JP3485524B2 - Method for producing polyhydroxyl compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a polyhydric alcohol or
If the specific hydroxyl group of the derivative is ketal or acetal
Deprotection of the compound protected by
A simple and efficient manufacturing method for manufacturing products
You. [0002] BACKGROUND OF THE INVENTION Problems to be Solved by the Invention
A specific hydroxyl group of a compound having a hydroxyl group is ketalized or
Is protected by acetalization and the remaining hydroxyl groups
To derivatize it, deprotect it if necessary,
Synthesizing polyhydroxyl compounds
It is a well-known method generally performed in the field of science. Here, usually, deprotection (deketalization, deprotection,
Acetalization) is carried out in the presence of excess water and
Mixture to which a solvent has been added to make the reaction system homogeneous.
It is carried out by hydrolyzing and then neutralizing the acid catalyst and producing
Excess ketone or aldehyde from the protected group
And the solvent is distilled off under reduced pressure.
This is done by filtering and obtaining a deprotected polyhydric alcohol.
(For example, in Japanese Patent Application Laid-Open No. Hei 6-145341,
Adjust the pH of the mixture to 1.0 using 0% aqueous hydrochloric acid
And stir at 60 ° C. for 1 hour, then add 50% sodium hydroxide
The pH of the mixture was adjusted to 6.5 with water,
The ketone produced by heating at 3.33 kPa or less for 1 hour
Disclosed is a method of distilling together with water and filtering out precipitated salts.
Is). [0004] However, in the above method, excessive water
And use solvent if necessary.
The yield is low, and considering industrial production,
Water and solvent are used as little as possible.
It is hoped that there is no. [0005] Further, a method using an excess of water as described above.
A compound having a hydrolyzable group such as an ester group
When deprotection is performed, the
It also causes hydrolysis of
Generation is inevitable. [0006] Further, a method using an excess of water as described above.
Then, after deprotection, the ketone or aldehyde
A step of removing excess water and solvent under reduced pressure is necessary.
In view of industrial production, simplification of the process is desired. Further, the acid used in the above method is an aqueous solution
If the water used is excessive because it is diluted and used in
Requires a corresponding amount of acid catalyst, which is neutralized
Salts formed by the process may be contained as impurities.
In industrial production, the amount used is also low in terms of cost.
Low is desired. Accordingly, an object of the present invention is to provide a polyhydric alcohol.
Or a specific hydroxyl group of a derivative thereof is ketal or aceta
Deprotection of the compound protected by the reaction with excess water and solvent
Method that is industrially simple and efficient without using
Is to provide. [0009] Means for Solving the Problems The present inventors have conventionally proposed
Deprotection performed in a reaction system using excess water (deketal
, Deacetalization) process while contacting with steam
In this case, a solid acid catalyst was used as the acid catalyst.
That the above issues can be solved
The invention has been completed. That is, the present invention relates to the general formula
(I) [0010] Embedded image [Wherein, R¹And R^TwoAre the same or different, water
An elemental atom, a linear or branched alkyl group having 1 to 22 carbon atoms
Or substituted with an alkenyl group or an alkyl group
Represents an aryl group having 6 to 30 carbon atoms which may be¹
And R^TwoMay together form a ring. X is R^ThreeO-
Represents a group or a halogen atom represented by R^ThreeIs a hydrogen atom,
Linear or branched saturated or unsaturated fats having 1 to 23 carbon atoms
An aromatic hydrocarbon group, an aliphatic acyl group having 1 to 22 carbon atoms,
Substituted with an alkyl group or an acyl group, or ketal or
Represents a glyceryl group which may be protected with an acetal
You. A represents an alkylene group having 2 to 4 carbon atoms;
May be the same or different. n is alkylene oxa
It is a number from 0 to 100 indicating the average number of added moles of the id. However
And when n is 0, X is not HO-. ] Represented by
If the two hydroxyl groups of the alcohol or its derivative are ketal or
Or compounds with a structure protected by acetal
(Deketalization, deacetalization) and the general formula (II) [0012] Embedded image [Wherein, X, A and n represent the above-mentioned meanings.
You. To produce a polyhydroxyl compound represented by
In this case, by contacting with steam in the presence of a solid acid catalyst,
Production method of polyhydroxyl compound to be deprotected
provide. [0014] BEST MODE FOR CARRYING OUT THE INVENTION
In the protected compound represented by the general formula (I), R¹Passing
And R^TwoAre the same or different and each represents a hydrogen atom, a linear or branched
An alkyl or alkenyl group having 1 to 22 carbon atoms,
Or 6 to 3 carbon atoms which may be substituted with an alkyl group.
0 represents an aryl group;¹And R^TwoTogether form a ring
, But preferably a hydrogen atom or carbon number
1 to 6 alkyl groups. X is R^ThreeA group represented by O- or a halogen atom
Show, R^ThreeIs a hydrogen atom, a linear or branched carbon number of 1 to 23
A saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms
Substituted with an aliphatic acyl group, or an alkyl group or an acyl group
Or ketal or acetal protected
It shows a good glyceryl group, but preferably has 1 to 18 carbon atoms.
An alkyl group or an aliphatic acyl group having 1 to 22 carbon atoms
is there. A represents an alkylene group having 2 to 4 carbon atoms
Is preferably an ethylene group or a propylene group. n is
0 to 10 indicating the average number of moles of alkylene oxide added
Although it is a number of 0, it is preferably a number of 0 to 30. The synthesis of the compound represented by the general formula (I)
For example, the polyhydric alcohol derivative is a glycerin derivative
Glycerin has two of the three hydroxyl groups
Of the general formula (III) [0018] Embedded image [Wherein, R¹And R^TwoHas the above-mentioned meaning. ]
Ketalized with a ketone or aldehyde represented by
Is converted to an acetal and has the general formula [0020] Embedded image [Wherein R¹And R^TwoHas the above-mentioned meaning. ]
To obtain the 1,3-dioxolane compound represented by
If alkylene oxide is added in the presence of a catalyst
And the compound represented by the general formula (V) R^FourCOOR^Five        (V) (Where R^FourIs a hydrogen atom or a C 1-22 fat
A residue obtained by removing a CO group from an aromatic acyl group;^FiveIs hydrogen field
From lower alkyl, lower alkyl group or fat^FourRemaining excluding COO group
Represents a group. Fatty acids represented by the formula
Esterification by reacting steal or fat or oil
Or the general formula (VI) R⁶-Y (VI) (Where R⁶Is a saturated or straight-chain or branched-chain having 1 to 23 carbon atoms.
Represents an unsaturated aliphatic hydrocarbon group, and Y represents a halogen.
You. Alkyl halide represented by the formula
By reacting hydrin, alkyl glycidyl ether, etc.
It can be obtained by etherification. Here, glycerin is represented by the general formula (III)
Reaction with ketones or aldehydes
Forms an acetal to protect the hydroxyl group and has the general formula (I
Method for obtaining 1,3-dioxolane compound represented by V)
Is a well-established process in the field of organic chemistry
These reactions are usually carried out in acid catalysts and solvents.
This solvent removes water generated during the reaction by azeotropic distillation.
To help create an equilibrium relationship,
Tar or acetal formation proceeds easily. The compound represented by the general formula (III) used in the above reaction
Acetone, methyl, etc.
Ketones such as ethyl ketone and cyclohexanone, form
Aldehydes such as aldehyde and acetaldehyde
Can be The 1,3-formula represented by the general formula (IV)
As dioxolane compounds, for example, commercially available 2,2-dimethyl
Cyl-dioxolan-4-methanol (general name: Solketa
) Can be used as it is. In the general formula (IV) obtained as described above,
The 1,3-dioxolane represented is optionally added
Alkylene oxide having 2 to 4 carbon atoms
Chelen oxide, specifically ethylene oxide,
Propylene oxide, butylene oxide, etc.
These may be added one or more kinds, and two or more kinds may be added.
When adding them, even if their addition state is random,
It may be lock-shaped. Used in this alkylene oxide addition reaction
The catalyst used is an alkali metal or alkaline earth metal.
Hydroxides, oxides, organic acid salts or alcoholates of the genus
Alkali metal compounds or alkaline earth metals selected from
Preferably, a compound is used. In the general formula (IV) obtained as described above,
1,3-dioxolane represented by the formula
General used for esterifying oxide adducts
Fatty acids represented by formula (V), fatty acid lower alkyl esters
Oils and fats such as caprylic acid, lauric acid,
Stinic acid, palmitic acid, stearic acid, oleic acid,
C 1-22 saturated or unsaturated such as isostearic acid
Japanese fatty acids, methyl, ethyl and propyl of these fatty acids
Esters or oils containing these fatty acids as constituents
And the like. Specific examples of fats and oils include palm kernel
Oil, palm oil, plant-derived oils such as coconut oil, or fish oil,
Animal-derived fats and oils such as beef tallow and the like can be mentioned. Preferably plant
It is derived from fats and oils. The reaction conditions for the esterification are not particularly limited.
In addition to the method using a normal base catalyst, it has esterification activity.
It can also be performed using an enzyme that performs the reaction. The general formula (I) obtained as described above
V) 1,3-dioxolane or its alkyl
Used to etherify the lenoxide adduct
As an alkyl halide represented by the general formula (VI)
Is a chloride having an alkyl group having 1 to 23 carbon atoms,
Bromide and the like. Other etherification reagents
Epoxy compounds such as epichlorohydrin or carbon
Alkyl glycidyl esters having alkyl groups of formulas 1 to 23
Acyl glycol having an acyl group having 1 to 22 carbon atoms
And sidyl ether. The reaction conditions for the etherification are not particularly limited.
It can be carried out using a usual phase transfer catalyst. In the present invention, the obtained
The compound represented by the general formula (I) is used in the presence of a solid acid catalyst.
Deprotection while in contact with water vapor (deketalization,
(Deacetalization). Typical examples of the solid acid catalyst used here are:
As described in the Catalyst Course (Catalyst Society of Japan)
Una, SiO_Two・ Al_TwoO_Three, SiO_Two・ MgO, SiO_Two・ ZrO_Two, Al_TwoO_Three
・ B_TwoO_Three, Al_TwoO_Three, Various zeolites, various heteropoly acids,
Various phosphates, various sulfates, H_ThreePO_Four/ Diatomaceous earth
Acid), cation exchange resin; (superacid), oxide-supported Sb
F_Five, SO_Four ^2-/ ZrO_TwoEtc., but in particular limited to these
Compounds that have acid sites on the solid surface
Can be used. Of these, it is easy to obtain,
Acid clay is advantageous for industrial use.
(Galeon Earth Series, manufactured by Mizusawa Chemical Co., Ltd.)
Ka alumina (Mizuka Ace series, Mizusawa Chemical Co., Ltd.)
), Finely divided silica (Silton series, Mizusawa Chemical)
Co., Ltd.), synthetic acid-treated zeolite (HSZ-640HOA, Toso
-Co., Ltd.). The representative method of deprotection in the present invention is
The compound represented by the general formula (I)
0.01-5.0% by weight of the medium, preferably 0.5-3.
0% by weight, 10 ° C to 120 ° C, preferably 30 ° C to
At a reaction temperature of 100 ° C., normal pressure, or 0.13-66.
66 kPa, preferably 1.33 to 13.33 kPa
It is performed while blowing water vapor under reduced pressure.
The ketone or aldehyde that forms is simultaneously distilled out of the system
You. The amount of steam blown per hour is 100 weight of raw material
0.1 to 100 parts by weight, preferably 0.2 to 100 parts by weight,
20 parts by weight is more preferable, and 1 to 10 parts by weight is further preferable.
New The total amount of steam blown until the end of the reaction
Is preferably 1 to 100 parts by weight based on 100 parts by weight of the raw material.
Preferably 2 to 60 parts by weight, more preferably 5 to 40 parts by weight.
Is more preferred. The raw material to be deketalized has an ester group or the like.
From the viewpoint of suppressing hydrolysis, the water in the reaction system
Preferably 5% by weight or less, more preferably 3% by weight or less
Lower, more preferably 1% by weight or less.
No. Here, when steam is blown at normal pressure,
After the reaction, remove the ketone or aldehyde and water
You may. After the completion of the reaction, perform removal operation such as filtration, and release
Protected polyhydroxyl compound represented by the general formula (II)
Get things. By performing such a method, two adjacent
Having two hydroxyl groups and derivatized only at the α-position
A loxyl compound can be obtained. [0037] The deprotection according to the present invention allows excess
It is not necessary to prepare water, solvent, etc.
High yield due to small changes in volume with the introduction of a team only
(High yield) and the desired product is obtained.
The process of distilling water, solvent, etc. is unnecessary, and the number of processes can be reduced.
This is advantageous as an industrial production method. Deprotection is possible under mild reaction conditions.
Therefore, decomposition of other functional groups (hydrolysis of ester groups)
Deprotection reaction can be performed while suppressing
It is possible to obtain a good quality compound with few impurities.
Noh. [0039] EXAMPLES In the following examples, percentages are by weight unless otherwise specified.
is there. Embodiment 1 (A) Ketalization reaction 230.3 g of glycerin in a 2 liter four-necked flask
(2.5 mol) and 270.4 g of methyl ethyl ketone
(3.75 mol) and 4.77 g of paratoluenesulfonic acid
(0.025 mol) and 109.7 g of heptane,
At a temperature of 75 to 98 ° C., while removing water generated in the reaction,
The reaction was carried out for 16 hours. Next, heptane and excess methyl
After the ethyl ketone was distilled off under reduced pressure,
Vacuum distillation is performed at 0 to 85 ° C. and represented by the following formula (VII).
310.7 g (2.13 mol) of glycerin ketal were obtained.
Was. Yield 85%. [0041] Embedded image (B) Esterification reaction The formula (VI) obtained by the above reaction was placed in a 1-liter four-necked flask.
169.6 g of glycerin ketal represented by I) (1.1
6 mol) and 303.2 g (1.76 mol) of capric acid
And immobilized lipase (Novozym 435, Novo Norde
10.8 g (manufactured by Disc Bio Industry Co., Ltd.)
(2.3% by weight), 0.67 kPa, 40
The reaction was carried out for 8 hours while removing water generated at ° C. Anti
Efficiency 98%. The immobilized lipase was removed from the reaction solution by filtration.
After removing, the temperature was raised to 170 ° C. at 0.67 kPa and excess
The capric acid was distilled off under reduced pressure.
Capric acid is removed by introducing 73.0 g of steam at 0 ° C.
And 1,3-dioxolanka represented by the following formula (VIII):
324.4 g (1.08 mol) of prinate ester were obtained.
Was. Yield 93%. [0043] Embedded image (C) Deketalization reaction 1,3-dioxolancapric acid obtained by the above reaction
220 g (0.73 mol) of stell is mixed with acid clay (Galeon)
2.2 g of Earth NV, manufactured by Mizusawa Chemical Co., Ltd.
° C, 13.3 kPa, 1,3-di / hour
2 to 4% of steamed oxolancapric acid ester
Gas into the reaction system to produce ketone (methyl ethyl
Dekettering while removing ketone) and excess water vapor out of the system
After the reaction for 7.5 hours, the catalyst was filtered off and 6.6
After dehydration at 5 kPa and 70 ° C. for 0.5 hour, the following formula (I
X) Capric acid monoglyceride represented by 169.0
g (0.69 mol) were obtained. In this deketalization reaction
The yield was 94%. Acid value 0.2 (calculated value 0), Ken
Chemical value 225 (calculated value 228). Gas chromatog
As a result of analysis by Raffi,
The area percentage of the alloy was 93%. Also, deketalization
Of the target product obtained for the raw materials charged in the reaction.
The incorporation yield was 76.8%. [0045] Embedded image Embodiment 2 (A) Esterification reaction 86.5 g (0.58 mol) of caprylic acid was used as a raw material
An esterification reaction was carried out in the same manner as in Example 1 except for the above. reaction
The rate is 97%. After performing the same post-processing as in Example 1, the following formula
1,3-dioxolancaprylic acid S represented by (X)
149.8 g of ter were obtained. Yield 93%. [0047] Embedded image (B) Deketalization reaction 1,3-dioxolancapri obtained by the above reaction as a raw material
Except for using 150 g (0.54 mol) of the phosphoric acid ester
A deketalization reaction was carried out in the same manner as in Example 1, and the following formula (X
98.1 g of caprylic acid monoglyceride represented by I)
(0.44 mol). The yield in this deketalization reaction
The rate was 89.3%. Acid value 0.3 (calculated value 0)
254 (calculated value 257). Gas chromatograph the product
As a result of analysis by graph, monoglyceryl caprylate
The area percentage of the id was 93%. Also, deketal
Of the target product obtained from the raw materials charged in the
The charging yield was 65.4%. [0049] Embedded image Embodiment 3 (A) Esterification reaction Using 116.2 g (0.58 mol) of lauric acid as a raw material
An esterification reaction was carried out in the same manner as in Example 1 except for the above. Anti
The response rate is 97%. After performing the same post-processing as in the first embodiment, the post-processing is performed.
Perform vacuum distillation at 170 to 185 ° C at 40 kPa, and
1,3-dioxolan laurate represented by the formula (XII)
177.4 g of stell were obtained. Yield 93%. [0051] Embedded image (B) Deketalization reaction 1,3-dioxolan lauri obtained by the above reaction as a raw material
Except that 150 g (0.46 mol) of the acid ester was used.
A deketalization reaction was carried out in the same manner as in Example 1, and the following formula (XI)
Lauric acid monoglyceride 117.7 represented by II)
g (0.44 mol) were obtained. In this deketalization reaction
The yield was 89.4%. Acid value 0.3 (calculated value 0),
Saponification value 205 (calculated value 204). Gas chromatograph the product
As a result of analysis by
The ride area percentage was 94%. Also, deketter
Target obtained from the raw materials charged in the reaction
Was 78.5%. [0053] Embedded image Embodiment 4 (A) Ketalization reaction 230.2 g of glycerin in a 2 liter four-necked flask
(2.5 mol) and 270.4 g of methyl ethyl ketone
(3.75 mol) and 4.77 g of paratoluenesulfonic acid
(0.025 mol) and 109.7 g of heptane,
At 75-98 ° C., while removing water produced by the reaction, 14
The reaction was performed for a time. Next, heptane and excess methyl
After the ketone is distilled off under reduced pressure, 50 to 8 at 0.67 kPa.
Distilled under reduced pressure at 5 ° C to obtain glycerol represented by the following formula (XIV).
310.5 g (2.13 mol) of linker were obtained. Income
Rate 83%. [0055] Embedded image (B) Ethylene oxide addition reaction In a 3.5 liter autoclave, the reaction
299.9 g of glycerin ketal represented by the formula (XIV):
(2.05 mol) and 0.55 g of potassium hydroxide (0.0
1 mol) and dehydrate at 2.67 kPa, 110 ° C.
After that, the temperature was raised to 165 ° C. After that, at the same temperature
542 g (12.3 mol) of oxide at a pressure of 0.29
The reaction was carried out while maintaining the pressure at ~ 0.49 MPa. After aging at the same temperature for 0.5 to 1 hour,
℃, KYOWARD 600S (Kyowa Chemical Co., Ltd.)
4.5 g (8% by weight to KOH%) and 4.00 k
Pressure reduction treatment for 1 hour at Pa, neutralization of the catalyst and unreacted ethylene
After removing the oxide, filtration is performed, and the following formula is used.
Ethylene oxa of glycerin ketal represented by (XV)
800.2 g (1.95 mol) of the id adduct were obtained. yield
96%. [0058] Embedded image (C) Esterification reaction In a 1-liter four-necked flask, the formula (X
V) Ethylene oxide of glycerin ketal
238.5 g (0.58 mol) of adduct and caprylic acid 1
26.6 g (0.88 mol) and immobilized lipase (No.
vozym435, Novo Nordisk Bioindustry
8.4 g (2.3% by weight).
Then, while removing water generated at 0.67 kPa and 40 ° C.
For 8 hours. 97% conversion. The immobilized lipase was removed from the reaction solution by filtration.
After removing, the temperature was raised to 170 ° C. at 0.67 kPa and excess
The caprylic acid was distilled off under reduced pressure.
At 0 ° C., 37.2 g (10%) of steam was introduced to
The acid is removed, and a glycerin keter represented by the following formula (XVI)
Ethyl oxide adduct caprylate 2
86.6 g (0.53 mol) were obtained. Yield 92%. [0061] Embedded image (D) Deketalization reaction Glycerin keta represented by the formula (XVI) obtained by the above reaction
Ester of ethylene oxide adduct of cellulose
150 g (0.28 mol) of acid clay (Galeon earth)
NV, manufactured by Mizusawa Chemical Co., Ltd.)
At 13.3 kPa, 2% to 4% per hour
Steam is introduced into the reaction system, and the resulting ketone (methyl
(Ketyl ketone) and excess water vapor
After the tarring reaction was performed for 8 hours, the mixture was filtered and filtered at 2.67 kP.
a, After dehydration at 80 ° C. for 0.5 hour, the following formula (XVII)
Α-polyoxyethylene glycerin monocapri represented
129.8 g (0.26 mol) of the oleic ester were obtained. This
The yield in the deketalization reaction was 96%. Acid value
0.2 (calculated value 0), saponification value 115.2 (calculated value 11
6). The product was analyzed by gas chromatography.
Fruit, α-polyoxyethylene glycerin monocaprylic acid
The area percentage of the ester was 92%. In addition,
Obtained for the raw materials charged in the reaction
The charge yield of the product was 86.5%. [0063] Embedded imageEmbodiment 5 (A) Etherification reaction Octyl chloride 32 in a 2-liter 4-neck flask
6.9 g (2.2 mol) and 264.3 g solketal
(2.0 mol) and tetrabutylammonium bromide
(TBAB) 127.0 g (0.4 mol) was charged.
Then, 785 g of a 48% aqueous potassium hydroxide solution at 80 ° C.
(6.8 mol) was added dropwise over 30 minutes, and the temperature was raised to 95 ° C.
Then, an etherification reaction was performed for 10 hours. Then water 300
g to dissolve the salt generated and remove the separated lower layer
Then, 300 g of cyclohexane is added thereto, and two more
Washed with turtle water. And excess with cyclohexane
Octyl chloride is distilled off under reduced pressure, and expressed by the following formula (XVIII).
Glycerin ketal octyl ether 415.3
g (1.7 mol) were obtained. Yield 85%. [0065] Embedded image (B) Deketalization reaction Glycer represented by the formula (XVIII) obtained by the above reaction
150 g of Linketal octyl ether (0.61 m
), A deketalization reaction was carried out in the same manner as in Example 1.
Octylglyceryl ether represented by the following formula (XIX)
119.7 g (0.60 mol) were obtained. This deketter
The yield in the oxidation reaction was 96%. Acid value 0.3 (calculated
Value 0), hydroxyl value 545 (calculated value 549). The product
As a result of analysis by
The area percentage of seryl ether was 97%. Also,
Obtained for the raw materials charged in the deketalization reaction
The charging yield of the desired product was 79.8%. [0067] Embedded image Embodiment 6 (A) Etherification reaction Instead of solketal, the formula obtained in (b) of Example 4
Ethylene oxa of glycerin ketal represented by (XV)
Except using 410.5 g (1.0 mol) of the id adduct
Performs the same etherification reaction as in Example 5 and has the following formula
Ethylene oxa of glycerin ketal represented by (XX)
470.5 g of octyl ether (0.9 m
Le). 89% yield. [0069] Embedded image (B) Deketalization reaction Glycerol represented by the formula (XX) obtained by the above reaction as a raw material
Octylate of ethylene oxide adduct of unketal
As in Example 1, using 150 g (0.29 mol) of tellurium
To a deketalization reaction, and the compound represented by the following formula (XXI)
130.5 g of butyl glyceryl ether ethoxylate
(0.27 mol). The yield in this deketalization reaction
The rate was 96%. Acid value 0.2 (calculated value 0), hydroxyl group
Value 237 (calculated 239.5). Gas chromatograph the product
Analysis of the octyl glyceryl ester
The area percentage of terethoxylate was 96%. Ma
In addition, for the raw materials charged in the deketalization reaction,
The charging yield of the obtained target product was 87.0%. [0071] Embedded image Embodiment 7 (A) Epoxidation reaction In a 1-liter four-necked flask, add epichlorohydrin 36
9.9 g (4.0 mol) and triethylbenzylammonium
2.3 g (0.01 mol) of um chloride and NaOH5
2.0 (1.3 mol) was charged and the example was carried out at 35 to 40 ° C.
146.2 g (1.0 g) of the glycerin ketal obtained in
Mol) was added dropwise over 1.5 hours and then ripened for 4.5 hours.
Done. The salt formed is removed by filtration, and
After distilling off lorhydrin under reduced pressure, the following formula was obtained by distillation under reduced pressure.
Epoxidized glycerin ketal represented by (XXII)
133.4 g (0.66 mol) were obtained. [0073] Embedded image (B) Ketalization reaction In a 1 liter four-necked flask, add methyl ethyl ketone 16
7.3 g (2.3 mol) and boron trifluoride ethyl ether
0.65 g (0.0046 mol)
Glycerin represented by the formula (XXII) obtained by the above reaction
116.2 g (0.57 mol) of epoxidized ketal
Was added dropwise at room temperature over 2 hours. 1 hour at 30 ° C
After aging, the catalyst was neutralized with an aqueous NaOH solution and excess
The butyl ethyl ketone was distilled off under reduced pressure and represented by the following formula (XXIII).
156.1 g of ketalized diglycerin (0.5
7 mol). Yield 99%. [0075] Embedded image (C) Deketalization reaction The starting material is a diglyme represented by the formula (XXIII) obtained by the above reaction.
Use 137.0 g (0.5 mol) of ketalized serine
The deketalization reaction was carried out in the same manner as in Example 1, and the following formula
79.8 g of diglycerin represented by (XXIV) (0.48
Mol). The yield in this deketalization reaction is 96%.
Met. Acid value 0.4 (calculated value 0), hydroxyl value 1345
(Calculated 1350). Products for gas chromatography
As a result of more analysis, the area percentage of diglycerin was 91%.
Met. The source charged in the deketalization reaction
The charging yield of the target product obtained with respect to the feed was 58.2%.
there were. [0077] Embedded image Embodiment 8 (A) Glyceryl etherification reaction The grease obtained in Example 4 was placed in a 2 liter four-necked flask.
146.2 g (1.0 mol) of serine ketal and tetrame
Chill-1,6-diaminohexane 3.4 g (0.02
) And stirred and mixed under nitrogen gas flow. Next
And 93.1 g of octyl glycidyl ether at 100 ° C.
(0.5 mol) was added dropwise over 2 hours. After dropping, reaction
After aging at 130-140 ° C for 6 hours, ion
200 g of exchanged water was added, salt was further added, and the mixture was allowed to stand and separated.
After separating the upper layer by liquid separation, the excess glycerol
After distilling off the unketal in vacuo, further vacuum distillation is performed,
Octyl of glycerin ketal represented by the following formula (XXV)
148.0 g (0.45 mol) of glyceryl ether was obtained.
Was. Yield 89.1%. [0079] Embedded image (B) Deketalization reaction Glyceryl represented by formula (XXV) obtained by the above reaction
132.9 g of octyl glyceryl ether of Nketal
(0.4 mol) and deketalization in the same manner as in Example 1.
After the reaction, octyldiglycerol represented by the following formula (XXVI)
106.9 g (0.38 mol) of serine were obtained. This
The yield in the tarification reaction was 96%. Acid value 0.2
(Calculated value 0), hydroxyl value 300 (calculated value 605). Generate
The product was analyzed by gas chromatography,
The area percentage of ludiglycerin was 92%. Also,
Obtained for the raw materials charged in the deketalization reaction
The charged yield of the desired product was 80%. [0081] Embedded imageEmbodiment 9 (A) Ketalization reaction Epichlorohydrin 13 in a 2 liter four-necked flask
9.1 g (1.5 mol) and acetone 479.1 g (8.
25 mol) and boron trifluoride ethyl ether complex 0.
Charge 69g (0.5% by weight vs. epichlorohydrin)
And react at 40 ° C for 3 hours.
Gas chromatography to confirm that the
Was. Next, excess acetone used was distilled off under reduced pressure, and 5% carbonic acid was removed.
Reaction with 100 g of potassium aqueous solution and 220 g of ion exchanged water
The product was washed with water, dehydrated under reduced pressure, and expressed by the following formula (XXVII).
Of 3-chloro-1,2-propanediol
165.7 g (1.0 mol) of the compound were obtained. Yield 73.
3%. [0083] Embedded image (B) Deketalization reaction The starting material is a 3-k represented by the formula (XXVII) obtained by the above reaction.
Ketalized product of loro-1,2-propanediol 67.
Using 8 g (0.45 mol), the decanting was performed in the same manner as in Example 1.
The reaction is carried out to obtain a 3-cyclohexene represented by the following formula (XXVIII).
46.4 g of loro-1,2-propanediol (0.42 g)
Mol). The yield in this deketalization reaction is 93%.
Met. Acid value 0.4 (calculated value 0), hydroxyl value 1010
(Calculated 1015). Products for gas chromatography
As a result of further analysis, 3-chloro-1,2-propanedi
The area percentage of the tool was 92%. Also, deketal
Of the target product obtained from the raw materials charged in the
The charging yield was 68.4%. [0085] Embedded image Embodiment 10 (A) Esterification reaction In a 500 mL four-necked flask, the same as (a) of Example 1
100.87 g of glycerin ketal obtained in
(0.69 mol) and 224.20 g of palm kernel oil fatty acid
(1.035 mol) and immobilized lipase (Novozy)
m435, Novo Nordisk Bioindustry
After charging 7.48 g (2.3% by weight),
While removing water generated at 0.67 kPa and 40 ° C., 8
The reaction was performed for a time. Conversion rate 98%. From the reaction solution by filtration
After removing the immobilized lipase, 22 at 0.67 kPa
Temperature is raised to 0 ° C to remove excess palm kernel oil fatty acids under reduced pressure
And steam was introduced at 2.67 kPa and 220 ° C.
To remove palm kernel oil fatty acids, represented by the following formula (XXIX)
Glycerin ketal palm kernel oil fatty acid monoester 3
24.1 g were obtained. 94% yield. [0087] Embedded image (Wherein R represents carbohydrate from palm kernel oil fatty acid)
The residue excluding the sil group is shown. ) (B) Deketalization reaction Glycerin ketal palm kernel fat obtained by the above reaction
150g of fatty acid monoester and acid clay (Galeon earth)
4.5 g of NV, manufactured by Mizusawa Chemical Co., Ltd .;
Glycerin ketter per hour at 3.3 kPa
Of palm kernel oil fatty acid monoesters
Steam is introduced into the reaction system, and the resulting ketone (methyl
(Ketyl ketone) and excess water vapor
After performing the taration reaction for 5 hours, the catalyst was filtered, and 6.6 was removed.
After dehydration at 5 kPa and 70 ° C. for 0.5 hour, the following formula (XX)
X) Palm kernel oil fatty acid monoglyceride 14 represented by
6.6 g were obtained. The yield in this deketalization reaction is 87
%Met. Acid value 0.53 (calculated value 0), saponification value 36
9.5 (calculated 386). Gas chromatograph the product
Analysis of palm kernel oil fatty acid monoglycera
The area percentage of the id was 89.9%. [0089] Embedded image (Wherein R represents carbohydrate from palm kernel oil fatty acid)
The residue excluding the sil group is shown. )

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C07C 43/178 C07C 43/178 67/29 67/29 69/30 69/30 (72) Inventor Takehiro Takenaka 1334 Minato 1334 Minato, Wakayama-shi, Wakayama Prefecture. In the laboratory, Inc. (72) Inventor Hiroshi Nagumo, 1334 Minato, Wakayama-shi, Wakayama Kao Corporation In the laboratory (56) References JP-A-2001-39914 (JP, A) JP-A-11-322675 (JP, A) JP-A-11-228466 (JP, A) JP-A-6-145341 (JP, A) JP-A-63-482231 (JP, A) JP-A-57-197235 (JP, A) JP-A-51-39614 (JP) Special table 2002-542216 (JP, A) Special table Hei 5-505623 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 29/10 C07C 31/00 C07C 41 / 00 C07C 43/00 C07C 67/00 C07C 69/00

Claims (1)

(57) [Claim 1] The general formula (I) [In the formula, R ¹ and R ² are the same or different and each have a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or a total of 6 carbon atoms which may be substituted with an alkyl group. And 30 to 30 aryl groups, and R ¹ and R ² may together form a ring. X represents a group or a halogen atom represented by R ³ O-, R ³ is a hydrogen atom, a straight-chain or branched-chain saturated or unsaturated aliphatic hydrocarbon group having a carbon number of 1 to 23, 1 to 22 carbon atoms A glyceryl group which may be substituted with an aliphatic acyl group, an alkyl group or an acyl group, or protected with a ketal or acetal. A represents an alkylene group having 2 to 4 carbon atoms, and n A's may be the same or different. n is a number from 0 to 100 indicating the average number of moles of alkylene oxide added. Where n is 0
Then X is not HO-. A compound having a structure in which the two hydroxyl groups of the polyhydric alcohol or a derivative thereof represented by the above formula is protected by a ketal or an acetal (deketalization and deacetalization), to obtain a compound represented by the general formula (II): [Wherein, X, A and n have the above-mentioned meanings. A method for producing a polyhydroxyl compound represented by the formula (1), wherein the polyhydroxyl compound is deprotected by contacting with water vapor in the presence of a solid acid catalyst.