JP7683216B2 - Fragrance imparting method - Google Patents

Description

The present invention relates to a method for imparting an aroma to food and beverages, and more particularly to a method for imparting an aroma (in particular, a garlic aroma) to food and beverages, which comprises heating, in edible oil, a specific compound that develops sulfides upon thermal decomposition.
The present invention also relates to a method for imparting an aroma (particularly a garlic aroma) to food or drink, which comprises heating, in a solvent, at least one selected from the group consisting of pyridine derivatives having a specific structure and Lewis acidic metal compounds, and a specific compound that generates sulfides upon thermal decomposition.

Garlic contains about 1% S-allyl-L-cysteine sulfoxide, commonly known as alliin (hereinafter sometimes referred to as "ALCSO"), a cysteine derivative that is a precursor to the aroma. Alliin is present in the cytoplasm. When garlic is cut with a knife, alliinase, an alliin-decomposing enzyme localized in the vacuole in the cell, comes into contact with the ALCSO, which is enzymatically decomposed. As a result, alliin is converted via allicin into sulfur-containing compounds such as sulfides and thiophenes, which become the aroma components characteristic of garlic (Non-Patent Document 1).

There have already been reports on the methods for decomposing ALCSO; for example, it is known that ALCSO is decomposed by irradiating an aqueous solution of ALCSO with gamma rays (Non-Patent Documents 2 to 4). In these reports, it is presumed that ALCSO is decomposed via a reaction caused by hydroxyl radicals generated by gamma ray irradiation. However, even when ALCSO is decomposed by such a method, no sulfide compounds, which are the main components of garlic aroma, are detected, and the characteristic garlic aroma has not been confirmed sensorily.

Rose, P. et al. Nat. Prod. Rep., 2005, 22, 351-368 Nishimura, H. et al. Agric. Biol. Chem. 1970, 34, 609-616 Nishimura, H. et al. Agric. Biol. Chem. 1973, 37(2), 213-217 Nishimura, H. et al. Agric. Biol. Chem. 1973, 37(7), 1749-1750

Garlic is a very important ingredient that determines the flavor quality of various seasonings and processed foods, and demand is increasing worldwide. This has caused the price of garlic to rise sharply, making it difficult to procure. Therefore, in order to overcome this issue, there is a strong demand for the development of alternative materials to garlic and efficient methods for imparting garlic aroma.

As a result of intensive research into the above-mentioned problems, the inventors have found that it is possible to efficiently express aroma components by heating in edible oil a specific compound (e.g., ALCSO) capable of generating sulfides, the main components of garlic aroma, by thermal decomposition, without using garlic as a raw material. The inventors have also found that by mixing and heating in a solution a specific compound (e.g., ALCSO) capable of generating sulfides, the main components of garlic aroma, by thermal decomposition, with a specific compound having the property of promoting the decomposition of the specific compound (sometimes referred to as a "decomposition enhancer" in this specification), the decomposition of the specific compound capable of generating sulfides is promoted, and aroma components can be efficiently expressed. The inventors have further researched based on such findings and have completed the present invention.

In one aspect, the present invention is as follows.
[1] A method for imparting aroma to food or beverage, comprising heating, in edible oil, at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC).
[2] The method according to [1], wherein the sulfide precursor compound is ALCSO.
[3] The method according to [1] or [2], wherein the heating temperature is 110°C to 250°C.
[4] A method for producing an aroma-imparted food or beverage, comprising heating, in edible oil, at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC).
[5] The method according to [4], wherein the sulfide precursor compound is ALCSO.
[6] The method according to [4] or [5], characterized in that the heating temperature is 110°C to 250°C.
[7] A fragrance imparting agent comprising at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC).
[8] The agent according to [7], wherein the sulfide precursor compound is ALCSO.
[9] A flavoring agent comprising a thermal decomposition product in an edible oil of at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC).
[10] The agent according to [9], wherein the sulfide precursor compound is ALCSO.
[11] A food or drink comprising the agent according to any one of [7] to [10].

In another aspect, the present invention is as follows.
[12] (1) A pyridine derivative represented by the following general formula (I):

(wherein R ¹ is hydrogen or an optionally substituted C _1-5 alkyl group, R ² is hydrogen, an optionally substituted C _1-5 alkyl group, or a phosphate group, and n is 0, 1, or 2); and
At least one selected from the group consisting of Lewis acidic metal compounds;
(2) at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC);
and heating the mixture in a solution.
[13] The method according to [12], wherein the pyridine derivative is at least one selected from the group consisting of pyridoxal-5'-phosphate and pyridoxal.
[14] The method according to [12] or [13], wherein the Lewis acidic metal compound is at least one selected from the group consisting of iron chloride (III) and aluminum chloride.
[15] The method according to any one of [12] to [14], wherein the sulfide precursor compound is ALCSO.
[16] The method according to any one of [12] to [15], wherein the heating temperature is 40°C to 250°C.
[17] The method according to any one of [12] to [16], wherein the heating time is from 30 seconds to 48 hours.
[18] (1) A pyridine derivative represented by the following general formula (I):

(wherein R ¹ is hydrogen or an optionally substituted C _1-5 alkyl group, R ² is hydrogen, an optionally substituted C _1-5 alkyl group, or a phosphate group, and n is 0, 1, or 2); and
At least one selected from the group consisting of Lewis acidic metal compounds;
(2) at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC);
and heating the mixture in a solution.
[19] The method according to [18], wherein the pyridine derivative is at least one selected from the group consisting of pyridoxal-5'-phosphate and pyridoxal.
[20] The method according to [18] or [19], wherein the Lewis acidic metal compound is at least one selected from the group consisting of iron chloride (III) and aluminum chloride.
[21] The method according to any one of [18] to [20], wherein the sulfide precursor compound is ALCSO.
[22] The method according to any one of [18] to [21], wherein the heating temperature is 40°C to 250°C.
[23] The method according to any one of [18] to [22], wherein the heating time is 30 seconds to 48 hours.
[24] (1) A pyridine derivative represented by the following general formula (I):

(wherein R ¹ is hydrogen or an optionally substituted C _1-5 alkyl group, R ² is hydrogen, an optionally substituted C _1-5 alkyl group, or a phosphate group, and n is 0, 1, or 2); and
At least one selected from the group consisting of Lewis acidic metal compounds;
(2) at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC);
A fragrance imparting agent comprising:
[25] The agent according to [24], wherein the pyridine derivative is at least one selected from the group consisting of pyridoxal-5'-phosphate and pyridoxal.
[26] The agent according to [24] or [25], wherein the Lewis acidic metal compound is at least one selected from the group consisting of iron chloride (III) and aluminum chloride.
[27] The agent according to any one of [24] to [26], wherein the sulfide precursor compound is ALCSO.
[28] (1) A pyridine derivative represented by the following general formula (I):

(wherein R ¹ is hydrogen or an optionally substituted C _1-5 alkyl group, R ² is hydrogen, an optionally substituted C _1-5 alkyl group, or a phosphate group, and n is 0, 1, or 2); and
using at least one selected from the group consisting of Lewis acidic metal compounds;
(2) A fragrance imparting agent comprising a thermal decomposition product of at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC).
[29] The agent according to [28], wherein the pyridine derivative is at least one selected from the group consisting of pyridoxal-5'-phosphate and pyridoxal.
[30] The agent according to [28] or [29], wherein the Lewis acidic metal compound is at least one selected from the group consisting of iron chloride (III) and aluminum chloride.
[31] The agent according to any one of [28] to [30], wherein the sulfide precursor compound is ALCSO.
[32] A food or drink comprising the agent according to any one of [24] to [31].

According to the present invention, it is possible to efficiently impart aroma (e.g., garlic aroma) to food, beverage, etc. In particular, since the present invention does not use enzymes such as alliinase to decompose alliin, it does not involve the problem of enzyme deactivation during high-temperature heating, which is a problem in enzymatic conversion. Therefore, it is possible to impart aroma during high-temperature heating.

The present invention is described in detail below.

In this specification, specific compounds that can generate sulfides (e.g., diallyl disulfide, diallyl sulfide, etc.), the main components of garlic aroma, through thermal decomposition are referred to as "sulfide precursor compounds."

As a first aspect of the present invention, we describe the imparting of aroma to food and beverages by heating a sulfide precursor compound in edible oil or fat.

1. Method for adding aroma to food and beverages 1
The present invention provides a method for imparting aroma to food or drink (hereinafter, may be referred to as "Method 1 of the present invention"), which comprises heating, in edible oil, at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC).

Examples of sulfide precursor compounds that can be used in the method 1 of the present invention include the following compounds:
(1) S-allyl-L-cysteine sulfoxide (ALCSO, CAS number: 556-27-4);
(2) S-methyl-L-cysteine sulfoxide (MCSO, CAS number: 6853-87-8);
(3) S-propyl-L-cysteine sulfoxide (PCSO, CAS number: 17795-24-3);
(4) S-1-propenyl-L-cysteine sulfoxide (PeCSO, CAS number: 3836-24-6);
(5) S-allyl-L-cysteine (ALC, CAS number: 21593-77-1);
(6) S-methyl-L-cysteine (MC, CAS number: 7728-98-5);
(7) S-propyl-L-cysteine (PC, CAS number: 1115-93-1); and (8) S-1-propenyl L-cysteine (PeC, CAS number: 49621-03-6).
Any of the above compounds can be produced or extracted by a method known per se, or can be produced by chemical synthesis, etc. Furthermore, commercially available products may be used as these compounds.

The amount of the sulfide precursor compound used in the method 1 of the present invention can be appropriately set according to the strength of the aroma to be imparted, the balance with the flavor and taste inherent to the food or drink, or the consumer's preferences, but is usually 0.001% by weight or more, preferably 0.01% by weight or more, more preferably 0.05% by weight or more, even more preferably 1% by weight or more, and particularly preferably 1.5% by weight or more, based on the amount of edible oil used. In addition, the upper limit is not particularly limited, but is usually 10% by weight or less, preferably 9% by weight or less, more preferably 8% by weight or less, even more preferably 7% by weight or less, and particularly preferably 5% by weight or less. In one embodiment, the amount of the sulfide precursor compound (e.g., ALCSO) used can be usually 0.001% by weight to 10% by weight, preferably 0.01% by weight to 9% by weight, more preferably 0.05% by weight to 8% by weight, even more preferably 1% by weight to 7% by weight, and particularly preferably 1.5% by weight to 5% by weight.

The edible oil in method 1 of the present invention is not particularly limited as long as it is edible, and either animal or vegetable oils and fats may be used, but vegetable oils and fats are preferably used. Vegetable oils and fats include, but are not limited to, olive oil, wheat germ oil, rice oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, sunflower oil, cottonseed oil, peanut oil, and castor oil. Animal oils and fats include, but are not limited to, lard, fish oil, squalane, and beeswax. Two or more of these may be combined to form the edible oil.

The edible oil in the present invention may contain not only edible oil that does not contain any other components than oil, but also other components than oil (e.g., water). For example, when preparing fried products (e.g., fried chicken, tempura, etc.) using the method 1 of the present invention, it is assumed that water from food ingredients will flow into the edible oil. In this case, the disulfide precursor compound will be heated in a mixture of edible oil and water. However, if the ratio of edible oil in the mixture is sufficiently large compared to the ratio of water, and therefore the sulfide precursor compound can be sufficiently thermally decomposed in the mixture, the desired effect of the present invention can be obtained. The ratio of oil in the mixture that can obtain the desired effect of the present invention can be at least 90% by weight or more, preferably 93% by weight or more, more preferably 95% by weight or more, even more preferably 96% by weight or more, and particularly preferably 97% by weight or more.

Targets to which aroma can be imparted using method 1 of the present invention include, but are not limited to, general foods and beverages (including pharmaceuticals, etc.), but from the viewpoint that aroma can be imparted easily by simply carrying out a normal cooking process, foods and beverages that undergo a process of cooking ingredients in edible oil during cooking are preferred. Examples of foods and beverages to which aroma can be imparted using method 1 of the present invention include, but are not limited to, fried foods (e.g., fried chicken, tempura, etc.), stir-fried dishes (fried rice, etc.), and retort foods.

As described above, the method 1 of the present invention can be applied to various foods and beverages. In other words, the heating temperature and heating time in the method 1 of the present invention can be changed according to the type of food and beverage and the cooking process thereof. Therefore, the heating temperature is not particularly limited, but in one embodiment, it is usually 110°C or higher, preferably 115°C or higher, more preferably 120°C or higher, even more preferably 125°C or higher, and particularly preferably 135°C or higher, and the upper limit can be usually 250°C or lower, preferably 230°C or lower, more preferably 210°C or lower, even more preferably 200°C or lower, and particularly preferably 190°C or lower. In one aspect, the heating temperature can be usually 110°C to 250°C, preferably 115°C to 230°C, more preferably 120°C to 210°C, even more preferably 125°C to 200°C, and particularly preferably 135°C to 190°C. Similarly, the heating time is not particularly limited, but in one embodiment, it is usually 30 seconds or more, preferably 1 minute or more, more preferably 5 minutes or more, even more preferably 7 minutes or more, and particularly preferably 10 minutes or more, and the upper limit is usually 60 minutes or less, preferably 50 minutes or less, more preferably 40 minutes or less, even more preferably 30 minutes or less, and particularly preferably 20 minutes or less. In one aspect, the heating time can be usually 30 seconds to 60 minutes, preferably 1 minute to 50 minutes, more preferably 5 minutes to 40 minutes, even more preferably 7 minutes to 30 minutes, and particularly preferably 10 minutes to 20 minutes.

In addition, even if the food or drink is not heated in edible oil during cooking, the aroma can be imparted by the method 1 of the present invention. Briefly, a sulfide precursor compound is first heated in edible oil to generate sulfides, which are the main components of garlic aroma. Sulfide precursor compounds such as ALCSO are generally water-soluble before decomposition, but sulfides after decomposition generally become oil-soluble, so that the sulfides generated by decomposition are dissolved and present in the oil liquid. Therefore, the oil liquid is collected and diluted as necessary, and then mixed, coated, sprayed, etc. with the food or drink to which the aroma is to be imparted before, during, or after cooking, or immediately before eating, thereby imparting aroma to the food or drink. Alternatively, the sulfides that bring about the garlic aroma may be isolated and purified from the oil liquid rich in the sulfides by a method known per se. Furthermore, the garlic aroma can also be imparted to food or beverages by mixing, applying, adding, or otherwise flavoring the refined sulfides that impart the garlic aroma to the food or beverage before, during, or after cooking, or immediately before eating.

In one aspect, method 1 of the present invention may be carried out in combination with other methods for imparting aroma and/or flavor. Thus, in such an embodiment, the food or drink to which aroma is imparted by method 1 of the present invention may have other aromas and/or flavors in addition to the aroma derived from the present invention, or may exhibit a synergistic flavor.

2. Method for producing aroma-imparted food and drink 1
The present invention also provides a method for producing an aroma-imparted food or drink, which comprises heating, in an edible oil, at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC) (hereinafter, this may be referred to as "Production Method 1 of the Present Invention").

The sulfide precursor compound, edible oil, heating temperature, heating time, etc. used in manufacturing method 1 of the present invention are the same as those described above in "1. Method 1 for imparting aroma to food and beverages."

In one embodiment of the manufacturing method 1 of the present invention, the raw materials of the food and drink to which the aroma is to be imparted and a sulfide precursor compound are heated in edible oil to produce a food and drink to which the aroma is to be imparted. In addition, even if the food and drink does not undergo a heat treatment in edible oil during cooking, the aroma can be imparted by the method 1 of the present invention. Briefly, the sulfide precursor compound is first heated in edible oil to generate sulfides, which are the main components of garlic aroma. Sulfide precursor compounds such as ALCSO are generally water-soluble before decomposition, but sulfides after decomposition are generally oil-soluble, so that the sulfides generated by decomposition are dissolved in the oil liquid and exist. Therefore, the oil liquid is collected and diluted as necessary, and then mixed, applied, sprayed, etc. with the food and drink to which the aroma is to be imparted before, during, or after cooking, or immediately before eating, to impart aroma to the food and drink. Alternatively, the sulfides that impart the garlic aroma may be isolated and purified from an oil liquid rich in the sulfides by a method known per se, and the garlic aroma can be imparted to a food or drink by mixing, applying, adding, or otherwise flavoring the purified sulfides that impart the garlic aroma to the food or drink before, during, or after cooking, or immediately before eating.

In one aspect, the manufacturing method 1 of the present invention can be carried out in combination with other aroma and/or flavor imparting methods. Therefore, in such an embodiment, the food or drink produced by the manufacturing method 1 of the present invention may have other aromas and/or flavors in addition to the aroma derived from the present invention, or may exhibit a synergistic flavor.

3. Fragrance imparting agent 1
The present invention also provides a fragrance imparting agent (hereinafter, sometimes simply referred to as "agent 1 of the present invention") comprising at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC).

The sulfide precursor compounds, etc. used in the agent 1 of the present invention are the same as those described above in "1. Method 1 for imparting aroma to food and beverages."

The amount of the sulfide precursor compound in agent 1 of the present invention is not particularly limited as long as the desired effect is obtained, but it can usually be 0.01% by weight to 100% by weight, preferably 1% by weight to 100% by weight, more preferably 10% by weight to 100% by weight, even more preferably 50% by weight to 100% by weight, and particularly preferably 70% by weight to 100% by weight, based on the weight of the entire agent.

In addition to the sulfide precursor compound, the agent 1 of the present invention may further contain other ingredients that can be added to food and beverages. Examples of such other ingredients include, but are not limited to, pH adjusters, antioxidants, preservatives, sweeteners, flavorings, seasonings, nutritional enhancers, colorants, thickeners, stabilizers, and emulsifiers. In one embodiment, the agent 1 of the present invention may be combined with these other ingredients and formulated in the form of a "flavor seasoning" or the like.

The agent 1 of the present invention can be prepared in any form, such as a solid form such as a powder or granules, a liquid form, a gel form, a slurry form, etc., but from the viewpoints of transportation and storage, a solid form is preferred.

When the food or drink to which the aroma is to be imparted is a food or drink that is heated in edible oil in the cooking process, the agent 1 of the present invention is added before or during the heat treatment of the food or drink in edible oil, and the mixture is heated to produce a food or drink to which the aroma is imparted. When the agent 1 of the present invention is used to impart a garlic aroma to a food or drink that is not heated in edible oil in the normal cooking process, the agent 1 of the present invention is first added to edible oil and heated to obtain a solution rich in sulfides, which are the main components of garlic aroma. Although sulfide precursor compounds such as ALCSO are generally water-soluble before decomposition, the sulfides generated by decomposition are generally oil-soluble, and therefore the sulfides generated by decomposition dissolve in edible oil. Therefore, the edible oil after heating is recovered and diluted as necessary, and then mixed, coated, sprayed, etc. with the food or drink before, during, or after cooking, or immediately before eating, to impart a garlic aroma to the food or drink. Alternatively, the sulfides that give the garlic aroma may be isolated and purified from the heated edible oil that is rich in the sulfides by a method known per se. The purified sulfides that give the garlic aroma may be mixed, applied, sprayed, or the like to food or drink before, during, or after cooking, or immediately before eating, to impart a garlic aroma to the food or drink. The amount of the agent 1 of the present invention to be added to the food or drink may be appropriately determined depending on the strength of the aroma to be imparted, the balance with the aroma, flavor, and taste that the food or drink originally has, or the preferences of the consumer.

As described above, the agent 1 of the present invention may contain various other seasonings, and therefore when formulated as a flavor seasoning, it is possible to impart aromas and flavors that are a complex combination of various flavors, but at least a garlic aroma can be imparted. Therefore, in one embodiment, the aroma imparting agent of the present invention can be said to be for imparting a garlic aroma.

In another embodiment of the agent 1 of the present invention, as exemplified in the above-mentioned "When agent 1 of the present invention is used to impart a garlic aroma to food or beverages that are not subjected to heat treatment in the normal cooking process", the active ingredient may be an aroma component obtained by previously thermally decomposing a sulfide precursor compound in edible oil (i.e., a group of compounds containing sulfides or a purified product of the group of compounds containing sulfides, etc.). That is, the present invention may be an aroma imparting agent comprising a thermal decomposition product in edible oil of at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC).

In this embodiment, the sulfide precursor compound, edible oil, heating temperature, heating time, etc. are the same as those in "1. Method 1 for imparting aroma to food and beverages" described above. The amount of sulfide precursor compound used and other ingredients that may be included may be appropriately set with reference to the conditions described in "1. Method 1 for imparting aroma to food and beverages" and "3. Aroma imparting agent 1" described above. Since this agent uses the aroma component itself as an active ingredient, it can easily impart aroma by adding it appropriately to food and beverages. In addition, this agent may also contain various other seasonings, as in the agent 1 of the present invention, so when it is formulated as a flavor seasoning, it is possible to impart aroma and flavor with a complex combination of various flavors, but at least a garlic aroma can be imparted. Therefore, in one embodiment, this agent can be said to be for imparting a garlic aroma.

In this specification, the present invention has been described in detail from the viewpoint of imparting aroma (e.g., garlic aroma), but when the method 1 and agent 1 of the present invention are applied to food and beverages that originally have some aroma (e.g., garlic aroma), it goes without saying that the method 1, manufacturing method 1, and agent 1 of the present invention can be rephrased as a method for enhancing aroma (e.g., garlic aroma), a manufacturing method for food and beverages with enhanced aroma (e.g., garlic aroma), or an agent for enhancing aroma (e.g., garlic aroma), respectively. In addition, when the present invention is applied to food and beverages that originally contain a certain amount of sulfide precursor compounds, the sulfide precursor compounds can be added so that the sum of the amount of sulfide precursor compounds contained in the food and beverage and the amount of sulfide precursor compounds added from the outside is within the above range.

As a second aspect of the present invention, we describe the imparting of aroma to food and beverages by heating a sulfide precursor compound together with a decomposition enhancer.

A "halogeno group" is fluoro, chloro, bromo, or iodo.

The " _C1-5 alkyl group" means a straight-chain or branched alkyl group, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 2-pentyl, and 3-pentyl.

The "C _1-5 alkyl group" may have a substituent, and examples of such a substituent include the following.
(1) a halogeno group,
(2) a hydroxyl group,
(3) a cyano group,
(4) a nitro group,
(5) a carboxyl group,
(6) a phosphate group,
(7) alkenyl groups ( _C2-10 alkenyl groups; e.g., vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, butadienyl, hexatrienyl, and each isomer thereof),
(8) Alkynyl groups (C _2-10 alkynyl groups; e.g., ethynyl, propynyl, butynyl, pentynyl, hexynyl, and each isomer thereof),
(9) halogenoalkyl groups (e.g., monofluoromethyl, difluoromethyl, trifluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, chloromethyl, chloroethyl, dichloroethyl, and each isomer thereof);
(10) Cyclic alkyl groups (which may contain a heteroatom in the ring) (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydropyranyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, morpholinyl),
(11) Aryl groups (e.g., phenyl, naphthyl).

When two or more substituents are present, they may be the same or different.

4. Method for imparting aroma to food and beverages 2
The present invention relates to a pyridine derivative represented by the following general formula (I):

(wherein R ¹ is hydrogen or an optionally substituted C _1-5 alkyl group, R ² is hydrogen, an optionally substituted C _1-5 alkyl group, or a phosphate group, and n is 0, 1, or 2 (hereinafter, in this specification, these may be referred to as the "pyridine derivative used in the present invention" or simply as the "pyridine derivative")), and at least one selected from the group consisting of Lewis acid metal compounds, and (2) S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC), (hereinafter, may be simply referred to as "Method 2 of the present invention"), which comprises mixing in a solution at least one sulfide precursor compound selected from the group consisting of:

The pyridine derivative used in the present invention is not particularly limited as long as it is a compound represented by the above general formula (I) and can be added to foods and beverages. Examples of the pyridine derivative include pyridoxal (in general formula (I), R ¹ is a methyl group, R ² is a methyl group substituted with a hydroxyl group, and n=0, CAS number: 66-72-8) and pyridoxal-5'-phosphate (in general formula (I), R ¹ is a methyl group, R ² is a methyl group substituted with a phosphate group, n=0, CAS number: 41468-25-1), etc.

[Pyridoxal]

[Pyridoxal-5'-phosphate]

The above pyridine derivatives can be produced by known methods, or commercially available products can be used.

The "Lewis acid metal compound" used in method 2 of the present invention is also not particularly limited as long as it can be added to food and drink and can obtain the desired effects of the present invention, but examples include aluminum chloride and iron(III) chloride. These Lewis acid metal compounds can also be produced by known methods, or commercially available products may be used. In this specification, the term "Lewis acid" refers to an atom that has an empty orbital that can accommodate an electron pair, and in particular includes substances that behave as a Lewis acid with respect to ALCSO.

Examples of sulfide precursor compounds that can be used in the method 2 of the present invention include the following compounds:
(1) S-allyl-L-cysteine sulfoxide (ALCSO, CAS number: 556-27-4);
(2) S-methyl-L-cysteine sulfoxide (MCSO, CAS number: 6853-87-8);
(3) S-propyl-L-cysteine sulfoxide (PCSO, CAS number: 17795-24-3);
(4) S-1-propenyl-L-cysteine sulfoxide (PeCSO, CAS number: 3836-24-6);
(5) S-allyl-L-cysteine (ALC, CAS number: 21593-77-1);
(6) S-methyl-L-cysteine (MC, CAS number: 7728-98-5);
(7) S-propyl-L-cysteine (PC, CAS number: 1115-93-1); and (8) S-1-propenyl L-cysteine (PeC, CAS number: 49621-03-6).
Any of the above compounds can be produced or extracted by a method known per se, or can be produced by chemical synthesis, etc. Furthermore, commercially available products may be used as these compounds.

The amount of the sulfide precursor compound used in the method 2 of the present invention is not particularly limited as long as the desired effect of the present invention can be obtained, and can be set appropriately. For example, when the purpose is to efficiently convert the sulfide precursor compound into an aroma component, the amount of the sulfide precursor compound used is usually 500 ppm by weight or more, preferably 1,000 ppm by weight or more, more preferably 4,000 ppm by weight or more, even more preferably 10,000 ppm by weight or more, and particularly preferably 30,000 ppm by weight or more relative to the solvent. In addition, the upper limit is not particularly limited, but is usually 100,000 ppm by weight or less, preferably 80,000 ppm by weight or less, more preferably 60,000 ppm by weight or less, even more preferably 50,000 ppm by weight or less, and particularly preferably 35,000 ppm by weight or less. In one embodiment, the amount of the sulfide precursor compound (e.g., ALCSO) used can be 500 ppm by weight to 100,000 ppm by weight, preferably 1,000 ppm by weight to 80,000 ppm by weight, more preferably 4,000 ppm by weight to 60,000 ppm by weight, even more preferably 10,000 ppm by weight to 50,000 ppm by weight, and particularly preferably 30,000 ppm by weight to 35,000 ppm by weight.

In addition, the amount (mol) of the pyridine derivative and/or Lewis acid metal compound used in the present invention is not particularly limited as long as the desired effect of the present invention can be obtained. For example, the amount (mol) of the sulfide precursor compound used is usually 0.15 equivalents or more, preferably 0.2 equivalents or more, more preferably 0.5 equivalents or more, even more preferably 0.6 equivalents or more, and particularly preferably 0.75 equivalents or more. In addition, the upper limit is not particularly limited, but is usually 100 equivalents or less, preferably 50 equivalents or less, more preferably 30 equivalents or less, even more preferably 10 equivalents or less, and particularly preferably 5 equivalents or less. In addition, when multiple types of pyridine derivatives and/or Lewis acid metal compounds are used, the amount used can be determined so that the sum of each component falls within the above range, for example. In one embodiment, the amount (mol) of the pyridine derivative and/or Lewis acidic metal compound used in the present invention can be generally 0.15 equivalents to 100 equivalents, preferably 0.2 equivalents to 50 equivalents, more preferably 0.5 equivalents to 30 equivalents, still more preferably 0.6 equivalents to 10 equivalents, and particularly preferably 0.75 equivalents to 5 equivalents, relative to the amount (mol) of the sulfide precursor compound (e.g., ALCSO) used.

The solvent in method 2 of the present invention is usually water, but is not particularly limited as long as the desired effect is obtained. In one embodiment, the water solvent may contain various ingredients derived from seasonings and ingredients, may be soup, or may be a mixture with cooking oil, etc.

Targets to which aroma can be imparted using method 2 of the present invention include, but are not limited to, general foods and beverages (including pharmaceuticals, etc.); however, from the viewpoint that aroma can be imparted easily by simply carrying out a normal cooking process, foods and beverages that contain a relatively large amount of water during cooking (e.g., 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more of the total weight of ingredients is water) and that undergo a heating process during cooking are preferred. In addition, examples of the heating process in this specification include processes such as baking, deep-frying, sautéing, stewing (cooking), steaming, and boiling, and may also involve two or more of these processes. Examples of foods and drinks to which aroma can be imparted by method 2 of the present invention include baked dishes (e.g., aqua pazza), fried dishes (e.g., tempura, etc.), stir-fried dishes (e.g., stir-fried vegetables), simmered dishes (e.g., nikujaga, takikomi gohan), steamed dishes (e.g., shumai), boiled dishes (e.g., spaghetti), etc., as well as various soups, fried dishes (e.g., fried chicken), retort foods, etc., to which method 2 of the present invention can be applied. In particular, soups and stir-fried vegetables are preferred examples.

As described above, the method 2 of the present invention can be applied to various foods and beverages. In other words, the heating temperature and heating time in the method 2 of the present invention can be changed according to the type of food and beverage and the cooking process thereof. Therefore, the heating temperature is not particularly limited, but in one embodiment, it is usually 40°C or higher, preferably 50°C or higher, more preferably 60°C or higher, even more preferably 70°C or higher, and particularly preferably 80°C or higher, and the upper limit can be usually 250°C or lower, preferably 230°C or lower, more preferably 200°C or lower, even more preferably 190°C or lower, and particularly preferably 180°C or lower. In one aspect, the heating temperature can be usually 40°C to 250°C, preferably 50°C to 230°C, more preferably 60°C to 200°C, even more preferably 70°C to 190°C, and particularly preferably 80°C to 180°C. Similarly, the heating time is not particularly limited, but in one embodiment, it is usually 30 seconds or more, preferably 1 minute or more, more preferably 5 minutes or more, even more preferably 7 minutes or more, and particularly preferably 10 minutes or more, and the upper limit is usually 48 hours or less, preferably 24 hours or less, more preferably 6 hours or less, even more preferably 3 hours or less, and particularly preferably 1 hour or less. In one aspect, the heating time can be usually 30 seconds to 48 hours, preferably 1 minute to 24 hours, more preferably 5 minutes to 6 hours, even more preferably 7 minutes to 3 hours, and particularly preferably 10 minutes to 1 hour.

In a specific embodiment of the method 2 of the present invention, the above-mentioned various components are added and mixed with the food or drink to which the aroma is to be imparted, and the mixture is heated to impart the aroma to the food or drink. Specifically, for example, when a garlic aroma is to be imparted to a beverage (such as soup, etc.), the above-mentioned components are directly added to the beverage, and the beverage is heated to impart the garlic aroma to the beverage. Alternatively, when a garlic aroma is to be imparted to stir-fried vegetables, the above-mentioned components are added when the vegetables are fried in a cooking utensil such as a frying pan, and a rich garlic aroma is imparted to the stir-fried vegetables by going through a normal cooking process. In addition, when a garlic aroma is to be imparted to a food or drink that is not subjected to a heat treatment in a normal cooking process or a food or drink that has a relatively low moisture content, first, the above-mentioned components are added to a solvent in which water and oil are mixed, and the resulting mixture is heated to obtain a solution rich in sulfides, which are the main components of garlic aroma. ALCSO and other sulfide precursor compounds are generally water-soluble before decomposition, but sulfides after decomposition are generally oil-soluble, so that the sulfides generated by decomposition are abundantly contained in the oil fraction of the solution. Therefore, the oil fraction is recovered, and after diluting the recovered oil fraction as necessary, the food or drink before cooking, during cooking, after cooking, or immediately before eating can be mixed, coated, sprayed, etc., to impart garlic aroma to the food or drink. Alternatively, the sulfides that bring about the garlic aroma may be isolated and purified from the oil fraction rich in the sulfides by a method known per se. The purified product of the sulfides that bring about the garlic aroma can also be mixed, coated, sprayed, etc., to impart aroma to the food or drink before cooking, during cooking, after cooking, or immediately before eating, thereby imparting garlic aroma to the food or drink. The concentration of the sulfides obtained by Method 2 of the present invention in a food or drink at the time of consumption is not particularly limited, and may be appropriately set depending on the strength of the aroma to be imparted, the balance with the inherent flavor and taste of the food or drink, or consumer preferences, etc.

In one aspect, method 2 of the present invention may be carried out in combination with another method for imparting aroma and/or flavor. Thus, in such an embodiment, the food or drink to which aroma is imparted by method 2 of the present invention may have other aromas and/or flavors in addition to the aroma derived from the present invention, or may exhibit a synergistic flavor.

5. Method for producing aroma-imparted food and drink 2
The present invention also relates to a pyridine derivative represented by the following general formula (I):

(wherein R ¹ is hydrogen or an optionally substituted C _1-5 alkyl group, R ² is hydrogen, an optionally substituted C _1-5 alkyl group, or a phosphate group, and n is 0, 1, or 2), and at least one selected from the group consisting of Lewis acidic metal compounds; and (2) S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC), and at least one sulfide precursor compound selected from the group consisting of (PeC), in a solution, and heating the mixture (hereinafter, sometimes simply referred to as "Production Method 2 of the present invention").

The pyridine derivative, Lewis acid metal compound, sulfide precursor compound, solvent, heating temperature, heating time, food and beverages, etc. used in manufacturing method 2 of the present invention are the same as those described above in "4. Method 2 for imparting aroma to food and beverages."

As a specific embodiment of the manufacturing method 2 of the present invention, the above-mentioned various components are added and blended to the food or drink to which the aroma is to be imparted, and then the resulting product is heated to produce the food or drink imparted with the aroma. In addition, when imparting a garlic aroma to a food or drink that is not heat-treated in the normal cooking process or a food or drink that has a relatively low moisture content, the above-mentioned components are first added to a solvent in which water and oil are mixed, and the resulting solution is heated to obtain a solution rich in sulfides, which are the main components of garlic aroma. Although sulfide precursor compounds such as ALCSO are generally water-soluble before decomposition, the sulfides produced by decomposition are generally oil-soluble, so that the sulfides produced by decomposition are abundantly contained in the oil fraction of the solution. Therefore, the oil fraction is recovered, and the recovered oil fraction is diluted as necessary, and then mixed, applied, sprayed, etc. with the food or drink before, during, or after cooking, or immediately before eating, to impart a garlic aroma to the food or drink. Alternatively, the sulfides imparting the garlic aroma may be isolated and purified from an oil fraction rich in the sulfides by a method known per se, and the garlic aroma can be imparted to food or drink by mixing, applying, spraying, or the like with the purified sulfides imparting the garlic aroma to the food or drink before, during, or after cooking, or immediately before eating.

In one aspect, the manufacturing method 2 of the present invention can be carried out in combination with other aroma and/or flavor imparting methods. Therefore, in such an embodiment, the food or drink produced by the manufacturing method 2 of the present invention may have other aromas and/or flavors in addition to the aroma derived from the present invention, or may exhibit a synergistic flavor.

6. Fragrance imparting agent 2
The present invention also relates to a pyridine derivative represented by the following general formula (I):

(wherein R ¹ is hydrogen or an optionally substituted C _1-5 alkyl group, R ² is hydrogen, an optionally substituted C _1-5 alkyl group, or a phosphate group, and n is 0, 1, or 2), and at least one selected from the group consisting of Lewis acid metal compounds; and (2) at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC).

The pyridine derivatives, Lewis acid metal compounds, sulfide precursor compounds, etc. used in agent 2 of the present invention are the same as those described above in "4. Method 2 for imparting aroma to food and beverages."

The amounts of the sulfide precursor compound and the pyridine derivative and/or Lewis acid metal compound in the agent 2 of the present invention are not particularly limited as long as the desired effect can be obtained. For example, the amount (mol) of the sulfide precursor compound and the amount (mol) of the pyridine derivative and/or Lewis acid metal compound used in the present invention can be usually 1:0.3-10, preferably 1:0.5-5, more preferably 1:0.6-3, even more preferably 1:0.7-2, and particularly preferably 1:0.75-1.5. When multiple types of pyridine derivatives and/or Lewis acid metal compounds used in the present invention are used, the amounts can be determined so that the sum of the components falls within the above range.

In addition to the above-mentioned components, agent 2 of the present invention may further contain other components that can be added to food and beverages. Examples of such other components include, but are not limited to, pH adjusters, antioxidants, preservatives, sweeteners, flavorings, seasonings, nutritional enhancers, colorants, thickeners, stabilizers, and emulsifiers. In one embodiment, agent 2 of the present invention may be combined with these other components and formulated in the form of a "flavor seasoning" or the like.

The agent 2 of the present invention can be prepared in any form, such as a solid form such as a powder or granules, a liquid form, a gel form, a slurry form, etc., but from the viewpoints of transportation and storage, a solid form is preferred.

In the case where the food or drink to which the aroma is to be imparted has a relatively high water content and is heated in the cooking process, the agent 2 of the present invention can be added before or during the heat treatment of the food or drink, and the mixture can be heated to produce the food or drink to which the aroma is imparted. In addition, when using the agent 2 of the present invention to impart a garlic aroma to food or drink that is not heated in the normal cooking process or to food or drink that has a relatively low water content, the agent 2 of the present invention is first added to a solvent in which water and oil are mixed, and the resulting solution is heated to obtain a solution rich in sulfides, which are the main components of garlic aroma. Although sulfide precursor compounds such as ALCSO are generally water-soluble before decomposition, the sulfides generated by decomposition are generally oil-soluble, so that the sulfides generated by decomposition are abundantly contained in the oil fraction of the solvent. Therefore, the oil fraction is recovered, and the recovered oil fraction is diluted as necessary, and then mixed, applied, sprayed, etc. with the food or drink before, during, or after cooking, or immediately before eating, to impart a garlic aroma to the food or drink. Alternatively, the sulfides that give rise to the garlic aroma may be isolated and purified from an oil fraction rich in the sulfides by a method known per se. The purified product of the sulfides that give rise to the garlic aroma may be mixed, applied, sprayed, or the like to food or drink before, during, or after cooking, or immediately before eating, to impart a garlic aroma to the food or drink. The amount of the agent 2 of the present invention to be added to the food or drink may be appropriately determined depending on the strength of the aroma to be imparted, the balance with the aroma, flavor, and taste that the food or drink originally has, or the preferences of the consumer.

As described above, the agent 2 of the present invention may contain various other seasonings, and therefore when formulated as a flavor seasoning, it is possible to impart aromas and flavors that are a complex combination of various flavors, but at least a garlic aroma can be imparted. Therefore, in one embodiment, the aroma imparting agent 2 of the present invention can be said to be for imparting a garlic aroma.

In another embodiment of the agent 2 of the present invention, as exemplified in the above-mentioned "When using the agent 2 of the present invention to impart a garlic aroma to foods and beverages that are not heat-treated in the normal cooking process or foods and beverages with a relatively low moisture content", the active ingredient may be an aroma component (i.e., a group of compounds containing sulfides or a purified product of a group of compounds containing sulfides, etc.) obtained by previously thermally decomposing a precursor compound of sulfides using a decomposition enhancer. That is, the present invention relates to (1) a pyridine derivative represented by the following general formula (I);

(wherein R ¹ is hydrogen or an optionally substituted C _1-5 alkyl group, R ² is hydrogen, an optionally substituted C _1-5 alkyl group, or a phosphate group, and n is 0, 1, or 2), and (2) a thermal decomposition product of at least one sulfide precursor compound selected from the group consisting of S-allyl-L-cysteine sulfoxide (ALCSO), S-methyl-L-cysteine sulfoxide (MCSO), S-propyl-L-cysteine sulfoxide (PCSO), S-1-propenyl-L-cysteine sulfoxide (PeCSO), S-allyl-L-cysteine (ALC), S-methyl-L-cysteine (MC), S-propyl-L-cysteine (PC), and S-1-propenyl L-cysteine (PeC), using at least one selected from the group consisting of Lewis acid metal compounds.

In this embodiment, the pyridine derivative, Lewis acid metal compound, sulfide precursor compound, etc. are the same as those described in "4. Method 2 for imparting aroma to food and beverages". The amount of each component used, the heating conditions, and other components that may be included may be appropriately set with reference to the conditions described in "4. Method 2 for imparting aroma to food and beverages" and "6. Aroma imparting agent 2" above. Since this agent uses the aroma component itself as an active ingredient, it can easily impart aroma by adding it appropriately to food and beverages. In addition, this agent may also contain various other seasonings, as in the agent 2 of the present invention, so that when it is formulated as a flavor seasoning, it is possible to impart a flavor with a complex combination of various flavors, but at least a garlic aroma can be imparted. Therefore, in one embodiment, this agent can be said to be for imparting a garlic aroma.

In this specification, the present invention has been described in detail from the viewpoint of imparting aroma (e.g., garlic aroma), but when the method 2 and agent 2 of the present invention are applied to food and beverages that originally have some aroma (e.g., garlic aroma), it goes without saying that the method 2, manufacturing method 2, and agent 2 of the present invention can be rephrased as a method for enhancing aroma (e.g., garlic aroma), a manufacturing method for food and beverages with enhanced aroma (e.g., garlic aroma), or an agent for enhancing aroma (e.g., garlic aroma), respectively. In addition, when the present invention is applied to food and beverages that originally contain a certain amount of sulfide precursor compounds and/or pyridine derivatives and/or Lewis acid metal compounds used in the present invention, the amount of sulfide precursor compounds and/or pyridine derivatives and/or Lewis acid metal compounds used in the present invention contained in the food and beverage and the amount of sulfide precursor compounds and/or pyridine derivatives and/or Lewis acid metal compounds used in the present invention added from the outside can be added so that the total amount falls within the above range.

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

[Example 1: Study of conditions for promoting decomposition of ALCSO 1]
In order to screen conditions that can promote the decomposition of ALCSO in a manner that can efficiently impart a garlic aroma, ALCSO was heated in edible oil under various conditions shown in Table 2 below to confirm whether aroma components were produced. Specifically, ALCSO and edible oil ("Smooth Canola Oil", manufactured by J-Oil Mills, Inc.) or a mixture of ALCSO, edible oil, and water were mixed in a vial (ICHEM vial), which was then placed on a heating stirrer and heated. At that time, in order to carry out a reaction in an open system close to actual cooking conditions, only the inner lid of the vial was removed and the vial was covered with aluminum foil from above. The time when a predetermined temperature was reached was defined as heating time 0 minutes, and after the predetermined heating time had elapsed, the vial was cooled with ice water to stop the reaction.

[Pre-analysis of heating tests]
For each reaction solution reacted according to the above-mentioned experimental conditions, Milli-Q water and edible oil were added to the vial so that the water and oil were 4 mL, and the mixture was thoroughly stirred with a vortex. The entire solution (8 mL) was placed in a 50 mL Falcon tube and centrifuged at 9,000 rpm for 10 minutes. The reaction solution was separated into an upper layer (oil layer) and a lower layer (aqueous layer).

[Study on the decomposition rate of ALCSO]
10 μL of the lower layer (i.e., the aqueous layer) of the centrifuged aqueous solution was collected and diluted 10,000-fold with Milli-Q water, and the resulting aqueous solution was filtered through a filter (GL Sciences, model number 5040-28510). 200 μL of the filtered aqueous solution was placed in an LC vial, and the decomposition rate of ALCSO was calculated using the analytical conditions (LC/MS) and calculation formula detailed in Table 1 below.

The ALCSO decomposition rate was calculated using the following formula.

ALCSO decomposition rate =
(1 - (ALCSO concentration after reaction [ppm by weight])/(ALCSO concentration before reaction [ppm by weight])) x 100 [%]

[Examination of the presence and strength of garlic aroma]
A sensory test was performed to evaluate whether the decomposition product of ALCSO using the candidate compound had a garlic odor. The sensory test was specifically performed as follows. The test samples after the reaction were diluted to 300 ppm by weight equivalent to the amount of ALCSO before decomposition (for example, when the reaction was performed with 30,000 ppm by weight of ALCSO before decomposition, the test sample after the reaction was diluted 100 times with a water/oil = 50/50 solution). A panel of one expert evaluated the obtained diluted samples for the presence and intensity of garlic odor using the following criteria.

++: Strong garlic scent +: Garlic scent -: No garlic scent

The results are shown in Table 2.

As shown in Table 2, it was confirmed that ALCSO decomposes accompanied by the generation of sulfides, which are aroma components, when the heating temperature is above a certain level and the oil content in the solvent is above a certain level.

[Example 2: Study of conditions for promoting decomposition of ALCSO 2]
In order to investigate the optimal heating temperature and heating time, the following experiment was carried out. ALCSO (concentration 3% by weight (30,000 ppm by weight)) was added to edible oil ("Smooth Canola Oil", manufactured by J-Oil Mills Co., Ltd.), and the mixture was heated at various temperatures (140°C, 160°C, 180°C, and 200°C) and times (5 minutes, 10 minutes, and 15 minutes), and the decomposition rate of ALCSO was analyzed. In addition, whether or not the garlic aroma could actually be sensed was evaluated by a sensory test.

The method for analyzing the decomposition rate of ALCSO was the same as that used in Example 1. Specifically, the sensory test was conducted as follows. The test sample after the reaction was diluted 100 times with a 50/50 water/oil solution (i.e., diluted to 300 ppm by weight equivalent to the ALCSO before decomposition). A panel of one expert evaluated the diluted sample for the presence and intensity of garlic aroma using the following criteria:

++: Strong garlic scent +: Garlic scent -: No garlic scent

The results are shown in Tables 3 and 4.

As shown in Table 3, it was confirmed that ALCSO was efficiently decomposed regardless of the heating time and heating temperature. In addition, as shown in Table 4, although a different aroma (pungent odor) was sometimes generated at the same time (conditions marked with "*" in Table 4), the generation of garlic aroma was confirmed regardless of the heating time and heating temperature.

[Example 3: Study using ACSOs other than ALCSO]
The following experiment was carried out using MCSO (S-Methyl-L-cysteine sulfoxide), PCSO (S-Propyl-L-cysteine sulfoxide), and PeCSO (S-1-Propenyl-L-cysteine sulfoxide), which are cysteine sulfoxides similar to ALCSO. MCSO, PCSO, or PeCSO (3% by weight) was added to a mixture (weight ratio 97:3) of edible oil ("Smooth Canola Oil", manufactured by J-Oil Mills, Inc.) and water, and the mixture was heated at 140°C for 10 minutes, after which the decomposition rates were analyzed. In addition, whether an aroma resembling that of Allium plants (garlic, onion, green onion, etc.) was detected was also evaluated by a sensory test.

The method for analyzing the decomposition rate was the same as that used in Example 1, except that the target ions in the analysis conditions were changed as shown in Table 5. Specifically, the sensory test was performed as follows. The test samples after the reaction were diluted 100-fold with a 50/50 water/oil solution (i.e., diluted to 0.03% by weight equivalent to MCSO, PCSO, and PeCSO before decomposition). A panel of one expert evaluated the diluted samples for the presence and intensity of an Allium-like aroma using the following criteria:

++: Has a strong onion-like scent +: Has an onion-like scent -: Does not have an onion-like scent

The results are shown in Table 6.

As shown in Table 6, when MCSO and PeCSO were used, it was confirmed that decomposition was efficient and an Allium-like scent was generated. When PCSO was used, the decomposition rate was not so high, but it was confirmed that an Allium-like scent was generated.

[Example 4: Consideration of use in cooking]

The following experiment was conducted to confirm the effect of the invention on deep-frying. 15 g of chicken breast meat was thoroughly coated with the batter of the composition shown in Table 7. As a control test, chicken breast meat coated with a batter that did not contain ALCSO was prepared. These were fried in edible oil ("Smooth Canola Oil", manufactured by J-Oil Mills Co., Ltd.) at 170°C for 4 minutes, and evaluated by a sensory test.

[Examination of the presence and strength of garlic scent]
The fried chicken pieces after cooking were evaluated by a sensory test to determine whether they had a garlic aroma. In the sensory test, a panel of one expert evaluated the presence and intensity of the garlic aroma using the following criteria:

++: Strong garlic scent +: Garlic scent -: No garlic scent

The results are shown in Table 8.

As shown in Table 8, it was confirmed that only the test area in which ALCSO was incorporated into the batter produced a strong garlic aroma.

[Example 5: Screening of candidate compounds that promote the degradation of ALCSO]
In order to screen for compounds capable of promoting the decomposition of ALCSO in a manner capable of efficiently imparting a garlic aroma, the following experiment was carried out. A vial (ICHEM vial) containing a sample prepared according to the composition in Table 9 was placed on a heating stirrer and heated. In order to carry out the reaction in an open system similar to the actual cooking conditions, only the inner lid of the vial was removed and covered with aluminum foil from above. The time when the temperature reached a predetermined temperature was set as 0 minutes of heating time, and the reaction was stopped by cooling the vial with ice water after the specified time in Table 9 had elapsed. The candidate compounds were as follows: pyridoxal-5'-phosphate, pyridoxal, furfural, salicylaldehyde, pyridoxine, aluminum chloride, iron (III) chloride, copper (II) chloride, zinc chloride, zinc oxide, and iron chloride tetrahydrate. The amount of each candidate compound added was 1 equivalent to the amount of substance [mol] of ALCSO.

The reagents, instruments, etc. used in this screening are shown in Table 10 below.

[Pre-analysis of heating tests]
For each reaction solution reacted according to the above-mentioned experimental conditions, Milli-Q water and salad oil were added to a vial so that the water and oil were 4 mL, and the mixture was thoroughly stirred with a vortex. The entire solution (8 mL) was placed in a 50 mL Falcon tube and centrifuged at 9,000 rpm for 10 minutes. The reaction solution was separated into an upper layer (oil layer) and a lower layer (aqueous layer).

[Study on the decomposition rate of ALCSO]
10 μL of the lower layer (i.e., the aqueous layer) of the centrifuged aqueous solution was collected and diluted 10,000-fold with Milli-Q water, and the resulting aqueous solution was filtered through a filter (GL Sciences, model number 5040-28510). 200 μL of the filtered aqueous solution was placed in an LC vial, and the decomposition rate of ALCSO was calculated using the analytical conditions (LC/MS) and calculation formula detailed in Table 11 below.

[About various calculation formulas]
The ALCSO decomposition rate was calculated using the following formula.

ALCSO decomposition rate =
(1 - (ALCSO concentration after reaction [ppm by weight])/(ALCSO concentration before reaction [ppm by weight])) x 100 [%]

[Examination of the presence and strength of garlic aroma]
A sensory test was performed to evaluate whether the decomposition product of ALCSO using the candidate compound had a garlic odor. The sensory test was specifically performed as follows. The test samples after the reaction were diluted to 300 ppm by weight equivalent to the amount of ALCSO before decomposition (for example, when the reaction was performed with 30,000 ppm by weight of ALCSO before decomposition, the test sample after the reaction was diluted 100 times with a water/oil = 50/50 solution). A panel of one expert evaluated the obtained diluted samples for the presence and intensity of garlic odor using the following criteria.

++: Strong garlic scent +: Garlic scent -: No garlic scent

[result]
The results of the sensory test regarding the decomposition rate of ALCSO and the presence and intensity of garlic aroma when the decomposition of ALCSO was promoted using various candidate compounds are shown in the following Table 12. The meanings of "◎", "◯", and "×" in the table are as follows:

◎: Decomposition rate 80% or more ○: Decomposition rate 60% or more but less than 80% ×: Decomposition rate less than 60%

As shown in Table 12, it was shown that the decomposition of ALCSO with a garlic odor was promoted when a pyridine derivative having an aldehyde group at the 4-position, such as pyridoxal or pyridoxal-5'-phosphate, and a free hydroxyl group in the molecule, or a Lewis acid metal compound was added.

Without intending to be bound by theory, it is possible that a pyridine derivative having an aldehyde group at the 4-position and a free hydroxyl group in the molecule condenses with the amino group of ALCSO to form a Schiff base, which may promote the subsequent decomposition of ALCSO accompanied by the garlic aroma. Also, a Lewis acidic metal compound may coordinate to the double bond or oxygen atom of ALCSO, which may promote the subsequent decomposition of ALCSO accompanied by the garlic aroma.

[Example 6: Study on the concentration of sulfide precursor compounds added]
In order to determine the concentration of the sulfide precursor compound capable of imparting a desirable aroma, various concentrations of the sulfide precursor compound were thermally decomposed in a solvent using a decomposition enhancer using the same experimental apparatus as that used in Example 5, and the aroma imparting effect was examined. Pyridoxal-5'-phosphate (1 equivalent amount relative to the amount of ALCSO used) was used as the decomposition enhancer. ALCSO was used as the sulfide precursor compound. ALCSO and pyridoxal-5'-phosphate were dissolved in a solvent (a mixture of Milli-Q water (80 wt% (4000 mg)) and salad oil (20 wt% (1000 mg))) and heated at 100°C for 10 minutes. The obtained samples were evaluated for their aroma imparting effect by a sensory test by one expert panel. The evaluation criteria were the same as those used in Example 5. The results are shown in Table 13.

As shown in Table 13, it was shown that the use of a certain amount or more of ALCSO can provide a fragrance-imparting effect.

[Example 7: Examination of the amount of decomposition enhancer added]
In order to determine a preferred amount of decomposition enhancer to be added, a sulfide precursor compound was thermally decomposed in a solvent using the same experimental equipment as used in Example 5 and various amounts of decomposition enhancer added, and the aroma-imparting effect was examined. ALCSO (amount used: 30,000 ppm by weight) was used as the sulfide precursor compound. Pyridoxal-5'-phosphate was used as the decomposition enhancer. The solvent composition, heating temperature, and heating time were the same as in Example 6. The amount of decomposition enhancer added is shown relative to the amount (mol) of ALCSO used. The results are shown in Table 14.

As shown in Table 14, it was shown that an aroma-imparting effect can be obtained by using a certain amount or more of pyridoxal-5'-phosphate relative to the amount (mol) of ALCSO used. Although no studies have been conducted with addition amounts exceeding one equivalent, it is believed that the greater the amount of decomposition enhancer added, the more likely the reaction between the sulfide precursor compound and the decomposition enhancer will proceed, and therefore it is expected that a favorable aroma-imparting effect can be obtained even when the addition concentration exceeds one equivalent.

[Example 8: Examination of reaction temperature]
In order to determine the temperature range capable of imparting a desirable aroma, a sulfide precursor compound was thermally decomposed in a solvent using a decomposition enhancer at various temperatures using the same experimental equipment as that used in Example 5, and the aroma imparting effect was examined. ALCSO (amount used: 30,000 ppm by weight) was used as the sulfide precursor compound. Pyridoxal-5'-phosphate (0.75 equivalents relative to the amount of ALCSO used) was used as the decomposition enhancer. The solvent composition and heating time were the same as in Example 6. The results are shown in Table 15.

As shown in Table 15, it was shown that a fragrance-imparting effect can be obtained by heating at a certain temperature or higher. Although no studies have been conducted at temperatures above 100°C, it is believed that sulfide precursor compounds are more susceptible to thermal decomposition the higher the heating temperature, and therefore it is expected that a favorable fragrance-imparting effect can be obtained even when heated at temperatures above 100°C.

[Example 9: Consideration of heating time]
In order to determine the shortest heating time that can impart a desirable aroma, a sulfide precursor compound was heated in a solvent for 1 minute using a decomposition enhancer using the same experimental apparatus as that used in Example 5, and the aroma imparting effect was examined. ALCSO (see Table 17 below for the amount used) was used as the sulfide precursor compound. Pyridoxal-5'-phosphate (0.75 equivalents relative to the amount of ALCSO used) was used as the decomposition enhancer. The solvent composition and heating temperature were the same as those in Example 6. Under the conditions shown in Table 16 below, the amount of diallyl disulfide present in the sample 1 minute after the start of heating was shown as a peak area value using a gas chromatograph (manufactured by Agilent Technology). Specifically, in the sample spectrum analyzed under the conditions shown in Table 16 below, when searching by molecular weight (Mw: 146), the peaks appearing at retention times of 5.4 min to 5.6 min were integrated, and the values were recorded. In addition, when no odor was detected by the above method, it was recorded as "N.D. (not detected)." In addition, the obtained samples were evaluated for the presence or absence of odor by a sensory test by one expert panel. The evaluation criteria were the same as those used in Example 5. The results are shown in Table 17.

As shown in Table 17, the aroma component (i.e., diallyl disulfide) was detected one minute after the start of heating, and the sensory evaluation confirmed that it had a garlic aroma, indicating that the aroma-imparting effect of the present invention can be obtained immediately after the start of heating.

According to the present invention, it is possible to efficiently impart a garlic aroma to food and beverages even with a reduced amount of garlic used, which is useful in the food and beverage manufacturing industry.

This application is based on patent application No. 2018-211747 (filing date: November 9, 2018) and patent application No. 2018-211748 (filing date: November 9, 2018) filed in Japan, the contents of which are incorporated in their entirety into this specification.

Claims (15)

For food and beverages,
(1) at least one Lewis acidic metal compound selected from the group consisting of iron(III) chloride and aluminum chloride ;
(2) S-allyl-L-cysteine sulfoxide (ALCSO),
and heating the mixture. (1) at least one Lewis acidic metal compound selected from the group consisting of iron(III) chloride and aluminum chloride;
(2) S-allyl-L-cysteine sulfoxide (ALCSO),
and the like are added to a solvent mixture of water and oil, and the mixture is heated to obtain a solution containing sulfides, which are aroma components;
The method for imparting aroma to food or beverage comprises recovering an oil fraction from the solution and mixing, applying or spraying the oil fraction onto the food or beverage. The method according to claim 2, wherein the recovered oil fraction is diluted and then mixed, applied or sprayed onto a food or beverage. The method according to any one of claims 1 to 3 , characterized in that the heating temperature is from 40°C to 250°C. 5. The method according to claim 1 , wherein the heating time is between 30 seconds and 48 hours. For food and beverages,
(1) at least one Lewis acidic metal compound selected from the group consisting of iron(III) chloride and aluminum chloride ;
(2) S-allyl-L-cysteine sulfoxide (ALCSO),
and heating the mixture. (1) at least one Lewis acidic metal compound selected from the group consisting of iron(III) chloride and aluminum chloride;
(2) S-allyl-L-cysteine sulfoxide (ALCSO),
and the like are added to a solvent mixture of water and oil, and the mixture is heated to obtain a solution containing sulfides, which are aroma components;
The method for producing an aromatized food or beverage includes recovering an oil fraction from the solution and mixing, applying, or spraying the oil fraction onto the food or beverage. The method according to claim 7, wherein the recovered oil fraction is diluted and then mixed with, applied to, or sprayed on a food or beverage. The method according to any one of claims 6 to 8 , wherein the heating temperature is 40°C to 250°C. The method according to any one of claims 6 to 9 , wherein the heating time is from 30 seconds to 48 hours. (1) at least one Lewis acidic metal compound selected from the group consisting of iron(III) chloride and aluminum chloride ;
(2) S-allyl-L-cysteine sulfoxide (ALCSO),
and heating the mixture . (1) at least one Lewis acidic metal compound selected from the group consisting of iron(III) chloride and aluminum chloride;
(2) S-allyl-L-cysteine sulfoxide (ALCSO),
and the like are added to a solvent mixture of water and oil, and the mixture is heated to obtain a solution containing sulfides, which are aroma components;
and recovering an oil fraction from the solution. The method of claim 12, further comprising diluting the recovered oil fraction. The method according to any one of claims 11 to 13, wherein the heating temperature is 40°C to 250°C. The method according to any one of claims 11 to 14, wherein the heating time is from 30 seconds to 48 hours.