JP5626953B2 - Method for producing allyl compounds - Google Patents

Description

  The present invention relates to a method for producing an allyl compound, and more particularly to a method for producing an allyl compound using a glycerin compound as a raw material.

  An allyl compound is a monomer having a polymerizable double bond, and is an important chemical raw material used as a base for polymerization and copolymerization in polymer synthesis. It is also an important chemical base used as a raw material for pharmaceuticals, glycidol, epichlorohydrin and the like. Specific examples of the allyl compound include allyl alcohol, allylamine, allyl halide, allyl ether, acrolein, and allyl acetate.

  As a method for producing allyl alcohol, isomerization of propylene oxide, direct oxidation of propylene, and the like are industrially performed. However, propylene oxide and propylene which are raw materials are petrochemical raw materials, and establishment of a synthesis method from renewable raw materials such as plant resources is desired. From such a viewpoint, it is considered to produce allyl alcohol from glycerin obtained mainly from plant resources.

As an example of synthesizing allyl alcohol from glycerin, for example, Patent Document 1 and Non-Patent Document 1 disclose a method of synthesizing allyl alcohol by reacting glycerin with formic acid. However, this method consumes an equimolar amount of glycerin and formic acid, resulting in low production efficiency.
For example, Non-Patent Document 2 discloses a method of synthesizing allyl alcohol by reacting glycerin with triphenylphosphine (PPh ₃ ) using a cyclopentadienyl trioxorhenium complex (CpReO ₃ ) solid catalyst. ing. However, this method has low production efficiency because PPh _{3 in an} equimolar amount with glycerin is consumed as triphenyl phosphate (O = PPh ₃ ).
For example, Patent Document 2 discloses a method for synthesizing allyl alcohol from glycerin using a solid catalyst containing at least one element selected from molybdenum, iron, and vanadium. It is disclosed that allyl alcohol is produced as a by-product during the synthesis of acrolein using an acid catalyst. However, these methods have low yields and selectivities of allyl alcohol.

International Publication No. 2008/092115 JP 2008-162907 A

“Organic Synthesis”, Vol. 1, p. 1921 (1941) “Journal of American Chemical Society”, Vol. 118, Iss. 39, p. 9448-9449 (1996) “Catalysis Letters”, Vol. 127, no. 3-4, p. 419-428 (2009)

  The subject of this invention is providing the method of manufacturing an allyl compound with a sufficient yield from a glycerol compound as a raw material.

  In producing an allyl compound from a glycerin compound, the present inventor can produce an allyl compound at a low cost and without using an expensive metal catalyst by reacting a halogen compound with a glycerin compound. I found it.

（式中、Ｒ¹、Ｒ²及びＲ³は各々独立に、水素原子、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基もしくはアルケニル基、−ＣＯＲ⁴基、又は水酸基及び／もしくはカルボキシ基で置換された全炭素数１〜２０の直鎖状もしくは分岐状のアルキル基もしくはアルケニル基を表す。Ｒ⁴は、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基もしくはアルケニル基、又は水酸基及び／もしくはカルボキシ基で置換された全炭素数１〜２０の直鎖状もしくは分岐状のアルキル基もしくはアルケニル基を表す。） That is, this invention provides the manufacturing method of the allyl compound which makes a halogen compound and the glycerol compound represented by following General formula (1) react.

Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, a —COR ⁴ group, a hydroxyl group and / or a carboxy group. Represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, and R ⁴ represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, Or a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms and substituted with a hydroxyl group and / or a carboxy group.

  According to the present invention, an allyl compound can be produced at a low cost and in a high yield without using an expensive metal catalyst using a glycerin compound, which is a renewable raw material, as a raw material.

[Glycerin compound]
The glycerin compound used in the present invention has a structure represented by the general formula (1). In the general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, a —COR ⁴ group, or a hydroxyl group. And / or a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms and substituted with a carboxy group. R ⁴ is a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 20 carbon atoms substituted with a hydroxyl group and / or a carboxy group. Or represents an alkenyl group.

Specific examples of the linear alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like. Specific examples of the branched alkyl group having 1 to 20 carbon atoms include isopropyl, methylpropyl, ethylpropyl, dimethylpropyl, methylbutyl, propylbutyl, dimethylbutyl, trimethylbutyl, methylpentyl, ethylpentyl, dimethylpentyl, methylhexyl, and ethylhexyl. , Methylnonyl, dimethyloctyl and the like.
Specific examples of the linear or branched alkenyl group having 1 to 20 carbon atoms include ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, isopropenyl, methylpropenyl, methylbutenyl, methylpentenyl, ethylpropenyl, ethylbutenyl Dimethylpropenyl, dimethylbutenyl, methylhexenyl, ethylhexenyl, methylnonenyl, dimethyloctenyl and the like.

Specific examples of the linear or branched alkyl group having 1 to 20 carbon atoms substituted with hydroxyl groups include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyoctyl, hydroxydecyl , Hydroxydodecyl, hydroxytetradecyl, hydroxyhexadecyl, hydroxyoctadecyl, hydroxyicosyl, hydroxyisopropyl, hydroxymethylpropyl, hydroxymethylbutyl, hydroxyethylpropyl, hydroxymethylpentyl, hydroxymethylhexyl, hydroxyethylhexyl, hydroxymethylnonyl, hydroxy Examples thereof include dimethyloctyl and hydroxytetramethyloctyl.
Specific examples of the linear or branched alkenyl group having 1 to 20 carbon atoms substituted with a hydroxyl group include hydroxyethenyl, hydroxypropenyl, hydroxybutenyl, hydroxypentenyl, hydroxyhexenyl, hydroxyoctenyl, hydroxyde Senyl, hydroxydodecenyl, hydroxytetradecenyl, hydroxyhexadecenyl, hydroxyoctadecenyl, hydroxyicosenyl, hydroxyisopropenyl, hydroxymethylpropenyl, hydroxymethylbutenyl, hydroxymethylpentenyl, hydroxy Examples include ethylpropenyl, hydroxyethylbutenyl, hydroxymethylpentenyl and the like.

Specific examples of the linear or branched alkyl group having 1 to 20 carbon atoms substituted with a carboxy group include carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxypentyl, carboxyhexyl, carboxyoctyl, carboxy Decyl, carboxydodecyl, carboxytetradecyl, carboxyhexadecyl, carboxyoctadecyl, carboxyisopropyl, carboxymethylpropyl, carboxymethylbutyl, carboxyethylpropyl, carboxymethylpentyl, carboxymethylhexyl, carboxyethylhexyl, carboxymethylnonyl, carboxydimethyloctyl, Carboxytetramethyloctyl etc. are mentioned.
Specific examples of the linear or branched alkenyl group having 1 to 20 carbon atoms substituted with a carboxy group include carboxyethenyl, carboxypropenyl, carboxybutenyl, carboxypentenyl, carboxyhexenyl, carboxyoctenyl, carboxy Decenyl, carboxydodecenyl, carboxytetradecenyl, carboxyhexadecenyl, carboxyoctadecenyl, carboxyisopropenyl, carboxymethylpropenyl, carboxymethylbutenyl, carboxymethylpentenyl, carboxyethylpropenyl, carboxy Examples include ethyl butenyl and carboxymethylpentenyl.

  The total carbon number of the linear or branched alkyl group or alkenyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3, from the viewpoint of reactivity.

Examples of the glycerin compound represented by the general formula (1) include glycerin, glycerin ether compounds, and glycerin ester compounds. Specific examples of the glycerol ether compound include 1,2,3-trimethoxypropane, 1,2,3-triethoxypropane, 1,2,3-tripropoxypropane, 1,2,3-tributoxypropane, , 2,3-tripentoxypropane, 1,2-dimethoxypropane, 1,3-dimethoxypropane, 1-methoxypropane, 2-methoxypropane, 1,2,3-tri (monocarboxypentoxy) propane, 2,3-tri (monohydroxypentoxy) propane and the like. Specific examples of the glycerol ester compound include glycerol triacetate, glycerol tripropionate, glycerol tributyrate, glycerol tripentylate, glycerol diacetate, glycerol monoacetate, glycerol tri (monohydroxy) pentylate and the like.
The glycerin ether compound and the glycerin ester compound can be obtained as a reaction product of glycerin and a reaction solvent and / or a halogen compound, or as a reaction product of the reaction product and glycerin. The glycerol compound represented by the general formula (1) may be a reaction product other than the glycerol ether compound and the glycerol ester compound.
As the glycerin compound represented by the general formula (1), glycerin or a glycerin ester compound is preferable, and glycerin is most preferable. In this invention, the said glycerol compound can be used individually or in combination of 2 or more types.

[Halogen compounds]
Specific examples of the halogen compound used in the present invention include metal halides, hydrogen halides, alkyl halides and the like.

Preferred examples of the metal halide include halides of Group 1-12 metals in the periodic table. Among these, alkali metal halides and alkaline earth metal halides are more preferable from the viewpoint of cost.
Specific examples of the alkali metal halide include iodides such as lithium iodide, potassium iodide, sodium iodide and cesium iodide, bromides such as lithium bromide, potassium bromide, sodium bromide and cesium bromide. It is done. Specific examples of the alkaline earth metal halide include iodides such as magnesium iodide, calcium iodide and barium iodide, and bromides such as magnesium bromide, calcium bromide and barium bromide. Specific examples of the hydrogen halide include hydrogen iodide and hydrogen bromide.

As an alkyl halide, Preferably it is a C1-C10 alkyl halide, More preferably, a C1-C4 alkyl halide is mentioned.
Specific examples of alkyl halides include alkyl iodides such as methyl iodide, ethyl iodide and propyl iodide, bromides corresponding to these alkyl iodides (alkyl bromides such as methyl bromide and propyl bromide) and chlorides. Product (alkyl chloride such as methyl chloride).

A halogen compound can be used individually or in combination of 2 or more types.
As the halogen compound, metal iodide, hydrogen iodide and alkyl iodide are preferable, and alkyl iodide is more preferable among them. From the viewpoint of reactivity, methyl iodide is particularly preferred.

  The addition amount of the halogen compound in the reaction system is preferably 0.001 to 50% by mass, more preferably 0.01 to 40% by mass, and still more preferably 0.00% to 50% by mass with respect to the entire liquid phase system from the viewpoint of reactivity. It is about 03-30 mass%.

  From the viewpoint of reactivity, the amount of the halogen compound used is preferably from 0.001 to 1.0 mol, more preferably from 0.005 to 0.5 mol, based on 1 mol of the glycerol compound as the reaction substrate.

[Production of allyl compounds]
In the method of the present invention, an allyl compound is produced by reacting the halogen compound with the glycerin compound represented by the general formula (1).
From the viewpoint of reaction efficiency, the reaction temperature is preferably 30 to 300 ° C, more preferably 100 to 250 ° C, and still more preferably 150 to 230 ° C. The reaction time is preferably 0.5 minutes to 20 hours, more preferably 1 to 15 hours, and further preferably 2 to 10 hours from the viewpoint of reaction efficiency.

  The reaction may be performed in the presence or absence of a solvent. The reaction solvent is not particularly limited as long as the reactivity and separation or purification efficiency are not lowered, and various solvents can be used. From the viewpoint of catalyst stability, it is preferable to use an acidic solvent or a neutral solvent. From the viewpoint of solubility of the substrate and the product, a polar solvent is preferable, and among them, carboxylic acid is preferable. As a preferred carboxylic acid, a monocarboxylic acid or dicarboxylic acid having 2 to 10 carbon atoms is more preferred, and a monocarboxylic acid having 2 to 6 carbon atoms is still more preferred. For example, acetic acid, propionic acid, butanoic acid, glutaric acid and the like can be used, and acetic acid is particularly preferable.

[Reaction product]
As a specific example of the allyl compound produced by the method of the present invention, when glycerin is used as a raw material, acetic acid is used as a solvent, and iodide is used as a halogen compound, allyl alcohol, allyl acetate, and allyl iodide are selected from the group consisting of There is at least one selected. Allyl acetate and allyl iodide can be easily converted to allyl alcohol by hydrolysis. Therefore, allyl alcohol can be selectively extracted from the mixture by hydrolysis after completion of the reaction.

Example 1
In a 120 ml titanium autoclave, 0.31 g (2.2 mmol) of methyl iodide (MeI, manufactured by Tokyo Chemical Industry Co., Ltd.), 1.5 g (16.3 mmol) of glycerin (trade name: purified glycerin, manufactured by Kao Corporation) ) And 2.92 g (49.0 mmol) of acetic acid were added. Thereafter, the inside of the autoclave was replaced five times with nitrogen in the container, and further pressurized to 0.35 MPa at room temperature. While stirring at 600 rpm, the temperature was raised to 190 ° C., and the reaction was carried out for 3 hours after the temperature was raised. After completion of the reaction, the autoclave was cooled.
Analysis of low boiling point compounds in the reaction solution is a gas chromatograph analyzer using DB-FFAP (trade name, manufactured by Agilent Technologies) or TC-FFAP (trade name, manufactured by GL Sciences) as the column. It was performed by HP6890GC (trade name, manufactured by Hewett Packard) (temperature range: 40 ° C to 230 ° C). For analysis of high boiling point compounds in the reaction solution, the reaction completion solution is treated with TMS (trimethylsilylation), didodecyl ether is used as an internal standard, and Ultra ALLOY (trade name, manufactured by Frontier Laboratories) is used as a column. And a gas chromatograph analyzer HP6890GC (trade name, manufactured by Hewlet Packard) (temperature range: 40 ° C. to 350 ° C.). The analysis of the gas component was performed by a high-speed, small gas analyzer CP4900 micro GC (trade name, manufactured by Varian) using MS5A and PPQ (both trade names, manufactured by Varian) as columns.
Since glycerin is an acetylated product (monoacetin, diacetin, triacetin) and is difficult to determine, the total molar amount of the produced compound was regarded as a converted product, and the conversion rate and selectivity were calculated.
As a result, the conversion of glycerin was 17 mol%, and an allyl compound was obtained with a selectivity of about 38 mol% (allyl alcohol: 7.9 mol%, total of allyl iodide and allyl acetate: 30.3 Mol%).

Example 2
The reaction was conducted and analyzed in the same manner as in Example 1 except that the reaction time was 5 hours.
As a result, the conversion of glycerin was 57 mol%, and an allyl compound was obtained with a selectivity of about 46 mol% (allyl alcohol: 9.3 mol%, total of allyl iodide and allyl acetate: 36.3). Mol%).

  From the above results, the number of moles of product per mole of methyl iodide, that is, the turnover number (TON) was calculated to be 1.9. Considering the result of Comparative Example 1 as well, the case where TON exceeds 1 means that catalytic activity is exhibited. Therefore, it was found that methyl iodide was the catalyst and the reaction proceeded.

Comparative Example 1
The reaction was performed and analyzed in the same manner as in Example 1 except that methyl iodide was not used. As a result, the reaction did not proceed at all.

  According to the method of the present invention, an allyl compound can be efficiently produced using a glycerin compound, which is a renewable resource, as a raw material. The allyl compound obtained by the method of the present invention is useful as a raw material for polymerization and copolymerization in polymer synthesis and as a raw material for pharmaceuticals, glycidol, epichlorohydrin and the like.

Claims (3)

The manufacturing method of the allyl compound which makes the alkyl iodide and the glycerol compound represented by following General formula (1) react for 5 to 10 hours.

Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, a —COR ⁴ group, a hydroxyl group and / or a carboxy group. Represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, and R ⁴ represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, Or a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms and substituted with a hydroxyl group and / or a carboxy group. The amount of the alkyl iodide, glycerin based on 1 mol of the compound is 0.001 to 1.0 mol, the production method according to claim 1. The production method according to claim 1 or 2 , wherein the allyl compound is at least one selected from the group consisting of allyl alcohol, allyl acetate, and allyl iodide.