Abstract:
A compound represented by the following general formula I; ##STR1## wherein R 1 , R 2  and R 3  independently represent a hygrogen atom, alkyl group or aryl group, provided that at least one of R 1 , R 2  and R 3  represents 3,7,11,15-tetramethylhexadecyl group, 3,7,11-trimethyldodecyl group or 3,7-dimethyloctyl group, or a salt thereof. The compound may have R- or S- configuration with respect to each asymmetric carbon contained therein and it may be present as a racemate. The compounds of the present invention are useful as surfactants, lubricants, dispersants, emulsifiers, additives, stabilizers, solubilizers, water-repellants, antistatic agents and the like.

Description:
BACKGROUND OF THE INVENTION 
     The present invention relates to novel alkyl phosphates having a branched alkyl group, which are useful as surfactants, lubricants, dispersants, emulsifiers, additives, stabilizers, solubilizers, water-repellants, antistatic agents and the like. 
     Hitherto, trialkyl phosphate compounds have been widely used as additives such as plastisizers and stabilizers, lubricants, dispersants or the like. Most of trialkyl phosphate compounds used as plastisizers are higher alkyl phosphates in view of volatility and water-solubility of the compounds. Typical examples of such alkyl phosphates include trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate and octyldiphenyl phosphate. Triaryl phosphates are more advantageous as plastisizers, but they have a problem of low-temperature resistance. 
     Dialkyl phosphates and monoalkyl phosphates are generally used as surfactants. The alkyl phosphate surfactants are used, for instance, as wetting agents such as disclosed in R. Oda et al., &#34;Surfactants and Applications thereof&#34;, Maki Shoten, p98, (1957), collecting property improving agents for fibers such as disclosed in Japanese Patent Application Laying-open (KOKAI) (referred to as &#34;J.P. KOKAI&#34; hereinafter) No. Sho 47 39788, antistatic agents such as disclosed in Japanese Patent Publication (KOKOKU) No. Sho 42-11480 and softening agents. Alkyl phosphates having a branched alkyl group, in particular, are known to be useful as lubricants for treating fibers such as disclosed in J.P. (KOKAI) No. Sho 48-19892. 
     While various alkyl phosphate compounds have been developed and practically used as described above, it is still sought to improve the various properties of the alkyl phosphates. 
     On the other hand, it has been known that cell membranes of archaebacteria are composed of glycerolipids having a hydrophobic group comprising linear isoprenoids bonded with ether bonds. Recently, in investigations of the functions of cell membranes of archaebacteria and application thereof for liposomes, reported was synthesized glycerophospholipids having isoprenoid side chains, which imitate the lipids constituting the cell membranes of archaebacteria (Yamauchi et al., J. Am. Chem. Soc., 112, p3188 (1990); Toda et al., Preprints for Spring Conference (1990) of the Chemical Society of Japan, p1793). As a result of these investigations, it was found that these glycerophospholipids having isoprenoid side chains have a low phase transition point and that the lipid bilayer membrane constituted by the glucerophospholipids has an excellent barrier property. 
     Further, also known were lipid bilayer membranes and lipid-bilayer-membrane-immobilized polymer films utilizing quaternary ammonium salts having isoprenoid chains as disclosed in J.P. (KOKAI) No. Hei 2-288849 and it was found that those lipid bilayer membranes have fluidity similar to that of biological membranes as well as excellent flexibility and strength. However, any alkyl phosphate having isoprenoid side chains, which may be suitably used as surfactants and dispersants, is not reported. 
     SUMMARY OF THE INVENTION 
     In view of the circumstances described above, an object of the present invention is to provide alkyl phosphates having excellent stability, solubilizing property, dispersibility and low temperature resistance. 
     The above-described object of the invention has been achieved by a discovery of compounds represented by the following general formula I and salts thereof. ##STR2## 
     In the general formula I, R 1 , R 2  and R 3  independently represent a hygrogen atom, alkyl group or aryl group, provided that at least one of R 1 , R 2  and R 3  represents 3,7,11,15-tetramethylhexadecyl group (phytanyl group), 3,7,11-trimethyldodecyl group or 3,7-dimethyloctyl group. The compounds may have either of R or S-configuration with respect to each asymmetric carbon contained therein. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The novel compounds according to the present invention are the alkyl phosphates represented by the above general formula I and the salts thereof. 
     Preferred examples of the alkyl group include butyl, hexyl, octyl, 2-ethylhexyl and the like. Preferred examples of the aryl group include phenyl. 
     As regards the stereochemistry of the compounds, they may have R- or S-configuration with respect to each asymmetric carbon contained therein and they may be present as racemates. 
     Preferred salts of the compounds according to the present invention are alkali metal and alkaline earth metal salts. 
     The compounds of the present invention are, in other words, tri-, di- and monoalkyl phosphates at least one of which alkyl chains is an isoprenoid chain. 
     The alkyl phosphates of the present invention may be prepared by a conventional method for preparing alkyl phosphates, namely, by reacting phosphorous oxychloride with an alcohol corresponding to the alkyl group under a basic condition or by introducing hydroxyl groups with equivalent amount of water after the reaction of phosphorous oxychloride and alcohol. Alternatively, they may be prepared by reacting a phosphorylating agent such as phenyl phosphorodichloridate, methyl phosphorodichloridate, bromoethyl phosphorodichloridate and diphenyl phosphorochloridate with an alcohol corresponding to the alkyl group under a basic condition and then deprotecting. 
     Most of the alkyl phosphates of the present invention can be obtained as an oily product in spite of the large carbon number thereof and have a significantly lower melting point as compared with a corresponding alkyl phosphates having linear alkyl chain with the same carbon number. In addition, the alkyl phosphates of the present invention exhibit extremely excellent dispersibility. Hence, the alkyl phosphates of the present invention are useful as surfactants, lubricants, dispersants, emulsifiers, additives, stabilizers, solubilizers, water-repellants, antistatic agents and the like. In particular, the alkyl phosphates of he present invention are useful as dispersants because of the excellent dispersibility thereof. Further, thanks to the low melting points of the compounds, they hardly precipitate in use thereof, for instance, as lubricants. 
     The present invention is hereinafter explained more in detail by reference to the following non limitative examples. 
     EXAMPLE 1 
     Synthesis of 3RS,7R,11R,15 tetramethylhexadecanol 
     (7R,11R)-phytol (200 g) was dissolved in ethanol (1000 ml), added with platinum oxide (1 g) and stirred for 6 hours at room temperature under hydrogen atmosphere. After the completion of the reaction, insoluble material was removed by filtration through a Celite layer and the filtrate was concentrated under reduced pressure to obtain 201 g of 3RS,7R,11R,15tetramethylhexadecanol ((3RS, 7R,11R)-phytanol). 
     EXAMPLE 2 
     Synthesis of 3,7,11-trimethyldodecanol 
     Farnesol (200 g) was dissolved in ethanol (1000 ml), added with platinum oxide (1 g) and stirred for 24 hours at room temperature under hydrogen atmosphere. After the completion of the reaction, insoluble material was removed by filtration through a Celite layer and the filtrate was concentrated under reduced pressure to obtain 3,7,11-trimethyldodecanol (195 g). 
     EXAMPLE 3 
     Synthesis of 3,7-dimethyloctanol 
     Geraniol (100 g) was dissolved in ethanol (500 ml), added with platinum oxide (500 mg) and stirred for 24 hours at room temperature under hydrogen atmosphere. After the completion of the reaction, insoluble material was removed by filtration through a Celite layer and the filtrate was concentrated under reduced pressure to obtain 3,7-dimethyloctanol (100 g). 
     EXAMPLE 4 
     Synthesis of tri(3RS,7R,11R,15-tetramethylhexadecyl) phosphate 
     Phosphorous oxychloride (200 g) was dissolved in dichloromethane (100 ml), added with a solution of 3RS,7R,11R,15 tetramethylhexadecanol (8.94 g), triethylamine (3.0 g) and N,N-dimethylaminopyridine (200 mg) in dichloromethane (50 ml) dropwise and stirred for 24 hours. After washing the reaction mixture with water and then with 10% aqueous solution of citric acid, the organic layer was dried over anhydrous sodium sulfate and the dichloromethane was evaporated under reduced pressure. Resulted residue was purified by silica gel chromatography and fractions of hexane/ethyl acetate=97/3 were collected to obtain tri(3RS,7R,11R,15-tetramethylhexadecyl) phosphate (6.8 g). 
     IR Spectra (neat) cm -1  : 2960, 2925, 2870, 1460, 1380, 1290, 1270, 1150, 1140, 1000, 920 
     FAB-MASS: (M+H) +  939 
     EXAMPLE 5 
     Synthesis of tri(3,7,11-trimethyldodecyl) phosphate 
     By using 3,7,11-trimethyldodecanol, tri(3,7,11-trimethyldodecyl) phosphate was obtained in the same manner as used in Example 4. 
     IR Spectra (neat) cm -1  : 2960, 2925, 2870, 1460, 1380, 1290, 1270, 1150, 1140, 1000, 920 
     FAB-MASS (M+H) +  729 
     EXAMPLE 6 
     Synthesis of tri(3,7-dimethyloctyl) phosphate 
     By using 3,7-dimethyloctanol, tri(3,7-dimethyloctyl) phosphate was obtained in the same manner as used in Example 4. 
     IR Spectra (neat) cm -1  : 2960, 2925, 2870, 1460, 1380, 1290, 1270, 1150, 1140, 1000, 920 
     FAB-MASS: (M+H) +  519 
     EXAMPLE 7 
     Synthesis of di(3RS,7R,11R,15-tetramethylhexadecyl)phenyl phosphate 
     Phenyl phosphorodichloridate (6.3 g) was dissolved in dichloromethane (100 ml), added with a solution of 3RS,7R,11R,15-tetramethylhexadecanol (18 g), triethylamine (6.1 g) and N,N-dimethylaminopyridine (200 mg) in dichloromethane (50 ml) dropwise and stirred for 24 hours. After washing the reaction mixture with 10% aqueous solution of citric acid and then with saturated aqueous solution of sodium hydrogen carbonate, the organic layer was dried over anhydrous sodium sulfate and the dichloromethane was evaporated under reduced pressure. Resulted residue was purified by silica gel chromatography and fractions of hexane/ethyl acetate=95/5 were collected to obtain di(3RS,7R,11R,15-tetramethylhexadecyl) phenyl phosphate (15 g). 
     IR Spectra (neat) cm -1  : 3060, 2960, 2925, 2870, 1600, 1495, 1460, 1380, 1290, 1220, 1160, 1050, 950, 760, 690 
     FAB-MASS: (M+H) +  735 
     EXAMPLE 8 
     Synthesis of di(3,7,11-trimethyldodecyl)phenyl phosphate 
     By using 3,7,11-trimethyldodecanol, di(3,7,11-trimethyldodecyl)phenyl phosphate was obtained in the same manner as used in Example 7. 
     IR Spectra (neat) cm -1  : 3060, 2960, 2925, 2870, 1600, 1495, 1460, 1380, 1290, 1220, 1160, 1050, 950, 760, 690 
     FAB-MASS (M+H) +  595 
     EXAMPLE 9 
     Synthesis of di(3,7-dimethyloctyl)phenyl phosphate 
     By using 3,7-dimethyloctanol, di(3,7-dimethyloctyl)phenyl phosphate was obtained in the same manner as used in Example 7. 
     IR Spectra (neat) cm -1  : 3060, 2960, 2925, 2870, 1600, 1495, 1460, 1380, 1290, 1220, 1160, 1050, 950, 760, 690 
     FAB-MASS: (M+H) +  455 
     EXAMPLE 10 
     Synthesis of 3RS,7R,11R,15-tetramethylhexadecyldiphenyl phosphate 
     Diphenyl phosphorochloridate (13.4 g) was dissolved in dichloromethane (100 ml), added with a solution of 3RS,7R,11R,15-tetramethylhexadecanol (14.9 g), triethylamine (4.04 g) and N,N-dimethylaminopyridine (200 mg) in dichloromethane (50 ml) dropwise and stirred for 24 hours. After washing the reaction mixture with 10% aqueous solution of citric acid and then with saturated aqueous solution of sodium hydrogen carbonate, the organic layer was dried over anhydrous sodium sulfate and the dichloromethane was evaporated under reduced pressure. Resulted residue was purified by silica gel chromatography and fractions of hexane/ethyl acetate=95/5 were collected to obtain 3RS,7R,11R,15-tetramethylhexadecyldiphenyl phosphate (27 g). 
     IR Spectra (neat) cm -1  : 3060, 2960, 2925, 2870, 1600, 1495, 1460, 1380, 1290, 1220, 1190, 1160, 1050, 950, 750, 690 
     FAB-MASS: (M+H) +  531 
     EXAMPLE 11 
     Synthesis of 3,7,11-trimethyldodecyldiphenyl phosphate 
     By using 3,7,11-trimethyldodecanol, 3,7,11-trimethyldodecyldiphenyl phosphate was obtained in the same manner as used in Example 7. 
     IR Spectra (neat) cm -1  : 3060, 2960, 2925, 2870, 1600, 1495, 1460, 1380, 1290, 1220, 1190, 1160, 1050, 950, 750, 690 
     FAB-MASS: (M+H) +  461 
     EXAMPLE 12 
     Synthesis of 3,7-dimethyloctyldiphenyl phosphate 
     By using 3,7-dimethyloctanol, 3,7-dimethyloctyldiphenyl phosphate was obtained in the same manner as used in Example 7. 
     IR Spectra (neat) cm -1  : 3060, 2960, 2925, 2870, 1600, 1495, 1460, 1380, 1290, 1220, 1190, 1160, 1050, 950, 750, 690 
     FAB-MASS (M+H) +  391 
     EXAMPLE 13 
     Synthesis of di(3RS,7R,11R,15-tetramethylhexadecyl) phosphate 
     Di(3RS,7R,11R,15-tetramethylhexadecyl)phenyl phosphate (15 g) was dissolved in a mixture of methanol, ethyl acetate and acetic acid (5/5/1, 120 ml) and added with platinum dioxide (300 mg) to carry out hydrogenolysis for 2 days. After the completion of the reaction, insoluble material was removed by filtration through a Celite layer and the filtrate was concentrated under reduced pressure to obtain di(3RS,7R,11R,15-tetramethylhexadecyl) phosphate (12.5 g). 
     IR Spectra (neat) cm -1  : 2960, 2925, 2870, 1460, 1380, 1220, 1190, 1020, 920, 740 
     FAB MASS: (M+H) +  659 
     EXAMPLE 14 
     Synthesis of di(3,7,11-trimethyldodecyl) phosphate 
     By using di(3,7,11-trimethyldodecyl)phenyl phosphate, di(3,7,11-trimethyldodecyl) phosphate was obtained in the same manner as used in Example 13. 
     IR Spectra (neat) cm -1  : 2960, 2925, 2870, 1460, 1380, 1220, 1190, 1020, 920, 740 
     FAB-MASS: (M+H) +  519 
     EXAMPLE 15 
     Synthesis of di(3,7-dimethyloctyl) phosphate 
     By using di(3,7-dimethyloctyl)phenyl phosphate, di(3,7-dimethyloctyl) phosphate was obtained in the same manner as used in Example 13. 
     IR Spectra (neat) cm -1  : 2960, 2925, 2870, 1460, 1380, 1220, 1190, 1020, 920, 740 
     FAB-MASS: (M+H) +  379 
     EXAMPLE 16 
     Synthesis of 3RS,7R,11R,15-tetramethylhexadecyl phosphate 
     3RS,7R,11R,15-tetramethylhexadecyldiphenyl phosphate (27 g) was dissolved in acetic acid (200 ml) and added with platinum dioxide (300 mg) to carry out hydrogenolysis for 2 days. After the completion of the reaction, insoluble material was removed by filtration through a Celite layer and the filtrate was concentrated under reduced pressure to obtain 3RS,7R,11R,15-tetramethylhexadecyl phosphate (14.0 g). 
     IR Spectra (neat) cm -1  : 2960, 2925, 2870, 1460, 1380, 1150, 1030 
     FAB MASS: (M+H) +  379 
     EXAMPLE 17 
     Synthesis of 3,7,11-trimethyldodecyl phosphate 
     By using 3,7,11-trimethyldodecyldiphenyl phosphate, 3,7,11-trimethyldodecyl phosphate was obtained in the same manner as used in Example 16. 
     IR Spectra (neat) cm -1  : 2960, 2925, 2870, 1460, 1380, 1150, 1030 FAB-MASS: (M+H) +  309 
     EXAMPLE 18 
     Synthesis of 3,7-dimethyloctyl phosphate 
     By using 3,7-dimethyloctyldiphenyl phosphate, 3,7-dimethyloctyl phosphate was obtained in the same manner as used in Example 16. 
     IR Spectra (neat) cm -1  : 2960, 2925, 2870, 1460, 1380, 1150, 1030 
     FAB-MASS: (M+H) +  239 
     EXAMPLE 19 
     Synthesis of 3RS,7R,11R,15-tetramethylhexadecylphenyl phosphate 
     3RS,7R,11R,15-tetramethylhexadecyldiphenyl phosphate (27  g) was dissolved in ethyl acetate (200 ml) and added with platinum dioxide (300 mg) to carry out hydrogenolysis for a day. After the completion of the reaction, insoluble material was removed by filtration through a Celite layer and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel chromatography (chloroform/methanol=8/2) to obtain 3RS,7R,11R,15-tetramethylhexadecylphenyl phosphate (12.8 g). 
     IR Spectra (neat) cm -1  : 2960, 2925, 2870, 1600, 1490, 1460, 1380, 1200, 1030, 950, 770, 690 
     FAB-MASS: (M+H) +  455