JPS5910536A - Tricyclic aliphatic compound derivative, its preparation and perfume composition containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R1 is H, CH3 or C2H5; R2 is CH3, C2H5, n-propyl or isopropyl; the combination of the dotted line with the solid line is the single bond or double bond). EXAMPLE:1-{6-Ethyltricyclo[2.2.1.0<2>,<6>]heptan-3-yl}-2-methyl-1-pent en-3-ol. USE:A perfume having woody aroma as a base tone varying from floral-deep aroma. PROCESS:A tricyclic aliphatic aldehyde of formula II is reacted with an ethyl alkyl ketone or methyl alkyl ketone in the presence of an aldol condensation catalyst, e.g. an alkali hydroxide or tertiary amine, at 0-200 deg.C, preferably 50- 150 deg.C, and the reaction product is then dehydrated and reduced to give the aimed compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel bicyclic aliphatic compound derivative having a specific substituent, a method for producing the same, and a fragrance composition containing the same.

Traditionally, various fragrances have been synthesized to replace or supplement various natural fragrance ingredients.
Among them, norbornane, Sunawachi bicyclo-[2,2
, 1]-Heptane rings have been proposed.

That is, U.S. Pat. Nos. 3,673,261 and 3,673,263 describe 2-methyl-3-(5'-hydroxyalkyl)-norbornane,
Further, cyclic acetals of norbornane carboxyaldehydes are described in US Pat. No. 3,748,344.

Further, U.S. Pat. No. 3,860,635 describes a method for etching vinylnorbornanone, and U.S. Pat.
No. 076.853 describes alphaallyl or metaallyl-3,3-trimethyl-2-norbornylmethanol.

However, bicyclic aliphatic compound derivatives having specific substituents as in the present invention have not been known so far.

The present inventors completed the present invention as a result of extensive research into bicyclic aliphatic compounds useful as fragrance ingredients.

That is, the present invention relates to a bicyclic aliphatic compound derivative represented by formula (1), a method for producing the same, and a fragrance composition containing the same.

H In the above formula, R1 represents hydrogen, methyl group or ethyl group, R2 represents methyl group, ethyl group, n-propyl group or inozolobil group, and the combination of solid line and dotted line represents a single bond or double bond. represent.

The bicyclic aliphatic compound derivative of the formula (1) is a bicyclic aliphatic 6-rdehyde represented by the following formula (R1).
Ethyltricyclo(2,2,1,O”61heptyl=3
- An aldehyde and an ethyl alkyl ketone or a methyl alkyl ketone in the presence of an aldol condensation catalyst
It is produced by reacting at 200°C followed by dehydration and reduction.

The ethyl alkyl ketone or methyl alkyl ketone to be subjected to aldol condensation with the bicyclic aliphatic aldehyde of the above formula (III) includes methyl ethyl ketone, noethyl ketone, ethyl alkyl ketone, and ethyl lower alkyl ketone such as ethyl inov-o-lopyl ketone; Methyl lower alkyl ketones such as acetone, methyl propyl ketone and methyl isozorobyl ketone.

-1, the bicyclic aliphatic aldehyde of formula (III) is 6
-Ethyltrinochloro(2,2,1,02.6]]Iheph0tan-3-A and an alkyl monohalokinoacetate are reacted in the presence of a basic catalyst to perform dehalogenation/hydrogenation. It can be obtained by forming Nisder glycidate and then hydrolyzing and decarboxylating it.

An acidic substance or a basic substance is used as the aldol condensation catalyst. Examples of acidic catalysts include inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid or sulfamino acid, Lewis acids such as boron trifluoride, benzenesulfonic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, and naphthalenesulfonic acid. , trifluoroacetic acid, trichloroacetic acid, and their salts. In addition, as basic substance catalysts, metal hydroxides, for example,
There are alkali hydroxides such as lithium hydroxide, hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, potassium hydroxide, etc. Methylate, sodium methylate, sodium methylate, potassium chloride, methylate, aluminum isozolate, potassium t-butoxide, etc. are effective, and weak alkalis such as sodium carbonate are effective.
- Alkali carbonates such as potassium carbonate, potassium acetate, and potassium fluoride are also often used. Furthermore, other basic catalysts and [7] hydrogenated triuno 1
, alkali hydrides such as lithium hydride and potassium hydride, alkali amides such as lithium amide, sodium amide and potassium amide, tertiary amines, quaternary ammonium bases, activated methylene-j' alkali compounds, alkali fluorides , alkali metal oxides, alkaline earth metal oxides, and cyclic amines. Among these,
Industrially important alkali hydroxides, alkali carbonates, alkali amides, tertiary amines, cyclic amines, and alkali salts of weak organic acids.

The reaction temperature for alcohol condensation is 0 to 200'C, preferably] ~
The temperature is 50 to 150°C, and the reaction pressure may be normal pressure, increased pressure, or reduced pressure, as long as a predetermined temperature can be maintained.

During the reaction, it is not necessary to use a solvent, but a solvent may be used to bring the raw materials and catalyst into sufficient contact and to maintain a uniform reaction temperature. As a solvent, the alkyl ketone itself used in excess, alcohols,
One or a mixture of two or more of saturated hydrocarbons, water, needles and halogenated hydrocarbons can be used.

In the present invention, dehydration is carried out after the aldol condensation of the ternary aliphatic aldehyde and the ketone, but normally, if the reaction conditions are appropriately selected, the dehydration reaction can also be carried out after the aldol condensation is achieved. Since the dehydration can be carried out continuously, no special dehydration step is required in such cases. However, depending on the reaction conditions, such as when the condensation reaction temperature is selected to be relatively low, the condensation reaction may be followed by heating or by adding a dehydrating agent and heating. It is necessary to set up a

By the method described above, an α,β-unsaturated ketone represented by formula (IV) in the reaction scheme shown above can be obtained. In the reaction formula of I'' g+-, 6-ethyltricycloL2.2.1.02.6
, taking as an example the process of reducing the ketone obtained by reacting 1heptyl-3-aldehyde and noethyl cutone,
It is shown schematically.

(■)0H Said anti-1. C7, as shown in the formula, the formula (IV) magko reduces the ketone represented by the formula (Vl),
Thus, the bicyclic aliphatic compound derivatives (V) and (■) of the present invention can be obtained.

In this anti-L[5, formula, it is important to selectively reduce only the carbonyl group to a hydroxyl group in the reduction in steps C and D. Therefore, the reducing agents are usually metal hydrides, -rluminos, alcohols and alcohols, or alkoxides of alkali metals or alkaline earth metals and alcohols. It's convenient to have one. In addition, catalytic hydrogen reduction in the presence of a suitable catalyst under mild conditions
1-7 may be one, and electrolytic reduction can also be used.

Examples of metal hydrides include sodium borohydride, lithium borohydride, lithium aluminum hydride, sodium aluminum hydride, aluminum hydride complex salts,
Preferred are lithium hydride, tutorium hydride, hydride, sodium bis(methoxyethyl)aluminum hydride, and the like. As a combination of alcohol and aluminum, isozoropyl alcohol and aluminum isozoropyl alcohol and the like are used.

As solvents for reduction reactions using these reducing agents, alcohols such as methyl alcohol, ethyl alcohol, and inopropyl alcohol, as well as nooxane, noethyl ether, ethylene glycol methyl dimethyl,
Nidels such as tetrahydro-7rane, saturated aliphatic hydrocarbons, aromatic solvents such as toluene, or a mixture of two or more of fatty acid alkyl Nisdels, or a mixture of these and water are used.

The reduction temperature is usually 0-150'C. After the reduction reaction is completed, the unreacted components and the solvent are separated (1), and the organic layer containing the target product is collected and subjected to purification operations such as precision distillation to obtain the target product, a bicyclic aliphatic compound derivative.

In addition, the reduction in steps B and E of the above reaction formula reduces the carbon-carbon double bond under conditions that do not change the carbonyl group or hydroxyl group, but usually catalytic hydrogenation under mild conditions is performed. It is enough. Catalysts for this catalytic hydrogenation include nickel, conochrite, ruthenium,
For L<, it is preferable to use a catalyst based on a group 8 metal of the periodic table such as platinum, and the catalyst of Toh et al. is preferably used with activated carbon, barium sulfate, alumina, aluminum carbonate, etc. as a carrier. is generally convenient.

The reaction pressure of this catalytic hydrogenation ranges from normal pressure to 10 K9/
cs! The reaction temperature may be 0 to 150°C.

Further, the reduction in step A of the reaction formula involves simultaneously reducing the carbon-carbon double bond and reducing the carbonyl group to a hydroxyl group, and can be easily carried out particularly by catalytic hydrogenation. In this case, it is important to select appropriate conditions so as not to cause hydrogenolysis of hydroxyl groups, but nickel, co-Glut, platinum, copper chromite, ruthenium, rhodium-based catalysts, etc. are usually used as catalysts. It is also possible to use activated carbon or alumina as a support for them.It is not necessary to use all the solvents in the reaction, but if used, alcohols such as ethanol, chlorohexane, etc. Suitable ring-type saturated hydrocarbons are used.The reaction temperature for catalytic hydrogenation is 30 to 300°C, and the reaction pressure is 2 to 300°C.
Kg/crA is suitable.

By reducing the reducing power and the following, 1) IR general formula of the present invention (
All bicyclic aliphatic compound derivatives represented by 1) can be produced.

Examples of the bicyclic aliphatic compound derivative represented by the general formula (1) of the present invention include the following compounds. i.e. ■-16-nityl linklo C2,2,1,0"t6)
Heshita/-3-yl)-2-methyl-1-harden-3
-ol, 1--(6-ethyltrinchloro[2,2,1
,0””, 1-heptan-3-yl)-2-methylzencun-3-ol, 4-(6-ethyltricyclo(2,
2,1,02,6) Haf0 tano-3-yl)-3-methyl-3-buten-2-ol, 4-16-ethyltricyclo(2,2,t,o2-6)butane-3 -il)-
3-Methylbutan-2-ol, 1-(6-ethyldrincroC2,2,1,02.6]hebutan-3-yl)
-1-inten-3-ol, 1=(6-ethyltrinchloro(2,2,1,02+6)heptano-3-yl)
inotan-3-ol, 4-(6-ethyltrinchloro(
2,2,1,02+61・\butano-3-yl)-3-
Buty/-2-ol, 4-(6-ethyldrinchloro['
2.2.1.02・6. 1-heptan-3-yl)butan-2-ol, ■-(6-ethyltricyclo[2,2,
1,02・6:)hegekun-3-yl)-2-methyl-
1---\kiln-3-ol, ■-(6-ethyldrinchloro[2,2,1,02.6,1heptano-3-yl 1-2-methylhexan-3-ol, etc.).

These bicyclic aliphatic compound derivatives have essentially i′cl
The scent is based on a woody scent, but it varies from a floral scent to #thick and #scented, and includes not only a woody note, but also a 70-lar note, a fubi r note, a moss note, an unplained note, and a leather note. It can be suitably blended into , ri-guco note, -r normal note, /truss note, renonas note, green note, aldehyde note, etc., and various excellent fragrance compositions can be prepared.

Therefore, the bicyclic aliphatic compound derivative of the present invention is important as a base fragrance for various types of fragrances, and this base R1 can be used for perfumes, cosmetics, detergents, daily necessities, toiletries, bleaching agents, antiperspirants, deodorants, and aerosol products. In addition to being used as a flavoring agent in bath additives, aromatic products, etc., it can also be used in a wide range of applications, such as flavor components, synthetic essential oil components, and diluents.

In addition, in the bicyclic aliphatic compound derivative of the present invention, a hydrogen atom is also substituted on the carbon of the ring which is substituted with a side chain having a hydroxyl group, so that the hydrogen source r- and the side chain are Depending on body position, endo isomers and exo isomers are
) isomers, both of which are useful in the perfume applications mentioned above.

Next, the present invention will be explained in further detail with reference to Examples.

Example 1 l-(6-ethyltricyclo(2,2,1,02+621heptane-3-yl)-2-methyl-1-pentene-
Synthesis of 3-ol Noethyl ketone 6.9 fj! (0,08 mol) and 4
1.37% potassium hydroxide in 28ml 1VC of ethanol
Dissolve, 6-ethyl link "L2.2.1.02'
)-\F o-1- /L-3-r Lutecht 4.61i
'(0,03 mo/L) f drop T' L k rlk
The mixture was heated to reflux for 3 q. Thereafter, ethanol was distilled off from the reaction mixture, and the residue was extracted with ether. The needle extract was washed with water, dried, the ether was distilled off, and the α,β-unsaturated ketone l-(6
-+z -y-4 tricyclo1.2, 2.1, o
2.fi, + heptane-3-yl)-2-methyl-
1-zenden-3-. (Yield, 59.3%
; boiling point: 95-96°C, 10, 25mmHg).

This α, β-unsaturated ketone is IR (neat), NMR
(CCI4) The structure of the formula (IV) according to the structure -
I confirmed that there is a C.

Elemental analysis (c15H22o and shite) C (%)
H (%) Calculated value 82.6 10.1 Actual value
82.9 10.0IR (neat): 1670 cm' (C=Q offshore vibration of α, β-unsaturated ketone) 1630 cm' (C=C stretching vibration) NMR
(CC14): 1.80δ (-double line, 3■()0.80-2.
00δ (multiplet, 16H) 2.40~2.80δ
(Quartet, 2H) 6.20-6.50δ
(Double line, 1) () Next, 1.31 lithium aluminum hydride was added to 200 me of tetrahydrofurano, and while stirring under water cooling, α and β obtained in the same manner as described above were added.
- 7.07 (0.03 mol) of unsaturated ketone were slowly added dropwise. After stirring the mixture at room temperature, ethyl acetate was added to remove excess reducing agent, and dilute sulfuric acid was added to make the mixture slightly acidic, followed by needle extraction. Extract Mk After washing with water and drying, the ether gold was distilled off, followed by distillation under reduced pressure to obtain the title 1-(6-ethyltricyclo(2,2,1,02+'
) hebutan-3-yl)-2-methyl-1-zenten-3-ol 5.3F (yield, 74.6%; boiling point 109~
111°C (10.4% Hg) was obtained.

Elemental analysis (as C15H0) C (%) H (ch) Measured Sakaki value 81.8 10.9 Actual value
82.1 10.7IR (neat): Characteristic absorption at 3400 cm-' (0-H stretching imaging) was observed, but 1670 cffL' (α, β~c=o stretching vibration of unsaturated ketone) disappeared. was.

NMR (CCI4): 1.60δ (-double line, 3H) 0.70-1
,80δ (multiplet, 17H)2.20~2.5
0δ (quartet, 2H) 3.60-3.90δ
(Sanyaku Line, IH) 4.95-5.30δ
(22 lines, IH) The resulting composite has a warm woody aroma and is extremely useful for the composition of oriental perfumes, floral perfumes, woody perfumes, etc.

Examples 2 to 4 In Example 1, the ketones shown in the following table were used instead of dimethyl ketone, and α, β-unsaturated ketones were obtained by carrying out -r Le condensation alloy. Ta. Then, in the same manner as in Example 1, this α,β-unsaturated ketone was reduced. The results are summarized in the table below.

Real /if! 1fall 5 1-(6-ethyltrinchloro(2,2,1,02,6)hebutan-3-yl)-2- obtained in Example 1
Mejiru 1. -! ! Ten-3-one 5.02 (0,
023 mol) was dissolved in 100 me of methanol, put into a 200 cc autoclave together with 0.32 ml of Raney nickel, and after repeating deaeration and nitrogen replacement twice, hydrogen gas was pressurized and reacted at room temperature for 3 hours at a pressure of 4 Kylol. Ta. The catalyst was separated from the reaction mixture, methanol was distilled off, and 1-(6-ethyltricyclo(2,2,1,0"6J heptan-3-yl)-2-
Methylzentan-3-ol 4.7 F (yield, ■,
2%; boiling point, 96-97°C, 70.2+mHg).

Elemental analysis (as C1sH260) C (ch) H (%) Word value 81.1 11.7 Actual value 81.2 11.4 IR (neat): 3300 cm-' (0-H stretching motion) NMR (CC1
4): 0670~2.50δ (multiplet, 24H) 3.2
0δ (broad singlet, IH) 3.55-3.80
δ (Triple line, IH) Example 6 1-16-ethyl) obtained in Example 1) II 7chloroC2,2,1,02,6)hebutan-3-yl)-2-
The following fragrance was prepared using methyl IJ ten-32ol (hereinafter referred to as the "synthetic product").

β-phenylethyl alcohol 140 f/α-
Hexyl cinnamic aldehyde 100F benzyl acetate) 100 S'hydroxycitronellal 909 Lilial (manufactured by Sibodan) 851 Lavender oil 85F Nerol
652 Coumarin
401 Musk Ketone 405
'Musk amplet 40f roll
251
20g Oikenol
201 ylang ylang oil extra 201 no p jiko ri oil
157 Wanili/loy β-Iron 5g compound
100 f words 1000 g The fragrance prepared from this compound is a bouquet-like, exotic, floral-based fragrance that is excellent as a fragrance agent for soaps, cosmetics, room air fresheners, etc.

Claims (6)

[Claims] (1) A bicyclic aliphatic compound derivative represented by the formula (1), H in which R1 represents hydrogen, a methyl group or an ethyl group, and R2 represents a methyl group, an ethyl group, an n-70ropyl group or an ino fr+represents a pyl group, and a combination of a solid line and a dotted line represents a single bond or a double bond. (2) The bicyclic aliphatic compound derivative according to claim 1, wherein the bicyclic aliphatic compound derivative is represented by the following formula (formerly). (3) Bicyclic aliphatic 7 / represented by the following formula (11)
In the presence of a condensation catalyst, O to
A method for producing a bicyclic aliphatic compound derivative represented by the following formula 4), il, which is characterized by carrying out a reaction at 000C, followed by dehydration and reduction, wherein R1 is hydrogen, a methyl group or an ethyl group. represents,
R2 represents a methyl group, ethyl group, n-propyl group or isozolobyl group, and a combination of a solid line and a dotted line represents a single bond or a -7-fold bond. (4) A patent claim characterized in that a bicyclic aliphatic compound derivative represented by -F formula 41) is produced by using noethyl quinone as the ethyl quinone or methylargyl ketone. A method for producing a bicyclic aliphatic compound derivative according to item 3. H (5) "rs+: A fragrance composition containing a bicyclic aliphatic compound derivative represented by the formula (1), H. In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a methyl group, an ethyl group, or a n- It represents a propyl group or an isopropyl group, and a combination of a solid line and a dotted line represents a single bond or a double bond. (6) The bicyclic aliphatic compound derivative is described in F (11)
Represented by #! A fragrance composition comprising the bicyclic aliphatic compound derivative according to claim 5.