Gelling agent for oil

A compound represented by the following general formula (I), wherein R 1 and R 2 represent a hydrocarbon group having 1 to 26 carbon atoms, preferably a linear or branched alkyl group, R3 represents a hydrocarbon group having 7 to 10 carbon atoms, preferably a linear or branched alkyl group, n represents 1 or 2 provided that the acidic amino acid residue in the molecule is L-aspartic acid residue when n is 1 and said acidic amino acid residue is L-glutamic acid residue when n is 2, and a gelling agent for an oil comprising said compound. 1

EXAMPLES The present invention will be explained more specifically with reference to the following examples. However, the present invention is not limited to the following examples. 
 Example 1 
 Preparation of N-2-(R,S)-ethylhexanoyl-L-glutamic Acid Dibutylamide 110 g of sodium glutamate monohydrate was dissolved in 140 g of water and 78 g of 27% aqueous sodium hydroxide and the solution was cooled to 10° C. The solution was added with 110 g of acetone and added dropwise with 87 g of 2-ethylhexanoyl chloride and 78 g of 27% aqueous sodium hydroxide. The reaction mixture for the acylation was diluted with 100 g of water and neutralized with 63 g of 95% sulfuric acid to separate an oil. The aqueous layer was removed, and the oil layer was concentrated under reduced pressure to obtain an oily substance. The resulting oily substance was dissolved in 742 g of methanol, and the solution was added with 6.2 g of 95% sulfuric acid and refluxed for 9 hours. The reaction mixture was left stand for cooling to 35° C. and neutralized with 8.8 g of n-butylamine, and then the methanol was evaporated to obtain an oily substance. The resulting oily substance was added with 643 g of toluene and 271 g of n-butylamine and the mixture was stirred with heating at 90° C. for 10 hours. The reaction mixture was added with 506 g of warm water and 130 g of 95% sulfuric acid to separate an oil, and the aqueous layer was removed. The oil layer was added with 1200 g of warm water, and the solvent was removed under ordinary pressure to obtain slurry of white solid. This solid was collected by filtration and dried in vacuo at 50° C. to obtain 2-ethylhexanoylglutamic acid dibutylamide. (a) 13 C-NMR peaks (solvent: CDCl 3 ): 12.04, 12.07, 13.74, 13.96, 13.99, 20.08, 20.11, 22.70, 22.74, 26.01, 29.83, 31.56, 31.60, 32.37, 33.05, 39.29, 39.53, 49.37, 52.53, 52.56, 171.29, 173.03, 176.66 (ppm) (b) 1 H-NMR peaks (CDCl 3 ) &dgr;:3.248 (m, 4H), 4.373 (m, 1H), 6.199 (brs, 1H), 7.079 (brs, 1H), 7.169 (brs, 1H) (c) Wave number of infrared absorption spectrum: 3291.7, 2961.0, 2932.5, 1638.2, 1551.2, 1452.6 (cm −1 ) (d) MS: 382.3 (M−H) − 
 Example 2 
 Preparation of N-octanoyl-L-glutamic Acid Dibutylamide 110 g of sodium glutamate monohydrate was dissolved in 140 g of water and 78 g of 27% aqueous sodium hydroxide and cooled to 10° C. The solution was added with 110 g of acetone and added dropwise with 87 g of octanoyl chloride and 90 g of 27% aqueous sodium hydroxide. The reaction mixture for the acylation was diluted with 100 g of water and neutralized with 64 g of 95% sulfuric acid to separate an oil. The aqueous layer was removed, and the oil layer was concentrated under reduced pressure to obtain an oily substance. The resulting oily substance was dissolved in 742 g of methanol, and the solution was added with 6.2 g of 95% sulfuric acid and refluxed for 9 hours. The reaction mixture was left stand for cooling to 35° C. and neutralized with 10.5 g of n-butylamine, and then the methanol was evaporated to obtain an oily substance. The resulting oily substance was added with 630 g of toluene and 191 g of n-butylamine and the mixture was stirred with heating at 90° C. for 10 hours. The reaction mixture was added with 500 g of warm water and 178 g of 95% sulfuric acid to separate an oil, and the aqueous layer was removed. The oil layer was added with 645 g of warm water, and the solvent was removed under ordinary pressure to obtain slurry of white solid. The resulting solid was collected by filtration and dried in vacuo at 50° C. to obtain octanoylglutamic acid dibutylamide. (a) 13 C-NMR peaks: 14.10, 14.43, 20.44, 22.98, 26.07, 29.38, 29.61, 29.86, 31.92, 31.97, 32.06, 33.44, 37.07, 39.69, 39.88, 52.91, 171.61, 173.33, 174.17 (ppm) (b) 1 H-NMR peaks (CDCl 3 ) &dgr; :3.247 (m, 4H), 4.360 (m, 1H), 6.201 (brs, 1H), 6.987 (brs, 1H), 7.039 (brs, 1H) (C) Wave number of infrared absorption spectrum: 3292.8, 2958.3, 2930.4, 1640.1, 1543.0, 1450.3 (cm −1 ) (d) MS: 382.3 (M−H) − 
 Example 3 
 Preparation method of N-decanoyl-L-glutamic Acid Dibutylamide In a manner similar to that of the aforementioned Example 1, N-decanoyl-L-glutamic acid dibutylamide was prepared. (a) 13 C-NMR peaks: 14.10, 14.47, 20.44, 20.48, 23.04, 26.07, 29.65, 29.67, 29.73, 29.83, 29.88, 31.92, 31.97, 32.24, 37.08, 39.70, 39.88, 52.90, 171.60, 173.33, 174.17 (ppm) (b) 1 H-NMR peaks (CDCl 3 ) &dgr; :3.250 (m, 4H), 4.360 (m, 1H), 6.190 (brs, 1H), 6.980 (brs, 1H), 7.030 (brs, 1H) (c) Wave number of infrared absorption spectrum: 3294.8, 2959.0, 2927.5, 1637.9, 1556.0, 1466.6 (cm −1 ) (d) MS: 410.5 (M−H) − Ethyloylglutamic acid dibutylamide, hexanoylglutamic acid dibutylamide, myristoylglutamic acid dibutylamide and palmitoylglutamic acid dibutylamide used in the following comparative examples were produced in a similar manner. 
 Examples 4 to 6 
 Preparation of Gel Compositions 0.2 g of each N-acylglutamic acid dibutylamide shown in Table 1 was added to 20 g of each oil and dissolved by heating on an oil bath at 150° C., and then the resulting solution was left stand at 23° C. for 15 hours for cooling to obtain each gel composition. Gel strength of each of the resulting gel compositions was measured by using a rheometer (FUDOH RHEO METER NRM-2010-J-CW). An adapter for plume and viscoelasticity, 10 &phgr;, was used, and the sample stage velocity was 6 cm/min. The results are shown in Table 1. As clearly understandable from the results shown in Table 1, N-2-(R,S)-ethylhexanoyl-L-glutamic acid dibutylamide, N-octanoyl-L-glutamic acid dibutylamide and N-decanoyl-L-glutamic acid dibutylamide have higher gel forming ability than the other gelling agents and can exert superior gel forming ability irrespective of a type of an oil. 1 TABLE 1 Gelling ability of various N-acylglutamic acid dibutylamides Gel Liquid composition Acyl group IPM TOG paraffin Example 4 Octanoyl 99 156 136 Example 5 2-Ethylhexanoyl 175 209 145 Example 6 Decanoyl 120 183 154 Comparative Acetyl 18 48 Insoluble Example 1 Comparative Hexanoyl Not gelled Not gelled Insoluble Example 2 Comparative Dodecanoyl (lauroyl) 95 116 92 Example 3 Comparative Tetradecanoyl 67 72 80 Example 4 (myristoyl) Comparative Pentadecanoyl — — 30 Example 5 IPM: Isopropyl myristate TOG: Triocanoic acid glyceride Unit: gel strength (g/cm 2 ) 
 Examples 7 to 10 
 Preparation of Gel Compositions 0.4 g of each gelling agent shown in Table 2 was added to 20 g of an oil and dissolved by heating on an oil bath at 150° C., and then the resulting solution was left stand at 23° C. for 15 hours for cooling to obtain gel compositions. Gel strength of each of the resulting gel compositions was measured by using a rheometer (FUDOH RHEO METER NRM-2010-J-CW). An adapter for plume and viscoelasticity, 10 &phgr;, was used, and the sample stage velocity was 6 cm/min. Further, transparency of each of the resulting gel compositions was determined by visual inspection. The results are shown in Table 2. It is understandable that the gel compositions of Examples 7 to 9 have higher gel strength than the gel compositions of Comparative Examples 6 to 8. Further, it is also understandable that the gel compositions of Examples 8 to 10 have higher transparency than the gel compositions of the comparative examples. 2 TABLE 2 Gelling ability of various N-acylglutamic acid dibutylamides Comparative Comparative Comparative Example 7 Example 8 Example 9 Example 10 Example 6 Example 7 Example 8 N-2-Ethylhexanoylglutamic 0.4 0.3 0.2 0.1 — — — acid dibutylamide (Compound of Example 1) N-Lauroylglutamic acid — 0.1 0.2 0.3 0.4 0.15 — dibutylamide 12-Hydroxystearic acid — — — — — 0.25 0.4 Octyldodecanol 4 4 4 4 4 4 4 Cyclometicon D-5* 16 16 16 16 16 16 16 Gel strength (g/cm 2 ) 650 380 400 190 330 280 0 Transparency Opaque Translucent Translucent Translucent Opaque Opaque Opaque *TORAY-DOW CORNING SILICONE CORP., SH245 
 Examples 11 and 12 
 Preparation of Antiperspirant Gel Sticks Each gelling agent shown in Table 3 was dissolved in an oil by heating, then the resulting solution added with aluminum zirconium trichlorohydrex glycine and left for cooling with stirring to obtain an antiperspirant gel stick. Gel strength of each of the resulting antiperspirant gel sticks was measured by using a rheometer (FUDOH RHEO METER NRM-2010-J-CW). An adapter for plume and viscoelasticity, 10 &phgr;, was used, and the sample stage velocity was 6 cm/min. The results are shown in Table 3. The results indicate that the gel sticks of Examples 11 and 12 have higher gel strength than the gel sticks of the comparative example, and thus superior antiperspirants is obtainable. 3 TABLE 3 Gelling ability of various N-acylglutamic acid dibutylamides Comparative Example 9 Example 11 Example 12 N-Lauroylglutamic acid 2 1 — dibutylamide N-2-Ethylhexanoylglutamic — 1 2 acid dibutylamide (Compound of Example 1) 12-Hydroxystearic acid 7 7 7 Octyldodecanol 14 14 14 Cyclometicon D-5* 48 48 48 Aluminum zirconium 26 26 26 trichlorohydrex glycine Gel strength (g/cm 2 ) 1847 2250 2650 *TORAY-DOW CORNING SILICONE CORP., SH245 **Westwood Chemical Corporation, Westchlor ZR 30B DM CP-5 
 Example 13 
 Preparation of Lipstick A lipstick was prepared in a conventional manner by using the composition shown in Table 4. 4 TABLE 4 Lipstick Example 13 (Weight %) Octyl palmitate 14 Lanolin 8.5 Isopropyl palmitate 8.5 Cetyl ricinoleate 5 Dimeric acid isopropyl ester 13 N-2-Ethylhexanoylglutamic acid 1.5 dibutylamide Red No. 223 12 Lecithin 0.7 Polyethylene glycol distearate 3.25 Sorbitan monooleate 5 Choresteryl hydroxystearate 2 Dipentaerythritol 2 Glycerol 9 Panthenol 1 Ozokerite 3.5 Paraffin 3.25 Candelilla wax 4.65 Bees wax 3 Tocophenol 0.1 Propylparaben 0.05 The lipstick obtained was superior in strength and excellently free from sweating. 
 Example 14 
 Preparation of Transparent Lipstick A transparent lipstick was prepared in a conventional manner by using the composition shown in Table 5. 5 TABLE 5 Stick type transparent lipstick Example 14 (Weight %) N-2-Ethylhexanoylglutamic acid 3 dibutylamide Aliphatic acid starch ester 5 12-Hydroxystearic acid 1.5 Diglyceryl triisostearate 80.45 Rosin acid pentaerythritol ester 10 Red No. 223 0.05 The transparent lipstick obtained was superior in strength, and moreover, had highly transparent appearance and satisfactory stability. 
 Example 15 
 Preparation of Candle A candle was prepared in a conventional manner by using the composition shown in Table 6. 6 TABLE 6 Candle Example 15 (Weight %) Hydrogenated polyisobutene* 87.4 Hydrogenated polyisobutene** 6.7 Isostearyl alcohol 5.5 N-2-Ethylhexanoylglutamic acid 0.4 dibutylamide *Panalane ™ H300E (Amoco Chemical) **Panalane ™ L14E (Amoco Chemical) The candle obtained was superior in strength and had highly transparent appearance.