JP6443328B2 - Flavor material manufacturing method - Google Patents

Description

  The present invention relates to a method for producing a flavor material containing cycloten for imparting aroma and / or flavor to food or drink.

  Cycloten is one of cyclopentene derivatives, and its CAS registration number is 80-71-7. Cycloten is known to have a sweet caramel-like fragrance similar to maple and walnut (Non-Patent Document 1), and is considered to impart a favorable fragrance and / or flavor to foods and drinks.

  Cycloten is known to be contained in a very small amount in wine and Wasanbon sugar (Non-patent Documents 2 and 3).

  Non-Patent Document 4 reports that 0.008 to 0.987% of cycloten is contained in a wood vinegar solution prepared from cedar sapwood. However, wood vinegar has a problem that its production method is not suitable for use in foods, and there is a method for producing a flavor material containing a sufficient amount of cycloten that can give a preferred aroma and / or flavor to foods and drinks. It was desired.

  Non-Patent Document 5 describes about 20 kinds of compounds as a reaction product of glucose and proline by heating, and cycloten is described as one of them. Furthermore, in Non-Patent Document 6, cycloten is described as one of the compounds generated by thermal decomposition of 2,3-dihydro-3,5-dihydroxy-6-methyl-4 (H) -pyran-4-one. Yes. However, in any case, the amount of cycloten produced is not reported at all.

  In Non-Patent Document 7, about 40 kinds of compounds are reported as heating reaction products of glucose and glutamic acid, and one of them is cycloten (3-Methylcyclopent-2-en-2-ol-1-one). However, the amount of production is not reported at all. Furthermore, as shown in a comparative example described later, the amount of cycloten produced in the heated reaction product of this method was below the detection limit (0.01 ppm), and it was difficult to say that it contained a sufficient amount of cycloten.

Synthetic fragrances-Chemistry and product knowledge, Motoichi Into, Chemical Industry Daily, pp. 287-288 (2005) J. Agric. Food Chem. Vol. 47, 2837-2846, 1999 J. Nutr. Sci. Vitaminol. Vol. 27, 563-572, 1981 The Chemical Society of Japan No.3, 385-391, 2002 J. Agric. Food Chem. Vol. 41, 547-553, 1993 J. Agric. Food Chem. Vol. 44, 282-289, 1996 Z. Lebensm Unters Forsch Vol. 182, 219-223, 1986

  In view of the above circumstances, the problem to be solved by the present invention is to provide a method for producing a flavor material containing a sufficient amount of cycloten in order to impart flavor and / or flavor to foods and drinks suitable for food use. There is.

  The present inventors include one or more amino acids selected from the group consisting of aspartic acid, glutamic acid, methionine, valine and histidine, and salts thereof, or salts thereof, ribose, xylose, arabinose, glucose, fructose, By heating one or more sugars selected from the group consisting of sucrose, maltose, and lactose in an aqueous solution or suspension, a flavor material containing a sufficient amount of cycloten can be obtained. The headline and the present invention were completed.

  That is, the present invention provides aspartic acid, glutamic acid, methionine, valine, histidine, and one or two or more amino acids selected from the group consisting of these salts or salts thereof in an amount of 0.1-8.5M, and ribose, xylose. Heating an aqueous solution or suspension containing one or more saccharides selected from the group consisting of arabinose, glucose, fructose, sucrose, maltose and lactose at a final concentration of 0.1 to 6.7M And a process for producing a flavor material containing 0.1 ppm or more of cycloten.

  That is, the present invention is as follows.

[1] Aspartic acid, glutamic acid, methionine, valine, histidine, and one or two or more amino acids selected from the group consisting of these salts or salts thereof in an amount of 0.1-8.5M, and ribose, xylose, arabinose Heating an aqueous solution or suspension containing one or more sugars selected from the group consisting of glucose, fructose, sucrose, maltose and lactose at a final concentration of 0.1 to 6.7M. The manufacturing method of the flavor raw material which contains 0.1 ppm or more of cyclotenes.
[2] The method according to [1], comprising a step of heating an aqueous solution containing an amino acid or a salt thereof and a saccharide.
[3] The method according to [1] or [2], wherein the saccharide is one or more selected from the group consisting of xylose, glucose and fructose.
[4] The method according to any one of [1] to [3], wherein the amino acid or a salt thereof is sodium glutamate.
[5] The method according to any one of [1] to [4], wherein the pH when starting the heating is 5 to 9.
[6] The method according to any one of [1] to [5], wherein the heating temperature is 50 to 180 ° C.
[7] The method according to any one of [1] to [6], further including a step of adjusting the pH to 7 to 9 after the heating is started.
[8] A flavor material obtained by the method according to any one of [1] to [7].
[9] A food or drink containing the flavor material according to [8].
[10] A method for producing a food or drink comprising the step of adding the flavor material according to [8] such that the cycloten content per food or drink is 0.001 ppb to 100 ppm.
[11] Aspartic acid, glutamic acid, methionine, valine, histidine and one or two or more amino acids selected from the group consisting of these salts or salts thereof in an amount of 0.01 to 8.5 M, and ribose, xylose, arabinose , One or more saccharides selected from the group consisting of glucose, fructose, sucrose, maltose, and lactose at a final concentration of 0.01 to 6.7M, and further, moles of saccharides with respect to amino acids or salts thereof Aqueous solution or suspension containing a ratio of 0.01 to 105 moles per mole of amino acid or salt thereof, and the final concentration of amino acid or salt thereof and the final concentration of sugars both being less than 0.1M The manufacturing method of the flavor raw material which contains the process of heating a liquid and contains 0.1 ppm or more of cyclotenes.

According to the production method of the present invention, it is possible to provide a flavor material that is suitable for food use and contains a sufficient amount of cycloten to impart flavor and / or flavor to food and drink.
Moreover, the flavor raw material of this invention can provide preferable aroma and / or flavor to food-drinks.

The relative value of the amount of cyclotenes in the sample after the heating of Example 2 is shown. The amount of cyclotenes in the sample after the heating of Example 3 is shown. The amount of cyclotenes in the sample after the heating of Example 4 is shown. The sensory evaluation result of Example 5 is shown.

  In the present specification, “fragrance” means a fragrance (orthonasal flavor) that can be felt only by the nose without eating or drinking. The “flavor” means a fragrance (retro nasal flavor) that is felt during eating and drinking from the oral cavity to the nose.

  In the present specification, “%” means “% by weight” unless otherwise specified. In the present specification, “ppm” means “weight ppm” unless otherwise specified. Further, in the present specification, “M” means “mol / L (mol / liter)” unless otherwise specified.

In the present specification, the “sufficient amount of cycloten” means cycloten in an amount capable of imparting a preferred aroma and / or flavor to food and drink, specifically 0.1 ppm or more, preferably 1 ppm or more, more Preferably it means 5 ppm or more, most preferably 10 ppm or more of cycloten.

(1) Method for Producing Flavor Material of the Present Invention The method for producing a flavor material of the present invention (hereinafter also simply referred to as “the method of the present invention”) is a method for producing a flavor material containing 0.1 ppm or more of cycloten. Aspartic acid, glutamic acid, methionine, valine, histidine and one or more amino acids selected from the group consisting of these salts or salts thereof in an amount of 0.1-8.5M, and ribose, xylose, arabinose, glucose Heating an aqueous solution or suspension containing one or more saccharides selected from the group consisting of fructose, sucrose, maltose and lactose at a final concentration of 0.1-6.7M. Of course, other steps may be included.
The “final concentration” in an aqueous solution or suspension containing an amino acid or a salt thereof and a saccharide refers to the concentration in the aqueous solution in the case of an aqueous solution, and is heated and solubilized in the case of a suspension. The concentration in the aqueous solution after being applied. Moreover, also when performing pH adjustment of aqueous solution or suspension, the density before pH adjustment is said.

  The amino acid or salt thereof used in the method of the present invention is one or more selected from the group consisting of aspartic acid, glutamic acid, methionine, valine and histidine, and salts thereof, preferably sodium aspartate and / or Or it is sodium glutamate, More preferably, it is sodium glutamate. When an amino acid other than the above or a salt thereof is used, a sufficient amount of cycloten sufficient to impart a preferred aroma and / or flavor to the food or drink is not produced.

The amino acid salt used in the method of the present invention is not particularly limited as long as it is an edible salt. For example, for an acidic group such as a carboxyl group, a salt with an alkali metal such as sodium or potassium; Salts with alkaline earth metals such as calcium and magnesium; ammonium salts; aluminum salts; zinc salts; salts with organic amines such as triethylamine, ethanolamine, morpholine, pyrrolidine, piperidine, piperazine, dicyclohexylamine; arginine, lysine, etc. Mention may be made of salts with basic amino acids.
For basic groups such as amino groups, salts with inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrobromic acid; acetic acid, citric acid, benzoic acid, maleic acid, fumaric acid, tartaric acid , Salts with organic carboxylic acids such as succinic acid, tannic acid, butyric acid, hybenzic acid, pamoic acid, enanthic acid, decanoic acid, teocric acid, salicylic acid, lactic acid, oxalic acid, mandelic acid, malic acid; methanesulfonic acid, benzene Examples thereof include salts with organic sulfonic acids such as sulfonic acid and p-toluenesulfonic acid.

  The amino acid used in the method of the present invention includes D-form and L-form. In the present invention, either of them may be used, and a DL-form that is a racemic mixture may be used. Further, these amino acids can be purified products, and food materials containing these amino acids (for example, yeast extract, protein hydrolyzate, etc.) can be used, and are not particularly limited.

  The final concentration of the amino acid or salt thereof in the aqueous solution or suspension in the method of the present invention is usually 0.1M or higher, preferably 0.2M or higher, more preferably 0.5M or higher, most preferably 1M or higher. Usually, it is 8.5M or less, preferably 7M or less, more preferably 5M or less, further preferably 3M or less, and most preferably 2.7M or less. Specifically, for example, it is 0.1 to 8.5M, preferably 0.2 to 5M, more preferably 0.5 to 3M, still more preferably 1 to 3M, and most preferably 1 to 2.7M. In addition, when using 2 or more types of amino acids or its salt, the sum of the final concentration should just be in the said range. Here, as described above, the “final concentration of amino acid or salt thereof” refers to the concentration in the aqueous solution when it is an aqueous solution containing amino acid or salt thereof, and is a suspension containing amino acid or salt thereof. In the case, it means the concentration in the aqueous solution after the suspension is heated and solubilized.

  Saccharides used in the method of the present invention are preferably reducing monosaccharides and disaccharides, and examples thereof include monosaccharides such as ribose, xylose, arabinose, glucose and fructose, and disaccharides such as sucrose, maltose and lactose. Preferably, xylose, glucose and fructose can be mentioned, and glucose is particularly preferable. These may be used alone or in combination of two or more.

  The final concentration of the saccharide in the aqueous solution or suspension in the method of the present invention is usually 0.1 M or more, preferably 0.2 M or more, more preferably 0.5 M or more, most preferably 1 M or more, and usually 6 0.7M or less, preferably 6M or less, more preferably 5M or less, still more preferably 3M or less, and most preferably 2.7M or less. Specifically, for example, it is 0.1 to 6.7M, preferably 0.2 to 5M, more preferably 0.5 to 3M, still more preferably 1 to 3M, and most preferably 1 to 2.7M. In addition, when using 2 or more types of saccharides, the sum total of the final concentration should just be in the said range. Here, as described above, the “final concentration of saccharide” refers to the concentration in the aqueous solution in the case of an aqueous solution containing saccharide. In the case of a suspension containing saccharide, the suspension is heated. The concentration in the aqueous solution after being solubilized.

  In addition, the molar ratio of the saccharide to the amino acid or salt thereof in the aqueous solution or suspension is not particularly limited, but is usually 0.01 to 10 mol, preferably 0.1 to 1 mol of amino acid or salt thereof. 5 mol, more preferably 0.5 to 2 mol.

  Furthermore, in another embodiment of the method of the present invention, the amino acid or salt thereof is contained at a final concentration of 0.01 to 8.5 M, and the saccharide is 0.01 to 6.7 M, and further in an aqueous solution or suspension. In addition, the molar ratio of saccharide to amino acid or salt thereof is in the range of 0.01 to 105 mol with respect to 1 mol of amino acid or salt thereof, and the final concentration of amino acid or salt thereof and the final concentration of saccharide are both 0. If the amino acid or a salt thereof and a saccharide are contained so as not to be less than 1M, the aqueous solution or suspension can be heated to produce 0.1 ppm or more of cycloten.

The amino acid or salt thereof and saccharide used in this embodiment are the same as described above.
In addition, the final concentration of the amino acid or salt thereof in the aqueous solution or suspension in this embodiment is usually 0.01M or more, preferably 0.1M or more, more preferably 0.2M or more, and further preferably 0.5M or more. Most preferably, it is 1M or more, usually 8.5M or less, preferably 7M or less, more preferably 5M or less, still more preferably 3M or less, and most preferably 2.7M or less. Specifically, for example, 0.01 to 8.5M, preferably 0.1 to 7M, more preferably 0.2 to 5M, still more preferably 0.5 to 3M, even more preferably 1 to 3M, most preferably Preferably it is 1-2.7M. When two or more kinds of amino acids or salts thereof are used, the total final concentration may be within the above range.
The final concentration of the saccharide in the aqueous solution or suspension in this embodiment is usually 0.01M or higher, preferably 0.1M or higher, more preferably 0.2M or higher, still more preferably 0.5M or higher, most preferably 1M. These are usually 6.7M or less, preferably 6M or less, more preferably 5M or less, still more preferably 3M or less, and most preferably 2.7M or less. Specifically, for example, 0.01 to 6.7M, preferably 0.1 to 6M, more preferably 0.2 to 5M, still more preferably 0.5 to 3M, still more preferably 1 to 3M, most preferably Preferably it is 1-2.7M. When using 2 or more types of saccharides, the sum of the final concentration should just be in the said range.

Furthermore, in this embodiment, the molar ratio of the saccharide to the amino acid or salt thereof in the aqueous solution or suspension is usually 0.01 to 105 mol, preferably 0.01 to mol per mol of amino acid or salt thereof. It is 10 mol, More preferably, it is 0.1-5 mol, More preferably, it is 0.5-2 mol.
Also, the amino acids or salts thereof and saccharides are contained in an aqueous solution or suspension so that their final concentrations are not less than 0.1M, and preferably their final concentrations are not less than 0.2M. As included. When the final concentration of the amino acid or salt thereof and the saccharide in the aqueous solution or suspension is both less than 0.1 M, 0.1 ppm or more of cycloten is not produced.

  In the method of the present invention, the amino acid or a salt thereof and the saccharide are preferably weighed in a desired amount, mixed with water, and heated as an aqueous solution or suspension. As the water, it is preferable to use tap water such as city water and town water, or purified water such as distilled water and deionized water. The amount of water used is such that the final concentration of each of the amino acids or their salts and saccharides is within the above range depending on the amount of each amino acid or salt thereof and saccharide used. The heating temperature of the aqueous solution or suspension is usually 50 to 180 ° C, preferably 70 to 160 ° C, more preferably 90 to 160 ° C, still more preferably 90 to 150 ° C, particularly preferably. 95-150 ° C. When the heating temperature is less than 50 ° C., cycloten tends not to be generated sufficiently. On the other hand, when the heating temperature exceeds 180 ° C., a burnt odor is generated and the flavor material tends to have a different flavor.

  The heating method of the aqueous solution or suspension is not particularly limited as long as the heating temperature is within the above range, and may be either direct heating or indirect heating, for example, heating by direct fire, electric heater, microwave, or the like. Can be mentioned. Further, stirring during heating may or may not be performed. Examples of the apparatus used for heating include an oil bath, a water bath, a thermostatic bath, a heat block, a kneader, and a combination mix. Of course, it is not limited to these.

In the method of the present invention, the pH when heating of the aqueous solution or suspension is started is usually 5 to 9, preferably 6 to 9, and more preferably 7 to 9. If the pH is less than 5, there is a tendency that cycloten is not sufficiently generated, and if the pH exceeds 9, the flavor material tends to have a different flavor.
Hereinafter, the pH at the start of heating the aqueous solution or suspension is also referred to as “initial pH”.

  Adjustment of pH of the said aqueous solution or suspension can be performed using the pH adjuster generally used for food-drinks. Although there is no limitation in particular in the pH adjuster which can be used in this invention, Hydrochloric acid, phosphoric acid, a citric acid, a formic acid, sodium hydroxide, potassium hydroxide, aqueous ammonia etc. are preferable from a distribution | circulation point. Of course, it is not limited to these.

Although the heating time of the said aqueous solution or suspension in the method of this invention should just be set suitably according to heating temperature etc., it is 1 to 64 hours normally, Preferably it is 2 to 32 hours. When the heating time is less than 1 hour, there is a tendency that cycloten is not sufficiently generated. On the other hand, when the heating time exceeds 64 hours, a burnt odor is generated, and the flavor material tends to have a different flavor.
Moreover, it is preferable to heat at 95-160 degreeC from the point of the production amount of a cycloten for 1 to 7 hours, and it is more preferable to heat at 150 degreeC for 1 to 5 hours, or at 160 degreeC for 1 to 3 hours.

  In the method of the present invention, a step of adjusting the pH again (hereinafter, also referred to as “second stage pH adjustment”) may be added during the heating reaction. The timing of the second stage pH adjustment may be appropriately adjusted according to the concentration of amino acid or salt thereof and saccharide in the aqueous solution or suspension and the heating temperature, for example, 0.5 to 4 hours after the start of heating, Preferably after 1 to 2 hours. Further, the second-stage pH adjustment is preferably performed so that the pH of the aqueous solution or suspension becomes 7 to 9, regardless of the pH at the start of heating, that is, the initial pH. It is more preferable. The heating time when the second stage pH adjustment is performed during the heating reaction may be appropriately set according to the heating temperature or the like, but the heating is first started as in the case where the second stage pH adjustment is not performed. The total time from the start to the end is usually 1 to 64 hours, preferably 2 to 32 hours, and more preferably 4 to 16 hours.

  The heating temperature when the second stage pH adjustment is performed is usually 50 to 180 ° C., preferably 70 to 160 ° C., more preferably 90 to 150 ° C., similarly to the case where the second stage pH adjustment is not performed. It is.

The flavor material obtained by the method of the present invention contains cycloten. The content of cycloten in the flavor material is usually 0.1 ppm or more, preferably 1 ppm or more, more preferably 10 ppm or more, and most preferably 50 ppm or more. Moreover, content of the cycloten in this flavor raw material is 1,000 ppm or less normally, Preferably it is 500 ppm or less, More preferably, it is 200 ppm or less. If cycloten content in a flavor raw material is the range of 0.1-1,000 ppm, a preferable aroma and / or flavor can be provided to food-drinks.
The cycloten content in the flavor material obtained by the method of the present invention can be quantified by a gas chromatograph-mass spectrometer (GC-MS) or the like.

  The flavor material containing cycloten obtained by the method of the present invention may be used as it is after completion of the reaction, or may be appropriately subjected to purification treatment or the like, as long as the object of the present invention is not impaired. (Eg gum arabic, processed starch, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, branched cyclodextrin, soybean polysaccharide, gelatin, dextrin, skim milk powder, lactose, oligosaccharide, etc.) Or may be used.

  In addition, after completion of the heating reaction of the method of the present invention, the reaction product may be frozen and used as a flavor material after undergoing a step of crystallizing and removing unreacted amino acids contained in the reaction product. The reaction product is preferably frozen at −10 to −15 ° C. for 12 to 36 hours, more preferably at −15 to −20 ° C. for 12 to 36 hours. The precipitated unreacted amino acid can be removed by a method such as natural sedimentation or filtration.

(2) Flavor material of the present invention The flavor material obtained by the method of the present invention (hereinafter also simply referred to as “the material of the present invention”) has a swelled flavor, sweet flavor and / or flavor, and sustainability in food and drink. A preferred aroma such as a flavor and / or flavor can be imparted. The “swelling flavor” means a flavor spread in the oral cavity that is felt from 2 seconds to 4 seconds after food or drink is contained in the mouth. In addition, “sweet flavor and / or flavor” means a sweet caramel-like flavor and / or flavor similar to maple or walnut. In addition, “persistent flavor” means a flavor that lasts in the mouth from 4 seconds to 6 seconds after food or drink is contained in the mouth.

  In the present invention, the “content” of cycloten in the material of the present invention is the content calculated by excluding the weight of the added excipient, etc., when the material of the present invention is formed by adding an excipient, etc. Means quantity.

  Specifically, the cycloten content in the material of the present invention is usually 0.1 ppm or more, preferably 1 ppm or more, more preferably 10 ppm or more, most preferably 50 ppm or more, and usually 1000 ppm or less, preferably 500 ppm or less, More preferably, it is 200 ppm or less. When the content of cycloten in the material of the present invention is within the above range, there is an effect of imparting a preferred flavor and / or flavor such as a swelled flavor, sweet flavor and / or flavor, and a sustained flavor to foods and beverages. high.

  The cycloten content in the material of the present invention can be quantified by a gas chromatograph-mass spectrometer (GC-MS) or the like.

  The form of the material of the present invention is not particularly limited, and examples thereof include liquid (including oily, slurry, etc.), solid (including powder, granule, etc.), gel, and paste.

  The food and drink to which the material of the present invention is added include, for example, seasonings, processed foods processed from soup, livestock, chicken, seafood, etc., sprinkles, instant foods, snack foods, canned foods, milk or dairy products And emulsified foods, and the like. However, the present invention is not limited thereto, and the material of the present invention can be added to a wide variety of other foods. The foods and drinks to which the flavor material of the present invention is added are imparted with a preferred flavor and / or flavor such as a swelled flavor, sweet flavor and / or flavor, and sustained flavor.

  The concentration of the material of the present invention added to food or drink is usually 10 ppm to 10%, preferably 50 ppm to 6%, more preferably 100 ppm to 3%, although it depends on the form and cycloten content. is there. If the added concentration of the flavor material of the present invention is too low, a preferable aroma and / or flavor imparting effect cannot be obtained, and if the added concentration is too high, it is not natural as a food or drink and an artificial aroma and / or flavor is imparted. There is a tendency to be.

  As shown in Example 5 below, the material of the present invention can impart a preferred aroma and / or flavor to foods and drinks at a lower concentration of cycloten than when a commercially available cycloten fragrance is used alone. .

(3) Food / beverage products containing a flavor material obtained by the production method of the present invention The present invention is also a food / beverage product containing a flavor material obtained by the production method of the present invention (hereinafter simply referred to as “the food / beverage product of the present invention”). Provide).
The food or drink to which the material of the present invention is added contains 0.001 ppb to 100 ppm, preferably 0.005 ppb to 60 ppm, more preferably 0.01 ppb to 30 ppm of cycloten, and has a swelling flavor, sweet flavor and / or flavor. , Have a preferred aroma and / or flavor, such as a persistent flavor.

(4) Manufacturing method of food and drink of the present invention By adding the material of the present invention to food and drink, a preferred flavor and / or flavor such as a swelled flavor, sweet flavor and / or flavor, and a sustained flavor. The food / beverage products to have can be manufactured. Therefore, this invention also provides the manufacturing method of food-drinks including the process of adding the raw material of this invention to food-drinks. The target food or drink in the method of the present invention is not particularly limited, and specific examples include those exemplified above.

The time at which the flavor material of the present invention is added to the food or drink is not particularly limited. For example, when the food or drink is manufactured or cooked, it may be added together with other raw materials, or after the production of the food or drink. It may be added after cooking, or may be added immediately before and / or during the eating of the food or drink.
Moreover, the flavor raw material of this invention may be added directly to food-drinks, and may be mixed and added to water, stock, cooking oil, etc.
The flavor material of the present invention is added so that the cycloten content per food and drink is 0.001 ppb to 100 ppm, preferably 0.005 ppb to 60 ppm, more preferably 0.01 ppb to 30 ppm.

  In addition, the food / beverage products of this invention can be manufactured similarly to a well-known food / beverage product using the raw material similar to a well-known food / beverage product except the process of adding the flavor raw material of this invention to food / beverage products.

  The present invention will be described more specifically in the following examples, but the present invention is not limited to these examples.

The production conditions for flavor materials and the measurement conditions for the amount of cyclotenes in the flavor materials in the following examples and comparative examples are as follows.
(1) Amino acids or their salts and saccharides used in the heating reaction Unless otherwise noted, amino acids or their salts and saccharides were manufactured by Wako Pure Chemical Industries, Ltd.
(2) Heating reaction conditions The amount of amino acid or salt thereof and saccharide shown in each Example and Comparative Example are placed in a 30 mL glass vial, added with 10 g of water, mixed at room temperature for 10 minutes, dissolved or suspended. did. Thereafter, the pH of the aqueous solution or suspension was adjusted with a 2M aqueous sodium hydroxide solution or a 2M aqueous hydrochloric acid solution, and the aqueous solution or suspension was heated for a certain time while stirring with a heat block (manufactured by IKA, RCT basic). The heating temperature and time are as described in each example and comparative example. The heated reaction solution was cooled and then subjected to gas chromatography.
(3) Measuring method of the amount of cyclotenes in a flavor raw material It measured on the conditions shown below with the gas chromatograph-mass spectrometer (GC-MS).
<Analytical instruments>
GC-MS; manufactured by Agilent, part number 5973-N
Autosampler (pretreatment, injection device); manufactured by GESTER, part number MPS2
<Pre-analysis processing>
5 mL of a sample was placed in a 20 mL vial with a septum, and solid phase microextraction (SPME) fiber (85 μm Polyacrylate 57294-U: White) was exposed to the headspace portion for 60 minutes while heating to 70 ° C. to adsorb the components. .
<Analysis conditions>
Column; DB-WAX (60 m × 0.25 mm × 0.25 μm) manufactured by Agilent
Injection conditions: 220 ° C
Mode; splitless head pressure; initial pressure = increased from 105 kPa to 13 kPa / min to 200 kPa and held at 200 kPa for 4 minutes.
Oven conditions: After holding at 50 ° C. for 0.6 minutes, the temperature was raised to 230 ° C. at 25 ° C./min and held at 230 ° C. for 4.2 minutes.

[Comparative example]
7.4 mg of glutamic acid and 0.9 mg of glucose were weighed into a 30 mL glass vial, and 10 g of water was added and mixed. The final concentration of glutamic acid and glucose in the aqueous solution was 5 mM each. The aqueous solution was heated at 150 ° C. for 1 hour without adjusting the pH. The cycloten content in the sample after heating was below the detection limit. The detection limit of cycloten is 0.01 ppm.

[Example 1] Examination of cycloten production using various saccharides As Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-3, 9.35 g of sodium glutamate and various saccharides (glucose 9 g, fructose 9 g, Xylose (7.5 g) was weighed into a 30 mL glass vial, and 10 g of water was added and mixed. The final concentration of sodium glutamate in the aqueous solution was 1.8M, and the final concentration of sugar was 1.8M each. Table 1 shows amino acids or salts and saccharides used in each experimental section. The pH of each aqueous solution was adjusted to 8 with 2M aqueous sodium hydroxide solution, and then heated at 95 ° C. for 8 hours. Table 2 shows the measurement results of the cycloten content in each sample after heating. In addition, the unit of the measured value of cycloten content in Table 2 is ppm.

  As can be seen from the results in Table 2, in Comparative Examples 1-1 to 1-3 in which only glucose, fructose or xylose was present in the water and no sodium glutamate was present, cycloten was below the detection limit. On the other hand, in Examples 1-1 to 1-3 in which these sugars and sodium glutamate coexist in water, generation of about 17 to 33 ppm of cycloten was observed.

[Example 2] Examination of cycloten production using various amino acids or salts thereof As Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-17, various amino acids or salts thereof and glucose were measured in vials. 10 g of water was added and mixed to prepare an aqueous solution. The final concentration of each amino acid or salt thereof and the final concentration of glucose in the aqueous solution were each 1M. Table 3 shows amino acids or their salts and saccharides used in each experimental section.
The pH of each aqueous solution was adjusted to 7 with a 2M aqueous sodium hydroxide solution or a 2M aqueous hydrochloric acid solution, and then heated at 95 ° C. for 17 hours. FIG. 1 shows the relative value of the amount of cyclotenes when other amino acids or salts thereof are used when the amount of cyclotenes in a sample (Example 2-1) after heating an aqueous solution containing sodium glutamate and glucose is taken as 100. Shown in

  As can be seen from the results of FIG. 1, when the amino acid or its salt to be reacted with glucose is sodium glutamate, sodium aspartate, methionine, valine or histidine hydrochloride, the formation of cyclotenes is observed, particularly sodium glutamate or sodium aspartate. In the case of, a large amount of cycloten was formed as compared with the case of other amino acids or salts thereof.

[Examples 2A to 2C] Examination of influence of final concentration of amino acids or salts thereof and sugars When the amount of sodium glutamate was changed with the amount of fructose constant (Example 2A), the amount of fructose was changed with the amount of sodium glutamate constant. The amount of cycloten produced was examined in the case where the respective amount was changed (Example 2C), assuming that the molar ratio of fructose to 1 mole of sodium glutamate was 1 (Example 2B).
As sodium glutamate, sodium L-glutamate monohydrate (manufactured by Ajinomoto Co., Inc.) was used, and as fructose, pure fructose S (manufactured by Kato Chemical Co., Inc., 99.9% fructose) was used. The amounts of the sodium glutamate and fructose shown in Table 4 were weighed into 30 mL glass vials, 10 mL of distilled water was added, and the mixture was stirred and mixed at room temperature to dissolve or suspend. The pH of the aqueous solution or suspension is measured, adjusted with 2M aqueous sodium hydroxide or 2M aqueous hydrochloric acid so that the pH is 7.0 ± 0.5, and then heated at 95 ° C. for 5 hours in an oil bath. did. It was then cooled, transferred to an SPME vial, and cycloten was quantified by GC-MS.
The quantitative results are also shown in Table 4.

  As shown in Table 4, when the final concentrations of sodium glutamate and fructose were each 0.1 M or more, the production of 0.1 ppm or more of cycloten was observed (Examples 2A-3 to 2A-8, 2B-3 to 2B-8, 2C-1 to 2C-5). In addition, even when the final concentration of sodium glutamate is less than 0.1 M, the molar ratio of fructose to 1 mol of sodium glutamate is 103.5 or 49.0 (Examples 2A-1, 2A-2), or Even when the final concentration of fructose is less than 0.1 M, when the molar ratio of fructose to 1 mol of sodium glutamate is 0.01 or 0.02 (Examples 2B-1 and 2B-2), 0. The production of 1 ppm or more of cycloten was observed. However, when the final concentrations of sodium glutamate and fructose were both less than 0.1 M, formation of 0.1 ppm or more of cycloten was not observed (Comparative Examples 2C-1 and 2C-2).

[Example 3] Examination of heating temperature and heating time (1) As Examples 3-1 to 3-12, 10 g of fructose-glucose liquid sugar F-55 (manufactured by Nippon Starch Co., Ltd.) and sodium glutamate (manufactured by Ajinomoto Co., Inc.) ) 9.4 g was weighed into a vial and mixed to prepare an aqueous solution. The fructose-glucose liquid sugar F-55 contains 34% glucose and 41% fructose. The final concentration of sodium glutamate in the aqueous solution was 2.6M, and the final concentration of saccharides (glucose and fructose) was 2.2M.
After adjusting the pH of each aqueous solution to 8.5 with a 2M aqueous sodium hydroxide solution, each sample was heated under the conditions (temperature and time) described in Table 5. The amount of cyclotenes in the sample after heating is shown in FIG.

  As can be seen from the results in FIG. 2, 10 to 90 ppm of cycloten was produced at a heating temperature of 95 to 150 ° C. and a heating time of 2 to 6.5 hours. In particular, when the heating temperature was 150 ° C., 70 to 90 ppm of cycloten was formed.

(2) As Examples 3-13 to 3-40, 9.4 g of sodium L-glutamate monohydrate (manufactured by Ajinomoto Co., Inc.) and 9 g of pure fructose S (manufactured by Kato Chemical Co., Ltd., fructose 99.9%) Was weighed into a 30 mL glass vial, 10 mL of distilled water was added, and the mixture was stirred and mixed at room temperature. The final concentrations of sodium glutamate and fructose were both 1.8M. After measuring the pH of the suspension and adjusting the pH to 7.0 ± 0.5 with a 2M aqueous sodium hydroxide solution or a 2M aqueous hydrochloric acid solution, the conditions (temperature and Time). It was then cooled and transferred to an SPME vial and the cycloten was quantified by GC-MS.
The quantitative results are also shown in Table 6.

As shown in Table 6, even when a suspension containing sodium glutamate and fructose was heated, generation of 0.1 ppm or more of cycloten was observed when heated at 95 ° C. to 160 ° C. for 1 to 7 hours. .
In particular, about 70 ppm when heated at 150 ° C. for 1 to 3 hours (Examples 3-33 to 3-35) and when heated at 160 ° C. for 2 to 3 hours (Examples 3-38 and 3-39). Formation of the above cycloten was observed.

[Example 4] Examination of pH adjustment in second stage
As Examples 4-1 to 4-16, 9 g of pure fructose S (manufactured by Kato Chemical Co., Inc., fructose 99.9%) and 9.4 g of sodium glutamate (manufactured by Ajinomoto Co., Inc.) were weighed into a vial, and 10 g of water was measured. Add and mix to prepare an aqueous solution. The final concentration of sodium glutamate and fructose in the aqueous solution was 1.8M each.
The pH of each aqueous solution was adjusted to 5 to 9 with a 2M aqueous sodium hydroxide solution or a 2M aqueous hydrochloric acid solution (described as “initial pH” in Table 7), and heated at 95 ° C. for 1 hour. Thereafter, the pH was adjusted to 7-9 with a 2M aqueous sodium hydroxide solution (described as “second stage pH” in Table 7), and further heated at 95 ° C. for 4 hours. Table 5 shows the pH conditions in each experimental group, and FIG. 3 shows the amount of cyclotene in the sample after heating.

  As can be seen from the results in FIG. 3, although depending on the initial pH, the amount of cycloten in the reaction sample tended to increase by adjusting the pH to 7 to 9 one hour after the start of the heating reaction. In particular, when the initial pH is 5 to 7, by setting the second stage pH to 8 or 9, and when the initial pH is 9, by setting the second stage pH to 9, Increased significantly.

[Example 5] Manufacture of tit cocoon broth <Manufacture of flavor material>
Fructose-glucose liquid sugar F-55 (manufactured by Nippon Starch Co., Ltd.) and 9.4 g of sodium glutamate (manufactured by Ajinomoto Co., Inc.) were weighed into a vial to prepare an aqueous solution. A sample in which the pH of the aqueous solution was adjusted to 8.5 with a 2M aqueous sodium hydroxide solution and a sample without pH adjustment (pH = 5.8) were heated under the conditions (temperature and time) shown in Table 8, respectively. Invention product 1 and invention product 2 were designated. In addition, neither the present product 1 nor the present product 2 was subjected to the second stage pH adjustment during heating.
The amount of cyclotenes of Invention Product 1 and Invention Product 2 was 44 ppm and 28 ppm, respectively.

<Preparation of Tit Kochu soup>
Titkochun soup was prepared as follows.
Raw materials were 200 g of pork belly, 50 g of onion, 5 g of garlic, 5 g of ginger, 17 g of Nyokumam, 26 g of sugar and 163 g of water. Pork belly was baked in a frying pan for several minutes until the surface was colored. Sautéed onion, garlic, and ginger, put pork belly, nycoomum, sugar and water, and simmered for about 30 minutes to obtain broth.
In Examples 5-1 and 5-2 and Comparative Examples 5-1 and 5-2, the resulting Titkochun soup was mixed with a commercially available cycloten fragrance (manufactured by Sigma Aldrich), the present invention product 1, and the present invention product 2. Were added as described in Table 9. The cycloten concentration (calculated value) in the obtained broth is as shown in Table 9.

<Evaluation of flavor and / or flavor of Titkochun soup>
With regard to the Tit Kochu soup obtained above, the aroma and / or flavor score of the soup for 90 minutes of cooking time is 5.0 points, and the aroma and / or flavor score of the soup for 30 minutes of cooking time is 1.0 points. As a result, sensory evaluation was conducted with a panel of five experts. The evaluation items are “sweet flavor”, “bulge from middle to later” (described as “middle to later bulge” in FIG. 4), “sustainability”, and “similarity to boiled soup for 90 minutes” (Denoted as “similarity” in FIG. 4). “Sweet flavor” is a sweet caramel-like scent and / or flavor similar to maple or walnut, and “bulge from the middle to the back” is 4 seconds after the broth is included in the mouth. It is a flavor that spreads in the oral cavity until 2 seconds later. Moreover, "persistence" is the flavor lasting in the oral cavity which is felt from 4 seconds to 6 seconds after the broth is contained in the mouth. The sensory evaluation results are shown in FIG.

As can be seen from FIG. 4, the commercially available cycloten flavored broth (Comparative Example 5-2), the present product 1 added broth (Example 5-1) and the present product 2 added broth (Example 5-2) Compared with the additive-free product (Comparative Example 5-1), sweet flavor, swelling from the inside to the end and sustainability were imparted, and it was confirmed that the product was closer to the stewed product for 90 minutes. In addition, in the present invention product 1 and the present invention product 2 added broth, the cycloten concentration (calculated value) in the broth is about 1/60 and 1/90 of the commercially available cycloten flavored broth, but the commercially available cycloten flavor is added. The same fragrance and / or flavor as boiled broth was observed.
Therefore, it was confirmed that the flavor raw material of the present invention has a very high aroma and / or flavor imparting effect as compared with a commercially available cycloten fragrance.

ADVANTAGE OF THE INVENTION According to this invention, it is suitable for food use and can provide the manufacturing method of the flavor raw material containing a sufficient quantity of cyclotenes to give aroma and / or flavor to food-drinks, and this flavor raw material.
Moreover, the flavor raw material of this invention can manufacture and provide the food / beverage products to which preferable aroma and / or flavor were provided.

  This application is based on Japanese Patent Application No. 2013-063871 (filing date: March 26, 2013) filed in Japan, the contents of which are incorporated in full herein.

Claims (10)

1 to 3 M salts of one or two amino acids selected from sodium aspartate and sodium glutamate, and 1 selected from the group consisting of ribose, xylose, arabinose, glucose, fructose, sucrose, maltose and lactose A method for producing a flavor material containing 1 ppm or more of cycloten, comprising the step of heating an aqueous solution or water suspension containing seeds or two or more sugars at a final concentration of 1 to 3 M, wherein cycloten is isolated and purified A method for producing a flavored material, which does not include a process to be performed.   The method of Claim 1 including the process of heating the aqueous solution containing the salt of an amino acid, and saccharides.   The method according to claim 1 or 2, wherein the saccharide is one or more selected from the group consisting of xylose, glucose and fructose.   The method according to any one of claims 1 to 3, wherein the amino acid salt is sodium glutamate.   The method according to any one of claims 1 to 4, wherein the pH when the heating is started is 5 to 9.   The method according to any one of claims 1 to 5, wherein the heating temperature is 50 to 180 ° C. The flavor raw material obtained by the method of any one of Claims 1-6 . Food / beverage products containing the flavor raw material of Claim 7 . The manufacturing method of food-drinks including the process of adding the flavor raw material of Claim 7 so that cycloten content per food-drinks may be 0.001ppb-100ppm. A salt of one or two amino acids selected from sodium aspartate and sodium glutamate is selected from the group consisting of 0.1 to 8.5 M and ribose, xylose, arabinose, glucose, fructose, sucrose, maltose and lactose A step of heating an aqueous solution or aqueous suspension containing one or more saccharides at a final concentration of 0.1-6.7M, and after starting the heating, the pH is further adjusted to 7-9 A method for producing a flavor material containing 1 ppm or more of cycloten, including a step of adjusting, and does not include a step of isolating and purifying cycloten.