JPS58210033A - Bicyclo(2.2.1)heptane derivative, its preparation and perfume composition containing the same - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is formyl or hydroxymethyl linked to the 5- or 6-position; the dotted line is single bond or double bond). EXAMPLE:2-Ethylidene-5(or 6)-formylbicyclo[2.2.1]heptene. USE:A component in a perfume composition, having green, floral or spicy strong fragrance, and usable by adding to usable cosmetics, soaps, detergents, shampoos, waxes, aromatic agents, etc. PROCESS:2-Ethylidenebicyclo[2.2.1]heptene expressed by formula II is reacted with CO and H2 in the presence of a rhodium catalyst to give the compound of formula I (the dotted line is double bond), which is then reacted with a metallic hydride to afford the compound of formula I (R is hydroxymethyl). The resultant compound of formula I (R is hydroxymethyl) is then hydrogenated in the presence of a metallic catalyst to give the compound of formula I (but the dotted line is a single bond).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel bicyclo [2°2.1
] Hebutane derivatives, more specifically, the following general formula (1) (wherein, R represents a formyl group or hydroxymethyl group bonded to the 5th or 6th position, and the dotted line represents a single bond or a double bond. The present invention relates to a bicyclo(2,2,1)hebutane derivative represented by the following formula, a method for producing the same, and a fragrance composition containing the same.

The present inventor discovered that 2-ethylidenebicyclo(2,2゜1)henotene (2,2゜1)henotene (
After synthesizing various derivatives using [hereinafter sometimes abbreviated as EBHJ] as a raw material and evaluating their unnecessaryness, we discovered that a new compound of formula (+) derived from EBH has a strong aroma. , completed the invention.

That is, in formula (1), R is 2-ethylidene-5 (or 6)-formylbicyclo(2
, 2, 1) hebutane/(la)Et and 2-ethyl-5(or 6)-formylbicyclo[2°2.1]hebutane (1
d) has a strong green, floral aroma, and has a bright R.
2-ethylidene-5 represented by a hydroxymethyl group
(or 6)-hydroxymethylbicyclo(2,2,1)
Hebutane (1b) and 2-ethyl-5(6)-hydroxymethylbicyclo(2,2,1)hebutane (+) has a strong spicy, floral, green aroma.

(Ia) (11)) (IC
) (1d) Therefore, the compound of the present invention of formula (1), alone or in combination with other fragrance ingredients, can be used in products requiring the addition of fragrance, such as perfumes, cosmetics, soaps, detergents, shampoos, waxes, etc. It can be used by adding it to fragrances, etc.

The compound (1) of the present invention is produced, for example, by the method shown in the following reaction formula.

(11) (Ia) (Ib)
CIC), that is, E B H (I
I) is reacted with carbon oxide and hydrogen in the presence of a rhodium catalyst to produce 2-ethylidene-5(or 6)-formylbicyclo(2,2,1)hebutane (1a), and then (
2-ethylidene-5 by reacting 1a) with a metal hydride
(or 6)-hydroxymethylbicyclo(2,2,1)
By producing hebutane (1b) and further reacting hydrogen with hydrogen in the presence of a metal catalyst, 2-ethyl-5 (or 6)-hydroxybicyclo (2,2,1) hebutane (
IC) can be manufactured. Furthermore, by hydrogenating compound (1a) in the presence of a metal catalyst, 2-ethyl-
5 (or 6)-formylbicyclo[2,2°1]hebutane (1d) can be produced.

1 [1] Conventionally, there is a method of hydroformylating EBH (U.S. Pat. No. 3,894.995), but this method involves hydroformylating both of the two disubbonds of KBH to form the following formula ( 1) It is a method for obtaining a diformyl compound represented by the following, and there is no mention of a method for obtaining a monoformyl compound as in the present invention.

The manufacturing method will be explained in more detail below.

Production of (la): The catalyst used in this reaction is rhodium halide, oxide, carboxylate, nitrate, or phosphine, amine, olefin, carbon oxide, hydrogen, etc. as a ligand. Examples include complexes that Specific examples include RhX3 (X is a halogen atom), I (h203, [Rh
(OCOCH3)2]2, Rh(NO3)3, Rh6(
CO), 6, [RhX(CO)2]2, RhX3(C5
H5N)3, (Rhx(C8H12))2, Rh(ac
ac)3, Rh(PR',)3 (R' has 6 to 12 carbon atoms
aromatic group), RhX(CO)(PR'3)2, RhH
(00)(PR', )3 etc. are exemplified, but especially R
hH(Co)(PR', )3 is excellent. These rhodium compounds may be used as a homogeneous catalyst, or may be supported on a porous solid support such as activated carbon, alumina, or silica and used as a heterogeneous catalyst. -The amount of medium is EBHi
IX 10"-" to IX 10-6 mol, preferably IX 10-2 to 1x10-5 mol per mole. In this reaction, the tertiary phosphine is catalyzed by IJν
Adding 1 to 100 times the mole per mole can provide advantages such as suppressing decomposition of the catalyst and lowering the reaction pressure.

The reaction temperature is 150°C or 50°C.
C to 160°C. The mixing pressure ratio of -6 carbon and hydrogen is in the range of 0.5 to 2.0, preferably in the range of 0.68 to 1.2, and the reaction pressure is in the range of 1 to 200 atm, preferably in the range of 20 to 2.0.
The pressure is 150 atm.

As a reaction solvent, hydrocarbons such as hexane, heptane, benzene, toluene, and xylene, tetrahydrofuran,
Although ethers such as dioxane are used, the reaction can also be carried out without a solvent.

In this reaction, it is safe to stop the reaction when 0.1 to 1.6 moles of -carbon oxide and hydrogen are both consumed per mole of KBH, and particularly preferably 0.1 to 1.6 moles of -carbon oxide and hydrogen are consumed.
It is in the range of 1 to 1.1 mol. Otherwise, if the reaction is carried out until the consumption amount exceeds 1.1 mol, a diformyl compound will start to be produced as a by-product, and the yield of the target product will decrease. Furthermore, even when the reaction is carried out at a lower conversion rate in order to increase the selectivity to the desired formyl compound, if it is less than 0.1 mol, the yield per reaction is small and uneconomical.

It is proven from the following that the product thus obtained has the structure represented by (1a).

1. That is, in 'H-NMR of FBH, two types of olefin protons are observed, and the corresponding peaks are around δ-5,20 (complex multiplet, IH) and around δ-5,20 (complex multiplet, IH).
-5,85 (relatively simple multiplet, 2H), and based on their area ratios, the former can be easily assigned to the olefinic hydrogen of a 1-nylidene group, and the latter to the nor-4-grunene type olefinic hydrogen. On the other hand, in the water reaction product's H-NMR, the hydrogen of the formyl group is seen at -948 (1 Dennou, IH), but the olefinic hydrogen around δ = 5.85 disappears, and b
=5.25 (complex multiplet, IH) only olefinic hydrogen is observed. Therefore, it can be seen that this reaction product has a chemical structure represented by the formula (la) in which a formyl group is introduced into a norbornene type olefin, but not into an ethylidene group.

Production of (1b): As the metal hydride, for example, lithium aluminum hydride, sodium borohydride, etc. are used. The reaction conditions are general reduction methods using metal hydrides, for example,
F, Fieser and M, Fieser”
Reagents for Organic 5ynt
hesi8' John Wileyand 5ons
It is carried out according to the conditions set forth in New York (1967).

Production of (1c): This hydrogenation reaction is carried out by a general catalytic reduction method using a gold kJ4 catalyst such as Raney nickel, platinum oxide, palladium-activated carbon, or ruthenium-activated carbon. In this case, especially the hydrogen pressure is 10 to 150 atm and the reaction temperature is 30 to 150 atm.
It is clever to do it at °C.

Production of (1d): In the hydrogenation reaction to hydrogenate (1a) to obtain (1d),
Ha・I! (Solid catalysts such as Raney nickel, platinum oxide, palladium-activated carbon, and ruthenium-activated forms as Bj;
RhXPR' (X hahaoden atom, R1 has 6 carbon atoms
A homogeneous catalyst with ~12 aromatic groups) is used. When a solid catalyst is used, the formyl group is reduced and the compound (IC)
Therefore, if you want to obtain only (1d) with particularly high purity, it is better to use RhC:tPPh3.

When (1d) is obtained by hydrogenation of (1a), the reaction is preferably carried out at a hydrogen pressure of 10 to 150 atm and a temperature of 60 to 150°C.

Next, an example will be given and explained.

Example 1 Ratio BH225, l/(1,88 mol), trisphenylphosphine rhodium chloride 2. ? (2.2 mmol) and 1 g of triphenylphosphine are placed in a 500 ml autoclave, and the air in the autoclave is replaced with carbon monoxide. - Pressurize with a partial pressure of 40 atm of carbon oxide and 40 atm of hydrogen (total 80 atm) and stir at a temperature of 80°C. The autoclave is cooled with 1.88 moles each of -M carbon and hydrogen consumed (the consumption is read by pressure r-di), the power is returned to normal pressure, and the contents are taken out.

By distilling this under reduced pressure, 2-ethylidene-5
(or 6)-formylbicyclo(2,2,1)hezotene is obtained. This compound had a very strong green, floral odor.

Boiling point: 96-97°C/16 Dragon H9 Yield: 1849 (yield 65.2%) Elemental analysis (as c,.H,,O) Calculated value (%): 0.79.96; H,9, 39
Actual value (%): C, 79,81: H, 9,50I
R (number of films, cm-1): 3050.2810.2
710.1720.1690'H-NMR (CDCt3 solvent, TMS internal standard, δ)
;9.48 (IH, -0!O) 5.25 (complex multiplet, 1H, -=c seconds -〇H3
) 6.3 to 1.2 (complex multiplet, 12H) MS (relative intensity): This compound has at least four isomers;
The results of gas mass measurement using on 600T, column length 40nl are shown below.

Beak 1 (9%): 150 (M+, 13), 122
(7), 121(10), 10(S(6), 94(
28), 93 (100), 91 (25), 79 (26
), 77 (22), 55 (5) Beak 2 (65%): 150 (M”, 12), 1
22(8), 121(9), 106(6), 94 (
29), 93 (100), 91 (25), 79 (24)
, 77 (22), 55 (7) Beak 5 (50%): 150 (M”, 53), 12
1 (45), 106 (20), 94 (29), 93 (
100), 92 (16), 91 (5o), 79 (54
), 77 (56), 55 (15) Beak 4 (6%): 150 (M”, 33), 121
(20), 106(20), 94(56), 93(
100), 92 (14), 91 (52), 79 (56
2.9 (
2-ethylidene-5(or 6)-formylbicyclo(2,2 ,1
) Hebutane 206.2,! il (yield 76.0) was obtained.

Example 3 Lithium aluminum hydride 6.79 (0.1 mol)
and 200 ml of dried diethyl ether 5Qrnl
Pour the 4 flasks into a flask and stir at room temperature. Here, 15 g (0.1 mol) of 2-ethylidene-5 (or 6)-formylbicyclo(2,2,1)hebutane obtained in Example 1 was added.
Toguf? , slowly add a mixture of 50 ml of dry diethyl ether. After finishing the preparation, let it return for another 1 hour and cool to room temperature. Here, water 6*7 nlb, 15
%z2i', 7 ml of Z-da aqueous solution filtration, and 11 ml of water were added in order to precipitate the aluminum compound.

Separate the precipitate using a glass filter and wash thoroughly with diethyl ether. After thoroughly washing the organic layer with saturated brine, it is dried over anhydrous magnesium. After filtration, the bath water is distilled off and further distilled under reduced pressure to obtain 2-ethylidene-5 (
or)-hydroxymethylbicycloC2,2,1)butane is obtained.

This compound had a strong spicy, 70-ral, green odor.

Boiling point: 60-62°G / 0.15 ml H9 convergence: 14.8.9 (yield 97.4%) Elemental analysis (C engineering. H
Yo. 0) Pi1゛ Calculated value (%): 0.78.90; H,1
0.59 Actual value (%): 0.79.41; H,
10,32IR (Q film, Cm-1): 5600-310
0 (broad absorption), 605D, 169D, 103
0'H-NMR (CDC43 bath medium, TMS internal standard, δ)
:5.6 (rough multiplex, 1H1-CH-C■(3)3
．． 35 (2m line, 2M, -0■2-0H) 6.0~0.
8 (complex multiplet, 16H) MS (relative intensity): 152 (M”, 40), 121 (34), 119 (
22), 105(18), 94(27), 95(
100), 91(35), 79(60), 77(
27) Example 4 2-ethylidene-5 (nu is 6) obtained in Tue 7/iII Example 6
-Hydroxymethylbicyclo[2,2,1)hebutane 5
g (32.8 mmol), 5% palladium-activated carbon 50
0 mg of ethanol and 5 Q rnl of ethanol were placed in a 100 mJ autoclave and stirred at a hydrogen pressure of 50 atm and a temperature of 100°C. When the absorption of hydrogen has stopped, the autoclave is cooled to room temperature, the hydrogen pressure is returned to normal pressure, and the contents of 1-6 are taken out. -5(or 6)-hydroxymethylbicyclo(2,2,1)butane is obtained. This compound had a strong spicy, green odor.

Boiling point: 49°G~50'C/0.09mm Hg
Soaking: 4.8 g (yield 94.9%) elemental content (Cl
0I (as 180) Total of 3 items Toy Direct (%): C, 77, 87:
H, 11, 76 actual measurement value factory): 0.77.59
;H,11,83IR(iMI]A,C7n-”)
:3600-3100 (g wide absorption), 1040.10
20"H-NMR (CDC43M medium, TM8 internal
) 2 3.40 (2 Tare Pass, 2H1-Tori 2-OH) 3.30
(Singlet, iH, -0 view) 2.65-0.4 (complex multiplet, 15H) MS (relative intensity); 154 (M+, 0.4), 124 (10), 1
23 (100), 107 (9), 95 (16), 8
1 (<57), 80 (12), 79 (19), 67C6
5), 55(19) Example 5 2-ethylidene-5 (or 6)-formylbicyclo(2,2,1)hebutane obtained in Example 1 60,! 9(0,2
mol), benzene 2 Q ml, (Rh(1!tP
Ph3']190In9 (0.2mm0l) for 100m
1 in an autoclave, hydrogen pressure 90 atm, temperature 10
The reaction is carried out at 00C. When hydrogen absorption stops, the autoclave is cooled to room temperature, the hydrogen pressure is returned to normal pressure, and the contents are taken out. After the solvent is distilled off, 2-ethyl-5(or 6)-formylbicyclo(:2.2.1)butane is obtained by distillation under reduced pressure.

This compound had a strong sweet green odor.

Yield 25.1.9 (yield 82.4%) Boiling point: 95°
~98°C/17 Hg Elemental analysis calculation value (%): 0.78.90; l(,10,
59 Actual measurement value (%): 0.78.52: )(,1
0,71 engineering R (liquid film, CnI'-1)-2820,27
20,172DIH-NMR (ODOz3 solvent, TMS
Internal standard, 15) 9.65 (IH, -Cdan) 2.8-0.5 (complex multiplet, 15H) MS (relative intensity); 152 (M”, 1), 123 (57), 108 (20)
, 95 (55), 81 (90), 79 (18), 6
7 (100), 66 (19), 55 (29), 41 (3
9) Example 6 01zu-like fragrance composition: r Rayuol 130 (,
! 9) Citronellol 70
Phenylethyl alcohol 593 Nerol 50 Geranium oil 20 Palmarose oil
20 benzyl acetate
20 hydroxycitronellal
40 linalool 2
5 octatool 1 octanal 1 delanyl acetate 10 phenyl ether acetate 10 citronyl acetate 10000 To 1000 g of the fragrance composition obtained above was added 2-ethylidene-5 (father is 6)-formylbicyclo [2° Example 7 Flavor composition for shampoo: Linalool 50G)
Zoyasmine azosolute oil 20 phenylethyl alcohol 150 rhodinol
150 Rose absolute oil 10 Hydroxycitronellol 600 Indole
24-(4-Hydroxy-4-methylpentyl)-(5-cyclohexene-1-carboxaldehyde) 75 α-hexyl cinnamic aldehyde 150 Cyclamen alkylene chloride 40 Sandalwood oil 50 Phenyl acetaldehyde 3000 Obtained above fragrance composition 1000. ? 2-ethylidene-5(or 6)-hydroxymethylbicycloC2,2
, 1) By adding hebutane, a novel fragrance composition with a fresh lily of the valley-like aroma was created.

Example 8 Fragrance composition for cologne: Lemon oil 35Q (,9
+Bergamot oil 300 Orange oil 150 Petidarene bigarede oil 100 Neroli bigarede oil 20 Lavender oil
70 sandal wood oil
1D000 Perfume composition obtained above 1ooo, r with 2-ethyl-
5(or 6)-hydroxymethylbicyclo(2,2,1
) By adding 50 g of hebutane, a new perfume composition for a sweet and fresh cologne was obtained.

Example 9 Lime tree-like fragrance composition: Hydroxycitroneller/'18
0η) Linalool
180α-ionone 1
00 tert, -butyl-α-methylhydrocinnamic aldehyde 100 Phenylethyl alcohol 10 [Hexyl salicylate 50 Linalyl anthraniley) 50 Galbanum oil
2 0-Manchamomyl oil 1 Eikesol 5 Coumarin 5 Dinolobylene glycol 227000 2-Ethyl-5 to the above obtained fragrance composition 1000F
By adding 2 g of (or 6)-formylcyclo(2,2°1)hebutane'c, a new fragrance composition with a stronger, more natural aroma, linden flower-like, was obtained.

that's all Applicant: Kao Soap Co., Ltd. 1, j.

Shi・− Continuation of page 1 0 shots: Yoshiaki Inamoto 970-63 Himurocho, Utsunomiya City 0 shots clearer Motoki Nakajima 1 Miyashirodai, Miyashiro-cho, Minamisaitama-gun, Saitama Prefecture 22-6 13

Claims (1)

[Claims] 1. General formula (1) (In the formula, R represents a formyl group or a hydroxymethyl group bonded to the 5th or 6th position, and the dotted line represents a single bond or a double bond. ) A bicyclo(2,2,1)hebutane derivative represented by: 2. 1 mole of 2-ethylidenebicyclo(2,2゜1)hezotene represented by the following formula (■) is reacted with carbon oxide and 0.1 to 1.3 moles of hydrogen in the presence of a rhodium catalyst. A method for producing 2-ethylidene-5 (or 6)-formylbicyclo(2,2,1)hebutane represented by the following formula (1a) characterized by: 6 2-ethylidene-5 represented by the following formula (1a) (or 6)-Formylbicyclo(2,2,1)hebutane is reacted with a metal hydride, and the 2-
A method for producing ethylidene-5(or 6)-hydroxymethylbicyclo(2,2,1)hebutane. 4. The following formula, characterized in that 2-ethylidene-5 (or 6)-hydroxymethylbicyclo(2,2,1)hebutane represented by the following formula (1b) is subjected to a hydrogenation reaction in the presence of a metal catalyst. 5. Method for producing 2-ethyl-5 (or 6)-hydroxymethylbicyclo(2,2,1) hezotane represented by (1). )-formylbicyclo(2,2,1)hebutane is reacted with hydrogen in the presence of a hydrogenation catalyst to obtain 2-ethyl-5(or 6)-formylbicyclo represented by the following formula (1d) (2,2,1) Production method of hebutane. 6. General formula (1) (wherein, R represents a formyl group or a hydroxymethyl group bonded to the 5th or 6th position, and the dotted line represents a single bond or 2 bicyclo(2,
2,1) A fragrance composition containing a hebutane derivative.