JPH0621088B2 - Method for producing isodiglyceryl ether - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing isodiglyceryl ether.

[Conventional technology]

Glycerin monoalkyl ether (hereinafter referred to as glyceryl ether) is a useful compound having W / O type emulsifying properties and other pharmacological actions such as hematopoiesis promoting action, anti-inflammatory action and anti-tumor action in bone marrow. Kosho 49-10
No. 724, Japanese Patent Publication No. 52-18171), and in particular, it has been widely applied to cosmetic base materials and the like by utilizing the W / O type emulsifying property (Japanese Patent Laid-Open Nos. 49-87612 and 49-9).
No. 2239, JP-A No. 52-12109, Japanese Patent Publication No. 57-
No. 36260).

Focusing on the fact that glyceryl ether is a unique surfactant having many such properties, various compounds having a molecular structure similar to glyceryl ether, that is, an ether bond and a hydrophilic OH group, are incorporated into the molecule. Attempts have been made to derivatize the polyol ether compound included in US Pat.
No. 8,892, Japanese Patent Publication No. 52-18170, Japanese Patent Laid-Open No. 53-1
37905, JP-A-54-145224 and the like). The polyol ether compound thus obtained has a W / O type emulsification property and other useful properties similar to glyceryl ether, and is a cosmetic base material (West German Published Patent No. 2,455,2).
87), and is used as an antibacterial and antifungal agent.

The present inventors focused their attention on such usefulness of the polyol ether compound and previously described the following general formula (IV): (In the formula, R ⁴ represents an aliphatic hydrocarbon group having 8 to 24 carbon atoms,
R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms) and an isodiglyceryl ether represented by the following formula is used, and an alkyl glycidyl ether (V) which can be easily produced from alcohol is used as a raw material. A method for producing according to the reaction formula was provided (JP-A-59-93022 and JP-A-59-175445). In the reaction formula, R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms, R ⁷ represents a hydrogen atom or a hydrocarbon group, R ⁸ represents a hydrocarbon group, X represents a halogen atom, and R ⁴
And R ⁵ has the same meaning as described above.

[Problems to be Solved by the Invention] However, these production methods have various problems as described below when they are industrially implemented.

In the reaction for obtaining the compound (VIII) from the compound (VII) or the compound (XII) from the compound (XI), since the reaction product is easily colored, a strict neutralization operation, a complicated distillation such as distillation at a high vacuum degree, etc. A purification operation is required.

In the reaction for obtaining the compound (IV) from the compound (VIII) or the compound (XIII) from the compound (XII), since the reaction is carried out in a water-containing solvent, an extraction operation with a large amount of ether, the reaction product is colored, and thus the column is used. Purification by chromatography is required.

In the reaction for obtaining the compound (IX) from the compound (VII), strict temperature control is required, the yield is low, an extraction operation with a large amount of ether is required, and the reaction product is easily colored.

In the reaction for obtaining the compound (IV) from the compound (IX),
Since the reaction is carried out in a water-containing solvent, extraction operation with a large amount of ether is required.

In the reaction for obtaining the compound (IV) from the compound (XIII), a large amount of expensive palladium-carbon is required and the reaction product is colored due to the slow progress of the reaction.

[Means for solving problems]

The present inventors have overcome the various drawbacks of the conventional method, and carried out diligent research on a method for producing isodiglyceryl ether with high yield, high purity and simply, using a glycidyl ether derivative as a raw material, By reacting penzyl alcohol in the presence of a base, side reactions do not occur in the epoxide ring-opening reaction, and dependylation proceeds in high yield by using a hydrogenolysis reaction. Found and completed the present invention.

That is, the present invention is represented by the general formula (II) (In the formula, R ¹ represents a linear or branched alkyl group having ¹ to 26 carbon atoms or an aryl group, and R ³ represents a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group, or a benzyl group.) A glycidyl ether derivative represented by reacting benzyl alcohol in the presence of a base, and then subjecting the resulting product to a hydrogenolysis reaction in the presence of a metal catalyst, the general formula (I) (Wherein R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms or an aryl group, and R ¹ is the same as the above), and a method for producing the isodiglyceryl ether. is there.

The reaction method of the present invention is as follows.

(In the formula, R ¹ , R ² and R ³ are the same as above) In the compounds (I), (II) and (III) of the present invention, R ¹ is a linear or branched alkyl group having ¹ to 26 carbon atoms. , Methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-
Nonyl, n-decyl, n-undecyl, n-dodecyl,
n-Tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n- Linear primary saturated alkyl groups such as pentacosyl and n-hexacosyl; 2-ethylhexyl, 2-butyldecyl, 2-ethyldodecyl, 2-butyldodecyl,
2-ethyltradecyl, 2-hexyldecyl, 2-butyltetradecyl, 2-ethylhexadecyl, 2-hexyldecyl, 2-butylhexadecyl, 2-ethyloctadecyl, 2-hexyltetradecyl, 2-octyldodecyl, 2-butyl octadecyl, 2-ethyl eicosyl, 2-hexyl hexadecyl, 2-octyl tetradecyl, 2-butyl eicosyl, 2-ethyl docosyl, 2
-Hexyl octadecyl, 2-octyl hexadecyl,
2-Butyldocosyl, 2-ethyltetracosyl, 2-hexyleicosyl, 2-octyloctadecyl, 2-heptylundecyl, 2- (1,3,3-trimethylbutyl) octyl, 2-decyltetradecyl, 2- Dodecyl hexadecyl, 2-tetradecyl octadecyl, 5,
7,7-Trimethyl-2- (1,3,3-trimethylbutyl) octyl, and the following formula (In the formula, m is an integer of 4 to 10, n is an integer of 5 to 11, m + n is 11 to 17, and m = 7 and n = 8.
A branched primary saturated alkyl group such as methyl-branched isostearyl represented by the formula: 2-propyl, sec-butyl, sec-pentyl, sec-hexyl, sec
Secondary saturated alkyl groups such as -heptyl, sec-octyl, sec-nonyl, sec-decyl, sec-undecyl, sec-dodecyl are mentioned. As the aryl group, phenyl,
2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl Examples thereof include enyl and 3,5-dimethylphenyl.

Examples of the linear or branched alkyl group having 1 to 8 carbon atoms of R ³ include methyl, ethyl, n-propyl, n-butyl and n.
-Pentyl, n-hexyl, n-heptyl, n-octyl, and other straight-chain primary saturated alkyl groups; 2-ethylhexyl and other branched-chain primary alkyl groups; 2-propyl, sec-butyl, sec-pentyl, sec- Hexyl, sec-heptyl, s
Secondary saturated alkyl groups such as ec-octyl can be mentioned. Examples of the aryl group are the same as those for R ¹ .

The reaction of reacting the glycidyl ether derivative (II) with benzyl alcohol to obtain the benzyl ether derivative (III) is an alcohol addition reaction to the epoxide derived from the terminal olefin. When an acid catalyst is used, the epoxide is protonated, and the alcohol attacks the carbonium ion generated thereby, which facilitates a side reaction. However, when the reaction is carried out in the presence of a base as in the present invention, the reaction is SN
Since the reaction proceeds in 2, the steric hindrance of the produced secondary alcohol is large and a side reaction does not occur, so that the yield is extremely high.

The base used in this reaction is an alkali metal (L
i, Na, K, etc.), alkali metal hydrides (LiH, NaH, K)
H, etc.), alkali metal hydroxides (LiOH, NaOH, KON, etc.), alkali metal alcoholates (NaOMe, NaOEt, KOtB)
u) or tertiary amines (triethylamine, tributylamine, tetramethylethylenediamine, tetramethyl-1,3-diaminopropane, tetramethyl-
1,6-diaminohexane, triethylenediamine, pyridine, dimethylaniline, quinoline, etc.) and the like.

In the above reaction, 1 mol of glycidyl ether derivative (II) is generally used in an amount of 1 to 20 mol, preferably 2 to 10 mol of benzyl alcohol, and 0.001 to 0.5 mol of a base, preferably 0.01 to 0.5 mol. 0.25 mol added, 20 to
The reaction proceeds at a temperature of 150 ° C, preferably 40 to 100 ° C. The benzyl ether derivative (III) thus obtained can be easily purified by a means such as distillation after distilling off excess benzyl alcohol.
The yields are always above 85% and in most cases quantitative.

The reaction to obtain the diglyceryl ether derivative (I) by hydrogenolyzing the benzyl ether derivative (III) is carried out by adding 0.0001 to 10% by weight of the benzyl ether derivative (III) to the solvent (III) in the absence of solvent or solution. Preferably 0.001-5
A metal catalyst in an amount of wt% is added, and hydrogen pressure is 1 to 150 atm, preferably 50 to 120 atm, reaction temperature is 20 to 200 ° C., preferably 80 to 120 ° C. for 2 to 24 hours, preferably 5
By reacting for ~ 15 hours. Although the desired product (I) can be quantitatively obtained by this reaction, 0.01 to 1% by weight, preferably 0.1 to 0.75% by weight of a mineral acid is added to the benzyl ether derivative (III). Makes the reaction easier.

Examples of the solvent used in this reaction include all solvents that dissolve the benzyl ether derivative (III),
Alcohol solvents such as methanol, ethanol and isopropanol are preferable. As the metal catalyst, palladium-carbon, palladium black, Raney-Nitzkel, rhodium-carbon, ruthenium-carbon, rhenium-carbon and the like can be used, but 5% palladium carbon, 10% palladium carbon and palladium black are preferable. Examples of the mineral acid to be added include hydrochloric acid, sulfuric acid, perchloric acid, etc. Among them, hydrochloric acid is preferable.

In most cases, the products obtained as a result of the above reactions are
The desired isodiglyceryl ether (I) can be obtained in a pure state simply by filtering off the metal catalyst and distilling off the solvent. When an acid is added, pure (I) can be obtained by simple purification such as steaming or treatment with activated carbon. The metal catalyst separated by filtration can be reused.

In this reaction, the conventional debenzylation reaction 1) must use a large amount of expensive metal catalyst, so that the increase in product price is inevitable. 2) Generally, the reaction is carried out under hydrogen pressure of 1 atm. Therefore, the reaction may be slow in some cases, and 3) it has drawbacks such as the need for isolation and purification of the debenzylated product, even though it is a reaction with few by-products, while 1)
Use only a very small amount of metal catalyst 2) Reaction time 2
The reaction is surely completed in 24 hours. 3) It is literally a quantitative reaction and isolation and purification of the debenzylated product is not necessary in many cases. If necessary, simple means such as steaming or activated carbon treatment is sufficient. It is excellent in various points such as
It is advantageous in that it can be industrially manufactured.

[Operation and effect of the invention]

As mentioned above, the present invention provides isodiglyceryl ether (I)
It is an extremely excellent method which can easily obtain the compound with high yield and high purity.

〔Example〕

 Next, the present invention will be described with reference to examples.

Example 1 (i) 1-O-tetradecyl-3-O-methyl-2-O
-2 ', 3'-epoxypropyl glycerin (II) (R ¹
= C ₁₄ H ₂₉ , R ³ ═CH ₃ ): 2 equipped with reflux condenser, thermometer, dropping funnel and stirrer
302.5 g (0.956 mol) of 1-O-tetradecyl-3-O-methylglycerin, n- in a 4-necked flask.
203 g of hexane, 32.5 g (0.0478 mol) of 50% tetrabutylammonium hydrogen sulfate aqueous solution, and 176.9 g (1.9126 mol) of epichlorohydrin are added in this order. The inside of the flask is heated to 40 ° C. and stirred at a stirring speed of 400 rpm. 243.8 g (2.869 mol) of 48% aqueous sodium hydroxide solution is added dropwise thereto over 0.5 hours while maintaining the reaction temperature at 55 ° C or lower, and after completion of the dropping, the mixture is stirred at 50 to 55 ° C for 5 hours. After cooling, the aqueous layer was removed, the n-hexane layer was washed with water, and then 6.5 g (9.56 mmol) of a 50% aqueous solution of tetrabutylammonium hydrogensulfate and 35.4 g (0.383 g of epichlorohydrin).
Mol) and heat and stir at 40 ° C. as before, adding 4
243.8 g of an 8% aqueous sodium hydroxide solution (2.869
Mol) is added dropwise over 20 minutes while maintaining the reaction temperature at 55 ° C or lower. After completion of dropping, the mixture was stirred at 50 to 55 ° C. for 4.5 hours, post-treated in a usual manner and then distilled under reduced pressure to give 1-O-tetradecyl-3-O-methyl-2-O-2 ', 3'-epoxypropyl. 290.8 g (yield 84.8%) of glycerin was obtained.

Boiling point: 175-180 ° C./0.15 Torr IR (liquid film, cm ⁻¹ ): 3050sh, 2925, 2855, 1460, 1110 NMR (CDCl ₃ , δ): 0.87 (3H, t, J =
5.6Hz), 1.28 (24H, brs), 2.4 ~ 2.8 (2H,
m), 3.33 (3H, s), 3.0 to 4.0 (10H, m) (ii) 1-O-tetradecyl-3-O-methyl-2-O
Synthesis of 3'-benzyloxy-2'-hydroxypropyl glycerine ^{(III) (R 1 = C} 14 H 29, R 3 = CH 3): distillation head, thermometer, inlet tube, with the dropping funnel and a stirrer Benzyl alcohol 87 on 24 mouth brass
5.9 g (8.10 mol) and 28% NaOMe methanol solution 15.63 g (0.081 mol) were added, and the mixture was heated at 150 to 180 ° C. for 5 hours while blowing N ₂ to remove the distilling methanol. Replace the distillation head with a reflux condenser and
Cool to ° C. 290.5 g (0.81 mol) of 1-O-tetradecyl-3-O-methyl-2-O-2 ', 3'-epoxypropylglycerin obtained in Reference Example 1 (i) was added thereto over 1 hour. Drop it. After completion of dropping, the mixture is stirred at 60 ° C. for 7 hours, and the disappearance of the raw materials is confirmed by gas chromatography. After allowing to cool, neutralize with 6N hydrochloric acid and use a water washing pump to
Benzyl alcohol is distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain 343.7 g (yield 90.9%) of 1-O-tetradecyl-3-O-methyl-2-O-3'-benzyloxy-2'-hydroxypropylglycerin as a colorless liquid.

Boiling point: 230-240 ° C / 0.18 Torr IR (liquid film, cm ^-1 ): 3430br, 2920, 2850, 1450, 110
0,730,695,685 NMR (CDCl ₃ , δ): 0.87 (3H, t, J =
5.8Hz), 1.28 (24H, brs), 3.33 (3H,
s), 3.4 to 4.2 (13H, m), 4.52 (2H, s), 7.29
(5H, s) (iii) 1-O-tetradecyl-3-O-methyl-2-
O-2 ', 3'-dihydroxypropyl glycerin (I)
Synthesis of _{^{(R 1 = C 14 H 29}} , R 2 = CH 3): 1-O obtained in the first autoclave in Example 1 (ii)
-Tetradecyl-3-O-methyl-2-O-3'-benzyloxy-2'-hydroxypropylglycerin 10
0.0 g (0.214 mol), 200 g of methanol, 5
% Palladium-carbon (5.0 g) and concentrated hydrochloric acid (0.5 g) were charged and sealed under a hydrogen pressure of 100 atm.
Heat and stir for 0 hours. After allowing to cool, 5% palladium-carbon is filtered off and the solvent is distilled off. The residue is steamed at 25%, 80 ml of methanol and 8 g of activated carbon are added, and the mixture is stirred at room temperature for 1 hour. Activated carbon was filtered off and methanol was distilled off to give 1-O-tetradecyl-3-O-methyl-2- as a colorless transparent oily substance.
O-2 ', 3'-dihydroxypropyl glycerin 7
6.7 g (yield 95.0%) was obtained.

Elemental analysis as C ₂₁ H ₄₄ O ₅ (calculated value) C: 67.05 (66.98), H: 11.62 (1
1.78) IR (liquid film, cm ⁻¹ ): 3410br, 2925, 2855, 1460, 1108 NMR (CDCl ₃ , δ): 0.87 (3H, t, J = 6.0H)
z), 1.25 (24H, brs), 2.7 to 3.0 (2H,
m), 3.33 (3H, s), 3.4 to 3.9 (12H, m) Example 2 (i) 1-O-tetradecyl-3-O-benzyl-2-
O-2 ', 3'-epoxypropyl glycerin (II) (R
Synthesis of ¹ = C ₁₄ H ₂₉ , R ³ = CH ₃ ): 2 equipped with reflux condenser, thermometer, dropping funnel and stirrer
In a 4-neck flask, 359.0 g (0.948 mol) of 1-O-tetradecyl-3-O-methylglycerin, n-
250 g of hexane, 32.08 g (0.0474 mol) of 50% tetrabutylammonium hydrogen sulfate aqueous solution, and 175.43 g (1.896 mol) of epichlorohydrin were charged and stirred with heating at 50 ° C. 227.6 g (2.845 mol) of a 50% sodium hydroxide aqueous solution is added dropwise thereto over 0.5 hour while keeping the temperature inside the flask at 50 to 55 ° C. After completion of dropping, the mixture is stirred at 50 ° C. for 4.5 hours. After cooling, the aqueous layer was removed, and 50% tetrabutylammonium hydrogen sulfate aqueous solution (6.44 g, 9.5 mmol) and epichlorohydrin (35.1 g, 0.379 mol) were added to the reaction solution at 45 to 50 ° C. Heat and stir. 50% here
227.6 g (2.845 mol) of aqueous sodium hydroxide solution is added dropwise over 20 minutes. After completion of the dropping, the reaction is carried out at 50 ° C. for 4 hours. After cooling, the mixture was post-treated in a conventional manner and then distilled under reduced pressure to give 1-O-tetradecyl-3-O-benzyl-
2-O-2 ', 3'-epoxypropyl glycerin 33
6.2 g (yield 81.6%) was obtained.

Boiling point: 211 ° C / 0.06 Torr to 215 ° C / 0.05To
rr IR (liquid film, cm ^-1 ): 3025, 2920, 2850, 1460sh, 145
0,1100,730,695,685 NMR (CDCl ₃ , δ): 0.90 (3H, t), 1.30
(24H, brs), 2.60 ~ 2.90 (2H, m), 3.00 ~
3.30 (1H, m), 3.40 to 4.10 (9H, m), 4.53 (2
H, s), 7.30 (5H, s) (ii) 1-O-tetradecyl-3-O-benzyl-2-O
Synthesis of 3'-benzyloxy-2'-hydroxypropyl glycerine ^{(III) (R 1 = C} 14 H 29, R 3 = PhCH 2): a reflux condenser, a thermometer, inlet tube, a dropping funnel and a stirrer Benzyl alcohol 83 in a 24-necked flask
Charge 5.9 g (7.73 mol), add 1.78 g (0.0773 mol) of sodium while blowing nitrogen, and stir at room temperature until the sodium is completely dissolved. 0.5% of 1-O-tetradecyl-3-O-benzyl-2-O-2 ', 3'-epoxypropyl glycerine 336.0 g (0.773 mol) obtained in Example 2 (i) was added thereto. Drop over time. After the completion of dropping, heating is performed at 75 to 85 ° C. for 5 hours. After cooling, it is neutralized, benzyl alcohol is distilled off, and the residue is applied to a silica gel short column. n
-Elution with hexane / ethyl acetate = 5/1 and evaporation of the solvent gave 1'-O-tetradecyl-3-O-benzyl-2.
402.0 g (yield 95.8%) of -O-3'-benzyloxy-2'-hydroxypropylglycerin was obtained.

IR (liquid film, cm ^-1 ): 3430, 2925, 2850, 1460sh, 145
0,1100,730,695,685 NMR (CDCl ₃ , δ): 0.87 (3H, t), 1.23 (24
H, brs), 3.3 to 3.9 (13H, m), 4.47 (4H,
s) (iii) 1-O-tetradecyl-2-O-2 ', 3'-
Dihydroxypropyl glycerin (I) (R ¹ = C ₁₄ H ₂₉ ,
Synthesis of R ² = H): 1-O obtained in Example 2 (ii) in 1 autoclave
-Tetradecyl-3-O-benzyl-2-O-3'-benzyloxy-2'-hydroxypropylglycerin 10
0.0 g (0.184 mol), 100 g of methanol, and 0.5 g of palladium black are charged, the mixture is sealed under a hydrogen pressure of 100 atm, and then heated and stirred at 100 ° C. for 10 hours. After cooling, the palladium black was filtered off and the solvent was distilled off to give 66.8 g of 1-O-tetradecyl-2-O-2 ', 3'-dihydroxypropylglycerin as a colorless waxy solid (yield 100
%) Was obtained.

Elemental analysis As C ₂₀ H ₄₂ O ₅ (calculated value) C: 66.25 (66.26), H: 11.64 (1
1.68); O: 22.32 (22.06) IR (liquid film, cm ^-1 ): 3480br, 2925, 2855, 1460, 110
0,1040br NMR (CDCl ₃ , δ): 0.89 (3H, t, J = 5.6H
z), 1.25 (24H, brs), 3.3 to 3.9 (14H, b
rm), 4.30 (1H, br) Example 3 (i) 1-O-dodecyl-3-O-benzyl-2-O-
2 ', 3'-epoxypropyl glycerin (II) (R ¹ =
Synthesis of C ₁₂ H ₂₅ , R ³ = PhCH ₂ ): 2 equipped with reflux condenser, thermometer, dropping funnel and stirrer
In a 4-neck flask, 317.8 g (0.907 mol) of 1-O-dodecyl-3-O-benzylglycerin, 222 g of n-hexane, 30.8 g (0.0453 mol) of 50% aqueous tetrabutylammonium hydrogensulfate solution, Charge 167.7 g (1.813 mol) of epichlorohydrin 45
Heat and stir at ℃. Here, 226.6% (2.72 mol) of a 48% sodium hydroxide aqueous solution was used in the flask.
The solution is added dropwise over 0.5 hour while keeping the temperature at 55 ° C.
After completion of dropping, the mixture is stirred at 50 ° C. for 5 hours. After cooling, the aqueous layer was removed, and 50% tetrabutylammonium hydrogen sulfate aqueous solution 6.2% (9.1 mmol) and epichlorohydrin 33.5 g (0.363 mol) were added to the reaction solution, and the mixture was heated to 40 ° C. Heat and stir at. 50% sodium hydroxide solution 2 here
26.6 g (2.72 mol) are added dropwise over 15 minutes.
After completion of dropping, the mixture is reacted at 45 ° C. for 5 hours. After cooling, the mixture was post-treated in a conventional manner and then distilled under reduced pressure to give 317.1 g of 1-O-dodecyl-3-O-benzyl-2-O-2 ', 3'-epoxypropylglycerin (yield 86.0). %) Was obtained.

Boiling point: 207-217 ° C / 0.13 Torr IR (liquid film, cm ^-1 ): 3025, 2920, 2850, 1460sh, 145
0,1100,730,695,685 NMR (CDCl ₃ , δ): 0.87 (3H, t), 1.25
(20H, brs), 2.5-2.8 (2H, m), 3.0-3.3
(1H, m), 3.3 to 4.0 (9H, m), 4.50 (2H,
s), 7.25 (5H, s) (ii) 1-O-dodecyl-3-O-benzyl-2-O-
Synthesis of 3'-benzyloxy-2'-hydroxypropyl glycerine ^{(III) (R 1 = C} 12 H 25, R 3 = PhCH 2): a reflux condenser, a thermometer, inlet tube, a dropping funnel and a stirrer Benzyl alcohol 84 in a 24-neck flask
Charge 2.5 g (7.79 mol), add 1.79 g (0.0779 mol) of sodium while blowing nitrogen, and stir at room temperature until the sodium is completely dissolved. 1-O-dodecyl-obtained in Example 3 (i)
55. 36.8 g (0.779 mol) of 3-O-benzyl-2-O-2 ', 3'-epoxypropylglycerin
Add dropwise over 1 hour at ° C. After completion of dropping, the mixture is heated at 60 ° C. for 8 hours. After cooling, the mixture is neutralized, benzyl alcohol is distilled off, and the residue is applied to a silica gel syrup column. Elution with n-hexane / ethyl acetate = 5/1 and evaporation of the solvent gave 1-O-dodecyl-3-O-benzyl-2-O-3 '.
324.5 g (yield 85.4%) of -benzyloxy-2'-hydroxypropylglycerin was obtained.

IR (liquid film, cm ^-1 ): 3460br, 3080, 3045, 2930, 286
0, 1460sh, 1452, 1100, 730, 700, 690 NMR (CDCl ₃ , δ): 0.86 (3H, t, J = 5.2H
z), 1.25 (20H, brs), 3.3 to 4.4 (13H,
m), 4.48 (4H, s ), 7.25 (10H, s) (iii) 1-O- dodecyl -2-O-2 ', 3'- dihydroxypropyl glycerine ^{(I) (R 1 = C} 12 H 25, R ²
= H) 1-O obtained in Example 3 (ii) in 1 autoclave
-Dodecyl-3-O-benzyl-2-O-3'-benzyl-2'-hydroxypropylglycerin 100.0 g
(0.194 mol), 200 g of methanol and 5.0 g of palladium black were charged, the mixture was sealed under a hydrogen pressure of 100 atm, and the mixture was heated and stirred at 100 ° C for 12 hours. After cooling, the palladium black was filtered off and the solvent was distilled off to give 1-O as a colorless waxy solid.
64.0 g (yield 98.5%) of -dodecyl-2-O-2 ', 3'-dihydroxypropylglycerin was obtained.

Elemental analysis as C ₁₈ H ₃₈ O ₅ (calculated value) C: 64.30 (64.63); H: 11.71 (1
1.45) IR (liquid film, cm ^-1 ): 3360br, 2920, 2855, 1460, 111
0,1040br NMR (CDCl ₃ , δ): 0.87 (3H, t, J = 5.0H
z), 1.25 (20H, brs), 3.3 to 4.2 (14H,
m), 4.62 (1H, br) Example 4 (i) 1-O-tetradecyl-3-O-butyl-2-O
Synthesis of 3'-benzyloxy-2'-hydroxypropyl glycerine ^{(III) (R 1 = C} 14 H 29, R 3 = C 4 H 9): reflux condenser, thermometer, inlet tube, dropping funnel and a stirrer In a 24-neck flask equipped with benzyl alcohol 81.
Charge 1 g (0.75 mol), add 172 mg (7.5 mol) of sodium while blowing nitrogen, and dissolve sodium at room temperature. Here, 1-O-tetradecyl-3-O-butyl-2- synthesized according to Examples 1 to 3 was used.
O-2 ', 3'-epoxypropyl glycerin (II) (R
30.0 g (0.075 mol) of ¹ = C ₁₄ H ₂₉ and R ³ = C ₄ H _{9 was} added dropwise at 55 ° C. over 0.5 hour. After completion of dropping, the mixture is heated at 60 ° C. for 8 hours. After cooling, it is neutralized, benzyl alcohol is distilled off, and the residue is applied to a silica gel short column. By eluting with n-hexane / ethyl acetate = 5/1 and distilling off the solvent, 35.2 g of 1-O-tetradecyl-3-O-butyl-2-O-3'-benzyloxy-2'-hydroxyglycerin (yield Rate of 92.4%).

IR (liquid film, cm ^-1 ): 3430br, 2920, 2850, 1450, 110
0,730,695,685 NMR (CDCl ₃ , δ): 0.87 (3H, t), 0.90
(3H, t), 1.25 (28H, brs), 3.4 to 4.2 (1
5H, m), 4.52 (2H, s), 7.27 (5H, s) (ii) 1-O-tetradecyl-3-O-butyl-2-O
-2 ', 3'-dihydroxypropyl glycerin (I)
Synthesis of _{^{(R 1 = C 14 H 29}} , R 2 = C 4 H 9): 1 obtained in the autoclave 100ml Example 4 (i)
-O-tetradecyl-3-O-butyl-2-O-3'-
Benzyloxy-2'-hydroxypropyl glycerin 3
0.0 g (0.059 mol), methanol 30 g, 5%
Charge 1.5 g of palladium on carbon and 0.15 g of concentrated hydrochloric acid,
After applying a hydrogen pressure of 100 atm and sealing, 100 ° C for 10
Stir for hours. After allowing to cool, 5% paradigm carbon is filtered off,
The solvent is distilled off. After 25% steaming the residue, 25 ml of methanol and 2.5 g of activated carbon are added and the mixture is stirred at room temperature for 1 hour.
Activated carbon was filtered off, and methanol was distilled off to obtain 1-O-tetradecyl-3-O-butyl-2-O- in a colorless transparent oily matter.
2 ', 3'-dihydroxypropyl glycerin (I) (R ¹
= C ₁₄ H ₂₉ , R ² = C ₄ H ₉ ) 24.0 g (yield 97.2)
%) Was obtained.

As elemental analysis C ₂₄ H ₅₀ O ₅ (calculated value) C: 68.92 (68.85), H: 11.89 (1
2.04) IR (liquid film, cm ^-1 ): 3430br, 2930, 2870, 1470, 138
5,1110 NMR (CDCl ₃ , δ): 0.85 (3H, t), 0.88
(3H, t), 1.25 (28H, brs), 2.7 to 3.0 (2
H, m), 3.3 to 3.9 (14 H, m) IR and NMR were completely in agreement with the standard.

Example 5 (i) 1-O- methyl-branched isostearyl -3-O-methyl -2-O-3'-benzyloxy-2'hydrosilation propyl glycerol ^{(III) (R 1 = iso} -C 18 H 37 , R ³ = C
Synthesis of H ₃ ): Benzyl alcohol 54.m in a 24-neck flask equipped with a reflux condenser, a thermometer, an introduction tube, a dropping funnel and a stirring device.
07 g (0.50 mol) was charged, 115 mg (5.0 mmol) of sodium was added while blowing nitrogen, and sodium was dissolved at room temperature. Here, 1-O-methyl branched isostearyl-3-synthesized according to Examples 1 to 3 was used.
O- methyl -2-O-2 ', 3'- epoxy propyl glycerol ^{(II) (R 1 = iso} -C 18 H 37, R 3 = CH 3) 2
0.73 g (0.05 mol) is added dropwise at 50 ° C. over 0.5 hour. After completion of dropping, the mixture is heated at 60 ° C. for 7 hours. After cooling, it is neutralized, benzyl alcohol is distilled off, and the residue is applied to a silica gel short column. By eluting with n-hexane / ethyl acetate = 5/1 and evaporating the solvent, 1-O-methyl branched isostearyl-3-O-methyl-2-O-3'-
Benzyloxy-2'-hydroxyglycerin 24.86
g (yield 95.1%) was obtained.

IR (liquid film, cm ^-1 ): 3440br, 2920, 2855, 1450, 136
0,1100,725,695,683 NMR (CDCl ₃ , δ): 0.8 to 2.0 (35H), 3.32
(3H, s), 3.4 to 4.2 (13H, m), 4.52 (2H,
s), 7.26 (5H, s ) (ii) 1-O- methyl-branched isostearyl -3-O-methyl -2-O-2 ', 3'- dihydroxypropyl glycerine ^{(I) (R 1 = iso} -C Synthesis of ₁₈ H ₃₇ , R ² = CH ₃ ): 1 obtained in Example 5 (i) in a 100 ml autoclave.
-O-methyl branched isostearyl-3-O-methyl-2
-O-3'-benzyloxy-2'-hydroxypropylglycerin 20.0 g (0.038 mol), methanol 20 g, and palladium black 50 mg were charged and sealed under a hydrogen pressure of 100 atm, and then heated at 100 ° C for 10 hours. Stir. After cooling, the palladium black was filtered off and the solvent was distilled off to give 1-O-methyl-branched isostearyl-3- as colorless colorless oil.
16.45 g (yield 100 g) of O-methyl-2-O-2 ′, 3′-dihydroxypropylglycerin was obtained.

Elemental analysis As C ₂₅ H ₅₂ O ₅ (calculated value) C: 69.53 (69.40); H: 11.97 (1
2.11) IR (liquid film, cm ^-1 ): 3420br, 2925, 2865, 1470, 138
0,1100 NMR (CDCl ₃ , δ): 0.8 to 2.0 (35H), 2.7 to
3.0 (2H, m), 3.35 (3H, s), 3.4 to 3.9 (12
H, m) IR and NMR were completely in agreement with the standard.

Example 6 The following compounds were obtained in the same manner as in Examples 1-5.

* 1-O-n-octyl-3-O-methyl-2-O-
2 ', 3'-dihydroxypropyl glycerin (R ¹ =
_{n-C 8 H 17, R} 2 = CH 3) · 1-O- methyl-branched isostearyl -3-O-n-
Octyl -2-O-2 ', 3'- dihydroxypropyl glycerin _{^{(R 1 = iso-C 18}} H 37, R 2 = n-C 8 H 17) · 1-O- hexadecyl -2-O-2', 3'-dihydroxypropyl glycerin _{^{(R 1 = n-C 18}} H 37, R 2
= H). 1-O-methyl branched isostearyl-2-O-
2 ', 3'-dihydroxypropyl glycerin (R ¹ = i
so-C ₁₈ H ₃₇ , R ² = H)

Claims (1)

[Claims] 1. General formula (II) (In the formula, R ¹ represents a linear or branched alkyl group having ¹ to 26 carbon atoms or an aryl group, and R ³ represents a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group, or a benzyl group.) A glycidyl ether derivative represented by reacting benzyl alcohol in the presence of a base, and then subjecting the resulting product to a hydrogenolysis reaction in the presence of a metal catalyst, the general formula (I) (In the formula, R ² is a hydrogen atom, a linear or branched alkyl group or aryl group having 1 to 8 carbon atoms, and R ¹ is the same as the above.).