JP2006117554A - Method for producing allyl ether compound and the resultant allyl ether compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop a method for producing an allyl ether compound. <P>SOLUTION: The method for producing a (meth)allyl ether compound having no primary hydroxy group and having only tertiary hydroxy group comprises the following process: For a reaction product obtained by reaction between a compound having primary hydroxy group and tertiary hydroxy group and a halogenated (meth)allyl compound in the presence of a base, the compound having primary hydroxy group and tertiary hydroxy group as unreacted component contained in the reaction product is extracted into aqueous solvent side and the objective (meth)allyl ether compound substantially having no primary hydroxy group and having tertiary hydroxy group in the reaction product is extracted into non-aqueous solvent side. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

    The present invention relates to a method for producing an allyl ether compound and an allyl ether compound obtained by the production method. More specifically, the present invention is a production method capable of industrial production, and has high yield and high purity with few side reactions. The present invention relates to a method capable of producing the above compound and an allyl ether compound obtained by the production method.

Conventionally, as a method for producing an allyl ether compound, a method in which a monohydric alcohol and an allyl halide, which is an allylating agent, or allyl bromide is directly reacted with an alkyl halide under basic conditions has been known (non- Patent Document 1).
In Non-Patent Document 1, mercury oxide, silver oxide, barium oxide, zinc oxide, sodium hydroxide, potassium hydroxide, sodium hydride and the like are described as basic substances, and under the basic conditions. In general, the reaction to be performed is performed under mild conditions in which the elimination reaction is suppressed.

Also known is a method of synthesizing a polysubstituted allyl ether compound using a polyhydric alcohol such as pentaerythritol (Patent Document 1) and trimethylolpropane (Patent Document 2) as an alcohol in the reaction between an alcohol and an allylating agent. is there.
Among these, Patent Document 1 describes a method for producing a polyvalent allyl ether using pentaerythritol. It is stated that polyvalent allyl ether is produced by using inexpensive allyl chloride and using 2 to 15 parts by weight of allyl alcohol as an accelerator for 100 parts by weight of pentaerythritol. However, allyl alcohol used as an accelerator here is a highly toxic substance that has been designated as a toxic substance and is a very dangerous compound for normal use.
Patent Document 2 describes a method for producing diallyl ether of trimerolpropane. Here, a metal hydroxide aqueous solution is used and a phase transfer catalyst is used to produce a diallyl ether compound, but several percent of impurities (trimethylolpropane monoallyl ether, trimethylolpropane triallyl ether) are produced. Production of high purity trimerol propane diallyl ether is difficult.

  In any of the production methods described in the above two patent documents, there is no description that an allyl ether compound containing a tertiary hydroxyl group is produced.

In addition to the above-mentioned documents, a method for producing allyl ether alcohol by reacting ethyl 3-allyl ether propionate with magnesium and methyl magnesium iodide prepared with methyl iodide is also known (Non-patent Document 2). .
However, the raw material used here is methyl iodide, which is toxic and very difficult to handle. Moreover, since ethyl 3-allyl ether propionate is very expensive, it is very difficult to carry out industrial production.

Sho 62-223141, Sho 60-252440 The Chemical Society of Japan 4th edition Experimental Chemistry Course Volume 20 Research on Chemical Intermediates, 11 (1989) 257-270

An object of the present invention is to provide a production method capable of industrial production and a method that enables production with high yield and high purity.

The method for producing an allyl ether compound according to the present invention comprises a compound having a primary hydroxyl group and a tertiary hydroxyl group under basic conditions (this may simply be abbreviated as “polyol compound”) and halogenation ( Methallyl or allylic compound (hereinafter, these may be combined and simply abbreviated as “halogenated allyl compound”) to react with the following formula 1

(Wherein n represents an integer of 0 or 1, R represents a divalent organic group having 1 to 24 carbon atoms, R ₁ , R ₂ and R ₃ represent a hydrogen atom and a C 1-6 lower alkyl group. , lower alkoxy C1-4, halogen atom, a cyano group or a nitro group, R ₄ and R ₅ represents a phenyl group which may have an alkyl group or a substituent of C1-4.)
It is characterized by obtaining the compound represented by these.

The method for producing an allyl ether compound according to the present invention preferably comprises the following step (1): a compound having a primary hydroxyl group and a tertiary hydroxyl group in the presence of basicity and a halogenated (methallyl or) allyl compound. A step of reacting to produce a reaction product represented by Formula 1 above,
(2) The reaction product obtained in the above step (1) has a primary hydroxyl group and a tertiary hydroxyl group of unreacted components contained in the reaction product using an aqueous solvent and a non-aqueous solvent. Liquid-liquid extraction to extract the compound to the aqueous solvent layer side and to extract the tertiary hydroxyl group-containing (methallyl or) allyl ether compound having substantially no primary hydroxyl group of the reaction product to the non-aqueous solvent layer side Process.
In the method for producing an allyl ether compound according to the present invention, preferably, in the liquid-liquid extraction step of the above step (2), the primary hydroxyl group is substantially a reaction product present in the non-aqueous solvent layer. The weight ratio of the non-existing tertiary hydroxyl group-containing (methallyl or) allyl ether compound to the unreacted primary hydroxyl group and tertiary hydroxyl group compound is in the range of 95: 5 to 100: 0. .

The allyl ether compound according to the present invention is produced by the above-described method for producing an allyl ether compound.
The allyl ether compound according to the present invention is preferably a tertiary hydroxyl group-containing (methallyl or) allyl ether compound which has substantially no primary hydroxyl group as the reaction product in the allyl ether compound and the above-mentioned allyl ether compound. The content of the reaction product is 95% by weight or more in terms of the total weight of the unreacted compound having a primary hydroxyl group and a tertiary hydroxyl group.

  According to the present invention, when the polyol compound and the allyl halide compound are allowed to coexist and react, the allyl halide compound selectively reacts with and bonds to the primary hydroxyl group. It is possible to produce the allyl ether compound of the present invention having no hydroxyl group and no tertiary hydroxyl group disappearing.

  Using an aqueous solvent and a non-aqueous solvent in which the allyl ether compound obtained by the production method is not substantially mixed with each other, an unreacted compound having a primary hydroxyl group and a tertiary hydroxyl group is an aqueous solvent. Since the tertiary hydroxyl group-containing allyl ether compound which is a reaction product and has substantially no primary hydroxyl group is extracted to the non-aqueous solvent layer side, the reaction product and the unreacted product and the reaction product Separation is easy, and the separated reaction product is substantially free of unreacted products, so that a highly pure allyl ether compound can be produced.

  The allyl ether compound obtained by the production method is highly purified by separation and purification for the reasons described above.

The method for producing an allyl ether compound of the present invention comprises reacting a polyol compound and an allyl halide compound under basic conditions to form the following formula 1

(Wherein n represents an integer of 0 or 1, R represents a divalent organic group having 1 to 24 carbon atoms, R ₁ , R ₂ and R ₃ represent a hydrogen atom and a C 1-6 lower alkyl group. , lower alkoxy C1-4, halogen atom, a cyano group or a nitro group, R ₄ and R ₅ represents a phenyl group which may have an alkyl group or a substituent of C1-4.)
It is a manufacturing method which obtains the compound represented by these.

In the present specification, the halogen atom includes chlorine, bromine, fluorine and the like.
The polyol compound used in the production method of the present invention is used as a component for introducing an allyl ether group and a tertiary hydroxyl group into the molecule.
Examples of the polyol compound include those represented by the following formula 2, and conventionally known compounds can be used.
Formula 2

(In the formula, R, R ₄ and R ₅ have the same meaning as described above.)
Examples of the C _{1 to} C ₄ alkyl group represented by the above formulas 1 and 2 and the following formula 7 include, for example, a methyl group, an ethyl group, an n-propyl group, a sec-propyl group, an n-butyl group, and a sec-butyl group. Ter-butyl group.
In the above formulas 1 and 2, the divalent organic group having 1 to 24 carbon atoms as R is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a combination thereof. Are included. Further, some or all of the hydrogen atoms constituting the aromatic ring may be substituted with a C1-6 lower alkyl group or a halogen atom. Further, a part of hydrogen atoms constituting the aliphatic hydrocarbon group may be substituted with a halogen atom.

Specific examples of R include the following.
Examples of the divalent aromatic hydrocarbon group include the following formula 3

Etc.
Examples of the divalent aliphatic hydrocarbon group, for _{example, -CH 2 -, - C 2} H 4 -, - C 3 H 6 -, - C 4 H 8 -, - C 5 H 10 -, - C 6 H _{12 -, - C 10 H 20} -, - C 12 H 24 -, - C 16 H 32 - , and the like.
As the divalent alicyclic hydrocarbon group, for example,
Formula 4

Etc.
In the organic group described above, an aliphatic hydrocarbon group and an aromatic hydrocarbon group or an alicyclic hydrocarbon group may be combined.
As this, for example,
Formula 5

In the above formulas 1 and 2, R is an organic group that can contain an atom other than a carbon atom (for example, a heteroatom), but in order to form a tertiary hydroxyl group, it is bonded to a carbon atom of HO-C. The first R group to be must be a carbon atom.

  Moreover, in R of said Formula 1, 2, the hetero atom which can be contained in a C1-C24 bivalent organic group is atoms other than a carbon atom, for example, oxygen, sulfur, nitrogen, etc., A heteroatom can be a single atom or a group bonded to other atoms, for example, a straight chain such as an ether group, an ester group, a thioether group, an amide group, or atoms of two or more elements (in addition to carbon, Heterocyclic compounds whose rings are composed of nitrogen, oxygen, sulfur, etc.) are included. Examples of the heterocyclic compounds include divalent organic groups having 1 to 24 carbon atoms, such as furan, thiophene, pyrrole, pyridine, cyclic ether, lactone, cyclic imine, and lactam. It has an introduced heterocyclic residue.

  In addition, the divalent organic group having a hetero atom includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alicyclic hydrocarbon group in which a hetero atom is bonded to the end of the aliphatic hydrocarbon group. And those in which a hetero atom is bonded between the bond between an aliphatic hydrocarbon group and an aromatic hydrocarbon group or an alicyclic hydrocarbon group, or between the bond between an aromatic hydrocarbon group and an alicyclic hydrocarbon group. .

Examples of the above-described ether group, ester group, thioether group or amide group which may have a C 1-20 linear or branched divalent organic group include:
Equation 6

Can be mentioned.

As the above-described polyol compound, for example, 2-methyl-1,2-propanediol, 3-methyl-1,3-butanediol, 4-methyl-1,4-butanediol and the like are preferably used.
The allyl halide compound to be reacted with the above polyol compound is represented by the following formula 7

(Wherein R ₁ , R ₂ and R ₃ have the same meaning as described above, and X represents a halogen atom.)
Is mentioned.

Among the above formulas, R ₁ , R ₂ and R ₃ are particularly preferably a hydrogen atom, and X is preferably a chlorine atom. Specific examples of the halogenated allyl compound include, for example, allyl chloride, methallyl chloride, allyl bromide, methallyl bromide, allyl fluoride, and methallyl fluoride.

The production method of the present invention may be carried out by a method that satisfies the above-mentioned conditions. Specifically, the following step (1) is carried out by reacting a polyol compound and an allyl halide compound in the presence of basicity, and the above formula. A step of producing a reaction product represented by 1;
(2) The reaction product obtained in the above step (1) is mixed with an unreacted compound having a primary hydroxyl group and a tertiary hydroxyl group to the aqueous solvent layer side using an aqueous solvent and a non-aqueous solvent. The reaction product is produced by a step of extracting the tertiary hydroxyl group-containing allyl ether compound, which is a reaction product, to the non-aqueous solvent layer side. Specifically, the reaction product exists in the non-aqueous solvent layer. The production method is a liquid-liquid extraction step in which the ratio of the tertiary hydroxyl group-containing allyl ether compound to the unreacted primary hydroxyl group and the compound having a tertiary hydroxyl group is 95: 5 to 100: 0.
In the production method of the present invention, step (1) is a reaction represented by the above formula 1 by reacting a compound having a primary hydroxyl group and a tertiary hydroxyl group with an allyl halide compound in the presence of basicity. It is a process for producing a product.

  Specifically, the step (1) can be carried out by the following method.

Step (1):
In order to make it basic in the above-described step (1), it can be made basic using a basic compound.

  The reaction under basic conditions in the step (1) is a method of reacting a polyol compound and an allyl halide compound under basic conditions (1-a below) or reacting a basic compound with a polyol. In addition, a method of once producing an intermediate and then reacting the intermediate with an allyl halide compound (1-i and ii below) is also included.

Although it does not specifically limit as a basic compound which can be used, For example, it is preferable to use a metal hydroxide, a metal hydride, etc.
Specific examples of the metal hydroxide include hydroxides of alkali metals such as sodium, potassium and lithium, and hydroxides of alkaline earth metals such as calcium and magnesium.
Specific examples of the metal hydride include hydrides of alkali metals such as sodium, potassium and lithium, hydrides of alkali metal earths such as calcium and magnesium, antimony hydride, and silicon hydride.

If the blending ratio of the polyol compound and the allyl halide compound is determined in consideration of the number of primary hydroxyl groups possessed by the polyol compound, the number of (methallyl groups) or allyl groups introduced into the molecule, etc. Usually, it is in the range of 0.5 to 5 equivalents, preferably 0.8 to 3 equivalents of the allyl halide compound per primary hydroxyl group of the polyol compound.
When the compounding amount of the halogenated allyl compound is less than 0.5 equivalent, the amount of allyl group (methallyl group or) introduced into the molecule is reduced, the yield of the allyl ether compound is very low, the reaction time However, if it exceeds 5 equivalents, the amount of unreacted allyl halide compound increases, which is not preferable.

The mixing ratio of the basic compound may be determined in consideration of the number of primary hydroxyl groups of the polyol compound or the number of (methallyl groups) or allyl groups introduced into the molecule. The range is from 0.1 to 100 equivalents, preferably from 0.2 to 50 equivalents, of the allyl halide compound per primary hydroxyl group of the compound.
When the blending amount of the basic compound is less than 0.1 equivalent, the reaction with the polyol compound does not proceed, and the target compound yield becomes very low. If more than 100 equivalents are blended, a reaction with a tertiary hydroxyl group that is not intended to be reacted will occur, and not only the target compound but also a product containing a large amount of impurities will be obtained.
In the reaction process between the polyol compound and the allyl halide compound, the reaction process is slightly different in the case of using a metal hydroxide and a metal hydride (process through the above-described intermediate) as the basic compound. The reaction process is described below.

When using metal hydroxide:
When the metal hydroxide is used,
(1-a) The reaction can be carried out by reacting a polyol compound and an allyl halide compound in the presence of a basic compound containing a metal hydroxide.
In the reaction step, the basic compound and the polyol compound are preferably reacted in water, a catalyst (phase transfer catalyst) if necessary, and a solvent in which an organic solvent is blended if necessary.

The solvent concentration (preferably an aqueous solution) of the basic compound and the polyol compound is not particularly limited, but is preferably 30 to 80% by weight because of easy handling.
It is preferable to use a quaternary ammonium salt as the phase transfer catalyst. Specifically, for example, tetramethylammonium halides such as tetrabutylammonium bromide and tetramethylammonium chloride; benzyltrialkylammonium halides such as benzyltrimethylammonium chloride; octyltriethylammonium chloride and dodecyltrimethyl iodide Other examples include ammonium and hexadecyltrimethylammonium bromide.

As the usage-amount of a quaternary ammonium salt, it is 0.1-20 mol% with respect to a polyol compound, Preferably it is 1-10 mol%. When the amount of the quaternary ammonium salt used is less than 0.1 mol%, the catalytic effect is low. On the other hand, even if it is used in an amount exceeding 20 mol%, no further catalytic effect can be expected.
The quaternary ammonium salt is generally known as a phase transfer catalyst, and it is usually said that its catalytic effect is effective in a reaction system that forms two layers of an aqueous layer and an organic layer. In the invention, it is effective even in one layer (that is, only an aqueous system not using an organic solvent).
The reaction temperature is 0 ° C to 120 ° C, preferably 20 ° C to 110 ° C. If it is 0 ° C. or lower, the reaction rate is slow, and if it is 120 ° C., side reactions become violent.
After the reaction of the polyol compound and the allyl halide compound is completed in the presence of basicity including the metal hydroxide in the step (1-a), the next step, step (2), is performed.

When using metal hydrides:
When the metal hydride is used, the following step (1-i) is a step of producing an intermediate by reacting with a polyol compound in the presence of a basic containing a metal hydride.
(1-ii) The reaction can be carried out by reacting the intermediate obtained in the step (1-i) with an allyl halide compound.
In the reaction step (1-i), it is preferable to react each raw material of a basic compound and a polyol compound by dissolving them in a reaction solvent.
As the reaction solvent to be used, those which dissolve each raw material and are substantially inert to the raw material to be used and the reaction product produced in the step (1) and the step (2) are used.
Examples of usable reaction solvents include solvents such as tetrahydrofuran and dioxane. However, it is preferable to use those with less moisture. That is, if water exists in the reaction system, the water and the metal hydride react with each other, the metal hydride is inactivated, and the allyl group cannot be reliably introduced into the primary hydroxyl group.

The mixing ratio of the reaction solvent is usually 1 to 50% by weight, particularly 2 to 40% by weight, in terms of solid content.
In step (1-i), for example, the inside of the reaction vessel is replaced with nitrogen, and then metal hydride is charged. Since paraffin (used to improve the storage stability by inactivating the metal hydride) may adhere to the metal hydride in advance, this paraffin was washed with a solvent such as hexane. Preference is given to using metal hydrides. This washing can increase the purity of the reaction product.
In this step, since hydrogen is generated, it is dropped while confirming the generation amount.
Since the reaction involves an exothermic reaction, the reaction temperature is preferably maintained in the range of 0 ° C to 120 ° C, preferably 20 ° C to 110 ° C. If it is 0 ° C. or lower, the reaction rate is slow, and if it is 120 ° C., side reactions become violent.
The step (1-ii) is a step of reacting the reaction product of the intermediate obtained in the step (1-i) with an allyl halide compound.

The reaction can be carried out by dropping an allyl halide compound into the intermediate reaction product.
The reaction conditions are stirring at a reaction temperature of 10 to 100 ° C. for 1 hour to 1 week. After completion of the reaction, the reaction solvent is completely removed, and the remaining metal hydride is removed with a solvent such as water or alcohol. The removal of the residual metal hydride may be performed simultaneously with the step (2).
After the reaction of the intermediate which is the step (1-ii) with the allyl halide compound, step (2) which is the next step is performed.

Step (2):
In the above step (2), the reaction product obtained in the above step (1) is obtained by using an aqueous solvent and a non-aqueous solvent, and a compound having a primary hydroxyl group and a tertiary hydroxyl group that are unreacted ( This is a separation and purification step of extracting the polyol compound) to the aqueous solvent layer side, and extracting the tertiary hydroxyl group-containing allyl ether compound, which is a reaction product, to the non-aqueous solvent layer side.
The aqueous solvent used in step (2) is a solvent that is compatible with the non-aqueous solvent used in combination with the aqueous solvent and can be separated, and is an unreacted polyol compound. Is a solvent that can be dissolved or dispersed. The solvent may be appropriately selected according to the type of polyol compound or non-aqueous solvent used, and is preferably water, an alcohol-based solvent, or a mixed solvent of water and an alcohol-based solvent.
On the other hand, the non-aqueous solvent is a solvent that is incompatible with the aqueous solvent and can be separated, and can be dissolved or dispersed in the tertiary hydroxyl group-containing allyl ether compound of the reaction product. The solvent may be appropriately selected according to the type of reaction product, the structure, the type of aqueous solvent used in combination, and the like, but the following are preferable.

The compatibility of the aqueous solvent and the non-aqueous solvent is such that the two solvents are mixed in, for example, a test tube, mixed and stirred, and then purified and separated so as to have a ratio to be actually mixed. For example, after being allowed to stand at 20 ° C. for 24 hours, it can be confirmed by visually observing whether or not the mixed solvent is separated.
Examples of the alcohol solvent include methanol, ethanol, iso-propanol, n-butanol, and iso-butanol.
Examples of the non-aqueous solvent include alicyclic hydrocarbons such as cyclohexane, aliphatic hydrocarbons such as n-hexane, n-heptane, n-decane, I-octane, and I-decane, benzene, toluene, xylene, Aromatic hydrocarbons such as ethylbenzene, chloroform, methylene chloride and the like are preferable.

In step (2) of the present invention, the tertiary hydroxyl group-containing allyl ether compound which is a reaction product finally present in the non-aqueous solvent layer and the unreacted primary hydroxyl group and tertiary hydroxyl group It is preferable that the ratio of the compound having a ratio of 95: 5 to 100: 0, and when the primary hydroxyl group and the tertiary hydroxyl group are 5% or more based on the tertiary hydroxyl group-containing allyl ether compound, the subsequent reaction When used, it is not preferable because a product obtained by reacting the primary hydroxyl group as an impurity is produced, which adversely affects various properties such as physical properties.
Furthermore, after the completion of the step (2), the non-aqueous solvent liquid (layer) can be concentrated as needed to obtain a concentration for use. Further, the concentration can be performed under reduced pressure. Moreover, it can take out as a crystallized substance after distillation under reduced pressure.

  The allyl ether compound of the present invention is produced by the production method described above and represented by the above formula 1.

The allyl ether compound of the present invention can be used as an active energy ray curable compound or a curable compound using a peroxide catalyst by utilizing the allyl ether group of the compound.
Further, the allyl ether group can be epoxidized and used in coatings, printing, adhesives, electronic materials, etc. in combination with an epoxy curing agent as necessary.
In addition, the tertiary ether bond of the compound can be used to destroy the crosslinked structure by heating the cured product and easily remove the entire cured product or a part of the cured product with a solvent. Can also be used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto.

Example 1
After the inside of a 2 liter glass container is purged with nitrogen, 50 g of sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) is added, and 50 ml of hexane is added to remove paraffin adhering to the sodium hydride. Thereafter, 500 ml of dehydrated tetrahydrofuran is added. While confirming hydrogen generating 143.2 g of 3-methyl-1,3-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), it is gradually dropped. Since heat may be generated at this time, it is necessary to check the temperature. After completion of dropping, the mixture is stirred overnight at room temperature. After the reaction to the sodium salt is completed, 175.4 g of allyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) is added. Then, let it stir for 3 days. After completion of the reaction, tetrahydrofuran as a reaction solvent is removed by a rotary evaporator. 200 ml of water is put into the reaction solution to deactivate the remaining sodium hydride, and 300 ml of hexane is put therein to extract the reaction product. The extraction process with hexane is performed three times.
Extraction is performed with hexane and water, and the organic layer and the aqueous layer are subjected to gas chromatography (solvent THF injection temperature 270 ° C. column temperature 50 ° C. 3 minutes → 10 ° C./min retention time peak of 7.2 minutes is the raw material 3 -Methyl-1,3-butanediol, and the peak at about 9.1 min was measured by the product 4-allyloxy-2-methyl-butan-2-ol).
As a result, the peak area ratio in the organic layer was 94% for 4-allyloxy-2-methyl-butan-2-ol and 0.2% for 3-methyl-1,3-butanediol as a raw material. Further, 93.7% of the aqueous layer was 3-methyl-1,3-butanediol as a raw material, and the peak of 4-allyloxy-2-methyl-butan-2-ol as a product did not exist. From this, it is shown that separation and purification can be performed very easily with water and a water-insoluble organic solvent.
The organic layer is then dried over magnesium sulfate and concentrated. The concentrated product was distilled under reduced pressure (1 torr 60 ° C.) to obtain 148 g of the desired product.

  The yield was 90%. The purity was 99% (gas chromatography).

  FIG. 1 shows the NMR (nuclear magnetic resonance spectrum) of the product of Example 1, FIG. 2 shows the IR analysis chart (IR), and FIG. 3 shows the NMR of the starting 3-methyl-1,3-butanediol used in FIG. As shown in FIG.

The analysis method is described below.
1. Nuclear magnetic resonance spectrum (NMR)
As for the nuclear magnetic resonance spectrum of the reaction product, 1H-NMR spectrum data was obtained with EX400FT-IR (400 MHz) manufactured by JEOL Ltd. using tetramethylsilane as a reference substance and heavy dimethyl sulfoxide as a solvent.

2. Infrared absorption spectrum measurement (IR)
The reaction product was applied to a potassium bromide plate and measured with a Fourier transform infrared spectrometer FT / IR-610 manufactured by JASCO Corporation.

The NMR result of the product is shown in FIG. 1 (non-aqueous solvent layer).
In FIG. 1, the 1H-NMR spectrum has the following meaning.
δ (ppm): 5.85-5.95 (m 1H)
δ (ppm): 5.27 (d 1H J = 17)
δ (ppm): 5.19 (d 1H J = 10.2)
δ (ppm): 3.99 (d 2H J = 5.4)
δ (ppm): 3.68 (t 2H J = 6.1)
δ (ppm): 3.28 (s 1H)
δ (ppm): 1.79 (t 1H J = 6.1)
δ (ppm): 1.24 (s 6H)
The IR result of the product is shown in FIG. 2 (non-aqueous solvent layer).
In FIG. 2, the absorption wavelengths are as follows.
3433 cm −1 is absorbed by OH structure 3080 cm −1 is absorbed by H ₂ C═CH structure 2971 cm −1 is absorbed by CH structure 2935 cm −1 is absorbed by CH structure 2870 cm −1 is absorbed by CH structure 1646 cm −1 is H ₂ Absorption by C = CH structure 1364 cm −1 is absorption by COH structure,
1146 cm-1 is absorbed by the COH structure,
1098 cm-1 is absorbed by the COC structure,
994 cm −1 is absorbed by the H ₂ C═CH structure,
923 cm −1 indicates absorption by the H ₂ C═CH structure.
From the above results, it was confirmed that the reaction product obtained by the above reaction was 4-allyloxy-2-methyl-butan-2-ol.

Comparative Example 1
Manufacture and synthesis were performed in the same manner as in Example 1. After completion of the reaction, THF was distilled off, and residual sodium hydride was deactivated by adding methanol. Thereafter, methanol was distilled off, followed by direct distillation. The purity of the distillate (1 torr 60 ° C.) was measured by gas chromatography. Solvent THF Injection temperature 270 ° C. Column temperature 50 ° C. 3 minutes → 10 ° C./min The peak of retention time about 7.2 min is 3-methyl-1,3-butanediol, which is the raw material, and the peak of about 9.1 min is the product As a result, the peak area ratio was 78% for 4-allyloxy-2-methyl-butan-2-ol, and 3-methyl-1 as a raw material. , 3 butanediol was 19%. Therefore, the compound having unreacted primary hydroxyl group and tertiary hydroxyl group is extracted to the aqueous layer side by liquid-liquid extraction with water and a water-insoluble organic solvent, and only the tertiary hydroxyl group as a reaction product is extracted. It was found that in the case where the step of extracting the (meth) allyl ether compound to the organic layer side was not performed, a large amount of unreacted primary hydroxyl group and tertiary hydroxyl group-containing compounds were contained after distillation.

2 is an NMR of the allyl ether compound obtained in Example 1. 2 is an IR of the allyl ether compound obtained in Example 1. FIG.

Claims (5)

A compound having a primary hydroxyl group and a tertiary hydroxyl group is reacted with a halogenated (methallyl or) allyl compound under basic conditions to form the following formula 1

(Wherein n represents an integer of 0 or 1, R represents a divalent organic group having 1 to 24 carbon atoms, R ₁ , R ₂ and R ₃ represent a hydrogen atom and a C 1-6 lower alkyl group. , lower alkoxy C1-4, halogen atom, a cyano group or a nitro group, R ₄ and R ₅ represents a phenyl group which may have an alkyl group or a substituent of C1-4.)
A method for producing an allyl ether compound, characterized in that a compound represented by the formula: Step (1) A reaction product represented by the above formula 1 is produced by reacting a compound having a primary hydroxyl group and a tertiary hydroxyl group with a halogenated (methallyl or) allyl compound in the presence of basicity. Process,
(2) The reaction product obtained in the above step (1) has a primary hydroxyl group and a tertiary hydroxyl group of unreacted components contained in the reaction product using an aqueous solvent and a non-aqueous solvent. Liquid-liquid extraction to extract the compound to the aqueous solvent layer side and to extract the tertiary hydroxyl group-containing (methallyl or) allyl ether compound having substantially no primary hydroxyl group of the reaction product to the non-aqueous solvent layer side The manufacturing method of Claim 1 including a process. In the liquid-liquid extraction step of the above step (2), a tertiary hydroxyl group-containing (methallyl or) allyl ether compound which is a reaction product present in the non-aqueous solvent layer and has substantially no primary hydroxyl group; The production method according to claim 2, wherein the weight ratio of the unreacted compound having a primary hydroxyl group and a tertiary hydroxyl group is 95: 5 to 100: 0. An allyl ether compound produced by the production method according to claim 1, 2 or 3. In the allyl ether compound, a tertiary hydroxyl group-containing (methallyl or) allyl ether compound that has substantially no primary hydroxyl group, which is a reaction product, and a primary hydroxyl group and a tertiary molecule, which are unreacted substances. The allyl ether compound according to claim 4, wherein the content of the reaction product is 95% by weight or more in terms of total weight with the compound having a hydroxyl group.

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