JPS59130879A - Tetrahydrofuran ester - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R is H, 2-4C alkyl, 2-4C alkenyl, phenyl). EXAMPLE:1-Methyl-1-(5'-methyl-5'-vinyltetrahydrofuran-2'-yl)ethyl propionate. USE:Persistent flavoring or flavor modifying agent: it has a wide range of nuance from light camphor to heavy woody smell, showing floral tone perfume, and is used in food, beverage, cosmetics, health and hygienic fields. PREPARATION:1-Methyl-1-(5'-methyl-5'-vinyltetrahydrofuran-2-yl)ethanol of formula II is allowed to react with a carboxylic acid of formula III (X is hydroxyl, halogen, O atom, where when X is hydroxyl or halogen, n is 1, when X is O, n is 2), its anhydride or acid halide in the absence or presence of a solvent, preferably in the presence of a catalyst, to produce the compound of formula I , inexpensively in high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to the use of tetrahydrofuran
．． Its manufacturing method and history are related to its use.

In history, one investigation is to write the formula (11, where R
It represents a hydrogen atom, a C*-C, alkyl group, a C2-C1 alkenyl group, or a phenyl group.

It relates to tetrahydrofuran esters represented by

Furthermore, the present invention contains the compound of formula (1) above as an active ingredient? The present invention also relates to a persistent aroma and flavor imparting or flavor modulating agent, and also relates to a process for producing the compound of formula (1).

The present inventors have conducted extensive research on various furan derivatives. As a result, the tetrahydrofuran esters represented by the above formula (1) can be synthesized, and the compound (11) is a compound that has an excellent floral-based aroma and flavor and has excellent persistence, and is suitable for food and drink. It has been discovered that it is an extremely useful and unique ingredient as a long-lasting aroma and flavor imparting or modulating ingredient for cosmetics and other cosmetics (including luxury goods).

Furthermore, the compound Renbu (1) has excellent persistence and exhibits remarkable properties as a long-lasting flavor imparting or modulating agent.
It has been discovered that it is useful as an excellent long-lasting aroma and flavor imparting or modulating agent in a wide range of fields such as food and beverages, cosmetics, and health and hygiene fungi.

Therefore, the object of the present invention is to solve the above formula (1) which is not described in the US literature.
The present invention provides tetrahydrofuran esters represented by the following formulas and a method for producing the same. Another object of the present invention is to obtain the formula (1
) The purpose of the present invention is to provide a Me-retaining aroma and flavor imparting or modulating agent containing the compound as an active ingredient.

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

One example of the compound of formula (1) of the present invention is the following formula (2)
.

1-methyl-1-(5'-methyl-51-
Vinyltetrahydrofuran-2'-yl) ethanol and the following formula (3) % formula % (3) However, in the formula, R is a frozen candy atom, C! -, C, alkyl group,
Indicates C, NC, alkenyl group or phenyl group.

X represents -OIf, a halodane atom or an O atom,
Here, when X is -OH or a halodane atom, n is l, and when %X is an O atom, what? l is 2.

The above production example of the compound of formula (1) of the present invention allows the compound of formula (1) of the present invention to be produced industrially easily and inexpensively by contacting carboxylic acid, its anhydride, or acid halide represented by When shown in a process diagram, it can be shown as follows.

12) (3) (1) However, in the formula, R, X, and n are the same as described above.

The compound of formula (2) above can be easily synthesized, for example, by a known method of subjecting linalool to a peroxidation and ring-closing reaction, such as in the past, using perzolopion, and is also readily available on the market. It is a chemical compound.

The compound of the above formula (1) of the present invention is, for example, the compound of the above formula (
2) 1-methyl-1-(5'-methyl-5'-vinyltetrahydrofuran-2'-yl)ethanolto with the carboxylic acid of formula (3), its anhydride or vanolide in all solvents or It can be produced by contacting in the presence or absence of a catalyst in a bath-free medium. In the presence of a catalyst in a solvent or in the absence of a static solvent, the formula (2)
An example of a reaction in which a compound of formula (3) is brought into contact with an acid anhydride to produce the desired compound of formula (11) will be described. Examples of acid catalysts used in the above reaction include phosphorus, Examples include acid catalysts such as , polyphosphoric acid, ) radruenesulfonic acid, chain acids, salts, strongly acidic ion exchange resins such as 1R120, and the like. The amount of these acid catalysts to be used can be selected as appropriate, and for example, the relative weight of the acid catalyst can be exemplified from about 0.54 to about 1 (Nliid, H%) with respect to the compound of formula (2). Specific examples of the solvent used include n-hexane, toluene, xylene, benzene, cyclohexane, hydrocarbon solvents such as petroleum ether, and ether solvents such as tetrahydrofuran, isopropyl ether, butyl ether, and ethyl ether. can be exemplified.

These can be used alone or in combination. For example, there are no particular restrictions on the use of iK.

The amount used can be about 0.5 to about 10 times, more preferably about 1 to about 3 times as much as the compound of formula (2). This reaction is 1, for example, about 10 to about 13
It can be carried out at a temperature of 0°C, more preferably from about 20 to about 50°C. The reaction time can also be determined as appropriate; for example, a reaction time of about 1 to about 5 hours can be exemplified. Furthermore, the reaction molar ratio of the compound of formula (3) used in the above reaction can be selected as appropriate.

...For example, about 1 to about 3 mol of the compound of formula (3), more preferably about 1.1 to 3 mol, of the compound of formula (3) per 1 mol of the compound of formula (2).
An example of an amount is about 1.5 mol.

The above reaction completion tank, for example, injecting the reaction product into total water,
Medium-sized LIL is extracted with a suitable solvent such as ether, benzene, toluene, hexane, xylene, etc., washed with water, dried, and then condensed to form the new formula (1).
Tetrahydrofuran ester represented by #! can be obtained in high yield and purity.

If desired, it can be purified by means such as vacuum distillation or column chromatography.

For example, the compound of formula (2) of the present invention, which can be produced as described above, is a compound that has not been described in any literature, and exhibits a floral-based fragrance.

It is useful as a floral-based aroma substance with nuances ranging from a strong camphor feel to a heavy woody feeling. These representative compounds of the present invention and their respective compounds are shown below.

As exemplified above, the compound of formula (1) of the present invention has a variety of nuances, but it destroys the floral-based aroma and has excellent sustainability, so it can be used as a long-lasting aroma and flavor imparting or modulating agent. Useful.

The long-lasting aroma and flavor imparting or modulating agent has gained popularity in food and beverages due to its unique aroma and flavor and excellent persistence.
products), soaps, detergents, cosmetics, health and hygiene products,
It can demonstrate excellent effects in a wide range of fields including medical knowledge and other fields.

Therefore, it is possible to use the persistent aroma and flavor imparting or modulating agent of the present invention to add tetrahydrofuran esters represented by the formula (1) as a trace flavor component; 1) Sekiri, detergent, cosmetics pongee characterized by containing 9 momme compound as aroma 17M'; can be used for health, sanitary, pharmaceuticals, etc.

For example, for juices, fruit alcoholic beverages, milk drinks; milk drinks; carbonated drinks, etc. Chita ice creams, cold medicines such as popsicles; Western sweets; soyam≠^; bread wings ; chewing gum, : I-he, cocoa, black tea, etc.; various food and drink heavy oils, tani paste instant beverages and instant foods, etc., including @dark proboscis+; It is possible to provide mixed food and drinks. In addition, for example, the e equivalent (il-containing compound) can impart a unique aroma to shampoos, hair rinses, hair creams, pomades, other hair cosmetics, cosmetic soaps, and cosmetic facial cleansers. We can provide cosmetics.

Furthermore, laundry detergents, anti-zen detergents, deodorant cleaning products, and other health and sanitary detergents from Tanimune; toothpaste, tissues,
Toilet paper / e-'7 (It is suitable for imparting its unique aroma and flavor to all kinds of health and hygiene materials and medicines. It can be used to provide health, hygiene and medical products in all combinations or diversions.

The following is the number of implementations of the present invention! I will explain some examples of rC of Tora-sama with some examples.

Example 1 - Handan of methyl-1-(5'-methyl-51-vinyltetrahydrofuran-2'-yl)ethylpropionate.

Nomata k (, Shishi in the flask (Funamizu Zoropion r, f1s
61 (1,2-(5'-methyl-5-vinyltetrahydrofuran-2'-yl)ethanol 170y (1,0
mol) to react iW, I! j 1:00 and 2/2 at 30-40℃
After two games, I lost 7+t, -+.

After stirring for 3 hours at a reaction temperature of 40-50℃, the reaction was completed.The reaction was completed. It has a boiling point of 809-83℃/3 rsaHU and a trade volume of 1-
Methyl-1-(5'-methyl-5'-vinyltetrahydrofuran-21-yl)ethylpropionate 190
．． ! i' (yield 84 tab) was added to μl.

Example 2 Preparation of 1-methyl-1-(5'-methyl-5'-vinyltetrahydrofuran-21-yl)ethylbenzoate.

63 parts aqueous sodium 11.5 g (0
3 mol) and toluene at 200 m/fi.

To this, 1-methyl-1-(5'-methyl-5'-vinyltetrahydrofuran-2'-yl)ethyl alcohol 5
0.9 (0.3 mol) was added at 90-100°C with stirring. Shun Ishita continued stirring at 1:1'1iiJ 6i. Next, pendulchloride 41.9 (0,29
mol) is subjected to subpectoral reaction at 100 to 110° C. for 1 hour while stirring. After the completion of the subcutaneous reaction, stirring was continued for another 4 hours to complete the reaction. After the reaction is complete, the reaction product is placed in ice water, washed with alkali, and treated with a distillate until the boiling point T.
4oL"iso℃/3garlic HQ total fraction 1-methyl-
66 g of 1-(5'-methyl-5'-vinyltetrahydrofuran-2'-yl)ethyl benzoate (yield: 80.
3%).

Example According to the method of Example 1, tetrahydrofuran esters were synthesized. Its arrival is shown in Cloth-1.

The compound of the formula (11) had a floral tone with nuances ranging from a light camphor feeling to a heavy woody feeling, for example, a camphor feeling, a sweet floral feeling, a sweet woody feeling, and a woody feeling, and showed good persistence.

Example 11 A fragrance composition for shampoo was produced by mixing each component (parts by weight).

Linalool 5 Agsolute Jasmine 2β-Phenylethyl Alcohol 150 Sonol
15 Absolute Rose
1 Hydroxycitronellol
30 Indole 10% benzyl benzoate solution 2 Staylac oil 3 Hexyl cinnamic aldehyde 15 Cyclamen aldehyde
4 Sandal Wood Oil
5 Phenylacetaldehyde 104
300 The above composition 95. By applying P[1-methyl-1-(5'-methyl-5'-vinyltetrahydrofuran-2'-yl)ethylpropionate 5I, it has a fresh flower-like (lily of the valley) character and is maintained. A novel composition with a high degree of properties was obtained.

Colleagues' results show that l-methyl-1-(s'-methyl-5'
-vinyltetrahydrofuran-2-yl)ethyl formate, 1-methyl-1-(5'-methyl-5'-vinyltetrahydrofuran-2'-yl)ethyl mebutyrate, 1-methyl-1-(5'-Methyl-5'-vinyltetrahydro7ran-2'-yl)ethylvalerate, 1
-Methyl-1-(5'-methyl-5'-vinyltetrahydrofuran-2'-4yl)ethyl crotonate, l-methyl-1-(5'-methyl-51-vinyltetrahydrofuran-2'-yl)ethyl were obtained by using Henshade, respectively.

Claims (1)

[Claims] 1. The following formula fil υ In the formula, R is a hydrogen atom, C! -, C, alkyl4.
Tetrahydrofuran esters coated with C("-represents a C4 alkenyl group or phenyl group.