Claims:
1. A fragrance composition comprising an ester derivative of a vegetable oil and a perfumery alcohol of Formula I for rendering a long-lasting fragrance effect.

(Formula I)
wherein
R5, R6, R7 is selected from OH, a C2—C24 fatty acid moiety and an aromatic alcohol
and at least one of R5, R6, R7 is an aromatic alcohol.

2. The fragrance composition of claim 1, wherein the ester derivative renders a fragrance that is prominent until at least eight hours of application.

3. The fragrance composition of claim 1, comprising an ester derivative of 0-95% of a vegetable oil and 0.1-10% of a perfumery alcohol in addition to 0.1-2% of a profragrance, 0-95% of mineral oil, and 0.1-2% of herbal extracts.

4. The composition of claim 3, wherein the perfumery alcohol is especially, but not limited to, phenyl ethyl alcohol or benzyl alcohol; and the said vegetable oil is selected from the group consisting of, but not limited to, soy bean oil, corn oil, sunflower seed oil, high-oleic sunflower seed oil, canola oil, safflower oil, cuphea oil, jojoba oil, coconut oil and palm kernel oil.

5. The composition of claim 3, wherein the herbal extract is an extract from the herbs selected from the group consisting of, but not limited to, methi, garlic, amla, bringhraj, brahmi, and hibiscus.

6. A process for the preparation of an ester derivative of vegetable oil and a perfumery alcohol having a fragrance effect according to claims 1 - 3, comprising the transesterification in the presence of a lipase enzyme with constant stirring in the absence of oxygen.
7. A process for the preparation of the said ester derivative of claim 6, comprising the steps of
a. addition of a perfumery alcohol to a refined vegetable oil;
b. addition of a lipase enzyme;
c. stirring the slurry in the absence of oxygen for 6 – 24 hours; and
d. purification of the product through column chromatography.

8. The process according to claims 6 and 7, wherein the enzyme used in the process for the preparation of the said ester derivative, is Novozym 435-a lipase or Rhizomucor miehei.

9. The process according to claims 6 and 7, wherein the reaction is optimally conducted in the absence of oxygen, such as in vacuum or under nitrogen.

10. The process according to claims 6 and 7, wherein the temperature conditions for the reaction may range from about 45°C to about 70°C, more preferably about 55°C to about 60°C.
, Description:FIELD OF THE INVENTION

The present invention relates to a long-lasting fragrance rendering ester derivative obtained by reacting a perfumery alcohol, such as phenyl ethyl alcohol or benzyl alcohol, and a vegetable oil, such as coconut oil. The invention also relates to a process for the preparation of the said ester derivative of a perfumery alcohol and a vegetable oil, such as triglycerides of a vegetable oil.

BACKGROUND OF THE INVENTION

Since early antiquity, spices and resins from animal and plant sources have been used extensively for perfumery and flavor purpose, and to a lesser extent for their observed or presumed preservative properties. Fragrance and flavor materials vary from highly complex mixtures to stand alone chemicals. Their history began when mankind discovered that the characteristic of the aroma of natural products could be enriched using simple techniques.

The current problem associated with the fragrance industry is the retention or long-lasting effect of the fragrance. Different types of fragrance based products are available in the market which include perfumes, deodorants, gels, hair oils, etc.. But, the lingering issue is that the fragrance is not long lasting, and does not remain beyond an hour or so after which the consumer does not sense the odour. Therefore, there is a continuing need for a long-lasting fragrance or agent with enhanced effectiveness.

To fulfil their biological activity, volatile organic molecules have to be efficiently evaporated and transported by diffusion through the air to eventually reach a specific target where they are perceived as a selective signal. Bioactive volatiles are therefore generally characterized by a unique molecular structure as a prerequisite for selective recognition, combined with relatively low molecular weights, typically correlating with high vapour pressures (volatilities), to allow for an efficient evaporation into the environment. Once released into the air, the high vapour pressures of the volatile compounds result in a limited duration of their biological activity as a consequence of rapid diffusion. Nevertheless, by generating volatiles from non-volatile precursors, nature has set up a mechanism for the selective and timely release of volatile compounds to ensure their structure-related perception after delivery to the biological target via transport through the air.
As a consequence of their pleasant taste or smell to humans, many bioactive volatiles have been used since antiquity as flavours and fragrances in our everyday life. Due to their low olfactory threshold, flavours and fragrances can easily be detected by humans, even when used in very low concentrations.

As the performance of perfumed consumer articles is often judged by the duration of fragrance perception, the development of delivery system to control the release of natural and synthetic fragrance raw materials has become an important research area in the flavours and fragrance industry.

The release of natural and synthetic fragrance raw materials has become an important research area in the flavours and fragrance industry. Apart from the development of specific matrices or capsules for the diffusion-controlled release of volatiles, the preparation of fragrance precursors, the so called ‘profragrances’ (if a single perfumery raw material is released) or ‘properfumes’ (if multiple volatiles can be generated from the same molecule) has systematically been investigated. The active volatile is covalently bound to a well-defined substrate to form an ideally non-volatile and odourless precursor, the size of which can range from small molecular systems to polymer structures. For the release of the fragrance, the covalent bond has to be cleaved under mild conditions which are prevalent in the environment during the application of the product. Typical triggers that have successfully been used to release volatiles from their corresponding precursors comprise variations of temperature, duration and extent of exposure to light, aqueous hydrolysis (including change in pH), oxidation and the action of enzymes from different microorganisms or bacteria.

To overcome the aforementioned problems, the inventors have come up with an ester derivative of a perfumery alcohol and a vegetable oil, which exhibits a long-lasting effect.

OBJECT OF THE PRESENT INVENTION

The primary object of the present invention is to provide a fragrance composition which has a long-lasting effect.

Another object of the present invention is to provide long-lasting fragrance rendering ester derivative of phenyl ethyl alcohol, benzyl alcohol or any other perfumery alcohol, and a vegetable oil, particularly coconut oil.

Still another object of the present invention is to provide a process for the preparation of an ester derivative of a perfumery alcohol and the triglycerides of a vegetable oil which imparts a long-lasting effect.

SUMMARY OF THE PRESENT INVENTION

The present invention relates to a long-lasting fragrance rendering ester derivative of phenyl ethyl alcohol, benzyl alcohol or any other perfumery alcohol, and a vegetable oil, particularly coconut oil. The perfumery alcohol used in fragrances imparts a characteristic smell. For instance, phenyl ethyl alcohol corresponds to rosy smell. The invention also relates to a process for the preparation of an ester derivative of a perfumery alcohol and a vegetable oil, particularly triglycerides of a vegetable oil such as coconut oil.

In accordance with the present invention, the said ester derivative is obtained by the trans-esterification of triglycerides of the vegetable oil and a perfumery alcohol such as phenyl ethyl alcohol as shown in fig. 1.

In accordance with another embodiment of the present invention, the said ester derivative is obtained by the trans-esterification of triglycerides of the vegetable oil and benzyl alcohol as shown in fig. 2.

The present invention also provides a process for the preparation of an ester derivative of a vegetable oil and a perfumery alcohol such as phenyl ethyl alcohol (I) and benzyl alcohol which imparts a fragrance effect that is long-lasting. The process comprises of the reaction of a refined vegetable oil comprising triglycerides, with the perfumery alcohol in the presence of Novozym® 435 while stirring at 45 - 70°C under nitrogen followed by the purification of the product to remove the excess reactant present in the reaction mixture.

The present invention also provides a fragrance composition comprising the aforementioned ester derivative of a vegetable oil and a perfumery alcohol apart from a pro-fragrance, mineral oil, and herbal extracts.

For the accomplishment of the above and related objects, the invention may be embodied in the form described in the following description. Attention is called to the fact, however, that the examples presented are illustrative only and not to be considered to be limiting. Variations are contemplated as being part of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a schematic representation of trans-esterification of coconut oil with phenyl ethyl alcohol;
Fig. 2 is a schematic representation of trans-esterification of coconut oil with benzyl alcohol;
Fig. 3 & Fig. 4 represent the thin layer chromatogram (TLC) of the product in phosphomolybdic acid and in an UV chamber respectively where the perfumery alcohol is phenyl ethyl alcohol;
Fig. 5 & Fig. 6 represent the TLC of the product in phosphomolybdic acid and in an UV chamber respectively where the perfumery alcohol is benzyl alcohol;
Fig. 7 is a HPLC-MS chromatogram for the premix of coconut oil with phenyl ethyl alcohol;
Fig. 8 is a HPLC-MS chromatogram for the product after the reaction of coconut oil with phenyl ethyl alcohol;
Fig. 9 is an UV spectra of the ester of phenyl ethyl alcohol which confirms the lambda max value is around 258 nm;
Fig. 10 is a FTIR spectra which confirms the presence of a C=O group at around 1736 cm-1.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

In the present invention, the ester derivative of a perfumery alcohol such as phenyl ethyl alcohol and benzyl alcohol, and a vegetable oil, is claimed which is employed for achieving a fragrance effect that is long-lasting.

In the present invention, the formation of the ester derivative of a perfumery alcohol such as phenyl ethyl alcohol and benzyl alcohol, with a vegetable oil, is also claimed which is employed for achieving a fragrance effect that is long-lasting.

In accordance with the present invention, the said product of the present invention is obtained by the trans-esterification of triglycerides of the vegetable oil and phenyl ethyl alcohol, benzyl alcohol or any other perfumery alcohol.

The present invention also provides a process for the preparation of an ester derivative of a vegetable oil and a perfumery alcohol such as phenyl ethyl alcohol (I) which imparts a fragrance effect, comprising of
a. transfer of 1 mole ratio of refined vegetable oil comprising triglycerides, to a round bottom flask;
b. addition of 1 mole ratio of phenyl ethyl alcohol (Sigma-Aldrich®);
c. addition of Novozym® 435 while stirring at 45 - 70°C under nitrogen for 30-60 mins;
d. stirring the slurry for 6 to 24 hrs.

The said enzyme used in the process of the preparation of the ester is Novozym 435-a lipase obtained from Candida antarctica or Rhizomucor miehei. This is enzyme on an inert support and is produced by Novozymes (Krogshoejvej, 2880 Denmark).

The trans-esterification (glycerolysis) reaction is optimally conducted in the absence of oxygen, such as in vacuum or under nitrogen.

According to one embodiment, the reaction may be carried out in a solvent-free system.

According to another embodiment, alcohol-free solvents may be used or alternatively solvents such as toluene or any other solvent like mesitylene, xylene, DMSO, DMF suitable for usage with the triglycerides, phenyl ethyl alcohol and the lipase catalyst, may be considered.

The temperature conditions for the reaction may range from about 45 – 70 °C, with the preferred temperatures being in the range of about 55 - 60 °C.

In laboratory experiments with phenyl ethyl alcohol or any other perfumery alcohol and coconut oil in a solvent-free system, the reaction attained equilibrium in approximately 6 – 24 hours.

The said triglycerides are sourced from a vegetable oil selected from the group consisting of but not limited to, coconut oil, soy bean oil, corn oil, sunflower seed oil, high-oleic sunflower seed oil, canola oil, safflower oil, cuphea oil, jojoba oil, and palm kernel oil.

The said substituted triglycerides of the present invention consist of a glycerol backbone in which one of the terminal hydroxyls is substituted with a phenyl ethyl moiety as shown in Fig. 1.

The said coconut ester of the phenyl ethyl alcohol is colorless to light yellow and white when it is in the solid form. The melting point is 15°C and has a specific gravity of 0.9353 at 25ºC and a refractive index of 1.4301 at 40ºC.

Fig. 9 and Fig. 10 represent the UV-Vis and FTIR spectra of the said derivative of the present invention, respectively.

Further purification of the product was done to remove excess reactant through column chromatography using 98:2 ratios of hexane and ethyl acetate and the collected fraction was analyzed by HPLC/Mass and TLC.

The combined yield of the reaction product was around 90% (based on the total peak area by Mass and UV spectrophotometer).

The present invention also provides a fragrance composition comprising the aforementioned ester derivative of 0-95% of a vegetable oil and 0.1-10% of a perfumery alcohol in addition to 0.1-2% of a profragrance, 0-95% of mineral oil, and 0.1-2% of herbal extracts.

The following examples and experimental studies are provided for illustrative purposes only and are not limiting to this disclosure in any way. Various modifications of the invention, in addition to those shown and described herein, will become apparent to those skilled in the art from the following examples and the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

EXPERIMENTAL STUDIES

The results of the thin layer chromatography of the product of the trans-esterification of phenyl ethyl alcohol with coconut oil in phosphomolybdic acid and in an UV chamber are presented in Fig. 3 & Fig. 4 respectively. Spot-1 depicts the pure phenyl ethyl alcohol that is visible in the UV chamber as this molecule has a chromophore. Spot-2 depicts the pure coconut oil compound where the circled spot represents the triglyceride molecule and the rest represent the minor component(s). Spot-3 depicts the crude reaction mixture where the circled spot represents the ester of phenyl ethyl alcohol with coconut oil and the remaining are the unreacted raw materials. Spot-4 depicts the pure product of the coconut ester of phenyl ethyl alcohol by column chromatography.

The results of the thin layer chromatography of the product of trans-esterification of benzyl alcohol with coconut oil in phosphomolybdic acid and in UV chamber are presented in Fig. 5 and Fig. 6 respectively. Spot-1 depicts the pure benzyl alcohol that is visible in the UV chamber as this molecule has a chromophore. Spot-2 depicts the pure coconut oil compound where the circled spot represents the triglyceride molecule and the rest represent the minor component(s). Spot-3 depicts the crude reaction mixture where the circled spot represents the ester of benzyl alcohol with coconut oil and remaining are the unreacted raw materials. Spot-4 depicts the pure product of the coconut ester of benzyl alcohol by column chromatography.

Analysis of product by APCI LC/MS with UV spectroscopy
LC/MS and UV analysis of coconut oil was conducted as per the chromatographic parameters that offer the ease of an LC separation plus the specificity of mass detection.

Analysis was performed using an Agilent 1260 Infinity series (Santa Clara, CA, United States of America), consisting of an auto sampler® G1329B, Quat Pump® G1311B, VWD® G1314F and Quadrupole LC/MS® 6120 from Agilent. The HPLC column used for the analysis was Kinetex C18 (150x4.6mm, 100 A, Phenomonex®, Torrance, Calif.). The solvent was filtered using Whatman filter of 0.45µm, nylon membrane filters (Sigma-Aldrich) and degassed prior to the usage. The chromatographic parameters are as shown below.
LC Conditions:
Column: Kinetex C18, (150x4.6mm, 100 A, Phenomonex®, Torrance, Calif.)
Mobile phase: A: 70:30 Acetonitrile and Isopropyl alcohol + 25mm Ammonium
Formate
B: 10:10:80 Water: Isopropyl alcohol: n-butanol + 25mm Ammonium Formate
Gradient: Start with 20% B
at 10 min 30 % B
at 15 min 50% B
at 40 min 50% B
at 45 min 20% B
at 50 min 20% B
Flow rate: 0.5 mL/min
Column Temperature: 30 °C
Injection volume 10µL

MS Conditions
Source: APCI
Ion Mode: Positive
Vcap Voltage: 4000V
Nebulizer: 50psig
Drying gas flow: 4 L/min
Drying Gas temp: 325 0C
Corona: 4 µA
Vaporizer Temp: 300 0C
Scan range: 300-1100 m/z
Step size: 0.1 m/z
Peak width: 0.3 min
Fragmentor: 80 V

Trans-esterification of phenyl ethyl alcohol with coconut oil:
Accurately weighed 20 g (0.03 mol) of refined coconut oil was transferred to a round bottomed flask and 3.8 g (0.03 mol) of phenyl ethyl alcohol (Sigma-Aldrich®) was added. While stirring at 60oC under nitrogen for 30 mins, 2.0 g of Novozym® 435 was added and the slurry was stirred for 6 hrs. 20 µL aliquots were periodically drawn for analysis using thin layer chromatography (TLC) and HPLC-MS. The reaction reached equilibrium at 6 hrs. The combined yield of the reaction product was about 95% (based on the total peak area by Mass and UV spectrophotometer) after subjecting to column chromatography. Both the samples of the premix and the post-trans-esterification product were analyzed through LCMS using UV-Visible spectroscopy. The schematic representation of the trans-esterification of coconut oil with phenyl ethyl alcohol has been presented in Fig. 1.

Chromatogram I (shown in Fig. 7) shows the LC-MS spectra of the premix coconut oil and phenyl ethyl alcohol; the mass spectra clearly show the peaks corresponding to the triglyceride of coconut oil at different molecular weights. Chromatogram II (Fig. 7) shows the UV spectra of the same sample which confirms the presence of phenyl ethyl alcohol. Chromatogram III (Fig. 8) shows the LC-MS spectra of post-trans-esterification which confirms the presence of very little amount of coconut oil, as a major portion of the coconut oil has reacted with phenyl ethyl alcohol to form the ester derivative. Chromatogram IV (Fig. 8) confirms the UV spectra of the end product with the different peaks confirming that all the triglycerides that were initially present have converted into the desired product.

The UV spectra presented in Fig. 9 confirms that the presence of the lambda max at about 258 nm corresponds to the ester of phenyl ethyl alcohol. The FTIR spectra presented in Fig. 10 confirms the presence of C=O group which is at about 1736 cm-1. This confirms the ester formation.

Long-lasting effects on consumers:
A panel of three consumers who were trained experts was selected for this experiment and applied the product on their hair. At 0 hr, they were unable to smell any fragrance which indicated that the product was in the ester form. After one hour, they could smell the rosy fragrance which confirmed the release of phenyl ethyl alcohol by body lipase enzymes. The trained expert panel confirmed the same profiles which establish that the product formed during the reaction is long lasting.

EXAMPLE 1
Rose Formulation
The following rose mixture was prepared:
Table 1
Ingredient Parts by Weight (w/v)
Coconut oil 20
Butylated hydroxyl toluene (BHT) 0.05
Methi seed extract 0.00125
Perfume Hol 0.75
Rose oil extract 0.01
Mineral oil 80.97

According to the formulation presented in Table 1, perfume rose which is one of the ingredients has phenyl ethyl alcohol as one of the fragrance actives. The above formulation is available commercially.

EXAMPLE 2
Rose Formulation + 1% Long-lasting fragrance active
A rose mixture was prepared by adding 1% long-lasting fragrance active with a composition presented in Table 2. This formulation comprising the said long-lasting active of the present invention in an amount specified in Table 2 was compared with the formulation presented in Table 1 which is a commercially available formulation.
Table 2
Ingredient Parts by Weight (w/v)
Coconut oil 20
Butylated hydroxyl toluene (BHT) 0.05
Methi seed extract 0.00125
Perfume Hol 0.75
Rose oil extract 0.01
Mineral oil 79.18
Long-lasting fragrance active 1.00
EXAMPLE 3
Rose Formulation + 0.5% Long-lasting fragrance active
A rose mixture was prepared by adding 0.5% of the long-lasting fragrance active. This formulation comprising the said long-lasting active of the present invention in the amount specified in Table 3 was compared with the formulation presented in Table 1 which is a commercially available formulation.

Table 3
Ingredient Parts by Weight (w/v)
Coconut oil 20
Butylated hydroxyl toluene (BHT) 0.05
Methi seed extract 0.00125
Perfume Hol 0.75
Rose oil extract 0.01
Mineral oil 79.18
Long-lasting fragrance active 0.50

EXAMPLE 4
Rose Formulation + 1.5% Long-lasting fragrance active
The rose mixture presented in Table 4 was prepared by adding 1.5% of the long-lasting fragrance active. This formulation comprising the said long-lasting active of the present invention in the amount specified in Table 4 was compared with the formulation presented in Table 1 which is a commercially available formulation.

Table 4
Ingredient Parts by Weight (w/v)
Coconut oil 20
Butylated hydroxyl toluene (BHT) 0.05
Methi seed extract 0.00125
Perfume Hol 0.75
Rose oil extract 0.01
Mineral oil 79.18
Long-lasting fragrance active 1.50

Comparative studies
All the above formulations prepared in accordance with aforementioned procedures were provided to trained expert panel to evaluate the long-lasting benefit of the products in a coded format. The Standard format for evaluation was also provided to them along with the rating format as described in Table 5 and Table 6 respectively.

Table 5: Expert panel formulation evaluation
Time 1% in product Pure Product
0 Hr 5.8 5.2
2 Hrs 5.3 4.2
4 Hrs 5.0 3.2
8 Hrs 4.2 1.8

Table 6: Rating format
1 Nil
2 Very low
3 Low
4 Mild
5 Strong
6 Very Strong
It can be seen that the trained expert panel could easily recognize the difference between samples with and without the added long-lasting fragrance active after two hours of application. Initially, the trained expert panel felt that all the formulations had the same impact of the rosy smell. But after two hours, a decrease in the fragrance was observed with the control formulation while the sample containing the 1% long-lasting fragrance active was stable and its profile was the same as in the initial stage. After four hours, the control formulation showed further decrease in the fragrance intensity but the sample with the long-lasting fragrance active showed slight decrease compared to the initial stage. After eight hours, the control formulation showed very low fragrance profile while the sample with the long-lasting fragrance active showed slight decrease in the fragrance intensity. These studies confirmed that the long-lasting fragrance formulation of the present invention showed significant difference in terms of fragrance intensity compared to the control formulation. These studies prove the theory of a long-lasting fragrance effect of the formulation of the present invention that is prominent until at least eight hours of application.

While this invention has been described with reference to an illustrative embodiment, this description is not intended to be construed in a limiting sense. Various modifications of the illustrative embodiment will be apparent to persons skilled in the art upon reference to this description. It is therefore contemplated that the appended claims will cover any such modifications or embodiments as fall within the true scope of the invention.