the preparation of 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-a-D-manno-pyranosyloxy)-phenyl] hexane (I) according to claim 1, comprising the following process steps:

a) (2'-Methoxy-biphenyl-3-yl)-acetic acid (A) is converted under acidic conditions to form (2'-Methoxy-biphenyl-3-yl)-acetic acid ethyl ester which then is reacted with adipoyl chloride in a solvent to obtain 1,4-Bis-[3-(3-carboethoxymethylphenyl)-methoxybenzoyl] -butane (B), without the isolation of the intermediate (2'-Methoxy-biphenyl-3-yl)-acetic acid ethyl ester, b) 1,4-Bis- [3 -(3 -carboethoxymethylphenyl)-4-methoxybenzoyl] -butane (B) is reduced by using hydrogen and a metal catalyst to form 1,6-Bis-[3-(3-carboethoxy-methylphenyl)-4-methoxyphenyl]-hexane (C), c) 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-methoxyphenyl]-hexane (C) is reacted with boron tribromide in a solvent to obtain 1,6-Bis-[3-(3-carboethoxymethyl-phenyl)-4-hydroxyphenyl]-hexane (D), d) 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-hydroxyphenyl]-hexane (D) is reacted with a mannopyranosyl-derivative, in particular a tetra-O-pivaloyl-D-manno-pyranosyl-halide or a tetra-O-acetyl-D-mannopyranosyl-halide, to obtain 1,6-Bis-
[3-(3-carboethoxy-methylphenyl)-4-(tetra-O-pivaloyl-.alpha.-D-mannopyranosyl-oxy)-phenyl]-hexane (E), or the corresponding 1,6-Bis-[3-(3-carboethoxy-methylphenyl)-
4-(tetra-O-acetyl-.alpha.-D-mannopyranosyl-oxy)-phenyl]-hexane, e) 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-(tetra-O-pivaloyl-.alpha.-D-mannopyranosyl-oxy)-phenyl]-hexane (E) or the corresponding 1,6-Bis-[3-(3-carboethoxy-methyl-phenyl)-4-(tetra-O-acetyl-.alpha.-D-mannopyranosyl-oxy)-phenyl]-hexane is reacted under basic reaction conditions to form 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl] hexane (I), f) optionally the 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl]-hexane is recrystallized from one or several organic solvents and/or water or mixtures thereof to obtain the product of formula (I), Bimosiamose.

3. Process for the preparation of 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-manno-pyranosyloxy)-phenyl] hexane (I) according to claim 1 or 2, comprising the following process steps:

a) (2'-Methoxy-biphenyl-3-yl)-acetic acid (A) is converted under acid conditions to form (2'-Methoxy-biphenyl-3-yl)-acetic acid ethyl ester which then is reacted with adipoyl chloride and a Lewis acid in a solvent to obtain 1,4-Bis-[3-(3-carboethoxy-methylphenyl)-4-methoxybenzoyl] -butane (B) in a purity of more than 95% and a yield of at least 70%, without isolation of the intermediate (2'-Methoxy-biphenyl-3-yl)-acetic acid ethyl ester, b) 1,4-Bis-[3-(3-carboethoxymethylphenyl)-4-methoxybenzoyl]-butane (B) is reduced using hydrogen and a metal catalyst to form 1,6-Bis-[3-(3-carboethoxy-methylphenyl)-4-methoxyphenyl]-hexane (C), c) 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-methoxyphenyl]-hexane (C) is reacted with boron tribromide in a solvent at a temperature range between -20°C
to +20°C
to obtain 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-hydroxyphenyl]-hexane (D), d) 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-hydroxyphenyl]-hexane (D) is reacted with a tetra-O-pivaloyl-D-mannopyranosyl-halide in the presence of a catalytic amount of a Lewis acid and at a temperature range between -10°C to +15°C to obtain 1,6-Bis-[3-(3-carboethoxy-methylphenyl)-4-(tetra-O-pivaloyl-.alpha.-D-manno-pyranosyloxy)-phenyl]-hexane (E), e) 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-(tetra-O-pivaloyl-.alpha.-D-mannopyranosyl-oxy)-phenyl]-hexane (E) is reacted with sodium methylate and subsequently with aqueous sodium hydroxide to form 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl] hexane (I), f) 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl]-hexane is recrystallized from an organic solvent or from a mixture of an organic solvent and water to obtain the product of formula (I), Bimosiamose, in a purity of more than 98%.

4. Process for the preparation of 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-manno-pyranosyloxy)-phenyl] hexane (I) according to one of the claims 1 to 3, comprising the following process steps:

a) (2'-Methoxy-biphenyl-3-yl)-acetic acid (A) is prepared from 2-Methoxyphenyl-boronic acid and a molar excess of 10% or more of 3-Bromophenylacetic acid at a temperature range between +60°C to +99°C, and then the (2'-Methoxy-biphenyl-3-yl)-acetic acid (A) is converted under acid conditions to form (2'-Methoxy-biphenyl-3-yl)-acetic acid ethyl ester which then is reacted with adipoyl chloride and aluminum chloride in a solvent to obtain 1,4-Bis-[3-(3-carboethoxy-methylphenyl)-4-methoxybenzoyl]-butane (B), without isolation of the intermediate (2'-Methoxy-biphenyl-3-yl)-acetic acid ethyl ester, b) 1,4-Bis-[3-(3-carboethoxymethylphenyl)-4-methoxybenzoyl]-butane (B) is reduced using hydrogen, a Pd-catalyst and a mixture of ethanol, ethylacetate and trifluoroacetic acid to form 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-methoxyphenyl]-hexane (C), c) 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-methoxyphenyl]-hexane (C) is reacted with boron tribromide in dichloromethane at a temperature range from -
5°C to +5°C to obtain 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-hydroxyphenyl]-hexane (D), followed by hydrolysis of the reaction mixture with an excess of ethanol, and subsequent treatment of the hydrolyzed mixture in boiling ethanol in order to re-convert dimers and condensation products into the reaction product 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-hydroxyphenyl]-hexane (D), d) 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-hydroxyphenyl]-hexane (D) is reacted with tetra-O-pivaloyl-D-mannopyranosyl fluoride in the presence of a catalytic amount of boron trifluoride diethyletherate at a temperature range from -5°C to +10°C to obtain 1,6-Bis-[3-(3-carboethoxy-methylphenyl)-4-(tetra-O-pivaloyl-.alpha.-D-mannopyranosyloxy)-phenyl]-hexane (E), e) 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-(tetra-O-pivaloyl-.alpha.-D-mannopyranosyl-oxy)-phenyl]-hexane (E) is reacted with sodium methylate in a mixture of tetrahydrofuran and methanol at a temperature range between +15°C to +25°C and subsequently with aqueous sodium hydroxide at a temperature range between 0°C
to +10°C to form 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyl-oxy)-phenyl] hexane (I), f) 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl]-hexane (I) is recrystallized from tetrahydrofuran or from a mixture of tetrahydrofuran and water to obtain the product of formula (I), Bimosiamose, in a purity of more than 98.5 % and in the crystal form of its polymorph FORM 2.

5. Process for the preparation of 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-manno-pyranosyloxy)-phenyl] hexane (I) according to one of the claims 1 to 4, in which as step a) the compound (2'-Methoxy-biphenyl-3-yl)-acetic acid (A) is converted to (2'-Methoxy-biphenyl-3-yl)-acetic acid ethyl ester by first reacting compound (A) with thionyl chloride and then reacting with ethanol.
6. Process for the preparation of 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-manno-pyranosyloxy)-phenyl] hexane (I) according to one of the claims 1 to 5, in which as a step f) the compound 1,6-bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl]-hexane (I) is recrystallized from an ethanol/water mixture in order to obtain Bimosiamose in the crystal form of its polymorph FORM 2.
7. Process for the preparation of 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-manno-pyranosyloxy)-phenyl] hexane (I) according to one of the claims 1 to 5, in which as step f) the compound 1,6-bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl]-hexane (I) is recrystallized from an isopropanol/water mixture to obtain Bimosiamose with a purity of at least 99.0% and in the crystal form of its polymorph FORM 2.
8. Process for the preparation of 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-manno-pyranosyloxy)-phenyl] hexane (I) according to one of the claims 1 to 7, in which as step b) the intermediate 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-methoxyphenyl]-hexane (C) and in step c) the intermediate 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-hydroxyphenyl]-hexane (D) are not isolated as solid products.
9. Process for the preparation of 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl] hexane (I) according to one of the claims 1 to 8, in which as step d) the intermediate 1,6-Bis-[3-(3-carboethoxymethylphenyl)-4-hydroxyphenyl]-hexane (D) is reacted with a mixture of the .alpha./.beta.-stereoisomers of tetra-O-pivaloyl-D-mannopyranosyl halide.
10. 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl]
hexane (I) prepared by a process according to one of the claims 1 to 9 and having a purity of at least 99 %, in particular 99.5 %.
11. Pharmaceutical composition comprising 1,6-Bis-[3-(3-carboxymethylphenyl)-4-(2-.alpha.-D-mannopyranosyloxy)-phenyl] hexane (I) prepared by a process according to one of the claims 1 to 9 and having a purity of at least 99 %, in particular 99.5 %, and at least one further pharmaceutically acceptable carrier.
12. Bimosiamose and/or a salt of Bimosiamose and/or a stereoisomeric or polymorphic form thereof for the treatment, prophylaxis or diagnosis of hypersensitivity pneumonitis and pulmonary sarcoidosis.
13. Pharmaceutical composition comprising Bimosiamose and/or a salt of Bimosiamose and/or a stereoisomeric or polymorphic form thereof and at least one further pharmaceutically inactive ingredient for the treatment, prophylaxis or diagnosis of hypersensitivity pneumonitis and/or pulmonary sarcoidosis.
14. Pharmaceutical composition comprising Bimosiamose and/or a salt of Bimosiamose and/or a stereoisomeric or polymorphic form thereof and at least one further pharmaceutically active ingredient for the treatment, prophylaxis or diagnosis of hypersensitivity pneumonitis and pulmonary sarcoidosis.
15. Bimosiamose and/or a salt of Bimosiamose and/or a stereoisomeric or polymorphic form thereof for the treatment, prophylaxis or diagnosis of particular inflammations, pulmonary emphysema and eye diseases, where particular inflammations means:
eye inflammation, anaphylaxis, periodontal disease, otitis, ulcer, ulcerative colitis, mucitis, pneumonia, abdominal inflammation, and cystitis; and where eye diseases means:
corneal injury, corneal ulcer, infectious diseases in the ophthalmologic field, dry eye sensation, eye diseases, retinal macular degeneration, pterygium, uveitis and lacrimal gland disease.
CA2798383A 2010-05-07 2011-05-04 Process for the preparation of bimosiamose Abandoned CA2798383A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10162276.9 2010-05-07
EP10162276 2010-05-07
PCT/EP2011/057130 WO2011138365A1 (en) 2010-05-07 2011-05-04 Process for the preparation of bimosiamose

Publications (1)

Publication Number Publication Date
CA2798383A1 true CA2798383A1 (en) 2011-11-10

Family

ID=44276097

Family Applications (1)

Application Number Title Priority Date Filing Date
CA2798383A Abandoned CA2798383A1 (en) 2010-05-07 2011-05-04 Process for the preparation of bimosiamose

Country Status (8)

Country Link
EP (1) EP2566580A1 (en)
JP (1) JP2013525467A (en)
KR (1) KR20130056238A (en)
CN (1) CN103002951A (en)
AU (1) AU2011249843A1 (en)
CA (1) CA2798383A1 (en)
RU (1) RU2012152633A (en)
WO (1) WO2011138365A1 (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5444050A (en) * 1994-04-29 1995-08-22 Texas Biotechnology Corporation Binding of E-selectin or P-selectin to sialyl Lewisx or sialyl-Lewisa
UA52607C2 (en) 1995-06-29 2003-01-15 Тексіс Байотекнолоджі Корпорейшн Biphenyls derivatives, a pharmaceutical composition on basis thereof and a process for inhibition (variants)
US5712387A (en) * 1996-05-20 1998-01-27 Texas Biotechnology Corporation High yield stereospecific mannosylation
US5919768A (en) 1996-06-26 1999-07-06 Texas Biotechnology Corporation Di- and trivalent small molecule selectin inhibitors
EP1903049A1 (en) * 2006-09-08 2008-03-26 Revotar Biopharmaceuticals AG Crystalline forms of 1,6-Bis [3-(3-carboxymethylphenyl)-4-(2-alpha -D-mannopyranosyloxy)-phenyl] hexane
EP1897533A1 (en) * 2006-09-08 2008-03-12 Revotar Biopharmaceuticals AG Use of 1,6-Bis [3-(3-carboxymethylphenyl)-4-(2-alpha -D-mannopyranosyl-oxy)-phenyl] hexane for the preparation of cosmetic compositions
EP1958637A1 (en) * 2007-02-14 2008-08-20 Revotar Biopharmaceuticals AG Pharmaceutical composition for the treatment of IL-8 mediated diseases

Also Published As

Publication number Publication date
JP2013525467A (en) 2013-06-20
KR20130056238A (en) 2013-05-29
CN103002951A (en) 2013-03-27
WO2011138365A1 (en) 2011-11-10
AU2011249843A1 (en) 2012-11-29
RU2012152633A (en) 2014-06-20
EP2566580A1 (en) 2013-03-13

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