JP5300010B2 - Novel compounds and perfume compositions - Google Patents
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Abstract
Description
本発明は、香料化合物として有用な新規化合物および該化合物を有効成分として含有する新規な香料組成物、ならびに該化合物の製造方法に関する。 The present invention relates to a novel compound useful as a fragrance compound, a novel fragrance composition containing the compound as an active ingredient, and a method for producing the compound.
近年、消費者の嗜好性の多様化により、飲食品等に使用する香料においても天然感、フレッシュ感あふれる素材が求められており、従来の香料物質を組み合わせることではその要求に十分対応しきれないのが現状であり、従来にない新しい香料素材に対する要望が高くなっている。 In recent years, due to the diversification of consumer preferences, there is a demand for materials with a natural and fresh feel in fragrances used in foods and drinks, etc., and the combination of conventional fragrance substances cannot fully meet the demand. However, there is a growing demand for new fragrance materials that have never existed before.
ある種のチオール類が香料素材として有用であることが知られている。例えば、1−プロパンチオール(プロピルメルカプタン)は、希釈するとオニオンないしキャベツ香となり、オニオンなどのフレーバーとして使用され、2−プロペン−1−チオール(アリルメルカプタン)は、強いガーリック、オニオン様の拡散性ある匂いがあり、スープ、肉製品、スパイス系のフレーバーとして使用されることが示されている(非特許文献1参照)。また、特許文献1には、分岐鎖状アルカンチオール類がロース肉香味を与えるための香料として有用であることが開示されている。 Certain thiols are known to be useful as perfume materials. For example, 1-propanethiol (propyl mercaptan) becomes an onion or cabbage scent when diluted, and is used as a flavor of onion or the like, and 2-propene-1-thiol (allyl mercaptan) has strong garlic and onion-like diffusibility. It has an odor and has been shown to be used as a soup, meat product, or spice flavor (see Non-Patent Document 1). Patent Document 1 discloses that branched alkanethiols are useful as a fragrance for imparting a loin meat flavor.
しかしながら、飲食品などの香料素材として使用されている上記した従来のチオール類は、香気や香味の質および強度の点で単調であったり、フレッシュ感などの点で十分とはいえず、多様化している賦香製品に、フレッシュ感その他の香味を賦与する要望に十分対応できていなかった。 However, the above-mentioned conventional thiols used as fragrance materials for foods and drinks are monotonous in terms of aroma and flavor quality and strength, and are not sufficient in terms of freshness, etc. It was not possible to meet the demand for adding a fresh feeling and other flavors to the perfumed products.
本発明の目的は、飲食品などにフレッシュ感その他の香味を賦与することができる新規化合物、および該化合物を含有する新規な香料組成物ならびに該化合物の製造方法を提供することにある。 An object of the present invention is to provide a novel compound capable of imparting a fresh feeling or other flavor to food and drink, a novel fragrance composition containing the compound, and a method for producing the compound.
本発明者らは、前述の課題を解決するために鋭意検討した結果、今回、従来にないチオール化合物を合成し、そのチオール化合物の物性などについて検討したところ、該チオール化合物がオニオンなどの野菜の調理感、肉の調理感、ゴマの煎りたて感、擂りたて感など嗜好性の高い香気、特にフレッシュなロースト感を有すること、他の香料と併用したときに調和性に優れていること、従来知られている1−プロパンチオール、2−プロペン−1−チオールその他の類似化合物では不十分であった、フレッシュなロースト感などの香気、香味を賦与することができることを見出し本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have synthesized a thiol compound that has not been used in the past and examined the physical properties of the thiol compound. A taste of cooking, a feeling of cooking meat, a freshly roasted feeling of sesame, a freshly savory feeling, especially a fresh roasted feeling, and excellent harmony when used in combination with other fragrances The present invention was completed by finding that a conventionally known 1-propanethiol, 2-propene-1-thiol and other similar compounds can be imparted with an aroma and flavor such as a fresh roasted feeling. It came to do.
かくして本発明は、下記式(1) Thus, the present invention provides the following formula (1):
(式中、波線の結合はシス型もしくはトランス型またはシス型とトランス型の任意の割合の混合物であることを示し、R1が水素の場合、R2はメチル基を示し、R1がメチル基の場合、R2は水素を示す。)
で表される化合物を提供することができる。
(Wherein the wavy bond indicates cis-type or trans-type or a mixture of cis-type and trans-type in an arbitrary ratio. When R1 is hydrogen, R2 represents a methyl group and R1 is a methyl group. , R2 represents hydrogen.)
The compound represented by these can be provided.
また本発明は、前記式(1)の化合物を有効成分として含有することを特徴とする香料組成物を提供することができる。 Moreover, this invention can provide the fragrance | flavor composition characterized by containing the compound of said Formula (1) as an active ingredient.
さらに本発明は、下記式(3) Furthermore, the present invention provides the following formula (3)
(式中R1が水素の場合、R2はメチル基を示し、R1がメチル基の場合、R2は水素を示す。)
で表される化合物を熱分解することを特徴とする下記式(1)
(In the formula, when R1 is hydrogen, R2 represents a methyl group, and when R1 is a methyl group, R2 represents hydrogen.)
The compound represented by the following formula (1)
(式中、波線の結合はシス型もしくはトランス型またはシス型とトランス型の任意の割合の混合物であることを示し、R1が水素の場合、R2はメチル基を示し、R1がメチル基の場合、R2は水素を示す。)
で表される化合物の製造方法を提供することができる。
(Wherein the wavy bond indicates cis-type or trans-type or a mixture of cis-type and trans-type in an arbitrary ratio. When R1 is hydrogen, R2 represents a methyl group and R1 is a methyl group. , R2 represents hydrogen.)
The manufacturing method of the compound represented by these can be provided.
本発明の式(1)の化合物は、野菜の調理感、肉の調理感、ゴマの煎りたて感、擂りたて感など嗜好性の高い香気、特にフレッシュなロースト感を増強することができ、飲食品などに用いる香料組成物の調合素材として有用である。 The compound of the formula (1) of the present invention can enhance the taste of vegetables, the feeling of cooking of meat, the feeling of freshly roasted sesame, the feeling of freshly roasted, especially the fresh roasted feeling. It is useful as a preparation material for a fragrance composition used for food and drink.
以下、本発明の前記式(1)の化合物、その製造方法および香料組成物としての用途について、さらに詳細に説明する。 Hereinafter, the compound of formula (1) of the present invention, its production method, and use as a fragrance composition will be described in more detail.
本発明の式(1)の化合物、具体的には、3−メチル−1−ブテン−1−チオール(R1が水素で、R2がメチル基の場合)または2−メチル−1−ブテン−1−チオール(R1がメチル基で、R2が水素の場合)は、従来、文献未記載の新規化合物であり、次の反応経路1に従って化学的に合成することができる。 Compounds of formula (1) of the present invention, specifically 3-methyl-1-butene-1-thiol (when R1 is hydrogen and R2 is a methyl group) or 2-methyl-1-butene-1- A thiol (when R1 is a methyl group and R2 is hydrogen) is a novel compound not described in the literature, and can be chemically synthesized according to the following reaction pathway 1.
(式中、波線の結合はシス型もしくはトランス型またはシス型とトランス型の任意の割合の混合物であることを示し、R1が水素の場合、R2はメチル基を示し、R1がメチル基の場合、R2は水素を示す。)
式(2)のアルデヒドと硫化水素との反応は、文献(例えば、新実験化学講座14有機化合物の合成と反応[III]10−1711参照)に記載されている条件にて実施することができる。溶媒としては、例えば、エーテル(例:ジエチルエーテル、ジイソプロピルエーテル、メチルt−ブチルエーテル、1,4−ジオキサン、テトラヒドロフランなど)、ハロゲン化炭化水素(例:ジクロロメタン、クロロホルムなど)、芳香族炭化水素(例:ベンゼン、トルエン、キシレンなど)、アルコール(例:メタノール、エタノール、イソプロピルアルコール、エチレングリコールなど)、エステル(酢酸メチル、酢酸エチル、グリセリンエステルなど)、または極性溶媒(例:ジメチルホルムアミド、ジメチルスルホキシド、アセトニトリルなど)が挙げられ、特にジメチルスルホキシドなどの極性溶媒が好適である。
(Wherein the wavy bond indicates cis-type or trans-type or a mixture of cis-type and trans-type in an arbitrary ratio. When R1 is hydrogen, R2 represents a methyl group and R1 is a methyl group. , R2 represents hydrogen.)
The reaction of the aldehyde of formula (2) with hydrogen sulfide can be carried out under the conditions described in the literature (for example, see New Experimental Chemistry Lecture 14, Synthesis of Organic Compounds and Reaction [III] 10-1711). . Examples of the solvent include ethers (eg, diethyl ether, diisopropyl ether, methyl t-butyl ether, 1,4-dioxane, tetrahydrofuran, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, etc.), aromatic hydrocarbons (eg, : Benzene, toluene, xylene, etc.), alcohol (eg, methanol, ethanol, isopropyl alcohol, ethylene glycol, etc.), ester (methyl acetate, ethyl acetate, glycerin ester, etc.), or polar solvent (eg, dimethylformamide, dimethyl sulfoxide, Acetonitrile, etc.), and polar solvents such as dimethyl sulfoxide are particularly suitable.
反応には酸触媒、塩基触媒いずれも使用することができ、例えば、酢酸、塩酸、p−トルエンスルホン酸、塩化亜鉛などの酸触媒、アミン類(例:アンモニア、モルホリン、ピロリジン、DBU、プロリンなど)が挙げられ、これらの触媒の使用量は、式(2)のアルデヒドに対して、通常0.001〜10当量、好ましくは0.01〜1当量の範囲内とすることができる。 Either an acid catalyst or a base catalyst can be used in the reaction. For example, an acid catalyst such as acetic acid, hydrochloric acid, p-toluenesulfonic acid, zinc chloride, and amines (eg, ammonia, morpholine, pyrrolidine, DBU, proline, etc.) The amount of these catalysts to be used is generally 0.001 to 10 equivalents, preferably 0.01 to 1 equivalent, relative to the aldehyde of formula (2).
また、式(2)のアルデヒドに対する硫化水素の使用量は、通常1〜100当量、好ましくは5〜50当量の範囲内とすることができる。 Moreover, the usage-amount of hydrogen sulfide with respect to the aldehyde of Formula (2) is 1-100 equivalent normally, Preferably it can be in the range of 5-50 equivalent.
反応温度としては、通常、−78〜100℃、好ましくは、−10〜40℃の範囲で、反応時間としては、通常0.5〜24時間、好ましくは1〜8時間の範囲で行うことができる。 The reaction temperature is usually −78 to 100 ° C., preferably −10 to 40 ° C., and the reaction time is usually 0.5 to 24 hours, preferably 1 to 8 hours. it can.
式(3)のジチオールの熱分解反応は通常、100〜500℃、好ましくは、300〜400℃の範囲で行うことができ、減圧下(0.01kPa〜10kPa)で行うことが好ましい。このような分解反応の条件は、FVP(瞬間真空熱分解法)の条件を利用することで簡便に実施でき、そのような手法を利用したい場合は、たとえば、Organic Syntheses 82巻、p.99に記載されている方法などに従って市販の電気炉からFVP装置を組み立てて用いることができる。 The thermal decomposition reaction of the dithiol of formula (3) is usually 100 to 500 ° C., preferably 300 to 400 ° C., preferably under reduced pressure (0.01 kPa to 10 kPa). Such decomposition reaction conditions can be easily carried out by using the FVP (instantaneous vacuum pyrolysis method) conditions. If such a method is desired, see, for example, Organic Synthesis Volume 82, p. 99 can be used by assembling an FVP apparatus from a commercially available electric furnace.
反応には高沸点の溶媒を使用することもでき、例えば、流動パラフィン、ODO、植物オイルなどが挙げられる。またこの際、反応を促進するために、式(3)のジチオールに対して0.01〜20重量%、好ましくは0.1〜5重量%の酸や塩基を加えることができる。例えば、無機酸としては硫酸やリン酸、ホウ酸やあるいは12−モリブドリン酸やタングストリン酸などのヘテロポリ酸、また有機酸としてはパラトルエンスルホン酸、メタンスルホン酸、さらに塩基としては水酸化ナトリウム、水酸化バリウム、酸化マグネシウム、アルミナ、ピリジン、キノリン、1,8−ジアザビシクロ[5.4.0]−7−ウンデセン、N,N,N‘,N’−テトラメチルエチレンジアミン、テトラメチルグアニジンなどを挙げることができる。 A high-boiling solvent can also be used for the reaction, and examples thereof include liquid paraffin, ODO, and vegetable oil. At this time, in order to accelerate the reaction, 0.01 to 20% by weight, preferably 0.1 to 5% by weight of acid or base can be added to the dithiol of the formula (3). For example, inorganic acids include sulfuric acid, phosphoric acid, boric acid, or heteropolyacids such as 12-molybdophosphoric acid and tungstophosphoric acid, organic acids include paratoluenesulfonic acid, methanesulfonic acid, and bases include sodium hydroxide, Barium hydroxide, magnesium oxide, alumina, pyridine, quinoline, 1,8-diazabicyclo [5.4.0] -7-undecene, N, N, N ′, N′-tetramethylethylenediamine, tetramethylguanidine, etc. be able to.
かくして、用いる反応条件により、波線の結合におけるシス:トランス比が一般に3:7〜7:3の範囲内にある式(1)の化合物を幾何異性体混合物の形態で得ることができる。 Thus, depending on the reaction conditions used, the compound of formula (1) having a cis: trans ratio in the wavy bond generally in the range of 3: 7 to 7: 3 can be obtained in the form of a mixture of geometric isomers.
上記した方法により得られる新規な式(1)の化合物は、そのまま飲食品などに極微量配合することにより野菜の調理感、肉の調理感、ゴマの煎りたて感、擂りたて感など嗜好性の高い香気、特にフレッシュなロースト感を増強することができるが、他の成分と混合して香料組成物を調製し、該香料組成物を用いて飲食品などに野菜の調理感、肉の調理感、ゴマの煎りたて感、擂りたて感など嗜好性の高い香気、特にフレッシュなロースト感を増強することもできる。該香料組成物の前記式(1)の化合物と共に含有し得る他の香料成分としては、各種の合成香料、天然香料、天然精油、植物エキスなどを挙げることができる。 The novel compound of the formula (1) obtained by the above-described method can be added to foods and drinks and the like as it is, so that the cooking feeling of vegetables, the cooking feeling of meat, the sensation of sesame, the freshness of cooking It is possible to enhance a highly aromatic flavor, particularly a fresh roasted feeling, but it is mixed with other ingredients to prepare a fragrance composition, and the fragrance composition is used for food and drink, etc. It is also possible to enhance the taste of cooking, the sensation of sesame, the sensation of freshness, especially the fresh roasted feeling. Examples of other fragrance components that can be contained together with the compound of formula (1) of the fragrance composition include various synthetic fragrances, natural fragrances, natural essential oils, plant extracts, and the like.
本発明の香料組成物における式(1)の化合物の含有量は、混合される他の香料成分により異なり一概にはいえないが、通常、該香料組成物の重量を基準として10−4〜104ppm、好ましくは10−3〜103ppmの濃度範囲とすることができる。式(1)の化合物の含有量が10−4ppm未満であれば香味増強効果が得られず、104ppmを越える含有量であれば不快臭が強くなってしまい好ましくない。 The content of the compound of formula (1) in the fragrance composition of the present invention varies depending on other fragrance components to be mixed and cannot be generally specified, but is usually 10 −4 to 10 based on the weight of the fragrance composition. The concentration range is 4 ppm, preferably 10 −3 to 10 3 ppm. If the content of the compound of the formula (1) is less than 10 −4 ppm, the flavor enhancing effect cannot be obtained, and if the content exceeds 10 4 ppm, the unpleasant odor becomes strong, which is not preferable.
式(1)の化合物を含有する本発明の香料組成物には、必要に応じて、香料組成物において通常使用されている、例えば、水、エタノール等の溶剤;エチレングリコール、プロピレングリコール、ジプロピレングリコール、グリセリン、ヘキシルグリコール、ベンジルベンゾエート、トリエチルシトレート、ジエチルフタレート、ハーコリン、中鎖脂肪酸トリグリセライド、中鎖脂肪酸ジグリセライド等の香料保留剤を含有することができる。 The fragrance composition of the present invention containing the compound of the formula (1) is usually used in the fragrance composition as necessary, for example, a solvent such as water or ethanol; ethylene glycol, propylene glycol, dipropylene A fragrance retaining agent such as glycol, glycerin, hexyl glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hercoline, medium chain fatty acid triglyceride, medium chain fatty acid diglyceride and the like can be contained.
本発明の式(1)の化合物は、上記したようにそれ自体単独で、または式(1)の化合物を含有する香料組成物を調製して、各種の製品、例えば、飲食品などに野菜の調理感、肉の調理感、ゴマの煎りたて感、擂りたて感など嗜好性の高い香気、特にフレッシュなロースト感を増強することができる。 As described above, the compound of the formula (1) of the present invention can be used alone or as a perfume composition containing the compound of the formula (1) to prepare various kinds of products such as food and drink. It is possible to enhance the taste of cooking, the cooking feeling of meat, the freshly roasted feeling of sesame, the freshly roasted feeling, particularly the fresh roasted feeling.
本発明の式(1)の化合物または式(1)の化合物を含有する香料組成物によって野菜の調理感、肉の調理感、ゴマの煎りたて感、擂りたて感など嗜好性の高い香気、特にフレッシュなロースト感を増強することができる飲食品の具体例としては、何ら限定されるものではなく、炭酸飲料、清涼飲料、果汁飲料類、果実酒類、乳飲料類、乳酸菌飲料類、ドリンク剤類、豆乳、茶飲料などの飲料類;アイスクリーム、アイスミルク、ラクトアイス、氷菓、ヨーグルト、プリン、ゼリー、デイリーデザートなどのデザート類;キャラメル、キャンディー、錠菓、クラッカー、ビスケット、クッキー、パイ、チョコレート、スナック、チューインガム、饅頭、羊羹などの菓子類;和風スープ、洋風スープ、中華スープなどのスープ類;パン類;ジャム類;マヨネーズ、ドレッシングなどの調味料類;各種インスタント飲料類;各種インスタント食品類などを挙げることができる。 Fragrance having high palatability such as vegetable cooking feeling, meat cooking feeling, sesame freshly roasted feeling, freshly savory feeling by the compound of formula (1) or the fragrance composition containing the compound of formula (1) of the present invention In particular, specific examples of foods and drinks that can enhance a fresh roasted feeling are not limited at all, and carbonated drinks, soft drinks, fruit juice drinks, fruit liquors, milk drinks, lactic acid bacteria drinks, drinks Beverages such as pharmaceuticals, soy milk, tea drinks; desserts such as ice cream, ice milk, lact ice, ice confectionery, yogurt, pudding, jelly, daily dessert; caramel, candy, tablet confectionery, crackers, biscuits, cookies, pies, Chocolate, snacks, chewing gum, buns, mutton and other sweets; Japanese soups, Western soups, Chinese soups and soups; Breads; Jas Kind; mayonnaise, seasonings such as dressing; various types of instant beverages; and the like can be mentioned various kinds of instant foods.
上記した各種の製品への式(1)の化合物の添加量は、製品の種類や形態に応じて異なり一概にはいえないが、通常、製品の重量を基準として10−2〜106ppb、好ましくは10−1〜105ppbの濃度範囲とすることができる。式(1)の化合物の含有量が10−2ppb未満であれば野菜の調理感、肉の調理感、ゴマの煎りたて感、擂りたて感など嗜好性の高い香気、特にフレッシュなロースト感を増強することができず、106ppbを越える含有量であれば不快臭が強くなってしまい好ましくない。 The amount of the compound of formula (1) added to the various products described above varies depending on the type and form of the product and cannot be generally specified, but is usually 10 −2 to 10 6 ppb based on the weight of the product, The concentration range is preferably 10 −1 to 10 5 ppb. If the content of the compound of the formula (1) is less than 10 −2 ppb, the taste of cooking of vegetables, the feeling of cooking of meat, the feeling of freshly roasted sesame, the feeling of freshness, especially fresh roast If the content cannot be enhanced and the content exceeds 10 6 ppb, the unpleasant odor becomes strong, which is not preferable.
以下、実施例により本発明をさらに具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
実施例1:2−メチルブタン−1,1−ジチオール(式(3)−1の化合物)の合成
1Lフラスコに、2−メチルブタナール150.4 g(1.75mol)、ジメチルスルホキシド(750.1g)、ピロガロール0.45 g(0.3mmol)を加え、冷却して反応液の温度を0〜20℃に保ちながら、硫化水素ガスを通じた。2時間後、反応液を氷水1Lに攪拌しながら加え、エーテル500mLを加えて抽出し、得られた有機層を水100mLで2回、飽和食塩水100mLで1回洗浄し、硫酸マグネシウム乾燥し、減圧下で溶媒を留去した。得られた残渣171.3gを減圧蒸留(65〜69℃/2.2kPa)し、蒸留品61.0gを得、10%の亜硫酸水素ナトリウム水溶液162gで3回洗浄し、30mLの飽和食塩水で予備脱水し、硫酸マグネシウムで乾燥し、2−メチルブタン−1,1−ジチオール55.6g(0.41mol,収率24%,純度97%)を得た。
Example 1: Synthesis of 2-methylbutane-1,1-dithiol (compound of formula (3) -1) In a 1 L flask, 150.4 g (1.75 mol) of 2-methylbutanal and dimethyl sulfoxide (750.1 g) ), 0.45 g (0.3 mmol) of pyrogallol was added and cooled, and hydrogen sulfide gas was passed through while maintaining the temperature of the reaction solution at 0 to 20 ° C. After 2 hours, the reaction solution was added to 1 L of ice water with stirring, 500 mL of ether was added for extraction, and the resulting organic layer was washed twice with 100 mL of water and once with 100 mL of saturated brine, dried over magnesium sulfate, The solvent was distilled off under reduced pressure. 171.3 g of the resulting residue was distilled under reduced pressure (65 to 69 ° C./2.2 kPa) to obtain 61.0 g of a distilled product, which was washed 3 times with 162 g of a 10% aqueous sodium hydrogen sulfite solution, and 30 mL of saturated saline solution. Preliminary dehydration and drying with magnesium sulfate were performed to obtain 55.6 g (0.41 mol, yield 24%, purity 97%) of 2-methylbutane-1,1-dithiol.
式(3)−1の化合物の物性
1H−NMR(CDCl3,400MHz,結合定数J[Hz]):δ 0.92(3H,t,J=7.2),1.04(3H,d,J=6.4),1.27−1.38(1H,m),1.51−1.61(1H,m),1.71−1.80(1H,m),2.14(1H,d,J=6.4),2.29(1H,d,6.4),4.23(1H,dt,J=3.6,6.4)
13C−NMR(CDCl3,100MHz):δ 11.6,14.8,26.7,43.7,44.2.
MS(m/z):34(31),41(100),61(37),69(57),79(17),87(23),102(78),103(46),136(M+,8)
Physical properties of compound of formula (3) -1
1 H-NMR (CDCl 3 , 400 MHz, coupling constant J [Hz]): δ 0.92 (3H, t, J = 7.2), 1.04 (3H, d, J = 6.4), 1 .27-1.38 (1H, m), 1.51-1.61 (1H, m), 1.71-1.80 (1H, m), 2.14 (1H, d, J = 6. 4), 2.29 (1H, d, 6.4), 4.23 (1H, dt, J = 3.6, 6.4)
13 C-NMR (CDCl 3 , 100 MHz): δ 11.6, 14.8, 26.7, 43.7, 44.2.
MS (m / z): 34 (31), 41 (100), 61 (37), 69 (57), 79 (17), 87 (23), 102 (78), 103 (46), 136 (M + , 8)
実施例2:3−メチルブタン−1,1−ジチオール(式(3)−2の化合物)の合成
実施例1において、2−メチルブタナールの代わりに3−メチルブタナールを用いる他は、実施例1と同様の方法で3−メチルブタン−1,1−ジチオールを得た。収量45.5g(0.33mol),収率19%。
Example 2: Synthesis of 3-methylbutane-1,1-dithiol (compound of formula (3) -2) In Example 1, except that 3-methylbutanal was used instead of 2-methylbutanal, Example 3-methylbutane-1,1-dithiol was obtained in the same manner as in Example 1. Yield 45.5 g (0.33 mol), yield 19%.
式(3)−2の化合物の物性
1H−NMR(CDCl3,400MHz,結合定数J[Hz]):δ 0.92(6H,t,J=6.4),1.74(2H,t,J=7.2),1.79−1.93(1H,m),2.36(2H,d,J=6.4),4.11(1H,quint,J=6.4)
13C−NMR(CDCl3,100MHz):δ 21.9,26.7,37.2,52.6.
MS(m/z):34(44),41(100),47(24),53(24),60(66),69(96),79(10),87(32),102(55),103(55),136(M+,12)
Physical properties of compound of formula (3) -2
1 H-NMR (CDCl 3 , 400 MHz, coupling constant J [Hz]): δ 0.92 (6H, t, J = 6.4), 1.74 (2H, t, J = 7.2), 1 79-1.93 (1H, m), 2.36 (2H, d, J = 6.4), 4.11 (1H, quint, J = 6.4)
13 C-NMR (CDCl 3 , 100 MHz): δ 21.9, 26.7, 37.2, 52.6.
MS (m / z): 34 (44), 41 (100), 47 (24), 53 (24), 60 (66), 69 (96), 79 (10), 87 (32), 102 (55 ), 103 (55), 136 (M + , 12)
実施例3:2−メチル−1−ブテン−1−チオール(式(1)−1の化合物)の合成
窒素ガス気流下、2−メチルブタン−1,1−ジチオール1.1g(8.1mmol)を少量ずつFVP(瞬間真空熱分解)反応管(内温380℃、内圧0.3kPa)に供し、分解物をドライアイス−アセトン浴で冷却したトラップ管に捕集し、2-メチル−1−ブテン−1−チオール0.6g(5.8mmol、収率72%、純度90%)を得た。これはE−体とZ−体の幾何異性体混合物で、比率はE:Z=60:40であった。
Example 3: Synthesis of 2-methyl-1-butene-1-thiol (compound of formula (1) -1) Under a nitrogen gas stream, 1.1 g (8.1 mmol) of 2-methylbutane-1,1-dithiol was added. A small amount is supplied to an FVP (instantaneous vacuum pyrolysis) reaction tube (internal temperature 380 ° C., internal pressure 0.3 kPa), and the decomposition product is collected in a trap tube cooled in a dry ice-acetone bath, and 2-methyl-1-butene is collected. 0.6 g (5.8 mmol, yield 72%, purity 90%) of -1-thiol was obtained. This was a mixture of geometric isomers of E-form and Z-form, and the ratio was E: Z = 60: 40.
(2E)−メチル−1−ブテン−1−チオールの物性
1H−NMR(CDCl3,400MHz,結合定数J[Hz]):δ 1.00(3H,t,J=7.6),1.72(3H,s),2.07(1H,q,J=7.6),2.54(1H,d,J=7.2),5.71(1H,dq,J=1.2,7.2)
13C−NMR(CDCl3,100MHz):δ 12.4,22.4,32.1,106.4,140.6.
MS(m/z):41(100),45(67),47(26),53(63),59(29),69(77),73(22),85(12),102(M+,100)
Physical properties of (2E) -methyl-1-butene-1-thiol
1 H-NMR (CDCl 3 , 400 MHz, coupling constant J [Hz]): δ 1.00 (3H, t, J = 7.6), 1.72 (3H, s), 2.07 (1H, q , J = 7.6), 2.54 (1H, d, J = 7.2), 5.71 (1H, dq, J = 1.2, 7.2)
13 C-NMR (CDCl 3 , 100 MHz): δ 12.4, 22.4, 32.1, 106.4, 140.6.
MS (m / z): 41 (100), 45 (67), 47 (26), 53 (63), 59 (29), 69 (77), 73 (22), 85 (12), 102 (M + , 100)
(2Z)−メチル−1−ブテン−1−チオールの物性
1H−NMR(CDCl3,400MHz,結合定数J[Hz]):δ 1.00(3H,t,J=7.6),1.75(3H,s),2.16(1H,q,J=7.6),2.51(1H,d,J=7.2),5.67(1H,dd,J=1.2,7.2)
13C−NMR(CDCl3,100MHz):δ 11.4,17.0,25.8,106.6,141.1.
MS(m/z):41(100),45(37),47(13),53(33),59(15),68(61),73(22),87(17),102(M+,63)
Physical properties of (2Z) -methyl-1-butene-1-thiol
1 H-NMR (CDCl 3 , 400 MHz, coupling constant J [Hz]): δ 1.00 (3H, t, J = 7.6), 1.75 (3H, s), 2.16 (1H, q , J = 7.6), 2.51 (1H, d, J = 7.2), 5.67 (1H, dd, J = 1.2, 7.2)
13 C-NMR (CDCl 3 , 100 MHz): δ 11.4, 17.0, 25.8, 106.6, 141.1.
MS (m / z): 41 (100), 45 (37), 47 (13), 53 (33), 59 (15), 68 (61), 73 (22), 87 (17), 102 (M + , 63)
実施例4:3−メチル−1−ブテン−1−チオール(式(1)−2の化合物)の合成
実施例3において、2−メチルブタン−1,1−ジチオールの代わりに3−メチルブタン−1,1−ジチオールを用いる他は、実施例3と同様の方法で3−メチル−1−ブテン−1−チオールを得た。収量0.5g(4.8ミリモル),収率60%。これはE−体とZ−体の幾何異性体混合物で、比率はE:Z=55:45であった。
Example 4: Synthesis of 3-methyl-1-butene-1-thiol (compound of formula (1) -2) In Example 3, instead of 2-methylbutane-1,1-dithiol, 3- 3-Methyl-1-butene-1-thiol was obtained in the same manner as in Example 3 except that methylbutane-1,1-dithiol was used. Yield 0.5 g (4.8 mmol), yield 60%. This was a mixture of geometric isomers of E-form and Z-form, and the ratio was E: Z = 55: 45.
(3E)−メチル−1−ブテン−1−チオールの物性
1H−NMR(CDCl3,400MHz,結合定数J[Hz]):δ 0.97(6H,d,J=6.4),2.30(1H,sextuplet,J=6.4),2.68(1H,d,J=8.0),5.74(1H,dd,J=15.2,6.4),5.76(1H,dd,J=15.2,6.4)
13C−NMR(CDCl3,100MHz):δ 22.1,31.9,111.0,141.4.
MS(m/z):27(15),39(33),41(79),45(67),47(22),53(65),59(30),69(100),85(24),87(83),102(M+,76)
Physical properties of (3E) -methyl-1-butene-1-thiol
1 H-NMR (CDCl 3 , 400 MHz, coupling constant J [Hz]): δ 0.97 (6H, d, J = 6.4), 2.30 (1H, sextuplet, J = 6.4), 2 .68 (1H, d, J = 8.0), 5.74 (1H, dd, J = 15.2, 6.4), 5.76 (1H, dd, J = 15.2, 6.4) )
13 C-NMR (CDCl 3 , 100 MHz): δ 22.1, 31.9, 111.0, 141.4.
MS (m / z): 27 (15), 39 (33), 41 (79), 45 (67), 47 (22), 53 (65), 59 (30), 69 (100), 85 (24 ), 87 (83), 102 (M + , 76)
(3Z)−メチル−1−ブテン−1−チオールの物性
1H−NMR(CDCl3,400MHz,結合定数J[Hz]):δ 0.98(6H,d,J=6.8),2.61(1H,dt,J=6.4,1.2),2.62(1H,d,J=8.0),5.48(1H,t,J=9.2),5.87(1H,dt,J=9.2,1.2)
13C−NMR(CDCl3,100MHz):δ 22.0,27.8,112.0,138.5.
MS(m/z):27(15),39(31),41(80),45(69),47(24),53(64),59(32),69(100),85(24),87(90),102(M+,81)
Physical properties of (3Z) -methyl-1-butene-1-thiol
1 H-NMR (CDCl 3 , 400 MHz, coupling constant J [Hz]): δ 0.98 (6H, d, J = 6.8), 2.61 (1H, dt, J = 6.4, 1.. 2), 2.62 (1H, d, J = 8.0), 5.48 (1H, t, J = 9.2), 5.87 (1H, dt, J = 9.2, 1.2) )
13 C-NMR (CDCl 3 , 100 MHz): δ 22.0, 27.8, 112.0, 138.5.
MS (m / z): 27 (15), 39 (31), 41 (80), 45 (69), 47 (24), 53 (64), 59 (32), 69 (100), 85 (24 ), 87 (90), 102 (M + , 81)
実施例5:ゴマ油への式(1)の化合物の添加効果
ゴマ油(かどや製油社製)100gに2−メチル−1−ブテン−1−チオール(本発明品1)、3−メチル−1−ブテン−1−チオール(本発明品2)、1−プロパンチオール(比較品1)および2−プロペン−1−チオール(比較品2)をそれぞれ1mg(ゴマ油に対して10ppm)を添加して本発明品1、本発明品2、比較品1および比較品2の香料組成物を調製した。それぞれの香料組成物の0.1%エタノール溶液をよく訓練されたパネラーにより香気評価を行った。香気評価は30mLサンプル瓶に前記0.1%エタノール溶液を用意し、瓶口の香気およびその溶液をにおい紙につけて行った。無添加品のゴマ油を対照品として、よく訓練された5名のパネラーの平均的な香気評価を表1に示す。
Example 5: Effect of addition of compound of formula (1) to sesame oil 2-methyl-1-butene-1-thiol (product 1 of the present invention) and 3-methyl-1-butene were added to 100 g of sesame oil (manufactured by Kadoya Oil Co., Ltd.). 1 mg of thiol (Invention product 2), 1-propanethiol (Comparative product 1) and 2-propene-1-thiol (Comparative product 2) were each added (10 ppm relative to sesame oil). 1. Perfume compositions of the present invention product 2, comparative product 1 and comparative product 2 were prepared. Aroma evaluation was performed by a well-trained panel for 0.1% ethanol solution of each fragrance composition. The fragrance evaluation was performed by preparing the 0.1% ethanol solution in a 30 mL sample bottle and applying the fragrance of the bottle mouth and the solution to odor paper. Table 1 shows the average aroma evaluation of five well-trained panelists, with additive-free sesame oil as a control.
表1の評価結果から明らかなように、2−メチル−1−ブテン−1−チオール、3−メチル−1−ブテン−1−チオールを配合したゴマ油は、構造類似化合物である1−プロパンチオール、2−プロペン−1−チオールを配合したゴマ油に比べて格段にゴマの煎りたて感、擂りたて感、特にフレッシュなロースト感が増強されていた。 As is apparent from the evaluation results in Table 1, sesame oil blended with 2-methyl-1-butene-1-thiol and 3-methyl-1-butene-1-thiol is a structurally similar compound, 1-propanethiol, Compared to sesame oil blended with 2-propene-1-thiol, the sesame freshly roasted and freshly squeezed feeling, particularly a fresh roasted feeling, was enhanced.
実施例6:ゴマ様基本調合香料組成物への添加検討
ゴマ様の調合香料組成物として、下記表2に示す成分からなる基本調合香料組成物(対照品)を調製した。
Example 6: Study of addition to sesame-like basic fragrance composition As a sesame-like fragrance composition, a basic fragrance composition (control product) comprising the components shown in Table 2 below was prepared.
上記対照品のゴマ様基本調合香料組成物100gに2−メチル−1−ブテン−1−チオール1mgを混合して、新規なゴマ様の調合香料組成物(本発明品3)を調製した。本発明品3と対照品の香気について、専門パネラー10人により比較した。その結果、専門パネラー10人の全員が本発明品3は、対照品に比べて、ゴマの煎りたて感、擂りたて感、特にフレッシュなロースト感が格段に増強され、かつ持続性の点でも優れていると評価した。 1 mg of 2-methyl-1-butene-1-thiol was mixed with 100 g of the sesame basic blended fragrance composition as a control product to prepare a novel sesame-like blended fragrance composition (Product 3 of the present invention). The fragrances of the product 3 of the present invention and the control product were compared by 10 expert panelists. As a result, all 10 panelists of the present invention, the product 3 of the present invention, compared with the control product, sesame freshly roasted, freshly baked, especially fresh roasted, and has a sustainability point. But it was evaluated as excellent.
2−メチル−1−ブテン−1−チオールに代えて3−メチル−1−ブテン−1−チオールを使用した以外は上記と同様に処理して新規なゴマ様の調合香料組成物(本発明品4)を調製したところ、本発明品4は本発明品3と同様な評価結果であった。 A novel sesame-like blended fragrance composition treated in the same manner as above except that 3-methyl-1-butene-1-thiol was used instead of 2-methyl-1-butene-1-thiol (product of the present invention) When 4) was prepared, the product 4 of the present invention had the same evaluation results as the product 3 of the present invention.
実施例7:ゴマ風味ドレッシングへの賦香例
食酢20g、コーンサラダ油38g、ゴマ油2g、市販練りゴマ10gおよび水30gを混合した分離型ドレッシング100gとした中に、実施例6で得られたゴマ様調合香料組成物(本発明品3および本発明品4)およびゴマ様基本調合香料組成物(対照品)をそれぞれ1g配合して、それぞれのゴマ風味ドレッシングを作製した。それぞれのドレッシングについて、よく訓練された専門パネラー10名にて香味の評価を行った。その結果、専門パネラー10名全員が本発明品3および本発明品4のゴマ様調合香料組成物を使用したものの方が対照品を使用したものに比べ、ゴマの煎りたて感、擂りたて感、特にフレッシュなロースト感が格段に優れ、かつ香味の持続性もあると評価した。
Example 7: Perfume example to sesame-flavored dressing Sesame-like obtained in Example 6 in a detachable dressing 100 g in which 20 g of vinegar, 38 g of corn salad oil, 2 g of sesame oil, 10 g of commercial kneaded sesame and 30 g of water were mixed. 1 g of each of the blended fragrance composition (present product 3 and present product 4) and the sesame-like basic blend fragrance composition (control product) was blended to prepare each sesame-flavored dressing. Each dressing was evaluated for flavor by 10 well-trained professional panelists. As a result, all 10 expert panelists used the sesame-like fragrance composition of the present invention product 3 and 4 of the present invention, compared to the control product, and the freshly baked sesame sensation It was evaluated that the feeling, particularly the fresh roasted feeling, was remarkably excellent and the flavor was persistent.
実施例8:ミート様基本調合香料組成物への添加効果
ミート様の調合香料組成物として、下記表3に示す成分からなる基本調合香料組成物(対照品)を調製した。
Example 8: Effect of addition to a meat-like basic blended fragrance composition As a meat-like blended fragrance composition, a basic blended fragrance composition (control product) comprising the components shown in Table 3 below was prepared.
上記対照品のミート様基本調合香料組成物100gに2−メチル−1−ブテン−1−チオール1mgを混合して、新規なミート様の調合香料組成物(本発明品5)を調製した。本発明品5と対照品の香気について、専門パネラー10人により比較した。その結果、専門パネラー10人の全員が本発明品5は、対照品に比べて、ミート様の調理感、特に、フレッシュなロースト感が格段に増強され、かつ持続性の点でも優れていると評価した。 1 mg of 2-methyl-1-butene-1-thiol was mixed with 100 g of the above-described meat-like basic blended fragrance composition to prepare a novel meat-like blended fragrance composition (Product 5 of the present invention). The fragrances of the product 5 of the present invention and the control product were compared by 10 expert panelists. As a result, all 10 professional panelists said that the product 5 of the present invention has a meat-like cooking feeling, particularly a fresh roasted feeling, and is excellent in sustainability compared to the control product. evaluated.
2−メチル−1−ブテン−1−チオールに代えて3−メチル−1−ブテン−1−チオールを使用した以外は上記と同様に処理して新規なミート様の調合香料組成物(本発明品6)を調製したところ、本発明品6は本発明品5と同様な評価結果であった。 A novel meat-like blended fragrance composition treated in the same manner as above except that 3-methyl-1-butene-1-thiol was used instead of 2-methyl-1-butene-1-thiol (the product of the present invention) When 6) was prepared, the product 6 of the present invention had the same evaluation results as the product 5 of the present invention.
Claims (3)
で表される化合物。 Following formula (1)
A compound represented by
で表される化合物を有効成分として含有することを特徴とする香料組成物。 Following formula (1)
The fragrance | flavor composition characterized by containing the compound represented by these as an active ingredient.
で表される化合物を熱分解することを特徴とする下記式(1)
で表される化合物の製造方法。 Following formula (3)
The compound represented by the following formula (1)
The manufacturing method of the compound represented by these.
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