WO2000004871A1

WO2000004871A1 - Fragrance composition

Info

Publication number: WO2000004871A1
Application number: PCT/AU1999/000586
Authority: WO
Inventors: Stephanie Smith
Original assignee: Bretts Pty. Limited
Priority date: 1998-07-22
Filing date: 1999-07-21
Publication date: 2000-02-03
Also published as: AUPP483698A0

Abstract

An extract from the genus Callitris, the extract containing components that offer an attractive fragrance that should find use in perfumes, colognes and perfumed articles. The preferred members of the genus Callitris are Callitris glaucophylla, Callitris intratropica and Callitris columellaris. The extract is obtained by steam distillation and the resultant oil is washed with sodium bicarbonate solution.

Description

TITLE: FRAGRANCE COMPOSITION

THIS INVENTION relates to perfumery. In particular, it is directed, but not limited, to a fragrance composition of use in perfumes, colognes and perfumed articles.

The cosmetic industry is a multi-billion dollar industry world wide. Of particular interest are perfumes. A number of companies and individuals are famous for perfumes, their distinctive fragrance recognisable as originating from a particular source. This distinctiveness represents a valuable commodity for the individual company responsible for that particular fragrance. Perfumes and related cosmetics are often based on essential oils obtained from plant extracts. Although some natural fragrances can be reproduced by synthetic means, today's consumers are turning more and more to products derived from natural sources.

With the general public increasingly questioning the use of synthetic chemicals, and governments promulgating legislation which bans the use of such chemicals, there remains a demand for perfumes and related products which are derived from natural products, thus eliminating, or at least reducing, the environmental concerns expressed by the public in the use of synthetic chemicals.

Further, timber remains a favoured material used in the construction of buildings and furniture. Pine timber is particularly popular. Of all the Australian pines (conifers), the genus Callitris has the most extensive geographical distribution. Two of its varieties, the "white cypress pine" and to a lesser extent the "black cypress pine" have achieved considerable importance as sources of an aromatic and highly durable timber. The wood is termite resistant and is used for fence posts and in house building for foundation posts, wood panelling etc.

White cypress pine is preferred to black cypress pine owing to fewer knots present in the timber. Apart from very extensive natural stands, white cypress pine is grown on a very large scale in several State forests. As a consequence of the popularity of timber as a construction material, the timber processing industry has large quantities of sawdust which have to be disposed of, once again, according to strict government regulations. A favoured method of disposal is by burning. Therefore, if at least some of this sawdust could be further processed to provide a new and valuable product for the timber industry, this would also reduce the quantity of sawdust to be disposed of by burning with a consequent reduction in running costs for the timber mills.

Thus, any chemical which is naturally occurring and functions effectively as a cosmetic, particularly as a perfume, and which can be manufactured from a material which is currently simply disposed of, would be of value.

It is a general object of the present invention to overcome, or at least ameliorate, one or more of the above disadvantages.

It has been discovered that the general object can be achieved using an extract from the genus Callitris, the extract containing components that offer an attractive fragrance.

According to a first aspect of the present invention, there is provided an extract from the genus Callitris of use in perfumery, said extract prepared by:

a. extracting a member of the genus Callitris with a solvent that removes from said member at least those components which exhibit a fragrance suitable for said use;

and

removing said solvent to obtain said extract.

Preferably, the member is selected from the group Callitris glaucophylla, Callitris intratropica and Callitris columellaris. More preferably, the member is Callitris columellaris F. Muell or Callitris columellaris var. campestris Silba.

Preferably, said solvent is water and said extract is obtained by steam distillation.

Preferably, said extract is further treated to remove any acids present therein.

More preferably, said acids are removed by washing said extract with a sodium bicarbonate solution.

Optionally, the extracts of the present invention may also include a carrier, diluent or adjuvant.

As used throughout the specification, the term "carrier or diluent" denotes an organic or inorganic, natural or synthetic material with which the aforementioned extract is combined in order to facilitate the use of that extract in perfumery. This carrier or diluent is generally inert. Similarly, the term "adjuvant" has the usual meaning in the art to describe a material which aids the operation of the extract.

Preferred embodiments of the present invention will now be described with reference the following examples.

Example A

Extraction Procedure

Callitris columellaris F. Muell sawdust (3480g) was covered with water and heated under reflux for 24 hours with a Dean-Stark trap attached. The water was separated from the resultant oil to yield a sweet smelling oil (48g) having the following physical properties:

Refractive Index = 1.4895 at 20°C. Density = 0.9677g/ml at 20°C.

Solubility in ethanol = 10ml of oil/50ml of 70% ethanol to give a clear solution.

Flash Point = 105°C.

Optical rotation = +4.327° at 21.8°C with path length of 100.02mm and wavelength Na 589nm.

Chemical Analysis of Extract

A few mg of Example A were dissolved in dichloromethane and analysed on a BP- 5 column. The library matches from the resultant chromatogram are reported in the table on the following page. In general only matches of 90% or greater are reported. Peak areas have been normalised to the largest peak at 100.

CAS registry numbers for selected compounds:

Compound (1): 1 ,2,3a,4,5,6,7-octahydro-3,8-tetramethyh-5-azulenemethanol. CAS 022451-73-6 Compound (2): 3,5,8,-trimethyl-3a,4,4a,5,6,7,9,9a-octahydrozuleno-

(6,5b)furan-2(3H)- one. CAS 066873-38-9.

Compound(3): 5,8-dimethyl-3-methylene-3a,4,4a,5,6,7,9,9a- octahydrozuleno-(6,5b)furan-2(3H)-one. CAS 066873-37-8.

^* Identity of this peak was confirmed as guaiol by comparison of retention times with an authentic sample.

Analysis of a further Example B, prepared by a method similar to that described above with reference to Example A, established that the oil contained about 30% acids, a percentage usually too high for use in perfumery. The oil was thus washed with sodium bicarbonate according to the following procedure.

The wood oil (10g) was dissolved in light petroleum (b.p.60-80°C) (60ml_) and the slightly opalescent solution was shaken with several lots of saturated aqueous sodium bicarbonate solution (5 x 50ml_) until all effervescence had ceased. The organic (upper) layer was separated, dried with anhydrous sodium sulphate and decanted from the drying agent. The solution was then distilled to remove the bulk of the light petroleum (using a rotatory evaporator). The product was a pale brown oil which partly crystallised on standing at 20°C.

As the thus washed oil had partly crystallised, the crystals were dissolved by warming at 60°C prior to analysis. A few mg of the oil were then dissolved in dichloromethane and analysed on a BP-5 column. The library matches of the resultant chromatogram are reported in the following table. In general only matches of 90% or greater are reported. Peak areas have been normalised to the largest peak at 100.

CAS registry numbers for selected compounds:

Compound (1): 1,2,3,3a,4,5,6,7-octahydro-3,8-tetramethyl-5- azulenemethanol. CAS 022451-73-6 Compound (2): 3,5,8-trimethyl-3a,4,4a,5,6,7,9,9a-octahydrozuleno-

(6,5b)furan-2(3H)-one.

CAS 066873-38-9

Compound (3): 5,8-dimethyl-3-methylene-3a,4,4a,5,6,7,9,9a- octahydrozulene-(6,5)furan-2(3H)-one.

CAS 066873-37-8

Compound (4): 1 ,2,3,4,4a,5,6,8a-octahydro-4a,8-dimethyl-2-(1 methylethenyl)-napthalene

CAS 000473-13-2

Identify of this peak was confirmed as guaiol by comparison of retention times with an authentic sample.

This re-analysis of the de-acidified oil confirmed the absence of acids. The fragrance of this de-acidified oil, although differing slightly from that prior to de- acidification, remained floral/woody, characteristic of the freshly cut wood.

Following the extraction procedure described in Example A, six further extracts (Samples 1 to 6) were obtained and prepared for washing with sodium bicarbonate solution according to the following procedure.

Each of samples 1 to 6 were first dried with anhydrous sodium sulphate and their appearance noted (refer to table on following page).

A mixture of wood oil (40g) and cold saturated aqueous sodium bicarbonate solution (200mL; contained about 14g of sodium bicarbonate) was stirred magnetically. After about 2 hours (when the initial evolution of carbon dioxide had subsided), an additional amount of solid sodium bicarbonate (8g) was added to the reaction mixture and stirring continued at room temperature (15°C to 20°C) for a total of 20 hours.

The resulting emulsion was diluted with water (about lOOmL) and poured into a separating funnel. For most samples, some solid floated on the surface of the liquid. A small amount of purified light petroleum (b.p. about 60°C; sometimes called "petroleum ether") was added which dissolved the solid. The upper organic layer was separated and dried with anhydrous sodium sulphate. The dry (perfectly clear) liquid was decanted from the drying agent and the bulk of the light petroleum removed by distillation under a weak vacuum. The pale brown residual oil changed on standing at room temperature (approx. 15°C to 20°C) into a partly crystallised slurry.

The yields of de-acidified wood oil are presented in the table on the following page.

It was noted that the partly crystallised products exhibited a marked thixotropic behaviour; that is, they became significantly more liquid on being stirred with a glass rod.

The physico-chemical properties of the now de-acidified Samples 1 to 6 were determined.

Refractive Index

Refractive indices were determined according to ISO 280. Owing to the semi-solid nature of the oils they were first melted at around 40 ⁼C and then slowly cooled to about 20-25 °C. The actual refractive index measurements were effected on the super-cooled liquids and are recorded in the following table:

^* The correction used was 0.0004/°C; the refractive index decreases as the temperature rises.

Optical Rotation

Due to the relatively dark colour of the oils as well as to their semi-solid state, optical rotations had to be measured in solution according to ISO 592. The precision of this test is ±0.17°.

Approximately 20%WΛ solutions were prepared by dissolving about 2g of oil, accurately weighed, in absolute ethanol and making up the solution with additional ethanol to 10ml_ in a 10ml_ volumetric flask at 20°C. The rotations were measured using a 25mm tube and are presented in the following table:

Relative Density at 20 °C

Due to the semi-solid state of the oil at 20 °C as well as its very high viscosity when supercooled to 20°C, a precise determination of the relative density at 20°C or 25°C was not feasible in the manner described in ISO/FDIS 279: 1998. An approximate value was obtained by weighing 10ml_ of the super-cooled oil using a volumetric flask of the required capacity. Using this method the approximate density at 20°C (of the supercooled liquid) ranged from 0.95 to 0.99 for the six samples of oil.

Miscibility in 80%V/V Ethanol at 20°C

The miscibility was determined according to ISO/DIS 875.

1g aliquots of each oil dissolved to a clear solution in 0.7 to LOmL of 80%V/V ethanol at 20°C.

Determination of flash point

The flash point was determined using the closed Ford cup method.

Chemical composition (by GC/MS)

The GC analysis was carried out using a DB-Wax capillary column. The results of the GC/MS are presented in the table on the following page.

The identity of these compounds was not determined conclusively.

Acid value

Acid values were determined in accordance with ISO 1242.

Ester value

Ester values were determined in accordance with ISO 709.

The results demonstrate that the present invention should find use in the cosmetic industry.

Further, it is envisaged that at least some of the sawdust that is currently burnt by the timber processing industry could be further processed to obtain the extract of the present invention thus, not only providing a new valuable commercial product to the timber industry, but also reducing the quantity of sawdust to be disposed of with a consequent reduction in running costs for the timber mills and pollution of the environment.

It will be appreciated that the above examples are illustrative only of the present invention and that modifications and alterations can be made thereto without departing from the inventive concept as defined in the following claims.

Claims

1. An extract from the genus Callitris of use in perfumery, said extract prepared by:

a. extracting a member of the genus Callitris with a solvent that removes from said member at least those components which exhibit a fragrance suitable for said use; and

b. removing said solvent to obtain said extract.

2. An extract as defined in Claim 1 , wherein said member is selected from the group Callitris glaucophylla, Callitris intratropica and Callitris columellaris.

3. An extract as defined in Claim 2, wherein said member is Callitris columellaris F. Muell or Callitris columellaris war. campestris Silba.

4. An extract as defined in any one of Claims 1 to 3, wherein said solvent is water and said extract is obtained by steam distillation.

5. An extract as defined in any one of Claims 1 to 4, wherein said extract is further treated to remove any acids present therein.

6. An extract as defined in Claim 5, wherein said acids are removed by washing said extract with a sodium bicarbonate solution.

7. An extract from genus Callitris of use in perfumery, said extract having properties:

refractive index of about 1.4895 at 20┬░C;

density of about 0.9677g/ml at 20┬░C;

solubility in ethanol of about 10ml/50ml of 70% ethanol; and

flash point of about 105┬░C.

8. An extract from genus Callitris of use in perfumery, said extract having properties:

refractive index in the range of about 1.5000 to about 1.5049 at 20┬░C;

an angle of rotation in the range of about +0.25 to about +0.5 at 20┬░C;

a specific rotation in the range of about +5.84 to about +9.75 at 20┬░C;

density in the range of about 0.95 to about 0.99g/ml at 20┬░C;

flash point of about 107┬░C;

an acid value in the range of about 13.5 to about 20.0; and

an ester value in the range of about 104.8 to about 124.1.

9. An extract as defined in any one of Claims 1 to 8, which further includes a carrier, diluent or adjuvant.

10. A perfume, cologne or perfumed article which includes an extract as defined in any one of Claims 1 to 9.