JP4345115B2 - New seasoning ingredients - Google Patents

Description

【０００６】
【化４】

【０００７】
（分子量）：１６７
（分子式）：Ｃ7Ｈ9Ｎ3Ｏ2
（構造式）：▲１▼１，６−ジメチル−３，５−ジオキソ−２，３，５，６− テトラヒドロ−イミダゾ［１，２−ｂ］イミダゾール
【化５】

▲２▼１，５−ジメチル−３，６−ジオキソ−２，３，５，６− テトラヒドロ−イミダゾ［１，２−ｂ］イミダゾール
【化６】

【０００８】
本物質は、既存の天然エキスの加工品および代替物、あるいは基本だし類に添加すれば、これらの調味力を増強し、味全体をひきたて、味に「濃厚感」と「持続性」を付与できることを見出し、本発明を完成するに至った。
また、本化合物は、いやな後味を有する各種食品に添加する事により、後味のしつこさを弱めて、すっきりした味に変える効果を有する事を見出した。
【０００９】
【発明の実施の形態】
本発明は、クレアチンまたはクレアチニンと糖類またはそのオソン類を反応させることで得られた上記一般式（１）および（２）（例えば、構造式▲１▼▲２▼）で表される新規クレアチニン誘導体に関する。
本発明の新規クレアチニン誘導体または本物質を含む溶液を上記の天然エキス加工品および代替品、あるいは基本だし類に添加することにより、これら既存の調味料にコクを付与でき、天然エキスに類似した高品質の呈味を持つ天然エキス加工品および代替品の製造法を提供し、また高品質の基本だしの製造法を提供できる。
【００１０】
本発明に用いるクレアチンまたはクレアチニンは試薬以外に、牛肉、豚肉、鶏肉、魚肉などから抽出したもの、またはこれら肉類の抽出液や市販の水産物類のエキス、畜肉類のエキスおよび加工食品製造時に副生物として得られる、水産物類、畜肉類の煮汁、蒸煮液、クッカージュースおよびフィッシュソルブルなどを任意に使用することができる。また、これらの酵素消化物および魚醤を使用することも可能である。
【００１１】
また、糖類はグルコースやフラクトースなどの単糖類、または二糖類を任意に使用できる。さらに、グルコソンなどのオソン類やソルビットなどの糖アルコールやグルコン酸などのアルドン酸を用いても構わない。また、水飴や糖蜜、異性化糖、野菜エキス、果汁など、上記の糖類を多量に含む食品や調味料を使用することも可能である。
【００１２】
コクを付与する新規クレアチニン誘導体を得る方法は、例えば水にクレアチン１〜１００ｍＭと、糖類例えばメチルグリオキサールを１〜１００ｍＭになるように混合する。このときのｐＨは１〜１４、温度は５〜９５°Ｃ、混合時間は７２時間以内で良い。
【００１３】
このようにして得られた混合溶液を、濃縮後、アルコール類を加えて室温放置しておくと、結晶が析出し、この新規クレアチニン誘導体を得ることができる。
【００１４】
このようにして得られたコクを付与する、分子量１６７の上記構造を有する新規クレアチニン誘導体を、日本料理のだし、たとえば、かつお節、鶏肉、魚貝、こんぶ、牛肉、シイタケなどの素汁に添加、または、西洋料理のスープストック、たとえば、牛肉、鶏肉、豚肉、魚貝などの素汁に添加、中華料理のタン、たとえば、牛肉、鶏肉、豚肉、ハム、貝柱、アワビ、エビ、スルメ、シイタケ、ハクサイ、セロリなどの素汁に添加することにより、これらにコクを付与し、その呈味機能を増強させることが判明した。また、前述のごとく、上記の天然エキスの加工品および代替品、特にアミノ酸混合物として比較的安価に利用できるＨＶＰ、ＨＡＰ、酵母エキスに添加し、安価なビーフエキスに添加した場合も、味全体をひきしめ、味の増強がみられ、高品質なものに改良することができる。
尚、コクを付与する新規クレアチニン誘導体の濃度は、添加対象とする食品、調味料に応じてその至適と思われる使用範囲が異なるが、上記のいずれの場合も、液中濃度が０．０１％〜０.５％（固型物重量）となるように添加することにより、従来のだしなどに欠けていたコクを付与し、味全体を整え、味のぼけを抑制することができた。また、本化合物は、いやな後味を有する各種食品に添加する事により後味のしつこさを弱めて、すっきりした味に変える効果を有していた。
【００１５】
本発明のコクを付与する新規クレアチニン誘導体は、強い呈味発現機能を有し、調味料としての利用、各種加工食品、栄養食品、医療食等への添加が可能で、さらには畜産物、水産物資源の有効利用に貢献し得るものである。添加方法としては、そのまま添加しても良いし、水などにあらかじめ溶解させた後で添加しても良い。
【００１６】
【実施例】
以下に、コクを付与する上記新規クレアチニン誘導体を得る方法と添加効果を製造例、実施例をあげて、説明する。尚、本発明はこれら製造例、実施例によって制限されるものではない。
【００１７】
（製造例１：加熱生成法）
クレアチンとメチルグリオキサールをそれぞれ５０ｍＭになるように水に溶解し、ｐＨを１０、温度を５°Ｃで２時間攪拌を行い、その後温度を９５°Ｃにしてさらに１２時間加熱を行い、上記新規クレアチニン誘導体（４）を３．８ｍＭ得た。このときの収率は、７．６％（モル換算）であった。
【００１８】
（製造例２：加熱生成法）
クレアチニンとメチルグリオキサールをそれぞれ１００ｍＭになるように水に溶解し、ｐＨを６、温度を９５°Ｃで４時間攪拌を行い、上記新規クレアチニン誘導体（４）を１４．３ｍＭ得た。このときの収率は、１４．３％（モル換算）であった。
【００１９】
（製造例３：加熱生成法）
クレアチン誘導体であるＮ-（５-メチル-４-オキソ-１-イミダゾリン-２-イル）ザルコシン１００ｍｇを少量の水に溶解しシロップ状にした後に、温度を１２０°Ｃで２時間加熱を行い、上記新規クレアチニン誘導体（４）を６．２ｍｇ得た。このときの収率は、６．９％（モル換算）であった。
【００２０】
（製造例４：加熱生成法）
クレアチン誘導体であるＮ-（１-メチル-４-ヒドロキシ-３-イミダゾリン-２，２-イリデン）アラニンを１０ｍＭになるよう水に溶解し、ｐＨを２、温度を６０°Ｃで１時間加熱を行い、上記新規クレアチニン誘導体（３）を０．２８ｍＭ得た。このときの収率は、２．８％（モル換算）であった。
【００２１】
（呈味機能評価）
このようにして得た新規クレアチニン誘導体のコク味付与機能を市販コンソメスープに、０.０５％（固型物重量）となるように上乗せ添加し、その呈味をパネル５名にてプロファイル評価した。この結果、上記新規クレアチニン誘導体を添加したサンプルは、市販コンソメにコクを付与した。
【００２２】
さらに、新規クレアチニン誘導体の適性添加量を調べる目的で、同様に市販コンソメスープに同画分を０．００５％、０.０１％、０.０２％、０.０５％、０.１％、０.２％、（固型物重量）添加し、同様にパネルを用いて評価した。この結果、同画分を添加したサンプルは、いずれもコントロールである市販コンソメスープのもつ風味を変える事なく、コク味、あつみの増強に加えて、いわゆる味全体をひきしめることが判明した。しかし、その添加効果は、０.１％以上の添加では、大差がみられず、経済的な事を考えると０.０１％程度の添加で充分であると推定された。
【００２３】
このようにして新規クレアチニン誘導体を市販コンソメスープに添加し、官能評価を実施した。配合比は次の通りとした。すなわち、市販コンソメキューブ一個（５ｇ）および本発明の新規クレアチニン誘導体粉末０．０６ｇに水（湯）を加えて全量を３００ｍｌとした。
【００２４】
対照として、無添加のコンソメスープを調製し、２種類のスープについて、２点比較法で味覚パネル２０名による官能評価を実施した。結果を表１に示した。
【００２５】
【表１】

【００２４】
【発明の効果】
本発明の新規クレアチン誘導体の製法は、天然エキス加工品、その代替物、あるいは基本だしなどに添加することにより、これら既存の調味料にコクを付与でき、天然エキスに類似した高品質の呈味を持つ天然エキス加工品、代替品叉は基本だしを提供できる。
【図面の簡単な説明】
【図１】製造例で得た単離サンプル（３）の１Ｈ-ＮＭＲ チャート。
【図２】製造例で得た単離サンプル（３）の１３Ｃ-ＮＭＲチャート。
【図３】製造例で得た単離サンプル（４）の１Ｈ-ＮＭＲチャート。
【図４】製造例で得た単離サンプル（４）の１３Ｃ-ＮＭＲチャート。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel substance that exhibits richness in various foods.
[0002]
[Prior art]
As a base for various dishes, natural extracts such as livestock meat extract, chicken extract, seafood extract, and vegetable extract are widely used for business purposes. The functions of these natural extracts are said to give the food a complex taste and breadth, give it richness, and make up for the lack of taste of the food material.
[0003]
[Problems to be solved by the invention]
However, since these natural extracts are expensive and difficult to obtain, generally, processed products and substitutes using some of these natural extracts are manufactured, marketed and used. In addition, basic soups such as bonito, dried boiled fish, dashi kelp, shiitake mushrooms, and flavor seasonings in which these natural materials are mixed with salt, sugar, umami seasonings, amino acids, etc. are also widely used. These commercial natural extract processed products and substitutes are composed mainly of low molecular weight substances such as amino acids, nucleic acids, and organic acids mainly composed of sodium glutamate. In comparison, the taste is simple and has the disadvantage of being blurred. Conventionally, in order to make up for such drawbacks, the addition of HVP (vegetable protein degradation product), HAP (animal protein degradation product), yeast extract, etc., gives a rich taste and complex taste, and improves taste. However, HVP and HAP have a decomposition odor, and since yeast extract has a flavor peculiar to yeast, the amount of its use is naturally limited, and so-called models are used. The taste and flavor are clearly different from natural extracts, which is not satisfactory. In particular, there is a problem that there is a significant difference in the taste as shown by the words “sour taste with sourness” and “shimari”, which tastes the whole taste and gives a taste and depth to the taste. Yes.
[0004]
[Means for Solving the Problems]
Thus, as a result of repeated research aimed at enhancing the seasoning power of natural extract substitutes and basic soup stock, and providing richness, the present inventors have conducted dialysis membranes and electrodialysis membranes, gel filtration chromatography, partition chromatography, reverse chromatography. Using a phase chromatography etc., the fraction which gives "atsushi acidity" from the beef hot water extract was fractionated, and the creatine derivative was successfully isolated. In addition, the present inventors succeeded in obtaining the creatine derivative by mixing and heating the commercially available reagent creatine and the commercially available reagent methylglyoxal.
By further heating this compound, a novel related compound of the creatine derivative represented by the general formula (1) or (2) was successfully obtained (example: structural formula (1) (2))
[0005]
[Chemical 3]

[0006]
[Formula 4]

[0007]
(Molecular weight): 167
(Molecular formula): C7H9N3O2
(Structural Formula): (1) 1,6-Dimethyl-3,5-dioxo-2,3,5,6-tetrahydro-imidazo [1,2-b] imidazole

(2) 1,5-dimethyl-3,6-dioxo-2,3,5,6-tetrahydro-imidazo [1,2-b] imidazole

[0008]
If this substance is added to processed products and substitutes of existing natural extracts, or basic soup stocks, it enhances the seasoning power and subtracts the whole taste to make the taste rich and durable. The present invention has been completed.
Further, the present compound has been found to have an effect of reducing the persistence of the aftertaste and changing it to a refreshing taste by adding it to various foods having an unpleasant aftertaste.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a novel creatinine derivative represented by the above general formulas (1) and (2) (for example, structural formulas (1) and (2)) obtained by reacting creatine or creatinine with a saccharide or osones thereof. About.
By adding the novel creatinine derivative of the present invention or a solution containing this substance to the above processed natural extracts and substitutes, or basic stocks, it is possible to impart richness to these existing seasonings, which is similar to natural extracts. It is possible to provide a method for producing a natural extract processed product having a taste of quality and a substitute product, and a method for producing a high quality basic stock.
[0010]
Creatine or creatinine used in the present invention is extracted from beef, pork, chicken, fish meat, etc. in addition to the reagents, or extracts of these meats, extracts of commercially available marine products, extracts of livestock meats, and by-products when manufacturing processed foods Marine products, livestock meat boiled juice, steamed liquid, cooker juice, fish solver, and the like can be arbitrarily used. It is also possible to use these enzyme digests and fish sauce.
[0011]
Moreover, monosaccharides, such as glucose and fructose, or disaccharide can be used arbitrarily as saccharides. Further, osones such as glucosone, sugar alcohols such as sorbit, and aldonic acids such as gluconic acid may be used. It is also possible to use foods and seasonings containing a large amount of the above sugars such as syrup, molasses, isomerized sugar, vegetable extract, fruit juice and the like.
[0012]
The method of obtaining the novel creatinine derivative which provides richness mixes creatine 1-100 mM and saccharides, for example, methylglyoxal so that it may become 1-100 mM, for example in water. At this time, the pH may be 1 to 14, the temperature may be 5 to 95 ° C., and the mixing time may be within 72 hours.
[0013]
When the mixed solution thus obtained is concentrated, alcohols are added and the mixture is allowed to stand at room temperature, crystals are precipitated, and this novel creatinine derivative can be obtained.
[0014]
A novel creatinine derivative having the above structure having a molecular weight of 167, which gives the richness thus obtained, is added to Japanese soup stock, for example, bonito, chicken, fish shell, kombu, beef, shiitake and other soups, Or Western soup stock such as beef, chicken, pork, fish shellfish, etc. It has been found that, by adding to a soup such as Chinese cabbage and celery, the body is given richness and its taste function is enhanced. In addition, as described above, when added to processed products and substitutes of the above natural extracts, particularly HVP, HAP, and yeast extract that can be used relatively inexpensively as amino acid mixtures, and added to inexpensive beef extracts, the whole taste is crushed. The taste is enhanced and can be improved to high quality.
In addition, the concentration of the new creatinine derivative imparting richness varies depending on the food and seasoning to be added, and the range of use considered to be optimal, but in any of the above cases, the concentration in the liquid is 0.01 By adding so that it might become% -0.5% (solid weight), the richness lacking in the conventional stock could be imparted, the whole taste was adjusted, and blurring of the taste could be suppressed. Moreover, this compound had the effect which weakens the persistentness of aftertaste and adds it to the refreshing taste by adding to various foodstuffs with a bad aftertaste.
[0015]
The novel creatinine derivative imparting richness of the present invention has a strong taste expression function, can be used as a seasoning, can be added to various processed foods, nutritional foods, medical foods, etc. It can contribute to the effective use of resources. As an addition method, it may be added as it is or after it is dissolved in water or the like in advance.
[0016]
【Example】
Hereinafter, the method for obtaining the above-mentioned novel creatinine derivative imparting richness and the effect of addition will be described with reference to production examples and examples. The present invention is not limited by these production examples and examples.
[0017]
(Production Example 1: Heat generation method)
Creatine and methylglyoxal are each dissolved in water to 50 mM, stirred for 2 hours at a pH of 10 and a temperature of 5 ° C., then heated to 95 ° C. for another 12 hours, and the above novel creatinine Derivative (4) 3.8 mM was obtained. The yield at this time was 7.6% (molar conversion).
[0018]
(Production Example 2: Heat generation method)
Creatinine and methylglyoxal were each dissolved in water to 100 mM, and stirred at pH 6 and temperature of 95 ° C. for 4 hours to obtain 14.3 mM of the novel creatinine derivative (4). The yield at this time was 14.3% (molar conversion).
[0019]
(Production Example 3: Heat generation method)
A creatine derivative N- (5-methyl-4-oxo-1-imidazolin-2-yl) sarcosine 100 mg was dissolved in a small amount of water to form a syrup, and then heated at 120 ° C. for 2 hours. 6.2 mg of the novel creatinine derivative (4) was obtained. The yield at this time was 6.9% (molar conversion).
[0020]
(Production Example 4: Heat generation method)
The creatine derivative N- (1-methyl-4-hydroxy-3-imidazoline-2,2-ylidene) alanine is dissolved in water to 10 mM, and heated at a pH of 2 and a temperature of 60 ° C. for 1 hour. Then, 0.28 mM of the novel creatinine derivative (3) was obtained. The yield at this time was 2.8% (molar conversion).
[0021]
(Taste function evaluation)
The richness imparting function of the novel creatinine derivative thus obtained was added to commercially available consomme soup so that it would be 0.05% (solid weight), and the taste was profiled by five panelists. . As a result, the sample to which the novel creatinine derivative was added imparted richness to a commercially available consomme.
[0022]
Further, for the purpose of examining the appropriate addition amount of the novel creatinine derivative, 0.005%, 0.01%, 0.02%, 0.05%, 0.1%, 0% .2% (solid weight) was added and evaluated in the same manner using the panel. As a result, it was found that the samples to which the same fraction was added all soaked the so-called taste in addition to enhancing the richness and the taste without changing the flavor of the commercially available consomme soup as a control. However, the addition effect of 0.1% or more shows no significant difference, and it is estimated that the addition of about 0.01% is sufficient in view of economic reasons.
[0023]
Thus, the novel creatinine derivative was added to the commercially available consomme soup, and sensory evaluation was implemented. The blending ratio was as follows. That is, water (hot water) was added to one commercially available consomme cube (5 g) and 0.06 g of the novel creatinine derivative powder of the present invention to make a total amount of 300 ml.
[0024]
As a control, an additive-free consomme soup was prepared, and sensory evaluation by 20 taste panels was performed on the two types of soup by a two-point comparison method. The results are shown in Table 1.
[0025]
[Table 1]

[0024]
【The invention's effect】
The method for producing the novel creatine derivative of the present invention can add richness to these existing seasonings by adding them to processed natural extracts, substitutes thereof, or basic dashi, and has a high quality taste similar to natural extracts. Natural extract processed products, alternative products or basic stock can be provided.
[Brief description of the drawings]
FIG. 1 is a 1H-NMR chart of an isolated sample (3) obtained in Production Example.
FIG. 2 is a 13C-NMR chart of an isolated sample (3) obtained in Production Example.
FIG. 3 is a 1H-NMR chart of an isolated sample (4) obtained in Production Example.
FIG. 4 is a 13C-NMR chart of an isolated sample (4) obtained in Production Example.

Claims (1)

A novel creatinine derivative consisting of any one of the following general formulas (1) to (2).

R is H, CH3, CH2-CH2OH, CH2-CHOH-CHOH-CH2OH

R is H, CH3, CH2-CH2OH, CH2-CHOH-CHOH-CH2OH

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