JPH0363238A - Substituted cyclic alcohol, preparation of compound thereof and composition containing said compound - Google Patents

Abstract

NEW MATERIAL: A compound of formula I (a dotted line represents single or double bond.).

USE: Perfume.

PREPARATION: Acetoacetic ester of formula II (R is a lower alkyl) and 2,2,3- trimethyl-3-cyclopentene-1-acetaldehyde are reacted with each other in the presence of a base (for example piperidine, morpholine), to obtain a compound of formula IV, which is decarboxylated by a base, LiBr/DMF or DMSO/NaCl aqueous solution, and then the reaction product is reacted with sodium borohydride, to obtain the compound of formula I.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION The aromatic properties and use of alkyl-substituted cyclohexanols and cyclohexanols as perfume materials are well known.

One example is the general structure It is carveol with

(-)-Ruveol is a natural component of spearmint oil. (+)-Ruveol is found in the oils of Fortunella margarita, Anetum graveolesis, and Heracleum canescens.

Still other examples are found in Actander, Pafneem and Flavor Chemicals (1969)1
For example, ortho-tertiary-butylcyclohexanol, which has the structural formula 1, is described as having a strong camphor-piney, generally minty, and somewhat persistent tarry odor. Compound No. 433 of Actander has the structural formula Trimethylcyclohexanol is registered as Compound No. 2998 of Actander. Its aromatic properties are described in the same book as having a strong odor similar to mint, but more similar to camphor, and having a less cooling sensation than mint.

Regarding the flavor, it is said to be similar to camphor and to have a WI flavor.

Actander Compound No. 432 has the structure nol and is extremely dry. It is described as having an almost tar odor with woody, camphor-like, and leather-like base odors. It is useful in perfume compositions to increase fragrance intensity and diffusivity. It is used in soap perfumery with wood perfumes, ionones, cedarwood oil derivatives, etc.

Compound No. 566, a 3-(iso-camphyyl-5)-cyclohexanol actander, has the following structure. This compound is less sweet than sandalwood oil and has a very persistent, soft sandalwood-type odor that is less palsam-like and exhibits less odor intensity in effective use. This substance is used in perfume compositions because of its sandalwood properties and economic stability.

2.2.3 - Chemicals having a trimethylcyclopentane skeleton are well known in the art of fragrance and flavor chemistry. For example, 2,2,3-trimethyl-3-cyclopentene-1-acetaldehyde having the structural formula is found in the oils of Unipers communis L. and lavadeine. The corresponding acid is found in frankincense oil.

U.S. Patent No. 4,052,341 has the structural formula 3-
Methyl-5-(2,2,3-trimethylcyclobento-
3-en-1-yl)-pentan-2-ol is disclosed for use in aromatic compositions.

This compound has a strong, noble woody aroma reminiscent of blackberry oil.

[Summary of the invention]

According to the present invention, a compound having a structural formula useful as an aromatic material has been discovered. Here, the dotted line is either a carbon-carbon single bond or a carbon-carbon double bond.

It will be appreciated that the chemical entities of this invention may exist in several stereoisomeric forms. The above structural formulas are intended to encompass individual stereoisomers as well as mixtures of the various stereoisomers of the substituted cyclic alcohols of this invention.

The present invention also provides an effective and economical method of making these compounds. Thus, for example, when decarboxylated by treatment with a base, a compound having the structure formula 5, where R is a lower alkyl group, is prepared.

acetoacetic acid ester having the formula and 2,2 having the structural formula
．． The product of this reaction is reacted with 3-trimethyl-3-cyclopentene-1-acetaldehyde in the presence of a base, and the product of this reaction is then subjected to conventional treatment to produce a compound, the reduction of which gives compound 1.

The compound having the structural formula is an acetoacetate similar to that described above and 2.2.3-trimethyl-3-cyclopentene-
It can be obtained by reaction with 1-acetaldehyde. The product of this reaction is then decarboxylated and hydrogenated to produce compound 2.

Mixtures of Compound 1 and Compound 2 are also useful as aromatic materials in place of each compound alone.

The mixture is acetoacetate (3) and 2.2.3
-trimethyl-3-cyclopentene-1-acetaldehyde (4) in the presence of an organic base to produce compound 7. Compound 7 is decarboxylated by treatment with base.

Compound 8 is obtained by reduction with a reagent such as sodium borohydride, which after mixing yields a mixture of compound 1 and compound 2.

Finally, according to the invention it has been found that aromatic compositions can be obtained by adding Compound 1 or Compound 2 or a mixture thereof to these compositions in an amount effective to impart fragrance to the composition.

[Detailed description of the invention]

Exhibits a soft, mild, woody aroma with a structural hue. These compounds have similar aromatic properties and may be used in perfumery applications, each alone or in mixtures.
Geometric and optical isomers of these compounds may be separated by techniques well known in the art, however, since mixtures of such isomers can be used directly without further separation. , such a separation is not necessary; furthermore, mixtures of these compounds may represent either carbon-carbon single bonds or carbon-carbon double bonds, but those of the individual compounds It has similar aromatic properties.

The reaction diagrams below illustrate various methods of the present invention for conveniently and inexpensively making such compounds.

Here, the dotted line is either a carbon-carbon single bond or a carbon-carbon double bond.

A compound having the following was obtained. The compounds are in powder form (see margin below) which makes these compounds useful as aromatic materials. In particular, compound 1 is an acetoacetate (3) - where R is lower alkyl, i.e. R is preferably methyl from C8 to C5. or ethyl- with 2.2.3-trimethyl-3-cyclopentene-1-acetaldehyde (4) in the presence of amines such as piperidine, morpholine, and pyrrolidine. This reaction proceeds via an intermediate between compounds 5 and 6 to yield compound 7. Although the intermediates of compounds 5 and 6 can be separated separately, in the practice of this invention it is preferred that the reaction proceed directly to compound 7, which is then subjected to conventional treatments such as sodium hydroxide or Decarboxylation by treatment with a base such as potassium hydroxide or other known systems such as lithium bromide/dimethylformamide or dimethyl sulfoxide/aqueous sodium chloride produces compound 8; gives reduced compound 1 by treatment with a metal hydride, such as diisobutylaluminum hydride.

Compound 2 would be prepared in a similar manner.

First, acetoacetate (3) is 2.2.3-trimethyl-3-cyclopentene-1-acetaldehyde (
4) to form compound 7. Compound 7
is decarboxylated to produce compound 8.

Compound 8 is then hydrogenated to form compound 9 by conventional techniques such as treatment with hydrogen gas in the presence of a catalyst such as a palladium-on-carbon catalyst. Reduction of compound 9 provides compound 2 by treatment with a suitable metal hydride, such as lithium aluminum hydride.

Alternatively, compound 2 can be prepared directly from compound 8 by reducing the double bond and carbonyl group of the six-membered ring with hydrogen at high temperature and pressure in the presence of a catalyst and a solvent such as butyl- or isopropyl-alcohol. can be manufactured by

As mentioned above, the mixture of compounds 1 and 2 has aromatic properties similar to each individual compound. Such mixtures can therefore easily be replaced with the respective compounds in perfumery applications. Such mixtures can be prepared by combining separately prepared compounds in the desired amounts. Additionally, the mixture can be prepared directly by reacting compounds 8 to 8 with a reducing agent such as sodium borohydride.

Compounds 1 and 2 or mixtures thereof are easily incorporated into aromatic compositions for use in detergents, soaps, perfumes, bath preparations, hair preparations, cosmetic preparations, etc. When so used, the compound or mixture desirably contains from about 0.8 to about 80% by weight, based on the weight of the composition.
should be present in an amount of

〔Example〕

A number of examples are provided below to illustrate desirable methods of synthesis of compounds of the invention. The following equipment was used to characterize the compounds of the invention.

Gas-liquid chromatography (GLC) analysis was obtained with a Hewlett Paracard Model 5840 or Perkin Elmer Model 3920; 3% 0V on Cromosorb II HP100/120
A 12ft, 2III JD Karasu column filled with -101 is used. Nuclear magnetic resonance (NMR) spectra were obtained using Varian Associates T-6OA or XL-10 using tetramethylsilane as an internal standard.
Recorded by 0. Infrared (IR) spectra were obtained with a PerkinElmer 137 Infracord. Weight spectra (MS) were obtained on a Hewlett Paracard 5985 mass spectrometer.

Weight is given in durams, temperature is given in degrees Celsius, pressure is ■
Denoted as Hg and not otherwise designated as 1, N.

Examples illustrating fragrance compositions containing the compounds of the invention are also described. All of these examples are merely illustrative of preferred embodiments of the invention and are not intended to limit its scope in any way.

Piperidene (0,8 g) in ethanol (3,0 ml)
ethyl acetoacetate (143 g) while maintaining the reaction temperature at -5 to -10° C. for 0.5 h.

1.1 mol) and 2.2.3-trimethyl-3-cyclopentene-1-acetaldehyde (81.3 g, approximately 0.5 mol).

The reaction mixture was then kept at 0° for 15 hours.

Piperidene (0,3
A further quantity of g) was added with stirring and the mixture was kept at O° for a further 24 hours. Furthermore, ethanol (3,
Piperidene (0.3 g) in 1) was added and the mixture was allowed to stir for a further 24 hours at 20' and then heated to reflux temperature for 7 hours. Piperidene, water and methanol were evaporated to give the product as crude product (149.5g).

ex), IR(neat)2995, 1675
, 1650, 805cm-1, MS (m/e) 1
09.122,95,121,232 were prepared.

The product of Example 1 (147g) was mixed with methanol (400ml
) dissolved in sodium hydroxide (21,
A solution of 3 g, 0.53 mol) in water (400 ml) was added in portions. The mixture was heated to gentle reflux for 19 hours, then cooled and poured into 5% sodium bicarbonate solution (800+1). The organic products were extracted with benzene (3x200+*l) and the combined extracts were washed with brine (3x200ml). The solvent is evaporated and the residue is distilled to give the desired product, b, , 126-133° (8
0.9g), NMR (CDC1,) 60.8 (3H,s
), 1.0 (3H, s), 1.6 (3H, m), 2.0
(3B1w+), 5.3 (1B, m), 5.9 (LH,
Peng), 1.0-3.0 (IOH, CO garden pi product of Example 2 (70 g, Q, 3 mol), methanol (25 1
A solution of sodium borohydride (100 g, 0.26 mol) in methanol (125 ml) is stirred for 0.8 hours with cooling so that the reaction temperature is maintained between -5 and -21. was added dropwise to the solution.

The mixture was then warmed to 20" and stirring continued for 4 hours. The mixture was cooled once more (0") before being acidified with dilute hydrochloric acid (dropwise) and the organic products were diluted with diethyl ether (3x 100ml). The extracted and combined extracts were sequentially diluted with water (3x100 sol), 5% sodium bicarbonate solution (100+ al) and water (3xl
ooml).

The organic layer is dried, the solvent is evaporated and the residue is distilled to form b2. . Oil at 129-130℃ (43,0g
) was obtained, and the oil was shown to be a mixture of alcohols 1 and 2 by GLC and spectral analysis.

Example 4 The utility of a mixture of Compound 1 and Compound 2 as described above in a sandalwood-based fragranced composition is illustrated below.

Sandwood base parts by weight Composition 20 Greek balsam oil 80 Amyris oil 100 Osilol BBA 800 Mixture of compounds 1 and 2 000 Many modifications, variations and modifications that will be obvious to those skilled in the art are within the scope of the claims. It is intended to be practiced in the practice of the invention as described without departing from the spirit and scope of the invention.

Claims (1)

[Claims] 1. Structural formula ▲ Numerical formula, chemical formula, table, etc. ▼ The dotted line here is a carbon-carbon single bond. There are compounds with the structural formula▲mathematical formulas, chemical formulas, tables, etc.▼The dotted line here is a carbon-carbon double bond. Mixture 2 with a compound having the structural formula ▲ Numerical formula, chemical formula, table, etc. ▼ Here R is lower alkyl. Acetoacetic acid ester having the structural formula ▲ Numerical formula, chemical formula, table, etc. are available▼ is reacted with 2,2,3-trimethyl-3-cyclopentene-1-acetaldehyde having the structural formula ▲ Numerical formula, There are chemical formulas, tables, etc. ▼ To produce a compound having the structural formula ▲ Mathematical formula, chemical formula , tables, etc. ▼ and reacting this compound with sodium borohydride to produce a compound having the structural formula ▲ mathematical formulas, chemical formulas, tables, etc. There are chemical formulas, tables, etc. ▼ Method for producing mixtures with compounds having 3, Structural formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ The dotted line here is a carbon-carbon single bond. There are compounds with the structural formula▲mathematical formulas, chemical formulas, tables, etc.▼The dotted line here is a carbon-carbon double bond. A fragrance consisting of an amount effective to emit the aromatic properties of a mixture with a compound having a combination of ordinary aromatic ingredients