GB2026482A - 2,5-Dialkyl dihydrofuranones and 2,4,5-trialkyl dihydrofuranones, mixtures of same and organoleptic uses thereof - Google Patents
2,5-Dialkyl dihydrofuranones and 2,4,5-trialkyl dihydrofuranones, mixtures of same and organoleptic uses thereof Download PDFInfo
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- GB2026482A GB2026482A GB7924688A GB7924688A GB2026482A GB 2026482 A GB2026482 A GB 2026482A GB 7924688 A GB7924688 A GB 7924688A GB 7924688 A GB7924688 A GB 7924688A GB 2026482 A GB2026482 A GB 2026482A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
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- 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
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/205—Heterocyclic compounds
- A23L27/2052—Heterocyclic compounds having oxygen or sulfur as the only hetero atoms
Abstract
Novel compounds having the structures: <IMAGE> and a process for augmenting or enhancing the taste or aroma of a foodstuff comprising the step of adding to said foodstuff from about 0.1 ppm up to about 50 ppm by weight of said foodstuff of at least one such dialkyl or trialkyl substituted dihydrofuranones and flavor augmenting or enhancing compositions.
Description
SPECIFICATION 2,5-Dialkyl dihydrofuranones and 2,4,5-trialkyl dihydrofuranones, mixtures of same and organoleptic uses thereof
This invention relates to 2,5-dialkyl dihydrofuranones and 2,4,5-trialkyl dihydrofuranones having the structures:
and their uses in augmenting or enhancing the flavour or aroma of foodstuffs, chewing gums and toothpaste.
More specificallly this invention relates to certain novel 2,5-dialkyl dihydrofuranones and 2,4,5-trialkyl dihydrofuranones having the structures:
and the uses thereof in foodstuffs and foodstuff flavourings chewing gums and toothpastes having sweet, brown sugar, pineapple-like, caramel, buttery, scolded butter-like, dried hazelnut and earthy aromas, and sweet, brown sugar-like, pineapple-like, caramel, buttery, cheese-like, roasted, vanilla-like, dried hazelnut and earthy tastes and has for an object the provision of a composition and process for improving the flavor and aroma of foodstuffs.
There has been considerable work performed relating to substances which can be used to impart, (or enchance) flavors to (or in) various foodstuffs, chewing gums and toothpastes. These substances are used to diminish natural materials, some of which may be in short supply, and to provide more uniform properties in the finished product. Sweet, brown sugar, pineapple-like, caramel, buttery, scolded butter-like, dried hazelnut and earthy aromas, and sweet brown sugar-like, pineapple-like caramel, buttery, cheese-like, roasted, vanilla-like, dried hazelnut and earthy tastes are desirable for many uses in foodstuff flavors, chewing gum flavors and tooth pasts flavors as well as foodstuffs per se, chewing gums per se and toothpastes per se, for example, maple, caramel, vanilla, butterscotch, rum, dairy, cereal, pineapple, roasted almond, and mushroom flavored foodstuffs.
German Offenlegungsschrift 2,359,891, published on June 6, 1974 entitled "4-ALKYL-3/8-(2H )-fu ranones" discloses the use of individual compounds having the generic structure:
wherein R'1 is hydrogen, hydroxyl, carboxylic acid, or carboxylic acid ester and wherein R'2 is C1-C4 alkyl and wherein R'3 is hydrogen, or C1-C7 alkyl for use in foodstuffs and foodstuff flavors. The specific compound having the structure:
is also disclosed in said German Offenlegungsschrift 2,359,891.However, the compounds which are novel of our invention having the structures:
and the mixtures of our invention containing the compounds:
have aroma and flavor intensities and substantivities which are significantly greater than and improved over the compounds of Offenlegungsschrift 2,359,891; and are so unexpectedly advantageous in quality of aroma that these compounds and mixtures represent an advance in the art over the disclosure of German
Offenlegungsschrift 2,359,891. Furthermore, the compounds of the instant case which are novel having the structures:
and the mixture of the four compounds having the structures:
cannot be prepared by any process but that disclosed in the instant application.In addition, the processes set forth in Offenlegungsschrift 2,359,891 cannot be used to prepare the novel compounds of our invention or for that matter the mixtures of our invention.
The compounds of our invention and the mixtures of 2,5-diakyl dihydrofuranones and 2,4,5-trialkyl dihydrofuranones of our invention, which 2,5-dialkyl dihydrofuranones and 2,4,5-trialkyl dihydrofuranones have the structures:
can be prepared according to a process as described in U.S. Patent 3,980,675. However, said process described in U.S. Patent 3,980,675 is limited to the production of 2,5-dimethyl-3-(2H)-furanone having the structure:
and there is no suggestion concerning a method which can be used to prepare the compounds useful in our invention or the mixtures of the four compounds of our invention.Thus, whereas the process of 3,980,675 is limited to dimerization of the compound diacetyl followed by hydrolysis in acid media according to the reaction sequence:
the process of our invention is embodied in the reaction sequence:
Accordingly, the process of our invention also represents an advance in the art over the process of U.S.
Patent 3,980,675.
The dialkyl and trialkyl dihydrofuranones and mixtures of our invention are obtained by carrying out processes described in detail in United States Patent 3,980,675 according to the following reaction scheme:
wherein 2,3-pentane-dione is first dimerized in the presence of an aldol condensation catalyst which can be a base such as potassium hydroxide, sodium hydroxide, barrium hydroxide, zinc hydroxide, sodium acetate, potassium acetate or zinc acetate at temperatures of between -10"C and 50"C; preferably at temperatures of between 0 C and 10 C. The resulting dimers of 2,3-pentane-dione are four in number. These dimers are then hydrolyzed according to the procedure in detail in U.S.Patent 3,980,675 at temperatures in the range of 0 C up to 140"C in the presence of mineral or organic acids or in the presence of catrionic resins or water itself.
The speed of hydrolysis and the yield of the diakyl and trialkyl dihydrofuranones are functions of several factors which are independent of each other insofar as the temperature, concentrations of acid used to catalyze the hydrolysis, type of acid used and duration of the reaction are concerned. Variations in the concentration of the starting dimerization product however do not appear to significantly effect the yield of mixture of compounds having the structures:
at least within the range of parameters for converting the dimer mixture to the dihydro furanone reaction product mixture in accordance with the preferred embodiments of our process and which are as follows:
(a) temperature:
between 20"C and 1200C (b) concentration of dimerization products (in grams/100 cc of solution): :
between 3 and 11 based on 100% conversion of the 2,3-pentane-dione in the aldol
condensation reaction;
(c) acid concentration:
(in grams)100 cc of solution) between 0.04 and 4.0;
(d) duration of reaction:
between 1 and 8 hours.
The hydrolysis product can readily be extracted from the aqueous solution in which it is formed and which optionally may be saturated with a mineral salt such as, for example, sodium chloride or potassium chloride, by means of solvents such as diethyl ether, chloroform, 1 ,2-dichloro ethane or tetrahydrofurane by conventional extracting techniques.
After the extracting agent is removed by flash distillation, the resulting crude material may be fractionally distilled in vacuum to yield a number of fractions each of which fraction contains varying quantities of the compounds having the structures:
as more particularly described in the following examples.
The resulting mixtures may also be separated by means of various chromotographictechniques such as gas chromotography, or liquid chromotography or high-pressure liquid chromotography whereby the following compounds having the following properties may be obtained:
Compound Structure Name Flavor property 0 2,4,5-trimethyl-2 A sweet, caramel 3-dihydro-3- buttery and scorched t0 /\ furanone butter aroma character with a sweet, caramel, buttery, cheesey roasted and vanilla flavor characteristic at Sppm in water.
0 2,4-dimethyl-5- A dried hazelnut ethyl-2,3-dihydro- earthy, carmel-like, V \ \ 34uranone and bumery aroma with a dried hazel nut, earthy, caramel like and buttery flavor at Sppm in water.
0 -4 2-ethyl-5-methyl- A buttery, brown sugar }/ \ 2,3-dihydro-3- like, pineapple-like 0 \o /V furanone caramel-like aroma and flavor character istic at 1 Oppm in water.
O 2,5-diethyl-2,3- A brown sugar-like fih/ dihydro-8furanone caramel and buttery V \o/ v aroma and flavor characteristic at 25ppm.
On aspect of our invention resides in its commercial importance as illustrated by the fact that is is not necessary to separate out the several di and tri substituted dihydrofuranones produced according to our invention but to leave the resulting distilled mixtures in that state whereby these mixtures may be used for their specific flavor nuances in caramel, butterscotch, rum, dairy, vanilla and roasted almond flavored foodstuffs and confections.
When the dialkyl or trialkyl dihydrofuranones or mixtures of dialkyl and trialkyl dihydrofuranones of our invention are used as food flavor adjuvants or are used to augment or enhance the flavor aroma characteristics of foodstuffs, the nature of the co-ingredients included with said 2,5-dialkyl dihydrofuranones and/or 2,4,5-trialkyl dihydrofuranones in formulating the product composition will also serve to augment the organoleptic characteristics of the ultimate foodstuff treated therewith.
As used herein in regard to flavors, the term "augment" in its various forms means "supplying or imparting flavor character or note to otherwise bland, relatively tasteless substances, or augmenting the existing flavor characteristic where a natural flavor is deficient is some regard, or supplementing the existing flavor impression to modify its quality, character or taste.
As used herein in regard to food flavors, the term "enhance" is used herein to means the intensification of a flavor or aroma characteristic or note without the modification of the quality thereof. Thus, "enhancement" of a flavor or aroma means that the enhancement agent does not add any additional flavor note.
As used herein, the term "foodstuff" includes both solids and liquids, and ingestible materials or chewable but non-ingestible materials such as chewing gum or chewable medicinal tablets. Such materials usually do, but need not, have nutritional value. Thus, foodstuffs include soups, convenience foods, beverages, gelatin desserts, dairy products, candies, vegetables, cereals, soft drinks, snacks, medicinal products such as cough mixtures and cough drops and the like.
Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known in the art for such use, being extensively described in relevant literature. Apart from the requirements that any such materials be organolepticallycompatible with the dialkyl and trialkyl substituted dihydrofuranones and mixtures thereof of our invention, non-reactive with the dialkyl and trialkyl dihydrofuranones and mixtures thereof of our invention and "ingestibly" acceptable and thus non-toxic or otherwise non-deleterious, nothing particularly critical resides in the selection thereof. Accordingly, such materials which in general may be characterised as flavoring adjuvants or vehicles comprise broadly stabilizers, thickeners, surface active agents, conditioners, other flavorants and flavor intensifiers.
Stabilizer compounds include preservatives, e.g. sodium chloride; antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2- and 3- tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene (2,6-di-tertiary-butyl-4-methyl phenol), propyl gal late and the like and sequestrants, e.g., citric acid.
Thickener compounds include carriers, binders, protective colloids, suspending agents, emuisifiers and the like, e.g., agar agar, carrageenan; cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums such as gum arabic, gum tragacanth, gelatin, proteinaceous materials, lipids; carbohydrates; starches, pectins and emulsifiers, e.g., mono- and diglycerides of fatty acids, skim milk powder, hexoses, pentoses, disaccharides, e.g., sucrose corn syrup and the like.
Surface active agents include emulsifying agents, e.g., fatty acids such as capric acid, caprylic acid, palmitic acid, myristic acid and the like, mono- and diglycerides of fatty acids, lecithin, defoaming and flavor-dispersing agents such as sorbitan monostearate, potassium stearate, hydrogenated tallow alcohol and the like.
Conditioners include compounds such as bleaching and maturing agents, e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch modifiers such as peracetic acid, sodium chloride, sodium hypochloride, propylene oxide, succinic anhydride and the like, buffers and neutralizing agents, e.g., sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar and the like; colorants, e.g., carminic acid, cochineal, tumeric, curcumin and the like, firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; texturizers, anti-caking agents, e.g., aluminum calcium sulfate and tribasic calcium phosphate; enzymes, e.g., mylase, yeast foods, e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g., iron salts such as ferric phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like.
Other flavorants and flavor intensifiers include organic acids, e.g., fatty saturated acids, unsaturated acids, and amino acids; alcohols, e.g., primary and secondary alcohols; esters, carbonyl compounds including aldehydes and ketones as well as lactones; cyclic organic materials including benzene derivatives; isocyclics; heterocyclics such as furans, particularly 2,5-dimethyl-3-acetal furan and 2-methyl-2,3dihydrofuran-3-one, pyridines, pyrazines (particularly monoalkyl, dialkyl, trialkyl and tetraalkyl substituted pyrazines) and the like, sulfur-containing materials including thiazoles, disulfides, thiols, sulfides, aldehydes, (for example, 3-phenyl-4-pentenal, 3-phenyl-3-pentenal, 3-phenyl-2-pentenal, 2-phenyl-2-pentenal and 2-phenyl-3-methyl-2-butenal); disulfides and the like; other flavor potentiators such as monosodium glutamate; guanylates, inosinates, natural and syntheticflavorants such as vanillin, ethyl vanillin, diacetyl, phenethyl-2-furoate, maltol, ethyl maltol, natural gums and the like; spices, herbs, essential oils and extractives including "bitterness principles" such as theobromin, caffein, naringin and other suitable materials creating a bitter effect.
The specific flavoring adjuvant selected for use may be either solid or liquid depending upon the desired physical form of the ultimate product, i.e., foodstuff, whether simulated or natural, and should, in any event, be capable of providing an environement in which the 2,5-dialkyl dihydrofuranones and/or 2,4,5-trialkyl dihydrofuranones can be dispersed or admixed to provide a homogeneous medium. In addition, selection of one or more flavoring adjuvants as well as the quantities thereof will depend upon the precise organoleptic character desired in the finished product. Thus, in the case of flavoring compositions, ingredient selection will vary in accordance with the foodstuff to which the flavor and aroma are to be imparted. In contradistinction, in the preparation of solid products, e.g., simulated foodstuffs, ingredients capable of providing normally solid compositions should be selected such as various cellulose derivatives.
As will be appreciated by those skilled in the art, the amount of 2,5-dialkyl dihydrofuranones and/or 2,4,5-trialkyl dihydrofuranones employed in a particular instance can vary over a relatively wide range whereby to its desired organoleptic effects having reference to the nature of the product are achieved. All parts and percentages given herein are by weight unless otherwise specified. Thus, correspondingly greater amounts would be necessary in those instances wherein the ultimate food composition to be flavored is relatively bland to the taste, whereas relatively minor quantities may suffice for purposes of enhancing the composition merely deficient in natural flavor or aroma.Thus, the primary requirement is that the amount selected to be effective, i.e. sufficient to alter the organoleptic characteristics of the parent composition, whether foodstuff per se or flavoring composition. Thus, the use of insufficient quantities of 2,5-dialkyl dihydrofuranones and/or 2,4,5-trialkyl dihydrofuranones will, of course, substantially vitiate any possibility of obtaining the desired results while excess quantities prove needlessly costly and in extreme cases, may disrupt the flavor-aroma balance, thus proving self-defeating. Accordingly, the terminology "effective amount" and "sufficient amount" is to be accorded a significance in the context of the present invention consistent with the obtention of desired flavoring effects.
Thus, and with respect to ultimate food compositions, it is found that quantities of 2,5-dialkyl dihydrofuranones and/or 2,4,5-trialkyl dihydrofuranones ranging from a small but effective amount, e.g., 0.1 part per million up to about 50 parts per million by weight based on total composition are suitable when used alone without other cyclic di-ketones. Further, when used with such cyclic di-ketones as maltol, cyclotene, and 2,5-dimethyl-4-hydroxy-3(2H)furanone, the concentration of 2,5-dialkyl dihydrofurnanones and/or 2,4,5-trialkyl dihydrofuranones can be as low as 0.05 part per million. Concentrations in excess of the maximum quantities stated are not normally recommeded since they fail to provide commensurate enhancement of organoleptic properties.In those instances wherein the 2,5-dialkyl dihydrofuranones and/or 2,4,5-trialkyl dihydrofuranones is added to the foodstuff as an integral component of a flavoring composition, it is, of course, essential that the total quantity of flavoring composition employed by sufficient to yield an effective 2,5-dialkyl dihydrofuranone and)or 2,4,5-trialkyl dihydrofuranone concentration in the foodstuff product.
Food flavoring compositions prepared in accordance with the present invention preferably contain the 2,5-dialkyl dihydrofuranones and/or trialkyl dihydrofuranones in concentrations ranging from about 0.1% up to about 10% by weight based on the total weight of said flavoring composition when the 2,5-dialkyl dihydrofuranone and/or 2,4,5-trialkyl dihydrofuranone is used without other cyclic di-ketones.
The compositions described herein can be prepared according to conventional techniques well known as typified by cake batters, and "fruit" juices can be formulated by merely admixing the involved ingredients within the proportions stated in a suitable blender to obtain the desired consistency, homogeneity of dispersion, etc. Alternatively, flavoring compositions in the form of particulate solids can be conveniently prepared by admixing the 2,5-dialkyl dihydrofuranones and/or 2.4.5-trialkyl dihydrofuranones with, for example, gum arabic, gum tragacanth, carrageenan and the like, and thereafter, spray drying the resultant mixture whereby to obtain the particular solid product.Pre-prepared flavor mixes in powder form, e.g. a vanilla powder or "maple sugar" flavored powder obtained by mixing the dried solid components, e.g., starch, sugar and the like and 2,5-dialkyl dihydrofuranones and/or 2,4,5-trialkyl dihydrofuranones in a dry blender until the requisite degree of uniformity is achieved.
It is presently preferred to combine with the 2,5-dialkyl dihydrifuranones and/or 2,4,5-trialkyl dihydrofuranones the following adjuvants.
Eugenol
Guaiacol
Vanillin
Sucrose
Heliotropin
Ethyl Vanillin
Maltol
Ethyl Maltol
Cyclotene
Ethyl Cyclotene
Methyl Cyclopentenolone Butyrate
2,5-Dimethyl-4-Hyd roxy-3-(2H)-Fu ranone
Isovaleraldehyde
5-Methyl Furfural
Rum Ether
Pyruvic acid and Ethyl Butyrate The following examples are given to illustrate embodiments of the invention as it is presently preferred to
practice it. It will be understood that these examples are illustrative and that the invention is not to be
considered as restricted thereto except as indicated in the appended claims.
EXAMPLE 1 PREPS ERA TION OF MIXTURE OF 24,5- TRIMETH YL-2,3 DIll YDRO-3-FURA NONE; 2,4DIMETHYL-5-ETHYL- 2,3-DIHYDRO-3-FURANONE; 2-ETll YL-5-METll YL-2-3-DIll YDRO-3-FURA NONE; and 2, 5-DIMETH YL-2,3- Dill YDRO-3-FURA NONE Reaction:
PartA. Preparation of compounds:
Into a 2 liter reaction flask equipped with mechanical stirrer, condenser, addition funnel and thermometer is placed 2.5 moles (250 grams) of 2,3 pentane dione. Over a period of 1.5 hours at a temperature range of from -2 C up to +6"C, 350ml of 20% KOH solution (acqueous) is added to the reaction mass with stirring.The reaction mass pH is then adjusted to 7 using 50% hydrochloric acid. 40ml concentrated hydrochloric acid is then added to the reaction mass which is then heated using steam to 95 C and maintained at 95% over a period of 6.5 hours. The pH of the reaction mass is then adjusted to 7 using a 25% acqueous solution of sodium hydroxide. The reaction mass is saturated with sodium chloride then extracted with one portion of 500 ml anhydrous diethyl ether and two portions of 250ml each of anhydrous diethyl ether. The diethyl ether extracts are combined and washed to two 75ml portions of saturated sodium bicarbonate followed by three 150ml portions of saturated sodium chloride. The resulting extract is then concentrated yielding 262 grans of crude containing 55% solvent.The crude is then rush over-distilled in a 500ml distillation flask into 12 fractions. Half of the fractions 3-8 are combined and distilled on a spinning band column yielding 22 fractions. The fractional distillation data is as follows:
No. Vapor Liquid Vac. Wt. of Temp.( C) Temp.( C) mm. Hg. Fraction g.
1 23-75 40-104 40-38 10.2
2 87 120 38 14.5
3 96 130 38 11.1
4 98 135 38 11.0
5 101 144 38 11.4
6 103 151 38 8.6
7 108 159 38 10.9
8 114 164 37 9.3
9 130 166 28 14.6
10 128 172 18 17.6
11 160 190 18 19.4
12 160 198 16 24.6
The spinning band distillation data is as follows: No. Vapor Liquid Vac. Reflux Temp.( C) Temp.( C) mm.Hg Ratio
1 26 55-98 65 1:1
2 56 105 32 1:1
3 59 104 32 1:1
4 59 106 32 1:10
5 59 106 32 1:10
6 59 108 32 1:15
7 59 109 32 1:15
8 62 110 32 1:15
9 74 111 32 1:15
10 76 114 32 1:15
11 76 116 32 1:15
12 80 116 32 1:15
13 80 118 32 1:15
14 80 121 32 1:15
15 84 122 30 1:15
16 93 126 30 1:15
17 95 127 30 1:15
18 86 146 32 1:15
19 78 152 24 1:15
20 76 142 10 1:15
21 76 172 8 1:15
22 38 176 1 1:15
Fractions 3-8 from the rushover distillation yield contain the following compounds:
29% of compound having the structure:
12% of compound having the structure:
17% of compound having the structure:
12% of compound having the structure:
The spinning band distillation yields the following:
Fraction 7: 98% pure compound having the structure:
Fraction 10: 90% pure compound having the structure:
Fraction 15: 96% pure compound having the structure:
Fraction 19: 94% pure compound having the structure:
Figure 2 is the NRM spectrum for 2,4,5-trimethyl-2,3-dihydro-3-furanone produced according to EXAMPLE
Figure 3 is the NMR spectrum for 2,4-dimethyl-5-ethyl-2,3-dihydro-3-furanone produced according to Example I.
Figure 4 is the NMR spectrum for 2-ethyl-5-methyl-2,3-dihydro-3-furanone produced according to Example
Figure 5 is the NMR spectrum for 2,5-diethyl-2,3-dihydro-3-furanone produced according to Example I.
Figure 6 is the infrared spectrum for 2,4,5-trimethyl-2,3-dihydro-3-furanone produced according to
Example 1.
Figure 7 is the infrared spectrum for 2,4--dimethyl-5-ethyl-2,3-dihydro-3-furanone produced according to
Example
Figure 8 is the infrared spectrum for 2-ethyl-5-methyl-2,3-dihydro-3-furanone produced according to
Example I.
Figure 9 is the infrared spectrum for 2,5-diethyl-2,3-dihydro-3-furanone produced according to Example I.
Part B:
Commercial preparation of mixture of compounds having the structures:
Into a 3 liter reaction flask equipped with mechanical stirrer, condenser, addition funnel and thermometer are placed 500 grams of 2,3-pentane dione. The reaction mass temperature is kept at approximately -5"C using an isopropanol/dry ice bath. 100 ml of a 10% aqueous KOH solution is then added dropwise over a period of 30 minutes while maintaining the reaction mass temperature at between -5 C and +6"C. 480 ml of a 20% aqueous KOH solution is then added dropwise over 11/2 hours while keeping mass temperature at -50C - +60C. The pH of the resulting slurry is then adjusted to 7 using 80 ml of a 50% H2SO4 solution (aqueous) followed by 80 ml concentrated HCI addition. The reaction mass is then steam heated (at 95"C over a period of 7 hours). The reaction mass is then cooled and the pH of the slurry is adjusted to 7 using 125 ml of 25% NaOH folowed by adding 144 grams of sodium chloride. The reaction mass is then extracted with anhydrous diethyl dether (750 ml x 1; 500 ml x 2; and 250 ml x 1). The diethyl ether extracts are combined and washed twice with saturated sodium bicarbonate (250 ml, 200 ml and 100 ml) and 10% sodium carbonate (450 ml x 2).The ether extract is then washed with saturated sodium chloride (200 ml x 3) and dried over anhydrous sodium sulfate. The concentrated crude obtained (419 grams with solvent) or 326 grams without solvent is then analyzed: GC analysis indicates that this material contains 15% compound having the structure:
8.5% compound having the structure
12.5% compound having the structure:
7.8% compound having the structure;
Another 500 grams of 2,3 propane dione is reacted with KOH in a manner similar to that set forth above as follows: To 500 grams of 2,3 pentane dione 100 ml 10% aqueous KOH is added keeping the reaction temperature at -30C - +7"C. 450 ml 20% aqueous KOH is added over a period of 1.5 hours at -30C - +70C.The pH is adjusted to 7 using 80 ml 50% H to a sulfur followed by 80 ml concentrated hydrochloric acid. The reaction mass is steam heated at 950C for 7 hours. The slurry is admixed with 75 grams of sodium chloride and extracted with diethyl ether (500 ml x 2; 300 ml x 1). The ether extract is washed with saturated sodium chloride (250 ml x 2) and then washed with 10% Na2CO3 (200 ml x 3); 150 ml x 1). The ether extract is then washed again with saturated sodium chloride (200 ml x 2, 150 ml x 1) and dried over anhydrous sodium sulfate. The concentrate obtained weighs 327 grams and is analyzed as follows: 20.3% compound having the structure:
9.2% compound having the structure:
16.7% compound having the structure:
7.8% compound having the structure:
The combined crudes have a total weight of 800 grams.The combined crudes are then rushed over distilled yielding 13 fractions as follows:
No. Vapor Liquid Vac Weight of
Temp. ("C) Temp. ("C) mm. Hg Fraction g.
1 30-50 55-80 110 5.0
2 50-35 80-90 110-40 10.3
3 75 127 38 10.3
4 94 129 38 6.0
5 97 133 38 15.0
6 99 147 38 76.0
7 107 165 36 60.0
8 121 168 25 32.0
9 124 170 18 42.0 10 130 178 14 23.1 11 134 180 11 29.6 12 137 189 10 25.7 13 140 193 5 27.3
Combined fractions 6,7 and 8 from the rushover are the redistilled yielding the following reactions:
No. Vapor Liquid Vac. Reflux Wt. of
Temp. ("C) Temp. ("C) mm. Ratio Fraction g.
1 21-48 70-88 13 4:1 6.6
2 73 88 13 4:1 4.2
3 74 88 14 4:1 4.4
4 74 89 13 4:1 2.4
5 76 89 13 4:1 4.5
6 76 89 13 4:1 3.8
7 76 89 13 4:1 3.4
8 76 89 13 4:1 4.2
9 75 89 13 9:1 1.6 10 75 90 13 9:1 2.5 11 75 90 13 9:1 2.3 12 75 90 13 9:1 2.8 13 76 90 13 9:1 3.4 14 78 92 13 3:1 11.7 15 79 92 13 3:1 10.3 16 80 93 13 3:1 9.0 17 82 96 13 3:1 13.1 18 82 96 13 3:1 10.6 19 82 98 13 3:1 15.8 20 84 112 13 3:1 11.1 21 88 145 13 3:1 11.8 22 83 250 3 3:1 12.0
Fractions 6,7 and 8, prior to distillation contain 37% compound having the structure:
15.9% compound having the structure:
28.4% compound having the structure:
and 15.3%compound having the structure:
Figure lisa GC profile of the reaction product of Example 1 which contains a mixture of compounds having the structures::
having the names, respectively, 2,4,5-trimethyl-2,3-dihydro-3-furanone; 2,4-dimethyl-5-ethyl-2,3-dihydro-3furanone; 2-ethyl-5-methyl-2,3-dihydro-3-furanone; 2,5-diethyl-2,3-dihydro-34uranone.
The final distillation is carried out on a Goodloe column from which fractions 6-21 were combined and submitted for evaluation. This material has a sweet, caramel, diacetyl-like, buttery aroma characteristic with sweet, caramel, diacetyl-like, buttery and vanillin flavour characteristics. It is useful in caramel, butterscotch, rum, dairy, vanillia and roasted almond flavors. The level of useage may vary from 0.5 ppm up to 100 ppm with a preferred level of useage at 1-5 ppm.
Example II
Basic caramel flavor formulation
The following caramel flavor formulation is prepared:
Ingredients Parts by Weight
Palatone 3
Heliotropine 2
Cyclotene 2
Vanillin 2
Isovaleraldehyde 1
5-Methyl Furfural 2
Rum Ether 15
Pyruvic acid 5
Ethyl Butyrate 10
Propylene glycol 158
This basic caramel flavor is divided into two parts. To the first part, 5% by weight of the bulked fractions 3-E resulting from the rushover distillation of Example I, Part A, is added. To the second part nothing is added.
Both flavors are tested at the rate of 20 ppm in water by a bench panel of three flavor experts. All three members of the bench panel state that the formulation containing said mixture prepared according to
Example I, Part B has a more characteristic caramel, burnt sugar aroma and taste. In addition, there is a buttery mouthfeel in the flavor formulation containing the mixture prepared according to Example I, Part B.
Therefore the flavor containing the mixture prepared according to Example I, Part B is unanimously preferred as having a better caramel character.
Example Ill Isolation of 2,4,5-trimethyl-3(2ll)furanone from bacon flavor
500 pounds of Oscar Mayer bacon was firstly ground to 3/16" mesh and each batch (100 pounds) was cooked in steam jacked kettle from 50"F to 350"F over a period of one hour. Slurry obtained from 5 batches was about 300 pounds, about 200 pounds of water was lost during process. The slurry was subjected to vacuum steam - distillation in ten charges and each charge is distilled in two passes. The apparatus is set forth in Figure 10. The resulting distillate was saturated with NaCI and subjected to continuous extraction and concentrated to 1 liter.
A small portion is taken to estimate the total volatile weight which is approximately 3 grams. The total volatiles are chemically separated using the separation scheme as set forth in Figure 11. 400 mg of phenolic fraction obtained is fractioned on a silicon dioxide column (10% deactivated silica, 14 grams, column volume equals 30 ml/250 mm x 12 mm) using isopentane and then varying mixtures (1% - 100%) of diethyl ether in isopentane.
The fraction containing the 2,4,5-trimethyl 2-(2H)furanone is subjected to GLC analysis (conditions: stainless steel carbowax 20M column, n,1/s inch x 1 Oft., 60 - 220"C at40C/minute). The GLC chromatogram is set forth in Figure 12. The 2,4,5-trimethyl-3(2H)furanone synthesized according to Example I, PartA has a
GLC profile as set forth in Figure 13. The GLC profile retention time for said furanone in Figure 13 is identical to the GLC profile retention time of the furanone isolated from fried bacon flavor. The IR spectrum for the isolated furanone is set forth in Figure 14. The NMR spectrum for the isolated furanone is set forth in Figure 15. The mass spectrum for the isolated furanone is set forth in Figure 16.
Example IV
The following ingredients are homogeneously admixed at 25"C: Ingredients Parts
Vegetable shortening 622.7
Salt 321.7
Glutamic acid 5.1
L-cysteine hydrochloride 10.3
Glycine 5.1 ss-Alanine 1.3
Taurine 20.0
Mixture of di-sodium inosi
nate and di-sodium guranylate 3.3
The mixture is heated at 300"F for 30 seconds. After cooling to 1000F, 0.05 parts of a mixture of dialkyl and trialkyl dihydrofuranones having the structures:
prepared according to Example I. The resulting mixture has an excellent bacon aroma and taste
Example V
Cysteine hydrochloride in the amount of 8.8 g is refluxed at 21 50F under atmospheric pressure for four hours with a mixture of 309 g of hydrolyzed vegetable protein and 674 g of water.Subsequent to the reflux, the mixture is cooled and 0.05 g of a mixture of dialkyl and trialkyl dihydro furanones having the structures:
prepared according to Example I is added and intimately admixed with the composition. The mixture has an excellent fried bacon flavor of high tensity.
Example VI
To composition prepared in Example IV is dissolved in propylene glycol to provide a 0.1% solution. This solution in the amount of 0.966 g is added to 7.3 g of a soup base consisting of:
Ingredients Parts
Fine ground sodium chloride 35.62
Hydrolyzed vegetable protein 27.40
Monosodium glutamate 17.81
Sucrose 10.96
Beef fat 5.48
Sethness caramel color
(powder B & C) 2.73
The resulting mixture is added to 12 ounces of boiling water obtain a soup having an excellent bacon flavor.
Example VII
The composition prepared in Example V is dissolved in propylene glycol to provide a 0.1% solution. This solution in the amount of 0.966 g is added to 7.3 g of a soup base consisting of:
Ingredients Parts
Fine ground sodium chloride 35.62
Hydrolyzed vegetable protein
(Maggi 4BE) 27.40
Monosodium glutamate 17.81
Sucrose 10.96
Beef fat 5.48
Caramel color, bakers and
confectioner's powder grade 2.73
The resulting mixture is added to 12 ounces of boiling water to obtain a soup having an excellent bacon flavor.
Example VIII One-half gram of the soup base mixture of Example VI is emulsified in a solution containing 100 g grm arabic and 300 g water. The emulsion is spray-dried with a Bowen Lab Model Drier Utilizing 250 cfm of air with an inlet temperature of 500"F, an outlet temperature of 200"F, and a wheel speed of 50,000 rpm.
Twelve grams of the spray-dried material is mixed with 29.2 g of the soup base set forth in Example VI. The resulting mixture is then added to 12 ounces of boiling water and an excellent bacon flavored soup is obtained.
Example IX
Basic bacon flavor
The following basic bacon flavor is produced:
Ingredients Parts
Vanillin 2.0
Eugenol 1.0
Guaiacol 0.2
Para-vinyl guaiacol 0.2
Cyclotene 1.0
Trimethyl pyrazine 0.4
Acetyl pyridine 0.1 2,4-decadienal, 1% 0.1
Furfural 0.4
Benzaldehyde 1.0
Isovaleraldehyde 1.0
Methyl thiazole alcohol 7.6
Foodgrade ethyl alcohol 185.0
Hickory smoke flavor,
natural (Fleischmann Co., 800.0
New York, a Div. of Standard
Brands)
This basic bacon flavor is divided into two portions. The first portion at the rate of 0.02 ppm, the mixture of dialkyl and trialkyl dihydro furanones having the structures:
produced according to Example I. To the second portion of the basic bacon flavor nothing is added.The two flavors with and without the dialkyl and trialkyl dihydro furanone mixtures are compared at the rates of 100 ppm in water and evaluated by an expert flavorist panel. The flavor containing the dialkyl and trialkyl dihydro furanone mixture has a crisp bacon aroma and taste and additional port fat notes not present in the basic bacon flavor without the dialkyl and trialkyl dihydro furanone mixture. Therefore the flavor with the dialkyl and trialkyl dihydro furanone mixture is unanimously preferred.
Brief description of the drawings
Figure 1 is the gas chromotograph (GC) profile for the mixture of compounds each of which has the structure:
(2,4,5-tri methyl-2,3-di hydro-34uranone);
(2,4-dimethyl-5-ethyl-2,3-dihydro-3-furanone
(2-ethyl-5-methyl-2,3-dihydro-3-furanone
(2,5-diethyl-2,3-dihydro-3-furanone) produced according to Example I, and containing 37% compound having the structure:
(2,4,5-trimethyl-2,3-dihydro-3-fu ranone); 15% of compound having the structure:
(2-ethyl-5-methyl-2,3-dihydro-3-furanone); 27% of compound having the structure:
55 (2,4-dimethyl-5-ethyl-2,3-dihydro-3-fu ranone); and 15% of compound having the structure:
(2,5-diethyl-2,3-dihydro-3-furanone)
Figure 2 is the NMR spectrum for the compound having the structure:
(2P,S-trimethyl-2,3-dihydro-3-furanone) produced according to Example
Figure 3 is the NMR spectrum for the compound having the structure:
15 (2,4-dimethyl-5-ethyl-2,3-dihydro-3-furanone) produced according to Example
Figure 4 is the NMR spectrum for the compound having the structure:
(2-ethyl-5-methyl-2,3-dihydro-3-furanone) produced according to Example I.
Figure 5 is the NMR spectrum for the compound having the structure:
(2,5-diethyl-2,3-dihydro-3-furanone) produced according to Example I.
Figure 6 is the infrared spectrum for the compound having the structure:
(2,4,5-trimethyl-2,3-dihydro-3-furanone) produced according to Example I.
Figure 7 is the infrared spectrum for the compound having the structure:
(2,4-dimethyl-5-ethyl-2,3-dihydro-3-fu ranone) produced according to Example I.
Figure 8 is the infrared spectrum for the compound having the structure:
(2-ethyl-5-methyl-2,3-dihydro.34uranone) produced according to Example I.
Figure 9 is the infrared spectrum for the compound having the structure:
(2,5-diethyl-2,3-dihydro-3-fu ranone) produced according to Example I.
Figure 10 sets forth the vacuum steam distillation apparatus used in the isolation of 2,4,5-trimethyl-3-(2H)furanone from bacon flavor of Example Ill.
Figure 11 is an illustration of the chemical separation scheme of Example III.
Figure 12 is the GLC profile for the chromotographicfraction containing 2,4,5-trimethyl-3-(2H)-furanone produced in Example Ill.
Figure 13 is the GLC profile for 2,4,5-trimethyl-3(2H)-furanone produced according to Example Ill.
Figure 14 is the infrared spectrum for the isolated 2,4,5-trimethyl-3(2H)-furanone of Example Ill
Figure 75 is the NMR spectrum for the isolated 2,4,5-trimethyl-3(2H)4uranone produced according to
Example Ill.
Figure 16 is the mass spectrum for the isolated 2,4,5-trimethyl-3(2H)-furanone produced according to
Example Ill.
Claims (15)
1. A composition of matter which comprises at least one of the compounds having the structureS:
2. The composition of matter of Claim 1 which is a mixture of dialkyl and t?ialkVl substituted dihydro furanones having the structures:
3. The composition of matter of Claim 1 which is a compound having the structure:
4. The composition of matter of Claim 1 which is a compound having the structure:
5. The composition of matter of Claim 1 which is a compound having the structure:
6.A process for augmenting or enhancing the taste or aroma of a foodstuff comprising the step of adding to said foodstuff from about 0.1 ppm up to about 50 ppm by weight of said foodstuff of at least one dialkyl ortrialkyl substituted dihydrofuranone defined according to Claim 1 having a structure which is, in the alternative, one of:
or a mixture of dialkyl and trialkyl dihydrofuranones having the structures:
7. The process of Claim 6 wherein there is added to said foodstuff from about 0.1 ppm up to about 50 ppm of a mixture of di and trialkyl dihydrofuranones having the structures:
8.A flavor augmenting or enhancing composition comprising from about 0.1% up to 15% by weight based on the total weight of said flavoring composition of at least one dialkyl or trialkyl dihydrofuranones having a structure which is, in the alternative, one of:
or a mixture of dialkyl and trialkyl dihydrofuranones having the structures:
and the remainder of said composition being at least one adjuvant which is, in the alternative, one of:
Eugenol
Guaiacol
Vanillin
Sucrose
Heliotropin
Ethyl vanillin
Maltol
Ethyl maltol
Cyclotene Ethyl cyclotene Methyl cyclopentenolone butyrate 2,5-Dimethyl-4-hydroxy-3(2H)-furanone Isovaleraldehyde
5-Methyl furfural
Rum ether
Pyruvic acid and
Ethyl butyrate
9.The composition of Claim 8 wherein the flavor augmenting or enhancing composition comprises from about 0.1% up to about 15% by weight based on the total weight of said flavoring composition of a mixture of dialkyl and trialkyl dihydrofuranones having the structures:
or a mixture of dialkyl and trialkyl dihydrofuranones having the structures:
7. The process of Claim 6 wherein there is added to said foodstuff from about 0.1 ppm up to about 50 ppm of a mixture of di and trialkyl dihydrofuranones having the structures:
8.A flavor augmenting or enhancing composition comprising from about O.1% up to 15% by weight based on the total weight of said flavoring composition of at least one dialkyl or trialkyl dihydrofuranones having a structure which is, in the alternative, one of:
or a mixture of dialkyl and trialkyl dihydrofuranones having the structures:
and the remainder of said composition being at least one adjuvant which is, in the alternative, one of:
Eugenol
Guaiacol
Vanillin
Sucrose
Heliotropin
Ethyl vanillin
Maltol
Ethyl maltol
Cyclotene Ethyl cyclotene Methyl cyclopentenolone butyrate 2,5-Dimethyl-4-hydroxy-3(2H)-furanone Isovaleraldehyde
5-Methyl furfural
Rum ether
Pyruvic acid and
Ethyl butyrate
9.The composition of Claim 8 wherein the flavor augmenting or enhancing composition comprises from about 0.1% up to about 15% by weight based on the total weight of said flavoring composition of a mixture of dialkyl and trialkyl dihydrofuranones having the structures:
10. The process of Claim 6 substantially as herein described with reference to any one of Examples IV, V, Vl, VII, or Veil.
11. The composition of Claim 8 or Claim 9 substantially as herein described with reference to any one of
Examples II, IX.
12. The process of Claim 6 wherein the flavor of the foodstuff augmented or enhanced is a bacon flavor.
13. The composition of Claim 8 which is a bacon flavor composition.
14. The composition of Claim 8 which is a caramel flavor composition.
15. Any novel feature or combination of features described herein.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US92860678A | 1978-07-27 | 1978-07-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2026482A true GB2026482A (en) | 1980-02-06 |
| GB2026482B GB2026482B (en) | 1982-10-13 |
Family
ID=25456523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7924688A Expired GB2026482B (en) | 1978-07-27 | 1979-07-16 | 2,5-dialkyl dihydrofuranones and 2,4,5-trialkyl dihydrofuranones mixtures of same and organoleptic uses thereof |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1121651A (en) |
| GB (1) | GB2026482B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2112139A1 (en) | 2008-04-25 | 2009-10-28 | Laboratorios Del. Dr. Esteve, S.A. | Process for the preparation of naphthalen-2-yl-pyrazol-3-one intermediates useful in the synthesis of sigma receptor inhibitors |
| US9757358B2 (en) | 2010-02-04 | 2017-09-12 | Laboratorios Del Dr. Esteve, S.A. | Sigma ligands for potentiating the analgesic effect of opioids and opiates in post-operative pain and attenuating the dependency thereof |
| US9782483B2 (en) | 2010-05-21 | 2017-10-10 | Laboratories Del Dr. Esteve, S.A. | Sigma ligands for the prevention and/or treatment of emesis induced by chemotherapy or radiotherapy |
| US9789115B2 (en) | 2010-08-03 | 2017-10-17 | Laboratorios Del Dr. Esteve, S.A. | Use of sigma ligands in opioid-induced hyperalgesia |
| US9789117B2 (en) | 2011-05-18 | 2017-10-17 | Laboratorios Del Dr. Esteve, S.A. | Use of sigma ligands in diabetes type-2 associated pain |
| US9844516B2 (en) | 2010-02-04 | 2017-12-19 | Laboratorios De Dr. Esteve | Sigma ligands for use in the prevention and/or treatment of post-operative pain |
| US9914705B2 (en) | 2008-04-25 | 2018-03-13 | Laboratorios Del Dr. Esteve, S.A. | 1-aryl-3-aminoalkoxy pyrazoles as sigma ligands enhancing analgesic effect of opioids and attenuating the dependency thereof |
| US9931346B2 (en) | 2013-12-17 | 2018-04-03 | Laboratorios Del Dr. Esteve S.A. | Serotonin-norepinephrine reuptake inhibitors (SNRIs) and Sigma receptor ligands combinations |
-
1979
- 1979-05-09 CA CA000327292A patent/CA1121651A/en not_active Expired
- 1979-07-16 GB GB7924688A patent/GB2026482B/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2112139A1 (en) | 2008-04-25 | 2009-10-28 | Laboratorios Del. Dr. Esteve, S.A. | Process for the preparation of naphthalen-2-yl-pyrazol-3-one intermediates useful in the synthesis of sigma receptor inhibitors |
| US8329880B2 (en) | 2008-04-25 | 2012-12-11 | Laboratorios Del Dr. Esteve, S.A. | Process for the preparation of naphthalen-2-yl-pyrazol-3-one intermediates useful in the synthesis of sigma receptor inhibitors |
| US9914705B2 (en) | 2008-04-25 | 2018-03-13 | Laboratorios Del Dr. Esteve, S.A. | 1-aryl-3-aminoalkoxy pyrazoles as sigma ligands enhancing analgesic effect of opioids and attenuating the dependency thereof |
| US9757358B2 (en) | 2010-02-04 | 2017-09-12 | Laboratorios Del Dr. Esteve, S.A. | Sigma ligands for potentiating the analgesic effect of opioids and opiates in post-operative pain and attenuating the dependency thereof |
| US9844516B2 (en) | 2010-02-04 | 2017-12-19 | Laboratorios De Dr. Esteve | Sigma ligands for use in the prevention and/or treatment of post-operative pain |
| US9782483B2 (en) | 2010-05-21 | 2017-10-10 | Laboratories Del Dr. Esteve, S.A. | Sigma ligands for the prevention and/or treatment of emesis induced by chemotherapy or radiotherapy |
| US9789115B2 (en) | 2010-08-03 | 2017-10-17 | Laboratorios Del Dr. Esteve, S.A. | Use of sigma ligands in opioid-induced hyperalgesia |
| US9789117B2 (en) | 2011-05-18 | 2017-10-17 | Laboratorios Del Dr. Esteve, S.A. | Use of sigma ligands in diabetes type-2 associated pain |
| US9931346B2 (en) | 2013-12-17 | 2018-04-03 | Laboratorios Del Dr. Esteve S.A. | Serotonin-norepinephrine reuptake inhibitors (SNRIs) and Sigma receptor ligands combinations |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1121651A (en) | 1982-04-13 |
| GB2026482B (en) | 1982-10-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |