JPS60136553A - 2-alkylidene-3-methylthiopropanal and utilization thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> is 2-methylbutylidene or 3-methylbutylidene). EXAMPLE:2-(2-Methylbutylidene)-3-methylthiopropanal. USE:A unique component, very useful as a lasting flavoring and a modifier, and having a mild natural aroma with body and a spicy or herbal flavor. PREPARATION:m-Methylpropanal expressed by formula III is condensed with an alkanal expressed by the formula R-CHO (R is methyl, isopropyl, etc.) in the presence of an alkali if desired in an organic solvent, e.g. ethanol, at about 0 deg.C- 30 deg.C to give the compound expressed by formula I easily in high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 6% 2-alkylidene-3-methylthioprozonal, which is used as a fragrance substance and has not been described in any prior art literature.
Regarding. The present invention also relates to the preparation and use of the new compounds, including known compounds, and in particular their use as persistent aroma and flavor imparting or modulating agents.

In more detail, < means the present invention is represented by the following formula (1-1) provided that in the formula,
RI represents 2-methylbutylidene or 3-methylbutylidene, and relates to 2-alkylidene-3-methylthiopropanals represented by:

The present invention also encompasses novel compounds of the above formula (+-1), which include the following formula (1), where l? represents a group selected from the group consisting of ethylidene, 2-methylpropylidene, 2-methylbutylidene and 3-methylbutylidene, and contains 2-alkylidene-3-methylthiopropanals represented by as an active ingredient. The present invention also relates to a persistent aroma and flavor imparting or modulating agent characterized by the following.

Conventionally, among the compounds included in the above formula (1), 2-ethylidene-3-methylthiopropanal represented by the following formula (1-2) where R is ethylidene and the following formula where R is 2-methylpropyridi. (+
-3) For 2-(2-methylpropylidene)-3-methylthiopropanal, J, Al1゜Foo
d Chem, 21 (1) 31-33 (1973)
, it is introduced that it is a compound detected in the volatile components of potato chips. According to the above-mentioned literature, it is stated that the compound has an interesting aroma and that the compound probably contributes to some extent to the flavor of potato chips. There is no mention of the compound being useful for perfumery applications or of its synthesis.

The present inventors have been conducting research on alkylidene derivatives of 3-methylthiopropanal.

As a result, it was discovered that a novel 2-alkylidene-3-methylthiopronozonal represented by the above formula (+-1) could be easily synthesized, and the synthesis was successfully achieved. Furthermore,
Represented by the above formulas (1-2) and (+-3)? It was discovered that the known 2-alkylidene-3-methylthioprozonals detected in the volatile components of Tetotitubus can be easily synthesized by a similar method, and the synthesis was also successful.

Furthermore, the above formula (+-1) novel compound and the above formula (1-
2) The known compound of Narahini formula (+-3) is herbal-like,
It has been discovered that this compound exhibits a spice-like or green-like aroma and flavor and has excellent persistence, and is an extremely useful and unique component as a persistent aroma and flavor imparting or modulating agent component.

Furthermore, the above formula (1-1) novel compound and the above formula (1)
-2) and the known compounds of formula (+-3) exhibit remarkable properties as persistent aroma and flavor imparting or modulating agents, and are used in foods and drinks (including luxury goods), cosmetics, health and hygiene products, and pharmaceuticals. It has been discovered that it can be used as an excellent long-lasting aroma and flavor imparting or modulating agent in a wide range of fields such as...

Therefore, an object of the present invention is to solve the above formula (+-
1) To provide a compound and a method for producing the same, as well as a method for producing the known compounds of formulas (1-2) and (1-3). Another object of the present invention is to provide a long-lasting aroma and flavor imparting or modulating agent containing the compound of formula (1) including these as an active ingredient.

The above objects as well as many other objects and advantages of the present invention will become more apparent from the following description.

The following formula (+) includes the compound of formula (1-1) of the present invention, where j is a group consisting of ethylidene, 2-methylpropylidene, 2-methylbutylidene, and 3-methylbutylidene. 2-Alkylidene-3-methylthiopropanals represented by, which represent a group selected from, for example, 3-methylbutanal represented by the following formula (3) Below is the following formula (4) % formula % (41 where R represents a group selected from the group consisting of methyl, inglobil, 1-methylglobil, 2-methylzolobyl, and is subjected to a condensation reaction with an alkanal represented by It can be easily synthesized by

The above formula (3) compound and the above formula (4) compound of the present invention are compounds that are easily available on the market, and the above condensation reaction can be performed by, for example, combining the above formula (3) compound and the above formula (4) compound, For example, mixing under a temperature condition of about 06 to 30°C,
The reaction can be carried out by gradually adding an alkali to the mixed solution, for example, at a temperature of about 06 to 50°C for about 0.5 to about 6 hours, and thus the above formula 0
) compounds can be obtained easily and in high yields. The condensation reaction can be carried out in an organic solvent such as ethanol, methanol, gropanol, butanol, etc., if desired.

Specific examples of the compound of formula (4) used in the reaction include acetaldehyde, 2-methylpropanol, 2-methylbutanal, 3-methylbutanal, and the like. The amount of these alkanals to be used can be selected as appropriate, but for example, about 1 to about 3
An example is a range of about mol. The alkalis used in the above reaction include NaOH, KOH, and Meol.
Va, EtOLi.

Examples include EtONa and t-13uOK. At this time, if desired, the alkali can be dissolved in a small amount of water and diluted with the above-mentioned organic solvent. The amount of these alkalis to be used can be selected as appropriate, and may range, for example, from about 1 to about 50% by weight based on the compound of formula (3). After the reaction is completed, the compound of formula (1) can be obtained by neutralizing, washing with water, and distilling, for example, under reduced pressure, according to a conventional method.

The aroma and flavor characteristics and boiling point of the compound of formula (1) that can be obtained as described above are shown below.

The 2-alkylidene-3-methylthiopropanals of formula (I) which can be prepared as described above have been found to have utility as persistent aroma flavoring or flavoring agents. The compound of formula (1) has, for example, a herbal-like, spice-like, or green-like aroma and flavor, and has a mild and rich naturalness.2 It is particularly useful for various foods and drinks, cosmetics, health and hygiene.・Has excellent persistence and unique aroma and flavor as an aroma, flavor imparting, or modulating ingredient for pharmaceuticals, etc.

More specifically, when 2-alkylidene-3-methylthiopronozonals of the formula (1) are blended with synthetic essential oils such as bergamont oil, lemon oil, geranium oil, lavender oil, and mandarin oil, it becomes a natural essential oil. It is possible to adjust the mild, rich, and persistent aroma and flavor imparting or modulating agent inherent in It also harmonizes well with citrus essential oils such as orenzo, lime, lemon, grapefruit, etc., and can emphasize the characteristics of the essential oil, giving it a fresh, gentle, and more natural-like persistent aroma. It can provide a modulator effect. Furthermore, for example, strawberry, lemon, orenzo, grapefruit, apple,
When blended into a flavor composition such as /Soinarasol, it is possible to obtain an aroma and flavor imparting or modulating agent that is mild, rich, natural-looking, and has an emphasis on sustainability. Furthermore, the 2-alkylidene-3-methylthiopropanals of the above formula (+) harmonize well with each yuzu synthetic flavor and natural flavor, and can be used as a unique and long-lasting aroma imparting or flavor modulating agent. Obtainable. The formula (I
The amount of 2-alkylidene-3-methylthiopropanal (2-alkylidene-3-methylthiopropanal) to be blended can be changed as appropriate depending on the purpose and the type of compound of formula (1) to be blended, but for example, it is generally about 0.001% of the total amount. An example of the range is about 10% by weight.

Thus, according to the present invention, the 2-alkylidene-3-methylthiopropanals of the formula (1) can be used as a long-lasting aroma and flavor imparting or modulating agent or enhancer containing the 2-alkylidene-3-methylthiopropanals of the formula (1) as an active ingredient. Foods and beverages characterized by containing 2-alkylidene-3-methylthiopropanals as a flavor component, % characteristics containing 2-alkylidene-3-methylthiopropanals of formula (+) as a flavor component. tp! Cosmetics containing 2-alkylidene-3-methylthiopropanal of formula (1) as an aromatic flavor component. It is possible to provide health care, hygiene, medicines, etc.

For example, beverages such as fruit juice drinks, fruit juices, milk drinks, and carbonated drinks; frozen desserts such as ice cream, sherbet, and popsicles; Japanese and Western sweets, jams, chewing gum, bread, Coffee, cocoa, black tea, luxury goods such as tea; soups such as Japanese-style soups and Western-style soups; flavor seasonings, and the unique aroma and flavor imparted to various yuzu instant beverages and foods, snack foods, etc. Foods and beverages can be provided in appropriate amounts. For example, an appropriate amount that can impart a unique fragrance to shampoos, hair creams, pomades, and other hair cosmetic bases; as well as lipsticks, lipsticks, and other cosmetic bases and cosmetic detergent bases. We can provide cosmetics containing the following. In addition, laundry detergents, disinfectant detergents, deodorizing detergents, and various other health and hygiene detergents; various health and hygiene products such as toothpaste, tissues, and toilet paper; making it easier to take medicines; It is possible to provide health, hygiene, and pharmaceutical products that have been blended or applied in an appropriate amount to impart a unique flavor to health, hygiene, and pharmaceutical products, such as flavoring and flavoring agents.

EXAMPLES Below, several embodiments of production and usage examples of the compound of formula (1) of the present invention will be explained in more detail with reference to Examples.

Example 1 Synthesis of 2-ethylidene-3-methylthioprono (nal [formula (1-2)).

3-methylthiopropanal 104t (1.0 mol) and 80% acetaldehyde aqueous solution 275v (5.0 mol)
Add 102 of Hyousui Teio and 25% Na0E aqueous solution to the mixture.
Drop at 0 minutes. After reaction for 0.5 hour at 20-40°C, the reaction mixture was neutralized with acetic acid and then distilled to obtain 59f (yield 45%) of the desired product as a 64-66°C/6-square HQ fraction. The product is analyzed as follows.

MS: m/z 130 (M, 32), 82 (100)
, 54(97), 53(70).

39(59) Example 2 Synthesis of 2-(2-methylbutylidene)-3-methylthiopropanal [formula (+, -3)].

3-Methylthiopropanal 104y (1,0 mol) and 2-methylthiopropanal 72f (1,0 mol)
and 1N sodium methoxide-methanol solution 50m/m at 20-40°C in a mixture of 100m/methanol.
! was added dropwise for 10 minutes, and after reacting for 30 minutes, it was neutralized with acetic acid, and after recovering methanol, it was distilled under reduced pressure to 74-76°
The desired product of 50.5f (yield 32%) was obtained as a C/6*mEg fraction. This product is analyzed as follows.

Jf S”, tn/Z 158 (M+ 12)
, 110 (36), 95 (43), 67 (72), 4
1(100) Example 3 Synthesis of 2-(2-methylbutylidene)-3-methylthiopropanal [Formula (1-1)': I.

100 t of a methanol solution in which KOM2f was dissolved in a mixture of 3-methylthiopropanal 104f (1.0 mol) and 2-methylbutanal 86 t (1.0 mol) was added to 2
Lower /A in 0-3ooC0.5 hours.

After reacting for 1.5 hours, the reaction mixture was neutralized with acetic acid, and methanol was recovered and distilled under reduced pressure to obtain 331 (yield: 19%) of the desired product as 82-b.

This product is analyzed as follows.

MS: tn/z 172 (Jf r 30
), 124 (56), 109 (100), 81 (58
).

41(61) Example 4 Threat of 2-(3-methylbutylidene)-3-methylthiopropanal [Formula (1-1)].

] To a mixture of 3-methylthiopropanal 52 F (0.5 mol) and 3-methylbutanal 43 F (0.5 mol), add 20-30° 01N sodium ethoxide-ethanol solution 30- for 5 minutes. After dropping and reacting for 1 hour, it was neutralized with acetic acid, and after recovering ethanol, it was distilled under reduced pressure.
95°G/4 scale 11g fraction 242 (yield 2B
9 (,) targets were obtained. This product is analyzed as follows.

MS: 172 (M, 23), 124 (59), 10
9 (100), 81 (69), 41 (43) Example 5 A hyacinth-based fragrance composition was produced by mixing the following components (M section).

Phenylacetaldehyde 100 Cinnamic alcohol 5゜Hyacinth absolute 2゜Phenylethyl alcohol 100 α-ionone 3゜Benzyl propionate 7゜Ylang-ylang oil 2゜Amylcinnamic aldehyde 5゜Isoeugenol 4゜Pentyl alcohol 100 Norcarbinol 30 Galbanum resinoid 5゜Phenylacetaldehyde dimethyl acetal 8゜Lauryl alcohol 2゜Nerol 8゜Heliotropin 6゜1000 2-ethylidene-3- of the present invention product is added to the above composition 1001.
A novel fragrance composition was prepared by mixing methylthiopropanal 52. A novel hyacinth-based mixed fragrance composition was obtained which had an aroma that emphasized the aroma of natural hyacinth and had excellent sustainability. In addition, 2-(2-methylbutylidene) of the present invention is added to the above composition 1O01.
When -3-methylthiozolozonal 51 was mixed, a novel fragrance composition having a natural hyacinth fragrance with an emphasis on sweetness and excellent persistence was obtained.

Example 6 A tomato thread flavor composition was prepared by mixing the following ingredients (111 parts by weight).

Acetaldehyde 2 Valeric acid 2 Benzaldehyde 4 Isovaleraldehyde 4 Butyric acid 3 Vanillic acid 3 Phenylacetaldehyde 5 Dimethyl sulfide (1%) 10 Terbinyl butyrate 10 Cis-3-hexenol 60 Guaiacol phenylacetate 150 Methional 150 Methylhegutinone 270 Hexanal 310 Cis-3-hexenal 17 000 2-(3-methylbutylidene)-3-methylthiopropanal 4f of the present invention was mixed with 100V of the above composition to produce a new fragrance composition. A novel tomato-based flavor composition was obtained which had a fresh, blue-tinged, emphasized aroma and excellent persistence. A similar result is 2
-(2-methylbutylidene)-3-methylthioglo/-
? Obtained by mixing Naal. However, in this case, the aroma had an accentuated bluish tinge with a hint of spiciness.

Example 7 The following components (parts by weight) were mixed as a meat-like clayver composition.

2.4-Decasoenal 3 γ-Octalactone 2 γ-Decalactone 2 Methional 5 Noacetyl 10% ethanol solution 20 Diprobylsosulfide 10 Ethanol 872 000 2-(2-Methylbutylidene) of the present invention to 1000 of the above composition By adding 10 g of -3-methylthiop-20 nosonal, a new flavor composition was obtained which was excellent as a meat aroma and flavor component and had excellent persistence. Similar results were obtained by mixing 2-ethylidene-3-methylthiopropanal. However, the aroma in this case had an accentuated aroma of spice [7].

Patent applicant: Hasegawa Fragrance Co., Ltd.

Claims (1)

[Claims] 1. 2-alkylidene-3-methylthiopropanal represented by the following formula (+-1) 7?1, where R1 represents 2-methylbutylidene or 3-methylbutylidene. kind. 2 The following formula (1) (wherein, R is ethylidene, 2-methylpropylidene,
% indicates that it contains 2-alkylidene-3-methylthiopropanal as an active ingredient, which is a group selected from the group consisting of 2-methylbutylidene and 3-methylbutylidene. Persistent aroma and flavor imparting or modulating agent.