AU598480B2 - Sucrosetricarboxylic acid, process for its preparation, and its use - Google Patents

Sucrosetricarboxylic acid, process for its preparation, and its use Download PDF

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Publication number
AU598480B2
AU598480B2 AU63532/86A AU6353286A AU598480B2 AU 598480 B2 AU598480 B2 AU 598480B2 AU 63532/86 A AU63532/86 A AU 63532/86A AU 6353286 A AU6353286 A AU 6353286A AU 598480 B2 AU598480 B2 AU 598480B2
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AU
Australia
Prior art keywords
acid
catalyst
carried
sucrosetricarboxylic
oxidation
Prior art date
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Ceased
Application number
AU63532/86A
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AU6353286A (en
Inventor
Wolfram Fritsche-Lang
Ernst Ingo Leupold
Merten Schlingmann
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Hoechst AG
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Hoechst AG
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Publication date
Priority to DE19853535720 priority Critical patent/DE3535720A1/en
Priority to DE3535720 priority
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of AU6353286A publication Critical patent/AU6353286A/en
Application granted granted Critical
Publication of AU598480B2 publication Critical patent/AU598480B2/en
Anticipated expiration legal-status Critical
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/221Mono, di- or trisaccharides or derivatives thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A23B - A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/70Fixation, conservation, or encapsulation of flavouring agents
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A23B - A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/03Organic compounds
    • A23L29/035Organic compounds containing oxygen as heteroatom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H7/00Compounds containing non-saccharide radicals linked to saccharide radicals by a carbon-to-carbon bond
    • C07H7/02Acyclic radicals
    • C07H7/033Uronic acids

Description

~5-98,,4 8O0 P Form COMMONWEALTH OF AUSTRALIA PATEK~TS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class I t. Class Application Number: LoJged: 6s 3S 3 si.

Complete Specification Lodged: This docMent )t ,,I Accepted: CrE d I nd re Published: amnne -t IM l h Se IleiO fllad tne Priority: Printing. fidi orcor fdlaed Art: Name of Applicant: Addrass of Applicant: 01Actual Inventor: txess for Service.

HOECHST AKTIENGESELLSCHAFT 45 Bruningstrasse,D6230 Frankfurt/Main Federal Republic of Germany WOLFRAM FRITSCHELANG, ERNST INGO LEUPOLD, MERTEN SCHLINGMANN EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: SUCROSETRICARBOXYLIC ACID, PROCESS FOR ITS PREPARATION, AND ITS USE Thti following statement Is a full description of this invention, Including the best method of performing it known to la HOECHST AKTIENGESELLSCHAFT HOE 85/F 217 Dr.KH/mu Sucrosetricarboxylic acid, process for its preparation, and its use The present invention relates to sucrosetricarboxylic acid and its secondary products such az salts, lactones, esters, amides and the Like, to a process for preparing and using the same.

It is known that the catalytic oxidation of carbohydrates.

specifically that of the primary hydroxymethyl groups contained therein, proceeds slowly and in most cases nonuniformly. For instance, oligomeric carbohydrates such -as branched arabinoxylan from rye flour are oxidized in 4 days at 65 0 C in only 4% to iurnic acids. It is true that the oxidation of sucrose has also been mentioned, but statements about the isolation of the reaction products were 15 not mentioned at the time. It was merely stated that it was found in a subsequent total hydrolysis that the hydro- *ut lyzate contained only small amounts of glucuronic acid.

The oxidation of sucrose with a platinum-alumina catalyst and oxygen has also been previously described (German Patent 886,305, Example .3 and the corresponding US Patent 2,845,439, Example After a 6-hour treatment this oxidation gave only 60% of the theoretically expected yield of the corresponding glucuronic acid derivative. However, the isolation of this compound is not described.

The invention provides, then, sucrosetricarboxylic acid (B-D-arabinofuranaric-2-hexulosyL)-a-D-glucopyranosid7ronic acid) of the formula CO00 COOH o HO 41 H IO L 100DD

HO

HO OH v. bapice 1 7 1 2 The invention further provides a process for preparing sucrosetricarboxylic acid, which comprises oxidizing at a temperature in the range from 30 0 C to the boil and at a pH in the range of from 5 to 9 sucrose with oxygen, if desired in a mixture with inert gases, for example in the form of air, by means of a catalyst which contains a platinum metal on activated carbon and is significantly more effective than platinum/alumina, the catalyst containing from 5 to 10% by weight of metal. The suitable catalysts are those of platinum metals, such as palladium, but in particular platinum itself, on activated carbon, in particular the more active types. In addition to a distinct increase in the rate of oxidation, an increased selectivity of the oxidation Sbetween primary and secondary hydroxyl groups of the a carbohydrates, in particular of nonreducing carbohydrates, is achieved. Phe oxidation is carried out by o o treating the solid catalyst in an aqueous reaction medium with gaseous oxygen, i.e. in a three-phase reaction. This three-phase reaction is carried out for example in a bubble column reactor which can be operated not only batchwise but ao. also continuously. In preferred embodiments, highly u" concentrated oxygen is used and the reaction solution is recycled, which facilitates setting, and keeping constant, the pH. It is within the capacity of the skilled worker to set the reaction to a selected and suitable reaction temperature and to optimize the concentration ratio of substrate/catalyst or substrate/oxygen.

The process according to the invention is preferably carried a° out at 50 to 95 0 C, in particular 60 to 90 0 C. Conveniently atmospheric pressure is employed, but it is also possible to employ superatmospheric pressure, which is a way of increasing the supply of oxygen and/or the reaction temperature. In the process according to the invention, maintaining certain sucrose concentrations is particularly advantageous but not essential; concentrations below 5% by weight easily give rise to an over-oxidation and above by weight only to comparatively low conversions under atmospheric pressure. pH values of 6 to 8 are preferred.

The course of the reaction can be monitored by DBII/KJS:EK(11:18) i 3 sampling, for example by means of gas chromatography analysis of the derivatized, for example silylated, products.

The sucrosetricarboxylic acid formed is generally obtained in a mixture with less oxidized intermediates, i.e. various monocarboxylic and/or dicarboxylic acids. The oxidation can be discontinued at as early a stage as a tricarboxylic content of at least 20%. However, the oxidation is generally continued until at least 30 or 40 and preferably more than 60 or 70% of sucrosetricarboxylic acid has been formed. This sucrosetricarboxylic acid can be concentrated and isolated out of the reaction mixture in a conventional manner.

The process according to the invention can be carried out, for example, in a jacketed reactor which holds the suso pension of the catalyst in the aqueous medium and which 2 contains at the bottom a frit or another correspondingly oo 20 suitable porous membrane and through which a gas stream, Svery finely divided by this separating membrane, flows from the underside. For economic and safety reasons, the oxygen is expediently passed through the reaction medium at such a .rate that the catalytically activated oxygen is just con- 25 sumed at the upper end of the bubble column. To improve 05 the degree of mixing and to prolong the time of exposure to the oxygen, it can be advantageous to stir the reaction mixture.

On account of its chemical structure or structural elements, the sucrosetricarboxylic acid formed is suitable as such or in the form of its immediately obtainable reaction products, i.e. in particular mixtures with the intermediates, for applications in the field of complexing agents, for example analogously to gluconic acid and glucaric acid in washing agent formulations, as food additives, for example for the applications customary for citric acid, as a polyfunctional reactant (crosslinking) and also as a starting material for chemical reactions (hydrophilizing reagent).

4 The process according to the invention has made it possible to carry out the oxidation of sucrose in such a way as to form the hitherto unknown sucrosetricarboxylic acid.

Examples 1) In an externally heated, upright glass tube (diameter: 50 mm, Length: 80 cm) having a frit bottom and, installed at a point slightly thereabove, a discharge means for the reaction mixture, a stream of oxygen (about liters flows upwardly through a solution of 120g of sucrose in 1.2 liters of water and also 60 g of added platinum catalyst of Pt/active carbon). The acids formed by the oxidation are wholly or partly converted into the sodium salts either by feeding in sodium hydroxide o, solution, with the attendant possibility of pH control, or o by means of the corresponding molar amounts of initially introduced sodium hydrogencarbonate. At a temperature of o. 80 0 C in the oxidation and neutralization and a pH of 20 held constant during both stages, the products have after o 1 silylation and according to gas chromatography analysis the following compositions as a function of the reaction time (see Table 1): S 25 Table 1 Composition of oxidation products as a function of reaction time (in percent) 6 h 12 h 18 h Sucrose consumed Monocarboxylic acids 20.9 5.2 (2 isomers) Dicarboxylic acids 38.9 39.6 29.7 S(2 isomers) Tricarboxylic acid I 5.1 22.3 35.3 The reaction solution is filtered to remove the catalyst, and the filtrate is concentrated in a thin film evaporator and freeze-dried. Yield 104 g (86.7% by weight). The total acid content is 7.18 mEq/g (theoretical value for sucrosetricarboxylic acid 7.80 mEq/g).

5 To characterize the sucrosetricarboxylic acid (STA), the reaction mixture is converted by means of commercially available cation exchanger into the free acids and freezedried after filtration. After complete acetylation with an excess of acetic anhydride and equimolar amounts of p-toluenesulfonic acid (20 0 C, 20 the sirupy residue is chromatographed over silica gel (eluent: methylene chloride/ methanol 10:1 The pentaacetylated sucrosetricarboxylic acid obtained last with polar eluent in the chromatography is converted with catalytic amounts of sodium methanolate in methanol into the trisodium salt.

1 H-NMR (D 2 0, 400 MHz): 6 5.45 (d,H-1',Jp1' 2 3.75 Hz), 4.23-4.12 3.82, (struct. t, J3', 4 9.5 Hz, J 2 3 9.8 Hz), 3.54 (dd, J1',2'= 3.75 Hz, J2', 3 0= 9.8 Hz), 3.45 (struct. t,H-4',J 3 4

SJ

4 5 Hz).

0 0 a o 20 GC-MS (gas chromatography/mass spectroscopy) (after silylation, chemical ionization with isobutane) m/z 961 (M+1fragment of the 8-fold silylated compound, relative intensity about Cr S" 25 FAB-MS (fast atom bombardment) (sodium salt used, glycerol as matrix) m/z 451 (MH relative intensity 36%).

2) By the method of Example 1, 120 g of sucrose, dissolved in 1.2 liters of water, are oxidized at 60 0 C and pH 7.5 in a stream of oxygen. Table 2 shows the compositions determined by GC analysis.

-1 6 Table 2 Composition of oxidation products as a functi of reaction time (in percent) 8 h 28 h 52 h 8 Sucrose 1.1 MonocarboxyLic acids 28.9 10.3 5.7 4 (2 isomers) Dicarboxylic acids 35.8 36.1 27.3 23 (2 isomers) OxaLic acid 5.9 10.8 12.6 10 Tricarboxylic acid I 4.6 20.7 32.7 4C on 7 h ,.7 i.0 .9 1.9 Filtration to remove the catalyst and freeze-drying the filtrate leaves 93.8 g (78.0% by weight).

F'

I

A

14 ii

Claims (5)

  1. 7- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. Sucrosetricarboxylic acid (0-D-arabinofuranaric-2-hexulosyl)-a-D-glucopyranosideuronic acid) and its salts as a new compound. 2. A process for preparing sucrosetricarboxylic acid and its salts which comprises oxidizing at a temperature in the range from 30°C to the boil and at a pH in the range of from 5 to 9 sucrose with oxygen, if desired in a mixture with inert gases, by means of a catalyst which contains a platinum metal on activated carbon, the catalyst containing from 5 to 10% weight of metal. 3. The process as claimed in claim 2, wherein the reaction is carried out by treating the solid catalyst in an aqueous reaction medium in which sucrose is dissolved with gaseous, oxygen. C 4. The process as claimed in claim 3, wherein highly concentrated oxygen is used. The process as claimed in claim 2 or 3, wherein the oxidation is carried out at 50 to 95 0 C. 6. A process as claimed in claim 5, wherein the oxidation is carried out at 60 to 90 0 C. 7. A process as claimed in one or more of claims 2 to 6, wherein the reaction is carried out under atmospheric pressure.
  2. 8. The process as claimed in any one of claims 2 to 7, wherein the liquid reaction medium contains 5 to 20% by weight of sucrose.
  3. 9. The process as claimed in any one of claims 2 to 8, wherein the oxidation is carried out at a pH of 6 to 8. The process as claimed in any one of claims 2 to 9, wherein the catalyst is a platinum/activated carbon catalyst.
  4. 11. A method of using sucrosetricarboxylic acid as defined in claim 1 and its salts which comprises using an effective amount of said acid as an essential ingredient in 8- washing agent formulations.
  5. 12. A method of using sucrosetricarboxylic acid as defined in claim 1 and its salts which comprises using an effective amount of said acid as a food additive. DATED this 27th day of March, 1990 HOECHOT AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 2nd Floor "The Atrium" 290 Burwood Road •I HAWTHORN VICTORIA 3122 f' AUSTRALIA t 2.39:SC:(DBM) i 2.39:SC:(DBM)
AU63532/86A 1985-10-07 1986-10-06 Sucrosetricarboxylic acid, process for its preparation, and its use Ceased AU598480B2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19853535720 DE3535720A1 (en) 1985-10-07 1985-10-07 Saccharose tricarbonic acid, method for the production thereof and their use
DE3535720 1985-10-07

Publications (2)

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AU6353286A AU6353286A (en) 1987-04-09
AU598480B2 true AU598480B2 (en) 1990-06-28

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AU63532/86A Ceased AU598480B2 (en) 1985-10-07 1986-10-06 Sucrosetricarboxylic acid, process for its preparation, and its use

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EP (1) EP0218150B1 (en)
JP (1) JPH0778072B2 (en)
AT (1) AT59392T (en)
AU (1) AU598480B2 (en)
CA (1) CA1272481A (en)
DE (1) DE3535720A1 (en)
DK (1) DK165009C (en)
FI (1) FI84073C (en)
IL (1) IL80244A (en)
NZ (1) NZ217806A (en)
ZA (2) ZA8607595B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3803465A1 (en) * 1988-02-05 1989-08-17 Huels Chemische Werke Ag Method for producing oxidized substituted saccharides
DE3900677A1 (en) * 1989-01-12 1990-07-19 Hoechst Ag Method for producing a mixture of saccharose oxidation products
DE3916206A1 (en) * 1989-05-18 1990-11-22 Hoechst Ag Method for producing 1-fluor-glycuronic acids and their salts, and such new 1-flour-glycuronic acids and their salts
US5116961A (en) * 1990-12-07 1992-05-26 Hawaiian Sugar Planters' Association 1',6,6'-trimethacryloyl-2,3,3',4,4'-penta-O-methylsucrose
DE4304756C1 (en) * 1993-02-17 1994-09-08 Hoechst Ag Process for the preparation of salts, chiral, alpha-oxygen-functionalized carboxylic acids
DE19542287A1 (en) * 1995-11-14 1997-05-15 Suedzucker Ag Process for the preparation of di- and higher-oxidized carboxylic acids of carbohydrates, carbohydrate derivatives or primary alcohols
DE10319917B4 (en) * 2003-05-05 2009-01-02 Südzucker AG Mannheim/Ochsenfurt Method for selective carbohydrate oxidation using supported gold catalysts

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB679776A (en) * 1949-08-19 1952-09-24 Corn Prod Refining Co Improvements in or relating to preparation of uronic acids and derivatives thereof
US4761401A (en) * 1985-08-01 1988-08-02 Lever Brothers Company Oligosaccharides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB679776A (en) * 1949-08-19 1952-09-24 Corn Prod Refining Co Improvements in or relating to preparation of uronic acids and derivatives thereof
US4761401A (en) * 1985-08-01 1988-08-02 Lever Brothers Company Oligosaccharides

Also Published As

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AU6353286A (en) 1987-04-09
JPH0778072B2 (en) 1995-08-23
DK165009B (en) 1992-09-28
DK476586A (en) 1987-04-08
FI864021A (en) 1987-04-08
DE3535720A1 (en) 1987-04-09
JPS6293295A (en) 1987-04-28
EP0218150B1 (en) 1990-12-27
DK476586D0 (en) 1986-10-06
CA1272481A (en) 1990-08-07
EP0218150A3 (en) 1988-09-28
ZA8607595B (en) 1987-05-27
FI84073B (en) 1991-06-28
FI864021D0 (en)
ZA867595B (en) 1987-05-27
IL80244D0 (en) 1987-01-30
IL80244A (en) 1990-08-31
FI864021A0 (en) 1986-10-03
AT59392T (en) 1991-01-15
CA1272481A1 (en)
DK165009C (en) 1993-02-22
EP0218150A2 (en) 1987-04-15
NZ217806A (en) 1988-10-28
FI84073C (en) 1991-10-10

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