KR101451331B1 - Manufacturing method of 1-o-alkyl glycerol - Google Patents

Abstract

The present invention relates to a method for efficiently synthesizing and synthesizing alkyl glycerol, which is used as a physiologically active substance as well as an intermediate of a reaction product of pharmaceutical synthesis, polymer synthesis, and cosmetics.

Description

Technical Field [0001] The present invention relates to a method for producing 1-O-alkyl glycerol,

The present invention relates to a process for the production of 1-O-alkyl glycerol which is used as an intermediate or a physiologically active substance of a reaction product of pharmaceutical synthesis, polymer synthesis, cosmetics.

A method of hydrolyzing an alkyl glycidyl ether in the presence of an acid or an alkali, a method of reacting a halogenated alkyl or alkyl sulfonic acid ester with an alcoholate of 1,2-O-isopropylidene glycerol , A method of hydrolyzing is known.

Specifically, J. Org. Chem. 48, 1237-1242 (1983) is a glycidyl glycidyl ether (1 equivalent) in order to hydrolyze the ether, water (ca. 50 eq.) And 72% HClO put ₄ (0.01 eq.) For 24 hours at 80 ℃ Lt; / RTI > The reaction solution was cooled to room temperature, neutralized with a 5% aqueous solution of sodium carbonate, and then the water was evaporated under reduced pressure. The yield of alkyl glycerol was 83%.

(12 mol), boron trifluoride etherate (0.05 mol), and alkyl glycidyl ether were synthesized by using an alkyl glycidyl ether as a starting material, and JAOCS 65 (8), 1299-1302 Cydyl ether (1 mol) was added and stirred at room temperature for 2 hours. After treatment with sodium bicarbonate (0.1 mol), remove acetone and treat with 600 mL of water. The organic layer is obtained by decompression. Add dioxolane (1.0 mol), sulfuric acid (0.05 mol), methanol (500 mL) and water (500 mL) to the reaction mixture and heat the mixture for several hours. Cool the reaction mixture and neutralize with sodium hydroxide solution. After separating the organic layer, the organic solvent is removed by reduced pressure. Recrystallization or silica-gel column is purified using organic solvent ethyl acetate. The yield of 1-O-alkyl glycerol was 86 to 90%.

Acetic anhydride (5.0 mol), tertiary amine (0.05 mol) and alkyl glycidyl ether (1.0 mol) were added and reacted at 100 ~ 120 ℃ for 3 hours. Acetic anhydride is removed and neutralized with dilute hydrochloric acid solution. After separating the organic layer, the solvent is evaporated under reduced pressure to obtain 1-O-alkyl-2,3-di-O-acetyl glycerol. Add 30% sodium hydroxide solution (2.5 mol), ethanol (500 mL), and the obtained product (1.0 mol) and reflux for several hours. After cooling to room temperature, it is neutralized with 0.5N hydrochloric acid solution. Extract with ether (500 mL). The organic solvent is evaporated under reduced pressure. The yield is 86-90%.

Japanese Patent Laid-Open No. 1993-32578 (1993.02.09) discloses the use of dimethylformamide, diethylformamide, dimethylacetamide or the like as a reaction solvent in the hydrolysis of alkyl glycidyl ether, Is 85.1%.

The problems of this conventional method include not only the complicated reaction process in which the reaction is divided into several stages, but also the purification process in the process of using the catalyst, the reaction time is long and the yield is relatively low.

Japanese Patent Laid-Open No. 1993-32578 (1993.02.09)

J. Org. Chem. 48, 1237-1242 (1983) Journal of American Oil Chemists Society (JAOCS), 65 (8), 1299-1302 (1988)

When the alkyl group of 1-O-alkyl glycerol is long, the reaction yield is low. Therefore, in the present invention, it is an object of the present invention to economically synthesize a target compound at a high yield by using a low boiling point solvent and a cheap catalyst.

It is an object of the present invention to provide a process for producing 1-O-alkylglycerol which proceeds in a simple step of the reaction, proceeds to a simple purification step using one kind of catalyst, and has a short reaction time and a high yield.

The present invention provides a process for producing 1-O-alkyl glycerol having a long chain having 12 or more carbon atoms and having a high reaction yield. The process comprises reacting 1-O-alkyl glycerol obtained by hydrolysis reaction using 1,4- And a method for producing the same.

The present invention relates to a process for the hydrolysis of a saturated or unsaturated linear or branched (C12 to C24) alkyl glycidyl ether with a 1,4-dioxane solvent in the presence of an acid catalyst, To a process for producing glycerol.

In the present invention, the acid catalyst may be sulfuric acid.

In the present invention, the acid catalyst may have a concentration of 0.1-1.0N.

In the present invention, the reaction temperature in the hydrolysis reaction may be 90-100 ° C. and the reaction time may be 5-20 hours.

In the present invention, the weight ratio of the (C12-C24) alkyl glycidyl ether: 1,4-dioxane: acid catalyst may be 1: 0.3-0.7: 0.3-0.7.

In the present invention, after the hydrolysis reaction step,

Removing 1,4-dioxane as a solvent, and neutralizing by adding an aqueous solution of sodium hydroxide; And

Adding chloroform to the neutralized aqueous solution to extract the product;

As shown in Fig.

The present invention relates to 1-O-alkyl glycerol in a yield of 91 to 99.9% produced by the above production method.

The present invention can provide a process for producing 1-O-alkyl glycerol with a yield of 90% or higher by using 1,4-dioxane as a solvent and hydrolyzing in the presence of an acid catalyst.

Hereinafter, the method for producing 1-O-alkyl glycerol of the present invention will be described in more detail.

The present invention relates to a process for producing 1-O-alkyl glycerol having a long chain having 12 or more carbon atoms, which can be produced at a yield of 90% or more, more specifically 91 to 99.9% To a new manufacturing method.

The present inventors have found that the production of 1-O-alkyl glycerol having a long chain having 12 or more carbon atoms can be carried out at a high yield by using 1,4-dioxane as a reaction solvent used in the hydrolysis reaction, Completed. In addition, the present inventors have found that 1,4-dioxane is used as the reaction solvent and sulfuric acid is used as an acid catalyst, thereby further improving the yield.

The process for the preparation of 1-O-alkyl glycerol according to one embodiment of the present invention comprises reacting a saturated or unsaturated straight or branched (C 12 -C 24) alkyl glycidyl ether with 1,4-dioxane as solvent in the presence of an acid catalyst And subjecting the reaction mixture to a hydrolysis reaction.

More specifically, the process for preparing 1-O-alkyl glycerol according to one embodiment of the present invention comprises

Hydrolyzing a saturated or unsaturated straight or branched (C 12 -C 24) alkyl glycidyl ether with a solvent in the presence of an acid catalyst using 1,4-dioxane;

Removing 1,4-dioxane as a solvent, and neutralizing by adding an aqueous solution of sodium hydroxide; And

Adding chloroform to the neutralized aqueous solution to extract the product;

. ≪ / RTI >

The (C12-C24) alkyl glycidyl ether used as a starting material in the present invention has an epoxy group and easily undergoes a ring opening reaction by an electrophile, a nucleophile, an acid, a base, a reducing agent and an oxidizing agent. In addition, 1-O-alkyl glycerol can be obtained by a simple purification method in which a product and a catalyst are separated by adding water after completion of the reaction with the property that the alkyl group is long-liquor when the alkyl group is long.

More specifically, the alkyl of the (C 12 -C 24) alkyl glycidyl ether has from 12 to 24 carbon atoms and may include saturated or unsaturated straight or branched chains. Examples thereof include dodecyl glycidyl ether, oleyl glycidyl ether, octadecyl glycidyl ether, and the like.

In one embodiment of the present invention, at the hydrolysis reaction step, sulfuric acid, phosphoric acid, para-toluenesulfonic acid and the like can be used as the acid catalyst, and the yield can be further improved by using sulfuric acid. In the presence of other acid catalysts, the yield of alkyl glyceryl ether may be low, and coloration or purity may be lowered. When hydrochloric acid is used instead of sulfuric acid as an acid catalyst, chloride ions of hydrochloric acid react with each other to obtain 1-O-alkyl-3-hydroxy-2-chloroglycerol. When the concentration of sulfuric acid is increased, an undesired product such as a dehydration reaction is obtained. Therefore, the sulfuric acid catalyst preferably has a concentration of 0.1 to 1.0N. The content of the acid catalyst is preferably (C12 to C24) alkyl glycidyl ether: acid catalyst in a weight ratio of 1: 0.3 to 0.7. When the amount is less than 0.3 weight ratio, the reaction time is longer than 24 hours, and other products can be obtained according to a long reaction time. In the case of using more than 0.7 weight ratio, a side reaction also occurs and the yield of the desired glycerol decreases. 1-O-alkyl glycerol having a high yield and high purity can be produced in the above range.

In one aspect of the invention, during the hydrolysis reaction step, the solvent is characterized by the use of 1,4-dioxane. The content of the 1,4-dioxane is preferably 1: 0.3 to 1.0 in terms of the weight ratio of (C12-C24) alkyl glycidyl ether: 1,4-dioxane. When the amount of glycidyl ether is less than 0.3, the glycidyl ether can not be effectively dissolved. When the amount of glycidyl ether is more than 1.0, the reaction system becomes homogeneous. However, . Therefore, 1-O-alkyl glycerol having a high yield and high purity can be produced in the above range.

More preferably, the weight ratio of the (C12 to C24) alkyl glycidyl ether: 1,4-dioxane: acid catalyst is 1: 0.5: 0.5, and 1-O-alkyl glycerol can be synthesized with high yield and purified easily desirable.

In one embodiment of the present invention, at the hydrolysis reaction step, the reaction temperature is 90 to 100 ° C, and the reaction time is preferably 5 to 10 hours. When the temperature is higher than 100 ° C, the decomposition of the desired 1-O-alkyl glycerol is accelerated and the quality is lowered. Also, the dehydration reaction occurs and the yield decreases . The reaction time may vary depending on the catalyst content, the reaction temperature, and the content of the solvent, and is preferably in the range of 5 to 10 hours, since it can be produced with the highest yield.

In the present invention, 1-O-alkyl glycerol can be represented by the following general formula (1).

[Chemical Formula 1]

(R < _{1 >} is a saturated or unsaturated straight or branched chain (C12-C24) alkyl)

More specifically, it may be selected from the following formulas (2) to (4).

(2)

(3)

[Chemical Formula 4]

The 1-O-alkyl glycerol according to the present invention has a very high yield of 91 to 99.9%, and the purified purity can be 99.5% or more.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.

[Example 1]

Add 10 g of dodecyl glycidyl ether to a three-necked flask. 5 g of 1,4-dioxane, and 5 g of 0.4 N sulfuric acid. The reaction temperature is raised to 100 占 폚. React for 5 hours. After completion of the reaction, the solvent is removed, and then 10 mL of 0.1 N NaOH is added to neutralize the solution. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 9.5 g (yield 91.2%) of the product was obtained.

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ0.88 (t, 3H, -CH 3), δ1.29 (m, 16H, -CH 2 -), δ1.55 (m, 4H, -CH 2 - ), δ3.6 (m, 7H, -CH 2 -O-CH 2 -CH (OH) -CH 2 -OH). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.04 (C-1), 22.63 (C-2), 26.00 (C-3), 29.55 C-12), 70.57 (C-13), 71.70 (C-14), 72.31 (C-15). IR spectrum CH group vibration (aliphatic) (722 cm -1), CO stretching (ether) (1122 cm ^-1 ), CH stretching vibration (aliphatic) (2855-3000 cm ^-1 ), OH stretching (3460 cm ^-1 ).

The HR / MS formula was C ₁₅ H ₃₂ O _{3. The} calculated value was 260.2351 and the result was 260.2352.

[Example 2]

Add 10 g of oleyl glycidyl ether to a three-necked flask. 5 g of 1,4-dioxane, and 5 g of 0.4 N sulfuric acid. The reaction temperature is raised to 100 占 폚. React for 13 hours. After completion of the reaction, the solvent is removed, and then 10 mL of 0.1 N NaOH is added to neutralize the solution. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO4 and the solvent of the organic layer is removed by using a pressure reducer. 9.76 g (94.9%) of the product was obtained.

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ0.88 (t, 3H, -CH 3), δ1.29 (m, 20H, -CH 2 -), δ1.55 (m, 4H, -CH 2 - ), δ2.0 (m, 4H- CH 2 -C = C-CH 2 -), δ3.6 (m, 7H, -CH 2 -O-CH 2 -CH (OH) -CH 2 -OH), [delta] 5.3 (m, 2H, -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C -16), 69.40 (C-17), 72.28 (C-18), 72.86 (C-19) .IR spectrum CH group vibration (aliphatic) (722 cm -1), CO stretching (ether) (1122 cm ^-1 ), CH stretching vibration (aliphatic) (2855-3000 cm ^-1 ), C = C bending vibration (aliphatic) (3004 cm ^-1 ), OH stretching (3460 cm ^-1 ).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Example 3]

Add 10 g of octadecyl glycidyl ether to a three-necked flask. 5 g of 1,4-dioxane, and 5 g of 0.4 N sulfuric acid. The reaction temperature is raised to 100 占 폚. 7 hours. After completion of the reaction, the solvent is removed, and then 10 mL of 0.1 N NaOH is added to neutralize the solution. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 9.87 g (95.5%) of the product was obtained.

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ0.88 (t, 3H, -CH 3), δ1.28 (m, 28H, -CH 2 -), δ1.55 (m, 4H, -CH 2 - ), δ3.6 (m, 7H, -CH 2 -O-CH 2 -CH (OH) -CH 2 -OH). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.04 (C-1), 22.63 (C-2), 26.00 (C-3), 29.55 C-18), 70.57 (C-19), 71.73 (C-20), 72.31 (C-21). IR spectrum CH group vibration (aliphatic) (722 cm ^-1 ), CO stretching (ether) (1122 cm ^-1 ), CH stretching vibration (aliphatic) (2855-3000 cm ^-1 ), OH stretching (3460 cm ^-1 ).

The HR / MS formula was C ₂₁ H ₄₄ O _{3 The} calculated value was 344.3290 and the result was 344.3294.

[Comparative Example 1]

Add 4.85 g of dodecyl glycidyl ether to a three-necked flask. 1.8 g of water and 0.65 g of 40% tetrabutylammonium hydroxide (TBAH). The reaction temperature is raised to 100 占 폚. React at this temperature for 3 hours. The product is dissolved in a chloroform solvent, and the organic layer and the water layer are separated by putting in a separating funnel. The water of the organic layer is removed with MgSO ₄ , filtered, and then the organic solvent is removed under reduced pressure. 2.02 g (yield: 38.8%) of the product was obtained.

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ0.88 (t, 3H, -CH 3), δ1.29 (m, 16H, -CH 2 -), δ1.55 (m, 4H, -CH 2 - ), δ3.6 (m, 7H, -CH 2 -O-CH 2 -CH (OH) -CH 2 -OH). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.04 (C-1), 22.63 (C-2), 26.00 (C-3), 29.55 C-12), 70.57 (C-13), 71.70 (C-14), 72.31 (C-15). IR spectrum CH group vibration (aliphatic) (722 cm ^-1 ), CO stretching (ether) (1122 cm ^-1 ), CH stretching vibration (aliphatic) (2855-3000 cm ^-1 ), OH stretching (3460 cm ^-1 ).

The HR / MS formula was C ₁₅ H ₃₂ O _{3. The} calculated value was 260.2351 and the result was 260.2352.

[Comparative Example 2]

Add 6.49 g of oleyl glycidyl ether to a three-necked flask. 1.8 g of water and 0.65 g of 40% tetrabutylammonium hydroxide (TBAH). The reaction temperature is raised to 100 占 폚. React for 18 hours. The product is dissolved in a chloroform solvent, and the organic layer and the water layer are separated by putting in a separating funnel. The water of the organic layer is removed with MgSO ₄ , filtered, and then the organic solvent is removed under reduced pressure. 4.76 g (yield 69.43%) of the product was obtained.

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ0.88 (t, 3H, -CH 3), δ1.29 (m, 20H, -CH 2 -), δ1.55 (m, 4H, -CH 2 - ), δ2.0 (m, 4H- CH 2 -C = C-CH 2 -), δ3.6 (m, 7H, -CH 2 -O-CH 2 -CH (OH) -CH 2 -OH), [delta] 5.3 (m, 2H, -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C -16), 69.40 (C-17), 72.28 (C-18), 72.86 (C-19) .IR spectrum CH group vibration (aliphatic) (722 cm -1), CO stretching (ether) (1122 cm ^-1 ), CH stretching vibration (aliphatic) (2855-3000 cm ^-1 ), C = C bending vibration (aliphatic) (3004 cm ^-1 ), OH stretching (3460 cm ^-1 ).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Comparative Example 3]

Add 6.53 g of octadecyl glycidyl ether to a three-necked flask. 1.8 g of water and 0.65 g of 40% tetrabutylammonium hydroxide (TBAH). The reaction temperature is raised to 100 占 폚. React at this temperature for 15 hours. The product is dissolved in a chloroform solvent, and the organic layer and the water layer are separated by putting in a separating funnel. The water of the organic layer is removed with MgSO ₄ , filtered, and then the organic solvent is removed under reduced pressure. 4.82 g (yield 69.9%) of the product was obtained.

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ0.88 (t, 3H, -CH 3), δ1.29 (m, 20H, -CH 2 -), δ1.55 (m, 4H, -CH 2 - ), δ2.0 (m, 4H- CH 2 -C = C-CH 2 -), δ3.6 (m, 7H, -CH 2 -O-CH 2 -CH (OH) -CH 2 -OH), [delta] 5.3 (m, 2H, -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C -16), 69.40 (C-17), 72.28 (C-18), 72.86 (C-19) .IR spectrum CH group vibration (aliphatic) (722 cm -1), CO stretching (ether) (1122 cm ^-1 ), CH stretching vibration (aliphatic) (2855-3000 cm ^-1 ), C = C bending vibration (aliphatic) (3004 cm ^-1 ), OH stretching (3460 cm ^-1 ).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Comparative Example 4]

Add 10 g of dodecyl glycidyl ether to a three-necked flask. Add 10 g of 0.3N phosphoric acid and shake it well. The temperature of the reaction solution was raised to 100 ° C and allowed to react for 24 hours. The reaction solution is cooled to room temperature and neutralized by adding 10 mL of 0.1 N NaOH. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 6.02 g (yield: 57.8%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH ₃ ),? 1.29 (m, 16H, -CH ₂ -),? 1.55 ,? 3.6 (m, 7H, -CH2-O-CH2-CH (OH) -CH2-OH). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.04 (C-1), 22.63 (C-2), 26.00 (C-3), 29.55 C-12), 70.57 (C-13), 71.70 (C-14), 72.31 (C-15). IR spectrum CH group vibration (722 cm-1), CO stretching (ether) (1122 cm-1), CH stretching vibration (aliphatic) (2855-3000 cm-1) and OH stretching (3460 cm-1).

The HR / MS formula was C ₁₅ H ₃₂ O _{3. The} calculated value was 260.2351 and the result was 260.2352.

[Comparative Example 5]

Add 10 g of oleyl glycidyl ether to a three-necked flask. Add 10 g of 0.3 N phosphoric acid. The reaction temperature is raised to 100 占 폚. React for 20 hours. The reaction solution is cooled to room temperature and neutralized by adding 10 mL of 0.1 N NaOH. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 5.40 g (yield: 52.6%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH 3),? 1.29 (m, 20H, -CH 2 -),? 1.55 OH, -CH2-OH), 58.3 (m, 2H, < RTI ID = 0.0 > -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C-16), 69.40 (C-17), 72.28 (C-18), 72.86 (ether) (1122 cm -1), CH stretching vibration (aliphatic) (2855-3000 cm -1), C = C bending vibration (aliphatic) (3004 cm -1), OH stretching (3460 cm -1).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Comparative Example 6]

Add 10 g of octadecyl glycidyl ether to a three-necked flask. Add 10 g of 0.3 N phosphoric acid. The reaction temperature is raised to 100 占 폚. And reacted for 24 hours. The reaction solution is cooled to room temperature and neutralized by adding 10 mL of 0.1 N NaOH. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 6.58 g (yield: 63.7%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH 3),? 1.29 (m, 20H, -CH 2 -),? 1.55 OH, -CH2-OH), 58.3 (m, 2H, < RTI ID = 0.0 > -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C-16), 69.40 (C-17), 72.28 (C-18), 72.86 (ether) (1122 cm -1), CH stretching vibration (aliphatic) (2855-3000 cm -1), C = C bending vibration (aliphatic) (3004 cm -1), OH stretching (3460 cm -1).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Comparative Example 7]

Add 10 g of dodecyl glycidyl ether to a three-necked flask. Add 10 g of 0.2 N sulfuric acid. The reaction temperature is raised to 100 占 폚. React for 12 hours. The reaction solution is cooled to room temperature and neutralized by adding 10 mL of 0.1 N NaOH. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 7.90 g (yield 75.9%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH ₃ ),? 1.29 (m, 16H, -CH ₂ -),? 1.55 ,? 3.6 (m, 7H, -CH2-O-CH2-CH (OH) -CH2-OH). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.04 (C-1), 22.63 (C-2), 26.00 (C-3), 29.55 C-12), 70.57 (C-13), 71.70 (C-14), 72.31 (C-15). IR spectrum CH group vibration (722 cm-1), CO stretching (ether) (1122 cm-1), CH stretching vibration (aliphatic) (2855-3000 cm-1) and OH stretching (3460 cm-1).

The HR / MS formula was C ₁₅ H ₃₂ O _{3. The} calculated value was 260.2351 and the result was 260.2352.

[Comparative Example 8]

Add 10 g of oleyl glycidyl ether to a three-necked flask. Add 10 g of 0.2 N sulfuric acid. The reaction temperature is raised to 100 占 폚. React for 20 hours. The reaction solution is cooled to room temperature and neutralized by adding 10 mL of 0.1 N NaOH. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 7.99 g (yield 77.8%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH 3),? 1.29 (m, 20H, -CH 2 -),? 1.55 OH, -CH2-OH), 58.3 (m, 2H, < RTI ID = 0.0 > -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C-16), 69.40 (C-17), 72.28 (C-18), 72.86 (ether) (1122 cm -1), CH stretching vibration (aliphatic) (2855-3000 cm -1), C = C bending vibration (aliphatic) (3004 cm -1), OH stretching (3460 cm -1).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Comparative Example 9]

Add 10 g of octadecyl glycidyl ether to a three-necked flask. Add 10 g of 0.2 N sulfuric acid. The reaction temperature is raised to 100 占 폚. Let it react for 22 hours. The reaction solution is cooled to room temperature and neutralized by adding 10 mL of 0.1 N NaOH. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 7.57 g (yield: 85.74%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH 3),? 1.29 (m, 20H, -CH 2 -),? 1.55 OH, -CH2-OH), 58.3 (m, 2H, < RTI ID = 0.0 > -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C-16), 69.40 (C-17), 72.28 (C-18), 72.86 (ether) (1122 cm -1), CH stretching vibration (aliphatic) (2855-3000 cm -1), C = C bending vibration (aliphatic) (3004 cm -1), OH stretching (3460 cm -1).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Comparative Example 10]

Add 10 g of dodecyl glycidyl ether to a three-necked flask. Add 10 g of 0.1 N hydrochloric acid. The reaction temperature is raised to 100 占 폚. React for 20 hours. The reaction solution is cooled to room temperature and neutralized by adding 10 mL of 0.1 N NaOH. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 3.45 g (yield: 33.08%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH ₃ ),? 1.29 (m, 16H, -CH ₂ -),? 1.55 ,? 3.6 (m, 7H, -CH2-O-CH2-CH (OH) -CH2-OH). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.04 (C-1), 22.63 (C-2), 26.00 (C-3), 29.55 C-12), 70.57 (C-13), 71.70 (C-14), 72.31 (C-15). IR spectrum CH group vibration (722 cm-1), CO stretching (ether) (1122 cm-1), CH stretching vibration (aliphatic) (2855-3000 cm-1) and OH stretching (3460 cm-1).

The HR / MS formula was C ₁₅ H ₃₂ O _{3. The} calculated value was 260.2351 and the result was 260.2352.

[Comparative Example 11]

Add 10 g of oleyl glycidyl ether to a three-necked flask. Add 10 g of 0.1 N hydrochloric acid. The reaction temperature is raised to 100 占 폚. React for 20 hours. The reaction solution is cooled to room temperature and neutralized by adding 10 mL of 0.1 N NaOH. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO4 and the solvent of the organic layer is removed by using a pressure reducer. 0.81 g (yield 7.89%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH 3),? 1.29 (m, 20H, -CH 2 -),? 1.55 OH, -CH2-OH), 58.3 (m, 2H, < RTI ID = 0.0 > -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C-16), 69.40 (C-17), 72.28 (C-18), 72.86 (ether) (1122 cm -1), CH stretching vibration (aliphatic) (2855-3000 cm -1), C = C bending vibration (aliphatic) (3004 cm -1), OH stretching (3460 cm -1).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Comparative Example 12]

Add 10 g of octadecyl glycidyl ether to a three-necked flask. Add 10 g of 0.1 N hydrochloric acid. The reaction temperature is raised to 100 占 폚. And reacted for 24 hours. The reaction solution is cooled to room temperature and neutralized by adding 10 mL of 0.1 N NaOH. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 0.97 g (yield: 9.25%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH 3),? 1.29 (m, 20H, -CH 2 -),? 1.55 OH, -CH2-OH), 58.3 (m, 2H, < RTI ID = 0.0 > -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C-16), 69.40 (C-17), 72.28 (C-18), 72.86 (ether) (1122 cm -1), CH stretching vibration (aliphatic) (2855-3000 cm -1), C = C bending vibration (aliphatic) (3004 cm -1), OH stretching (3460 cm -1).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Comparative Example 13]

Add 10 g of octadecyl glycidyl ether to a three-necked flask. 5 g of 1,4-dioxane and 5 g of 0.3NH ₃ PO ₄ . The reaction temperature is raised to 100 占 폚. 7 hours. After completion of the reaction, the solvent is removed, and then 10 mL of 0.1 N NaOH is added to neutralize the solution. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO _4, and the solvent of the organic layer is removed using a pressure reducer. 4.05 g (yield 40.1%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH 3),? 1.29 (m, 20H, -CH 2 -),? 1.55 OH, -CH2-OH), 58.3 (m, 2H, < RTI ID = 0.0 > -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C-16), 69.40 (C-17), 72.28 (C-18), 72.86 (ether) (1122 cm -1), CH stretching vibration (aliphatic) (2855-3000 cm -1), C = C bending vibration (aliphatic) (3004 cm -1), OH stretching (3460 cm -1).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Comparative Example 14]

Add 10 g of octadecyl glycidyl ether to a three-necked flask. 5 g of diglyme, and 5 g of 0.4NH ₂ SO ₄ . The reaction temperature is raised to 100 占 폚. And reacted for 24 hours. After completion of the reaction, the solvent is removed, and then 10 mL of 0.1 N NaOH is added to neutralize the solution. The product is extracted with 20 ml of chloroform. The extracted organic layer is washed with MgSO4 and the solvent of the organic layer is removed by using a pressure reducer. 8.44 g (yield 80.5%) of the product was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz)? 0.88 (t, 3H, -CH 3),? 1.29 (m, 20H, -CH 2 -),? 1.55 OH, -CH2-OH), 58.3 (m, 2H, < RTI ID = 0.0 > -CH = CH-). ¹³ C-NMR (CDCl ₃ , 300 MHz) 14.03 (C-1), 22.59 (C-2), 25.99 (C-3), 27.13 C-15), 64.10 (C-16), 69.40 (C-17), 72.28 (C-18), 72.86 (ether) (1122 cm -1), CH stretching vibration (aliphatic) (2855-3000 cm -1), C = C bending vibration (aliphatic) (3004 cm -1), OH stretching (3460 cm -1).

HR / MS formula is C ₂₁ H ₄₂ O ₃ calculated value 342.3134, results came 342.3139.

[Table 1]

As shown in Table 1, it was confirmed that the yields of Examples 1 to 3 according to the present invention were as high as 91% or more.

[Table 2]

As shown in Table 2, when the solvent was not used, the yield was very low.

In addition, as shown in Comparative Example 13, it was confirmed that when phosphoric acid was used as the acid catalyst, the yield was as low as 40.1%.

Further, as shown in Comparative Example 14, it was confirmed that the yield was as low as 80.5% when diglyme was used as an ether solvent.

Claims (7)

A process for producing 1-O-alkyl glycerol comprising the step of hydrolyzing a saturated or unsaturated linear or branched (C 12 -C 24) alkyl glycidyl ether with 1,4-dioxane as a solvent in the presence of an acid catalyst . The method according to claim 1,
Wherein the acid catalyst is sulfuric acid. 3. The method of claim 2,
Wherein the acid catalyst has a concentration of 0.1 to 1.0 N. 2. The process for producing 1-O-alkyl glycerol according to claim 1, The method according to claim 1,
Wherein the reaction temperature in the hydrolysis reaction is 90 to 100 ° C and the reaction time is 5 to 20 hours. The method according to claim 1,
Wherein the weight ratio of (C12-C24) alkyl glycidyl ether: 1,4-dioxane: acid catalyst is 1: 0.3-0.7: 0.3-0.7. The method according to claim 1,
After the hydrolysis reaction step,
Removing 1,4-dioxane as a solvent, and neutralizing by adding an aqueous solution of sodium hydroxide; And
Adding chloroform to the neutralized aqueous solution to extract the product;
≪ RTI ID = 0.0 > 1-O-alkylglycerol. ≪ / RTI > delete