JPS6116366B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel heatable fragrance composition. BACKGROUND ART Traditionally, agarwood has been regarded as important as a fragrance material and an incense stick material, as it continues to emit a fragrance for a long time when heated. The agarwood is generally
Aquillariaagallocha Roxb.
It is said that when old trees of S. Thymelaeceae over 25 years old are attacked by pathogenic bacteria, the essential oil contained in the wood turns into resin, and there are several reports on the formation process and components [for example, S.
Arctander，Perfume And Flavor Materials of
Natural Origin, p49 (1960) and T. Nakanishi
et al., Phytochemistry, 20, 1957 (1981)], but there is still no report on the property of continuing to emit a fragrance for a long time when heated. The present inventors have conducted various studies on the aromatic components of agarwood, especially those that have a persistent aroma upon heating. It was thought that this would not contribute to the aromatic properties of agarwood, but when it is heated to the temperature at which ordinary smokers are heated, it undergoes thermal decomposition and releases aromatic substances, and this aromatic substance is We obtained new knowledge that the generation of substances continues for a long time. The above fact was also confirmed with the above chromone derivatives which were separately chemically synthesized by the present inventors. Furthermore, regarding a series of chromone derivatives represented by the general formula [] below, which have a similar structure to these, they themselves are odorless at room temperature, but they all decompose in almost the same way when heated above about 50°C. It was discovered that the aroma is sustained over a long period of time. The present invention was completed based on the above new knowledge, and its gist is that the general formula [In the formula, X and Y each represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and n is 2 to 4
indicates an integer. ) A heating type fragrance composition characterized by containing a chromone derivative represented by: The heating type fragrance composition of the present invention has the above general formula []
Based on the fact that it contains a chromone derivative represented by shall be. In addition, by using the chromone derivative represented by the above general formula [], for example, in the case of mixed fragrances, the volatility of other aromatic components can be appropriately adjusted, the original aroma of the mixed fragrance can be improved, and its retention property can be improved. is significantly increased. Therefore, the composition of the present invention is of course very useful as a smoker, an incense stick, etc., and can also be used indoors using a suitable heat source, such as an electric heater such as found in an electric mosquito repellent, a light bulb, or other heat source. It can be used as a new fragrance that can scent a specific space only when necessary. In the compound represented by the above general formula [] which is an essential component of the composition of the present invention, the lower alkyl group represented by
Examples of the alkyl group of No. 4 and lower alkoxy groups include alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, propyloxy, and butyloxy groups. The following are examples of typical compounds included in the general formula []. 2-(2-phenethyl)chromone 2-(2-phenethyl)-5-methoxychromone 2-[2-(p-methoxyphenyl)ethyl]chromone 2-[2-(p-methylphenyl)ethyl]chromone 2- [2-(p-ethoxyphenyl)ethyl]chromone 2-(3-phenylpropyl)chromone 2-(4-phenylbutyl)chromone 2-(4-phenylbutyl)-6-methylchromone 2-(3-(p -Methoxyphenyl)propyl]chromone The following describes in detail the manufacturing method of the following compounds.Some of the compounds represented by the above general formula It is isolated by steam distillation, treating the residue with, for example, sodium hydroxide to take out the neutral part, and separating it by column chromatography, recrystallization, etc. It also includes the compounds isolated from the above agarwood. , the compound of the general formula [] is obtained by combining a known carboxylic acid represented by the general formula [] or a functional derivative thereof such as an acid anhydride or an acid halide with an alcohol represented by the general formula [] according to the following reaction formula. Perform an ester reaction to obtain a compound of the general formula [], then react with a base such as potassium hydroxide to cause a rearrangement reaction to obtain a compound of the general formula [], and further subject the compound [] to a cyclization reaction. It can be produced by: <Reaction formula> [In each formula, X, Y and n are the same as above. ] The above esterification reaction is carried out under normal ester reaction conditions. Particularly when free carboxylic acids are used, the esterification is preferably carried out using a conventional dehydration catalyst such as sulfuric acid or phosphoric acid. The rearrangement reaction of the compound [] obtained by the esterification can be carried out using known methods such as Org.Syn.Col.Vol.
It can be carried out according to the method described in I.p478. Further, the subsequent reduction reaction of the compound [] can be carried out according to a known method [Jikken Chemistry Course, 21
-See below, p97-132]. Details of each of the above reactions will be explained in the production examples below. The target compound thus obtained can be isolated and purified by conventional methods such as recrystallization, distillation, column chromatography, etc. All of the compounds represented by the general formula [] obtained as described above have the characteristic that they gradually thermally decompose upon heating and release aromatic substances. The aromatic substances released by this thermal decomposition reaction are identified as the following aldehydes, as shown in the aromaticity test by heating described later. [In the formula, n and X are the same as above. ] The fragrance composition of the present invention can be used in the same manner as ordinary fragrance compositions of this kind, except that it uses the chromone derivative represented by the above general formula [ ] as an essential component, and can be used in combination with other natural fragrances or synthetic fragrances as necessary. It can be used as a smoked fragrance such as perfume sticks, or as a commonly mixed fragrance by impregnating and supporting a suitable carrier and making it a fragrance for limited spaces such as indoors and cars. When used as a smoked flavoring agent, the above chromone derivatives are preferably blended into the smoked flavoring agent in an amount of usually about 0.1 to 10% by weight (approximately 0.5 to 10% by weight as a whole flavor component), and this is done according to a conventional method. It is mixed with a suitable base material, such as a combustion base material such as tabacum powder, sandalwood powder, which is commonly used as an additive, and powdered fragrances such as incense and frankincense, and then shaped into an appropriate form and dried to form a product. be done. The obtained smoked flavor product is ignited by a suitable ignition source according to its general usage method, and heated as it burns (usually the combustion temperature is about 700-850°C), and this heating causes the above-mentioned thermal decomposition reaction. Fragrance components and other fragrance components are fumigated.
Other flavoring agents can be prepared by impregnating or mixing the chromone derivative of the present invention into a suitable carrier such as a mat base material such as an electric mosquito repellent mat or other inorganic powder in accordance with a conventional method. , in a suitable product form, which can be heated by any heating source, e.g. electrical means,
Heated by direct flame through a substance that acts as a heating element or a suitable container that acts as a heat transfer body,
As a result, it emits an aroma similar to the above-mentioned smoked fragrance. In this case, the heating temperature may be about 50°C or higher, since thermal decomposition of the chromone derivative of the present invention starts at a temperature around 50°C, and the upper limit is approximately 50°C.
It is best to keep the temperature up to 300℃. Usually preferably around 70
~200℃. Thus, by using the composition of the present invention, a spatial area can be scented with a very elegant fragrance by heating. Examples of the production of chromone derivatives represented by the general formula [] used in the present invention will be given below. Production Example 1 52g of Vietnamese agarwood was shaved into flakes, extracted three times using 400ml of acetone each, and the extracts were combined and the acetone was distilled off to obtain 28g of acetone extract (yield 53.84%). ). 25g of acetone extract is steam distilled and the distillate 5.5 is extracted with essential oil.
1.8g was obtained. The distillation residue was 22 g. the remainder
Treatment with 1N-NaOH yielded 11 g of neutral portion. neutral part
2.0g was subjected to column chromatography (Kieselgel G, Merck & Co., 70-230 mesh), and 0.14g of 2-[2-(p-methoxyphenyl)ethyl]chromone (referred to as compound A) was obtained from the benzene fraction.
and 2-(2-phenethyl)chromone (compound B
) 0.05g was obtained. Each compound was identified from the following instrumental analysis results. Γ Compound A Slight yellow viscous liquid IR (film); υmax=1644, 1606, 1510, 1460, 1380,
1243, 845, 821, 758, 677 cm ^-1 MS; 280 (M ⁺ , 11%), 161 [

[Formula] 2%] 121〔

[Formula] 100%] ¹³ C-NMR; δppm=178.10 (s), 168.50 (s), 158.32 (s), 156.46 (s), 133.42 (d), 129.24 (d, 2C), 125.60 (d), 124.92(d), 123.79(s), 117.81(d), 114.06(d, 2C), 110.21(d), 55.16(q), 36.30(t), 32.07(t), ^1H -NMR (80MHz, CDCl ₃ , TMS); δppm=2.86 (t, 2H), 2.92 (t, 2H), 3.75 (s, 3H), 6.11 (s, 1H), 6.75-7.64 (m, 9H), 8.18 (dd, 1H) , Γ Compound B Pale yellow needle crystal IR (KBr tablet); υmax=1642, 1613, 1601, 1568, 756 cm ^-1 MS; 250 [M ⁺ , 44%] 232 [M ⁺ -H ₂ O, 2.7%] 91〔

[Formula] 100%] ¹³ C-NMR; δppm=178.63 (s), 168.32 (s), 156.45 (s), 139.73 (s), 133.43 (d), 128.63 (d, 2C), 128.29 (d, 2C) ), 126.54 (d), 125.67 (d), 124.94 (d), 123.79 (s), 117.83 (d), 110.22 (d, 2C), 36.02 (t), 32.94 (t), ¹ H-NMR; δppm =2.93 (t, 2H), 2.96 (t, 2H), 6.12 (s, 1H), 7.22-7.62 (8H), 8.19 (dd, 1H), Production example 2 (1) o-(3-(p- methoxyphenyl)propionyloxy]acetophenone 3-(p-methoxyphenyl)propionic acid
11.5 g (0.06 mol) and thionyl chloride 8.0 g (0.06
mol) and heat the mixture for 40 minutes on a water bath.
After the evolution of hydrogen chloride gas and sulfur dioxide has ceased, the reaction mixture is cooled, 9.3 g (0.06 mol) of o-hydroxyacetophenone is added and heated again on a water bath for 25 minutes. Transfer the reaction container to a mantle heater, continue heating until it reaches 140°C, keep it at 140°C for 20 minutes, and then cool it. The reaction product was extracted with ether, washed with 1% sodium hydroxide, and then washed with water to remove sodium hydroxide.
The ether layer was dried over anhydrous sodium sulfate, and the ether was distilled off to obtain 10 g of crude o-[3-(p-methoxyphenyl)propionyloxy]acetophenone. (2) o-hydroxybenzoyl-3-(p-methoxyphenyl)propionyloxymethane 10 g of o-[3-(p-methoxyphenyl)propionyloxy]acetophenone obtained in (1) above
Dissolve it in 30ml of pyridine, add 2.0g of potassium hydroxide powdered in a mortar heated to 100℃,
Warm to °C and stir for 15 minutes. The obtained semi-solid reaction product was dissolved in 80 ml of 10% acetic acid and extracted with ether. After washing the ether layer with water and drying, the ether was distilled off to obtain 5.0 g of o-hydroxybenzoyl-3-(p-methoxyphenyl)propionyloxymethane. (3) 2-[2-(p-methoxyphenyl)ethyl]
Chromone (compound A) o-hydroxybenzoyl-3 obtained in (2) above
-(p-methoxyphenyl)propionyloxyoxymethane 5 g of crude product is dissolved in 30 ml of acetic acid, 2 ml of concentrated sulfuric acid is added and heated for 1 hour. After cooling, pour the reaction mixture onto crushed ice, and extract the precipitated oil with ether. After distilling off the ether, about 5 g of crude product was obtained. The crude product is purified by silica gel column chromatography to obtain 0.6 g of pure 2-[2-(p-methoxyphenyl)ethyl]chromone from 1 g of the crude product. The physical properties of the obtained target product (compound A) were as follows, and were consistent with those of the compound A obtained from the natural product obtained in Production Example 1. Viscous liquid, colorless and odorless. IR (film); shown in Figure 1. MS; shown in Figure 2. Production Example 3 (1) 4-phenylbutyryloxyacetophenone Using 0.04 mol each of 4-phenylbutyrylbutyric acid, thionyl chloride and o-hydroxyacetophenone,
In the same manner as in Production Example 2 (1), 6.0 g of crude 4-phenylbutyryloxyacetophenone was obtained (yield 52.5%). (2) 2-(3-phenylpropyl)chromone The 4-phenylbutyryloxyacetophenone obtained in (1) above was treated in the same manner as in Production Example 2 (2) and (3), 5.0 g of crude 2-(3-phenylpropyl)chromone (compound C) is obtained. This is subjected to column chromatography using 30 g of Kieselgel G, and the pure target product is obtained from the fraction eluted with benzene. The physical properties of the obtained compound C are as follows. Viscous liquid, colorless, odorless IR (film); shown in Figure 3. MS; shown in Figure 4. Production Example 4 (1) and (2) of Production Example 2 above using appropriate raw material compounds
By repeating the same operations as (3) and (3), the following compounds (compounds D and E) were obtained. Compound D; 2-(2-phenethyl)-5-methoxychromone (general formula []: X=H, Y
=5- _OCH3 , n=2) Compound E; 2-(4-phenylbutyl)-6-methylchromone (general formula []: X=H,
Y=6-CH ₃ , n=4) <Aromaticity test by heating> Put 10 to 50 mg of each of the chromone derivative samples of the present invention obtained in each of the above examples into a 10 ml round bottom flask, and add 1 ml per minute to the flask. The flask was heated in a silicone bath at a constant temperature ranging from 70°C to 300°C for 1 to 6 hours while bubbling air at high speed, and the air inside the flask (including the volatile substances generated) was transferred to Tenax GC.
(TenaxGC, manufactured by Nippon Chromato Kogyo Co., Ltd., 60 to 80 mesh, used after being heated in nitrogen at 230° C. for 8 hours) 50 mg was used to adsorb and collect volatile substances. The adsorbed substances were then desorbed using 1 ml of ether, concentrated, and analyzed using gas chromatography (GC) and gas chromatography mass spectrometry (GC-MS). GC and GC-MS conditions are as follows. GC conditions; Equipment Shimadzu GC-5A Column OV-1, 30m 0.28mm Temperature 70℃→230℃ Temperature increase rate 3℃/min Carrier gas N ₂ 0.46ml/min Detector HFID GC-MS conditions; Equipment Hitachi M -60 Ionization voltage 20eV Gas chromatograph section conditions: Same conditions as gas chromatography The results are shown in Table 2 below.

[Table] Examples of actual use of the fragrance composition of the present invention are listed below. Usage example 1 Use in incense sticks Ingredients Parts by weight Tabu flour 49.0 2-(2-phenethyl) chromone 0.1-2.0 2-[2-(p-methoxyphenyl)ethyl] chromone 0.1-2.0 Water Amount to make the total amount 100 Knead the above ingredients thoroughly, mold into an appropriate shape, and dry to finish. When the product is burnt, it covers up the unique burning odor caused by the burning of the raw material, tabular powder, and emits a sweet aroma. Example 2 Use in incense charges [A] [b] Component weight part part acetoyo -genol 100 100 100 sodal dwarf oil 80 80 80 Benzyiden acetone 20 Sistus Resinoid 20 20 Healing Wooden Oil 200 200 Shaam Anka Absoli Yuto 60 60 Cedrenol 60 60 Ambergris 70 70 Sohe oil 60 60 Vetiver oil 50 50 Perch lily oil 20 20 Benzyl benzoate 200 - 2-phenethylchromone - 200 A joss stick fragrance consisting of the above ingredients was prepared. [A]
The fragrance contains benzyl benzoate to improve retention, but the fragrance [B] of the present invention, which contains 2-phenythylchromone in place of this, can be left as it is on scented paper as a mixed fragrance. In the case of [A], the retention property is also significantly improved,
When incense sticks are added with 0.5 to 5% fragrance, the aroma when burned is similar to that of incense sticks containing natural agarwood. Application example 3 Use in mosquito repellent pine [A] [B] Ingredients Parts by weight Parts by weight Bergamot oil 100 100 Orange oil 280 280 Linalool 110 110 Linalool acetate 40 40 Petitgrain oil 40 40 Lemon oil 40 40 Geranium oil 30 30 Dihydrodiasmon Methyl acid 30 30 Cedrol methyl ether 80 80 Galaxolide 50 50 Dioctyl phthalate 200 - 2-[2-(p-methoxyphenyl)ethyl]chromone - 200 A mosquito repellent fragrance for pine containing the above ingredients was prepared. The fragrance [A] contains dioctyl phthalate as a retention agent, but instead of this, 2-[2-(p
-methoxyphenyl)ethyl] chromone of the present invention, the volatilization of low-boiling components is well suppressed compared to [A], and the fragrance lasts for a long time. For example, when scent paper was impregnated with equal amounts of [B] and [A] and left in the air for 24 hours, the strength of the scent was compared using a panel. ] The results showed that the retention was significantly improved and the scent remained strong. Moreover, when the above-mentioned compounded incense stick [B] of the present invention is impregnated into a mosquito repellent mat in an amount of 0.2 to 5% by weight and heated in an electric mosquito repellent (150 to 170°C), the sweet aroma lasts until the end of use.

[Brief explanation of the drawing]

Figure 1 is an infrared absorption spectrum analysis diagram of the compound (compound A) obtained in Production Example 2, Figure 2 is a mass spectrum analysis diagram of the same compound A, and Figure 3 is a diagram of the compound obtained in Production Example 3 (compound C). An infrared absorption spectrum analysis diagram of Compound C and a mass spectrum analysis diagram of the same compound C are shown in FIG. 4, respectively.

Claims (1)

[Claims] 1. General formula [In the formula, X and Y each represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and n is 2 to 4
indicates an integer. ] A heating type fragrance composition characterized by containing a chromone derivative represented by the following.