GB838709A - Improvements in or relating to aminoalcohol-n-sulphonic acid compounds - Google Patents

Improvements in or relating to aminoalcohol-n-sulphonic acid compounds

Info

Publication number
GB838709A
GB838709A GB28527/56A GB2852756A GB838709A GB 838709 A GB838709 A GB 838709A GB 28527/56 A GB28527/56 A GB 28527/56A GB 2852756 A GB2852756 A GB 2852756A GB 838709 A GB838709 A GB 838709A
Authority
GB
United Kingdom
Prior art keywords
amino
acid
sodium
sulphonate
aqueous
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
GB28527/56A
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.)
Pharmacia and Upjohn Co
Original Assignee
Upjohn Co
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 Upjohn Co filed Critical Upjohn Co
Publication of GB838709A publication Critical patent/GB838709A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0063Glycosaminoglycans or mucopolysaccharides, e.g. keratan sulfate; Derivatives thereof, e.g. fucoidan

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention comprises aliphatic amino alcohol-N-sulphonic acids containing only one nitrogen atom and free of O-sulphate groups, and alkali metal or alkaline earth metal salts thereof and a process for the preparation of these compounds and of N-sulphonic acids and their alkali metal and alkali earth metal salts, other amino alcohols containing a primary or secondary amino group, without sulphating the hydroxyl groups, which comprises reacting the amino alcohol with a pyridine-sulphur trioxide complex in an aqueous alkaline medium of an alkali metal or alkaline earth metal hydroxide or carbonate at a pH between about 7 and about 11.5, yielding the desired sulpho compounds in salt form from which the free sulpho acids may be obtained. Reaction is generally effected at about 0-50 DEG C. The resulting amino-alcohol-N-sulphonic acid salts may be isolated by concentrating to remove the pyridine, adding ethanol, treating the resulting oil layer with acetone to form a solid layer, heating the solid with ethanol, extracting with aqueous alcohol and fractionally precipitating the desired salt by addition of acetone. The amino alcohol N-sulpho compounds may alternatively be recovered, after removal of piperidine, by adding NaCl and ethanol, removing precipitated inorganic compounds by filtration and then adding acetone to precipitate the desired amino alcohol N-sulphonate. The free amino alcohol N-sulphonic acids may be obtained by treating aqueous solutions of their metal salts with a strong acid cation exchange resin. Numerous amino alcohols are specified including in addition to those named below, such aliphatic amino alcohols as monoethanolamine and its N-butyl derivative, various amino butanols, 2-amino-1,3-butane diol and tris (hydroxy methyl) amino methane and aromatic amino alcohols such as b -amino-a -phenyl ethanol and a -phenyl-b -methyl amino ethanol. The N-sulphonation products of amino primary alcohols may be converted into amino carboxylic acids by oxidation of the carbinol group to -COOH and hydrolysis of the N-sulpho group to give the -NH2 group. The N-sulphonation products of the amino sec. alcohols may be reacted with ethylene oxide under alkaline conditions to give ionic detergents. The N-sulphonation products of amino tert.-alcohols can be acylated with a long-chain fatty acid chloride in the presence of pyridine to yield detergents. In examples: (1) a pyridine/SO3 complex and aqueous NaOH are added gradually to an aqueous solution of 3-amino propanol at a pH of about 11.3 yielding sodium 3-amino propanol N-sulphonate from which are prepared (a) the free acid by treating an aqueous solution of the salt with a cationexchange resin; and (b) b -amino propionic acid hydrochloride by reacting an aqueous Na2CO3 solution of the salt with sodium permanganate, filtering and refluxing the solution with hydrochloric acid; (2) p diethanolamine is reacted as in (1) at a pH of 9-10 yielding sodium diethanolamine N-sulphonate from which are prepared the free sulpho acid and imino diacetic acid hydrochloride by the methods of 1(a) and 1(b); (3) the sodium salt of D,L-serine is reacted as in (1) yielding sodium D,L-serine N-sulphonate from which are likewise obtained the free sulpho acid and glycine hydrochloride. Specification 746,870 is referred to.ALSO:The invention comprises neo-hyaluronic acid-N-sulphonic acid and its alkali metal and alkaline earth metal salts and a method of the preparation of these compounds and corresponding compounds of other amino polysaccharides wherein primary or secondary amino groups are present in which method the parent amino polysaccharide is N-sulphated without sulphation of the hydroxy groups by reaction with a pyridine-SO3 complex in an aqueous alkaline medium of an alkali metal or alkaline earth metal hydroxide or carbonate at a pH between about 7 and about 11.5, yielding the metal salts of the desired N-sulphonic acids from which the free acids may be obtained, for example, by treating aqueous solution of their salts with a strong acid cation exchange resin. The amino polysaccharides specified are chitosan, neochondroitin sulphate and neohyaluronic acid, the latter being obtained by deacetylation of chondroitin sulphate and hyaluronic acid. The sulphation is generally effected at about 0-50 DEG C. The resulting N-sulphonic acid salts may be isolated by concentrating the reaction mixture to remove the pyridine, adding ethanol to the residue, treating the resulting oil layer with acetone, extracting the solid product with aqueous alcohol and fractionally precipitating the desired salt from the extract with acetone; alternatively, after removal of pyridine, the product is dialysed to remove inorganic sulphates, a salt such as NaCl is added and the desired product precipitated by means of alcohol or acetone. The N-sulpho products may be converted into compounds useful as anticoagulants by reaction with a hydroxy-group sulphating agent such as chlorsulphonic acid in carbon tetrachloride or SO3 dissolved in sulphur dioxide whereby hydroxy groups in the polysaccharide N-sulphonate are sulphated. In examples: (1) an aqueous suspension of a flocculent chitosan, obtained by dissolving chitosan in aqueous HCl and then precipitating it by gradual addition of aqueous NaOH, is stirred while adding a pyridine -SO3 complex portionwise, a pH of about 9-10 being maintained by means of aqueous NaOH and the product, sodium chitosan-N-sulphonate, is isolated by the dialysis method; the sodium salt is dissolved in water and treated with a cationexchanger and the free chitosan N-sulphonic acid recovered from the eluate; alternatively, the sodium chitosan N-sulphonate is suspended in liquid SO2 and O-sulphated with sulphur trioxide yielding sodium O-sulpho chitosan-N-sulphonate on working up by a method comprising the dialysis procedure above described; (2) following the procedure of (1), neo-hyaluronic acid is converted into sodium neohyaluronic acid N-sulphonate and the free N-sulphonic acid and into sodium O-sulpho neo-hyaluronic acid N-sulphonate; (3) neo-chondroitin sulphate is similarly converted into the corresponding neo-chondroitin sulphate N-sulphonic acid and its sodium salt and sodium O - sulpho - neochondroitin sulphate N - sulphonate. Specification 746,870 is referred to.
GB28527/56A 1955-09-22 1956-09-18 Improvements in or relating to aminoalcohol-n-sulphonic acid compounds Expired GB838709A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US838709XA 1955-09-22 1955-09-22

Publications (1)

Publication Number Publication Date
GB838709A true GB838709A (en) 1960-06-22

Family

ID=22181198

Family Applications (1)

Application Number Title Priority Date Filing Date
GB28527/56A Expired GB838709A (en) 1955-09-22 1956-09-18 Improvements in or relating to aminoalcohol-n-sulphonic acid compounds

Country Status (1)

Country Link
GB (1) GB838709A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0340628A2 (en) * 1988-05-02 1989-11-08 Crinos Industria Farmacobiologica S.p.A. Sulfoamino derivatives of chondroitin sulfates, of dermaten sulfate and of hyaluronic acid and their pharmacological properties
EP1607406A1 (en) * 2004-06-18 2005-12-21 Taiwan Hopax Chems. Mfg. Co., Ltd Chemically modified polyaminosaccharide by a hydrocarbyl sultone compound
CN112824369A (en) * 2019-11-21 2021-05-21 万华化学集团股份有限公司 High-yield vanillin synthesis process

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0340628A2 (en) * 1988-05-02 1989-11-08 Crinos Industria Farmacobiologica S.p.A. Sulfoamino derivatives of chondroitin sulfates, of dermaten sulfate and of hyaluronic acid and their pharmacological properties
EP0340628A3 (en) * 1988-05-02 1990-01-24 Crinos Industria Farmacobiologica S.P.A. Sulfoamino derivatives of chondroitin sulfates, of dermaten sulfate and of hyaluronic acid and their pharmacological properties
AU618346B2 (en) * 1988-05-02 1991-12-19 Crinos Industria Farmacobiologica S.P.A. Sulfoamino derivatives of chondroitin sulfates, of dermatan sulfate and of hyaluronic acid and their pharmacological properties
EP1607406A1 (en) * 2004-06-18 2005-12-21 Taiwan Hopax Chems. Mfg. Co., Ltd Chemically modified polyaminosaccharide by a hydrocarbyl sultone compound
US8263763B2 (en) 2004-06-18 2012-09-11 Taiwan Hopax Chemicals Manufacturing Company, Ltd. Chemically modified polyaminosaccharide by a hydrocarbyl sultone compound
CN112824369A (en) * 2019-11-21 2021-05-21 万华化学集团股份有限公司 High-yield vanillin synthesis process
CN112824369B (en) * 2019-11-21 2022-11-08 万华化学集团股份有限公司 High-yield vanillin synthesis process

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