JP3528072B2 - Fragrance composition containing (4R) -cis-4-methyl-2-substituted tetrahydro-2H-pyran derivative and method for improving fragrance using (4R) -cis-4-methyl-2-substituted tetrahydro-2H-pyran derivative - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to (4R) -cis-, which is capable of imparting a refreshing, bright, and rose-green feeling to the fragrance of a fragrance composition and has a high purity both chemically and optically. The present invention relates to a fragrance composition containing a 4-methyl-2-substituted tetrahydro-2H-pyran derivative and a fragrance improving method using the same.

[0002]

2. Description of the Related Art 4-Methyl-2- (2-methyl-1-propenyl) tetrahydro-2H-pyran (hereinafter sometimes abbreviated as rose oxide) is a compound discovered from Bulgarian rose oil in 1959. So, Hermanus, geranium, lily, pelargonium, stinking, gardenia,
It is present in essential oils such as peppermint, flavors such as apricots and tomatoes, and insect secretions such as musk cutlery.

Although there are geometrical isomers and optical isomers of rose oxide, it is found that (4R) -cis and trans-4-methyl-2 are found in natural plants such as rose and geranium. -(2-methyl-1-propenyl) tetrahydro-2H-pyran.

As a chemical synthesis method of rose oxide, a method using β-citronellol as a raw material and a method using dihydropyrans as a raw material are known, and the obtained rose oxide is a racemate.

The fragrance of rose oxide is generally refreshing and has flower-like green notes, but this fragrance is also slightly different depending on each isomer, and cis-rose oxide has geranium-like and mint-like green notes.
The trans-form has a slightly stronger aroma than the cis-form. Further, it is described that (4R) -rose oxide has a sweet floral scent and a strong green note, while the (4S) -body aroma is said to have a little spicy note. Also, adding 0.05 to 0.5% of rose oxide to the fragrance blended fragrance will make the top note lighter and more flower-like, so it can be used for many fragrance blended fragrances such as rose and geranium. (Perfume No. 178, 114 pages, 1993
However, there is no description of optically active substance.

4-methyl-2- (2-methylpropyl)
Tetrahydro-2H-pyran (hereinafter sometimes referred to as dihydrorose oxide) is synthesized from 3-methylbuten-3-ol-1 and 3-methylbutanal, and has a fragrance, heat, acid and light similar to those of rose oxide. It is described that it is more stable than rose oxide, but there is no description about the optically active substance (Perfumer & Flav.
arist Vol 11 June / July 29 (1986)).

[0007]

With the recent diversification of cosmetics, development of a new fragrance material with excellent physical properties such as safety, stability, palatability, freshness and natural feeling and aroma Is desired. Therefore, the present invention provides a fragrance composition containing rose oxides capable of imparting a freshness, a refreshing feeling, and a rose green feeling to the fragrance aroma, and a method for improving the aroma capable of imparting such aroma. The purpose is to

[0008]

[Means for Solving the Problems] The inventors of the present invention have conducted diligent research to solve the above-mentioned problems and carried out the following general formula (I):

[Chemical 2] Is a (4R) -cis-4-methyl-2-substituted tetrahydro-2H-pyran derivative having a chemical purity of 90
It was found that those having a weight percentage of at least 95% and an optical purity of at least 95% ee have a strong aroma, good scent quality, good biodegradability, and awakening effect, and a fragrance containing this. The present invention has been completed by confirming that the composition is useful as a perfume.

The present invention will be described in detail below. That is, the present invention is as follows. 1) Chemical purity of 90% by weight or more and optical purity of 95% ee
The following general formula (I)

[Chemical 3] A perfume composition containing a (4R) -cis-4-methyl-2-substituted tetrahydro-2H-pyran derivative represented by: 2) (4R) - content of cis-4-methyl-2-substituted-tetrahydro -2H- pyran derivative is 0.01 to 30 wt% 1) Symbol placement of the perfume composition. 3) Chemical purity of 90% by weight or more and optical purity of 95% ee
The fragrance improving method of the fragrance | flavor composition containing the (4R) -cis-4-methyl-2- substituted tetrahydro-2H-pyran derivative represented by the said General formula (I) which is above.

The (4R) -cis-4-methyl-2-substituted tetrahydro-2H-pyran derivative represented by the above general formula (I) used in the present invention is (4R) -cis-
Two types of 4-methyl-2- (2-methyl-1-propenyl) tetrahydro-2H-pyran (4R) -cis-4-methyl-2- (2-methyl-propyl) tetrahydro-2H-pyran are included. .

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION These compounds are disclosed in JP-A-62-33.
It can be synthesized from S-citronellol by the method described in JP-A-134.

That is, S-citronellol synthesized by the production method described in JACS, 109, 1596 (1987) was brominated in the presence of soda ash to give a bromide, and aliquot (Aliquat) was added with an acetonitrile solvent. It is debrominated below to lead to dehydrocitronellol, which is cyclized with an acid catalyst to rose oxide. Dihydrorose oxide can be obtained as a dihydro form by hydrogenating rose oxide with Raney nickel by a conventional method. These can be purified by precision distillation to obtain highly pure ones.

According to a scent check of the above compounds and other isomers described later by a professional panelist, that is, cis- (2S, 4R) rose oxide is different from the herbal scents of other isomers, and is floral. It has a basic scent of green, has clean, sharp, light, and rose green notes, has good dispersibility, has a stronger scent than the other three isomers, and is very excellent.

Cis- (2R, 4R) -dihydrorose oxide is different from the herbal scent of other isomers,
The basic scent is floral green, with clean, light, ripe fruit, rose green and leafy notes, with the strongest and best scent.

When the biodegradability was compared, only the (4R) -form was found to be biodegradable, and the (4S) -form was hardly decomposed. Furthermore, it was found that even between (4R) -forms, the cis-form decomposes several times faster than the trans-form, and the (4R) -cis form used in the present invention is also environmentally superior. Do you get it. Also, comparing CNV, (4R)-
Only the body had wakefulness.

In the fragrance composition or odor improving method of the present invention, the content of the (4R) -cis-4-methyl-2-substituted tetrahydro-2H-pyran derivative is 0.01 to 30.
It is preferably in the weight%. If the content is less than 0.01% by weight, the effect of imparting or improving the aroma is insufficient.
On the other hand, even if it exceeds 30% by weight, the effect is not changed.

The fragrance composition of the present invention comprises shampoo, conditioners, perfumes, colognes, hair tonics, hair creams, pomades, other hair cosmetic bases, white powder, lipsticks, other cosmetic bases and cosmetic detergents. , Soap, dishwashing detergent, laundry detergent, softeners, disinfecting detergents, deodorant detergents,
It can be used as an aroma-imparting agent or an aroma-improving agent for indoor fragrances, furnitia care, disinfectants, bactericides, bleaches, and other various health and hygiene detergents.

[0018]

EFFECT OF THE INVENTION Having the chemical purity and optical purity of the present invention
That rose oxide, of dihydro rose oxide (4
The R) -cis form has a strong fragrance, has a more desirable rose green scent than other isomers, and is very excellent as a floral green scent. By blending these, it is possible to prepare a fragrance composition having a fresh taste, a refreshing feeling and a rose green scent.

[0019]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

The equipment used in this test is as follows.・ [Α] D: JASCO, DIP-360 ・ NMR: Bruker, AMX-400 ・ MS: Hitachi, M-80B

[Method of measuring chemical purity] GC column: Neutrabond-1 (GL Science 0.25 mm-30
m) 100 ℃ (0 min) -10 ℃ / min-220 ℃ (0min) 1) Rose oxide cis: 4.72 min, trans: 4.93 min 2) Dihydrorose oxide cis: 4.04 min, trans: 4.35 min

[Measuring method of optical purity] GC column: Chiraldex G-TA (manufactured by ASTEC) 0.25 mm
-30m 1) Rose oxide Condition: 30 ℃ (20min) -2 ℃ / min (Temperature) -70 ℃ (40min) Holding time: cis- (2R, 4S): 58.9 min cis- (2S, 4R): 59.3 min trans- (2S, 4S): 63.5 min trans- (2R, 4R): 66.4 min 2) Dihydrorose oxide Condition: 50 ℃ (constant temperature) Retention time: cis- (2S, 4S): 33.7 min cis- (2R , 4R): 34.3 min trans- (2R, 4S): 50.3 min trans- (2S, 4R): 52.9 min

Synthesis Example 1 cis- (2S, 4R) -4-methyl-2- (2-methyl)
-1-Propenyl) tetrahydro-2H-pyran (rho
1) Synthesis of dehydrocitronellol (S) -citronellol (Takasago International Corporation) 15
1.56 g (1% by weight) of soda ash was added to 6.3 g (1 mol) (98% ee), nitrogen substitution was performed, and 156.8 g of bromine was maintained at 10-15 ° C.
(0.98 mol) is gradually added. After the reaction was completed, add 1.6 l of acetonitrile, add 3.12 g of Aliquot 336 (manufactured by Henkel) in a nitrogen stream, and add 224 g of potassium hydroxide (4 mol) at room temperature.
l) was added and the mixture was heated to 75 ° C and stirred for 16 hours, then 56 g (1 mol) of potassium hydroxide was added and the stirring was continued for 8 hours. After completion of the reaction, add 500 ml of hexane and add 500 ml of 5% hydrochloric acid.
Was added to neutralize, the hexane layer was separated, washed with water, washed 3 times with saturated brine, once with saturated sodium hydrogen carbonate,
The extract was washed once with saturated saline and then concentrated to obtain 144 g of a product.

2) Synthesis of cis- (2S, 4R) -Rose Oxide To 144 g of dehydrocitronellol obtained in 1) was added a double amount of 30% dilute sulfuric acid at room temperature, and the mixture was stirred for 16 hours. After completion of the reaction, the mixture is neutralized with saturated sodium hydrogen carbonate, washed three times with saturated saline, and the organic layer is separated and concentrated. Distill (7
5-77 degrees / 9 mmHg) 73.1 g of product was obtained. This was distilled with a precision distiller at 73-74 degrees / 12 mmHg to obtain 45.4 g of a rectified product.

[Α] D 24; -78.4 ° (c 1.2, CHCL3) ¹ H-NMR (400MHz, CDCl ₃ , ppm); 0.93 (d, 3H),
1.02 (dt, 1H), 1.21 (ddd, 1H), 1.49-1.70 (m, 3H), 1.68
(d, 3H), 1.72 (d, 3H), 3.47 (ddd, 1H), 3.93-4.01 (m, 2
H), 5.16 (m, 1H) MS (m / e); 154 (M ⁺ ), 139, 83, 69, 55, 41, 39 IR (cm ^-1 ); 2925, 1680, 1375, 1090

[Synthesis Example 2] Synthesis of cis- (2R, 4R) -dihydrorose oxide
Composition 200 g of ethanol was added to 100 g of the rose oxide prepared in Synthesis Example 1 and 0.5 g of Raney-nickel was added to 80 ° C.
To hydrogenate. The solvent is distilled off and then distilled to obtain 95 g of a purified product.

[Α] D 24; + 3.7 ° (C 1.0, CHCL3) ¹ H-NMR (400 MHz, CDCl ₃ , ppm); 0.85 (m, 1H),
0.89 (d, 6H), 0.92 (d, 3H), 1.12-1.23 (m, 2H), 1.44 (dd
d, 1H), 1.49-1.65 (m, 3H), 1.77 (m, 1H), 3.29 (m, 1H),
3.38 (ddd, 1H), 3.97 (ddd, 1H) MS (m / e); 156 (M ⁺ ), 99, 81, 69, 57, 55, 43, 42,
41, 39 IR (cm ^-1 ); 2950, 1460, 1095

[Synthesis Examples 3 to 8] Using (S) -citronellol or (R) -citronellol as a raw material, JO
According to rg.Chem.35,1097 (1970), the reaction conditions were changed to synthesize, and the product was purified by precision distillation to obtain the following isomers. Their properties were as follows.

Rose oxide (4R) -trans [(2R, 4R)]: [α] D 24; -2.9 ° (c 1.4, CHCL3) ¹ H-NMR (400MHz, CDCl ₃ , ppm); 1.07 (d, 3H),
1.25 (m, 1H), 1.37 (m, 1H), 1.59 (ddd, 1H), 1.70 (d, 3
H), 1.72 (d, 3H), 1.76 (m, 3H), 2.02 (m, 1H), 3.67-3.78
(m, 2H), 4.37 (dt, 1H), 5.29 (m, 1H) MS (m / e); 154 (M ⁺ ), 139, 83, 69, 55, 41, 39 IR (cm ^-1 ); 2925, 1670, 1080

(4S) -cis [(2R, 4S): [α] D 25; +78.7 ° (c 1.0, CHCL3)  (4s) -trans [(2S, 4S)]: [α] D 25; + 3.2 ° (c 1.1, CHCL3)

Dihydrorose oxide (4R) -2H-trans [(2S, 4R)]: [α] D 25; -11.8 ° (c 1.0, CHCL3) ¹ H-NMR (400MHz, CDCl ₃ , ppm); 0.90 (d, 6H),
1.04 (d, 3H), 1.09 (ddd, 1H), 1.26 (m, 1H), 1.35 (m, 1
H), 1.42-1.57 (m, 2H), 1.68-1.81 (m, 2H), 2.01 (m, 1
H), 3.60-3.73 (m, 3H) MS (m / e); 156 (M ⁺ ), 99, 81, 69, 57, 55, 43, 42,
41, 39 IR (cm ^-1 ); 2950, 1460, 1095

(4S) -2H-cis [(2S, 4S)]: [α] D 25; -3.5 ° (c 1.0, CHCL3)  (4S) -2H-trans [(2R, 4S)]: [α] D 25; + 11.0 ° (c 1.0, CHCL3)

[Test Example 1] Measurement of threshold value and aroma quality Measurement was carried out by 11 to 13 panelists by the three-point method of TE Acree et al. Of J. Agric. Food. Chem. 33, 425, (1985). The sample is
It was dissolved in 95% ethanol and then diluted with distilled water to a specific concentration. The threshold values of the measurement results are shown in Table 1 and the scents are shown in Table 2.

[0034]

[Table 1]

[0035]

[Table 2]

From Tables 1 and 2, both (R) -cis isomers of rose oxide and dihydrorose oxide have strong aroma, show a sharp clean and rose green odor, and are superior to other isomers.

[Test Example 2] Biodegradation test Using activated sludge (purchased from the Chemicals Inspection Society of Japan on January 20, 1994) "Testing method for new chemical substances" (Environmental preservation work No. 5) , Yakuhin No. 615, 49 Base No. 392, July 13, 1974) (degradation test of chemical substances by microorganisms, etc.). Test substance concentration 30 mg / l, activated sludge concentration 100 mg / l, test period 25 days

(4R) form of rose oxide [(4R) -cis
/ (4R) -trans = 71/29] and (4S) body [(4S) -cis / (4S) -tra
ns = 71/29]. (4R) -body is 9 in 28 days
0% decomposes, but the (4S) -form hardly decomposes.
A closer examination of the (4R) -body reveals that (4R) -trans
It was found that the (4R) -cis body was the best biodegradable since the body remained in a small amount.

Example 1 A perfume composition was prepared according to the following formulation. The numbers for each component are parts by weight. Men's colon cis- (2S, 4R) -Rose oxide 15 Ambroxane 3 α-Damascone (10% dipropylene glycol solution) 6 Armois oil (10% dipropylene glycol solution) 8 Basil oil 26 Benzyl salicylate 150 Bergamot fl -gc 150 Clary Sage ABS 15 Clove Bat Oil 10 Coumarin 25 Dehydromyrcenol 120 Methyldihydrojasmonate 201 Lavender ABS 6 Lemon Oil 30 Linalool 25 Oak Moss ABS 20 Patchouli Light 70 7-Acetyl-1,1,3,4,4 , 6- Hexamethyltetralin 50 Acetyl Cedrene 70 Total 1000

Aldehide bouquet (for soap) cis- (2S, 4R) -rose oxide 10 α-Damascone (10% dipropylene glycol solution) 10 Aldehyde C-10 (10% dipropylene glycol solution) 5 Aldehyde C-11 5 Aldehyde C-12 (50% benzyl benzoate solution) 6 Bergamot 20 Coumarin 60 Cyclamenaldehyde 8 Geranium 16 pt-Butyl-α-methylhydrocinnamic aldehyde 70 Tetrahydrolinalool 100 Linalool 80 Linalyl acetate 30 pt-Butylcyclohexyl 140 Patchouli oil 18 Raspberry ketone (10% dipropylene glycol solution) 10 Rose base 250 Rosephenone 20 Isobornyl cyclohexanol 60 Styralyl acetate 8 7-acetyl-1,1,3,4,4,6-hexamethyltetralin 60 4- (4-methyl -3-Pentenyl) -3-cyclohexenecarbaldehyde 14 Total 1000

Natural Rose cis- (2S, 4R) -Rose Oxide 3 α-Damascone (10% dipropylene glycol solution) 8 Aldehyde C-9 (10% dipropylene glycol solution) 10 β-ionone 18 cis-3 acetate -Hexenyl 1 Eugenol 4 Geraniol 110 Geranyl acetate 7 Phenylacetaldehyde (50% benzyl benzoate solution) 20 Yonone SP 8 Isocyclocitral 3 L-Citronellol 110 Citronellyl acetate 8 Citronellyl formate 3 cis-3-hexenol 2 Methyl eugenol 10 Nerol 20 phenyl Ethyl alcohol 480 Phenylethyl acetate 70 9-decen-1-ol (10% dipropylene glycol solution) 5 Total 900

Fresh green type (for household cleaners) cis- (2S, 4R) -Rose oxide 0.4 Amyl salicylate 30 Calamas oil 0.4 Dipropylene glycol 70 Galvanum oil 1.2 3,4-Methylenedioxy-α-methylhydrocinnamaldehyde 10 4- (4-hydroxy-4-methylpentyl) -3-cyclohexenecarbaldehyde 100 L-citronellol 8 citral 20 lemon oil 100 pt-butyl-α-methylhydrocinnamic aldehyde 94 tetrahydromugol 100 linalyl acetate 150 methylnaphthylketone 20 ethylene Brassulate 90 1- (2,2,6-Trimethylcyclohexyl) -3-hexanol 1 Petigrain oil 15 Phenylethyl alcohol 15 P-isobutyl-α-methylhydrocinnamic aldehyde 20 7-Acetyl-1,1,3,4, 4,6-hexamethyltetralin 40 dimethyltetrahydrobenzal Hydrate 15 total 900

As a result, the cologne for men has a sharp and bright green accent, and the Aldehide bouquet enhances the green of the body note, while the natural rose and the fresh green type have a better natural feeling, and have a palatability. A favorable evaluation was obtained as a fragrance having high freshness, refreshing feeling and rose green scent.

Similarly, cis- (2R, 4R) -rose oxide was used in place of cis- (2S, 4R) -rose oxide. The scent of rose green is slightly weak, but cis- (2
A formulation almost equivalent to S, 4R) -rose oxide was obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP 62-205200 (JP, A) JP 38-14937 (JP, B1) JP 43-5680 (JP, B1) Fragrance Journal, Vol. 22, No. 11, (1994), p. 80-84. (58) Fields investigated (Int.Cl. ⁷ , DB name) C11B 9/00 A61K 7/46 CA (STN) REGISTRY (STN) (54) [Title of Invention] (4R) -Cis- Fragrance composition containing 4-methyl-2-substituted tetrahydro-2H-pyran derivative and method for improving aroma using (4R) -cis-4-methyl-2-substituted tetrahydro-2H-pyran derivative

Claims (3)

(57) [Claims] 1. Chemical purity of 90% by weight or more, optical purity
Of 95% ee or more, represented by the following general formula (I): A perfume composition containing a (4R) -cis-4-methyl-2-substituted tetrahydro-2H-pyran derivative represented by: 2. The content of (4R) -cis-4-methyl-2-substituted tetrahydro-2H-pyran derivative is 0.01.
To claim 1 Symbol placement of the perfume composition is 30 wt%. 3. The chemical purity according to claim 1 is 90% by weight or less.
In the above, a fragrance composition containing a (4R) -cis-4-methyl-2-substituted tetrahydro-2H-pyran derivative represented by the general formula (I) having an optical purity of 95% ee or more. > How to improve aroma.