WO2015037648A1 - Freshness-maintaining agent having reduced off-flavor - Google Patents
Freshness-maintaining agent having reduced off-flavor Download PDFInfo
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- WO2015037648A1 WO2015037648A1 PCT/JP2014/074030 JP2014074030W WO2015037648A1 WO 2015037648 A1 WO2015037648 A1 WO 2015037648A1 JP 2014074030 W JP2014074030 W JP 2014074030W WO 2015037648 A1 WO2015037648 A1 WO 2015037648A1
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- glutarate
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
- C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
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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
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/52—Adding ingredients
- A23L2/56—Flavouring or bittering agents
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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
- A23L27/203—Alicyclic compounds
Definitions
- the present invention relates to a refreshing sensation agent comprising monomenthyl glutarate and dimenthyl glutarate, which are l-menthol derivatives, and particularly relates to a refreshing sensation agent with reduced miscellaneous taste.
- the present invention also relates to a method for producing a mixture of monomenthyl glutarate and dimenthyl glutarate, which contains monomenthyl glutarate in a high ratio.
- L-Menthol which is a major component of peppermint essential oil and mint essential oil, is known as a refreshing substance.
- l-menthol is highly volatile and does not maintain a refreshing sensation, and has the disadvantage of feeling bitter when added to food and drink.
- Monomenthyl glutarate which is an ester derivative of l-menthol and dibasic acid, is a compound that has been evaluated for its refreshing feeling and less bitterness associated with menthol than l-menthol. It is known that monomenthyl glutarate is present in a mixture with dimenthyl glutarate, for example, a component derived from dried lychee fruit (Non-patent Document 1). This mixture is used in confectionery such as chewing gum and candy, and in toothpaste, haptics, skin foods and other foods and cosmetics (Non-patent Document 2) monobasic monomenthol such as monomenthyl glutarate.
- Esters are compounds that have been published as tobacco taste improvers, and it is described that they can be obtained through an ester-forming reaction of dibasic acid anhydrides or dibasic acids with menthol as the production method (Patent Document 1). .
- Patent Document 1 does not describe a specific method for producing monomenthyl glutarate.
- menthyl glutarate As a more economical synthetic method to provide menthyl glutarate as a mixture of commercially desirable proportions of monomenthyl glutarate (hereinafter also referred to as “MMG”) and dimenthyl glutarate (hereinafter also referred to as “DMG”), Proposed a method to obtain menthyl glutarate in high yield by heating and dehydrating in the presence of solvent using stoichiometric excess glutaric acid with a glutaric acid weight ratio of 1.0-1.6. (Patent Document 2).
- a commercially desirable ratio of MMG / DMG referred to in this document is about 7/3. This document also mentions that menthyl glutarate obtained by a conventional method is separately separated into MMG and DMG, and these are blended in a desired ratio.
- menthyl glutarate as a method for producing menthyl glutarate that enhances the selectivity of MMG production, the molar ratio of glutaric anhydride to l-menthol is reacted in the presence of a basic catalyst at about 1/1.
- a method has been proposed in which a reaction mixture in which the molar ratio of MMG / DMG can be converted to about 17/1 at maximum from the analytical value is obtained (Patent Document 3). This document also suggests that the analytical value yield is 78% and that menthol monoesters have excellent physiological cooling properties.
- menthyl glutarate As mentioned above, several production methods for providing menthyl glutarate as a mixture of commercially desirable proportions of MMG and DMG are already known, and menthyl glutarate obtained by these methods has been widely used in the past. It has been used as a long-acting agent. However, some refreshing sensation sustaining agents containing this mixture as an active ingredient may feel a bitter taste, and are not always satisfactory considering a wide range of applications. Therefore, the problem to be solved by the present invention is to provide a refreshing sensation sustaining agent containing menthyl glutarate as an active ingredient and having a reduced miscellaneous taste. As described later, such miscellaneous tastes were found for the first time by the present inventors, and are extremely novel problems in this technical field.
- Menthyl glutarate obtained by a known synthetic method or extraction from a natural product contains dimentyl glutarate as a by-product or contaminants to a certain extent as described above.
- Dimenthyl glutarate itself is also known as a perfume compound, and even if dimenthyl glutarate is contained as a contaminant in monomenthyl glutarate, it has hitherto been particularly noted for use as a refreshing agent. There wasn't.
- mentill glutarate containing a large amount of dimenthyl glutarate as a by-product or contaminants feels more intense, and surprisingly, it is referred to as a mixture of the above-mentioned commercially desirable proportions of MMG and DMG. It has also been found that even the menthyl glutarate is strongly affected by the miscellaneous taste. Furthermore, as a result of conducting a sensory test on the mixing ratio of high-purity monomenthyl glutarate and dimentyl glutarate separately prepared and the refreshing effect, the above-mentioned drawbacks are eliminated by reducing the DMG content to a certain level or less. It was also found that it can be significantly reduced.
- the content ratio of DMG in the mixture of MMG and DMG does not necessarily become 0%, but if it is about 5% by mass or less, the miscibility in the aftertaste when such a mixture is included in the mouth Thus, it was confirmed that the refreshing effect was improved, and it was found useful as an active ingredient of the refreshing agent.
- the present inventors have provided an industrial process for producing menthyl glutarate that can be effectively used for the preparation of a mixture in which the content ratio of DMG is approximately 5% by mass or less in the mixture of MMG and DMG as described above.
- a composition containing commercially available MMG and DMG which is derived from a natural product or a chemical synthesis containing DMG at a certain content or more, is used as a starting material. It has been found that, when extracted with an aqueous solution, a mixture having a DMG content ratio of less than about 5% by mass in a mixture of MMG and DMG can be efficiently prepared.
- the purified mixture with increased content of MMG suppresses the formation of glutaric acid and menthol or dimenthyl glutarate due to disproportionation due to the acidity of MMG itself by distillation under high vacuum. It was also found that even higher purity MMG can be obtained in this state.
- such a preparation method can be applied to a composition in which the content ratio of DMG exceeds 5 mass% in a mixture of MMG and DMG.
- a refreshing sensation sustaining agent comprising monomenthyl glutarate (MMG) and dimenthyl glutarate (DMG), wherein MMG is present as a mixture of MMG and DMG in an amount of 95% by mass or more, and DMG A refreshing sensation persisting agent present at 5% by weight or less.
- MMG monomenthyl glutarate
- DMG dimenthyl glutarate
- a refreshing sensation persisting agent present at 5% by weight or less A fragrance composition containing the refreshing sensation sustaining agent according to (1) as an active ingredient.
- a method for preparing a purified composition comprising a high content of MMG from a composition comprising monomenthyl glutarate (MMG) and dimenthyl glutarate (DMG), (A) a step of extracting MMG in the composition containing MMG and DMG with an aqueous alkaline solution; (B) comprising a step of neutralizing the alkaline aqueous solution obtained in step (a) with an organic acid, and a step of recovering menthyl glutarate obtained through steps (c) and (b).
- MMG monomenthyl glutarate
- DMG dimenthyl glutarate
- the composition containing MMG and DMG is present as a mixture of MMG and DMG in an amount of more than 5% by weight of DMG;
- a method of preparation wherein in the purified composition, MMG is present as a mixture of MMG and DMG in an amount of 95% by mass or more.
- the preparation method according to (5) or (6) above, The composition containing MMG and DMG has a molar ratio of 9 to 6/1 to 4, preferably 8.5 to 6.5 / 1.5 to 4.5, more preferably 8 to 7/2 to 3. Preparation method, which is a mixture.
- dimentil glutarate a by-product
- a refreshing sensation sustaining agent obtained by the reaction of glutaric acid and l-menthol used in the food field.
- monomentyl glutarate a refreshing sensation sustaining agent that has been difficult to supply with high purity from an economical aspect, with high yield and high purity by a simple operation. Since the refreshing sensation persistence agent containing menthyl glutarate containing 95% by mass or more of monomenthyl glutarate obtained by the present invention as an active ingredient can be provided, a refreshing feeling with improved aftertaste can be imparted to a wide range of foods.
- Menthyl glutarate obtained by the reaction of glutaric acid and menthol is usually obtained as a mixture of monomenthyl glutarate obtained by reacting one molecule of menthol and dimenthyl glutarate obtained by reacting two molecules of menthol.
- such mixtures or crude monomenthyl glutarate are also referred to as menthyl glutarate.
- Menthyl glutarate a refreshing sensation persistence agent
- Menthyl glutarate is available from the market as a mixture of about 7/3 of its monoester / diester, and such a mixture is also the subject of the invention of Patent Document 2. Nonetheless, a refreshing sensation agent comprising such a mixture as an active ingredient is felt to have a refreshing sensation sustaining effect as described above. It was revealed that the aftertaste persisted.
- a drawback or problem of the prior art associated with such miscellaneous taste is a refreshing sensation sustaining agent comprising monomenthyl glutarate (MMG) and dimenthyl glutarate (DMG), which is provided as one aspect of the present invention, It is solved by a refreshing sensation agent in which MMG is present as a mixture of MMG and DMG in an amount of 95% by mass or more and DMG is in an amount of 5% by mass or less.
- MMG monomenthyl glutarate
- DMG dimenthyl glutarate
- the above problem can be solved more easily by providing an industrial preparation method of menthyl glutarate that can be effectively used for the preparation of the mixture.
- High purity of the mixture that is, when the total amount of MMG and DMG is 100% by mass, the content of MMG is 95% by mass or more and DMG is 5% by mass or less. It is defined as containing monomenthyl glutarate. In such a mixture, it is assumed that the content of DMG is as close to zero (0) as possible, but it is realistic or economical, or has the ease and expected characteristics of preparation of the mixture. Considering the balance, it can be several mass%, for example, up to about 2 mass%.
- such a mixture contains 95.5% by weight or more of MMG, preferably 96.0% by weight or more, more preferably 96.5% by weight, and even more preferably 97% by weight or more,
- MMG preferably 96.0% by weight or more, more preferably 96.5% by weight, and even more preferably 97% by weight or more
- Each contains DMG up to 4.5 wt%, preferably up to 4.0 wt%, more preferably up to 3.5 wt%, even more preferably up to 3.0 wt%.
- the starting material to be processed is a composition containing MMG and DMG, as long as the composition contains DMG in an amount of more than 5% by mass as a mixture of MMG and DMG. Included without questioning the origin.
- the composition has a molar ratio of MMG and DMG of 9 to 6/1 to 4, preferably 8.5 to 6.5 / 1.5 to 4.5, more preferably Can contain a mixture in a ratio of 8 to 7/2 to 3.
- the composition may be derived from a natural product or may be a chemically synthesized product.
- the preparation method according to the present invention comprises (a) a step of extracting MMG in a composition containing MMG and DMG with an aqueous alkaline solution, and (b) an aqueous alkaline solution obtained in step (a) is converted into an organic acid. And a step of recovering menthyl glutarate obtained through steps (c) and (b).
- an aqueous solution containing monomenthyl glutaric acid salt is added to the composition containing MMG and DMG, if necessary, together with a water-immiscible organic solvent, neutralized with an alkaline aqueous solution, and the treatment solution is allowed to stand.
- the composition is a chemically synthesized product, it can be further separated into an organic solvent layer containing menthol and glutaric anhydride as raw materials.
- the amount of alkali to be added is 1 to 5 equivalents, preferably 1 to 2 equivalents, more preferably 1.2 equivalents of alkali with respect to glutaric anhydride when MMG and / or chemically synthesized products are used. Is used as an aqueous solution obtained by dissolving an alkali in an appropriate amount of water.
- neutralizing alkali examples include sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, and more preferably sodium carbonate.
- a hydrocarbon solvent is generally used.
- DMG and the composition are chemically synthesized products in a hydrogen-based solvent, menthol and glutaric anhydride are further extracted or distributed or transferred to efficiently remove by-products or impurities. The content rate can be reduced.
- hydrocarbon solvents include toluene, xylene, heptane, hexane, pentane, particularly preferably heptane.
- the amount of the hydrocarbon solvent used is 1 to 10 times by weight, preferably 1 to 10 times by weight with respect to glutaric anhydride. 2 to 5 times the weight, more preferably 2 to 3 times the weight.
- the aqueous solution containing the monomenthyl glutarate alkali salt obtained in the step (a) is neutralized with an organic acid, and if necessary, in the presence of a water-immiscible organic solvent, as an oil layer, or Crude MMG can be obtained in a water immiscible organic solvent layer.
- organic acid used for neutralization any organic acid can be used, and examples thereof include citric acid, oxalic acid, succinic acid, and preferably organic acids such as citric acid. It is preferable to use an equivalent amount of the organic acid corresponding to the added alkali.
- water-immiscible organic solvent a hydrocarbon solvent is preferable, and toluene, xylene, heptane, hexane, pentane, particularly preferably heptane can be mentioned.
- the solvent can be removed by distillation under reduced pressure to obtain the MMG-containing composition of the present invention.
- MMG has a purity of 95% or more.
- DMG which is a contaminant, unreacted l-menthol, glutaric anhydride
- the content of the product is about several percent.
- the highly purified monomenthyl glutarate obtained in the step (c) is used in food and drink products and cosmetics as an active ingredient for imparting a refreshing feeling in this state by subjecting it to a known recovery step. Is possible.
- the MMG-containing composition is further refined by distillation at a high vacuum of 5 Pa to 100 Pa to further enhance the refreshing feeling and provide a high quality that does not feel a bitter taste or feel a bitter taste. Products are obtained.
- MMG monomentyl glutarate with high purity can be obtained without distillation.
- MMG thus obtained has a purity of 95% or more, preferably 96% or more, more preferably 96.5% or more, and still more preferably 97% or more, and DMG, 1-menthol, glutaric acid and The content of dimenthyl glutarate is extremely small, and the refreshing feeling is emphasized in sensory evaluation, and it is evaluated as a refreshing feeling sustaining agent that does not give an aftertaste.
- the raw material to be treated in the above preparation method can be a commercial product including a natural product-derived composition, but the chemicals that can be obtained by the following production method provided by the present inventors as a suitable one. It can also be a synthetic product.
- the composition can be obtained by reacting both raw materials under conditions where an ester is formed in a state where both menthol and glutaric anhydride are dissolved in a solvent.
- a solvent can be an ether solvent and is not limited to 1 selected from the group consisting of 1,2-dimethoxyethane, diisopropyl ether, 1,4-dioxane and methyl tertiary butyl ether. It can be a seed or two or more solvents.
- Menthol and glutaric anhydride as raw materials in the reaction can be used in a molar ratio of 1.2 to 1.0 / 1, respectively.
- menthol used as a synthetic raw material there are 8 types of isomers. Natural l-menthol having a refreshing refreshing feeling is preferable. L-Menthol can be synthesized even if it is extracted from natural products. Any of those manufactured by the method can be used.
- the other raw material, glutaric anhydride is a compound having a cyclic structure obtained by dehydrating one molecule of water from one molecule of glutaric acid, either synthesized by a known method or obtained from the market. be able to.
- menthol and glutaric anhydride are reacted under conditions where an ester can be formed to obtain a crude monomenthyl glutarate product.
- the conditions under which the ester can be formed can be those well known in the art as long as they meet the purpose of the present invention, but conform to the conditions under which an ester can be formed by a reaction between a general carboxylic acid and an alcohol. be able to.
- a solvent in which both menthol and glutaric anhydride are dissolved In view of selecting such conditions, for example, Patent Document 3 This is one of the features of the present invention.
- both menthol and glutaric anhydride are dissolved at room temperature or reaction temperature, and both are reacted at a similar molar ratio to form a diester and Residues can be avoided or significantly reduced, and monomenthyl glutarate can be efficiently produced.
- Menthol is sparingly soluble in water, but easily soluble in many organic solvents such as ether, ethanol, chloroform, acetic acid and liquid paraffin, and is generally esterified in the state of solution even in conventional reactions. Often subjected to reaction.
- glutaric anhydride which is the other raw material, dissolves in ethanol, benzene, and toluene, but the solubility is not so high, and there are not many solvents that dissolve glutaric anhydride in a high concentration.
- a solvent in which glutaric anhydride is soluble at room temperature is used.
- the solvent in which glutaric anhydride can be dissolved at normal temperature is not particularly limited as long as glutaric anhydride is soluble in normal temperature, but as described above, ether solvents are preferable, for example, 1,2-dimethoxyethane. , Diisopropyl ether, 1,4-dioxane, and / or methyl tertiary butyl ether can be exemplified by one or more solvents or solvent systems, among which 1,2- Mention may be made of dimethoxyethane.
- the amount or ratio of the solvent used is not particularly limited, but is preferably 10 to 10 times, preferably 1 to 3 times the weight of glutaric anhydride. To do. As a result, a crude reaction product is obtained in which glutaric anhydride having an adverse effect on the reaction post-treatment operation is not recrystallized.
- the ester formation reaction is preferably carried out in the presence of an acid catalyst.
- the acid catalyst include p-toluenesulfonic acid / monohydrate, methanesulfonic acid, and benzenesulfonic acid, and more preferably p-toluenesulfonic acid / monohydrate.
- the usage-amount of an acid catalyst is not specifically limited, 0.005 equivalent to 0.05 equivalent based on the glutaric anhydride to be used, Preferably 0.01 equivalent can be mentioned.
- the molar ratio of menthol / glutaric anhydride is preferably 1.2 to 1.0 / 1.0, more preferably 1/1.
- reaction temperature and reaction time are not particularly limited, but the reaction is performed near the boiling point of the solvent used, and the reaction end point can be determined by monitoring the reaction using, for example, gas chromatography (GC).
- GC gas chromatography
- the ratio of MMG / DMG in the reaction product obtained is about 8 to 7/2 to 3, preferably about 8/2.
- the refreshing sensation sustaining agent containing high-purity menthyl glutarate as an active ingredient which can be conveniently obtained by the above preparation method, can be used alone, but can be used by mixing with other refreshing sensation maintaining agents.
- a blendable refreshing agent menthyl 3-hydroxybutyrate, menthol glycerin ether (Cooling Agent 10, registered trademark of Takasago Inc.), [(1R, 2S, 5R) -5-methyl-2-propane- 2-ylcyclohexyl] 2-hydroxypropanoic acid (Frescolate ML, registered trademark of Symrise AG), monomenthyl succinate (Physical, registered trademark of Mane Fris), N-ethyl-p-menthane carboxylic acid amide (WS-3), Ethyl 2-[(5-methyl-2-propan-2-ylcyclohexanecarbonyl) amino] acetic acid (WS-5), N- (4-methoxyphenyl) -5-methyl-2-propan
- the refreshing sensation agent includes sweeteners, colorants, preservatives, thickeners, stabilizers, gelling agents, pastes, antioxidants, acidulants, seasonings, and nutrient fortifiers. Can be used. Add the fragrance to the preparation obtained here and use it for foods such as citrus, fruit, mint, spice, nut, meat, milk, seafood, vegetable, tea / coffee, vanilla A fragrance composition can be prepared, and the fragrance composition can be used to impart or enhance a refreshing sensation sustaining action to foods and drinks.
- fragrance various surfactants, polyhydric alcohols, waxes, higher fatty acids and the like can be added and used as cosmetic preparations. It is possible to add a fragrance to the preparation obtained here to give the fragrance having a citrus note, a floral note, a white floral note, a floral bouquet note, an oriental note, a green note, and a shiple note, a refreshing sensation. it can.
- hydrocarbon compound examples include monoterpenes such as pinene, myrcene, camphene, and limonene, sesquiterpenes such as cedrene, caryophyllene, and longifolene, 1,3,5-undecatriene, and the like.
- Linear / saturated alkanols such as butanol, pentanol and hexanol as alcohol compounds, linear / unsaturated alcohols such as (Z) -3-hexen-1-ol and 2,6-nonadienol, linalool, geraniol, citronellol, farnesol , Terpene alcohols such as nerolidol and cedrol, and aromatic alcohols such as benzyl alcohol, phenylethyl alcohol, and furfuryl alcohol.
- linear / saturated alkanols such as butanol, pentanol and hexanol as alcohol compounds
- linear / unsaturated alcohols such as (Z) -3-hexen-1-ol and 2,6-nonadienol
- linalool geraniol
- citronellol farnesol
- farnesol Terpene alcohols
- Terpene alcohols such as nerolid
- aldehyde compounds linear and saturated aldehydes such as acetaldehyde, hexanal and decanal, linear and unsaturated aldehydes such as (E) -2-hexenal and 2,4-octadienal, terpene aldehydes such as citronellal and citral, benzaldehyde, Aromatic aldehydes such as cinnamyl aldehyde, vanillin, ethyl vanillin, furfural, heliotropin and the like can be mentioned.
- ketone compounds linear, saturated and unsaturated ketones such as 2-heptanone, 2-undecanone and 1-octen-3-one, acetoin, diacetyl, 2,3-pentadione, maltol, ethyl maltol, 2,5-dimethyl- Derived from linear and cyclic diketones such as 4-hydroxy-3 (2H) -furanone and terpene decomposition products such as hydroxy ketones, terpene ketones such as carvone, menthone and nootkatone, ⁇ -ionone, ⁇ -ionone and ⁇ -damerone Aromatic ketones such as ketone and raspberry ketone can be mentioned.
- furan ether compounds include cyclic ethers such as rose oxide, linalool oxide, mentfuran and theaspirane.
- Ester compounds of fatty alcohols such as ethyl acetate and isoamyl acetate, terpene alcohol acetates such as linalyl acetate and geranyl acetate, fatty acids such as ethyl butyrate and ethyl caproate, and lower alcohol esters such as benzyl acetate and methyl salicylate
- fatty alcohols such as ethyl acetate and isoamyl acetate
- terpene alcohol acetates such as linalyl acetate and geranyl acetate
- fatty acids such as ethyl butyrate and ethyl caproate
- lower alcohol esters such as benzyl acetate and methyl salicylate
- An aromatic ring may be an ester.
- lactone compound examples include saturated lactones such as ⁇ -decalactone, ⁇ -dodecalactone, ⁇ -decalactone, and ⁇ -dodecalactone, and unsaturated lactones such as 7-decen-4-olide and 2-decen-5-olide.
- the acid compound examples include saturated / unsaturated fatty acids such as butyric acid, octanoic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid.
- nitrogen-containing compounds examples include indole, skatole, pyridine, alkyl-substituted pyrazine, methyl anthranilate and the like.
- sulfur-containing compounds examples include methanethiol, dimethyl sulfide, dimethyl disulfide, and allyl isothiocyanate.
- examples of synthetic fragrances for cosmetics include ⁇ -amylcinnamyl aldehyde, dihydrojasmon, methylionone, ⁇ -damascone, acetyl cedrene, methyl dihydrojasmonate, and cyclopentadecanolide.
- Natural essential oils include orange, lemon, bergamot, mandarin, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang ylang, anise, clove, ginger, nutmeg, cardamom, cedar, Hinoki, vetiver, patchouli, and lovedanum.
- herb / spice extracts coffee / green tea / tea / oolong tea extracts, milk or processed milk products, and enzyme degradation products such as lipases / proteases are also included.
- a solvent such as water or ethanol, ethylene glycol, propylene glycol, dipropylene glycol, 1, Perfume retention agents such as 3-butylene glycol, glycerin, hexylene glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hercoline, fatty acid triglyceride, and fatty acid diglyceride can be contained.
- the refreshing sensation agent of the present invention can be used alone or by preparing a fragrance composition containing a refreshing sensation persistence agent. The characteristic that lasts is given.
- Beverages soft drinks such as fruit juice drinks, vegetable drinks, sports drinks, honey drinks, soy milk, vitamin supplement drinks, mineral supplement drinks, nutrition drinks, nourishment drinks, lactic acid bacteria drinks, milk drinks; green tea, black tea, oolong tea, herbal tea Taste drinks such as milk tea and coffee drinks; alcoholic drinks such as chu-hi, cocktail drinks, sparkling liquor, fruit liquor, and condiments; dairy products such as butter, cheese, milk, and yogurt; ice cream, lacto ice, ice confectionery, Manufactures desserts such as yogurt, pudding, jelly, daily dessert and the like Mixes such as caramel, candy, tablet confectionery, crackers, biscuits, cookies, pie, chocolate, snacks and other mixes such as cake mixes for producing them; bread, soup, various instant foods, etc. General foods; however, it is
- the blending amount of the refreshing sensation sustaining agent comprising the highly purified monomenthyl glutarate of the present invention as an active ingredient is, for example, 0.0001% (1.0 ppm) to 20% (2.0 ⁇ 10 4) in the fragrance composition. 5 ppm), preferably 0.001% (10 ppm) to 10% (1.0 ⁇ 10 5 ppm).
- the refreshing agent containing purified monomentyl glutarate as an active ingredient is 0.
- a range of 1 ppm to 10,000 ppm, preferably 1 ppm to 1000 ppm can be exemplified. Within these ranges, a refreshing refreshing feeling is maintained particularly for food and drink, and it has excellent characteristics that do not impair the flavor of food and drink with added aftertaste.
- reaction crude product and the product were measured using the following analytical instruments.
- Molecular distillation apparatus Simple molecular distillation apparatus MDU60-05J manufactured by Asahi Seisakusho Co., Ltd.
- Example 1 Synthesis example 1 of monomenthyl glutarate using an ether solvent-1 1,2-Dimethoxyethane (70 g) was added to 1-menthol (62.5 g, 0.4 mol), and the mixture was heated to reflux at 100 ° C. to dissolve menthol. A mixture of glutaric anhydride (45.6 g, 0.4 mol) and paratoluenesulfonic acid monohydrate (0.8 g, 0.004 mol) dissolved in 1,2-dimethoxyethane (100 g). was added dropwise over 30 minutes at the same temperature. After completion of the dropwise addition, the reaction was completed by further heating to reflux for 9 hours. The GC analysis value of MMG / DMG at the completion of the reaction was 8/2.
- the organic layer (C) was washed successively with 1% aqueous sodium acetate solution (100 g), 5% aqueous sodium acetate solution (100 g), and 10% brine (100 g), and the solvent was recovered under reduced pressure to obtain MMG (85.2 g). , Purity 95.8%).
- MMG 85.2 g
- Purity 95.8% Next, further purified MMG (77.8 g) was obtained by obtaining a fraction by thin-film molecular distillation (plate temperature 150 ° C., degree of vacuum 12-38 Pa).
- the obtained MMG had a purity of 96.8% by GC analysis, and contained other 1-menthol 1.3% and DMG 1.9%.
- the organic layer (B) is similarly washed successively with 1% aqueous sodium acetate solution (100 g), 5% aqueous sodium acetate solution (100 g), and 10% saline solution (100 g), and the solvent is recovered under reduced pressure. This gave crude DMG (25.0 g).
- Example 2 Synthesis example 2 of monomenthyl glutarate using an ether solvent-2 1,4-Dioxane (70 g) was added to 1-menthol (62.5 g, 0.4 mol), and the mixture was heated to reflux at 120 ° C. to dissolve menthol. A mixed solution in which glutaric anhydride (45.6 g, 0.4 mol) and paratoluenesulfonic acid monohydrate (0.8 g, 0.004 mol) were dissolved in 1,4-dioxane (100 g) was added. It dripped over 30 minutes under the same temperature. After completion of the dropwise addition, the reaction was completed by heating at reflux for 6 hours. The GC analysis value of MMG / DMG at the completion of the reaction was 7/3.
- This esterification reaction solution was subjected to the same operation as in Example 1 to obtain MMG having a purity of 95.2%. Further, MMG (68.1 g, purity 96.1%) was obtained by purification by thin film molecular distillation.
- Example 3 Synthesis example 3 of monomenthyl glutarate using an ether solvent-3 Diisopropyl ether (70 g) was added to 1-menthol (62.5 g, 0.4 mol), and the mixture was heated to reflux at 90 ° C. to dissolve menthol. A mixed solution of glutaric anhydride (45.6 g, 0.4 mol) and paratoluenesulfonic acid monohydrate (0.8 g, 0.004 mol) dissolved in diisopropyl ether (100 g) was added at the same temperature. Then, it was dropped over 30 minutes. After completion of the dropwise addition, the reaction is completed by heating at reflux for 9 hours. The GC analysis value of MMG / DMG at the completion of the reaction was 8/2.
- This esterification reaction solution was subjected to the same operation as in Example 1 to obtain MMG having a purity of 95.4%. Further, MMG (74.8 g, purity 96.2%) was obtained by purification by distillation.
- the organic layer (D) was washed successively with 1% aqueous sodium acetate solution (100 g), 5% aqueous sodium acetate solution (100 g), and 10% brine (100 g), and the solvent was recovered under reduced pressure to obtain MMG (72.4 g). , Purity 95.4%).
- Comparative Example 1 Purity of monomenthyl glutarate according to the degree of vacuum during distillation Comparison of the purity of monomenthyl glutarate and the distillation state in the distillate due to the difference in the degree of vacuum in the crude MMG distillation step before the distillation step obtained in Example 1 A comparison was made.
- Experimental equipment Oil rotary vacuum pump and 5 cm short path distillation tower under glass branch.
- Comparative Example 1-1 when simple distillation was performed at a reduced pressure of 300 Pa and an internal temperature of 220 ° C., generation of menthol due to disproportionation was observed at around 200 ° C., and the purity of the distilled MMG was 85.6%. .
- Comparative Example 1-2 simple distillation was performed at a reduced pressure of 700 Pa and an internal temperature of 250 ° C. in the same manner as Comparative Example 1-1.
- Example 5 Sensory evaluation of monomenthyl glutarate and dimenthyl glutarate Crude DMG obtained from the organic layer (B) concentrate described in Examples 1 to 4 was purified by silica gel column chromatography, and DMG having a purity of 99% or more Got. The MMGs obtained in Examples 1 to 4 were also purified to MMG having a purity of 99% or more by silica gel column chromatography. Sensory evaluation of purified DMG and MMG was performed.
- Evaluation was carried out by preparing a 0.01% water dilute solution of monoester and diester, and 7 skilled panelists included the dilute solution in their mouths and evaluated the flavor. As an evaluation, the initial evaluation when it was put in the mouth as a flavor and the change in flavor when it was exhaled after the diluted solution was put in the mouth for about 1 minute were evaluated as a aftertaste.
- DMG was evaluated as having a characteristic of feeling a fat and oily taste in the aftertaste when used as a food or drink, although it has a refreshing effect.
- monomenthyl glutarate also had a refreshing feeling and a slight bitter taste, but was evaluated not to have the fat and oily taste that is a characteristic of diesters.
- Example 6 Flavor evaluation based on the content ratio of monomenthyl glutarate and dimenthyl glutarate According to the formulation described in Table 4, MMG and DMG high-purity products obtained in Example 5 were added to the mint-type brackish flavor added with menthol.
- the mixing ratio of MMG / DMG is 50/50 (reference product 1), 70/30 (reference product 2), 90/10 (reference product 3), 95/5 (present product 1), 98/2. (Invention product 2) was prepared.
- the flavor evaluation sample 0.1 g prepared above was diluted to 100 g with purified water, and 7 skilled panelists included the diluted solution in their mouths to evaluate the flavor.
- the evaluation was performed by setting the middle of each evaluation as 2 points and 4 points).
- the fragrance containing the refreshing agent of the present invention 1 and the present invention 2 containing monomenthyl glutarate purified to 95% or more by flavor evaluation as an active ingredient is an aftertaste immediately after eating and after 1 minute.
- a refreshing feeling was felt, and the evaluation score was high evaluation of 30 points or more out of 35 points for each item.
- Reference 1 to Reference 3 with a high content of dimentil glutarate The content of dimentil glutarate increased and the evaluation point regarding aftertaste was reduced. The content of dimentyl glutarate and the miscellaneous taste of the aftertaste were evident.
- the evaluation was highly correlated.
- the reference product 1 in which the same amount of monomenthyl glutarate and dimenthyl glutarate was mixed was poor in both refreshing feeling and aftertaste.
- Example 7 Effect of addition to mint-based blended fragrance
- the ingredients in Table 6 were formulated as mint-based fragrance compositions.
- the mint-based blended fragrance composition (Comparative product 1) was mixed with the highly purified MMG (purity 96.8%) obtained in Example 1 and purified in the present product 3 and Example 4.
- Inventive product 4 mixed with MMG (purity 97.2%) was prepared.
- a reference product 4 to which a 70/30 mixture of MMG and DMG purified in Example 5 was added and a reference product 5 to which a 90/10 mixture was added were prepared and subjected to sensory evaluation.
- Comparative product 1 containing no monomenthyl glutarate was inferior in the refreshing feeling, but the aftertaste was not appreciated and was highly evaluated.
- the products 3 and 4 of the present invention containing high-purity monomenthyl glutarate were highly evaluated with 30 points or more, with no items of refreshing feeling and sustainability and aftertaste.
- the reference product 4 and the reference product 5 were not highly evaluated for the refreshing feeling compared to the product 3 of the present invention and the product 4 of the present invention, and were particularly low in terms of aftertaste.
- the flavor aftertaste had a greasy feeling and the mint flavor was deteriorated.
- Example 8 Effect of addition to mint-based gum Based on the formulation shown in Table 8, sugars and solvents were added to a general gum base, and Comparative Product 1 and Reference Product 4 prepared in Example 7 as a fragrance. , A mint gum to which the reference product 5, the present invention product 3, and the present invention product 4 were added was prepared.
- Comparative product 2 is a mint-based gum that does not contain menthyl glutarate to which comparative product 1 is added, comparative product 2, and a mint-based gum that has 70% of monomenthyl glutarate content added to reference product 4 is a comparative product 3 and monomentyl glutarate content
- a mint-based gum to which 90% of the reference product 5 was added was added to the comparative product 4, the inventive product 3 and the inventive product 4 having a monomentyl glutarate content of 98% prepared in Examples 1 and 4.
- the mint-based gum is referred to as Invention Product 5 and Invention Product 6.
- Comparative product 2 which does not contain monomenthyl glutarate did not feel miscellaneous taste, and was highly evaluated for aftertaste.
- inventive product 5 and the inventive product 6 containing high-purity monomenthyl glutarate were highly evaluated with 30 points or more without the items of refreshing feeling and sustainability and the aftertaste after mastication.
- the comparative product 3 and the comparative product 4 high evaluation was not obtained for the persistence of the refreshing feeling, and particularly, the aftertaste was low.
- a decrease in refreshing feeling was not felt, but it was determined that the taste of mint gradually became unpleasant when chewing for 10 minutes.
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Abstract
Description
グルタル酸ジメンチルについては飲食品に使用することは記載されているが、官能的な特性、特に、清涼感と味に関する詳細な記載は見当たらない。 On the other hand, among the menthyl glutarate, as a method for producing menthyl glutarate that enhances the selectivity of MMG production, the molar ratio of glutaric anhydride to l-menthol is reacted in the presence of a basic catalyst at about 1/1. Thus, a method has been proposed in which a reaction mixture in which the molar ratio of MMG / DMG can be converted to about 17/1 at maximum from the analytical value is obtained (Patent Document 3). This document also suggests that the analytical value yield is 78% and that menthol monoesters have excellent physiological cooling properties. However, this document only discloses an analytical comparison regarding purity, and specifically describes how a product of menthyl glutarate with a high MMG content can be isolated and purified from the reaction mixture. No mention is made. Of course, there is no specific description as to what use the product of the menthyl glutarate has.
Although dimenthyl glutarate is described for use in foods and drinks, there is no detailed description regarding sensory characteristics, particularly refreshing feeling and taste.
かくして、本発明によればは以下の態様の発明が提供される。 Furthermore, the present inventors have provided an industrial process for producing menthyl glutarate that can be effectively used for the preparation of a mixture in which the content ratio of DMG is approximately 5% by mass or less in the mixture of MMG and DMG as described above. We have been eagerly researching to provide As a result, for example, a composition containing commercially available MMG and DMG, which is derived from a natural product or a chemical synthesis containing DMG at a certain content or more, is used as a starting material. It has been found that, when extracted with an aqueous solution, a mixture having a DMG content ratio of less than about 5% by mass in a mixture of MMG and DMG can be efficiently prepared. In addition, the purified mixture with increased content of MMG suppresses the formation of glutaric acid and menthol or dimenthyl glutarate due to disproportionation due to the acidity of MMG itself by distillation under high vacuum. It was also found that even higher purity MMG can be obtained in this state. Of course, such a preparation method can be applied to a composition in which the content ratio of DMG exceeds 5 mass% in a mixture of MMG and DMG.
Thus, according to the present invention, the following aspects of the invention are provided.
(2)(1)に記載の清涼感持続剤を有効成分として配合した香料組成物。
(3)(1)に記載の清涼感持続剤を添加した飲食品または香粧品。
(4)(2)に記載の香料組成物を添加した飲食品または香粧品。
(5)グルタル酸モノメンチル(MMG)およびグルタル酸ジメンチル(DMG)を含む組成物からMMGを高含有率で含んでなる精製された組成物の調整方法であって、
(a)該MMGとDMGを含む組成物中のMMGをアルカリ水溶液で抽出する工程、
(b)工程(a)で得られるアルカリ水溶液を、有機酸を用いて中和する工程、及び
(c)(b)の工程を経て得られたグルタル酸メンチルを回収する工程
を含んでなり、かつ、
該MMGおよびDMGを含む組成物がMMGとDMGからなる混合物としてDMGが5質量%を超えて存在し、
該精製された組成物において、MMGとDMGからなる混合物としてMMGが95質量%もしくはそれを超えて存在する、調製方法。
(6)上記(5)に記載の調整方法であって、さらに、
(d)MMGを、5Pa~100Paの高真空下で蒸留精製する工程
を含む、調製方法。
(7)上記(5)または(6)に記載の調製方法であって、
該MMGとDMGを含む組成物が、モル比で9~6/1~4、好ましくは8.5~6.5/1.5~4.5、より好ましくは8~7/2~3の混合物である、調製方法。
(8)上記(5)または(6)に記載の調整方法であって、該MMGとDMGを含む組成物がメントールおよびグルタル酸無水物のいずれもが溶媒に溶解した状態でエステルの形成される条件下で両原料を反応させることによって得られる、調製方法。
(9)上記(5)に記載の調製方法であって、
工程(a)及び(b)が水非混和性有機溶媒の共存下で実施され、グルタル酸モノメンチルが当該有機溶媒により抽出される、調製方法。
(10)上記(8)に記載の調製方法であって、溶媒がエーテル系溶媒である、調製方法。
(11)上記(10)に記載の調製方法であって、エーテル系溶媒が1,2-ジメトキシエタン、ジイソプロピルエーテル、1,4-ジオキサンおよびメチルターシャリーブチルエーテルからなる群より選ばれる1種または2種以上の溶媒である、調製方法。
(12)上記(8)に記載の調製方法であって、メントールおよびグルタル酸無水物が、それぞれモル比で、1.2~1.0/1である、調製方法。 (1) A refreshing sensation sustaining agent comprising monomenthyl glutarate (MMG) and dimenthyl glutarate (DMG), wherein MMG is present as a mixture of MMG and DMG in an amount of 95% by mass or more, and DMG A refreshing sensation persisting agent present at 5% by weight or less.
(2) A fragrance composition containing the refreshing sensation sustaining agent according to (1) as an active ingredient.
(3) Food / beverage products or cosmetics to which the refreshing sensation sustaining agent according to (1) is added.
(4) A food or drink or cosmetic to which the fragrance composition according to (2) is added.
(5) A method for preparing a purified composition comprising a high content of MMG from a composition comprising monomenthyl glutarate (MMG) and dimenthyl glutarate (DMG),
(A) a step of extracting MMG in the composition containing MMG and DMG with an aqueous alkaline solution;
(B) comprising a step of neutralizing the alkaline aqueous solution obtained in step (a) with an organic acid, and a step of recovering menthyl glutarate obtained through steps (c) and (b). And,
The composition containing MMG and DMG is present as a mixture of MMG and DMG in an amount of more than 5% by weight of DMG;
A method of preparation, wherein in the purified composition, MMG is present as a mixture of MMG and DMG in an amount of 95% by mass or more.
(6) The adjustment method according to (5) above, further comprising:
(D) A preparation method comprising a step of distilling and purifying MMG under a high vacuum of 5 Pa to 100 Pa.
(7) The preparation method according to (5) or (6) above,
The composition containing MMG and DMG has a molar ratio of 9 to 6/1 to 4, preferably 8.5 to 6.5 / 1.5 to 4.5, more preferably 8 to 7/2 to 3. Preparation method, which is a mixture.
(8) The adjustment method according to the above (5) or (6), wherein an ester is formed in a state where both the menthol and glutaric anhydride are dissolved in the solvent in the composition containing MMG and DMG. A preparation method obtained by reacting both raw materials under conditions.
(9) The preparation method according to (5) above,
A preparation method, wherein steps (a) and (b) are carried out in the presence of a water-immiscible organic solvent, and monomenthyl glutarate is extracted with the organic solvent.
(10) The preparation method according to (8) above, wherein the solvent is an ether solvent.
(11) The preparation method according to the above (10), wherein the ether solvent is selected from the group consisting of 1,2-dimethoxyethane, diisopropyl ether, 1,4-dioxane and methyl tertiary butyl ether. A preparation method that is a solvent of more than one species.
(12) The preparation method according to the above (8), wherein menthol and glutaric anhydride are each in a molar ratio of 1.2 to 1.0 / 1.
以下、実施例により本発明をさらに具体的に説明するが、これらの実施例により本発明が何ら限定されるものでない。 Although the blending amount of the fragrance composition in the product to be used varies depending on the purpose or the kind of the target, the refreshing agent containing purified monomentyl glutarate as an active ingredient is 0. A range of 1 ppm to 10,000 ppm, preferably 1 ppm to 1000 ppm can be exemplified. Within these ranges, a refreshing refreshing feeling is maintained particularly for food and drink, and it has excellent characteristics that do not impair the flavor of food and drink with added aftertaste.
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.
GC測定:GC-2014(島津製作所社製)およびクロマトパックC-R8A(島津製作所社製)
GCカラム:ジーエルサイエンス社製TC-1(長さ30m、内径0.53mm、液層膜厚1.50マイクロメータ)
GC/MS測定:5973N(Agilent社製)
GCカラム:ジーエルサイエンス社製TC-1701(長さ30m、内径0.25mm、液層膜厚0.25マイクロメータ)
分子蒸留装置:旭製作所株式会社製簡易分子蒸留装置MDU60-05J。 In the examples and comparative examples, the reaction crude product and the product were measured using the following analytical instruments.
GC measurement: GC-2014 (manufactured by Shimadzu Corporation) and Chromatopack C-R8A (manufactured by Shimadzu Corporation)
GC column: TC-1 manufactured by GL Sciences Inc. (length 30 m, inner diameter 0.53 mm, liquid layer film thickness 1.50 micrometers)
GC / MS measurement: 5973N (manufactured by Agilent)
GC column: TC-1701 (length 30 m, inner diameter 0.25 mm, liquid layer film thickness 0.25 micrometers) manufactured by GL Sciences Inc.
Molecular distillation apparatus: Simple molecular distillation apparatus MDU60-05J manufactured by Asahi Seisakusho Co., Ltd.
l-メントール(62.5g、0.4モル)に1,2-ジメトキシエタン(70g)を加え、100℃にて加熱還流し、メントールを溶解した。ここにグルタル酸無水物(45.6g、0.4モル)およびパラトルエンスルホン酸一水和物(0.8g、0.004モル)を1,2-ジメトキシエタン(100g)に溶解した混合液を同温度下で、30分かけて滴下した。滴下終了後、さらに9時間加熱還流することにより反応が完結した。反応完結時のMMG/DMGのGC分析値は8/2であった。 Example 1: Synthesis example 1 of monomenthyl glutarate using an ether solvent-1
1,2-Dimethoxyethane (70 g) was added to 1-menthol (62.5 g, 0.4 mol), and the mixture was heated to reflux at 100 ° C. to dissolve menthol. A mixture of glutaric anhydride (45.6 g, 0.4 mol) and paratoluenesulfonic acid monohydrate (0.8 g, 0.004 mol) dissolved in 1,2-dimethoxyethane (100 g). Was added dropwise over 30 minutes at the same temperature. After completion of the dropwise addition, the reaction was completed by further heating to reflux for 9 hours. The GC analysis value of MMG / DMG at the completion of the reaction was 8/2.
l-メントール(62.5g、0.4モル)に1,4-ジオキサン(70g)を加え、120℃にて加熱還流し、メントールを溶解した。ここにグルタル酸無水物(45.6g、0.4モル)およびパラトルエンスルホン酸一水和物(0.8g、0.004モル)を1,4-ジオキサン(100g)に溶解した混合液を同温度下で、30分かけて滴下した。滴下終了後、さらに6時間加熱還流し反応を完結した。反応完結時のMMG/DMGのGC分析値は7/3であった。 Example 2: Synthesis example 2 of monomenthyl glutarate using an ether solvent-2
1,4-Dioxane (70 g) was added to 1-menthol (62.5 g, 0.4 mol), and the mixture was heated to reflux at 120 ° C. to dissolve menthol. A mixed solution in which glutaric anhydride (45.6 g, 0.4 mol) and paratoluenesulfonic acid monohydrate (0.8 g, 0.004 mol) were dissolved in 1,4-dioxane (100 g) was added. It dripped over 30 minutes under the same temperature. After completion of the dropwise addition, the reaction was completed by heating at reflux for 6 hours. The GC analysis value of MMG / DMG at the completion of the reaction was 7/3.
l-メントール(62.5g、0.4モル)にジイソプロピルエーテル(70g)を加え、90℃にて加熱還流し、メントールを溶解した。ここにグルタル酸無水物(45.6g、0.4モル)およびパラトルエンスルホン酸一水和物(0.8g、0.004モル)をジイソプロピルエーテル(100g)に溶解した混合液を同温度下で、30分かけて滴下した。滴下終了後、さらに9時間加熱還流し反応を完結する。反応完結時のMMG/DMGのGC分析値は8/2であった。 Example 3: Synthesis example 3 of monomenthyl glutarate using an ether solvent-3
Diisopropyl ether (70 g) was added to 1-menthol (62.5 g, 0.4 mol), and the mixture was heated to reflux at 90 ° C. to dissolve menthol. A mixed solution of glutaric anhydride (45.6 g, 0.4 mol) and paratoluenesulfonic acid monohydrate (0.8 g, 0.004 mol) dissolved in diisopropyl ether (100 g) was added at the same temperature. Then, it was dropped over 30 minutes. After completion of the dropwise addition, the reaction is completed by heating at reflux for 9 hours. The GC analysis value of MMG / DMG at the completion of the reaction was 8/2.
市場より調達したMMG(120g、MMG/DMG=71/29、GCピーク面積による)をヘプタン(120g)に溶解した。10%炭酸ソーダ水溶液(425g、0.4モル相当)を加え撹拌し、水層(A)と有機層(B)とを分離する。水層(A)にクエン酸一水和物(90.5g、0.43モル)およびヘプタン(120g)を加え撹拌し、水層(C)と有機層(D)を分離する。有機層(D)を1%酢酸ソーダ水溶液(100g)、5%酢酸ソーダ水溶液(100g)、10%食塩水(100g)にて順次洗浄し減圧下にて溶媒を回収し、MMG(72.4g、純度95.4%)を得た。 Example 4: MMG (120 g, MMG / DMG = 71/29, depending on GC peak area) procured from a highly purified market of menthyl glutarate was dissolved in heptane (120 g). A 10% sodium carbonate aqueous solution (425 g, equivalent to 0.4 mol) is added and stirred, and the aqueous layer (A) and the organic layer (B) are separated. Citric acid monohydrate (90.5 g, 0.43 mol) and heptane (120 g) are added to the aqueous layer (A) and stirred, and the aqueous layer (C) and the organic layer (D) are separated. The organic layer (D) was washed successively with 1% aqueous sodium acetate solution (100 g), 5% aqueous sodium acetate solution (100 g), and 10% brine (100 g), and the solvent was recovered under reduced pressure to obtain MMG (72.4 g). , Purity 95.4%).
実施例1で得られた蒸留工程前の粗製MMG蒸留工程において減圧度の違いによる留出液中のグルタル酸モノメンチル純度と蒸留状態の比較を行った。
実験装置:油回転真空ポンプおよびガラス製枝下5cmショートパス蒸留塔。 Comparative Example 1: Purity of monomenthyl glutarate according to the degree of vacuum during distillation Comparison of the purity of monomenthyl glutarate and the distillation state in the distillate due to the difference in the degree of vacuum in the crude MMG distillation step before the distillation step obtained in Example 1 A comparison was made.
Experimental equipment: Oil rotary vacuum pump and 5 cm short path distillation tower under glass branch.
実施例1~実施例4に記載の有機層(B)濃縮物より得られる粗製DMGをシリカゲルカラムクロマトにより精製し、純度99%以上のDMGを得た。また、実施例1~実施例4で得たMMGも同様シリカゲルカラムクロマトにより純度99%以上のMMGに精製した。精製したDMGとMMGの官能評価を実施した。 Example 5: Sensory evaluation of monomenthyl glutarate and dimenthyl glutarate Crude DMG obtained from the organic layer (B) concentrate described in Examples 1 to 4 was purified by silica gel column chromatography, and DMG having a purity of 99% or more Got. The MMGs obtained in Examples 1 to 4 were also purified to MMG having a purity of 99% or more by silica gel column chromatography. Sensory evaluation of purified DMG and MMG was performed.
表4に記載した処方に従って、メントールを添加したミント系はっか香料に対して実施例5により得られたMMGとDMG高純度品を使用してMMG/DMGの混合比が50/50(参考品1)、70/30(参考品2)、90/10(参考品3)、95/5(本発明品1)、98/2(本発明品2)を調製した。 Example 6: Flavor evaluation based on the content ratio of monomenthyl glutarate and dimenthyl glutarate According to the formulation described in Table 4, MMG and DMG high-purity products obtained in Example 5 were added to the mint-type brackish flavor added with menthol. The mixing ratio of MMG / DMG is 50/50 (reference product 1), 70/30 (reference product 2), 90/10 (reference product 3), 95/5 (present product 1), 98/2. (Invention product 2) was prepared.
ミント系香料組成物として表6の成分を用いて調合した。ミント系調合香料組成物(比較品1)に対して実施例1で得られた高純度化されたMMG(純度96.8%)を混合した本発明品3および実施例4で高純度化されたMMG(純度97.2%)を混合した本発明品4を調製した。また、実施例5で高純度化したMMGとDMGを70/30の混合物を添加した参考品4、90/10の混合物を添加した参考品5を調製し、官能評価を行った。 Example 7: Effect of addition to mint-based blended fragrance The ingredients in Table 6 were formulated as mint-based fragrance compositions. The mint-based blended fragrance composition (Comparative product 1) was mixed with the highly purified MMG (purity 96.8%) obtained in Example 1 and purified in the present product 3 and Example 4. Inventive product 4 mixed with MMG (purity 97.2%) was prepared. Further, a reference product 4 to which a 70/30 mixture of MMG and DMG purified in Example 5 was added and a reference product 5 to which a 90/10 mixture was added were prepared and subjected to sensory evaluation.
表8に示した配合表を基に、一般的なガム基剤に糖類、溶剤を加え、香料として実施例7で調製した比較品1、参考品4,参考品5および本発明品3,本発明品4を添加したミント系ガムを調製した。比較品1を添加したグルタル酸メンチルを含まないミント系ガムを比較品2、グルタル酸モノメンチルの含有量が70%の参考品4を添加したミント系ガムを比較品3およびグルタル酸モノメンチルの含有量が90%の参考品5を添加したミント系ガムを比較品4、実施例1および実施例4で調製したグルタル酸モノメンチルの含有量が98%の本発明品3および本発明品4を添加したミント系ガムを本発明品5および本発明品6とする。 Example 8: Effect of addition to mint-based gum Based on the formulation shown in Table 8, sugars and solvents were added to a general gum base, and Comparative Product 1 and Reference Product 4 prepared in Example 7 as a fragrance. , A mint gum to which the reference product 5, the present invention product 3, and the present invention product 4 were added was prepared. Comparative product 2 is a mint-based gum that does not contain menthyl glutarate to which comparative product 1 is added, comparative product 2, and a mint-based gum that has 70% of monomenthyl glutarate content added to reference product 4 is a comparative product 3 and monomentyl glutarate content A mint-based gum to which 90% of the reference product 5 was added was added to the comparative product 4, the inventive product 3 and the inventive product 4 having a monomentyl glutarate content of 98% prepared in Examples 1 and 4. The mint-based gum is referred to as Invention Product 5 and Invention Product 6.
Comparative product 2 which does not contain monomenthyl glutarate did not feel miscellaneous taste, and was highly evaluated for aftertaste. On the other hand, the inventive product 5 and the inventive product 6 containing high-purity monomenthyl glutarate were highly evaluated with 30 points or more without the items of refreshing feeling and sustainability and the aftertaste after mastication. In the average evaluation of the panel, it was evaluated that the refreshing sensation persisted even after 10 minutes of chewing and that no miscellaneous taste that impairs the mint flavor was felt. The comparative product 3 and the comparative product 4, high evaluation was not obtained for the persistence of the refreshing feeling, and particularly, the aftertaste was low. In the average evaluation of the panel, a decrease in refreshing feeling was not felt, but it was determined that the taste of mint gradually became unpleasant when chewing for 10 minutes.
Claims (12)
- グルタル酸モノメンチル(MMG)およびグルタル酸ジメンチル(DMG)を含んでなる清涼感持続剤であって、MMGとDMGからなる混合物としてMMGが95質量%もしくはそれを超えて存在し、DMGが5質量%もしくはそれ未満存在する、清涼感持続剤。 A refreshing sensation agent comprising monomenthyl glutarate (MMG) and dimenthyl glutarate (DMG), wherein MMG is present as a mixture of MMG and DMG in an amount of 95% by mass or more, and DMG is 5% by mass. Or a refreshing agent that is less than that.
- 請求項1に記載の清涼感持続剤を有効成分として配合した香料組成物。 A fragrance composition containing the refreshing sensation sustaining agent according to claim 1 as an active ingredient.
- 請求項1に記載の清涼感持続剤を添加した飲食品または香粧品。 Food / beverage products or cosmetics to which the refreshing sensation sustaining agent according to claim 1 is added.
- 請求項2に記載の香料組成物を添加した飲食品または香粧品。 Food / beverage products or cosmetics to which the fragrance composition according to claim 2 is added.
- グルタル酸モノメンチル(MMG)およびグルタル酸ジメンチル(DMG)を含む組成物からMMGを高含有率で含んでなる精製された組成物の調整方法であって、
(a)該MMGとDMGを含む組成物中のMMGをアルカリ水溶液で抽出する工程、
(b)工程(a)で得られるアルカリ水溶液を、有機酸を用いて中和する工程、及び
(c)(b)の工程を経て得られたグルタル酸メンチルを回収する工程
を含んでなり、かつ、
該MMGとDMGを含む組成物がMMGとDMGからなる混合物としてDMGが5質量%を超えて存在し、
該精製された組成物において、MMGとDMGからなる混合物としてMMGが95質量%もしくはそれを超えて存在する、
調製方法。 A process for preparing a purified composition comprising a high content of MMG from a composition comprising monomenthyl glutarate (MMG) and dimenthyl glutarate (DMG),
(A) a step of extracting MMG in the composition containing MMG and DMG with an aqueous alkaline solution;
(B) comprising a step of neutralizing the alkaline aqueous solution obtained in step (a) with an organic acid, and a step of recovering menthyl glutarate obtained through steps (c) and (b). And,
The composition containing MMG and DMG is present as a mixture of MMG and DMG in an amount of more than 5% by weight of DMG;
In the purified composition, MMG is present as a mixture of MMG and DMG in an amount of 95% by mass or more,
Preparation method. - 請求項5に記載の調整方法であって、さらに、
(d)MMGを、5Pa~100Paの高真空下で蒸留精製する工程
を含む、調製方法。 The adjustment method according to claim 5, further comprising:
(D) A preparation method comprising a step of distilling and purifying MMG under a high vacuum of 5 Pa to 100 Pa. - 請求項5または6に記載の調製方法であって、
該MMGおよびDMGを含む組成物が、モル比でMMGおよびDMGを9~6/1~4の混合物を含む、調製方法。 The preparation method according to claim 5 or 6, comprising:
A method of preparation, wherein the composition comprising MMG and DMG comprises a mixture of MMG and DMG at a molar ratio of 9-6 / 1-4. - 請求項5または6に記載の調製方法であって、
工程(a)が水非混和性有機溶媒の共存下で実施され、MMGが当該有機溶媒により抽出される、調製方法。 The preparation method according to claim 5 or 6, comprising:
A preparation method, wherein step (a) is carried out in the presence of a water-immiscible organic solvent, and MMG is extracted with the organic solvent. - 請求項5または6に記載の調整方法であって、該MMGおよびDMGを含む組成物がメントールおよびグルタル酸無水物のいずれもが溶媒に溶解した状態でエステルの形成される条件下で両原料を反応させることによって得られる、調製方法。 The preparation method according to claim 5 or 6, wherein the composition containing MMG and DMG is obtained by using both raw materials under conditions in which an ester is formed in a state where both menthol and glutaric anhydride are dissolved in a solvent. A preparation method obtained by reacting.
- 請求項9に記載の調製方法であって、溶媒がエーテル系溶媒である、調製方法。 The preparation method according to claim 9, wherein the solvent is an ether solvent.
- 請求項10に記載の調製方法であって、エーテル系溶媒が1,2-ジメトキシエタン、ジイソプロピルエーテル、1,4-ジオキサンおよびメチルターシャリーブチルエーテルからなる群より選ばれる1種または2種以上の溶媒である、調製方法。 The preparation method according to claim 10, wherein the ether solvent is one or more solvents selected from the group consisting of 1,2-dimethoxyethane, diisopropyl ether, 1,4-dioxane and methyl tertiary butyl ether. The preparation method.
- 請求項9に記載の調製方法であって、メントールおよびグルタル酸無水物が、それぞれモル比で、1.2~1.0/1である、調製方法。
The preparation method according to claim 9, wherein menthol and glutaric anhydride are each in a molar ratio of 1.2 to 1.0 / 1.
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CN201480046116.7A CN105452430A (en) | 2013-09-13 | 2014-09-11 | Freshness-maintaining agent having reduced off-flavor |
JP2015536615A JP6130513B2 (en) | 2013-09-13 | 2014-09-11 | Refreshing agent with reduced miscellaneous taste |
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US6365215B1 (en) * | 2000-11-09 | 2002-04-02 | International Flavors & Fragrances Inc. | Oral sensory perception-affecting compositions containing dimethyl sulfoxide, complexes thereof and salts thereof |
JP2009519003A (en) * | 2005-10-05 | 2009-05-14 | キャドバリー アダムス ユーエスエー エルエルシー | Cool composition |
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