JPS6136257A - Cembrene derivative and flavor taste improver consisting of said compound - Google Patents

Abstract

NEW MATERIAL:A cembrene derivative expressed by the formula. USE:A tobacco flavor and taste improver, excellent for a sensitizer and perfume for the essential flavor and taste of the tobacco, and having remarkable inhibitory effect on irritation. PREPARATION:A flower bud of tobacco after harvesting is directly dipped in a hydrophilic solvent, e.g. ethanol or acetone, for about 2 weeks to give an extract solution, which is then distilled under reduced pressure to distil away the solvent. The resultant aqueous residue is then shaken with a nonhydrophilic organic solvent, e.g. ethyl acetate, and evaporated under reduced pressure to dryness. The resultant residue is then purified. The compound expressed by the formula is obtained as crystals by recrystallization from ethanol-water. The addition of the above-mentioned compound to cigarettes, cigars, regenerated tobacco or synthetic tobacco, etc. provides mellowness in flavor, and improves the taste and peculiarity. The amount of the compound to be added is 0.001-0.1wt%, preferably 0.01-0.05wt% in the final material to be smoked.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a compound represented by the first-order chemical structural formula and a tobacco flavor improver comprising the compound.

The compound represented by the above chemical structural formula is (2E).

6E) 11-hydroperoxy-2,6
, 12(20) -cembratrien -4,8
-dlol (hereinafter referred to as one compound) can be widely used in the field of tobacco manufacturing for the purpose of improving the aroma and taste of tobacco.

[Prior art]

Traditionally, in order to manufacture cigarettes that meet consumer tastes,
The aroma and taste of cigarettes is improved by adding various flavoring agents. For example, 3,7-dimethyl-6-octenoic acid ethyl ester (Japanese Patent Publication No. 5B-10069), 4-keto-α-citral (Japanese Patent Publication No. 57-42616), 4-( 3-oxo-2
, 6,6-)dimethylcyclohexy-1-enyl)-budo-3-en-2-one (4-oxo-beta ionone) (Japanese Patent Publication No. 55-27795).

[Problem that the invention seeks to solve]

The compound used as a tobacco flavor improver is preferably a natural product isolated from tobacco plants. This is the result of repeated studies aimed at searching and extracting useful chemical substances from among the chemical components contained in various plants of the tobacco genus.

Nicotiana tabacum C* V*, a cultivated tobacco species
The present compound, which is a new compound, was successfully isolated from MC.

Furthermore, as a result of examining the usefulness of this compound for its effect on improving tobacco aroma and taste, it was found that it is extremely effective as a sensitizer and flavoring agent for the original tobacco aroma and taste, leading to the completion of the present invention.

That is, an object of the present invention is to provide a new compound, particularly a new compound effective as a tobacco flavor improver.

[Means for solving problems]

This compound can be extracted and produced from tobacco in the following manner. That is, immediately after harvesting, tobacco flower buds are soaked in a hydrophilic solvent such as ethanol or acetone to obtain an extract. This extract is shaken off with a non-hydrophilic organic solvent such as ethyl acetate, which is an aqueous residue obtained by distilling off the solvent under reduced pressure. This extract is dried to dryness under reduced pressure, and the residue is purified three times through a silica gel column and then through a reverse phase column. Nine compounds can be obtained as crystals by recrystallization from ethanol-water.

The progress of structure determination of this compound will be described below.

Melting point: 152-153 degrees.

UV absorption; terminal absorption IR spectrum (Rho 1); 3371, 3274.

30g6,2992,1650.973.896M5 spectrum (m/z); 320,30213 CNMR,
Spectrum (ppm); t9, '1.20.
7°25.1. 28.7, 28.8.29.2, 31
．． 0. 32.5. 37.5°45.3.49.7,
73.2, 73.4.88.9, 113.3°124.
2,129.8,138.1. 138.8, 146.
41H NMR spectrum (ppm); 0.87 (d, 3l-1), 0.89 (d, 2H), 1
．． 25(!l.

3H), 1.32 (!1, 3H), 4.45 (t, LH
), N0O (d, IH), 5.04 (8,1H), 5.
34(a, IH).

s, a5 (m, tH), s, 54 (d, t) (), s,
69 (m, tH), 8.35 (ms, IH)
.

X-ray crystal analysis; orthorhombic system, space group, P2-12-12-
1, a=10.573(4)λ, b=t 9.6
10 (7) X, c=9.748 (2) A, α=β=r
=90. Volume, 2021.0A, Z=4, Dx
= 1.11 t/1-di large 2θ: 150.0 degrees C
uKa line (λ = 1.54184A) graphite monochromator 9' reflections used for structural analysis, 2663 (P
o2) 3.00 (FO2)), direct method, full matrices, Kuss analysis method, final R factor = 0.049° [Effects of the invention] The present compound obtained in this way does not have an aroma by itself. However, when it is decomposed by heat, it emits an aroma. Such properties exhibit extremely favorable effects when one compound is added to smoking materials.

In other words, when a small amount of this compound was added to various smoking products and a smoking flavor evaluation test was conducted, it was found that it harmonized well with the original tobacco aroma, rounded out the aroma, and suppressed the irritation of tobacco smoke. It has been found that it has many advantages. Smoking products whose aroma and taste can be improved by the addition of the present compound include 9 cigarettes manufactured from ordinary leaf tobacco, 1 cigar tobacco, and pipe tobacco, as well as recycled cigarettes manufactured from scrap tobacco, etc. or natural fibers or plants other than tobacco plants iI
This includes synthetic tobacco produced using fim cultures as raw materials.

The method of adding this compound to these smoking materials is not particularly limited, and the compound may be dissolved in an organic solvent such as ethanol and then added to shredded tobacco in the same way as other commonly used flavorings. Not only can it be used in cigarettes, but it can also be incorporated into materials for cigarette manufacturing, such as wrapping paper and glue. The amount of this compound added in the final smoking product is 0.
．． 001-0.1% (by weight), preferably o-oi-0
, 05% C heavy foot] is effective in improving the aroma and taste when added to the extent that it is contained.

Production example Nicotiana tabacum cvMc flower i1 part 100Kg (
Soak fresh type) in acetone 200 for 2 weeks.

The obtained extract was concentrated under wave pressure at 40°C. The aqueous formula 1 residue was adjusted to pH 2.5 with 1Nw#, and then partitioned with ethyl acetate to obtain an ethyl acetate layer. This operation was repeated two more times by adding fresh ethyl acetate. The obtained ethyl acetate layers were combined, washed twice with saturated sodium bicarbonate solution and twice with water, and then concentrated under reduced pressure.

The residue was filtered through a silica gel column (11,5crnX 58z
), benzene (tsj), +3% acetone-benzene, and the last 47 of the acetone-benzene elution area were dried under reduced pressure.
m), and the acetone concentration was increased sequentially to 3, 5, 6, 7, 8, and 9°12.20% using a hexane-acetone system. The capacity of each solvent is one. The mixture was fractionated into 20 mt portions, and both fractions containing the present compound among the 12% acetone-benzene elution fractions were collected and concentrated under reduced pressure. Preparative high performance liquid chromatography was then performed. The conditions are as follows.

Column: Silica gel (Kusano Kagaku Co., Ltd., Prepa, Kudo Column CPS-223-1-B) Solvent: Toluene-acetone (70:30°V/V) Flow rate: 5ml/min Under the above conditions, the elution time of the 9 compounds was It is 42 minutes.

Next, it was purified using a reverse phase column. The conditions are as follows.

Column: Microbondano C1B (manufactured by Waters) Solvent: Methanol-water (70:30.V/V) flow
Amount: 1 ml/min Under the above conditions, the elution time of this compound is more than 1 min.

Recrystallize from ethanol-water to obtain l, s, disc-shaped crystals 1
I got 5mf.

Example - Chopped yellow tobacco (MC, Konoha, etc.) 509
A 5% ethanol solution of the three compounds was added by spraying to a concentration of 0.01% (by weight) and rolled into paper, and the above rolled tobacco with no additives (■) was used as a control product. These were compared in terms of smell, taste, and habit when smoked using a two-point discrimination method. The evaluations of 20 professional 7-sun panelists are shown in Table 1.

Table 1 Classification Aroma Taste Habit Control product 2 2 2 Flavored product 18 18 1B Numbers in Table C indicate the number of people who rated it as good) 9 from the table above
It can be seen that this compound significantly improves the aroma, taste and habit of tobacco.

Example 2 Waste tobacco is extracted with hot water at 100°C and further divided into a water-soluble part and a water-insoluble part.The water-insoluble part is beaten, and 15% of the dry weight of softwood kraft pulp is added to it. A 5% (by weight) ethanol solution of 9 compounds was added to 50 liters of sheet-shaped recycled cigarettes prepared by adding the above water-soluble part back to the thin paper and adding the amount of this compound to 0.
．． After spraying and adding the tobacco to a concentration of 0.5% (by weight), it was chopped and rolled into 9 pieces.The above-mentioned rolled tobacco without the addition of compounds was used as a control product, and 2 points were evaluated regarding the aroma, taste, and irritation when smoking these. These smoking tastes were compared using an identification method. The evaluation by the 20 expert panelists is shown in Table 2.

Table 2 Classification Aroma Taste Stimulus control product
2 2 2 Flavored product 18 18 18 (The numbers in the table indicate the number of people who rated it as good.) The results show that the nine compounds improve aroma and taste and have a significant irritation-suppressing effect.

Claims (1)

[Claims] 1. A compound represented by the following chemical structural formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 2. A tobacco flavor improver consisting of a compound represented by the following chemical structural formula. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼