KR101897801B1 - Endo-5-O-alkyl isosorbide-2-O-alkyl sulfonate salt anionic surfactants and regioselective and effective preparation method thereof - Google Patents

Abstract

The present invention relates to an endo-5-O-alkyl isosorbide-2-O-alkyl sulfonate anionic surfactant and a regioselective and effective manufacturing method thereof. The manufacturing method according to the present invention adjusts a reaction condition such as a solvent or a catalyst and can introduce an alkyl chain into isosorbide in an endo type with high regioselective and excellent yield, thereby easily being used for manufacturing a 5-O-alkyl isosorbide-2-O-alkyl sulfonate. The anionic surfactant introducing a sulfonate acid group into the isosorbide manufactured by the manufacturing method exhibits a low surface tension and a high bubble power, thereby being easily used as the surfactant. The isosorbide-based anionic surfactant is represented by chemical formula 1.

Description

Endo-5-O-alkyl isosorbide-2-O-alkylsulfonate anionic surfactants and their positional and efficient production processes {Endo-5-O-alkyl isosorbide-2-O-alkyl sulfonate salt anionic surfactants and regioselective and effective preparation method thereof}

The present invention relates to an endo-5-O-alkylisosorbide-2-O-alkylsulfonate anionic surfactant and a method for its selective and efficient preparation.

The nonionic surfactants of the tween and span series are derived from sorbitol produced by a single dehydration process of the sorbitan ester and applied as an emulsifier in food, .

Isosorbide is produced by dehydration condensation of sorbitol through several stages of processing. Isosorbide, which is a chiral dianhydrohexitol, is a major product in the starch industry and has already replaced petrochemical compounds It is known as one of the biomass-derived materials that can be obtained.

In general, isosorbide is a diol compound having two hydroxyl groups in one molecule, and can be used for sulfation, sulfonation, ethoxylation, propoxylation, phosphorylation, etc. Cationic, amphoteric, and nonionic surfactant through the chemical reaction of anionic surfactants.

A number of studies have been made on nonionic derivatives related to the above, and related patents include compositions of detergents of derivatives of isosorbide for gasoline fuels (U.S. Patent No. 6,527,816), phosphates as materials, liposomes as membrane constituents Preparation of non-ionic derivatives such as liposome formulations (US Pat. No. 5,153, 000), including phosphates and cosmetics, aqueous coating compositions comprising at least one film-forming emulsion polymer and a polyglycerol derivative of a reactive surfactant (US Patent Registration No. 2011/0166287) (JP-A-2014/526482), cosmetics, crop protection formulations, detergent compositions, paints or coatings, which are suitable for use in cosmetics. The isosorbide monoester and the isosorbide di A composition patent of a non-ionic surfactant having a composition of the cosmetic, such as (US Patent 9,445,595), including also the open bar.

Further, the patent relating to isosorbide derivatives, a method of mixing a sorbitan ester component and a sorbitol ester component to form a surfactant composition (U.S. Patent No. 8,673,987), a cleaning action of a thickener for an aqueous composition, (U.S. Patent No. 8,008,246), processes for producing novel functional compounds using isosorbide, isomanide, and iso-idide, which are optical isomers of isosorbide (US Patent Registration No. 2010/0130759), as thickeners The use of isosorbide diester (US Patent No. 9,358,199), the polyamide compound of isosorbide ester and the ink composition containing it (Japanese Patent No. 6063791), a novel functional compound containing two optical isomers of isosorbide (Japanese Patent Registration No. 5250808) and the like have been disclosed.

On the other hand, as a patent for a process for producing a nonionic surfactant, a process for producing an environmentally friendly fatty acid-based surfactant (Korean Patent Registration No. 2017-00001305 A), a coating composition or a resist composition, (Korean Patent Registration No. 2016-0132829), a method for producing a nonionic surfactant with reduced toxicity and environmental hormone activity (Korean Patent No. 10-1675787), a water-soluble polymer, a silica (Korean Patent No. 2016-0114646) and ethoxylated surfactant (Korean Patent Registration No. 2016-0102210) suitable for cleaning and protection including nanoparticles, nonionic and anionic surfactants have been disclosed.

Patent applications relating to the composition of nonionic surfactants using isosorbide include the use of isosorbide derivatives of ethers or ester salts suitable for use in cosmetics (Japanese Patent Registration No. 2014/526482), cosmetics, crop protection formulations, detergent compositions, paints or A composition comprising isosorbide monoester and isosorbide diester (U.S. Patent No. 9,445,595), a method for forming a surfactant composition by mixing a sorbitan ester component and a sorbitol ester component to form a coating (US Patent No. 8,673,987 ), A process for producing a novel functional compound using isosorbide, isomanide, and isoside, which are optical isomers of isosorbide (US Patent Registration No. 2010/0130759).

In addition, as a patent for the production method of an anionic surfactant, a hair shampoo having bubble power performance and preventing the hair from being damaged, a composition of an amphiphilic amide lipid compound and a sulfate (US Patent No. 7,544,648), an anion isosorbide US Patent No. 8,334,318 discloses the use of cleansing agents or detergents of carboxylic acid derivatives (US Patent No. 8,334,318), and US Patent No. 8,546,446 discloses the preparation of anionic surfactants of sulfate using isosorbide from a constituent group of a water-soluble alkali metal containing detergents, detergents and cosmetic compositions Studies on the aqueous system of isosorbide derivatives with selected electrolytes have been disclosed in US Pat. No. 2017/0002295, and studies on anionic surfactants of sulfur-containing compounds including hydrophobic ester moieties and part of carboxylates have been disclosed.

Further, patents for the preparation of cationic surfactants include: metal-based cationic surfactant nanoparticles and methods for making them (US Patent No. 2017/0007642); purification of proteins with cationic surface active agents (US Patent No. 9,534,013 ), Mono-alkylamine cationic surface active agents, anionic polymeric membranes, and methods of making hair conditioning compositions comprising polyols (US Patent No. 2016/0374924).

However, in the above-mentioned study, only the production method and composition of ester, carboxylic acid, amide and sulfate derivatives using isosorbide were shown, and there is no study on the position selective production of isosorbide derivatives.

Accordingly, the inventors of the present invention have been studying a method for preparing an anionic surfactant 5-O-alkylisosorbide-2-O-alkylsulfonate in a position-selective manner efficiently introducing an alkyl chain into isosorbide in an endo- Since the production method according to the present invention can introduce the alkyl chain in endo form into isosorbide with high position selectivity and excellent efficiency by controlling the conditions such as solvent, catalyst, molar ratio, temperature and the like, 5-O-alkylisosorbide -2-O-alkylsulfonic acid salt. The anionic surfactant having a sulfonic acid group introduced into the isosorbide prepared by the above-mentioned process shows low surface tension and high bubble force, The present invention has been accomplished on the basis of this finding.

An object of the present invention is to provide an isosorbide anionic surfactant.

It is another object of the present invention to provide a method for the selective preparation of the isosorbide anionic surfactant.

In order to achieve the above object,

The present invention provides an isosorbide anionic surfactant represented by the following Formula 1:

[Chemical Formula 1]

(In the formula 1,

R < ¹ > is straight or branched chain _C1-20 alkyl;

L ¹ is linear or branched C _1-6 alkylene; And

M is an alkali metal).

Also, as shown in the following Reaction Scheme 1,

(Step 1) of obtaining a compound represented by the formula (4) by using a phase transfer catalyst in a mixed solvent of an organic solvent and water, with an isosorbide compound represented by the formula (2) and a compound represented by the formula (3);

Reacting the compound represented by the formula (4) and the compound represented by the formula (5) obtained in the above step 1 to obtain the compound represented by the formula (6) (step 2); And

(3) reacting the compound represented by the formula (6) and the compound represented by the formula (7) obtained in the step 2 to obtain a compound represented by the formula (1), wherein the isosorbide anionic surfactant The method provides:

[Reaction Scheme 1]

(In the above Reaction Scheme 1,

R ¹ , L ^1, and M are as defined in Formula 1; And

And each X is independently halogen.

The production process according to the present invention can introduce an alkyl chain in endo form to isosorbide at a high position selectivity and an excellent yield by controlling reaction conditions such as a solvent or a catalyst, and therefore, 5-O-alkylisosorbide- O-alkylsulfonic acid salt, and an anionic surfactant having a sulfonic acid group introduced into the isosorbide prepared by the above-described method shows low surface tension and high bubble force, and thus can be usefully used as a surfactant.

Hereinafter, the present invention will be described in detail.

The present invention provides an isosorbide anionic surfactant represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R < ¹ > is straight or branched chain _C1-20 alkyl;

L ¹ is linear or branched C _1-6 alkylene; And

M is an alkali metal.

Preferably,

R < ¹ > is straight or branched chain _C2-16 alkyl;

L ¹ is linear or branched C _1-3 alkylene; And

M is sodium or potassium.

More preferably,

R < ¹ > is straight or branched chain C < ₆ >

L ¹ is -CH ₂ -; And

M is sodium.

Preferred examples of the surfactant represented by Formula 1 according to the present invention include the following compounds:

(A)

;

;

[Chemical Formula B]

;

;

≪ RTI ID = 0.0 &

;

;

[Chemical Formula D]

.

.

Hereinafter, the isosorbide anionic surfactant represented by Formula 1 according to the present invention will be described in detail.

In order to evaluate the performance of the isosorbide anionic surfactant represented by Formula 1 according to the present invention, the surface tension was measured. As a result, the isosorbide anionic surfactant according to the present invention exhibited a low surface tension (See Experimental Example 1 and Table 3).

In order to evaluate the performance of the isosorbide anionic surfactant represented by the formula 1 according to the present invention, the isosorbide anionic surfactant according to the present invention exhibited high bubble strength (See Experimental Example 2 and Table 4).

Therefore, it can be seen that the isosorbide anionic surfactant according to the present invention exhibits excellent surface tension and foaming power and can be usefully used as a surfactant.

In addition,

As shown in Scheme 1 below,

(Step 1) of obtaining a compound represented by the formula (4) by using a phase transfer catalyst in a mixed solvent of an organic solvent and water, with an isosorbide compound represented by the formula (2) and a compound represented by the formula (3);

Reacting the compound represented by the formula (4) and the compound represented by the formula (5) obtained in the above step 1 to obtain the compound represented by the formula (6) (step 2); And

(3) reacting the compound represented by the formula (6) and the compound represented by the formula (7) obtained in the step 2 to obtain a compound represented by the formula (1), wherein the isosorbide anionic surfactant ≪ / RTI >

[Reaction Scheme 1]

In the above Reaction Scheme 1,

R ¹ , L ^1, and M are as defined in Formula 1; And

X is each independently halogen.

Hereinafter, a method of selectively producing an isosorbide anionic surfactant according to the present invention will be described in detail.

In the production method according to the present invention, the step 1 is a step of obtaining the compound represented by the general formula (4) by using a phase transfer catalyst in a mixed solvent of an organic solvent and water in the presence of an isosorbide compound represented by the general formula Specifically, the compound represented by the formula (3) is introduced into the hydroxy at the 2-position of the isosorbide compound represented by the formula (2) in a selective manner to form an exocyclic alkene group Is obtained.

At this time, the preferred temperature range for carrying out the step 1 is not particularly limited, but it can be carried out at 40-100 ° C. The reaction rate is slow at a temperature lower than 40 deg. C, and there is a problem in that the production of dimers into which the compound represented by the general formula (3) is introduced increases at both the 2 and 5 O positions of the isosorbide at 100 deg.

The preferred reaction time range for carrying out the step 1 is not particularly limited, but may be 1-8 hours.

The organic solvent is one selected from the group consisting of hexane, cyclohexane, toluene, xylene and mesitylene, and exhibits a very low yield without showing the position selectivity when the organic solvent is not used (Examples 1, Comparative Examples 1-7 and Table 2). On the other hand, it is preferable to use the water in an amount of 0.01-50 ^{% based} on the weight of the isosorbide compound represented by the formula (2). If the amount of the distilled water is out of the range, the position selectivity and the yield decrease.

The phase transfer catalyst is selected from 1-alkoxy-3-dialkylamino-2-propanol, 1-alkoxy-2-hydroxypropyl-3-trialkylammonium salt, tetrabutylammonium bromide wherein the anion portion of the salt is halide and methyl It is preferable to use sulfate. More specifically, it is preferable to use 3-methylamino-1-hexyloxypropan-2-ol, 3-dimethylamino-1-octyloxypropan- Ol, 3-dimethylamino-1-octadecyloxypropan-2-ol, 3-diethanolamino-1-hexyloxypropan-2-ol, 3- diethanolamino- 3-diethanolamino-1-dodecyloxypropan-2-ol, 3-diethanolamino-1-octadecyloxypropan-2-ol, 1-hexyloxy- Propyl-3-dimethylammonium methylsulfate, 1-octyloxy-2-hydroxypropyl-3-dimethylammonium methylsulfate, 1-dodecyloxy- Octyldimethylammonium methylsulfate, 1-octyloxy-2-hydroxypropyl-3-diethanolammonium methylsulfate, 1-octyloxy-2-hydroxypropyl- Hydroxypropyl-3-diethanolammonium methylsulfate, 1-octyloxy-2-hydroxypropyl-3-diethanolammonium methylsulfate, 1-hexyloxy- 1-dodecyloxy-2-hydroxypropyl-3-diethanolammonium methylsulfate and 1-octadecyloxy-2-hydroxypropyl-3-diethanolammonium methylsulfate Do. In the case of using methyltrioctylammonium chloride (Example 1, Comparative Example 7, Table 2), which is a commonly used phase transfer catalyst, not the phase transfer catalyst according to the present invention as the phase transfer catalyst, the yield was remarkably low, The selectivity to allyl isosorbide is not exhibited. Therefore, it can be understood that the phase transition catalyst according to the present invention must be used.

In step 1, a base may be used. The type of alkali metal hydroxide is not particularly limited, but an alkali metal hydroxide is preferable, and at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide is used More preferable.

The step 1 is preferably carried out at a ratio of 0.8-2.5 moles of the compound represented by the general formula (3), 1-2.5 moles of the base and 0.0001-0.1 mole of the phase transfer catalyst to 1 mole of the isosorbide compound represented by the general formula .

The compound represented by the general formula (3) is preferably used in the range of 0.8-2.5 molar ratio with respect to the isosorbide compound represented by the general formula (2). When the amount of the compound represented by the general formula (3) is less than 0.8 molar ratio, the reaction yield is remarkably decreased, , The position selectivity disappears and the generation of dimers into which the compound represented by the general formula (3) is introduced increases at both the 2-position and the 5-position, so it is preferable to use the compound in the range of 0.8-2.5 molar ratio in terms of yield and position selectivity.

The base is preferably used in an amount of 1-2.5 molar ratio with respect to the isosorbide compound represented by the general formula (2). When the amount of the base used is less than 1 mol, the yield is remarkably decreased. When the amount of the base is more than 2.5 mol, the amount of the dimer introduced with the compound represented by the general formula (3) increases at the positions 2 and 5, Is preferable in terms of yield and position selectivity.

The phase transfer catalyst is preferably used in an amount of 0.0001 to 0.1 mole ratio relative to the isosorbide compound represented by the general formula (2). If the catalyst is not used, the reaction rate and yield will be reduced.

In the production method according to the present invention, the step 2 is a step of reacting the compound represented by the formula (4) and the compound represented by the formula (5) obtained in the step 1 to obtain the compound represented by the formula (6) 1 and a compound represented by the formula (5) are reacted under the conditions including a solvent and a base to obtain a compound represented by the formula (6), wherein the compound represented by the formula (4) Is added dropwise to introduce an alkyl group in an endo form into the hydroxyl group at the 5-position to obtain a compound represented by the formula (6).

At this time, a preferable temperature range for carrying out the step 2 is not particularly limited, but it can be carried out at 40-120 ° C.

The preferred reaction time range for carrying out the step 2 is not particularly limited, but may be 1-8 hours.

The solvent is not particularly limited, but one selected from the group consisting of toluene, xylene, tetrahydrofuran, hexane, heptane, octane and cyclohexane can be used.

The base is not particularly limited, but an alkali metal hydroxide is preferable, and it is more preferable to use at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide.

The step 2 is preferably carried out using 0.5 to 2.5 moles of the compound represented by the general formula (5) and 1 to 3 moles of the base per mole of the compound represented by the general formula (4).

The compound represented by the formula (5) is preferably used in the range of 0.5 to 2.5 molar ratio, more preferably in the range of 1-2.5 molar ratio, and more preferably in the range of 1 to less than 1 molar ratio The excess of the unreacted compound represented by the general formula (4) remains to result in a remarkable decrease in the reaction yield. When the amount of the unreacted compound exceeds 2.5, the unreacted compound represented by the general formula (5) bonds to each other to form an alkyl polymer, 2.5 molar ratio is preferable in terms of yield and efficiency.

The base is preferably used in the range of 1 to 3 molar ratio with respect to the compound represented by the general formula (4). If the amount of the base used is less than 1 molar ratio, the yield is remarkably decreased. If the amount of the base is more than 3 molar ratio, a side reaction occurs to increase the amount of the side products, which is not efficient.

In the production method according to the present invention, the step 3 is a step of reacting the compound represented by the formula 6 and the compound represented by the formula 7 obtained in the step 2 to obtain the compound represented by the formula 1.

At this time, the preferable temperature range for carrying out the step 3 is not particularly limited, but it is preferably carried out at 50-100 ° C.

The preferred reaction time range for carrying out the step 3 depends on the length of the alkyl at the 5-position, preferably 5-24 hours.

The solvent which can be used in the reaction is not particularly limited, but water and one kind of organic solvent selected from the group consisting of isopropanol, propanol, tetrahydrofuran, ethanol and methanol can be mixed with water. The ratio of the water to the organic solvent is preferably 1: 1 to 1:10. If only water is used without using an organic solvent, or when the ratio exceeds the usage ratio of the organic solvent, decomposition of the product occurs, and it is preferable to use the above ratio.

The step 3 is preferably carried out in a ratio of 1-2.5 moles of the compound represented by the general formula (7) to 1 mole of the compound represented by the general formula (6).

When the amount of the compound of the formula (7) is less than 1 mol, the amount of the unreacted compound represented by the formula (6) is excessively large and the yield of the reaction is remarkably decreased. When the amount of the compound exceeds 2.5 mol, Therefore, it is preferable to use it in the range of 1 to 2.5 molar ratios in terms of yield and efficiency.

As a result of the production of the product of the example according to the invention, the process according to the invention is characterized in that 5-O-alkyl-isosorbide-2, in which alkyl is introduced in endo form with high position selectivity and sulfonic acid salt is introduced -O-alkylsulfonic acid salt can be prepared (see Examples 1 to 4 and Table 2).

The production process according to the present invention can introduce an alkyl chain in endo form to isosorbide at a high position selectivity and an excellent yield by controlling reaction conditions such as a solvent or a catalyst, and therefore, 5-O-alkylisosorbide- O-alkylsulfonic acid salt, and an anionic surfactant having a sulfonic acid group introduced into the isosorbide prepared by the above-described method shows low surface tension and high bubble force, and thus can be usefully used as a surfactant.

Hereinafter, examples and experimental examples of the present invention will be described in detail.

However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.

< Example  1 > 5-O- Hexyl  Chemical preparation of isosorbide-2-O-propylsulfonate

Step 1: Chemical preparation of 2-O-allylisosorbide

A thermometer, a condenser, a stirrer and an oil bath were placed in a three-necked reactor, and 102.2 g (0.7 mol) of isosorbide, 28 g (0.7 mol) of sodium hydroxide, 84.69 g (0.7 mol) of allyl bromide, 200 mL of xylene, 10 mL of 1-hexyloxy-2-hydroxypropyl-3-dimethylammonium methylsulfate (10.9 g, 0.034 mol) was added to a round bottom three-necked flask and stirred at a reaction temperature of 90 ° C for 3 hours. After completion of the reaction, the reaction mixture is extracted twice with xylene and 5% aqueous sodium chloride solution, and then the solvent is removed. The product was separated into ethyl acetate and hexane using column chromatography, and the product was identified by NMR. 2-O-allyl isosorbide and 5-O-allyl isosorbide exhibit a high 2 / O-allyl isosorbide selectivity of 23/1. (Yield 99%, 2-O-allylisosorbide / 5-O-allylisosorbide = 23/1, high 2-O-allyl isosorbide selectivity)

^{1 H NMR (300 MHz, CDCl} 3): δ 3.54-3.59 (m, 1H), 3.83-3.92 (m, 2H), 4.04-4.06 (m, 4H), 4.24-4.32 (m, 1H), 4.46- 4.48 (m, 1H), 4.61-4.64 (m, 1H), 5.19-5.33 (m, 2H), 5.83-5.96 (m, 1H).

Step 2: Chemical preparation of 5-O-hexyl-2-O-allyl isosorbide

A thermometer, a condenser, a stirrer and an oil bath were placed in a three-necked reactor, and 60 mL of toluene and 2.2 mL of distilled water were added to 22.4 g (0.12 mol) of 2-O-allyl isosorbide prepared in Example 1 and stirred . When the internal temperature reached 50 占 폚, 9.6 g (0.24 mol) of sodium hydroxide and 21.79 g (0.132 mol) of 1-bromohexane were added and stirred for 3 hours. After completion of the reaction, the reaction product is extracted twice with an aqueous solution of hexane and 5% sodium chloride, and then the solvent is removed using a rotary evaporator to obtain a product. A yellow liquid (27 g, 99%) is obtained.

¹ H NMR (300 MHz, CDCl ₃ ):? 0.86-0.89 (m, 3H), 1.29-1.33 (m, 6H), 1.57-1.64 (m, 2H), 3.41-3.47 (M, 2H), 3.90-4.04 (m, 7H), 4.51-4.52 (m, 1H), 4.62-4.64 ).

Step 3: Chemical preparation of 5-O-hexylisosorbide-2-O-propylsulfonate

Sodium hydride (2.52 g, 0.02 mol) and sodium hydrogen sulfite (2.03 g, 0.02 mol) were dissolved in 20 g of distilled water, and 50 g of methanol was added thereto. The mixture was stirred After adding 5-O-hexyl-2-O-allylisosorbide (9.2 g, 0.04 mol), the mixture was stirred at 60 ° C for 5 hours to obtain a pale yellow liquid (14 g, 99%).

^{1 H NMR (300 MHz, D} 2 O): δ 0.87 (m, 3H), 1.29-1.34 (m, 6H), 1.54-1.61 (m, 2H), 1.96-2.03 (m, 2H), 2.94-2.98 (m, 2H), 3.49-3.59 (m, 2H), 3.64-3.72 (m, 3H), 3.86-3.92 -4.24 (m, 1 H), 4.64 (m, 1 H), 4.73 (m, 1 H).

In Step 1 of Example 1, experiments were conducted under different reaction conditions, and the conditions and results (yield and selectivity) are shown in Table 1 below.

Step 1
Condition Organic solvent Distilled water
Whether or not to use Distilled water
usage Phase transition catalyst yield
(%) Selectivity 1-1
Xylene O 10% 1-hexyloxy-2-hydroxypropyl-3-dimethylammonium methyl sulfate 99 23/1 1-2 " O 10% 1-octyloxy-2-hydroxypropyl-3-dimethylammonium methyl sulfate 98 21/1 1-3 " O 10% 1-dodecyloxy-2-hydroxypropyl-3-dimethylammonium methylsulfate 98 22/1 1-4 " O 10% 1-octyloxy-2-hydroxypropyl-3-diethanolammonium methyl sulfate 98 20/1 1-5 " O 10% 1-octyloxy-2-hydroxypropyl-3-dimethylammonium bromide 98 21/1 1-6 " O 10% Tetrabutylammonium bromide 98 22/1 1-7 " O 10% 3-methylamino-1-hexyloxypropan-2-ol 98 21/1 1-8 " O 10% 3-dimethylamino-1-octyloxypropan-2-ol 98 20/1 1-9 " O 15% 1-hexyloxy-2-hydroxypropyl-3-dimethylammonium methyl sulfate 98 21/1 1-10 " O 0.01% " 98 22/1 1-11 " O One% " 98 21/1 1-12 " O 30% " 98 21/1 1-13 " O 50% " 98 22/1 1-14 Hexane O 10% " 98 21/1 1-15 Cyclohexane O 10% " 98 22/1 1-16 toluene O 10% " 98 21/1 1-17 Mesitylene O 10% " 98 23/1

In Table 1,

Condition 1-1 represents the conditions of Step 1 of Example 1 above;

Conditions 1-2 to 1-17 were carried out using the same method as in step 1 of Example 1 except that the conditions of the above table were different;

Selectivity represents the rate of formation of 2-O-allylisosorbide / 5-O-allyl isosorbide; And

The amount of distilled water used represents the weight of the isosorbide used as the starting material of Example 1 in relation to the used weight.

< Example  2 > 5-O- Octyl  Chemical preparation of isosorbide-2-O-propylsulfonate

Step 1: Chemical preparation of 2-O-allylisosorbide

A thermometer, a condenser, a stirrer and an oil bath were placed in a three-necked reactor, and 102.2 g (0.7 mol) of isosorbide, 28 g (0.7 mol) of sodium hydroxide, 84.69 g (0.7 mol) of allyl bromide, 200 mL of xylene, 10 mL of 1-hexyloxy-2-hydroxypropyl-3-dimethylammonium methylsulfate (10.9 g, 0.034 mol) was added to a round bottom three-necked flask and stirred at a reaction temperature of 90 ° C for 3 hours. After completion of the reaction, the reaction mixture is extracted twice with xylene and 5% aqueous sodium chloride solution, and then the solvent is removed. The product was separated into ethyl acetate and hexane using column chromatography, and the product was identified by NMR. 2-O-allyl isosorbide and 5-O-allyl isosorbide exhibit a high 2 / O-allyl isosorbide selectivity of 23/1. (Yield 99%, 2-O-allylisosorbide / 5-O-allylisosorbide = 23/1, high 2-O-allyl isosorbide selectivity)

^{1 H NMR (300 MHz, CDCl} 3): δ 3.54-3.59 (m, 1H), 3.83-3.92 (m, 2H), 4.04-4.06 (m, 4H), 4.24-4.32 (m, 1H), 4.46- 4.48 (m, 1H), 4.61-4.64 (m, 1H), 5.19-5.33 (m, 2H), 5.83-5.96 (m, 1H).

Step 2: Chemical preparation of 5-O-octyl-2-O-allyl isosorbide

A thermometer, a condenser, a stirrer and an oil bath were placed in a three-necked reactor, and 60 g of toluene and 2.2 mL of distilled water were added to 22 g (0.12 mol) of 2-O-allylisosorbide prepared in Example 1 and stirred . When the internal temperature reached 50 占 폚, 9.6 g (0.24 mol) of sodium hydroxide and 27.38 g (0.14 mol) of 1-bromooctane were added and stirred for 3 hours. After completion of the reaction, the reaction product is extracted twice with hexane and 5% aqueous sodium chloride solution, and then the solvent is removed using a rotary evaporator to obtain a product. A yellow liquid (35 g, 99%) is obtained.

¹ H NMR (300 MHz, CDCl ₃ ):? 0.86-0.89 (m, 3H), 1.29-1.33 (m, 10H), 1.57-1.64 (m, 2H), 3.41-3.47 (M, 2H), 3.90-4.04 (m, 7H), 4.51-4.52 (m, 1H), 4.62-4.64 ).

Step 3: Chemical preparation of 5-O-octylisosorbide-2-O-propylsulfonate

(2.32 g, 0.02 mol) and sodium bisulfite (1.92 g, 0.02 mol) were dissolved in 10 g of distilled water, 70 g of ethanol was added thereto, and the mixture was stirred After adding 5-O-octyl-2-O-allylisosorbide (11 g, 0.04 mol), the mixture was stirred at 60 ° C for 24 hours to obtain a pale yellow liquid (13 g, 99%).

^{1 H NMR (300 MHz, D} 2 O): δ 0.87 (m, 3H), 1.29-1.34 (m, 10H), 1.54-1.61 (m, 2H), 1.96-2.03 (m, 2H), 2.94-2.98 (m, 2H), 3.49-3.59 (m, 2H), 3.64-3.72 (m, 3H), 3.86-3.92 -4.24 (m, 1 H), 4.64 (m, 1 H), 4.73 (m, 1 H).

< Example  3> Chemical preparation of 5-O-decylisosorbide-2-O-propylsulfonate

Step 1: Chemical preparation of 2-O-allylisosorbide

A thermometer, a condenser, a stirrer and an oil bath were placed in a three-necked reactor, and 102.2 g (0.7 mol) of isosorbide, 28 g (0.7 mol) of sodium hydroxide, 84.69 g (0.7 mol) of allyl bromide, 200 mL of xylene, 10 mL of 1-hexyloxy-2-hydroxypropyl-3-dimethylammonium methylsulfate (10.9 g, 0.034 mol) was added to a round bottom three-necked flask and stirred at a reaction temperature of 90 ° C for 3 hours. After completion of the reaction, the reaction mixture is extracted twice with xylene and 5% aqueous sodium chloride solution, and then the solvent is removed. The product was separated into ethyl acetate and hexane using column chromatography, and the product was identified by NMR. 2-O-allyl isosorbide and 5-O-allyl isosorbide exhibit a high 2 / O-allyl isosorbide selectivity of 23/1. (Yield 99%, 2-O-allylisosorbide / 5-O-allylisosorbide = 23/1, high 2-O-allyl isosorbide selectivity)

^{1 H NMR (300 MHz, CDCl} 3): δ 3.54-3.59 (m, 1H), 3.83-3.92 (m, 2H), 4.04-4.06 (m, 4H), 4.24-4.32 (m, 1H), 4.46- 4.48 (m, 1H), 4.61-4.64 (m, 1H), 5.19-5.33 (m, 2H), 5.83-5.96 (m, 1H).

Step 2: Chemical preparation of 5-O-decyl-2-O-allyl isosorbide

A thermometer, a condenser, a stirrer and an oil bath were placed in a three-necked reactor, and 60 g of toluene and 2.2 mL of distilled water were added to 22 g (0.12 mol) of 2-O-allylisosorbide prepared in Example 1 and stirred . When the internal temperature reached 50 占 폚, 9.6 g (0.24 mol) of sodium hydroxide and 31.36 g (0.14 mol) of 1-bromodecane were added and stirred for 3 hours. After completion of the reaction, the reaction product is extracted twice with hexane and 5% aqueous sodium chloride solution, and then the solvent is removed using a rotary evaporator to obtain a product. A yellow liquid (38 g, 99%) is obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 0.86-0.89 (m, 3H), 1.29-1.33 (m, 14H), 1.57-1.64 (m, 2H), 3.41-3.47 (M, 2H), 3.90-4.04 (m, 7H), 4.51-4.52 (m, 1H), 4.62-4.64 ).

Step 3: Chemical preparation of 5-O-decylisosorbide-2-O-propylsulfonate

(2.51 g, 0.02 mol) and sodium hydrogensulfite (2.07 g, 0.02 mol) were dissolved in 10 g of distilled water, and 100 g of isopropanol was added thereto. The mixture was stirred After adding 5-O-decyl-2-O-allylisosorbide (13 g, 0.04 mol), the mixture was stirred at 60 ° C for 24 hours to obtain a pale yellow liquid (16 g, 99%).

^{1 H NMR (300 MHz, D} 2 O): δ 0.87 (m, 3H), 1.29-1.34 (m, 14H), 1.54-1.61 (m, 2H), 1.96-2.03 (m, 2H), 2.94-2.98 (m, 2H), 3.49-3.59 (m, 2H), 3.64-3.72 (m, 3H), 3.86-3.92 -4.24 (m, 1 H), 4.64 (m, 1 H), 4.73 (m, 1 H).

< Example  4 > 5-O- Dodecyl  Chemical preparation of isosorbide-2-O-propylsulfonate

Step 1: Chemical preparation of 2-O-allylisosorbide

A thermometer, a condenser, a stirrer and an oil bath were placed in a three-necked reactor, and 102.2 g (0.7 mol) of isosorbide, 28 g (0.7 mol) of sodium hydroxide, 84.69 g (0.7 mol) of allyl bromide, 200 mL of xylene, 10 mL of 1-hexyloxy-2-hydroxypropyl-3-dimethylammonium methylsulfate (10.9 g, 0.034 mol) was added to a round bottom three-necked flask and stirred at a reaction temperature of 90 ° C for 3 hours. After completion of the reaction, the reaction mixture is extracted twice with xylene and 5% aqueous sodium chloride solution, and then the solvent is removed. The product was separated into ethyl acetate and hexane using column chromatography, and the product was identified by NMR. 2-O-allyl isosorbide and 5-O-allyl isosorbide exhibit a high 2 / O-allyl isosorbide selectivity of 23/1. (Yield 99%, 2-O-allylisosorbide / 5-O-allylisosorbide = 23/1, high 2-O-allyl isosorbide selectivity)

^{1 H NMR (300 MHz, CDCl} 3): δ 3.54-3.59 (m, 1H), 3.83-3.92 (m, 2H), 4.04-4.06 (m, 4H), 4.24-4.32 (m, 1H), 4.46- 4.48 (m, 1H), 4.61-4.64 (m, 1H), 5.19-5.33 (m, 2H), 5.83-5.96 (m, 1H).

Step 2: Chemical preparation of 5-O-dodecyl-2-O-allyl isosorbide

A thermometer, a condenser, a stirrer and an oil bath were placed in a three-necked reactor, and 60.3 mL of toluene and 2.2 mL of distilled water were added to 22.3 g (0.12 mol) of 2-O-allyl isosorbide prepared in Example 1 and stirred . When the internal temperature reached 50 占 폚, 13.4 g (0.24 mol) of potassium hydroxide and 35.81 g (0.14 mol) of 1-bromododecane were added and stirred for 3 hours. After completion of the reaction, the reaction product is extracted twice with hexane and 5% aqueous sodium chloride solution, and then the solvent is removed using a rotary evaporator to obtain a product. A yellow liquid (42 g, 99%) is obtained.

¹ H NMR (300 MHz, CDCl ₃ ):? 0.86-0.89 (m, 3H), 1.29-1.33 (m, 18H), 1.57-1.64 (m, 2H), 3.41-3.47 (M, 2H), 3.90-4.04 (m, 7H), 4.51-4.52 (m, 1H), 4.62-4.64 ).

Step 3: Chemical preparation of 5-O-dodecylisosorbide-2-O-propylsulfonate

(2.52 g, 0.02 mol) and sodium bisulfite (2.03 g, 0.02 mol) were dissolved in 10 g of distilled water, 50 g of methanol was added thereto, and the mixture was stirred 2-O-allyl isosorbide (14.1 g, 0.04 mol) was added thereto, followed by stirring at 60 ° C for 24 hours to obtain a pale yellow liquid (17 g, 99%).

¹ H NMR (300 MHz, D ₂ O):? 0.87 (m, 3H), 1.29-1.34 (m, 18H), 1.54-1.61 (m, 2H), 1.96-2.03 (m, 2H), 3.49-3.59 (m, 2H), 3.64-3.72 (m, 3H), 3.86-3.92 -4.24 (m, 1 H), 4.64 (m, 1 H), 4.73 (m, 1 H).

As a result of the production of the products of Examples 1 to 4, the production process according to the present invention is characterized in that 5-O-alkyl-isosorbide- 2-O-propylsulfonic acid salt can be prepared.

< Comparative Example  1> Chemical preparation of 2-O-allylisosorbide

The reaction was carried out under the same conditions as in Step 1 of Example 1 except that distilled water was used in an amount of 100% based on isosorbide and reacted without adding an organic solvent. The reactivity was 20% and no selectivity for 2-O-allyl isosorbide was shown.

< Comparative Example  2> Chemical preparation of 2-O-allylisosorbide

The reaction is carried out under the same conditions as in step 1 of Example 1 except that dimethyl sulfoxide is used instead of xylene as an organic solvent and the reaction is carried out without mixing distilled water. The reactivity was 25%, and 2-O-allylisosorbide / 5-O-allyisosorbide = 5/5 was produced and no selectivity for 2-O-allylisosorbide was observed.

< Comparative Example  3> Chemical preparation of 2-O-allylisosorbide

The reaction was carried out under the same conditions as in Step 1 of Example 1 except that dimethyl sulfoxide was used instead of xylene as an organic solvent and distilled water was mixed in the same amount as in Step 1 of Example 1 to react. Reactivity was 28% and no selectivity for 2-O-allyl isosorbide was shown.

< Comparative Example  4> Chemical preparation of 2-O-allylisosorbide

The reaction was carried out under the same conditions as in Step 1 of Example 1 except that tetrahydrofuran was used instead of xylene as an organic solvent and distilled water was mixed in the same amount as in Step 1 of Example 1 and reacted. The reactivity was 25%, and 2-O-allylisosorbide / 5-O-allylisosorbide = 4/6 was produced and no selectivity for 2-O-allylisosorbide was observed.

< Comparative Example  5> Chemical preparation of 2-O-allylisosorbide

The reaction is carried out under the same conditions as in Step 1 of Example 1 except that chloroform is used instead of xylene as an organic solvent, and the reaction is carried out without mixing distilled water. The reactivity was 10% and no selectivity for 2-O-allyl isosorbide was shown.

< Comparative Example  6> Chemical preparation of 2-O-allylisosorbide

The reaction was carried out under the same conditions as in Step 1 of Example 1 except that chloroform was used instead of xylene as an organic solvent, and distilled water was mixed in the same amount as in Step 1 of Example 1 and reacted. The reactivity was 13% and no selectivity for 2-O-allyl isosorbide was shown.

< Comparative Example  7> Chemical preparation of 2-O-allyl isosorbide

The reaction was carried out under the same conditions as in step 1 of Example 1 except that chloroform was used instead of xylene as an organic solvent and distilled water was mixed in the same amount as in step 1 of Example 1 to obtain 1-hexyloxy-2 - &lt; / RTI &gt; hydroxypropyl-3-dimethylammonium methylsulfate instead of methyl trioctylammonium chloride. The reactivity was 10% and no selectivity for 2-O-allyl isosorbide was shown.

Table 2 summarizes the reaction conditions and the results (yield and selectivity) of the reaction conditions of Step 1 in Example 1 and Comparative Example 1-7.

Condition Organic solvent Distilled water
Whether or not to use Distilled water
usage Phase transition catalyst yield
(%) Selectivity 1-1
Xylene O 10% 1-hexyloxy-2-hydroxypropyl-3-dimethylammonium methyl sulfate 99 23/1 1-2 " O 10% 1-octyloxy-2-hydroxypropyl-3-dimethylammonium methyl sulfate 98 21/1 1-3 " O 10% 1-dodecyloxy-2-hydroxypropyl-3-dimethylammonium methylsulfate 98 22/1 1-4 " O 10% 1-octyloxy-2-hydroxypropyl-3-diethanolammonium methyl sulfate 98 20/1 1-5 " O 10% 1-octyloxy-2-hydroxypropyl-3-dimethylammonium bromide 98 21/1 1-6 " O 10% Tetrabutylammonium bromide 98 22/1 1-7 " O 10% 3-methylamino-1-hexyloxypropan-2-ol 98 21/1 1-8 " O 10% 3-dimethylamino-1-octyloxypropan-2-ol 98 20/1 1-9 " O 15% 1-hexyloxy-2-hydroxypropyl-3-dimethylammonium methyl sulfate 98 21/1 1-10 " O 0.01% " 98 22/1 1-11 " O One% " 98 21/1 1-12 " O 30% " 98 21/1 1-13 " O 50% " 98 23/1 1-14 Hexane O 10% " 98 21/1 1-15 Cyclohexane O 10% " 98 22/1 1-16 toluene O 10% " 98 21/1 1-17 Mesitylene O 10% " 98 23/1 Comparative Example
One X O 100% " 20 - Comparative Example
2 Dimethyl
Sulfur oxide X - " 25 5/5 Comparative Example
3 " O 10% " 28 - Comparative Example
4 Tetra
Hydrofuran O 10% " 25 4/6 Comparative Example
5 chloroform X - " 10 - Comparative Example
6 chloroform O 10% " 13 - Comparative Example
7 chloroform O 10% Methyltrioctylammonium chloride 10 -

In Table 2,

Condition 1-1 represents the conditions of Step 1 of Example 1 above;

Conditions 1-2 to 1-17 were carried out using the same method as in step 1 of Example 1 except that the conditions of the above table were different;

Selectivity represents the rate of formation of 2-O-allylisosorbide / 5-O-allyl isosorbide; And

The amount of distilled water used represents the weight of the isosorbide used as the starting material of Example 1 in relation to the used weight.

As shown in Table 2,

Step 1 of the production process according to the present invention shows that 2-O-allyl isosorbide is produced with high yield and high selectivity when an organic solvent and a phase transfer catalyst according to the present invention are used.

On the other hand, in the case of using dimethylsulfoxide, tetrahydrofuran and chloroform (Comparative Examples 3, 4 and 6) and not using an organic solvent and only using distilled water (Comparative Example 1) instead of the organic solvent according to the present invention as a solvent, , The selectivity to 2-O-allyl isosorbide is not exhibited, and the yield is also very low.

When the organic solvent other than the organic solvent according to the present invention was used alone or mixed with distilled water (Comparative Examples 2 to 6), the selectivity to 2-O-allylisosorbide was not exhibited and the yield was also very low You know,

From this, it can be seen that the desired 2-O-allyl isosorbide can be prepared with high selectivity and yield by mixing a solvent and distilled water according to the present invention.

In addition, when methyltrioctylammonium chloride (Comparative Example 7), which is a conventionally used phase transfer catalyst, was used instead of the phase transfer catalyst according to the present invention as the phase transfer catalyst, the yield was remarkably low and the yield of 2-O-allylisosorbide Selectivity is not exhibited. Therefore, it can be understood that the phase transition catalyst according to the present invention must be used.

< Experimental Example  1 > The 5-O- Alkyl  Surface tension measurement of isosorbide-2-O-propylsulfonate

The surface tension of the 5-O-alkylisosorbide-2-O-propylsulfonic acid salt obtained in Examples 1 to 4 according to the present invention was measured at a concentration of 0.1% at 25 ° C. The results are shown in Table 3 .

Example Synthetic anionic surfactant Surface tension
(mN / m) One 5-O-hexylisosorbide-2-O-propylsulfonate 29.78 2 5-O-octylisosorbide-2-O-propylsulfonate 25.81 3 5-O-decylisosorbide-2-O-propylsulfonate 27.24 4 5-O-dodecylisosorbide-2-O-propylsulfonate 30.63

As shown in Table 3,

The 5-O-alkylisosorbide-2-O-propylsulfonic acid salt obtained in the example prepared by the process according to the present invention shows low surface tension and thus can be used effectively as a surfactant.

< Experimental Example  2> The 5-O- Alkyl  Measurement of foaming power of isosorbide-2-O-propylsulfonate

The foaming power of 5-O-alkylisosorbide-2-O-propylsulfonate obtained in Examples 1 to 4 according to the present invention was measured. Specifically, 25 ml of a 0.1% solution was added to a 100 ml cylinder at 25 ° C., and the bubble height was read by shaking the bubble 20 times. The height of the bubble after 5 minutes was measured. The results are shown in Table 4 below.

Example Synthetic anionic surfactant Initial bubble height (ml) 5 minutes Late height (ml) One 5-O-hexylisosorbide-2-O-propylsulfonate 18 13 2 5-O-octylisosorbide-2-O-propylsulfonate 49 46 3 5-O-decylisosorbide-2-O-propylsulfonate 52 48 4 5-O-dodecylisosorbide-2-O-propylsulfonate 53 49

As shown in Table 4,

The 5-O-alkylisosorbide-2-O-propylsulfonate salt obtained in the example prepared by the process of the present invention has high initial bubble height and high bubble height after 5 minutes, The longer the length, the higher the bubble height.

Therefore, it can be seen that the 5-O-alkylisosorbide-2-O-propylsulfonate salt according to the present invention can be usefully used as a surfactant.

From the results of the above Examples and Experimental Examples, it can be seen that the process according to the present invention can introduce alkyl chains in endo form into isosorbide with high position selectivity and excellent efficiency by controlling the conditions of solvent or catalyst, Alkyl isosorbide-2-O-alkylsulfonate, and that the anionic surfactant incorporating a sulfonic acid group in the isosorbide produced by the above-mentioned preparation method has excellent surface tension and bubble strength It can be seen that it can be usefully used as a surfactant.

Claims (10)

As shown in Scheme 1 below,
The isosorbide compound represented by the general formula (2) and the compound represented by the general formula (3) are dissolved in a mixed solvent of one kind of organic solvent selected from the group consisting of hexane, cyclohexane, toluene, xylene and mesitylene and water, Hydroxypropyl-3-dimethylammonium methylsulfate, 1-octyloxy-2-hydroxypropyl-3-dimethylammonium methylsulfate, 1-dodecyloxy-2- , 1-octyloxy-2-hydroxypropyl-3-diethanolammonium methylsulfate, 1-octyloxy-2-hydroxypropyl-3-dimethylammonium bromide, tetrabutylammonium bromide, 3- 2-ol and 3-dimethylamino-1-octyloxypropane-2-ol to obtain a compound represented by the formula (4) (step 1);
Reacting the compound represented by the formula (4) and the compound represented by the formula (5) obtained in the above step 1 to obtain the compound represented by the formula (6) (step 2); And
Reacting the compound represented by the formula (6) and the compound represented by the formula (7) obtained in the step 2 to obtain a compound represented by the formula (1) (step 3); and reacting the isosorbide anion interface Location of active agent: Selective preparation method:
[Reaction Scheme 1]

(In the above Reaction Scheme 1,
R &lt; ¹ &gt; is straight or branched chain _C1-20 alkyl;
L ¹ is linear or branched C _1-6 alkylene;
M is an alkali metal; And
And each X is independently halogen.
The method according to claim 1,
Wherein the step 1 can further use at least one base selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide.
The method according to claim 1,
Wherein the compound represented by the general formula (3) in the step (1) is used in a ratio of 0.8-2.5 mol per 1 mol of the isosorbide compound represented by the general formula (2).
The method according to claim 1,
Wherein the phase transfer catalyst of step 1 is used in a proportion of 0.0001 to 0.1 mole per 1 mole of the isosorbide compound represented by the general formula (2). delete delete delete delete delete delete