JPS62149643A - Ester having substituted norbornyl group and perfume composition containing said ester - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (C2 is ethyl, vinyl or ethylidene substituted at the 5- or 6-position of the norbornane ring; R1 is 1-3C alkyl; R2 is carboxylic acid residue derived from acetic acid, benzoic acid, phenylacetic acid and cinnamic acid; the dotted line in the side chain constituting the ester indicates that the C-C bond is single or double bond). EXAMPLE:1-(5- or 6-Vinylnorbornan-2-yl)-2-methyl-3-acetoxy-1-pentene. USE:One component in perfume compositions, having improved fragrance, e.g. woody fragrance, floral woody fragrance, etc., and usable for perfume, hair dressing, interior perfume, deodorant, insecticide, soap, toiletry, etc. PREPARATION:An alcohol expressed by formula II is reacted and esterified with a chloride of a carboxylic acid, e.g. acetyl chloride, etc., or carboxylic acid, e.g. cinnamic acid, etc., in a solvent to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a novel ester having a substituted norbornyl group and a perfume composition containing the same.

[Prior art and its problems] US Pat. No. 4,524,017 discloses an alcohol having a substituted norbornyl group.

The present inventors have discovered that the above alcohol ester has an excellent aroma, and have completed the present invention.

[Structure of the Invention] That is, the present invention relates to an ester represented by the following formula (I) and a fragrance composition containing this ester.

In the above formula, q is either an ethyl group, a vinyl group or an ethylidene group substituted at the 5- or 6-position of the norbornane ring, and R is a linear or branched alkyl group having 1 to 3 carbon atoms. and R2 is acetic acid.

It is a carboxylic acid residue derived from benzoic acid, phenylacetic acid, or cinnamic acid, and the dotted line of the side chain constituting the ester indicates whether the carbon-carbon bond indicated by the dotted line is a single bond or a double bond. Indicates a bond. Here, the carboxylic acid residue refers to a portion of carboxylic acid other than the carboxyl group.

The invention will be further explained below.

The ester of the present invention is a carboxylic acid ester of an alcohol represented by the following formula (II).

H Here, the definitions of C2, R1 and the dotted line in the side chain are the same as in formula (I) above.

Specifically, the alcohol of the above formula is exemplified by the following.

1-(5- or 6-nitylnorpornan-2-yl)
-2-methylpentan-3-ol, 1-(5- or 6-nitylnorpornan-2-yl)-2-methyl-1
-Penten-3-ol.

1-(5- or 6-vinylnorbornan-2-yl)
-2-methylpentan-3-ol, 1-(5- or 6-pinylnorpornan-2-yl)-2-methyl-1
-penten-3-ol, 4- (5- or 6-vinylnorbornan-2-yl)-3-methylbutan-2-
ol, 4-(5- or 6-vinylnorbornane-2
-yl)-3-methyl-3-buten-2-ol, 1-
(5- or 6-nitylidenenorpornan-2-yl)
-2-methylpentan-3-ol and 1-(5- or 6-nitylidenenorpornan-2-yl)-2-methyl-1-penten-3-ol.

The above alcohols may be used, for example, in U.S. Patent No. 4.524
It can be manufactured by the method described in , No. 017.

The carboxylic acids used to prepare the esters of the alcohols mentioned above are acetic acid, benzoic acid, phenylacetic acid and cinnamic acid.

The above ester can be prepared by reacting the above alcohol with a carboxylic acid in the presence of a mineral acid such as sulfuric acid or hydrogen chloride or an organic acid such as toluenesulfonic acid according to a conventional method. Esterification can also be carried out in accordance with a conventional method using a chloride of the above carboxylic acid, for example, an acid chloride such as acetyl chloride, benzoyl chloride, phenylacetyl chloride, or cinnamoyl chloride, or an acid anhydride such as acetic anhydride.

After esterification, remove the solvent by distillation etc.

The desired ester is obtained by distillation under reduced pressure, recrystallization, etc.

Since the ester of the present invention has a crushed aroma, it can be used as a perfume, hair conditioner, indoor perfume, deodorant, insecticide, etc.
Can be used for Ishiki, toiletries, etc.

[Effects of the Invention] The ester of the present invention basically has a rich aroma that is different from that of a single alcohol.

[Example] The present invention will be explained in detail with reference to Examples below.

Example 1 l-(5- or 6-pinylnorpornan-2-yl)
Synthesis of -2-methyl-3-7cetoxy-1-hentene 1
-(5- or 6-pinylnorpornan-2-yl)-
4.3 g (0,020 mol) of 2-methyl-1-penten-3-ol (hereinafter referred to as VMS) was dissolved in dry Viridi 7501111, and 1.7 ml (1.9 g, 0.024 mol) was added thereto, followed by stirring for 2 hours. The mixture was stirred at room temperature overnight, poured into ice water, and extracted with ether. After drying the extract, the ether was distilled off, and the residue was distilled under reduced pressure to obtain 3.5 g of the liquid compound in a yield of 68.8%.

This compound has a woody odor, and its physical properties are as follows.

Boiling point: 98-99℃ 10.9 m+oHgI
R: The OH absorption at 3,400 cm'' disappeared, and in its place a carbonyl absorption appeared at 1725 am-'.

NMR(CI)C:+3): δ6.20~5
．． 50 (m, 2H) 5.15-4.80
(m, 2H) 3.85-3.75 (
t, 'IH)2.10 (s, 3H)1
．． 80 (s, 3H) 2.80-1. O
O (m, 15H) Elemental analysis (as C17H2602): C (%)
H(X) Calculated value 77.82 9.99 Actual value? ? , 78 9.91 Example 2 l-(5- or 6-pinylnorpornan-2-yl)
Synthesis of =2-methyl-3-cinnamoyloxy-1-pentene Esterification was carried out in the same manner as in Example 1 using VMS and cinnamic acid chloride. The product was separated and purified by column chromatography (Nizilica gel packing) to give the title compound in 65% yield.

This compound relieves flower-like wood fragrance, and its physical properties are as follows.

I R+ 3,400 cm'(7) 0) The absorption of 1 disappeared.

Instead, carbonyl absorption appeared at 1690 cm''.

NMR(CDCl2): δ 7.75-7.30 (m, 5H) 6.70-13
．． 55 (d, IH) 6.20-5.35
(m, 3H) 5.20-4. EiO'(m,
2H) 3.85-3.75 (t, IH) 1.
75 (s, 3H) 2.80~1.00 (m, 15H) Elemental analysis (C
As 24H3o02):C($) )I
(X) Calculated value 82.24 8.83 Theoretical value 82.31 8.59 Example 3 l-(5- or 6-nylidenenorpornan-2-yl)-2-methyl-3-cinnamoyloxy-1 - Synthesis of pentene Esterification was carried out in the same manner as in Example 1 using 1-(5- or 6-nitylidenenorpornan-2-yl)-2-methyl-1-penten-3-ol and cinnamic acid chloride. The obtained product was separated by column chromatography (Nizirica gel packing material).

After purification, the title compound was obtained in a yield of 55.0%.

This compound has a wooden component, and its physical properties are as follows.

IR: 3,400 am-1(7) OH absorption disappears, ester co absorption 1690 cm-
1 was seen.

NMR(C:DC+3): δ7.85-7.
35 (m, 5H) 6.65-6.55
(d, IH) 620~e, lo (d, I
H) 5.80-5.70 (d, IH) 5.5
0~5.05 (m, LH) 3.90~3.7
5 (t, IH) 1.90 (s,
3H) 2.75-1.00 (m, 17H) Elemental analysis (
as C24H3o02):C(%) H(%
) Calculated value 82.24 8.83 Theoretical value 82.21 8.74 Example 4 The compound obtained in Example 1 was blended in the following formulation.

A lavender fragrance for soap was obtained. This product can be used as a base fragrance for men's colognes.

Lavender oil 53.0 g Boad rose oil 13.5 g Bergamot oil
10.5 g Heli Otrobin 9
．． 0g Vanillin 8.5g Patchouli oil 4.5g Ester of Example 1
3.0 g total 100.0 g Example 5 The compound obtained in Example 2 was blended according to the following formulation to obtain a floral two-there perfume. This can be used as a base for indoor fragrances.

Phenylethyl alcohol 11.0 g Linalool 11. Og bergamot oil
10.0 g orris oil 6
．． 0g heliotlobin 5.0g coumarin 5.0g rose oil
5.Og linalylbenzoate) 5.
0 g Vanillin 5.0 g Linalyl Acetate 4.0 g Musk Ambrette 2. Og macrocyclic ketone (trade name: TMH-9P) 8.0 g Ester of Example 2 25.0 g Total to
o, o g Example 6 The compound obtained in Example 3 was blended according to the following formulation to obtain a chypre base fragrance. This can be used as a base for spray Sibley Eau de Toilette.

Bergamot oil 21.0 g Rose oil
17.0 g Vanillin
10.0 g terpineol
8.0g phenylethyl alcohol 8.0g methyl anthranilate 6.0g heliotrovin
5.0g methylionone
1. Ester of Og Example 3 24. Og meter
100.0 g

Claims (2)

[Claims] (1) Ester having a substituted norbornyl group represented by the following formula (I), ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) Here, C_2 is at the 5- or 6-position of the norbornane ring. It is either a substituted ethyl group, vinyl group or ethylidene group, R_1 is a straight chain or branched alkyl group having 1 to 3 carbon atoms, and R_2 is acetic acid, benzoic acid, phenylacetic acid or cinnamic acid. The dotted line of the side chain constituting the ester indicates that the carbon-carbon bond indicated by the dotted line is a single bond or a double bond. (2) A fragrance composition characterized by containing an ester having a substituted norbornyl group represented by the following formula (I), ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) Here, C_2 is norbornane It is either an ethyl group, a vinyl group or an ethylidene group substituted at the 5- or 6-position of the ring, R_1 is a straight chain or branched alkyl group having 1 to 3 carbon atoms, and R_2 is acetic acid or benzoic acid. It is a carboxylic acid residue derived from either phenylacetic acid or cinnamic acid, and the dotted line of the side chain constituting the ester means that the carbon-carbon bond indicated by this dotted line is a single bond or a double bond. .