JPS6150937B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel senecioic acid unsaturated esters and perfume compositions containing these esters as perfume ingredients. Senecionic acid unsaturated esters have the following general formula () (In the formula, R represents an alkenyl group having 5 to 6 carbon atoms.) The alkenyl group includes 3-methyl-2-butenyl, 3-methyl-3
-butenyl, tiglyl, cis-3-hexenyl, trans-2-hexenyl, etc., and therefore, the senecyonate esters () provided in the present invention include 3-methyl-2-butenylsenecyonate, 3- Methyl-3-butenyl senecyonate, tiglyl senethionate, cis-3-hexenyl senethionate, and trans-2-hexenyl senethionate, and these new unsaturated esters () have not been described in conventional literature. It is a new ester. Each of these new unsaturated esters () expresses a unique plant, flower, or fruit-like aroma, and as a result of compounding tests as a fragrance composition, it was found that they are extremely useful as aroma or flavor imparting and modulating agents. Ta. The senecyonate esters () of the present invention can be used alone or as an aromatic or flavoring agent, but they are usually used in combination with other known aromatic and flavoring ingredients. Examples of products to be scented include cosmetics, soaps, detergents, shampoos, and room air fresheners, while products to be flavored include foods, beverages, medicines, chewing gum, toothpaste, and the like. The blending ratio necessary to fully exhibit the desired aroma and flavor effects varies over a wide range, but it is not necessarily uniform depending on the form, type, purpose of use, and expected effect of the product to be scented. For example, excellent effects can be obtained by blending 0.1 to 10% by weight of a fragrance imparting agent in a perfume composition, and by blending 0.05 to 10% by weight of a flavoring agent in a perfume composition.
There is no particular problem even if it is used at a concentration other than this. Hereinafter, embodiments of the present invention will be explained in more detail with reference to prescription examples. Formulation example 1 Diasmine-based fragrance Fragrance name Weight (%) Hexylcinnamic aldehyde 6 Cis-diasmone 3 Geraniol 4 Citronellol 2 Benzyl acetate 42 Indole 10%DPG 6 Linalool 10 Linalyl acetate 6 Benzyl alcohol 4 Diasmolactone 0.6 Dihydromethyl diasmonate 6 Eugenol 1.4 Benzyl benzoate 6 3-Methyl-3-butenyl senecyonate
3 100 (%) As shown in the above formulation example, the addition and blending of 3% 3-methyl-3-butenyl senecyonate makes it even fresher, broadening the range of scent tones, and creating a light and attractive fragrance. A fragrance composition was obtained. Formulation example 2 Pine nut pull flavor base Fragrance name Weight (%) Acetic acid 1 Allyl caproate 16 Allyl cyclohexyl caproate 2 Iso-amyl butyrate 3 Benzyl alcohol 10 Ethyl butyrate 6 Ethyl caprate 8 Ethyl maltol 10 Ethyl iso-valerate 2 γ-Undecalactone 1 Iso-valeric acid 1 Trans-2-hexenylsenecyonate
2 Ethanol (solvent) 38 100 (%) A flavor composition obtained from the above Formulation Example-2, excluding trans-2-hexenyl senecyonate, and adding 2% ethanol instead. The object was designated as B. When both compositions A and B were compared in water at a concentration of 50 ppm, composition A had a milder, fresher green, banana-like pinenut pull flavor that was enhanced and was refreshing compared to composition B. It was hot. Next, one method for producing the senecioic acid ester represented by the general formula () will be described. This reaction can be carried out simply and with a good yield by adding an unsaturated alcohol having 5 to 6 carbon atoms to a lower alcohol ester of senecioic acid as a raw material and heating the mixture in the presence of a transesterification catalyst. Senecionic acid unsaturated esters can be prepared. The reaction formula is as follows. (wherein R' is a lower alkyl group, in particular a methyl group or an ethyl group, R is a _C5-6 alkenyl group) Examples of the above unsaturated alcohols having 5 to 6 carbon atoms include 3-methyl- 2-butenol, 3-methyl-
3-butenol, tiglyl alcohol, cis-6
-hexenol or trans-2-hexenol, the amount of which is used is 0.5 to 2 times the number of moles relative to the lower alcohol senecyonate. As the lower alcohol, methyl alcohol or ethyl alcohol is particularly preferred, and in either case, the desired unsaturated ester of senecioic acid can be obtained in good yield. In addition, the transesterification catalyst is selected from sodium methoxide, aluminum alcoholate, sodium hydride, etc., and is used at a temperature of 80 to
Stir the reaction at 180°C for several hours. The senecioic acid esters of the present invention can also be prepared by directly esterifying senecioic acid. That is, as shown in the formula below, in the presence of an acid catalyst, senecioic acid is reacted with 5 to 5 carbon atoms in an organic solvent.
An esterification reaction is carried out by the action of six unsaturated alcohols to obtain unsaturated senecioic acid esters in good yield. (In the formula, R is a _C5-6 alkenyl group.) As the acid catalyst for this esterification, mineral acids such as sulfuric acid, hydrochloric acid, methanesulfonic acid, or p-
It is selected from toluenesulfonic acid, etc., and the organic solvent is benzene, hexane, toluene, or xylene, and the temperature is 70 to 150°C.
Stir and react for some time. Next, preparation examples of the senecioic acid unsaturated esters of the present invention will be shown. Example 1 Preparation of 3-methyl-2-butenyl senecyonate 60 g (0.53 mol) of methyl senecyonate was placed in a 200 ml four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, a distillation device for produced alcohol, etc. ,
Take 60 g (0.7 mol) of 3-methyl-2-butenol and 1.2 g of sodium methoxide, and bring the temperature to 99~
The mixture was stirred at 141°C for 2 to 3 hours, and the methanol produced was distilled off to complete the reaction. The reaction mixture was shaken with 200 ml of benzene, and the benzene extract was washed with a 5% aqueous sulfuric acid solution, water, a 5% aqueous carbonic acid solution, and water in this order to obtain a neutral reaction solvent, and then dried by adding anhydrous sodium sulfate. , then distill off the benzene. The residue was distilled under reduced pressure to obtain a boiling point of 85-86℃/
Actual yield: 100% to obtain 60 g of 3-methyl-2-butenyl senecyonate at 6 mmHg. Physical constant; d ²⁵ ₂₅ 0.9306, n ²⁵ _D 1.4602 Mass spectrum (70eV); m/e168 (M ⁺ , 2
%), 101(5), 85(8), 84(6), 83(100), 69(56),
68 (40), 67 (22), 55 (28), 53 (13), 41
(49), 40(5), 39(18), Infrared absorption spectrum; 1720 (cm ^-1 ), 1660,
1230, 1150, 1080, 980, 850, nuclear magnetic resonance spectrum (δ ^CCl4 _ppn ); 1.74 (
6H,
br.s. _, =C( CH3 ) ₂ ), 1.87, 2.14(6H,
twod, =C( CH3 ) ₂ ), _4.50 (2H, d, -O-
CH2 _- CH=), 5.10-5.46 (1H, brt, _-CH2-
C H ), 5.48-6.67 (1H, br, =C H -) Example 2 Preparation of 3-methyl-3-butenyl senecyonate Using the same apparatus as in Example 1 and following the same operation,
From 60 g (0.53 mol) of methyl senecyonate, 60 g (0.7 mol) of 3-methyl-3-butenol and 1.2 g of sodium methoxide, a boiling point of 88-89°/
42 g of 3-methyl-3-butenyl senecyonate at 10 mmHg was obtained. Physical constant; d ²⁵ ₂₅ 0.9111, n ²⁵ _D 1.4581 Mass spectrum (70eV); m/e153 (M-
15), 101 (5%), 84 (5), 83 (100), 69 (10), 68
(79), 67 (19), 55 (43), 53 (11), 41 (28), 40
(5), 39(24), Infrared absorption spectrum; 1725cm ^-1 , 1660,
1230, 1150, 1080, 890, 850, nuclear magnetic resonance spectrum (δ ^CCl4 _ppn ); 1.70 (
3H,
S, [formula]) 1.80, 2.06 (6H, twod., C = C (CH ₃ ), 2.21 (2H, t,
[Formula] J = 7.0Hz), 4.02 (2H, t, -O-C H ₂ -CH ₂ -, J = 7.0Hz), 4.63
(2H, br, > C=C H ₂ ), 5.40-5.61 (1H, br,
=C H −) Example 3 Preparation of tiglyl senecyonate According to the preparation method of Example 1, 60 g (0.53 mol) of methyl theosinate, 40 g of tiglyl alcohol
(0.47 mol) and 1.2 g of sodium methylate, tiglyl senecyonate has the following properties:
Obtained 46g. Physical constant; boiling point 92-93℃/10mmHg, ^d25 ₂₅
0.9301, n ²⁵ _D 1.4646 Mass spectrum (70eV); m/e168 (M ⁺ , 1
%), 101(7), 85(4), 84(6), 83(100), 69(19),
68 (15), 67 (14), 55 (27), 53 (9), 41 (32), 39
(13), Infrared absorption spectrum; 1720cm ^-1 , 1655,
1230, 1140, 1080, 990, 850, nuclear magnetic resonance spectrum (δ ^CCl4 _ppn ); 1.62 (
6H,
br.s, [formula]), 1.88, 2.15 (6H, twod., -CH=C( CH ₃ ) ₂ ) 4.39 (2H, S,
[Formula]), 5.22-5.75 (2H, br, =C H-) Example 4 Preparation of cis-3-hexenyl senecyonate Four 500 ml tubes equipped with a thermometer, stirrer, reflux condenser and moisture meter In a neck flask, 60 g (0.6 mol) of senecionic acid and 75 g of cis-3-hexenol.
(0.75 mol), 3 g of methanesulfonic acid and 100 ml of benzene were stirred at a reflux temperature of 97-102°C for 5.7 hours. The reaction is completed by quantifying the water produced during that time. After the same post-treatment as in Example 1, the boiling point was 98~
78 g of cis-3-hexenyl senecyonate was obtained at 99°C/6 mmHg. Actual yield 130%, theoretical yield 71
%. Physical constants; d ²⁵ ₂₅ 0.9138, n ²⁵ _D 1.4595 Mass spectrum (70eV); m/e182 (M ⁺ , 0.1
%), 84(6), 83(100), 82(100), 81(8), 67
(100), 56(5), 55(97), 54(10), 53(9), 41
(17), 39(14), Infrared absorption spectrum; 1720cm ^-1 , 1650,
1265, 1240, 1050, 850, nuclear magnetic resonance spectrum (δ ^CCl4 _ppn ); 0.96 (
3H,
t, _-CH2 - CH3 , _J =6.6Hz), 1.74-1.93
(6H, [formula]), 4.03 (2H, t, -O-C H ₂ -CH ₂ -, J = 7.0Hz), 4.98-5.58 (2H,
m, -C H =C H -), 5.58-6.16 (1H, m, -C
H =) Example 5 Trans-2-hexenyl senecyonate Methyl senecyonate according to the method of Example 1
50g (0.4mol), trans-2-hexenol66
g (0.7 mol) and sodium methylate 0.5 g
56 g of trans-2-hexenyl senecyonate having the following properties is obtained. Physical constant; boiling point 107-108℃/10mmHg, ^d25 ₂₅
0.9059, n ²⁵ _D 1.4598 Mass spectrum (70eV); m/e182 (M ⁺ , 2
%), 137 (12), 125 (13), 101 (3), 84 (6), 83
(100), 82(8), 67(16), 57(5), 55(61), 54(6),
41(15), 39(7), Infrared absorption spectrum; 1710cm ^-1 , 1655,
1270, 1160, 1140, 970, 730, nuclear magnetic resonance spectrum (δ ^CCl4 _ppn ); 0.91 (
3H,
t, _-CH2 - CH3 , _J =6.0Hz), 1.63-1.92
(6H, [formula]), 4.49 (2H, d, -O-C H ₂ -CH=, J=4.6Hz), 5.43 (2H, m, -C H =
CH−), 6.50 to 6.97 (2H, m, -CH =)

Claims (1)

[Claims] 1 General formula () (In the formula, R represents an alkenyl group having 5 to 6 carbon atoms.) Senecionic acid unsaturated esters. 2 R in the above general formula () is 3-methyl-2-
Butenyl group, the following formula () The senecioic acid unsaturated esters according to claim 1, which are represented by: 3 R in the above general formula () is 3-methyl-3-
Butenyl group, the following formula () The senecioic acid unsaturated esters according to claim 1, which are represented by: 4 The following formula () in which R in the above general formula () is a tiglyl group The senecioic acid unsaturated esters according to claim 1, which are represented by: 5 The following formula () in which R in the above general formula () is a cis-3-hexenyl group The senecioic acid unsaturated esters according to claim 1, which are represented by: 6 The following formula () in which R in the above general formula () is a trans-2-hexenyl group The senecioic acid unsaturated esters according to claim 1, which are represented by: 7 General formula () A fragrance composition containing an unsaturated senecioic acid ester represented by the formula (wherein R represents an alkenyl group having 5 to 6 carbon atoms) as an active ingredient.