JPH0460454B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 1,1,2,2-tetramethylpupanol, a novel compound useful as a fragrance substance that has not been previously described in the literature. The invention also relates to the preparation of said compounds and their use.

More specifically, the present invention relates to 1,1,2,2-tetramethylpropanol represented by the following formula (A) OH (A). Furthermore, the present invention also relates to a long-lasting aroma and flavor imparting or modulating agent characterized by containing the compound of the above formula (A) as an active ingredient;
Regarding the manufacturing method of (A).

The present inventors have been conducting research and development on low-molecular-weight aliphatic alcohol-based compounds useful as fragrances.
As a result, the inventors discovered that it was possible to synthesize a novel compound 1,1,2,2-tetramethylpupanol, represented by the above formula (A) and which had not been previously described in any literature, and succeeded in its synthesis.

Furthermore, the present inventors have discovered that the compound of formula (A) has a unique, refreshing aroma similar to that of ginger, has sublimation properties, and also has excellent sustainability and a booster effect (in a blended fragrance composition). The compound has a useful effect as an aroma enhancer and a top note enhancer), and the compound can be produced industrially easily and inexpensively, and
It has been discovered that the compound has excellent long-lasting properties and is useful as a long-lasting flavor imparting or modulating agent for various fragrance compositions.

Conventionally, compounds with a structure similar to the above formula (A) compound, such as tertiary butyl alcohol and tertiary amyl alcohol, have been known, but there are almost no known examples of these being used for fragrances. Furthermore, its aroma is completely different from that of the compound of formula (A).

The above formula (A) compound of the present invention can be blended into various fragrance compositions, such as fruit-based, spice-based, tobacco-based, flower-based, green-based fragrance compositions, etc.
It is a useful compound that can be used as a long-lasting aroma and flavor imparting or modulating agent at the same time as having a boosting effect.
Moreover, the above formula (A) compound utilizes its sublimation property,
For example, it was found that it is a useful new compound that is expected to have insect repellent, deodorizing, antioxidant, and antibacterial effects, and is also useful as an intermediate for other organic synthesis.

Therefore, an object of the present invention is to provide a compound of the formula (A) which has not been described in any literature and a method for producing the same.

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

The above formula (A) compound of the present invention is, for example, 3,3-
It can be easily synthesized by bringing dimethyl-2-butanone and methylmagnesium halide into contact in an organic solvent.

In the above reaction, the amount of methylmagnesium halide used is, for example, 3,3-dimethyl-
About 0.9 to about 2-butanone (pinacolin)
A range of about 1.5 mol can be exemplified. or,
Examples of the organic solvent used in the above reaction include diethyl ether, tetrahydrofuran, and toluene. The amount of these organic solvents to be used can be selected as appropriate, and can range, for example, from about 2 to about 20% by weight relative to pinacoline. The temperature and time of the above reaction can be selected as appropriate, for example, from about -50° to about 100°
The reaction can be carried out at a temperature of about 0.degree. C. and for a period of about 0.5 to about 8 hours. After completion of the reaction, the reaction solution is poured into, for example, an aqueous ammonium chloride solution, extracted with ether, the ether layer is washed with brine, dried over magnesium sulfate, concentrated, and distilled, for example, to obtain the compound of formula (A). can be obtained easily. Alternatively, instead of the above production method, for example, the following reaction step (1)
The compound of formula (A) above can be easily synthesized using any of (5).

The above (A) 1, 1, which can be produced as described above
It has been discovered that 2,2-tetramethylpropanol is useful as a long-lasting aroma and flavor imparting or modulating agent as well as a booster effect.

The compound of formula (A) has a unique, refreshing, ginger-like aroma, has sublimation properties, and has excellent sustainability and boosting effects, and is particularly useful in various foods and beverages, fragrance products, and health care・It has excellent sustainability and unique aroma and flavor as an aroma or flavor component for hygiene products, pharmaceuticals, etc.

More specifically, when 1,1,2,2-tetramethylpropanol of formula (A) is blended with one or more types of synthetic single fragrances, for example, it imparts excellent long-lasting aromas with various new top notes. or modulators can be prepared. For example, bergamot oil, lemon oil,
When blended with synthetic essential oils such as geranium oil, mandarin oil, and lavender oil, it is possible to prepare an excellent long-lasting aroma and flavor imparting or modulating agent with a novel top note that is mild and rich, which is inherent in natural essential oils. For example, it blends well with natural essential oils such as orange oil, lime oil, lemon oil, grapefruit oil, oakmoss oil, citronella oil, vetiver oil, cinnamon oil, pachyoli oil, clove oil, bergamot oil, rose oil, etc. It is possible to prepare a novel top-note, long-lasting aroma imparting or modulating agent that emphasizes the characteristics of the essential oil.

Furthermore, among natural fragrances and synthetic single fragrances,
Compounded fragrances that are a combination of two or more types, such as single florals (single floral scents) of rose, diasmine, lilac, osmanthus, carnation, and miyuge, combined floral bouquets of these, and green notes, spicy notes, or aldehyde notes. When added to fragrance compositions such as modern floral bouquets or oriental bouquets, or flavor compositions such as strawberry, lemon, orange, grapefruit, apple, pineapple, etc., it has a mild, rich, natural appearance, and top notes. It is possible to obtain a novel aroma and flavor imparting or modulating agent that is excellent and long-lasting.

The amount of 1,1,2,2-tetramethylpropanol in (A) varies depending on the purpose and the aroma/flavor imparting or modulating agent, but for example, it is about 0.001 to about 20% of the total amount. A range of about % by weight can be exemplified.

Thus, according to the invention, 1, 1, 2,
Formula (A) 1,
Food and drink products characterized by containing 1,2,2-tetramethylpropanol as a flavor component, formula
Cosmetics characterized by containing 1,1,2,2-tetramethylpropanol of formula (A) as a fragrance ingredient, 1,1,2,2-tetramethylpropanol of formula (A) as a fragrance ingredient; It is possible to provide health, sanitation, and pharmaceutical products that are characterized by containing.

For example, beverages such as fruit juice drinks, fruit alcoholic beverages, milk drinks, and carbonated drinks; frozen desserts such as ice creams, sherbets, and ice candy;
Japanese and Western sweets, jams, chewing gums, breads, coffee, cocoa, black tea, luxury goods such as tea; soups such as Japanese-style soups and Western-style soups; flavor seasonings, various instant drinks and foods, It is possible to provide food and drink containing various snack foods and the like in an appropriate amount that can impart the unique aroma and flavor. Also, for example, shampoos, hair creams, pomades, and other hair cosmetic bases;
Cosmetics can be provided by blending Asiloy, lipstick, other cosmetic base materials, cosmetic detergent bases, etc. in an appropriate amount to impart the unique aroma. Furthermore, laundry detergents, disinfectant detergents, deodorant detergents,
Indoor air freshener deodorizers and other health and hygiene detergents: Toothpaste, toilet paper, and other health and hygiene materials: Flavoring and flavoring agents to make it easier to take medicines It is possible to provide health, hygiene, and pharmaceutical products that are blended or applied in an appropriate amount to impart a unique flavor.

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

Example 1-(1): Synthesis of 1,1,2,2-tetramethylpropanol [Formula (A) compound] A mixture of 20 g (0.2 mol) of pinacoline and 40 ml of dry diethyl ether was heated at 20 to 35°C for 30 minutes. The mixture was added dropwise to 110 ml of a commercially available methylmagnesium iodide (2 mol/diethyl ether) solution and reacted at room temperature for 1 hour. Next, the reaction solution was poured into a saturated aqueous ammonium chloride solution to separate the lower layer, and the ether layer was washed with brine, dried over _MgSO4 , the solvent was recovered, and the solvent was distilled under normal pressure to reduce the boiling point to 126-128℃. 20 g of the target compound was obtained. Yield 85%. The structure of this thing is
Confirmed by NMR. NMR( _CDCl3 )δ1.58
(1H, broads), 1.21 (6H, s) 0.87 (9H, s) This compound is crystalline at room temperature and has a melting point of 77
It was ~79℃.

Example 1-(2): Synthesis of compound of formula (A) After preparing a Grignard reagent of MeHgCl by blowing methyl chloride gas into 5.75 g of magnesium and 50 ml of diethyl ether at 0 to 10°C, Example 1-(1) It was treated and distilled in the same manner as above to obtain 21 g of the desired product. Yield 91%.

Example 1-(3): Synthesis of compound of formula (A) Magnesium 5.75g, methyl bromide 23.7g (0.25g)
After preparing a Grignard reagent of MeMgBr from 50 ml of tetrahydrofuran (mol) and 50 ml of tetrahydrofuran in a conventional manner, a mixed solution of 20 g (0.2 mol) of pinacoline and 50 ml of tetrahydrofuran is dropped into the MeMgBr solution over 30 minutes. After the dropwise addition, the reaction was further carried out at 70°C for 6 hours. After the reaction was completed, an ammonium chloride aqueous solution was poured into the reaction solution, and then extraction was performed with ether.
The ether layer was washed with brine, dried over magnesium sulfate, and the ether was recovered and distilled to obtain 20 g of the desired product. Yield 85%.

Example 2 A Lira type fragrance composition was produced by mixing the following components (parts by weight).

Phenylethyl acetate 10 Cinnamic alcohol 40 Terpineol 130 Cyclamenaldehyde 10 Heliotropin 50 Cinnamyl acetate 10 Carnation 20 Linalool 30 Indole 2 Stylacus resinoid 30 Ylang ylang 10 Hydroxycitronellal 290 Benzyl acetate 20 Anisaldehyde 20 Absolute Toji Yasmin 20 Phenylethyl Alcohol 278 Anise Alcohol 30 1000 A fragrance composition was prepared by mixing 100 g of the above composition with 10 g of 1,1,2,2-tetramethylpropanol. A new lira-type blended fragrance was obtained, which had a sharp, soft, fresh feeling and excellent persistence.

Example 3 A rose type fragrance composition was produced by mixing the following components (parts by weight).

Hydroxycitronellal 20 Nerol 30 Rose Oxide 20 Geraniol 100 Phenylethyl Propionate 30 Phenylethyl Alcohol 385 Citronellol 100 Cinnamic Alcohol 30 Musk Ketone 10 Rhodinol 85 Methyl Ionone 5 Phenylethyl Methyl Carbinol 100 Eugenol 5 Geranyl Acetate 80 100 above A fragrance composition was prepared by mixing 100 g of the composition with 5 g of 1,1,2,2-tetramethylpropanol. A new mixed fragrance of a new rose type having a sharp, soft and fresh feeling and excellent persistence was obtained.

Example 4 A bouquet-type fragrance composition was produced by mixing the following components (parts by weight).

Phenylethyl alcohol 180 Linalyl acetate 30 Bergamotu synthetic 40 Geranium 50 Benzyl acetate 60 Heliotropin 80 Geraniol 110 Lavender 20 β-ionone 100 Amyl salicylate 45 Terpinyl acetate 135 Cedar oil 100 Citronellol 50 100 To 100 g of the above composition 1 , 5 g of 1,2,2-tetramethylpropanol were mixed to prepare a fragrance composition. A novel bouquet-type blended fragrance having a sharp, soft, fresh feeling and excellent persistence was obtained.

Example 5 The following components (by weight) were mixed as an aroma and flavor composition for plums.

Amyl butyrate 20 Benzaldehyde 175 Butylfomate 10 Citronellol 1 Ethyl butyrate 50 Ethyl valerate 15 Isoamyl propionate 10 γ-nonalactone 5 Orange essential oil 15 2-Phenyl-1-propyl butyrate 100 γ-Undecalactone 3 Vanillin 10 Ethanol 586 Total 1000 100 g of the above composition was mixed with 5 g of 1,1,2,2-tetramethylpropanol to prepare an aroma and flavor composition. A novel aroma and flavor composition for plums was obtained which had a fresh and natural aroma and excellent sustainability.

Claims (1)

[Claims] 1. 1,1,2,2-tetramethylpropanol represented by the following formula (A) OH (A).