EP0236359A1 - Agents edulcorants aux peptides stabilises - Google Patents

Agents edulcorants aux peptides stabilises

Info

Publication number
EP0236359A1
EP0236359A1 EP86905110A EP86905110A EP0236359A1 EP 0236359 A1 EP0236359 A1 EP 0236359A1 EP 86905110 A EP86905110 A EP 86905110A EP 86905110 A EP86905110 A EP 86905110A EP 0236359 A1 EP0236359 A1 EP 0236359A1
Authority
EP
European Patent Office
Prior art keywords
group
dipeptide sweetener
sweetener
dipeptide
alkyl group
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.)
Withdrawn
Application number
EP86905110A
Other languages
German (de)
English (en)
Other versions
EP0236359A4 (fr
Inventor
Charles H. Stammer
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.)
University of Georgia Research Foundation Inc UGARF
Original Assignee
University of Georgia Research Foundation Inc UGARF
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 University of Georgia Research Foundation Inc UGARF filed Critical University of Georgia Research Foundation Inc UGARF
Publication of EP0236359A1 publication Critical patent/EP0236359A1/fr
Publication of EP0236359A4 publication Critical patent/EP0236359A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
    • C07K5/04—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing only normal peptide links
    • C07K5/06—Dipeptides
    • C07K5/06104—Dipeptides with the first amino acid being acidic
    • C07K5/06113—Asp- or Asn-amino acid
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/30—Artificial sweetening agents
    • A23L27/31—Artificial sweetening agents containing amino acids, nucleotides, peptides or derivatives
    • A23L27/32—Artificial sweetening agents containing amino acids, nucleotides, peptides or derivatives containing dipeptides or derivatives

Definitions

  • the present invention is related to peptide sweeteners for use in foods and beverages.
  • the invention is more specifically related to low caloric, non-toxic, edible synthetic dipeptide sweeteners.
  • glycoside steriosides which are essentially extracts from the leaf of a plant which grows in Paraguay and is quite sweet tasting.
  • These sweet tasting glycosides however suffer from a problem of aftertaste and are not believed by principal users to be the answer to the problem of stability.
  • an object of this invention to provide an artificial sweetener having sufficient sweetness and stability to more satisfactorily replace sugar in low-calorie foods and beverages than artificial sweeteners previously available.
  • Such stabilized sweeteners being resistant to enzymatic degradation and acid hydrolysis, also resist the production of undesirable by-products after consumption, thereby lessening the possibility of undesirable and possibly unsafe reactions that might occur.
  • X is H, Li, Na, or K; n is 0, 1, or 2; m is 1, 2, 3, or 4;
  • R is (1) OR 1 wherein R 1 is a C 1 C 7 alkyl group; a C 2 -C 7 alkenyl or alkynyl group; or said alkyl, alkenyl, or alkynyl group substituted with a C 1 -C 4 alkoxyl group, a hydroxyl group, or a halogen atom with the proviso that no substitution occurs on C 1 of R 1 ; (2) N(R 2 ) 2 wherein each R 2 independently represents H, an alkyl group containing at least 4 carbon atoms, or a 4-, 5- or 6-membered heterocyclic group containing one sulfur, oxygen, or nitrogen atom in the heterocyclic ring; or (3) R 3 wherein R 3 is R 1 or -CH 2 R 1 ; and
  • R' is H, halogen, or phenyl; or a pharmaceutically acceptable salt thereof.
  • the invention is also related to compositions containing compounds of the invention, such compositions also being referred to as dipeptide sweeteners or as sweetener compositions, depending on the context of the term. These compositions can also contain a stabilizing amount of an edible, food-grade stabilizing agent, which is typically a hydrocolloidal stabilizer, such as a polysaccharide gum. Compositions of the invention are particularly useful in preparing goods that will be baked as they can withstand baking temperatures and therefore make available readily produced dietetic baked goods.
  • the present invention has two principle aspects;
  • dipeptide compounds which themselves are sweet and are stabilized against acid and enzymatic hydrolysis by the presence of a cycloalkyl ring in the amino acid adjacent to the ester functionality and
  • compositions containing these dipeptides that are further stabilized by the presence of an additional stabilizing agent.
  • X is H, Li, Na, or K; n is 0, 1, or 2; m is 1, 2 , 3, or 4;
  • R is (1) OR 1 wherein R 1 is a C 1 -C 7 alkyl group; a C 2 -C 7 alkenyl or alkynyl group; or said alkyl, alkenyl, or alkynyl group substituted with a C 1 -C 4 alkoxyl group, a hydroxyl group, or a halogen atom with the proviso that no substitution occurs on C 1 of R 1 ; (2) N(R 2 ) 2 wherein each R 2 independently represents H, an alkyl group containing at least 4 carbon atoms, or a 4-, 5-, or 6-membered heterocyclic group containing one sulfur, oxygen, or nitrogen atom in the heterocyclic ring; or (3) R 3 wherein R 3 is R 1 or -CH 2 R 1 ; and
  • R' is H, halogen, or phenyl; or a pharmaceutically acceptable acid-addition salt thereof.
  • Preferred compounds of the invention are those in which X is H, Na, or K; n is 0 or 1; m is 1 or 2; and R is as defined above. Even more preferred are compounds in which n and m are both 1. Within these groupings, compounds in which R' is H are particularly preferred. When R' is not H, compounds in which the stereo-chemical configuration at the carbon to which R' is attached is the S configuration are preferred.
  • the non-cyclic, di-basic amino acid residue represented by the left portion of the formula as shown is preferably from an L-amino acid in all compounds of the invention.
  • Aspartame contains a phenylalanine residue, which is related to compounds in which R'
  • R' represents a phenyl group
  • compounds in which R' represents a hydrogen are preferred since these compounds are analogs of alanine, a less toxic amino acid, and are also not chiral, which simplifies synthesis.
  • R' is H and m is 1, the cyclic amino acid residue is a residue of cyclopropylalanine (1-aminocyclopropane carboxylic acid), a known constituent of apples and other fruit.
  • R' is halogen, fluorine, chlorine, bromine, and iodine are preferred halogens.
  • Patent 4,399,163 discloses that compounds of the formula Asp-D-Ser-NHR in which R represents an alkyl group or a heterocyclic group containing one sulfur atom in the heterocyclic ring with the alkyl or heterocyclic group containing at least four carbon atoms, are sweet. Accordingly, compounds of the invention having amides with similar bulky substituents
  • dipeptide sweeteners of the invention are those of which R 2 is -CHR 3 R 4 in which R 3 and R 4 independently represent alkyl groups containing 2-5 carbon atoms or R 3 and R 4 together represent (1) a divalent alkyl group wherein -CHR 3 R 4 represents a cycloalkyl group or (2) a divalent alkyl group containing a sulfur atom between the terminals of the divalent alkyl groups wherein -CHR 3 R 4 represents a heterocyclic group.
  • R 3 and R 4 independently represent propyl, isopropyl, or cyclopropyl groups as well as those compounds in which -CHR 3 R 4 represents a 5-or 6membered cycloalkyl group or a 4-membered heterocyclic ring containing one sulfur atom in the ring.
  • the sulfur in the heterocyclic ring can be either a divalent sulfur atom or an oxidized form of sulfur such as a sulfone or sulfoxide group.
  • R 1 can represent a C 1 -C 7 alkyl group; a C 2 -C 7 alkenyl or alkynyl group; or said alkyl, alkenyl or alkynyl group substituted with a C 1 -C 4 alkoxyl group, a hydroxyl group, or a halogen atom with the proviso that no substitution occurs on C 1 of R 1 .
  • alkyl represents both cyclic and acyclic alkyl groups.
  • an alkyl group containing 5 carbons can be either a cyclopentyl group, an n-pentyl group, a 2-pentyl group, a 3-methyl cyclobutyl group, a cyclobutylmethyl group, a 1,1dimethylpropyl group, or any other 5-carbon-containing alkyl group. Since the various combinations of organizing the atoms within these small alkyl groups are well known to those skilled in the art and are readily available either in the form of alcohols or inthe form of precursors of alcohols that can be used to make esters of the invention, all such alkyl groups are individually contemplated as if each such compound were individually named in this application.
  • a cyclopropylmethyl group falls within the scope of this definition of R and that this invention contemplates such esters as if they had been individually named, even if the cyclopropylmethyl group had not been individually written out.
  • Particularly preferred alkyl groups are those containing 2-5 carbon atoms, with those containing 3 or 4 carbon atoms being particularly preferred.
  • alkyl groups for those whose experience in organic chemistry is limited
  • examples of specific alkyl groups are ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, cyclopropylmethyl, methylcyclopropyl (substituted at the 1 or 2 position), n-pentyl, iso-pentyl, 1-methylbutyl, cyclopentyl, cyclobutylmethyl, methylcyclobutyl (the methyl being at the 1, 2, or 3 position), and cyclopentyl groups.
  • the ester substituent may also contain a C-C double bond, a C-C triple bond, or an electronegative substituent, with the proviso that the electronegative substituent is not on the carbon attached to the oxygen of the ester (i.e., not on C 1 ).
  • the alkenyl and alkynyl groups can contain up to 7 carbons. Particularly preferred groups are the propargyl and allyl groups.
  • Electronegative substituents may be present on either the alkyl, alkenyl, or alkynyl groups, although electronegative substituents are preferably present on alkyl groups rather than alkenyl or alkynyl groups.
  • Preferred electronegative substituents are C 1 -C 4 alkoxyl groups, hydroxyl groups, and halogen atoms. Fluorine is a preferred halogen atom with chlorine and bromine being less preferred in that order.
  • substituted esters include 2,2,2-trifluoroethyl, 2- methoxyethyl, 2,3-dihydroxypropyl, bis(hydroxymethyl)methyl, 2-hydroxyethyl, and 2,3- bis(methoxy)propyl.
  • esters in which R 1 is -CH 2 R 5 wherein R 5 is methyl, ethyl, or propyl substituted with a C 1 -C 4 alkoxyl group, a hydroxyl group, or a halogen.
  • Compounds which are ketones instead of esters are also encompassed by this invention when sweet. Such compounds have as the substituent R either R 1 or CH 2 R 1 . The latter substituent is preferred as the -CH 2 - replaces -O- in the esters.
  • Preferred ketones are those in which R 1 of -CH 2 R 1 is the same as a preferred R1 in an ester described above.
  • Another grouping of preferred compounds includes those compounds within the scope of the present disclosure but outside the scope originally claimed or specifically identified in U.S. Application Serial Nos. 636,091 and 677,901.
  • One method of synthesizing any of the desired cycloalkyl amino acids or ketones used in the invention is amination of the corresponding alpha-halo acid or ketone.
  • the necessary alpha-halo acids or esters can be prepared by the HellVolhard-Zelinsky halogenation of the unsubstituted acid, all of which are available commerically (e.g., cyclobutane carboxylic acid, cyclopentane carboxylic acid, and cyclohexane carboxylic acid).
  • R' is phenyl or halogen
  • compounds in which R' is hydrogen can be prepared from a ketone using a Strecker synthesis.
  • 2-phenylcyclohexanone can be reacted with KCN and ammonium carbonate to produce 2-phenyl- 1-cyanocyclohexylamine which is then hydrolyzed in acid to produce 1-amino-2-phenylcyclohexane-1-carboxylic acid.
  • compositions containing the sweeteners of the present invention are stabilized against heat, acid, and enzymes, further stabilization can be achieved against heat by including an ingestible polyhydroxypolyme'r, preferably a hydrocolloidal polysaccharide gum, in a composition containing the dipeptide compound of the invention.
  • the polyhydroxypolymer is not an essential component for producing stability to baking temperatures. However, the extra stability produced by the use of such a material is believed to result from the formation of a polyhydroxypolymer ester of the dipeptide sweetener by a transesterif ication reaction. Hydrocolloidal gums are thus preferred because they are known ingestible polyhydroxy polymers and typically contain catalytic amounts of acidic substances.
  • compositions include those in which a hydrocolloidal polysaccharide gum comprises a majority of the composition with the remainder being the compound of the invention, optionally mixed with other sweeteners or with binders, flavoring, colorings, or the like. Gum:peptide ratios are preferred to be in the range of from 100:1 to 2:1, with compositions in the range of 20:1 to 5:1 being preferred with a ratio of approximately 10:1 being most preferred.
  • these two components can be present in the presence of other materials (such as cake mixes and other solid materials described later in more detail), one preferred embodiment of the invention comprises a sugar-like sweetener that can be used as a dry sweetening composition and that consists essentially of the two components, optionally containing a binding or drying agent. In such a dry sweetening agent, the composition will preferably consist essentially of the two components:
  • B from 99 to 67 parts by weight of a hydrocolloidal polysaccharide gum, especially gum tragacanth, gum acacia, pectin, gum karaya, psyllium seed gum, larch gum, gum gatti, guar gum, locust bean gum, carrageenan, or agar.
  • a hydrocolloidal polysaccharide gum especially gum tragacanth, gum acacia, pectin, gum karaya, psyllium seed gum, larch gum, gum gatti, guar gum, locust bean gum, carrageenan, or agar.
  • Component A of such mixtures consists of the dipeptides sweeteners whose structure and composition has been previously described in this application.
  • hydrocolloidal, naturally occurring, polysaccharide gums are known, commercially available materials and are described in many references such as the ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY (3rd Edition 1983) Vol. 12, pages 57 to 67, published by John Wiley and Sons New York.
  • the term as currently used generally and as specifically used in this application refers to industrially useful polysaccharides and their derivatives that hydrate in water to form viscous solutions or dispersions.
  • Such gums are generally classified into two broad classes: natural and modified gums.
  • Natural gums includes gums obtained by microbial fermentation, plant exudates, sea weed extracts, and polysaccharides obtained from the seeds, roots, and other parts of plants. Modified gums are also referred to as semisynthetic gums. These include cellulose and starch derivatives and other industrially produced materials such as modified alginates (propylene glycol and triethylene alginate) and other modified natural gums (low-methyloxypextin, carboxymethyl bean gum, and carboxymethyl guar gum).
  • Gums are generally classified according to their polysaccharide content, which is in turn classified on the basis of the sugar constituents present in the polysaccharides.
  • gum tragacanth is a mixture of acidic polysaccharides containing galacturonic acid, galactose, fucose, xylose and arabinose. It is an exudate from the Astralaqus tree found in Iran, AMD and Turkey. Solutions are weakly acidic with a pH of 5.0 - 6.0 and a molecular weight range of 10,000 to 250,000.
  • gum acacia is a dried exudate obtained from the acacia tree found chiefly in the African Sudan. It has a large molecular weight in the range of 200,000 - 1,160,00 and is stable in a slightly acid pH to neutral range.
  • gums useful in the practice of the present invention include agar (obtained from marine algae belonging to the class Rhodophyceae), algin (a generic description for salts of alginic acid, obtained from the brown sea weed Phaeophyceae), carrageenan (a complex mixture of sulfated polysaccharides extracted from certain genera and species of Rhodophyceae), gum arabic (a dried exudate from species of the acacia tree), gum karaya (also known as sterculia gum, the dried exudate of the Sterculia urens tree), gum ghatti (an exudate from Anogeissus latifolia), guar gum (derived from the seed of the guar plant), locust bean gum (produced by milling the seeds from the lagomerous evergreen plant Ceratonia siliquia), tamarind gum (obtained from the seed colonels of the tamarind tree), psyllium seed gum (obtained from Plantaqo
  • compositions containing a hydrocolloidal gum and dipeptide of the invention can be readily prepared using known techniques. Typically, a dipeptide is dry blended with an appropriate amount of the selected hydrocolloidal gum. Further formulation may be conducted if desired (e.g., suspending agents, binders, flavorings, and the like can be added) but a simple mixture of the two components is sufficient to provide the increased stability described in this application. If desired, a liquid formulation can be prepared by dissolving the two components in water or any other ingestible solvent. In some cases, the composition will not dissolve completely but will instead form a stable suspension or dispersion. Such materials are usable in that form without further treatment.
  • polyhydroxypolymers useful in the practice of this aspect of the invention include polysaccharides, such as cellulose, starch, amylose, and amylopectin, and artificial polyhydroxy compounds such as polyvinylalcohol.
  • Polyethylene glycol which has two free hydroxy groups per molecule and has been used as a pharmaceutical carrier for peptides
  • No particular structure is required of the polyhydroxypolymer other than multiple hydroxy groups and ingestibility.
  • Preferred polymers have an average molecular weight of at least 100,000 daltons, preferably with a minimum molecular weight of 1,000 daltons.
  • the edible sweeteners of the present invention are particularly useful as stabilized sweeteners for fruit juices, fruit preparations, canned vegetables and fruits, dairy products such as egg products, milk drinks, ice cream, syrups, chocolate syrups and bars, candy, icing and dessert toppings, meat products and especially carbonated and non-carbonated beverages.
  • dairy products such as egg products, milk drinks, ice cream, syrups, chocolate syrups and bars, candy, icing and dessert toppings
  • meat products and especially carbonated and non-carbonated beverages are particularly useful as stabilized sweeteners for fruit juices, fruit preparations, canned vegetables and fruits, dairy products such as egg products, milk drinks, ice cream, syrups, chocolate syrups and bars, candy, icing and dessert toppings, meat products and especially carbonated and non-carbonated beverages.
  • A. SAMPLE FORMULATION OF SWEETENER COMPLEX In a suitable mixer of the Banberry type, dry blend 10 parts of the peptide product of Example 1 with 90 parts of a pulverulent dried exudate of the
  • This complex is the sweetener ingredient employed as a replacement for sugar in step B which involves the formation of a natural-tas.ting yellow cake which differs from prior cakes in a notable respect - it contains no sucrose.
  • a cake mix recipe such as a standard yellow cake taken from page 67 of Chapter 4 of the Better Homes and
  • the margarine is creamed and the synthetic sweetener as a wet paste is added slowly over 10 minutes with constant stirring until light.
  • the two eggs are then added along with the vanilla flavor ingredient.
  • the mixture is then beaten at moderate speed till it is fluffy.
  • the dry ingredients sweetener, cake flour, sodium bicarbonate, and salt are also mixed and sifted. They are then added slowly to the creamed mixture in several equal amounts with intermittent addition of whole milk and beating for 3 minutes after each addition.
  • n-Propyl a-Aminocycloprooane Carboxylate Hydrochloride 2 .
  • n-propanol (220 ml) and S0C1 2 (11 ml)
  • 1-aminocyclo ⁇ ro ⁇ ane-1-carboxylic acid 11.47 g, 0.11 mol
  • the solution was refluxed for 7 h.
  • N-Boc-aspartic acid- ⁇ -t-butyl ester 32.50 g, 0.11 mol
  • N-methylmorpholine NMM, 12.35 ml, 0.11 mol
  • Isobutylchloroformate 14.71 ml, 0.11 mol was added and the reaction mixture was stirred at -15oC for 10 min.
  • the precipitated zwitterion 1 was collected by filtration, washed with ice cold water, and dried to give finally 10 g of 1 .
  • Another 4.0 g of dipeptide were recovered from the mother liquor, after the mother liquor was allowed to stand at OoC for a few hours.
  • EXAMPLE 3 A series of evaluations of the stability and sweetening power of compounds of the invention have been conducted. These include an organoleptic evaluation of the sucrose equivalent sweetening power of various compounds at pH 7, an organoleptic evaluation of stability in baked goods versus Aspartame using a low-calorie cake formulation, an organoleptic evaluation of stability in various buffered solutions versus Aspartame at pH 3, 5, and 7 over three days at 75oC, and an analytical analysis by high pressure liquid chromatography of the buffer-stored samples.
  • the compounds tested were all alkyl esters of L-aspartyl- ⁇ -aminocyclo ⁇ ro ⁇ ane carboxylic acid.
  • Compound Dl was the methyl ether
  • D2 was the ethyl ester
  • D3 was the n-propyl ester
  • D4 was the iso-propyl ester
  • D5 was the n-butyl ester
  • D6 was the isobutyl ester.
  • Compounds D1-D6 were tested by a trained organoleptic evaluation panel to determine the sucrose equivalent sweetening power.
  • the sweetening factors set forth in the following table indicate the relative degree of sweetness of the various compounds. A value of 100 indicates that the compound achieved a sweetness equivalent to the indicated sucrose concentration at a concentration 1-100th of the indicated sucrose concentration. In other words, the compound D4 achieved a sweetness equivalent to 5% sucrose at a concentration of 0.05%.
  • a baking test was conducted to compare the survival of the compounds of the invention in a baking process to the survival of Aspartame.
  • Standard cake batters were prepared using either Aspartame or a compound of the invention. Sweetness levels were adjusted to produce similar sweetness in all batters. The batters were then baked in a small muffin tin and taste tested by a trained organoleptic panel. In each case tested the Aspartame sample was not sweet after baking, but the sample cakes containing compounds of the invention retained, sweetness. This test was qualitative rather than quantitative in determining sweetness after baking. Compounds D1-D6 all retained some sweetness.
  • sweeteners of the invention were significantly more stable than Aspartame under the same storage-conditions.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Genetics & Genomics (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Biophysics (AREA)
  • Biochemistry (AREA)
  • Nutrition Science (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Seasonings (AREA)
  • Peptides Or Proteins (AREA)

Abstract

Un édulcorant dipeptide comprend un composé ayant la formule (I), dans laquelle X représente H, Li, Na ou K; n représente 0, 1 ou 2; m représente 1, 2, 3 ou 4; R représente (1) OR1, où R1 représente un groupe alkyle C1-C7; un groupe alkényle ou alkynyle C2-C7; ou un tel groupe alkyle, alkényle, ou alkynyle substitué avec un groupe alcoxyle C1-C4, un groupe hydroxyle, ou un atome d'halogène, à condition que le C1 de R1 n'ait pas de substitution; (2) N(R2)2, où chaque R2 représente indépendamment H, un groupe alkyle contenant au moins 4 atomes de carbone, ou un groupe hétérocyclique à 4, 5 ou 6 membres contenant un atome de soufre, d'oxygène ou d'azote dans la chaîne hétérocyclique, ou (3) R3, où R3 représente R1 ou -CH2R1; et R' est H, halogène ou phényle; ou un de ses sels d'addition d'acide, ainsi que des compositions contenant ledit composé.
EP19860905110 1985-08-09 1986-08-06 Agents edulcorants aux peptides stabilises. Withdrawn EP0236359A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76400885A 1985-08-09 1985-08-09
US764008 1985-08-09

Publications (2)

Publication Number Publication Date
EP0236359A1 true EP0236359A1 (fr) 1987-09-16
EP0236359A4 EP0236359A4 (fr) 1987-11-23

Family

ID=25069421

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860905110 Withdrawn EP0236359A4 (fr) 1985-08-09 1986-08-06 Agents edulcorants aux peptides stabilises.

Country Status (6)

Country Link
EP (1) EP0236359A4 (fr)
JP (1) JPS63500634A (fr)
AU (1) AU6224086A (fr)
DK (1) DK182287D0 (fr)
FI (1) FI871543A0 (fr)
WO (1) WO1987000732A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572799A (en) * 1985-04-15 1986-02-25 General Foods Corporation L-Aminodicarboxylic acid amides
US9101160B2 (en) 2005-11-23 2015-08-11 The Coca-Cola Company Condiments with high-potency sweetener
US8017168B2 (en) 2006-11-02 2011-09-13 The Coca-Cola Company High-potency sweetener composition with rubisco protein, rubiscolin, rubiscolin derivatives, ace inhibitory peptides, and combinations thereof, and compositions sweetened therewith

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986003378A1 (fr) * 1984-12-11 1986-06-19 Patrick Joseph Joyce Edulcorants peptidiques thermostables

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4448716A (en) * 1982-03-04 1984-05-15 G. D. Searle & Co. Dipeptide sweetener-metal complexes
MX7527E (es) * 1983-08-16 1989-07-25 Univ Georgia Res Found Procedimiento para la sintesis de un aminoacido de ciclopropilo

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986003378A1 (fr) * 1984-12-11 1986-06-19 Patrick Joseph Joyce Edulcorants peptidiques thermostables

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8700732A1 *

Also Published As

Publication number Publication date
EP0236359A4 (fr) 1987-11-23
FI871543A (fi) 1987-04-08
DK182287A (da) 1987-04-09
JPS63500634A (ja) 1988-03-10
DK182287D0 (da) 1987-04-09
FI871543A0 (fi) 1987-04-08
WO1987000732A1 (fr) 1987-02-12
AU6224086A (en) 1987-03-05

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