JPS6153213A - Perfume composition and its production - Google Patents

Abstract

PURPOSE:The perfume composition that contains 2-(2'-formylpropoxy)-6-ethylidenebicyclo[2,2,1]heptane, thus having aldehyde-like smell such as green, herbal and spicy smells. CONSTITUTION:The objective composition contains 2-[2'(or 3')-formylpropoxy]- 6-ethylidenebicyclo[2,2,1]heptane of formula I and/or 1-ethyl-3-[2'(or 3')-formylpropoxy]tricyclo[2,2,1,0<2.6>]heptane. The compound of formula I is obtained by reaction between a mixture of 2-allyloxy-6-ethylidenebicyclo[2,2,1]heptane of formula IV and 1-ethyl-3-allyloxytricyclo[2,2,1,0<2.6>]heptane of formula V, which is obtained by addition reaction of allyl alcohol to ethylidene bicycloheptane of formula III in the presence of a strong acid, carbon monoxid and hydrogen in the presence of a rhodium catalyst and a tertiary phosphine.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel fragranced footwear, more specifically,
, 2-(2' (or 3')-formyl7'
mouth? −? -6-Nylidenepicy/E”(2
,2,1) hebutane and/or l-ethyl-3-[2' (or 3']-formylzolo?xy]tricyclo[2,2,1,0'') hebutane represented by the following formula CM), The present invention relates to a fragrance composition containing the above and a method for producing the same.

[Conventional technology]

Conventionally, ethylidene bicyclohezotene (hereinafter r
By adding allyl alcohol to EBHJ] in the presence of a strong acid, 2-alyl-6-nitrylidene bicyclo (2, 2,1) that a mixture of hebutane and l-ethyl-3-7lyloxytricyclo[2,22,6,1,0]hebutane is obtained and that this mixture has a fruity, anise-like and green color; It is known to have an aroma (%Kokai No. 57-82332).

[Problem that the invention seeks to solve]

However, the mixture of compounds (Jl) and (IV) described above had poor odor retention and was not fully satisfactory as a fragrance.

[Means for solving problems]

As a result of intensive research to obtain a fragrance with a stronger lingering aroma and a novel aroma from EBH, the present inventors discovered a compound (1) obtained by subjecting compounds (I[) and (IV) to an oxo reaction. The present invention was completed based on the discovery that a mixture of and (...) has a green, herbal, snowy, aldehyde-like aroma, and has a strong residual fragrance.

That is, the present invention provides a fragrance composition comprising compounds (1) and (1), which has excellent properties as a fragrance, and a method for producing the same.

The fragrance composition of the present invention is produced by reacting a mixture of compounds (1) and (IV) with carbon monoxide and hydrogen in the presence of a rhodium catalyst and a tertiary phosphine.

As a rhodium catalyst, the mosquito formula is RhH(Co)(PRIR2R3)3, RhCt(
CO)(PRIR2R3)2 or ahcz(pala2
a3)s (wherein R1% R2 and R3 are the same or different, an alkyl group, a cycloalkyl group, an aryl group,
or an aryl group substituted with an alkyl group or an alkoxy group having 1 to 6 carbon atoms], and in particular Rha(co) (pRI
R2a3)s is preferred. From the viewpoint of reactivity and economy, the amount of catalyst is 0.1 to 1000 rhodium equivalent to the substrate.
A range of ppm is suitable.

Tertiary phosphine is used for the purpose of suppressing the production of high-boiling substances, and its general formula is palit, R= (where R, %R
(2 and R3 have the same meanings as above) is preferable, and it is preferable to use 1 to 10,000 times the molar amount of the rhodium catalyst.

The reaction temperature is 0-170°C, preferably 80-130°C;
The reaction pressure is 20 to 250 atmospheres; the mixing ratio of carbon oxide and hydrogen (carbon oxide/hydrogen) is suitably 0.5 to 2.0.

This reaction can be carried out in the absence or presence of a solvent.

However, in consideration of the effort required for post-treatment, solvent-free treatment is preferred.

As the reaction solvent, hydroxide, benzene, toluene, ether, chloroform, etc. can be used.

The mixture obtained by the reaction can be purified and separated from the catalyst by distillation under reduced pressure.

The mixture obtained as described above or the compound (1) and (I
I) i-containing M means GC-Maaa
and lI (-confirmed by NMR, i.e. the mixture was subjected to capillary CC analysis (methyl silicon, 50 m)
As shown in Example 1, 15 peaks appeared when including small peaks, and the GC-Mass analysis results revealed that the mixture was an isomer mixture of monoaldehydes with a molecular weight of 208. did. Furthermore, IH-
As a result of NMR analysis, the raw materials compounds (Jl) and (I
V) Characteristic allyl terminal methylene peak (a;
5.0-5.3 ppm) disappeared, and only the methine peak of vinylidene (δ; 5.3 ppm) was observed.

From these facts, it can be seen that the main components in the mixture are monoaldehydes in which only the allyl terminal double bond of the starting compound has been hydroformylated, that is, compounds (1) and (...).

The perfume composition of the present invention can be used in a wide variety of products that require fragrance, such as high-grade perfume compositions, perfumes, soaps, shampoos, hair rinses, detergents, cosmetics, sprays, and fragrances.

〔Effect of the invention〕

The fragrance jilffi of the present invention includes green, herbal,
It has a strong aldehyde-like aroma and a strong lingering scent.

〔Example〕

Next, the non-explosion @I4 will be explained after referring to the reference examples and examples.

Reference example 1 Adduct of EBH and allyl alcohol [[cliff] and (■)
]: Allyl alcohol (139.2 g, 2.4 mol) and BF
A solution of 3.Et,O (8.4f, 0.059 mol) in toluene (125F7I7) was heated to 100°C and EBH (
240f, 2.0 mol) t - 90 min.

The reaction solution is then cooled to room temperature and decomposed by adding water (400 m). The organic layer was dissolved in a 10% aqueous sodium carbonate solution (2
50 m), and the solvent toluene and excess allyl alcohol were distilled off under reduced pressure. Finally, the product EBH-allyl alcohol adduct is obtained by distillation under reduced pressure at a yield of 243 f (68% yield based on the EBH charge).

Product t Capillary CC analysis (methyl silicon, 50
m) Then, if we include the small peak, we get a mixture of six isomers, and the main product is 4'! f1 class (GC ratio, 85%
).

Boiling point: 62.0-63.0℃/l mmH Elemental analysis: Analytical value; c, 80.7 H, 10,3 Calculated value; C, 80,8 HIIO12 IR (liquid! 1!""): 3070 (C=C-
1(), 1650(ν('=C), 1090(SiC-C
-0) IH-N (CDCt3 solvent, internal standard TMSI
δ] 0.7-3.1 (complex multi-weight), 3.6 (-0
-CI[.

complex multiplet), 3.9(-o-CH2,a), 5
．． 0-6.2 (Complex multiple glands) Example I Adduct of EBH and allyl alcohol (53,4t, o-
3 mol), RhH(Co)(PPh3)3 (27,6
"i sO,3XIO-' mol), triphenylphosphine" (0,79f, 0.3XIO-'-E-le) r10
After replacing the air in the autoclave with nitrogen, the autoclave was pressurized to a total of 100 atm with partial pressures of COSO and H250 atm], and then the autoclave was slowly heated to 110'Cm. 1 from 20℃
It took 35 minutes to heat up to 10°C. A decrease in gauge pressure is observed from around 100°C, but when the gauge pressure reaches 30 atm, equal partial pressures of CO and H! is added to make the pressure 100 atm. After 3 hours, gas absorption slowed down from 50 atm, so at this point the autoclave was cooled to room temperature and returned to normal pressure.

The contents were removed from the autoclave and distilled under reduced pressure to obtain the desired oxo reaction product. The distillation contents are as follows.

■ Recovered raw material stain: eo, o~62.0'C/0.5 mmH
? Yield: 17.5f (recovery rate 32.8%) ■ Target oxo reaction product boiling point near 8.0-8 2.0'C/0.5
mmH9 yield: ss, sr (yield 62.2% based on the charged raw materials, selectivity 92.5%) ■Residue yield: X, St Elemental analysis: Analysis value; c, 75.2 H, 9,7 calculation Value; C, 75,0M, 9.7 IR (liquid 'IN r art-'): 3050
(11=CH-), 272° (C-Co-H), 17
25 (&1C=O), 1095 (C-0-C) "H-" NMR (CDC1, solvent, TMS internal standard δ)
0.6-2.7 (complex multiplet), 3.3-3.7 (
-c...2-O-CH-, complex multiplet), 5.3 complex multiplet] GC-Masa (relative intensity) In GC analysis, capillary column (methyl silicon,
50m), it is divided into 15 peaks, including small peaks. Next, the typical peak G
Showing C-Masa's Q turn.

Peak 1 (GC ratio, 18%): 208αM*l),
109 (34), 107 (35), 106 (28,1,
93 (39), 91 (56), 79 (100), 77 (
31), 43(37), 41(98) peak 2 (GC
ratio, 14%): 179 (M-CHO112), 12
1 (92), 93 (99), 91 (40), 79 (10
0), 77 (25), 66 (29), 55 (53), 4
4 (21), 43 (51), 41 (39) peak 3 (
GC ratio, 12%): 93 (10), 91 (21),
79 (29), 77 (11), 71 (100), 66 (
14), 55 (13), 44 (15), 43 (44λ
41 (26) Peak 4 (GC ratio, 7%): 208 (M+, 5)
, 121(95), 120(75), 105(91),
93 (100), 92 (49), 91 (66), 79
[47), 77 (36), 41 (60) Note that peak 2
Regarding peak 3, m/e226 ((M+NH4)) is observed in the chemical ionization mass spectrum using ammonia as the reaction gas, so these peaks are also found to be monoaldehyde forms of the molecule [208.

Example 2 Muguet base formulation: Galpanum oil 2 Phenylacetaldehydozomethyl 50 Acetal 2.4-Dimethyl-3-cyclohexene 3-1-
Power Pulp Human Aldehyde C-10 10%DEP 5N Aldehyde C-12MN 10%DEP
5 Geraniol 190
α-hexyl cinnamic aldehyde)' 10
0β-phenylethyl alcohol 19
5 Methylzohydrozoyasmonate 50 Phenylethylzomethylcarbinol 20 Linalool 80
Acetyl Cedrene 50 By adding 50 s of the oxo reaction product obtained in Example 1 to 950 parts of the above Muguet paste, a stronger Muguet fragrance with a grass-like green-herbal feel was obtained.

Dilution solvent: diethyl phthalate (DEP).

that's all Taganito Kao Soap Co., Ltd.

Claims (1)

[Scope of Claims] 1. 2-[2' (or 3')-formylpropoxy]-6-ethylidenebicyclo [ 2.2.1] Heptane and/or 1-ethyl-3-[2' (or 3')-formylpropoxy] represented by the following formula (II), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) Tricyclo [2.2.1.0^2^
．． ^6] Flavor composition containing heptane. 2. 2-allyloxy-6-ethylidenebicyclo[2.2.1]heptane represented by the following formula (III), ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) and the following formula (IV), ▲Mathematical formula, There are chemical formulas, tables, etc.▼(IV) 1-ethyl-3-allyloxytricyclo[
2.2.1.0^2^. ^6] A method for producing a fragrance composition, which comprises reacting a mixture of heptane with carbon monoxide and hydrogen in the presence of a rhodium catalyst and a tertiary phosphine.