EP0116634A1 - Procede de production du mannitol et du sorbitol - Google Patents
Procede de production du mannitol et du sorbitolInfo
- Publication number
- EP0116634A1 EP0116634A1 EP83902934A EP83902934A EP0116634A1 EP 0116634 A1 EP0116634 A1 EP 0116634A1 EP 83902934 A EP83902934 A EP 83902934A EP 83902934 A EP83902934 A EP 83902934A EP 0116634 A1 EP0116634 A1 EP 0116634A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- glucosone
- mannitol
- sorbitol
- solution
- mixture
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/26—Hexahydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/02—Monosaccharides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Definitions
- the invention relates to a method for the production of the sugar alcohols mannitol and sorbitol in predetermined relative proportions using D-glucosone (hereafter, glucosone) as a substrate.
- D-glucosone hereafter, glucosone
- sugar alcohols or alditols, mannitol and sorbitol are used in many diverse fields including food, pharmaceuticals, cosmetics and textiles.
- Mannitol is used extensively in pharmaceutical applications as a base for chewable, multi-layered tablets.
- Sorbitol is used in numerous foods as an additive to impart body, texture and some sweetness.
- mannitol and sorbitol are widespread in nature, they are produced in commercial quantities by synthetic processes.
- a common industrial process for producing mannitol and sorbitol is through the catalytic hydrogenation of D-glucose, D-fructose (hereafter, glucose and fructose, respectively), or a mixture of the two sugars.
- Catalytic hydrogenation of invert sugar (50% glucose, 50% fructose)
- using a Raney nickel catalyst results in the production of sorbitol and mannitol in a ratio of about 3 moles of sorbitol per mole of mannitol.
- a similar ratio of products is obtained through nickel hydrogenation of high fructose corn syrup (50% glucose, 42% fructose).
- Nickel hydrogenation of pure D-fructose typically results in a 1:1 ratio of mannitol to sorbitol, whereas nickel hydrogenation of glucose typically results in only
- U.S. Patent No. 4,173,514 discloses a process for producing a mannitol-rich mixture of sorbitol and mannitol from glucose.
- the process involves the steps of epimerizing glucose in an acidic a ⁇ ueous solution to obtain a mixture of glucose and mannose, and treating this mixture with a glucose iso erase enzyme to convert a portion of the glucose in the mixture to fructose, resulting in a mixture of m'annose, fructose and glucose in a ratio of about 3 to 2 to 5.
- the mixture is catalytically hydrogenated, using a nickel catalyst, to yield a reaction product containing about 40% by weight mannitol, which is reported to be a significantly higher yield of mannitol than is obtainable by other known processes which use either glucose or sucrose as a starting material.
- the process is not satisfactory however, where mannitol-rich mixtures containing greater than 50% mannitol are desired.
- a more specific object of the invention is to provide a commercially practical method for producing a mixture of mannitol and sorbitol having a mannitol to sorbitol ratio which is substantially greater than that
- OMPI fa j , WIPQ. obtainable with known prior art methods used in producing mannitol and sorbitol commercially.
- Still another object of the invention is to provide a method for producing a mannitol-enriched mixture of products wherein the relative proportion of mannitol in the mixture may be controlled.
- the method of the invention in one form involves the preparation of a solution of glucosone and reduction of the glucosone by catalytic hydrogenation with a nickel catalyst in the presence of hydrogen.
- the reaction is terminated when a desired combined concentration of products is reached.
- the products may include the "intermediate" reduction products mannose, glucose and fructose, or the final reduction products mannitol and sorbitol.
- the method of the invention in its simplest form utilizes a solution of glucosone as the starting material.
- the glucosone may be obtained from any suitable source, and in a preferred form of the invention, is produced by the enzymatic oxidation of glucose, as taught in U.S. Patent No. 4,246,347.
- the glucose-oxidizing enzyme employed includes a carbohydrate oxidase, such as glucose-2-oxidase or pyranose-2-oxidase. Sources of these enzymes include the microorganisms Polyporous obtusus and Aspergillus oryzae.
- the concentration of the glucosone used may be as low as 1% or less, or as high as about 30% or greater.
- Examples I-III below are concerned with the conversion of a 3% glucosone solution.
- Example IV describes a reaction using a 30% glucosone solution.
- High-concentration glucosone solutions can be prepared, for example from enzymatically-produced, lyophilized glucosone.
- glucosone is reduced by catalytic hydrogenation with a nickel catalyst to produce a mixture of mannitol and sorbitol having a molar ratio of mannitol to sorbitol ranging from between about 1.5:1 to 3:1, depending upon reaction conditions, as discussed below.
- the production of a mannitol-enriched mixture of the two alditols from the catalytic hydrogenation of glucosone is unexpected for several reasons.
- U.S. Patent No. 4,321,324 discloses a method for converting glucose to fructose by catalytically hydrogenating glucosone at a preferred temperature of between about 100° and 150°C to produce fructose.
- the patent does not show any data relating to the yield of fructose from glucosone under the reaction conditions described.
- experiments performed in support of the present application have revealed the following: In the temperature range between about 20° and 80°C, the amount of fructose produced, if any, by hydrogenating glucosone in the presence of Raney nickel is quite small.
- glucosone itself is quite unstable at temperatures above 100°C, and therefore would not be expected to produce a pure reaction product under the elevated-temperature reaction conditions disclosed in the '324 patent.
- the cited patent does not show or suggest catalytically hydrogenating glucosone with a Raney nickel catalyst, under the reaction conditions in the method of the present invention, to yield a mannitol-enriched mixture of mannitol plus sorbitol.
- the prior art teaches catalytic hydrogenation of glucose, fructose or a mixture of the two sugars to produce a reaction mixture composed of mannitol plus sorbitol, and having a mannitol to sorbitol ratio of at most 1:1. None of these reactions suggest that glucosone would be a suitable starting material in a hydrogenation reaction to produce mannitol plus sorbitol, nor that the mixture obtained would be mannitol-enriched.
- the reduction of glucosone to a mannitol/sorbitol mixture is a two-step reaction.
- the first step involves reduction of glucosone to a mixture of mannose, glucose and fructose which predominates in mannose, i.e., contains more than about 50% mannose.
- each of the intermediate sugars is further reduced to mannitol or to a mannitol/sorbitol
- OMPI sfay. 1PO /?NA- ⁇ ixture The tv/o-step nature of the reaction can be best observed and exploited by using a high concentration-glucosone solution in the reaction. As will be seen in Example IV below, a 30% solution of glucosone is reduced quite slowly in the reaction, yielding predominantly mannose, fructose and glucose intermediates after about 7 days, and the final mannitol and sorbitol products after between about 14 to 19 da s ⁇ The invention thus can be practiced, by terminating the reaction at the intermediate stage, to produce a mixture of mannose, glucose and fructose which predominates in mannose.
- the preferred hydrogenation catalyst in the reaction of the invention is Raney nickel.
- Other catalysts which may be successfully employed in the invention include 5% ruthenium on carbon and 5% rhodium on carbon. Catalytic hydrogenation processes with Raney nickel are described in the prior art and are well known to those skilled in the art.
- the hydrogenation reaction is preferably carried out within a temperature range of between about 20° and 80°C. As will be seen in Example II, the ratio of mannitol to sorbitol produced in the reaction may be increased or decreased selectively by performing the hydrogenation reaction at the upper or lower end of the specified temperature range, respectively.
- the hydrogenation reaction in the method of the invention is preferably performed in a pressure range of between about 5 and 50psi.
- the pH of the reaction is preferably maintained between about 3 and 6. Reactions performed accordingly to the method of the invention and reported in Example II indicate that the greatest mannitol to sorbitol product ratios are achieved at a pH of around 4.5.
- the hydrogenation reaction is performed under
- a 3% aqueous solution (pH 4.5) of glucosone was prepared from glucose according to the teaching of above-cited U.S. Patent No. 4,246,347. To 4ml of this solution, placed in a micro-hydrogenator apparatus (Supelco Inc., Belleforte, PA), 250 mg of Raney nickel (Pfaltz and Bauer Co., Stamford, CN) was added. The mixture was stirred under 8psi hydrogen (h 2 ) gas at 25°C for 10 hours.
- h 2 8psi hydrogen
- the mixture was then analyzed by high performance liquid chromotography (HPLC) , using a BioRad Aminex Carbohydrate column, where the mobile phase was water at 85 ⁇ C, and the solvent flow through the column was set at 0.6 ml/ in. Detection was by refractive index.
- HPLC high performance liquid chromotography
- Known sugars and sugar alcohols have the following retention times on this HPLC system: glucosone- (12.3 min.), fructose (14.2 min.), mannitol (18.3 min.) and sorbitol (22.4 min.).
- the analysis showed complete conversion of glucosone to a product mixture containing mannitol and sorbitol in a ratio of 3.2:1.
- This example examines the production of a mannitol enriched mixture of mannitol and sorbitol from glucosone under different pH, pressure, and temperature reaction conditions.
- the general reaction procedure described in Example I was followed.
- the different reaction conditions and the results obtained for each are summarized in TABLE I.
- a comparison of reactions A and E in Table I shows that the ratio of mannitol to sorbitol formed in the product, mixture is increased significantly by raising the temperature at which the hydrogenation reaction is performed from 25 ⁇ C to 78°C.
- a comparison of reaction A with reactions B and C indicates that the ratio of mannitol to sorbitol in the reaction mixture is optimized by performing the reaction at a pH of around 4.5.
- a slight effect of reduced pressure on increasing the ratio of mannitol to sorbitol in the product mixture may be suggested by a comparison of reactions D and E.
- Example -III In the two examples above, the catalyst used was Raney nickel.
- the present example examines the effect of different catalyst on the hydrogenation reaction.
- the general reaction procedure for each catalyst was the same as that used in Example I, except that the period of reaction required for complete conversion of glucosone varied with different caalysts, as indicated in TABLE II.
- Raney nickel is a preferred catalyst in the present invention, producing a mannitol/sorbitol mixture having a ratio of mannitol to sorbitol about twice that produced by catalysis ' with 5% ruthenium on carbon or 5% rhodium on carbon.
- the ruthenium and rhodium catalysts were obtained from Englehardt Industries (Newark, NJ) .
- Example II illustrates the application of the method of Example I to a more concentrated glucosone solution.
- the general procedure of Example I was used, but the starting solution was a 30% aqueous glucosone solution, prepared by lyophilizing enzymatically-produced glucosone and redissolving to a concentration of 300 mg/ l.
- a small pressure reactor was charged with 3.5 ml of the glucosone solution and about 300 mg of Raney nickel.
- the reaction was carried at a room temperature at a hydrogen pressure of 40 psi, and was monitored by a HPLC, using conditions described in Example I.
- the reaction solution was monitored for glucosone, glucose, mannose, fructose, mannitol and sorbitol.
- the products consisted of about 97% mannitol and sorbitol in a ratio of about 2.5:1, the balance of the products being glucose and mannose.
- the total products formed represented about 90% of the starting material in the reaction. From the foregoing description and examples, it can be seen how various objects of the present invention are achieved. According to one important feature of the invention, it has been found that catalytic hydrogenation of glucosone with a catalyst such as Raney nickel produces a mannitol-enriched mixture of mannitol and sorbitol which may have a mannitol to sorbitol ratio of 3:1 or greater and a total content of mannitol and sorbitol, in the final reaction mixture, of 90% or greater.
- mannitol can be produced in an approximately 1:1 ratio with sorbitol by catalytic hydrogenation of fructose, and that essentially pure mannitol can be produced by catalytic hydrogenation of mannose.
- the relatively high cost " ⁇ f the starting material, fructose or mannose is a serious obstacle to commerical processes based on these reactions.
- the starting material, glucosone may be produced by a simple commerically practical reaction
- the process of the invention can be adapted by performing the hydrogenation reaction at a selected temperature and pH, to produce a mixture of mannitol and sorbitol having a desired ratio of mannitol to sorbitol.
- the method of the invention can be adapted by performing the reaction at a relatively high temperature to produce a mixture having a mannitol to sorbitol ratio of greater than 3:1.
- the reaction can be performed using high concentrations of glucosone, and may be terminated at an intermediate reaction stage to give a mixture of mannose, glucose and fructose which predominates in mannose.
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Procédé de production d'un mélange de mannitol et de sorbitol dont le rapport mannitol/sorbitol est d'au moins 1,5 pour 1,0. On oxyde enzymatiquement du glucose par l'enzyme pyranose-2-oxydase pour produire une solution de glucosone qui est réduite par une hydrogénation catalytique utilisant un catalyseur au nickel en présence d'hydrogène pour obtenir un mélange mannitol-sorbitol en mannitol enrichi que l'on peut utiliser dans des produits alimentaires, pharmaceutiques, cosmétiques et textiles.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US40999082A | 1982-08-20 | 1982-08-20 | |
US409990 | 1982-08-20 | ||
US51799683A | 1983-08-01 | 1983-08-01 | |
US517996 | 1990-05-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0116634A1 true EP0116634A1 (fr) | 1984-08-29 |
EP0116634A4 EP0116634A4 (fr) | 1985-04-24 |
Family
ID=27020823
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19830902934 Ceased EP0116634A4 (fr) | 1982-08-20 | 1983-08-16 | Procede de production du mannitol et du sorbitol. |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0116634A4 (fr) |
JP (1) | JPS59501414A (fr) |
CA (1) | CA1220748A (fr) |
DK (1) | DK115284A (fr) |
FI (1) | FI841584A0 (fr) |
WO (1) | WO1984000778A1 (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2734642B2 (ja) * | 1988-06-16 | 1998-04-02 | エスピーアイ・ポリオールス・インコーポレーテッド | 共晶マンニトール/ソルビトール多形体 |
FR2792935B1 (fr) | 1999-04-27 | 2001-07-27 | Roquette Freres | Procede de preparation d'un melange de mannitol et de sorbitol par hydrogenation continue de la glucosone |
FR2793797B1 (fr) * | 1999-05-17 | 2001-10-05 | Roquette Freres | Procede de preparation d'un melange de glucosyl-mannitol et de glucosyl-sorbitol par hydrogenation de la glucosyl-glucosone |
JP5823756B2 (ja) * | 2010-07-21 | 2015-11-25 | 国立大学法人北海道大学 | 糖アルコールの製造方法 |
FR2965819B1 (fr) * | 2010-10-08 | 2013-02-22 | Roquette Freres | Procede de fabrication de sirops de sorbitol de haute purete a partir de saccharose et utilisations |
CN115784838A (zh) * | 2022-12-07 | 2023-03-14 | 浙江华康药业股份有限公司 | 一种利用晶体葡萄糖联产甘露醇晶体和山梨醇晶体的方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH468326A (de) * | 1966-09-15 | 1969-02-15 | Hefti Ag | Verfahren zur Herstellung von Zuckeralkoholen mittels katalytischer Hydrierung |
WO1981003666A1 (fr) * | 1980-06-18 | 1981-12-24 | Standard Brands Inc | Procede de fabrication de fructose |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2983734A (en) * | 1961-05-09 | Catalytic hydrogenation | ||
GB1025813A (en) * | 1963-02-14 | 1966-04-14 | Atlas Chem Ind | Production of mannitol/sorbitol |
US3538019A (en) * | 1968-03-07 | 1970-11-03 | Atlas Chem Ind | Nickel phosphate-promoted supported nickel catalyst |
US3965199A (en) * | 1972-04-26 | 1976-06-22 | Ici United States Inc. | Hydrogenation and hydrogenolysis of carbohydrates with tungsten oxide promoted supported nickel catalyst |
US4173514A (en) * | 1977-06-02 | 1979-11-06 | Ici Americas Inc. | High mannitol process (enzymatic isomerization) |
US4292451A (en) * | 1978-03-30 | 1981-09-29 | Ici Americas Inc. | High mannitol process (alkaline hydrogenation in presence of alkali metal carbonate) |
FI791671A (fi) * | 1978-05-25 | 1979-11-26 | Ici Ltd | Foerfarande foer reducering av socker till sockeralkoholer |
US4182721A (en) * | 1978-08-30 | 1980-01-08 | Gaf Corporation | Catalytic hydrogenation of carbonyl containing organic compounds |
US4246347A (en) * | 1979-05-29 | 1981-01-20 | Cetus Corporation | Process for the production of fructose |
US4321324A (en) * | 1980-06-18 | 1982-03-23 | Standard Brands Incorporated | Process for making glucosone |
US4382150A (en) * | 1982-01-19 | 1983-05-03 | Uop Inc. | Method for hydrogenating aqueous solutions of carbohydrates |
-
1983
- 1983-08-16 WO PCT/US1983/001280 patent/WO1984000778A1/fr not_active Application Discontinuation
- 1983-08-16 JP JP50295783A patent/JPS59501414A/ja active Pending
- 1983-08-16 EP EP19830902934 patent/EP0116634A4/fr not_active Ceased
- 1983-08-19 CA CA000434965A patent/CA1220748A/fr not_active Expired
-
1984
- 1984-02-28 DK DK115284A patent/DK115284A/da not_active Application Discontinuation
- 1984-04-19 FI FI841584A patent/FI841584A0/fi not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH468326A (de) * | 1966-09-15 | 1969-02-15 | Hefti Ag | Verfahren zur Herstellung von Zuckeralkoholen mittels katalytischer Hydrierung |
WO1981003666A1 (fr) * | 1980-06-18 | 1981-12-24 | Standard Brands Inc | Procede de fabrication de fructose |
Non-Patent Citations (2)
Title |
---|
CARBOHYDRATE RESEARCH, vol. 113, 1983, pages 159-162, Elsevier Scientific Publishing Co., Amsterdam, NL; J. GEIGERT et al.: "Convenient, laboratory procedure for reducing D-glucosone to D-fructose" * |
See also references of WO8400778A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA1220748A (fr) | 1987-04-21 |
FI841584A (fi) | 1984-04-19 |
FI841584A0 (fi) | 1984-04-19 |
WO1984000778A1 (fr) | 1984-03-01 |
DK115284A (da) | 1984-03-01 |
JPS59501414A (ja) | 1984-08-09 |
DK115284D0 (da) | 1984-02-28 |
EP0116634A4 (fr) | 1985-04-24 |
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Legal Events
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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AK | Designated contracting states |
Designated state(s): BE CH DE FR GB LI NL SE |
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17P | Request for examination filed |
Effective date: 19840410 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
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18R | Application refused |
Effective date: 19870815 |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: MORELAND, MARGARET Inventor name: NEIDLEMAN, SAUL, LEWIS Inventor name: GEIGERT, JOHN |