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GB1585200A - Method for the preparation of esters of carbohydrates and other organic compounds containing hydroxyl groups - Google Patents

Method for the preparation of esters of carbohydrates and other organic compounds containing hydroxyl groups Download PDF

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Publication number
GB1585200A
GB1585200A GB4284777A GB4284777A GB1585200A GB 1585200 A GB1585200 A GB 1585200A GB 4284777 A GB4284777 A GB 4284777A GB 4284777 A GB4284777 A GB 4284777A GB 1585200 A GB1585200 A GB 1585200A
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water
glucose
solution
stirred
poured
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AHMEDABAD TEXTILE IND
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AHMEDABAD TEXTILE IND
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/04Compounds 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00Preparation of derivatives of starch
    • C08B31/02Esters
    • C08B31/04Esters of organic acids, e.g. alkenyl-succinated starch

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Description

(54) A METHOD FOR THE PREPARATION OF ESTERS OF CARBOHYDRATES AND OTHER ORGANIC COMPOUNDS CONTAINING HYDROXYL GROUPS (71) We, AHMEDABAD TEXTILE INDUSTRY'S RESEARCH ASSOCIA TION, a Society registered under Societies Registration Act of 1856, of P.O. Polytechnic, Ahmedabad-380 015, Gujarat, India, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to a method for the preparation of esters of carbohydrates and other organic compounds containing hydroxyl groups.
Polysaccharides are polymeric materials composed of monosaccharides, and are found abundantly in nature e.g. cellulose, starch and gums. Cotton is composed essentially of cellulose.
Esters of cellulose, starch and gums are of great industrial importance and find application in textile, paper. food and pharmaceutical industries. These esters are prepared by reacting the alcoholic compounds with an acid anhydride in the presence of an acidic or alkaline catalyst~such as sulfuric acid, perchloric acid. zinc chloride, pyridine, sodium hydroxide and sodium acetate. Depending upon the polysaccharide and the catalyst used, preparation of a simple derivative like acetate can take a long time, sometimes as much as 16 to 18 hours.
This invention is related to the use of a new catalyst system. which greatly enhances the rate of esterification of organic compounds. Thus, esterification of organic compounds, whether a monomer or a polymer, can be now completed within a short time.
The catalyst system as proposed herein consists of anhydrous ferric chloride or anhydrous ferric chloride in combination with chlorides of bi- and tri-valent metals.
The reaction is very quick and for simple carbohydrates like p-glucose and p-glucitol (sorbitol) complete esterification can be achieved in just five minutes whereas in the case of polysaccharides like cellulose esterification can be completed in a few hours.
The process of this invention also permits preparation of mixed esters by employing a mixture of acid anhydrides.
According to this invention there is provided a process for esterification of organic hydroxylic compounds comprising reacting the compound with an acid anhydride and a catalyst which is anhydrous ferric chloride with or without the addition of anhydrous chlorides of other di- and tri-valent metals, such as tin, aluminium and zinc, and isolating the ester by pouring the reaction mixture in cold water followed by filtration or decantation.
In one aspect of this invention the hydroxylic compound is added to a solution or suspension of the catalyst in an acid anhydride with stirring until the compound is esterified to the desired level.
In another aspect of this invention the acid anhydride and the catalyst are dissolved or suspended in a non-reactive organic solvent followed by addition of the organic compound. The reaction may be carried out at between 20 to 1000C.
An inert solvent may be used to minimize the use of the anhydride. Without in anyway limiting the scope of this invention, the following examples are cited.
EXAMPLE 1 Acetylation of D-glucose D-Glucose (6 g.) is stirred in acetic anhydride (35 ml) containing anhydrous ferric chloride (0.6 g). Within a few minutes (about 5 minutes) a clear solution is obtained which is poured into ice water. The precipitated material is filtered and washed with water to give a (-D-glucose pentacetate in 90% yield; m.p. 111-112"C and [a]D + 103 (c 1, CHCl3).
EXAMPLE 2 Acetylation of sorbitol Sorbitol (6 g) is added to a stirred solution of anhydrous ferric chloride (0.4 g) in acetic anhydride (35 ml). Within 5 minutes, a clear solution is obtained. This is poured into ice-water with stirring to give a solid. This is filtered, washed thoroughly with water and dried to give sorbitol hexaacetate; 11.4 g (82% yield), m.p. 97-98"C and [a]D + 9.9 (c 2, acetone).
EXAMPLE 3 Preparation of myo-inositol hexaacetate Dry myo-inositol (5.2 g) is added to a stirred solution of anhydrous ferric chloride (0.1 g) in acetic anhydride (30 ml). After 5-10 minutes, the reaction mixture is filtered and the residue washed with water. The filtrate is poured into ice-water and the precipitated acetate is filtered and washed.
Both the residue (10.2 g) and regenerated solid (2 g) are found to give the same melting point 211-212"C corresponding to the myo-inositol hexaacetate. Total yield 12.2 g (97%).
EXAMPLE 4 Acetylation of ss-naphthol Powdered Bnaphthol (10 g) is added to a stirred solution of anhydrous ferric chloride (1 g) in ascetic anhydride (40 ml). Within 2-3 minutes a clear solution is obtained. This is kept stirred for 10 minutes and poured into ice-water with stirring. Shortly, a colourless solid separates, with lumps. The lumps are broken. the broken solids filtered, washed and dried. Yield is 13 g (93%). m.p. 67-78 .
Recrystallization from petroleum ether (60 80"C) gives Il g (80%) recrystallized solid having m.p. 7()-71 C.
EXAMPLE 5 Preparnrion of cellobiose octapropionate To propionic anhydride (70 ml) 4-0-(3-D- glucopyranosyl-D-glucose (cellobiose, 10 g) and anhydrous ferric chloride (0.6 g) are added. The mixture is stirred at room temperature (30-35"C) for 18 hr., when a clear solution is obtained. It is poured with stirring into 500 ml ice-water to give 22.7 g of the propionate derivative as a solid (yield 98%) m.p. 174-175 , [a]D + 35 (CHCl3).
EXAMPLE 6 Preparation of starch acetate Dry Starch (14 g) is added to a solution of anhydrous ferric chloride (0.5 g) in acetic anhydride (40 ml) at 65"C. This is stirred for 48 hr., when almost all the starch goes into solution. The solution is poured with stirring into ice-water (1.1) to give 21 g. starch acetate (yield: 84% based on triacetate), m.p. 145-150"C, [a]D + 157.1 (C 1, CHCl3); having an acetyl content of 43.82% corresponding to a D.S. of 2.88.
EXAMPLE 7 Acetylation of D-glucose in the presence of a solvent D-Glucose (10 g) is stirred in dioxan (10 ml), as solvent, and acetic anhydride (8 ml) containing anhydrous ferric chloride (0.4 g) is added. The mixture is stirred for 15 minutes and then poured into ice-water mixture to give ci-D-glucose pentaacetate in 80% yield. After recrystallization the product has m.p. 111-112 C [a]D + 102" (CHCl3).
EXAMPLE 8 Acetylation of D-glucose using mixed catalyst To a stirred solution of anhydrous ferric chloride (0.2 g) and fused zinc chloride (0.2 g) in acetic anhydride (30 ml), D-glucose (10 g) is added. After 15 minutes, the solution is poured into 200 ml of ice-water mixture with vigorous stirring. The solid separated is filtered, washed and dried (yield 75%).
Recrystallization from ethyl alcohol gives a-D-glucose pentaacetate, m.p. 111-112 [cilD + 103 (c 2 CHCl3).
Process of the Example 8 can be successfully repeated by use of equivalent amounts of anhydrous tin chloride or anhydrous aluminium chloride instead of the zinc chloride. In these cases, however, a suspension of the chloride and not a solution will be formed.
WHAT WE CLAIM IS: 1. A process for esterification of organic hydroxylic compounds comprising reacting the compound with an acid anhydride and a catalyst which is anhydrous ferric chloride with or without the addition of anhydrous chloride of other di- and tri-valent metals, such as tin, aluminium and zinc, and isolating the ester by pouring the reaction mixture in cold water followed by filtration or
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (5)

**WARNING** start of CLMS field may overlap end of DESC **. solvent followed by addition of the organic compound. The reaction may be carried out at between 20 to 1000C. An inert solvent may be used to minimize the use of the anhydride. Without in anyway limiting the scope of this invention, the following examples are cited. EXAMPLE 1 Acetylation of D-glucose D-Glucose (6 g.) is stirred in acetic anhydride (35 ml) containing anhydrous ferric chloride (0.6 g). Within a few minutes (about 5 minutes) a clear solution is obtained which is poured into ice water. The precipitated material is filtered and washed with water to give a (-D-glucose pentacetate in 90% yield; m.p. 111-112"C and [a]D + 103 (c 1, CHCl3). EXAMPLE 2 Acetylation of sorbitol Sorbitol (6 g) is added to a stirred solution of anhydrous ferric chloride (0.4 g) in acetic anhydride (35 ml). Within 5 minutes, a clear solution is obtained. This is poured into ice-water with stirring to give a solid. This is filtered, washed thoroughly with water and dried to give sorbitol hexaacetate; 11.4 g (82% yield), m.p. 97-98"C and [a]D + 9.9 (c 2, acetone). EXAMPLE 3 Preparation of myo-inositol hexaacetate Dry myo-inositol (5.2 g) is added to a stirred solution of anhydrous ferric chloride (0.1 g) in acetic anhydride (30 ml). After 5-10 minutes, the reaction mixture is filtered and the residue washed with water. The filtrate is poured into ice-water and the precipitated acetate is filtered and washed. Both the residue (10.2 g) and regenerated solid (2 g) are found to give the same melting point 211-212"C corresponding to the myo-inositol hexaacetate. Total yield 12.2 g (97%). EXAMPLE 4 Acetylation of ss-naphthol Powdered Bnaphthol (10 g) is added to a stirred solution of anhydrous ferric chloride (1 g) in ascetic anhydride (40 ml). Within 2-3 minutes a clear solution is obtained. This is kept stirred for 10 minutes and poured into ice-water with stirring. Shortly, a colourless solid separates, with lumps. The lumps are broken. the broken solids filtered, washed and dried. Yield is 13 g (93%). m.p. 67-78 . Recrystallization from petroleum ether (60 80"C) gives Il g (80%) recrystallized solid having m.p. 7()-71 C. EXAMPLE 5 Preparnrion of cellobiose octapropionate To propionic anhydride (70 ml) 4-0-(3-D- glucopyranosyl-D-glucose (cellobiose, 10 g) and anhydrous ferric chloride (0.6 g) are added. The mixture is stirred at room temperature (30-35"C) for 18 hr., when a clear solution is obtained. It is poured with stirring into 500 ml ice-water to give 22.7 g of the propionate derivative as a solid (yield 98%) m.p. 174-175 , [a]D + 35 (CHCl3). EXAMPLE 6 Preparation of starch acetate Dry Starch (14 g) is added to a solution of anhydrous ferric chloride (0.5 g) in acetic anhydride (40 ml) at 65"C. This is stirred for 48 hr., when almost all the starch goes into solution. The solution is poured with stirring into ice-water (1.1) to give 21 g. starch acetate (yield: 84% based on triacetate), m.p. 145-150"C, [a]D + 157.1 (C 1, CHCl3); having an acetyl content of 43.82% corresponding to a D.S. of 2.88. EXAMPLE 7 Acetylation of D-glucose in the presence of a solvent D-Glucose (10 g) is stirred in dioxan (10 ml), as solvent, and acetic anhydride (8 ml) containing anhydrous ferric chloride (0.4 g) is added. The mixture is stirred for 15 minutes and then poured into ice-water mixture to give ci-D-glucose pentaacetate in 80% yield. After recrystallization the product has m.p. 111-112 C [a]D + 102" (CHCl3). EXAMPLE 8 Acetylation of D-glucose using mixed catalyst To a stirred solution of anhydrous ferric chloride (0.2 g) and fused zinc chloride (0.2 g) in acetic anhydride (30 ml), D-glucose (10 g) is added. After 15 minutes, the solution is poured into 200 ml of ice-water mixture with vigorous stirring. The solid separated is filtered, washed and dried (yield 75%). Recrystallization from ethyl alcohol gives a-D-glucose pentaacetate, m.p. 111-112 [cilD + 103 (c 2 CHCl3). Process of the Example 8 can be successfully repeated by use of equivalent amounts of anhydrous tin chloride or anhydrous aluminium chloride instead of the zinc chloride. In these cases, however, a suspension of the chloride and not a solution will be formed. WHAT WE CLAIM IS:
1. A process for esterification of organic hydroxylic compounds comprising reacting the compound with an acid anhydride and a catalyst which is anhydrous ferric chloride with or without the addition of anhydrous chloride of other di- and tri-valent metals, such as tin, aluminium and zinc, and isolating the ester by pouring the reaction mixture in cold water followed by filtration or
decantation.
2. A process as claimed in claim 1 in which the hydroxylic compound is added to a solution or suspension of the catalyst in an acid anhydride with stirring until the compound is esterified to the desired level.
3. A process as claimed in claim 1 in which the acid anhydride and the catalyst are dissolved or suspended in a non-reactive organic solvent followed by addition of the organic compound.
4. A process as claimed in claim 1 or 2 in which the reaction is carried out at a temperature ranging from 20"-100"C.
5. A process for esterification of organic hydroxylic compounds substantially as herein described particularly with reference to the examples.
GB4284777A 1978-04-12 1978-04-12 Method for the preparation of esters of carbohydrates and other organic compounds containing hydroxyl groups Expired GB1585200A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6977275B2 (en) 2002-01-16 2005-12-20 Eastman Chemical Company Carbohydrate esters and polyol esters as plasticizers for polymers, compositions and articles including such plasticizers and methods of using the same
DE102007005927A1 (en) * 2007-02-06 2008-08-14 Emsland - Stärke GmbH Process for the preparation of a hydrophobic starch derivative, hydrophobic starch derivative and use of the process
CN106977555A (en) * 2017-03-28 2017-07-25 华东师范大学 A kind of method of complete acetylization of saccharides in presence of solid acid catalyst
CN116217375A (en) * 2021-12-03 2023-06-06 中国科学院宁波材料技术与工程研究所 A kind of preparation method of highly selective calcium gluconate

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6977275B2 (en) 2002-01-16 2005-12-20 Eastman Chemical Company Carbohydrate esters and polyol esters as plasticizers for polymers, compositions and articles including such plasticizers and methods of using the same
US7276546B2 (en) 2002-01-16 2007-10-02 Eastman Chemical Company Carbohydrate esters and polyol esters as plasticizers for polymers, compositions and articles including such plasticizers and methods of using the same
DE102007005927A1 (en) * 2007-02-06 2008-08-14 Emsland - Stärke GmbH Process for the preparation of a hydrophobic starch derivative, hydrophobic starch derivative and use of the process
DE102007005927B4 (en) * 2007-02-06 2011-05-05 Emsland - Stärke GmbH Process for the preparation of a hydrophobic starch derivative
CN106977555A (en) * 2017-03-28 2017-07-25 华东师范大学 A kind of method of complete acetylization of saccharides in presence of solid acid catalyst
CN116217375A (en) * 2021-12-03 2023-06-06 中国科学院宁波材料技术与工程研究所 A kind of preparation method of highly selective calcium gluconate

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