JP2008189595A - Method for producing (1,3-dioxolan-4-yl)alkyl alcohol derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a high-quality (1,3-dioxolan-4-yl)alkyl alcohol derivative, wherein use is made of a reduced amount of a catalyst and the catalyst recovered can be reused as it is. <P>SOLUTION: The method for producing the (1,3-dioxolan-4-yl)alkyl alcohol derivative comprises the process of conducting a dehydration reaction between a carbonyl group-containing compound and an alkanetriol compound in the presence of at least one acetalization catalyst selected from the group consisting of rare earth metal sulfate, rare earth metal triflate, zirconium sulfate and zirconium acetylacetonate, followed by feeding, as recycled catalyst, the above acetalization catalyst recovered from the resultant reaction mixture to the dehydration reaction. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a (1,3-dioxolan-4-yl) alkyl alcohol derivative. More specifically, the present invention relates to a method for producing a (1,3-dioxolan-4-yl) alkyl alcohol derivative used for producing a dioxolane compound used for various coating agents, pressure-sensitive adhesives, printing inks, resists and the like.

  In recent years, development of a production method for obtaining a (meth) acrylate polymer with high purity and high yield has been desired. Since (meth) acrylate polymers are usually obtained by polymerizing (meth) acrylate monomers, (meth) acrylate monomers with sufficiently reduced impurities and highly reactive (meta) There is a need for acrylate monomers.

  In the method of Patent Document 1, the reaction between a carbonyl group-containing compound and glycerin is performed in the presence of an acetalization catalyst until the conversion rate of glycerin is 20 to 95%, and after the reaction, the glycerin layer is removed from the reaction solution. Thus, a (1,3-dioxolan-4-yl) methanol derivative can be obtained with high purity and high yield.

  In Patent Document 2, by reacting (meth) acrylic acid and alkylene oxide in the presence of a chromium compound and / or an iron compound, the formation of by-products is sufficiently suppressed, and water reduction, dispersibility, and durability are reduced. A method for producing a (meth) acrylate monomer excellent in various physical properties such as the above is disclosed.

On the other hand, Patent Document 3 has excellent properties by reacting with many other polymers by using an ethylenically unsaturated monomer containing a cyclic orthoester group having extremely high reactivity as a substituent. A polymer capable of forming a copolymer-containing composition can be obtained.
JP 2004-059435 A JP 2006-70147 A JP-A-5-39325

  However, although the conventional production method is excellent in terms of purity and yield, it is insufficient in terms of efficiency. That is, it is theoretically possible to recover and reuse the catalyst used in the production of the monomer after the reaction, but the recovered catalyst cannot be reused as it is. Since this requires a complicated operation, it is substantially difficult to reuse the catalyst used in the production of the monomer.

  An object of the present invention is to efficiently produce a high-quality (1,3-dioxolan-4-yl) alkyl alcohol derivative that can reduce the amount of catalyst used and can reuse the recovered catalyst as it is. It is to provide a method.

  The present invention relates to a compound of formula (I):

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a linear, branched or cyclic C 1-18 alkyl group or phenyl group)
A carbonyl group-containing compound represented by formula (II):

(Wherein R ^{3 to} R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and m represents 0 or an integer of 1 to 4)
A dehydration reaction with an alkanetriol compound represented by the formula: in the presence of at least one acetalization catalyst selected from the group consisting of rare earth metal sulfate, rare earth metal triflate, zirconium sulfate, and zirconium acetylacetonate. And a step of supplying the acetalization catalyst recovered from the obtained reaction mixture as a recycle catalyst to the dehydration reaction, the formula (III):

Wherein R ¹³ and R ¹⁴ are the same as R ¹ and R ² , R ^{8 to} R ¹² are the same as R ^{3 to} R ⁷ , and R ¹³ and R ¹⁴ are bonded to form a ring. (It may be formed, and n represents 0 or an integer of 1 to 4)
(1,3-dioxolan-4-yl) alkyl alcohol derivative represented by the formula.

  According to the present invention, since the recovered catalyst can be reused as it is, the amount of the catalyst used can be easily reduced, and a high-quality (1,3-dioxolan-4-yl) alkyl alcohol derivative can be efficiently produced. Can be manufactured.

  The present invention relates to a compound of formula (I):

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a linear, branched or cyclic C 1-18 alkyl group or phenyl group)
A carbonyl group-containing compound represented by formula (II):

(Wherein R ^{3 to} R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and m represents 0 or an integer of 1 to 4)
A dehydration reaction with an alkanetriol compound represented by the formula (III):

Wherein R ¹³ and R ¹⁴ are the same as R ¹ and R ² , R ^{8 to} R ¹² are the same as R ^{3 to} R ⁷ , and R ¹³ and R ¹⁴ are bonded to form a ring. (It may be formed, and n represents 0 or an integer of 1 to 4)
Wherein the acetalization catalyst is specific and the acetalization recovered from the reaction mixture obtained in the reaction is a method for producing a (1,3-dioxolan-4-yl) alkyl alcohol derivative represented by It has a great feature in that it includes a step of supplying a catalyst as a recycle catalyst to the dehydration reaction.

  The acetalization catalyst in the present invention is at least one selected from the group consisting of rare earth metal sulfates, rare earth metal triflates, zirconium sulfate, and zirconium acetylacetonate.

  Examples of the rare earth metal sulfate include lanthanum sulfate, neodymium sulfate, samarium sulfate, and the like. Examples of the rare earth metal triflate include lanthanum triflate, neodymium triflate, ytterbium triflate, and the like.

  The above compounds can be used alone or in combination of two or more thereof. Among these, lanthanum triflate is preferable from the viewpoint of price and usability, and from the viewpoint of low toxicity and high stability, sulfuric acid. Zirconium is preferred.

  In addition, as an acetalization catalyst used for the dehydration reaction of the raw material in the present invention, at least a part of the catalyst is recovered from the reaction mixture after the dehydration reaction (the reaction mixture after all or a part thereof has been subjected to the dehydration reaction). The acetalization catalyst thus made is used as a recycle catalyst. As used herein, “recovered acetalization catalyst” refers to any of a recovered catalyst when the acetalization catalyst itself is recovered from the reaction mixture and a residual catalyst when the reaction product is recovered from the reaction mixture. It also means.

  The recycled catalyst may be obtained from the same reaction system or may be obtained from different reaction systems.

  When the recycled catalyst is used as a recovered catalyst, the acetalization catalyst is a solid. For example, the reaction mixture may be distilled and the residue obtained to obtain the desired product may be recovered and used. When the acetalization catalyst is zirconium sulfate, it is possible to recover only the catalyst by simply filtering the reaction mixture, and it may be used as a molded product such as a pellet. The recovered residue or catalyst can be used as a recycle catalyst for a new dehydration reaction as it is or after washing with a raw material or a solvent.

  When the recycled catalyst is used as a residual catalyst, it can be used for a new dehydration reaction as it is or after being washed with the raw material or a solvent and then supplying the raw material to a reactor in which the residual catalyst is present.

  The amount of the acetalization catalyst is preferably 0.001 to 0.1 mole, more preferably 0.003 to 1 mole per alkanetriol compound from the viewpoint of improving the reaction rate and suppressing the generation of by-products. It is desirable that the amount be 0.05 mol, more preferably 0.005 to 0.02 mol. The “acetalization catalyst amount” as used herein refers to the amount of acetalization catalyst added during the dehydration reaction, and a catalyst (externally supplied catalyst) newly supplied to the reactor from the outside and a recycle catalyst. The total amount of

  In the present invention, the use amount of the recycle catalyst is not particularly limited, but the molar ratio to the amount of the externally supplied catalyst [recycle catalyst / (recycle catalyst + externally supplied catalyst)] is preferably 0.3 or more, more preferably Is 0.5 or more. In addition, the catalyst used for the dehydration reaction of the raw material may all be a recycled catalyst.

  The aspect of supplying the recycled catalyst to the reactor is not particularly limited, and may be directly supplied to the reactor, or may be mixed with the raw material and / or the externally supplied catalyst and supplied to the reactor.

  In the present invention, the carbonyl group-containing compound has the formula (I):

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a linear, branched or cyclic C 1-18 alkyl group or phenyl group)
It is a compound represented by these.

  Examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, stearyl group, cyclohexyl group and the like.

  Specific examples of the carbonyl group-containing compound represented by the formula (I) include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 4-pentanone, 3-methyl-2-butanone, n-butyl ethyl ketone, 2- Hexanone, methyl isobutyl ketone, 3,3-dimethyl-2-butanone, isoamyl methyl ketone, 2-octanone, 5-methyl-3-heptanone, 2-nonanone, 2,4-dimethyl-3-heptanone, 2,6- Examples include dimethyl-4-heptanone, 2,2,4,4-tetramethyl-3-heptanone, 2-dodecane, cyclohexanone, benzophenone, acetophenone, propiophenone, acetaldehyde, propionaldehyde, butyraldehyde, and benzaldehyde.

  Among the carbonyl group-containing compounds represented by the formula (I), acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone are preferable from the viewpoint of usability. When these ketones are reacted with glycerin, which is an alkanetriol compound represented by formula (II), as a (1,3-dioxolan-4-yl) alkyl alcohol derivative represented by formula (III) , (2,2-dimethyl-1,3-dioxolan-4-yl) methanol, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol, (2-methyl-2, respectively) -Isobutyl-1,3-dioxolan-4-yl) methanol and (cyclohexanespiro-2- (1,3-dioxolan-4-yl)) methanol are obtained.

  In the present invention, the alkanetriol compound has the formula (II):

(Wherein R ^{3 to} R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and m represents 0 or an integer of 1 to 4)
It is a compound represented by these.

  Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group.

  Specific examples of the alkanetriol compound represented by the formula (II) include glycerin, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2, 3-pentanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-2,3,4-butanetriol, 2-methyl-1,2,3-butanetriol, 2-ethyl-1, Examples include 2,3-butanetriol and 2,3,4-hexanetriol.

  Among the alkanetriol compounds represented by the formula (II), glycerin, 1,2,4-butanetriol, 1,2,5-pentanetriol, and 1,2,6-hexanetriol are preferable from the viewpoint of usability. Among these, glycerin is more preferable.

  The amount of the carbonyl group-containing compound represented by the formula (I) is preferably 0.5 to 5 mol, more preferably 0, per 1 mol of the alkanetriol compound from the viewpoint of improving the yield and increasing the production efficiency. It is desirable that it is 9-1.5 mol.

  The reaction between the carbonyl group-containing compound represented by the formula (I) and the alkanetriol compound represented by the formula (II) is, for example, a carbonyl group-containing compound represented by the formula (I), represented by the formula (II). The reaction raw material containing the alkanetriol compound and the acetalization catalyst to be mixed can be mixed with stirring.

  Since the reaction temperature varies depending on whether the carbonyl group-containing compound represented by the formula (I) is a ketone or an aldehyde, it cannot be determined unconditionally. When the carbonyl group-containing compound represented by the formula (I) is a ketone, the reaction temperature is preferably 50 to 200 ° C., more preferably from the viewpoint of improving the reaction rate and suppressing the generation of by-products. It is desirable that it is 60-120 degreeC. When the carbonyl group-containing compound represented by the formula (I) is an aldehyde, the reaction temperature is preferably 50 to 200 ° C., from the viewpoint of improving the reaction rate and suppressing the generation of byproducts. Preferably it is 60-100 degreeC.

  In the reaction of the carbonyl group-containing compound represented by the formula (I) and the alkanetriol compound represented by the formula (II), water is by-produced as acetalization proceeds, and the by-produced water is In order to inhibit the acetalization reaction, it is preferable to remove by-produced water. Removal of by-produced water can be performed by, for example, total reflux dehydration using a solvent such as n-hexane, isohexane, cyclohexane, heptane, toluene, xylene, and methylene chloride as an entrainer. These entrainers may be added from the start of the acetalization reaction, or may be added during or after the reaction, but are preferably added from the start of the reaction from the viewpoint of operability. . In addition, these entrainers may be supplied again to the reactor after removing water by-produced in the acetalization reaction by total reflux dehydration from the viewpoint of cost and practicality.

  In the reaction between the carbonyl group-containing compound represented by the formula (I) and the alkanetriol compound represented by the formula (II), the conversion rate of the alkanetriol is preferably 70 to 100%, more preferably 80 to 100%, More preferably, it is desirable to carry out until it becomes 95 to 100%. When the reaction is carried out until the conversion rate falls within the above range, a (1,3-dioxolan-4-yl) alkyl alcohol derivative represented by the formula (II) can be obtained with high purity and high yield. it can. From the viewpoint of recovering the catalyst from the reaction system more easily, the conversion rate is preferably 100%.

  Such a conversion rate is preferably appropriately determined according to the type of the carbonyl group-containing compound represented by the formula (I). For example, when the carbonyl group-containing compound represented by the formula (I) is a ketone such as methyl ethyl ketone, the conversion rate is (1,3-dioxolane represented by the formula (III) with high purity and high yield. From the viewpoint of obtaining a -4-yl) alkyl alcohol derivative, it is preferably 70 to 100%, more preferably 80 to 100%, and still more preferably 95 to 100%. Further, when the carbonyl group-containing compound represented by the formula (I) is an aldehyde such as benzaldehyde, the conversion rate is (1,3-dioxolane represented by the formula (III) with high purity and high yield. From the viewpoint of obtaining a -4-yl) alkyl alcohol derivative, it is preferably 70 to 100%, more preferably 80 to 100%, and still more preferably 90 to 100%.

  The “conversion rate of alkanetriol” is a value obtained according to the method described in “Example” described later.

  Thus, the carbonyl group-containing compound represented by the formula (I) and the alkanetriol compound represented by the formula (II) are reacted until the conversion rate of the alkanetriol reaches a predetermined value. It is preferable to complete the reaction by cooling the reaction solution up to. In addition, since the acetalization catalyst used in the present invention has a mild activity, for example, neutralization treatment required when sulfuric acid is used as the acetalization catalyst is unnecessary, and the remaining formula (I) It is not necessary to wash the reaction solution containing the carbonyl group-containing compound represented, the (1,3-dioxolan-4-yl) alkyl alcohol derivative represented by the generated formula (III) with water, There is no large amount of wastewater generated during cleaning.

  In the reaction solution, if necessary, a solvent such as an entrainer can be distilled off.

  In addition to the (1,3-dioxolan-4-yl) alkyl alcohol derivative represented by the formula (III) as the target compound, the reaction solution contains a carbonyl group-containing compound represented by the formula (I). Remains. Therefore, it is preferable to remove the remaining carbonyl group-containing compound. Removal of the carbonyl group-containing compound represented by the formula (I) can be performed, for example, by distilling the carbonyl group-containing compound represented by the formula (I) from the reaction solution under reduced pressure or normal pressure.

  The (1,3-dioxolan-4-yl) alkyl alcohol derivative represented by the formula (III) is recovered through a step of distilling the reaction solution after removal of the carbonyl group-containing compound represented by the formula (I). be able to. The residue in the distillation step contains an acetalization catalyst, and it is recovered by collecting the residue as it is or by simply treating the collected residue with a solvent or reaction raw material used for the reaction. Can be used. When the alkanetriol conversion is not 100%, the residue contains an alkanetriol compound represented by the formula (II), but the catalyst can be reused in the same manner as described above. Further, when the acetalization catalyst is zirconium sulfate, the catalyst can be recovered by filtering before distilling off the solvent. When the acetalization catalyst is recovered by filtration, the reaction solution may be filtered as it is using a Buchner filter or the like.

  Thus, formula (III):

Wherein R ¹³ and R ¹⁴ are the same as R ¹ and R ² , R ^{8 to} R ¹² are the same as R ^{3 to} R ⁷ , and R ¹³ and R ¹⁴ are bonded to form a ring. (It may be formed, and n represents 0 or an integer of 1 to 4)
A (1,3-dioxolan-4-yl) alkyl alcohol derivative represented by the following formula is obtained.

  In the case of obtaining a (1,3-dioxolan-4-yl) alkyl alcohol derivative represented by the formula (III) having higher purity, the (1,3-dioxolan-4-yl) alkyl alcohol derivative is obtained. May be purified by simple distillation.

  In the production method of the present invention, since the acetalization catalyst recovered from the reaction mixture is supplied as a recycle catalyst to the dehydration reaction, the raw material is supplied in an amount required for one batch, and the acetalization reaction is performed once. Moreover, it can implement also by the continuous type which supplies a raw material continuously and performs acetalization reaction. Among these, zirconium sulfate can be molded into pellets and the like, is not dissolved in the reaction solution, and is easy to recycle. Therefore, it is preferable to carry out the reaction in a continuous system having characteristics that allow the reaction to proceed efficiently.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to such examples.

[Conversion rate of alkanetriol]
The reaction solution was analyzed by gas chromatography, and the peak area of the alkanetriol compound and the peak area of the corresponding (1,3-dioxolan-4-yl) alkyl alcohol derivative were determined using the formula:
Conversion rate of alkanetriol (%) = [peak area of alkanetriol compound] ÷ [peak area of alkanetriol compound + peak area of (1,3-dioxolan-4-yl) alkyl alcohol derivative] × 100
According to the above, the conversion rate of alkanetriol is obtained.

<Analysis conditions for gas chromatography>
Inlet temperature: 270 ° C., detector temperature: 270 ° C., initial temperature: 80 ° C., initial temperature holding time: 10 minutes, temperature rising rate: 10 ° C./min, final temperature: 270 ° C., temperature rising final temperature holding time: 30 minutes, detector: flame ionization detector, carrier gas: helium gas, column: 30 m INEARCAP 1701 (capillary)

[Purity of produced compound]
The purity of the produced compound is measured by gas chromatography. Specific analysis conditions are as follows, and unless otherwise specified, the numerical values indicate area% in gas chromatography.

<Analysis conditions for gas chromatography>
Inlet temperature: 280 ° C., detector temperature: 280 ° C., initial temperature: 100 ° C., initial temperature holding time: 3 minutes, temperature rising rate: 10 ° C./min, final temperature: 250 ° C., temperature rising final temperature holding time: 20 minutes, detector: flame ionization detector, carrier gas: nitrogen gas, column: 30 m DB-1 (methyl silicon capillary)

Example 1
In a four-necked flask equipped with a distillation column, 184 g (2.0 mol) of glycerin, 216 g (3.0 mol) of methyl ethyl ketone (hereinafter referred to as MEK), 90 g of cyclohexane and 5.7 g (0.02 mol) of zirconium sulfate. Was heated to the boiling point (80 ° C.) of the reaction solution under a nitrogen stream and stirred.

  The produced water was removed from the reaction system as an azeotrope with cyclohexane, the reaction solution was condensed, and the generated water was removed with a separator. Thereafter, cyclohexane from which water was separated from the azeotrope was returned to the flask, and the reaction was continued. The reaction solution was analyzed by gas chromatography, and when the glycerin peak disappeared, the reaction solution was cooled to 30 ° C. to complete the reaction.

  This reaction solution was filtered using a Nutsche to recover zirconium sulfate, which was all reused as a recycling catalyst. Thereafter, MEK and cyclohexane contained in the filtrate (colorless, slightly turbid) recharged in the flask were distilled off, followed by distillation under reduced pressure (90 ° C., 0.9 kPa) to obtain a purity of 99.7%. 262.2 g of (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol was obtained (yield: 89.5%).

(2-Methyl-2-ethyl-1,3-dioxolan-4-yl) methanol was produced by the above operation. Three cycles of the reaction were carried out continuously with one cycle from the start of the dehydration reaction by supplying methyl ethyl ketone to the recovery of (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol. . The recycle catalyst was obtained from the same reaction system, and only the catalyst recovered by filtration in the previous cycle was used. Table 1 shows the conversion rate of glycerin in each cycle and the purity and yield of 2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol after each cycle. In addition, the supply amount of each raw material of 2nd cycle and 3rd cycle is as follows.
Second cycle: 184.0 g (2.0 mol) of glycerin, 216.1 g (3.0 mol) of MEK, 92 g of cyclohexane, 0 g (0 mol) of zirconium sulfate and 5.7 g of recycle catalyst
3rd cycle: 184.1 g (2.0 mol) of glycerin, 216.1 g (3.0 mol) of MEK, 92 g of cyclohexane, 0 g (0 mol) of zirconium sulfate and 6.2 g of recycle catalyst

Example 2
In a four-necked flask equipped with a distillation column, 184 g (2.0 mol) of glycerin, 216 g (3.0 mol) of MEK, 90 g of cyclohexane and 11.7 g (0.02 mol) of lanthanum triflate are charged, and under a nitrogen stream. To the boiling point (80 ° C.) of the reaction solution and stirred.

  The generated water is removed from the reaction system as an azeotrope with cyclohexane, the reaction solution is condensed, the generated water is removed with a separator, and then the cyclohexane separated from the azeotrope is returned to the flask. The reaction continued further. The reaction solution was analyzed by gas chromatography, and when the glycerin peak disappeared, the reaction solution was cooled to 30 ° C. to complete the reaction.

  MEK and cyclohexane were distilled off from this reaction solution (pale yellow), followed by distillation under reduced pressure (90 ° C., 0.9 kPa) to obtain (2-methyl-2-ethyl-1,3 having a purity of 99.4%. -Dioxolan-4-yl) methanol 256.2g was obtained (yield: 87.2%). The distillation residue remaining after distillation was reused as a recycled catalyst.

(2-Methyl-2-ethyl-1,3-dioxolan-4-yl) methanol was produced by the above operation. Three cycles of the reaction were carried out continuously with one cycle from the start of the dehydration reaction by supplying methyl ethyl ketone to the recovery of (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol. . In addition, in order to reuse the distillation residue as it is as a recycle catalyst, the raw material used for the next cycle was charged into a container in which the residue remained, and the reaction was continuously performed. Moreover, the recycle catalyst was obtained from the same reaction system, and only the residue remaining in the previous cycle was used. Table 1 shows the conversion rate of glycerin in each cycle and the purity and yield of 2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol after each cycle. In addition, the supply amount of each raw material of 2nd cycle and 3rd cycle is as follows.
Second cycle: 184.0 g (2.0 mol) of glycerin, 216.2 g (3.0 mol) of MEK, 92 g of cyclohexane, 0 g (0 mol) of lanthanum triflate and 30.1 g of recycle catalyst
Third cycle: 184.1 g (2.0 mol) of glycerin, 216.1 g (3.0 mol) of MEK, 92 g of cyclohexane, 0 g (0 mol) of lanthanum triflate and 44.7 g of recycle catalyst

Comparative Example 1
In a four-necked flask equipped with a distillation column, 184 g (2.0 mol) of glycerin, 216 g (3.0 mol) of MEK, 90 g of cyclohexane and 1.96 g (0.02 mol) of sulfuric acid are charged and reacted under a nitrogen stream. The solution was heated to the boiling point (80 ° C.) and stirred.

  The generated water is removed from the reaction system as an azeotrope with cyclohexane, the reaction solution is condensed, the generated water is removed with a separator, and then the cyclohexane separated from the azeotrope is returned to the flask. The reaction continued further. The reaction solution was analyzed by gas chromatography, and when the glycerin peak disappeared, the reaction solution was cooled to 30 ° C. to complete the reaction.

  MEK and cyclohexane were distilled off from this reaction solution (brown), followed by distillation under reduced pressure (90 ° C., 0.9 kPa) to obtain (2-methyl-2-ethyl-1,3-3-purity of 99.5%). 256.2 g of dioxolan-4-yl) methanol was obtained (yield: 87.1%). The distillation residue remaining after distillation was reused as a recycled catalyst.

  (2-Methyl-2-ethyl-1,3-dioxolan-4-yl) methanol was produced by the above operation. The cycle from the start of the dehydration reaction by supplying methyl ethyl ketone to the recovery of (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol is one cycle, and the recycling catalyst obtained above has two cycles. The raw material was supplied and the second cycle reaction was carried out, but the reaction was insufficient due to many impurities, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol was added. Couldn't get. Table 1 shows the conversion rate of glycerin in the first cycle and the purity and yield of 2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol in the first cycle.

  From the above results, in Examples 1 and 2, the recovered catalyst can be reused as it is, so that the amount of catalyst used can be reduced and high-quality (1,3-dioxolane-4- It can be seen that yl) alkyl alcohol derivatives can be produced efficiently. In Example 2, the amount of the recycling catalyst used increases as the number of times of recycling increases, but the amount of distillation residue of (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol increases. This is because the amount of lanthanum triflate used was not different between recycles.

Reference example 1
In a four-necked flask equipped with a distillation column, 430 g (5.0 mol) of methyl acrylate (hereinafter referred to as MA) and (2-methyl-2-ethyl-1,3-dioxolane obtained in Example 1) were obtained. -4-yl) methanol (hereinafter referred to as MEDOLOH) 292 g (2.0 mol), dioctyltin oxide (hereinafter referred to as DOTO) 3.6 g (0.01 mol), hydroquinone monomethyl ether (hereinafter referred to as MEHQ) 02 g was charged, stirred under an air stream, and heated to the boiling point (80 ° C.) of the reaction solution to conduct a transesterification reaction. During this time, methanol produced by the reaction was removed from the reaction system as an azeotrope with MA, and when the azeotrope stopped distilling, the completion of the transesterification was confirmed. The reaction time was 18 hours. The temperature of the reaction solution at this time rose to 85 to 100 ° C.

  Next, this reaction solution is distilled under reduced pressure (135 ° C., 0.7 kPa) to give (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate having a purity of 99.3%. 391.6 g was obtained (yield 97.9%).

  By the production method of the present invention, a dioxolane compound can be efficiently provided with high purity and high yield.

Claims (5)

Formula (I):

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a linear, branched or cyclic C 1-18 alkyl group or phenyl group)
A carbonyl group-containing compound represented by formula (II):

(Wherein R ^{3 to} R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and m represents 0 or an integer of 1 to 4)
A dehydration reaction with an alkanetriol compound represented by the formula: in the presence of at least one acetalization catalyst selected from the group consisting of rare earth metal sulfate, rare earth metal triflate, zirconium sulfate, and zirconium acetylacetonate. And a step of supplying the acetalization catalyst recovered from the obtained reaction mixture as a recycle catalyst to the dehydration reaction, the formula (III):

Wherein R ¹³ and R ¹⁴ are the same as R ¹ and R ² , R ^{8 to} R ¹² are the same as R ^{3 to} R ⁷ , and R ¹³ and R ¹⁴ are bonded to form a ring. (It may be formed, and n represents 0 or an integer of 1 to 4)
(1,3-Dioxolan-4-yl) alkyl alcohol derivative represented by the formula.   The production method according to claim 1, wherein the amount of the acetalization catalyst is 0.001 to 0.1 mol per mol of the alkanetriol compound.   The production method according to claim 1 or 2, wherein the dehydration reaction is continuously performed.   The alkanetriol compound is at least one selected from the group consisting of glycerin, 1,2,4-butanetriol, 1,2,5-pentanetriol, and 1,2,6-hexanetriol. The manufacturing method as described.   The production method according to claim 1, wherein the alkanetriol compound is glycerin.