JPS58159435A - Novel oxidated alicyclic compound, manufacture, method of rendering perfume characteristics, improving or modifying tobacco and tobacco flavor composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the formula: In the formula, f'ja is 0 or 1, and the dotted line represents a single bond (n
-1) or 2 [X'L (n = 0) or 3rd place (
n=1), and R1 to R6 each represent a hydrogen atom or a methyl group.

The present invention also provides a starting proboscis curve formula (Ivl: 5 [in the formula, a fit, phase number n, and R1-R6 are as shown above]): [in the formula] R is C1-3-
A compound proboscis indicated by alkyl JAY? First, we will discuss the method for making the compound shown in (1) below.

Historically, the present invention provides a chemical compound having an activity of 1.15 minutes and a flavor of K, 11 hl.

Furthermore, the present invention provides aromatic products, foods, beverages, millet or tobacco products containing the compound represented by formula (11) as a sieve or a strange active ingredient.

Indeed, one of the diaphragms of a tomb that has been extensively investigated is represented by this compound proboscis. This first class consists of chemicals that have very different properties, single or polycyclic compounds.
Alcohols, esters, ketones and ethers, as well as macrocyclic derivatives, are used. Some of the wood grains with alicyclic structure include ionone aliphatic ether conductors, such as compounds shown by: ? Can be cited. Said compound expresses f air in fruits, amber-like leaves; j4 or all trees with tobacco-like notes in some cases (see German Publication No. 2827656, Akira Tomo 9).

My late methyl isomer of β-ionone is S.

Perfume Unr Flavor Chemicals (Perf) by Arctand6r
ume and Flavor Chemicals
) [=2087, Montclair, Ny.
and Section 2088'].

The monocyclic alcohol represented by the formula:
oody-ambery) type of Aiki 7 is expressed (West Germany! Samurai Koshitsukyo Publication No. 2807584 Shihosoiwa Examination).

Even outside the body, the existence of zygote-like compounds has not been recognized so far. By the way, Hakuto Honde has shown that 44 oxygenated octocyclic bodies exhibit useful Nagikita characteristics, as shown in the book 1-
1 Therefore, it has been found that the four compounds can be used as a useful ingredient in perfumes and spices.

At every mood, Compound (1) is an elegant, warm and refined wood-ambassian descendant, informed by the intoxication tendency H, which is reminiscent of natural amphibians. In some cases, the ambient air of the compound may also be fruit or flowering plants.

(12) Compound v/J(II) is potent and exhibits moderate persistence.

Sometimes the compound is used to imitate the proboscis of the four-dimensional sex, such as chypre, rose, wood, etc. This imparts calmness and richness to these woven fabrics without compromising the desired balance of their wood-umber uA.

The compound (11) can be used for the purpose of promoting cosmetic products such as soaps, cleaning agents, and cosmetics for men, such as colognes or aftershave lotions. .

The proportion necessary to achieve the desired effect varies over a wide range. Those skilled in the art will appreciate that at these times a given composition'
It is understood that it depends on the sex bridge of the co-order components used in the proboscis and the sex nail of the product that adds the cough compound proboscis. Typically 1~
For the order of 25 ton appetizers, 60 [1 horizontal degree can also be used for 1 history.

In the combination-1, the compound represented by the formula (1) is defined as Ura and Amber, one stroke, and is characterized by Ura, Amber, and Aroma. The compound 'proboscis' (1) is associated with tobacco (and tobacco accessories) due to its 70-year-old properties.

The compounds can be used to impart the typical aroma characteristics of Oriental tobacco blends.

Compounds according to the invention or these compounds? Composition that affirms
The proboscis may be used in sequential form, but is preferably used for fecal use with bath liquid. The given compound is 111 in Gien! The cedar used is
The chemical properties, solubility, and gelatin properties of the compound depend on it. Granting of foreign rice may be done at any stage of the d transfer method. For example, flavorings can be added to the tobacco loading platform at any stage of tobacco processing, during aging, drying, drying, or storage prior to actual cigarette manufacturing. An advantageous method of flavoring tobacco consists in (4) infusing the tobacco with an alcohol bath of the compound or alkali. As an alternative to alcohol, it is also possible to use a mixed bath agent for this first scoop, for example a mixture of alcohol and propylene glycol.

σ) The proportion of floor cutting used in the present invention is 1, plus 1 and 1! ! ! If a particular product is desired for planting and mating, it may vary widely in size and size.

For example, the advantageous snoring [离观] is 1 for the combined product.
-100 ppm (10C15 minutes 4', Bamboo m
) is something that can be achieved with the help of the axis rotation. Typically 5
A ratio of ~10 ppm is advantageous: However, in any case, is this 1000% enough to achieve a specific Yotogaki combination? You can change it.

According to the present invention, from an alicyclic alcohol represented by the formula: [In the formula, R1 to R6, the index n and the dotted line represent Ai, the formula: (15): [In the formula, R is 01 to 3-alkyl group], the compound represented by formula (1) can be prepared.

The reaction, according to the process of the invention, is carried out in the presence of an alkali metal, such as a strong base such as sodium or lithium, or an alkali metal, such as sodium. In this respect, oxidation is also carried out in the presence of inert organic solvents such as ethers or iftfh or aromatic hydrocarbons, e.g. petroleum ether, toluene (in this regard) - Houben-Weyl
), Methodender Organischen (Methodender Organischen)
Chemie), Orc Thieme Verl (Georg Thieme Verl)
ag) 1965, Vol IV/68 +tN
l.

The formula (IVI(
16) The chestnut-style alcohol represented by the formula can be prepared from commercially available products or by reducing the corresponding first-use ketone by conventional methods.

Compounds directly obtained by the method of the present invention (1+?ma,
6＠Different loams; depending on the nature of the loam, it occurs in the form of many stereoisomers. The different isomers can be separated by conventional methods, for example by preparative gas chromatography.

The different isomers are characterized by the typical wood-ambassial uniformity of the main, but strike different nuances. However, for all applications, the mJ notation method allows direct nJ
It is preferable to use the isomer mixture obtained.

Next, the present invention will be explained in detail with reference to practical examples, but the present invention is not limited to these examples (temperatures are shown in degrees).

Example 1 2.6.6-) Limethyl-cyclohexanol 2.0g
and sodium hydride 0.354/T' mixture $lJy
g, qrl water) /l/en1 [] m1. Middle-1
(Heated for 244 hours at -30°C.) Next, 1°2-epoxy-pentane 1.2,!V
'l<IJnL, 24 hours after heating at 80"C, a glow appeared. After aging, the reaction mixture was poured into crushed ice.
Acidified with a cloth H2So, then washed with Prine until the organic phase was 1/7 fresh. Evaporation of retentate and potash <(bath melting 1w: 1411c''/7Pa) 4.M'1 vaporization 1
Finally, four products were obtained in about 75% yield. Analysis sample was analyzed by gas chromatography <-fin: IR: 34 5 Qt:tn''NMR:
1.0; 1.2-1.6: 2.5: 2.8
: Signal MS at 6.4 and 3.75 δppm: M”=228 C68); m/e: 1
57 (25), 1 4 2' (20n, 12
5(45), 1 09 (29n, 95(
16), 82 (69), 69 (1 [10), 55 (38), 41 (48) Olfactory evaluation 111h: Ugh V-Amber uniform; strong (A loading property: thick?, Bare-amper's course) Animal U patrol.

Example 2 Follow the same procedure as described in Example 1 to prepare a second compound. Niated starting materials prepared a: 2,6,6-)limethyl-cyclohexanol 1,2-epoxy-butane IR: 343Q (,i-1-1N: 1.0; 2.5; 2.8 and 3 .4-4.0δppm MS: M+=214(99); mz
〆'e: 143 (45), 125 (53), 109
(37), 95 (22), 82 (69 (100 in 90)
, 55 (66), 41 (51).

Olfactory site evaluation: Woo-ampa uniform, medium strength (19) -2-ol starting material side: 2,6.6-drimethyl-cyclohexy 2
-en-1-ol 1,2-epoxy-butane NMR 2 0.8 B, 0.97, 0.98
, 1.7 8; 2.5: 3.13; 3
．． 4 to 6.75 and 5.43δ 2 m and 1 number MS 2 M””2 12 (1); m/e:
1b6 (103), 126 (55), 107 (21
), 84 (100), 73 (4υn, 57
(39), 43(63).

Smell rating: Utsudo-sama, Shi → f - (1eather)
4.1-2-2.6.6-) 1-phmethyl-cyclohex-2-en-1-ol 1.2-Epoxy-bentan (20 ) NMR: 0.88; 0.93;
0.9 7; 1.79; 2.45; 3
．． Signal MS: m/e: 17 υ (52)
, 123 (28 people 107 (12 people), 84 (
IDO), 69(11), 55(16),
41(25).

・Shoukan Hyo 1 [111: Wood-like, slightly fruit-like; Slightly grape-like 11! 1 globule 11': 2,6,6-trimethyl-cyclohex-3-en-1-ol 1.2 -Epoxy-pentane NMR 2 1.0; 2.5 + 2.92: 6
~4.0 and 5.2~5.6δ'opm MS2 m/e: 1 5 8 (72)
, 1 2 3 (13), 107 (8),
97 (4), 7 (16+, 72 (1Do), 55
(14), 41(22) Olfactory evaluation 1lIIi = Typical Utsu-Amber Uniform-Strong Monol Starting Material' Face: 2.2.6.6-Titramethyl-Cyclohexanol 1.2-Epoxy-Butane ■R: 344 QI:rn, -1 NMR: 1.0: 2.67 and 3.45-3.9
Signal MS at δppm: M+ = 228 (1); m/e
: 138 (21), 109 (24), 82 (100), 69 (28), 55 (22), 41 (20) -2-ol starting material = #: 2,2,6,6-tetramethyl- Cyclohexanone 1.2-epoxy-pentane TR: 546 Qbtl NMR 2 0.9 5 ; 2.6 7 and 3.
4-4. Signal MS: M twelve 242 (1); m/e: 168 (21
109 (22), 82 (100), 69 (31), 55 (14J, 41 (21) 2-ol starting material' directly: 2,2,6.6-titramethyl-cyclohexanol 1,2- Epoxy IR: 3450m-1 NMR: 0.95; 2.58 and 3.4-4.0
Signal MS at δppm: M+=256 (1); m/e: 138
(2[]1゜109(24), 82(100), 69(30), 55(25) 41(31).

(23) h) 1-(2,5,6,6-titramethyl-cyclohexanol Starting material: 2,5,6,6-titramethyl-cyclohexanol 1,2-epoxy-pentane TR: 3450r1n” NMR : lJ, 9; 2.41 & 3.1-4.
Signal MS at 0δppm: M+=242 (42): m/e:
157 (22), 158 (99), 126 (40), 109 (22,), 96 (54 people 83
(95), 69 (100J, 55 (90), 41 (93) Sense of smell, li'F-IIIi: % characteristic tsumaan 7 and 7 uniform; natural amber type, 4 and 69); strong and persistent.

2-ol starting material: 2-ethyl-6,6-dimethyl-(24) cyclohexanol 1,2-epoxy-pentane TR: 3 4 5 0 I, -1 NMR: Q,
9; 2.53 and 3.2-4. Signal MS at QδDpm: M” = 242 (67); m/e
: 171(22), 139(221,109 (55);82(IO[]J, 69<78855C62
), 41 (79J.

Olfactory bond 1 [fll: Wood-amper; ; 2.5
; 3.25-3.95 δppm ys: M+ = 214 (27); rrθ: 111 (100
), 71 (57), 69 (97 in 55 (58)
, 41 (40n.

1 review: Slightly off-center all starting material α2C-2, t-6-dimethyl-cyclohexanol 1,2-epoxypemen NMR (90MH7): [J, 90 and 0.94
: 2.8~6・9δDpm MS: M+ = 2 1 4 (22)
: rye : 1 1 1 (100), 71
(38), 69 (83), 55 (44), 41' (29
) Sniff review 11ffi: Mr. Utsudo: Perspir
Example) A basic perfume composition for men's cologne was constructed by mixing the following ingredients.

Ingredients Synthetic bell motte oil 150 phosphoric acid 1 s/l/ (cedrgl) 15
0 galbanum resonoi)' 100 Italian lemon oil 80 Discolored oakmoss (prefectural tree) 10%*80 Clove oil 60 EXALTEX' 40 Musk ketone 40 Lavender oil
40 Anruka, root oil 10%*40 Salvia sage oil 60 Neroli bigarade 20
Guinea orenzo oil 20 Basilicum oil 10%*20 Synthetic jasmine (ring water) 10 FIXATEUR 404”) 10%*
10 (27) Mt. Armoise Y (Armoise oil)
104 pieces
920 in zoethyl phthalate.

1. Source: Firmenich, S.A. (Switzerland) The basic aroma material obtained in this way is to be fixed as a wood-mandarin orange. A new composition of 1-(2,6゜6-) IJ methyl-cyclohexy-
By adding 80.9 Y of 1-yloxy)-pentan-2-ol. This composition has a basic composition'
It has a more aromatic, more harmonious fragrance tone than the nose, and also has an elegant undertone. By replacing the compound with the same size, the following effect can be obtained: 1-(2,/1.<S-)dimethyl-cyclohexy-1
-yloxy)-butan-2-ol: similar effect; slightly blurred.

(28) 1-(2,6,6-driftyl-cyclohex-6-en-1-yloxynohentan-2-ol: A good Ura V-like infantile attack, me.

1-(2,5,6,6-tetramethyl-cyclohexy-
1-yloxynopentan-2-ol: Very elegant, wood-like, more vivid than the above compounds.

1-(2-ethyl-6,6-dimethyl-cyclohexy-
1-yloxy]-pentan-2-ol: Good ura-like effect, slightly blurred.

Example 4 “American Blend” type tobacco 7% compound 100
g, 1-(2,6,
6-) Dimethyl-cyclohex-1-yloxy)-pentan-2-ol 10! ``& Sprayed.Test using tobacco mixture treated in this way is reno)'
2IQ was constructed, and the smoke was evaluated by the panel members. These test tobacco cigarettes were found to be 100% more cigarettes than cigarettes made with tobacco.
Clear wood-Amber's arrival showed Kaoru Samurai.

The taste and aura of the smoke produced by cigarettes made with Oriental Tobacco Plain was far superior. In this example, 1-(2,6,61-limethyl-cyclohexy-1
-yloxynopentan-2-ol, the same, 1
-(2,5゜6.6-tetramethyl-cyclohexy-1
The same effect was observed by substituting -yloxy)-pentane-2-old.

Claims (1)

[Claims] 1. Formula: % Formula % ([In the formula, R represents CL to 3-alkyl group, The middle finger an is 0 or 1, and the dotted line represents the mu bond (n = 1) or the 21 tachi (n = 0) or the 21 "bond in the 3rd position (n = 1), and Hl - R6 is 7, respectively.
[representing an elementary atom or methyl o]]. 2, 1-(2,6,6-trimethyl-cyclohexyl-1-yloxy)-pentan-2-ol, 1-(2,
6,6-)Samethyl-cyclohex-6-en-1-yloxorahentan-2-ol, 1-(2,5,6
, 6-tetramethyl-cyclohex-1-yloxy)
-Pentan-2-ol, 1-(2°5.6.6-tetramethyl-cyclohex-1-yloxy)-pentan-2-ol, 1-(2-ethyl-6,6-dimethyl-
cyclohex-1-yloxy)-pentan-2-ol and 1-(2,6,/)-)riftyl-cyclohex-1-yloxy)-butan-2-ol; 6, Formula (1j: X-CH2-CH(OHJ-CH2-R(+1 [R in the formula
represents a 01-3-argyl group; 2nd place [n double] or 3 if (n
= 1) In order to define a compound represented by the formula flV], R1-R6 each represent a hydrogen atom or methyl group]
23 Compound represented by [the dotted line in the formula, index n and R1-R6 represent the above], formula (■): /\, CH2CH-CH2-R (III) [in the formula, R is the above-mentioned] 1. A method for producing a compound of formula fl, which comprises reacting the compound with a compound represented by: 4. Formula (I): X-CH2-CH(OH)-CH2-Rffl [in the formula R
represents a 01-3-alkyl group, X represents a 1-substituted cyclohexyloxy group represented by formula
+FAi combination (n = 1) 'l represents a double bond in the 2nd position (n = 0) or 3rd position (n = 1) button, R1-R
6 each represents a hydrogen atom or a methyl group] Adding aroma modulating amounts of one kind of compound represented by [6] represents a hydrogen atom or a methyl group, respectively;
A method of improving or modulating. 5. Formula (I): X-CH2-CHCOH)-CH2-Rffl [in the formula R
4 represents a C [~3-alkyl group, X represents a substituted cyclohexyloxy group represented by the formula: In the above formula, the index n is D or 1, and the dotted line represents
=1) or 2 (ffl (n double) or 3rd place (n=1
), and R1 and R6 each represent a hydrogen atom or a methyl group.
A composition containing as an effective aroma component. 6. Formula (I): X-CH2-CH(OH)-CH2-R (11 [in the formula R
represents a 01-3-alkyl group, X represents a substituted cyclohexyloxy group represented by the formula: R3, where n is O or 1, and the dotted line represents a single bond (n
= 1) or a double bond at the 2-position (n = 0) or the 6-position (n = 1), and R1-R6 each represent hydrogen or methyl group] - 1 of the proboscis 1: A method for improving or modulating the sensation and aroma of tobacco or tobacco products, characterized in that it contains 11111 functional components of various types. Z Formula (1): % Formula % (11 [In the formula, R represents a C-3-alkyl group, X represents a substituted cyclohexyloxy group represented by the formula: In the above formula, the index n is O or 1, and the dotted line is a single M & (
n = 1 or 2 + 6 (n = O) or 5th place (n =
1) represents a double bond, R1 to R6 each represent a hydrogen atom or a methyl group]
1. Tobacco flavor composition having 1.9% of tobacco as an effective flavoring ingredient.