FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
COMPLETE SPECIFICATION
(See Section 10 : Rule 13)
TITLE
Process for preparation of UV^absorbing derivative of coconut oil
APPLICANT
''Galaxy Surfactants Ltd.,
C-49/2, TTC Industrial Area, Pawne, Navi-Mumbai 400 703, Maharashtra, India.
A Public Limited Company Registered under Indian Company's Act -1956
The following specification particularly describes the nature of this invention and the manner in which it is to be performed :-

Field of invention
This invention relates to a process of manufacture of coconut oil derivative that contains cinnamoyl moiety for absorption of UV-radiation. The UV-absorbing derivative of coconut oil is useful for cosmetic preparations for both hair care and skin care.
Background and prior art
Photodegradative effect of UV-radiation on human hair is well documented. Continuous exposure to sunrays makes human hair rough and brittle, difficult to comb and lighten hair color. UV rays are reported to damage the proteins of cuticles. Prolonged irradiation results in diminished tensile strength. [R. Beyak et al, J. Soc. Cosmet. Chem. 22, 667 - 668 (1971), E. Hoting et al, J. Soc. Cosmet, Chem. 46, 85-99 (1995)]
Hair oiling is an Indian phenomenon and age old Indian habit. Hair oil, particularly coconut oil is perceived to provide benefits of nourishment, strengthening hair, faster and better growth and reducing problem of hair loss, Coconut oil also acts as conditioner and is useful for hair styling. It makes hair soft and shiny. [R. B. Mobile et al, J. Cosmet. Sci., 50, 327 - 339 (1999) and Y. K. Kamath et al, J. Cosmet. Sci, 52,169-184 (2001)]
In India alone the usage for everyday application of coconut oil for hair care is in the tune of 70,000 metric tonnes per annum. Coconut oil seems to have all the good properties for hair care. However, the only desirable property that it lacks is protecting hair from UV-radiation of sunrays.
Hence, to protect hair from damaging effect of UV-radiation of sunrays through everyday applications of coconut oil, it is necessary to incorporate a suitable oil soluble sunscreen. This can be achieved by either dissolving an UV-absorber in the oil or modifying a small percentage of coconut oil to impart UV-absorption properties. The second approach is more attractive because coconut oil doesn't lose its useful properties by partial derivatisation. Hence, it is marginally modified so as to make it useful for protecting hair on everyday basis. Thus, considering the serious damage caused by intense sunrays of Indian subcontinent and all the good virtues of coconut oil, especially for hair care, it is necessary to synthesise a derivative of coconut oil with UV-radiation absorbing unit.
Object of the invention
The main object of the present invention is to synthesise a coconut oil derivative with cinnamoyl moiety to provide protection to human hair from UV-radiation of sunrays.
Summary of the invention
The present invention provides a process for synthesis of a derivative of coconut oil containing cinnamoyl moiety, as represented by Formula Ia, Ib & Ic;
2


wherein; R is selected from saturated or unsaturated alkyl group containing from 8 to 18 carbon atoms and the percentage distribution of R is exactly the same as that of natural coconut oil;
Rx is a substituent, selected from H, halo, -OH, -NH2, -NO2, -OCH3, -N(CH3)2, alkyl groups containing from 1 to 6 carbon atoms, alkoxy groups containing from 1 to 6 carbon atoms, alkylamino or tyAf-dialkylamino groups containing from 1 to 6 carbon atoms;
n is an integer from 1 to 10;
percentage of UV-absorbing moiety from about 0.5 to 8.0 % w/w of the total coconut oil derivative;
comprising steps of

(i) reacting 1.0 mole of coconut oil of Formula la, wherein, R is an alkyl group, either saturated or unsaturated, containing from 8 to 18 carbon atoms, with 0.1 to 0.5 mole of glycerine in the presence of a basic catalyst to obtain rearranged coconut oil;
(ii) reacting rearranged coconut oil of step (i) with ethylene oxide (5 to 15 % w/w of the total quantity) at 120 - 200°C in the presence of a basic catalyst;
(iii) reacting ethylene oxide adduct of step (ii) with acid chlorides of cinnamic acid of Formula III, at 25 - 50°C in an inert solvent in the presence of a base.
Detailed description of the invention
The process described in the present invention involves three steps;
Step (i) Rearrangement of coconut oil (transesterification)
The first step involves conversion of part of coconut oil to monoglycerides and diglycerides of fatty acids. This step is carried out between coconut oil of Formula la (1.0 mole) and glycerine (0.1-0.5 mole) at about 120 - 230°C in the presence of a basic catalyst (0.2 - 2.0 % w/w) such as sodium hydroxide or sodium methoxide to give the rearranged oil which is a mixture of triglyceride (la), diglyceride (lib) and monoglyceride (Ha) with the former two being predominant. The reaction is continued till the unreacted glycerine level is less than 0.5 %. Based on saponification and hydroxyl numbers the approximate ratio of monoglyceride, Formula Ha : diglyceride, Formula lib : triglyceride :: 51 : 33 : 16 % w/w. For one mole of oil maximum two moles of glycerine can be used to give monoglyceride predominantly. However, the preferred rearranged oil is made with only 0.5 mole of glycerine and for 1.0 mole of coconut oil so that very small quantity of monoglyceride (4.2 % w/w) is generated, balanced quantity being both diglyceride and triglyceride (7 and 89 % w/w respectively). This is presumed to retain original properties of coconut oil. Thus, the percentage composition of R is the same as that is present in original fatty acid distribution of coconut oil.

Step (ii) Ethoxylation of rearranged coconut oil
After washing off the traces of unreacted glycerine from the product of step (i), it is ethoxyhted in the presence of a basic catalyst such as sodium hydroxide, methoxide, carbonate and the like,

so that the polyoxyethylene portion in the molecule is 5 - 15 % w/w of the total. The percentage of polyoxyethylene portion should not be so much to make the entire adduct or the part of the adduct water-soluble or water-dispersible. The ethoxylation is carried out at temperatures from about 120 - 200°C, preferably 150 - 160°C, with pressure ranging from 2 -10 kg/cm2. Therefore, preferable percentage w/w of ethylene oxide is 5.0 to 15 % of total ethylene oxide adduct. The purpose of adding ethylene oxide here is not to increase the hydrophilicity of coconut oil but to convert secondary hydroxyl groups in to primary hydroxyl groups for more reactivity for subsequent esterification. On ethoxylation the hydroxyl number as well as saponification number decrease by small values. Thus, n has values between 1 to 10, preferably between 2 to 4 and it represents average number of oxyethylene units. •
Step (iii) Esterification of ethylene oxide adduct
Depending upon the hydroxyl number (in other words availability of hydroxyl groups in the ethoxylated adduct) the intermediate of ethylene oxide adduct can be either completely or partly derivatised in to the corresponding cinnamoyl ester. The esterification to afford UV-absorbing derivative is done using acid chlorides of cinnamic acid in any non-protic solvent such as tetrahydrofuran, dichloromethane and the like. The organic bases employed in this step are pyridine, triethylamine or any other tertiary amine. The cinnamoyl chlorides used in the present invention can be with or without a substituent on the benzene ring. R1 is a substituent, selected from H, halo, -OH, -NH2, -NO2, -OCH3, -N(CH3)2, alky] groups containing from 1 to 6 carbon atoms, alkoxy groups containing from 1 to 6 carbon atoms, alkylamino or N,N-dialkylamino groups containing from 1 to 6 carbon atoms and the preferred position for the substituent is para. The ethoxylated adduct of rearranged triglyceride is esterified with derivatives of cinnamoyl chloride (Formula III) in the presence of bases like triethylamine or pyridine and the like. The esterification is carried out in solvents (50 - 80 % of total reaction mass) like dichloromethane or tetrahydrofuran under the blanket of nitrogen and at temperatures varying from 25 - 50°C. Thus, the ethylene oxide adduct of the rearranged coconut oil can either be fully or partly mnctionalised depending upon the desired degree of sunscreen loading.

In another embodiment, the process of the present invention relates to manufacture of UV-absorbing derivative of coconut oil, a mixture of three species represented by Formulae la, lb and Ic, in which R is an alkyl group representing fatty acids of coconut oil, R1 is para -OCH3, the average value of n = 3 from the rearranged coconut oil (a mixture of three species represented by FormuJae la, Ila and lib) that is ethoxylated (15 % w/w of oxyethylene groups) and subsequently esterified with p-methoxy cinnamoyl chloride (Formula III, R1 = -OCH3).

The product thus obtained is of pale yellow colour with E 1Cm of around 40 at λmax 310 nm in methanol. It has typical coconut oil aroma and is freely miscible with other vegetable oils. The photoprotective action on hair is demonstrated as described in Example II.
Examples
The invention will now be illustrated with the help of examples. The examples are by way of illustrations only and in no way restrict the scope of invention.
Example I
Coconut oil was purchased from Marico Industries Ltd., Mumbai. Ethylene oxide and p-methoxy cinnamoyl chloride were from Nocil and Galaxy Surfactants Ltd., Mumbai respectively.
Process for preparation of UVB-absorbing coconut oil derivative containing 4.0 % ofp-methoxv cinnamoyl unit:
It is a mixture of three species represented by Formulae la, lb and Ic, wherein, R is alkyl group from 8 to 18 carbon atoms, R1 = -OCH3 and n = 3.
The process involves three steps;
Step (i). rearrangement of coconut oil
A mixture of coconut oil (3000 g, 4.6 moles), glycerin (213 g, 2.31 moles) and sodium methoxide (0.2 % w/w on oil) was stirred under nitrogen at 220°C for 6 hours. It was then cooled and washed with water to remove traces of unreacted glycerin. Traces of water were removed under vacuum to yield pale yellow coloured rearranged coconut oil (3200 g).
It had saponification value of 239.5 and hydroxyl value of 125. The monoglyceride, diglyceride and triglyceride were found to be 16 %, 33 % and 51 % w/w respectively..
Step (ii\ ethoxvlation of intermediate obtained in step (i)
The rearranged coconut oil (30.0 g, 0.043 moles) of step (i) was reacted with ethylene oxide (5.3 g, 0.12 moles) in a pressure reactor under nitrogen blanket at 150 - 160°C (pressure of 3.0 - 5.0 kg / cm2) in the presence of sodium methoxide (0.06 g, 2.0 % of rearranged oil) for 4 hours. On cooling, the adduct was drained to give modified coconut oil as pale yellow liquid.
It had hydroxyl number of 110 and saponification value of 220. This modified oil is completely soluble in any vegetable oil and insoluble in water.
Step (iii). esterification of intermediate obtained in step (ii)
To a solution of modified coconut oil of step (ii) (50.0 g, 0.098 moles), triethylamine (3.24 g,
0.032 moles) in dichloromethane (50 ml), a solution of p-methoxy cinnamoyl chloride (2.1 g,

0.011 moles) in dichloromethane (25 ml) was added slowly and the reaction mass was stirred at room temperature for 6 hours under blanket of nitrogen After 6 hours some more dichloromethane (200 ml) was added to the reaction mass and was washed with water (100 ml). The organic layer obtained was washed with dilute hydrochloric acid (100 ml) followed by washing with water (100 ml). The solvent (dichloromethane) was evaporated using rotary evaporator to yield 48.8 g (97.6 % yield) of derivatised modified coconut oil as yellow coloured liquid.
E1% 1cm of this product was found to be 32 at λmax 310 nm in methanol.
IR (neat) : 1745 cm"1 (carbonyl of ester), 2850 - 2900 cm'1 (methylenes of alkyl), 3500 cm'1 (hydroxyl)
HPLC was performed with following chromatographic conditions;
Column: OmniSpher C18 - 5\x
Mobile phase : 60 : 40 :: Methanol: Water.
Flow rate : 1.0 ml / min.
UV detection at: 310 nm
Chromatographic analysis confirmed the covalent bonding of UV-absorbing moiety to coconut
oil.
'H NMR (CDC13): Showed the AB pattern for aromatic protons and the two doublets for vinylic
protons.
Thus, the NMR confirmed the presence of p-methoxy cinnamoyl unit on glycerides.
Example II
Process for preparation of UVB-absorbing coconut oil derivative containing 8.0 % of p-methoxv cinnamoyl unit:
It is a mixture of three species represented by Formulae la, lb and Ic, wherein, R is alkyl group from 8 to 18 carbon atoms, R1 = -OCH3 and n = 3.
The process involves three steps, the step (i) and step (ii) were performed exactly as per the procedure described in Example I.
Step (iii). esterification of intermediate obtained in step (ii)
To a solution of modified coconut oil of step (ii) (25.0 g, 0.0.049 moles), triethylamine (3.03 g, 0.030 moles) in dichloromethane (25 ml), a solution of p-methoxy cinnamoyl chloride (2.0 g, 0.010 moles) in dichloromethane (15 ml) was added slowly and the reaction mass was stirred at room temperature for 6 hours under blanket of nitrogen. After 6 hours some more dichloromethane (100 ml) was added to the reaction mass and was washed with water (50 ml). The organic layer obtained was washed with dilute hydrochloric acid (50 ml) followed by washing with water (50 ml). The solvent (dichloromethane) was evaporated using rotary evaporator to yield 24.3 g (97.2 % yield) of derivatised modified coconut oil as yellow coloured liquid.

E1o/o lcm of this product was found to be 66 at λmax 310 nm in methanol.
IR (neat) : 1742 cm-1 (carbonyl of ester), 2854 cm'1, 2924 cm'1 (methylenes), 3438 cm' (hydroxyl).
Photoprotection of hair :
Hair oil preparations containing 2.0 % of the compound of Example II in coconut oil was prepared. Hair tresses that were treated with above preparation as well as the untreated hair tresses were simultaneously exposed to UV-radiation for 100 hours. The intensity of UV lamp was 57 µW / cm2 at 350 nm The hair tresses were then washed with 10 % SLES solution. The protected hair showed 66 % protection compared to unprotected hair on the basis of combing work measurement on DiaStron Tensile Tester, MITT 170.

Advantage of the process of the present invention:
The main advantage of derivatised coconut oil is to incorporate an UV-absorbing unit for protecting hair from damaging effect of sunrays. Use of partially modified coconut oil of the present invention for hair care offers all the benefits of natural coconut oil with an additional property of being protective against UV-radiation and hence it is very useful for everyday use especially in the Indian subcontinent with intense sun radiation.
Many hair care preparations contain light sensitive natural ingredients, vitamins and cosmetic colorants. Thus, the UV-absorbing coconut oil is suitable not only for protecting human hair but it can protect the cosmetic preparation from the damaging effect of UV-radiation. Derivatised coconut oil of the present invention can also be used as sunscreen for skin. A skin care preparation containing UV-absorbing coconut oil of the present invention is particularly useful for 'beach products' because of their substantivity to skin, excellent spreadability and water repellency. Thus, it is useful for water-proof sunscreen preparations.

We claim
1. A process for preparation of UV-absorbing derivative of coconut oil containing cinnamoyl moiety, as represented by Formula Ia, Ib & Ic;

wherein; R is selected from saturated or unsaturated alkyl group containing from 8 to 18 carbon atoms and the percentage distribution of R is exactly the same as that of natural coconut oil;
R1 is a substituent, selected from H, halo, -OH, -NH2, -NO2, -OCH3, -N(CH3)2, alkyl groups containing from 1 to 6 carbon atoms, alkoxy groups containing from 1 to 6 carbon atoms, alkylamino or N,N-dialkylamino groups containing from 1 to 6 carbon atoms;
n is an integer from 1 to 10;

comprising steps of
(i) reacting 1.0 mole of coconut oil of Formula Ia, wherein, R is an alkyl group, either saturated or unsaturated, containing from 8 to 18 carbon atoms, with 0.1 to 0.5 mole of glycerine in the
presence of a basic catalyst to obtain rearranged coconut oil;
1 j
(ii) reacting rearranged coconut oil of step (i) with ethylene oxide (5 to 15 % w/w of the total quantity) at 120 - 200°C in the presence of a basic catalyst;
(iii) reacting ethylene oxide adduct of step (ii) with acid chlorides of cinnamic acid of Formula III,
at 25 - 50°C in an inert solvent in the presence of a base to give UV-absorbing Ib and Ic. along with
unreacted Ia as a mixture.

A process as claimed in claim 1, wherein, an UV-absorbing derivative of coconut oil is manufactured that is a mixture of three species represented by Formulae Ia, Ib and Ic, in which R is analkyl group representing fatty acids of coconut oil, R1 is para -OCH3, the average value
For GALAXY SURFACTANTS LTD.

Dated this 5th day of September, 2001.

Authorised Signatory
(Dr. Nirmal Koshti) Galaxy Surfactants Limited. C-49/2, TTC Industrial Area, Pawne, Navi Mumbai - 400 703 (Applicant)


Indian Patent Appln. No. 852 / Mum / 2001. Galaxy Surfactants Limited.

Two sheets Sheet No. 1
For GALAXY SURFACTANTS LTD.
Authorised Signatory (Applicant)


Indian Patent Appln. No. 852 / Mum / 2001. Galaxy Surfactants Limited.

Two sheets Sheet No.2
For GALAXY SURFACTANTS LTD.
Authorised Signatory
(Applicant)