Process for pongamol enrichment of karanja oil

Abstract

A cosmetic ingredient, that consists of a solution of at least one extract of karanja oil including pongamol (CAS 484-33-3) and karanjin (CAS 521-88-0) in at least one solvent selected from the group of the diesters having the following formula (I), or mixtures thereof: ##STR00001## In which: n is from 0 to 19; R and R, which may be identical or different, are alkyls derived from an esterification by a linear or branched alcohol of molecular formula C.sub.xH.sub.2x+2O, x being from 1 to 30, from 1 to 20, and from 1 to 10. R is either a hydrogen atom or a C.sub.1-C.sub.3 alkyl group, which also relates to a process of selective precipitation, to a cosmetic formulation and also to the uses thereof.

Claims

1. A cosmetic ingredient, that consists of a solution of at least one extract of karanja oil comprising pongamol (CAS 484-33-3) and karanjin (CAS 521-88-0) in at least one solvent selected from the group of compounds having the following formula (I), or mixtures thereof: ##STR00016## in which: n is from 0 to 19; R and R, which may be identical or different, are alkyls derived from an esterification by a linear or branched alcohol of molecular formula C.sub.xH.sub.2x+2O, x being from 1 to 30, R is either a hydrogen atom or a C.sub.1-C.sub.3 alkyl group.

2. The cosmetic ingredient according to claim 1, wherein at least one solvent is selected from the group consisting of the sebacates (n=7), the adipates (n=3), the succinates (n=1), the dodecanedioates (n=9), the azelates (n=6), the glutarates (n=2), the malonates (n=0), and mixtures thereof.

3. The cosmetic ingredient according to claim 1, wherein at least one solvent is selected from the group consisting of the sebacates (n=7).

4. The cosmetic ingredient according claim 1, wherein at least one solvent is diethyl sebacate (CAS 110-40-7).

5. The cosmetic ingredient according to claim 1, wherein the mass percentage of said at least one solvent in said solution is from 20% to 60%.

6. The cosmetic ingredient according to claim 1, wherein the mass percentage of pongamol in said solution is greater than 1.30%.

7. The cosmetic ingredient according to claim 1, wherein the mass percentage of karanjin in said solution is less than 6%.

8. The cosmetic ingredient according to claim 1, wherein the m.sub.pongamol/m.sub.karanjin ratio in said solution is greater than 0.5.

9. A cosmetic formulation, wherein: at least one cosmetic ingredient according to claim 1 and at least one cosmetically acceptable vehicle.

10. A method comprising applying a solar cosmetic formulation and/or as an anti-aging cosmetic formulation as a cosmetic formulation according to claim 9.

11. A process of selective precipitation of pongamol (CAS 484-33-3) in a karanja oil comprising pongamol (CAS 484-33-3) and karanjin (CAS 521-88-0), wherein: 1) at least one step of addition to said at least one karanja oil of at least one solvent selected from the group of the diesters having the following formula (I), or mixtures thereof: ##STR00017## in which: n is from 0 to 19; R and R, which may be identical or different, are alkyls derived from an esterification by a linear or branched alcohol of molecular formula C.sub.xH.sub.2x+2O, x being from 1 from 30, R is either a hydrogen atom or a C.sub.1-C.sub.3 alkyl group; said addition having the effect of forming a light phase in the form of a solution and a heavy phase in the form of a precipitate; and 2) at least one step of separation of the two phases obtained.

12. The process according to claim 11, wherein at least one solvent is selected from the group consisting of the sebacates (n=7), the adipates (n=3), the succinates (n=1), the dodecanedioates (n=9), the azelates (n=6), the glutarates (n=2), the malonates (n=0), and mixtures thereof.

13. The process according to claim 11, wherein at least one solvent is selected from the group consisting of the sebacates (n=7).

14. The process according to claim 11, wherein at least one solvent is diethyl sebacate (CAS 110-40-7).

15. The process according to claim 11, wherein in said step 1), the mass proportion of said at least one solvent introduced into said at least one karanja oil is from 60/40 to 20/80.

16. The process according to claim 11, wherein it includes, in addition, at least one preliminary step of deodorization of said at least one karanja oil and/or at least one preliminary step of distillation of said at least one karanja oil, said steps, when they are both present, being capable of being carried out in any order.

Description

EXAMPLES

Example 1: Determination of the Mass Percentage of Karanjin and of Pongamol by Liquid Phase Chromatography

(1) In all the following examples, the mass percentages of pongamol and of karanjin are measured by HPLC according to a conventional method.

(2) The column used is a Gemini NX-C18 column with reference 00G-4454-50, Phenomenex of which the characteristics are 2504.6 mm, 5 m, 110 .

(3) The reagents used are the following:

(4) TABLE-US-00001 TABLE 1 Reagents CAS number Supplier Quality, reference Water 7732-18-5 VWR HiPerSolv Formic acid 64-18-6 Aldrich Acetonitrile 75-05-8 VWR HiPerSolv Karanjin 521-88-0 Chromadex ASB-00011275-010 Pongamol 484-33-3 Biosynthis nd Dimethyl sulfoxide 67-68-5 Aldrich

(5) The analytical conditions are the following:

(6) TABLE-US-00002 TABLE 2 Parameters Set values Injector Ambient temperature Detector UV = 250 nm Oven 25 C. Flow rate 1.0 mL/min Mobile phase Pump A: Acidified water (0.1% of formic acid) Pump B: Acetonitrile t (min) % Acidified water % ACN Linear elution 0 95 5 gradient 42 0 100 45 95 5 50 95 5 Duration of 50 min the analysis Volume injected 10 L

(7) The calibration was carried out using a stock solution comprising 14.4 mg of raw karanjin standard (p=95.7%) and 33.4 mg of raw pongamol (p=90.0%) 50 mL of DMSO.

(8) The preparation of the series was carried out with DMSO.

(9) The retention times are the following:

(10) TABLE-US-00003 TABLE 3 Compounds Retention time Karanjin 28.8 min Pongamol 33.4 min

(11) The chromatogram of a calibration solution is given in FIG. 1.

(12) The chromatogram of a sample of karanja oil is given in FIG. 2.

(13) The software LC Solutions makes it possible to determine the concentration (mg/mL) of karanjin and pongamol.

Example 2: Process According to the Invention

(14) A karanja oil which has been subjected to a removal of mucilage and a deodorization, having the following concentrations of pongamol and karanjin, is used:

(15) TABLE-US-00004 TABLE 4 Acid index (mg KOH/g) 6 Pongamol mass percentage (%) 1.00 Karanjin mass percentage (%) 2.5 Pongamol/karanjin ratio 0.40
Step 1: Molecular Distillation

(16) A molecular distillation step is carried out using a KDL5 apparatus with the following conditions: distillation temperature 170 C., vacuum 10.sup.2 mbar, feed set at 250 mL/h.

(17) The mass balance of the distillation is given below:

(18) TABLE-US-00005 TABLE 5 Heavy phase (%) 91 Light phase (%) 9

(19) The light distillation phase is then characterized:

(20) TABLE-US-00006 TABLE 6 Acid index (mg KOH/g) 70.0 Pongamol mass percentage (%) 10.45 Karanjin mass percentage (%) 14.8 m.sub.pongamol/m.sub.karanjin ratio 0.71
Step 2: Precipitation of Karanjin

(21) An identical mass of dimethyl sebacate (CAS 110-40-7) is added to the karanja oil which has been subjected to the molecular distillation (the light distillation phase) (proportions 50/50).

(22) The mixture is stirred for 24 h at 15 C. A precipitate forms. The suspension obtained is then filtered through an 11 m filter.

(23) The balance of the precipitation is given below:

(24) TABLE-US-00007 TABLE 7 Light phase (supernatant) (%) 89.7 Heavy phase (precipitate) (%) 10.3

(25) The pongamol and karanjin contents in the light phase in the form of a solution and in the heavy phase in the form of a precipitate are then measured:

(26) TABLE-US-00008 TABLE 8 Pongamol mass percentage light phase (supernatant) (%) 5.58 Pongamol mass percentage heavy phase (precipitate) (%) 1.79 Karanjin mass percentage light phase (supernatant) (%) 3.18 Karanjin mass percentage heavy phase (precipitate) (%) 40.1 m.sub.pongamol/m.sub.karanjin ratio light phase (supernatant) 1.75 m.sub.pongamol/m.sub.karanjin ratio heavy phase (precipitate) 0.04

(27) The light phase or supernatant is a solution consisting of approximately 50% of diethyl sebacate (CAS 110-40-7) and approximately 50% of extract of karanja oil enriched with pongamol.

(28) The extraction yields are given below:

(29) TABLE-US-00009 TABLE 9 Pongamol extraction yield light phase 95.7 (supernatant) (%) Pongamol extraction yield heavy 4.3 phase (precipitate) (%) Karanjin extraction yield light phase 38.5 (supernatant) (%) Karanjin extraction yield heavy 61.5 phase (precipitate) (%)

(30) In conclusion, using diethyl sebacate (CAS 110-40-7) at 50/50, one gets: an elimination of 61.5% of the karanjin of the light phase or supernatant in the form of a solution; a change in the m.sub.pongamol/m.sub.karanjin ratio by a factor of 2.46 (1.75/0.71); an extraction yield of pongamol of 95.7%.

(31) The light phase or supernatant in the form of a solution, once it has been separated from the heavy phase in the form of a precipitate, is a cosmetic ingredient according to the invention consisting of a solution comprising an extract of karanja oil and diethyl sebacate (CAS 110-40-7). This cosmetic ingredient/this solution can, for example, be incorporated directly in a cosmetic formulation, without elimination of the diethyl sebacate (CAS 110-40-7) and without a step of solubilization of pongamol.

(32) This cosmetic ingredient consisting of a solution is characterized as follows:

(33) TABLE-US-00010 TABLE 10 Property Result Appearance Red/orange oil Color (Gardner scale) <16 Index of refraction (25 C.) 1.504 Density (20 C.; g/cm.sup.3) 1.034 Acid index (mg KOH/g) 36.1 Mass percentage pongamol (%) 5.58 Mass percentage karanjin (%) 3.18 Moisture content (K.F., %) <0.1

Example 3: Precipitation Tests with Other Solvents According to the Invention

(34) A molecular distillation of a karanja oil originating from another lot than the lot used in example 1 is carried out by means of an industrial thin-layer distiller, under the following conditions: distillation temperature 170 C., vacuum 10.sup.2 mbar. The karanja oil which has been subjected to the molecular distillation is characterized as follows:

(35) TABLE-US-00011 TABLE 11 Acid index (mg KOH/g) 67.0 Mass percentage pongamol (%) 2.65 Mass percentage karanjin (%) 15.5 m.sub.pongamol/m.sub.karanjin ratio 0.17

(36) The precipitation tests are then carried out on the karanja oil with different solvents: diethyl sebacate (CAS 110-40-7) (test 1); diisopropyl sebacate (CAS 7491-02-3) (test 2).

(37) The mixture is stirred for 24 h at 15 C. A precipitate forms. The suspension is then filtered through an 11 m filter.

(38) The mass balances of the tests are given below:

(39) TABLE-US-00012 TABLE 12 Test 1 2 diethyl diisopropyl sebacate (CAS sebacate (CAS Nature of the solvent 110-40-7) 7491-02-3) Solvent/karanja oil mass percentage 20/80 20/80 Light phase (supernatant) (%) 53.7 56.0 Heavy phase (precipitate) (%) 46.3 44.0

(40) The mass balances are similar.

(41) The pongamol and karanjin contents in the light phase in the form of a solution and in the heavy phase in the form of a precipitate are then measured:

(42) TABLE-US-00013 TABLE 13 Test 1 2 diethyl diisopropyl sebacate (CAS sebacate (CAS Nature of the solvent 110-40-7) 7491-02-3) Solvent/karanja oil mass percentage 20/80 20/80 Pongamol mass percentage light 2.67 2.51 phase (supernatant) (%) Pongamol mass percentage heavy 2.15 2.51 phase (precipitate) (%) Karanjin mass percentage light 0.72 4.19 phase (supernatant) (%) Karanjin mass percentage heavy 25.22 14.90 phase (precipitate) (%) m.sub.pongamol/m.sub.karanjin ratio light 3.70 0.60 phase (supernatant)

(43) The extraction yields are given below:

(44) TABLE-US-00014 TABLE 14 Test 1 2 diethyl diisopropyl sebacate (CAS sebacate (CAS Nature of the solvent 110-40-7) 7491-02-3) Solvent/karanja oil mass percentage 20/80 20/80 Pongamol extraction yield light 65.1 63.8 phase (supernatant) (%) Pongamol extraction yield heavy 34.9 36.2 phase (precipitate) (%) Karanjin extraction yield light 3.0 18.2 phase (supernatant) (%) Karanjin extraction yield heavy 97.0 81.8 phase (precipitate) (%)

(45) In conclusion, using diethyl sebacate (CAS 110-40-7) at 20/80, one gets: an elimination of 97.0% of the karanjin of the light phase or supernatant in the form of a solution; a change in the m.sub.pongamol/m.sub.karanjin ratio by a factor of 21.76 (3.70/0.17); an extraction yield of pongamol of 65.1%.

(46) In conclusion, using diisopropyl sebacate (CAS 7491-02-3) at 20/80, one gets: an elimination of 81.8% of karanjin of the light phase or supernatant in the form of a solution; a change in the m.sub.pongamol/m.sub.karanjin ratio by a factor of 3.53 (0.6/0.17); an extraction yield of pongamol of 63.8%.

(47) Diethyl sebacate is thus superior to diisopropyl sebacate insofar as its capacity to precipitate karanjin is concerned, the extraction yield of pongamol being similar.

(48) Here again, the light phase or supernatant in the form of a solution, once it has been separated from the heavy phase in the form of a precipitate, is a cosmetic ingredient according to the invention, consisting of a solution comprising an extract of karanja oil and a solvent (diethyl sebacate or diisopropyl sebacate). This cosmetic ingredient/this solution can, for example, be incorporated directly in a cosmetic formulation, without elimination of the solvent (diethyl sebacate or diisopropyl sebacate) and without a step of solubilization of pongamol.

Example 4: Precipitation Tests with Different Proportions of Diethyl Sebacate

(49) A molecular distillation is carried out under the same conditions as those described in example 1, using another lot of karanja oil. At the end of the molecular distillation, the karanja oil is characterized as follows:

(50) TABLE-US-00015 TABLE 15 Acid index (mg KOH/g) 67.0 Pongamol mass percentage (%) 3.25 Karanjin mass percentage (%) 11.4 m.sub.pongamol/m.sub.karanjin ratio 0.28

(51) Precipitation tests 1 to 8 are then carried out on the karanja oil with diethyl sebacate (CAS 110-40-7), according to different diethyl sebacate/karanja oil proportions.

(52) The light phase or supernatant in the form of a solution and the heavy phase or precipitate are separated by centrifugation.

(53) The mass balances of the tests are given below:

(54) TABLE-US-00016 TABLE 16 Test 1 2 3 4 5 6 7 8 Mass % 84/ 80/ 71.5/ 62.5/ 50/ 40/ 25/ 20/ diethyl 16 20 28.5 37.5 50 60 75 80 sebacate/ karanja oil Light phase 95.6 97.3 94.5 90.6 84.5 75.1 61.6 63.1 (supernatant) (%) Heavy phase 4.4 2.7 5.5 9.4 15.5 24.9 38.4 36.9 (precipitate) (%)

(55) The pongamol and karanjin contents in the light phase (supernatant) and in the heavy phase (precipitate) are then measured:

(56) TABLE-US-00017 TABLE 17 Test 1 2 3 4 5 6 7 8 Mass % 84/ 80/ 71.5/ 62.5/ 50/ 40/ 25/ 20/ diethyl 16 20 28.5 37.5 50 60 75 80 sebacate/ karanja oil Mass percent- 0.57 0.64 0.87 1.35 1.48 1.99 2.44 2.51 age pongamol light phase (supernatant) (%) Mass percent- 0.68 0.67 0.80 1.01 1.43 1.71 2.24 2.41 age pongamol heavy phase (precipitate) (%) Mass percent- 1.50 1.64 2.18 2.40 2.50 2.62 2.85 2.91 age karanjin light phase (supernatant) (%) Mass percent- 13.42 8.91 23.74 19.28 21.67 17.39 14.80 15.20 age karanjin heavy phase (precipitate) (%) m.sub.pongamol/ 0.38 0.39 0.40 0.56 0.59 0.76 0.86 0.86 m.sub.karanjin ratio light phase (supernatant) (%)

(57) The extraction yields are given below:

(58) TABLE-US-00018 TABLE 18 Test 1 2 3 4 5 6 7 8 Mass % 84/ 80/ 71.5/ 62.5/ 50/ 40/ 25/ 20/ diethyl 16 20 28.5 37.5 50 60 75 80 sebacate/ karanja oil Extraction 91.1 97.8 90.2 98.2 76.8 76.9 60.9 60.9 yield pongamol light phase (supernatant) (%) Extraction 8.9 2.2 9.8 1.8 23.2 23.1 39.1 39.1 yield pongamol heavy phase (precipitate) (%) Extraction 72.5 72.0 64.0 49.8 36.9 28.8 20.3 20.1 yield karanjin light phase (supernatant) (%) Extraction 27.5 28.0 36.0 50.2 63.1 71.2 79.7 79.1 yield karanjin heavy phase (precipitate) (%)

(59) A curve representing the extraction yields of pongamol and of karanjin in the light phase or supernatant in the form of a solution as a function of the diethyl sebacate proportion used is given in FIG. 3. FIG. 3 shows the change in the pongamol and karanjin extraction yields as a function of the diethyl sebacate proportion used.

(60) As a function of the pongamol and karanjin mass percentages, the proportion of solvent has to be adjusted in order to obtain a karanjin mass percentage that is in compliance with the specifications and in order to obtain a m.sub.pongamol/m.sub.karanjin ratio greater than or equal to 0.5.

(61) Here again, in particular for tests 4-8, the light phase or supernatant in the form of a solution, once it has been separated from the heavy phase or precipitate, is a cosmetic ingredient according to the invention consisting of a solution comprising an extract of karanja oil and diethyl sebacate. This cosmetic ingredient/this solution can, for example, be incorporated directly in a cosmetic formulation, without removal of the diethyl sebacate and without a step of solubilization of the pongamol.

Example 5: Formulation Example According to the Invention

(62) A formulation example according to the invention and an example of an operating procedure are given below:

(63) TABLE-US-00019 TABLE 19 % by Ingredient weight Supplier Phase A Light phase or supernatant in the form of a 7.5 Biosynthis solution = cosmetic ingredient according to the invention (solvent: diethyl sebacate) Ethylhexyl salicylate 5.0 Symrise Octocrylene (CAS 6197-30-4) 2.0 DSM Avobenzone (CAS 70356-09-1) 2.0 DSM Phase B Caprylyl Methicone (CAS 17955-883) 4.0 Dow Corning Coconut alkanes 3.0 Biosynthis Trimethylsiloxysilicate (and) 3.0 Dow Corning Polypropylsilsesquioxane PEG-12 Dimethicone (CAS 68937-54-2) 4.0 Dow Corning Phase C Decyl Glucoside 0.5 BASF Glycerol 5.0 Olon Deionized water 61.6 / Phase D Polyacrylamide (and) C13-14 Isoparaffin 2.0 Seppic (and) Laureth-7 Phase E Butylparaben (CAS 94-26-8) 0.4 Pharmco- AAPER

(64) The cosmetic formulation is prepared according to the following operating procedure which comprises 9 steps:

(65) 1) In a separate mixer, mix all the components of phase A, under stirring at 60 C. and until the homogenization is complete;

(66) 2) Cool to ambient temperature under constant stirring;

(67) 3) In parallel, in a second mixer, mix the constituents of phase B until complete homogenization;

(68) 4) At ambient temperature, add phases A and B, until the homogenization is complete;

(69) 5) In a third mixer, mix the constituents of phase C;

(70) 6) Mix phases (A+B) and C under stirring;

(71) 7) Stir for 20 minutes at 1500 rotations/minute;

(72) 8) Mix (A+B+C)+D, until the homogenization is complete;

(73) 9) Add E to (A+B+C+D) while maintaining the stirring.

Example 6: Protective Properties of a Cosmetic Formulation According to the Invention (In Vivo)

(74) A cosmetic ingredient according to the invention is produced according to the method presented in example 2; this cosmetic ingredient comprises approximately 50% of diethyl sebacate (supplied by ARKEMA) and approximately 50% of extract of karanja oil enriched with pongamol.

(75) The cosmetic ingredient according to the invention is then formulated; the cosmetic formulation according to the invention has the following qualitative and quantitative compositions:

(76) TABLE-US-00020 TABLE 20 % by Components weight Supplier cosmetic ingredient according to the invention 65 BIOSYNTHIS (solvent: diethyl sebacate, approximately 50%) Coconut oil gel 35 (INCI: Coconut oil and 30 BIOSYNTHIS dilinoleic acid/Propanediol/Octyldodecanol copolymer) Trihydroxystearin (CAS 139-44-6) 5 BASF/Cognis

(77) The Sun Protection Factor (SPF) was determined for the cosmetic formulation according to the invention according to the recommendations of the International Standard ISO 24444 (November 2010) using a panel of three subjects.

(78) The results obtained are presented in the table below:

(79) TABLE-US-00021 TABLE 21 iSPF iSPF formu- standard Photo- MED MED lation product Subject Age ITA type up p tested P2 Subject 1 54 50.7 II 31.1 1642.6 52.9 16.0 Subject 2 26 41.1 III 32.0 1946.7 60.8 16.0 Subject 3 48 52.6 II 26.0 1581.7 60.8 16.0 Mean 58.2 16.0 Standard deviation 4.6 0.0 MEDup: Minimal Erythemal Dose of the unprotected skin MEDp: Minimal Erythemal Dose of the protected skin iSPF: Individual Sun Protection Factor ITA: Individual Typology Angle

(80) The cosmetic formulation according to the invention has a mean SPF equal to 58.2, which corresponds to a high degree of sun protection.

(81) The good sunscreen properties of the cosmetic formulation according to the invention are thus confirmed in vivo.

Example 7: Protective Properties of a Cosmetic Ingredient According to the Invention (In Vitro)

(82) A cosmetic ingredient according to the invention is prepared according to the method presented in example 2; this cosmetic ingredient comprises approximately 50% of diethyl sebacate and approximately 50% of extract of karanja oil enriched with pongamol.

(83) For the cosmetic ingredient according to the invention and for a deodorized karanja oil, the Sun Protection Factor was determined by means of PMMA plates according to the method described in the publication Pissavini et al., Determination of the in vitro FPS, Cosmetics and toiletries, 2003, vol. 118, No. 10, pp. 63-72.

(84) The results obtained are presented in the table below:

(85) TABLE-US-00022 TABLE 22 UVA Mass protection/ percentage of SPF/ UVA IR Composition pongamol (%) SPF IR protection Deodorized Karanja oil 1.4 18.2/12.7 9.9/7.8 Cosmetic ingredient according 7.7 190/174 76/72 to the invention PMMA control NA 25.7 9.0 SPF: Sun Protection Factor IR: after irradiation SPF IR: Sun Protection Factor after irradiation

(86) The cosmetic ingredient according to the invention has a very high SPF compared to that of the deodorized Karanja oil.

(87) The good sunscreen properties of the cosmetic ingredient according to the invention are thus confirmed in vitro.

(88) One notes that the cosmetic ingredient according to the invention has an SPF increased by a factor of more than 10, and a UVA protection which is also increased by a factor close to 10.

(89) Also, the irradiation of the cosmetic ingredient according to the invention has relatively little influence on the SPF (from 190 to 174, the SPF is decreased by approximately 9%) and on the UVA protection (from 76 to 72, the UVA protection is decreased by approximately 5%), while the irradiation of the deodorized karanja oil has much influence on the SPF (from 18.2 to 12.7, the SPF is decreased by approximately 30%) and on the UVA protection (from 9.9 to 7.8, the UVA protection is decreased by approximately 20%).