Method for producing a dialkylzinc-containing composition

Abstract

To provide: a production method of a dialkylzinc with a lowered content of hydrogenated dialkylzinc by lowering the hydrogenated dialkylzinc contained in the dialkylzinc; and an additive which can be used for lowering the hydrogenated dialkylzinc contained in the dialkylzinc.SOLUTION: A production method of a dialkylzinc-containing composition includes mixing a mixture containing a hydrogenated dialkylzinc and a dialkylzinc with an additive, and obtaining the dialkylzinc-containing composition of which the content of the hydrogenated dialkylzinc is lowered than in the mixture. The additive is at least one compound selected from a group consisting of a carbonyl group-containing hydrocarbon compound, an aromatic amine compound, and a nitrogen-containing unsaturated cyclic hydrocarbon compound. A lowering agent is used for lowering a content of the hydrogenated dialkylzinc coexisting with the dialkylzinc, and is at least one compound selected from a group consisting of a carbonyl group-containing hydrocarbon compound, an aromatic amine compound, and a nitrogen-containing unsaturated cyclic hydrocarbon compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a dialkylzinc-containing composition in which the content of dialkylzinc hydrides is reduced, and to a reducing agent used to reduce the content of dialkylzinc hydrides coexisting with dialkylzinc. [Background technology]

[0002] Dialkylzinc has applications as a raw material for semiconductors, and some semiconductors are manufactured using metal-organic vapor deposition (MOCVD) by taking advantage of the low vapor pressure of dialkylzinc. However, impurities contained in dialkylzinc can cause problems during semiconductor manufacturing.

[0003] Hydrogenated dialkylzinc (R 1 ZnH) is more easily thermally decomposed than dialkylzinc. Therefore, when dialkylzinc is heated in the semiconductor manufacturing process, the zinc produced by the thermal decomposition of the dialkylzinc hydride can cause blockages in piping, leading to problems.

[0004] [ka]

[0005] The bond energy of the Zn-H bond is 228 kJ / mol, which is lower than the bond energy of the Zn-C bond in dialkylzinc, which is approximately 280 kJ / mol. Therefore, it is thought that bond cleavage is more likely to occur (Non-Patent Literature 1).

[0006] However, to the best of the inventor's knowledge, there is no known method for reducing the amount of dialkylzinc hydride contained in dialkylzinc. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] Organometallic Ion Chemistry, edited by Ben S. Freeser, Kluwer Academic Publishers, 1996, p.10 [Overview of the project] [Problems that the invention aims to solve]

[0008] Therefore, the present invention aims to provide a method for producing dialkylzinc with a reduced content of dialkylzinc hydrides by reducing the amount of dialkylzinc hydrides contained in dialkylzinc, and to provide an additive that can be used to reduce the amount of dialkylzinc hydrides contained in dialkylzinc. [Means for solving the problem]

[0009] The inventors of the present invention have discovered that the amount of dialkylzinc hydride contained in dialkylzinc can be reduced by mixing a specific additive with dialkylzinc containing dialkylzinc hydride and reacting the mixture with the hydride. Based on this discovery, the inventors have completed the present invention.

[0010] The present invention is as follows: [1] A method for producing a dialkylzinc-containing composition, comprising mixing a dialkylzinc hydride, a mixture containing dialkylzinc, and an additive to obtain a composition containing dialkylzinc in which the content of the dialkylzinc hydride is lower than that of the mixture, The manufacturing method wherein the additive is at least one compound selected from the group consisting of carbonyl group-containing hydrocarbon compounds, aromatic amine compounds, and nitrogen-containing unsaturated cyclic hydrocarbon compounds. [2] The method for producing a product according to [1], further comprising subjecting the obtained composition to distillation to obtain a composition containing dialkylzinc in which the content of the dialkylzinc hydride is lower than that of the aforementioned composition. [3] The production method according to [1] or [2], wherein the alkyl group contained in the dialkylzinc and the hydrogenated product of dialkylzinc is a methyl group or an ethyl group. [4] The production method according to any one of [1] to [3], wherein the carbonyl group-containing hydrocarbon compound is a ketone compound or an ester compound. [5] The production method according to [4], wherein the ketone compound is a hydrocarbon compound having 5 to 25 carbon atoms. [6] The production method according to [4], wherein the ketone compound is cyclohexanone, acetophenone or benzophenone. [7] The production method according to [4], wherein the ester compound is a hydrocarbon compound having 6 to 25 carbon atoms. [8] The production method according to [4], wherein the ester compound is methyl benzoate or benzyl benzoate. [9] The production method according to any one of [1] to [3], wherein the total number of carbon atoms and nitrogen atoms of the aromatic amine compound and the nitrogen-containing unsaturated cyclic hydrocarbon compound is 5 or more and 20 or less.

[10] The production method according to any one of [1] to [3], wherein the aromatic amine compound is N,N-dimethylaniline, and the nitrogen-containing unsaturated cyclic hydrocarbon compound is 1-methylimidazole, 2,4,6-collidine or pyridine.

[11] A reducing agent used for reducing the content of the hydrogenated product of dialkylzinc coexisting with dialkylzinc, The reducing agent, wherein the reducing agent is at least one compound selected from the group consisting of a carbonyl group-containing hydrocarbon compound, an aromatic amine compound and a nitrogen-containing unsaturated cyclic hydrocarbon compound.

Advantages of the Invention

[0011] According to the present invention, it is possible to produce dialkylzinc with a reduced content of dialkylzinc hydrides by reducing the amount of dialkylzinc hydrides contained in dialkylzinc. Furthermore, according to the present invention, it is possible to provide an additive that can be used to reduce the amount of dialkylzinc hydrides contained in dialkylzinc. [Modes for carrying out the invention]

[0012] <Method for producing a dialkyl zinc-containing composition> The present invention relates to a method for producing a dialkylzinc-containing composition, comprising mixing a dialkylzinc hydride, a mixture containing dialkylzinc, and an additive to obtain a composition containing dialkylzinc in which the content of the dialkylzinc hydride is lower than that of the mixture (hereinafter sometimes referred to as dialkylzinc-containing composition 1), wherein the additive is at least one compound selected from the group consisting of carbonyl group-containing hydrocarbon compounds, aromatic amine compounds, and nitrogen-containing unsaturated cyclic hydrocarbon compounds.

[0013] The alkyl group in the dialkylzinc and dialkylzinc hydride contained in the dialkylzinc hydride and the mixture containing dialkylzinc is preferably a methyl group or an ethyl group. When the alkyl group is an ethyl group, the mixture containing diethylzinc hydride and diethylzinc can be obtained as a product, for example, by synthesizing diethylzinc by the reaction of zinc chloride and triethylaluminum. In this case, the content of diethylzinc hydride in the mixture varies depending on the reaction conditions, but is, for example, in the range of 10 to 1000 ppm when converted to the hydrogen atom mass derived from diethylzinc hydride. However, this range is not intended to be limiting, but rather represents a typical content range. The case when the alkyl group is a methyl group is almost the same.

[0014] The additive used in the present invention is at least one compound selected from the group consisting of carbonyl group-containing hydrocarbon compounds, aromatic amines, and nitrogen-containing unsaturated cyclic hydrocarbon compounds.

[0015] Examples of carbonyl group-containing hydrocarbon compounds include ketone compounds, ester compounds, or carboxylic acid compounds. However, ketone compounds and ester compounds are preferred because they react mildly with the hydrogenated dialkylzinc.

[0016] Ketone compounds are suitable because they are readily available, have high boiling points, and are easy to handle, and therefore have 5 to 25 carbon atoms. Ketone compounds can be compounds represented by the following general formula (1), where R 2 and R 3 Independently, R is a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms; a linear or branched alkenyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms; a linear or branched alkynyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms; a substituted or unsubstituted phenyl group; or a substituted or unsubstituted benzyl group. 2 and R 3 The crosslinked group can be a substituted or unsubstituted cycloalkyl group having 5 to 15 carbon atoms, or a substituted or unsubstituted cycloalkenyl group having 5 to 15 carbon atoms. Examples of substituents include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, vinyl, allyl, hydroxy, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, i-butoxy, t-butoxy, fluoro, chloro, bromo, and iodo groups. Furthermore, the compound represented by the general formula (1) below may also be a compound having one or two additional carbonyl groups.

[0017] [ka]

[0018] Examples of ketone compounds include 2-hexanone, 2-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 5-nonanone, cyclopentanone, cyclohexanone, acetophenone, propiophenone, benzophenone, dibenzyl ketone, and p-benzoquinone. From the viewpoint of being readily available and having high boiling points that make them easy to handle, cyclohexanone (bp=155.6°C), acetophenone (bp=202°C), and benzophenone (bp=305.4°C) are preferred as ketone compounds.

[0019] Suitable ester compounds are hydrocarbon compounds with 6 to 25 carbon atoms, from the viewpoint of being readily available, having a high boiling point, and being easy to handle. The ester compound can be a compound shown in the following general formula (2), where R 4 and R 5 The substituents can be substituted or unsubstituted linear or branched alkyl groups having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms; substituted or unsubstituted linear or branched alkenyl groups having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms; substituted or unsubstituted linear or branched alkynyl groups having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms; substituted or unsubstituted phenyl groups; or substituted or unsubstituted benzyl groups. Examples of substituents include methyl groups, ethyl groups, n-propyl groups, i-propyl groups, n-butyl groups, s-butyl groups, i-butyl groups, t-butyl groups, vinyl groups, allyl groups, hydroxyl groups, methoxy groups, ethoxy groups, n-propoxy groups, i-propoxy groups, n-butoxy groups, s-butoxy groups, i-butoxy groups, t-butoxy groups, fluoro groups, chloro groups, bromo groups, and iodo groups.

[0020] [ka]

[0021] Examples of ester compounds include butyl acetate, amyl acetate, isoamyl acetate, octyl acetate, phenyl acetate, benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl benzoate, and benzyl benzoate. From the viewpoints of easy availability, high boiling point, and easy handling, methyl benzoate (bp = 199 °C) and benzyl benzoate (bp = 323 °C) are preferred.

[0022] From the viewpoints of easy availability, high boiling point, and easy handling, compounds having a total of 5 or more and 20 or less carbon atoms and nitrogen atoms are suitable as aromatic amine compounds and nitrogen-containing unsaturated cyclic hydrocarbon compounds. The aromatic amine compound can be a compound represented by the following general formula (3), and the nitrogen-containing unsaturated cyclic hydrocarbon compound can be a compound represented by the following general formulas (4) to (9), where R 6 、R 7 、R 14 and R 16 are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, a substituted or unsubstituted linear or branched alkenyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or a substituted or unsubstituted linear or branched alkynyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and R 8 ~R 13 and R 15 are a hydrogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, a substituted or unsubstituted linear or branched alkenyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or a substituted or unsubstituted linear or branched alkynyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. However, R 8 ~R 13 and R 15There can be one, two, or three substituents. Examples of substituents include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, vinyl group, allyl group, hydroxy group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group, fluoro group, chloro group, bromo group, and iodine group.

[0023] [ka]

[0024] Examples of aromatic amine compounds include N,N-dimethylaniline and N,N-dimethyl-p-toluidine, and nitrogen-containing unsaturated cyclic hydrocarbon compounds include 1-methylimidazole, 1-methylpyrazole, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-lutidine, 2,4,6-collidine, 4-dimethylaminopyridine, pyridazine, pyrimidine, and pyrazine. From the viewpoint of being readily available and having high boiling points that make them easy to handle, N,N-dimethylaniline (bp=194°C), 1-methylimidazole (bp=198°C), pyridine (bp=115°C), and 2,4,6-collidine (bp=170°C) are preferred, with N,N-dimethylaniline and pyridine being even more preferred.

[0025] The hydride of dialkylzinc, a mixture containing dialkylzinc, and an additive are mixed. The amount of additive added to the mixture can be appropriately determined considering the expected content of the hydride of dialkylzinc, and can be, for example, 0.5 to 5 times the equivalent amount of the hydride of dialkylzinc. Alternatively, the additive can be added to the mixture in a range of, for example, 0.1 to 10% by mass, without considering the content of the hydride of dialkylzinc.

[0026] The mixture containing the additive should be stirred and mixed at a predetermined temperature for a predetermined time, which is appropriate from the viewpoint of promoting the reaction between the hydrogenated dialkylzinc and the additive. The stirring temperature should be below the boiling point or thermal decomposition temperature of the dialkylzinc, and is preferably between 0°C and 60°C. If the dialkylzinc is dimethylzinc, the boiling point of dimethylzinc is 46°C, so a temperature of 0°C to 40°C is preferred. If the dialkylzinc is diethylzinc, the boiling point of diethylzinc is 117.6°C, so a temperature of 0°C to 60°C is preferred. There are no particular restrictions on the stirring time, but a period of 1 hour to 24 hours is preferred. The pressure during stirring can be either atmospheric pressure or pressurized pressure, but a pressure of 0 MPaG to 0.3 MPaG is preferred.

[0027] The reaction apparatus for mixing dialkylzinc and additives can be either vertical or horizontal, and there are no particular restrictions on its use. For example, a pressure-resistant autoclave containing a stirring bar can be stirred with a magnetic stirrer. Alternatively, an autoclave with a pressure-resistant stirring device can be used, and common types of stirring blades can be used, such as propellers, turbines, foudlers, maxblendes, and fulzones.

[0028] The reaction apparatus is preferably under an inert gas atmosphere such as nitrogen or argon, because moisture in the air reacts with dialkylzinc.

[0029] Hydrogenated dialkylzinc (R 1 By stirring and mixing a mixture containing ZnH) with an additive, the hydride of dialkylzinc reacts with the additive to obtain a composition containing dialkylzinc (dialkylzinc-containing composition 1) in which the content of the hydride of dialkylzinc is lower than that of the raw material. When the additive is a ketone compound shown in general formula (1), the hydride of dialkylzinc (R 1An example of a reaction with ZnH is shown in formula (10). The reaction when the additive is an ester compound shown in general formula (2) is shown in formula (11). An example of a reaction with an aromatic amine compound shown in general formula (3) is shown in formula (12), and examples of reactions with nitrogen-containing unsaturated cyclic hydrocarbon compounds shown in general formulas (4) to (9) are shown in formulas (13) to (18).

[0030] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0031] There are no particular restrictions on the content of dialkylzinc hydride in dialkylzinc-containing composition 1, which includes dialkylzinc in which the content of dialkylzinc hydride is lower compared to the raw material. However, when converted to the hydrogen atom mass derived from the dialkylzinc hydride, it is, for example, in the range of 1 to 200 ppm. However, this is not intended to limit the composition to this range, but rather represents a typical content range.

[0032] Dialkylzinc-containing composition 1 includes a reaction product between the hydride of dialkylzinc and an additive. Since the reaction product between the hydride of dialkylzinc and the additive has a higher boiling point than the hydride of dialkylzinc and dialkylzinc, its presence in the composition does not cause any problems in subsequent use.

[0033] <Distillation Process> The present invention's method for producing a composition containing dialkylzinc may further include subjecting the above-mentioned dialkylzinc-containing composition 1 to distillation to obtain a composition containing dialkylzinc (hereinafter sometimes referred to as dialkylzinc-containing composition 2) in which the content of the hydride of dialkylzinc is lower than that of the composition before distillation.

[0034] The dialkylzinc-containing composition 1 is distilled by separating the dialkylzinc fraction containing the hydride of dialkylzinc remaining in composition 1. The boiling points of dialkylzinc are, for example, 46°C for dimethylzinc and 117.6°C for diethylzinc. The boiling points of the hydrides of dialkylzinc vary depending on the type of hydride, but for example, analysis has shown that when diethylzinc containing the hydride of diethylzinc is distilled, the initial distillate is hydride-rich. The distillation conditions can be appropriately set considering the type of dialkylzinc (boiling point) and the fact that the initial distillate is hydride-rich.

[0035] Distillation yields a dialkylzinc hydride-rich fraction as the initial distillate, followed by a main distillate, which is a dialkylzinc fraction with a reduced dialkylzinc hydride content. The amount of dialkylzinc hydride recovered in the dialkylzinc fraction varies depending on the amount of the initial distillate and the amount of the main distillate recovered. Furthermore, the reaction product between the dialkylzinc hydride and the additive has a high boiling point, so it is recovered as a distillation residue or as dialkylzinc containing the reaction product.

[0036] To improve separation performance, a distillation column with packing is preferred. The packing can be commercially available or manufactured by known methods, and both ordered and irregular packing can be used. A higher number of theoretical stages is preferable, but an industrially advantageous height should be selected. A distillation column with 4 to 20 theoretical stages is preferred.

[0037] Since moisture in the air reacts with the organozinc composition inside the distillation apparatus, it is preferable to replace the air with an inert gas such as nitrogen or argon before starting the distillation.

[0038] The distillation temperature depends on the type of dialkylzinc and the degree of vacuum in the apparatus, but is preferably between 35°C and 100°C. The distillation pressure can be either atmospheric pressure or reduced pressure, but is preferably between 0.01 kPaA and 50 kPaA.

[0039] The dialkylzinc obtained by distillation (composition 2) has a reduced content of the dialkylzinc hydride compared to composition 1 used as the raw material, and the reaction product between the dialkylzinc hydride and the additive is separated as a distillation residue.

[0040] <Enhancement agent> The present invention includes a reducing agent used to reduce the content of dialkylzinc hydrogenates coexisting with dialkylzinc. This reducing agent is at least one compound selected from the group consisting of carbonyl group-containing hydrocarbon compounds, aromatic amine compounds, and nitrogen-containing unsaturated cyclic hydrocarbon compounds.

[0041] The carbonyl group-containing hydrocarbon compounds, aromatic amine compounds, and nitrogen-containing unsaturated cyclic hydrocarbon compounds in the reducing agent of the present invention are the same as those used in the production method of the present invention.

[0042] Examples of carbonyl group-containing hydrocarbon compounds include ketone compounds, ester compounds, or carboxylic acid compounds. However, ketone compounds and ester compounds are preferred because they react mildly with the hydrogenated dialkylzinc.

[0043] From the viewpoint of being readily available, having a high boiling point, and being easy to handle, ketone compounds having 5 to 25 carbon atoms are suitable. The ketone compound can be the compound shown in the general formula (1) above, and specifically, examples include 2-hexanone, 2-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 5-nonanone, cyclopentanone, cyclohexanone, acetophenone, propiophenone, benzophenone, dibenzyl ketone, and p-benzoquinone. From the viewpoint of being readily available, having a high boiling point, and being easy to handle, cyclohexanone (bp=155.6℃), acetophenone (bp=202℃), and benzophenone (bp=305.4℃) are preferred as ketone compounds.

[0044] Suitable ester compounds are hydrocarbon compounds having 6 to 25 carbon atoms, from the viewpoint of being readily available, having a high boiling point, and being easy to handle. The ester compound can be a compound represented by the general formula (2) above, and examples include butyl acetate, amyl acetate, isoamyl acetate, octyl acetate, phenyl acetate, benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl benzoate, and benzyl benzoate. From the viewpoint of being readily available, having a high boiling point, and being easy to handle, methyl benzoate (bp=199°C) and benzyl benzoate (bp=323°C) are preferred.

[0045] From the viewpoint of being readily available, having high boiling points, and being easy to handle, aromatic amine compounds and nitrogen-containing unsaturated cyclic hydrocarbon compounds are suitable if the total number of carbon atoms and nitrogen atoms is between 5 and 20. Aromatic amine compounds can be compounds represented by general formula (3), such as N,N-dimethylaniline and N,N-dimethyl-p-toluidine. Nitrogen-containing unsaturated cyclic hydrocarbon compounds can be compounds represented by general formulas (4) to (9), such as 1-methylimidazole, 1-methylpyrazole, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-lutidine, 2,4,6-collidine, 4-dimethylaminopyridine, pyridazine, pyrimidine, and pyrazine. From the viewpoint of being readily available, having a high boiling point, and being easy to handle, N,N-dimethylaniline (bp=194°C), 1-methylimidazole (bp=198°C), pyridine (bp=115°C), and 2,4,6-collidine (bp=170°C) are preferred, with N,N-dimethylaniline and pyridine being more preferred.

[0046] The reducing agent of the present invention is used by adding it to a mixture containing a hydride of dialkylzinc and dialkylzinc, and then mixing them together.

[0047] The amount of reducing agent added to a mixture containing dialkylzinc hydride can be appropriately determined considering the expected content of dialkylzinc hydride, and can be, for example, 0.5 to 5 times the equivalent amount of dialkylzinc hydride. Alternatively, it can be added to the mixture in a range of, for example, 0.1 to 10% by mass, without considering the content of dialkylzinc hydride. [Examples]

[0048] The present invention will be described in more detail below based on examples. However, the examples are illustrative of the present invention and are not intended to limit the present invention to these examples.

[0049] <Method for analyzing the hydride components of dialkylzinc> A solution of dialkylzinc containing a dialkylzinc hydride was diluted fourfold with liquid paraffin and added dropwise to an acidic aqueous solution to obtain a hydrolysis solution of dialkylzinc. The hydrogen gas generated from the dialkylzinc hydride was detected using a Shimadzu gas chromatograph-barrier discharge ionization detector (GC-BID) Nexis GC-2030, and the amount of dialkylzinc hydride contained in the dialkylzinc-containing composition was calculated.

[0050] Example 1 In a 30 mL stainless steel autoclave (manufactured by Pressure Glass Industry Co., Ltd.) purged with nitrogen, 21.97 g of diethylzinc (manufactured by Tosoh Finechem Co., Ltd.) containing 166 ppm of diethylzinc hydride (calculated by hydrogen atomic mass) and 0.21 g of benzophenone (manufactured by Fujifilm Wako Pure Chemical Industries, purity 98%, 1% by weight relative to diethylzinc), which had been preheat-dried, were added and stirred at room temperature for 5 hours. The amount of diethylzinc hydride in this reaction composition decreased to 50 ppm (70% reduction rate) (calculated by hydrogen atomic mass). The analytical results are shown in Table 1.

[0051] Example 2 The procedure was the same as in Example 1, except that the amount of additive was 0.3% by weight relative to diethylzinc. The analysis results of the obtained composition are shown in Table 1.

[0052] Example 3 The procedure was the same as in Example 1, except that the stirring temperature between diethylzinc and the additive was set to 50°C. The analysis results of the obtained composition are shown in Table 1.

[0053] Example 4 The procedure was the same as in Example 1, except that the type of additive used was cyclohexanone (manufactured by Fujifilm Wako Pure Chemical Industries, 99% purity). The analysis results of the obtained composition are shown in Table 1.

[0054] Example 5 The procedure was the same as in Example 1, except that the type of additive used was acetophenone (manufactured by Fujifilm Wako Pure Chemical Industries, 99% purity). The analysis results of the obtained composition are shown in Table 1.

[0055] Example 6 The procedure was the same as in Example 1, except that the type of additive used was benzyl benzoate (manufactured by Fujifilm Wako Pure Chemical Industries, 99% purity). The analysis results of the obtained composition are shown in Table 1.

[0056] Example 7 The procedure was the same as in Example 1, except that the type of additive used was methyl benzoate (manufactured by Fujifilm Wako Pure Chemical Industries, 98% purity). The analysis results of the obtained composition are shown in Table 1.

[0057] Example 8 The procedure was the same as in Example 1, except that the type of additive used was pivalic acid (manufactured by Fujifilm Wako Pure Chemical Industries, 98% purity). The analysis results of the obtained composition are shown in Table 1.

[0058] Example 9 The procedure was the same as in Example 1, except that the type of additive used was pyridine (manufactured by Fujifilm Wako Pure Chemical Industries, purity 99.5%) that had been pre-dehydrated with zeolam. The analysis results of the obtained composition are shown in Table 1.

[0059] Example 10 The procedure was the same as in Example 1, except that the type of additive used was 2,4,6-collidine (manufactured by Tokyo Chemical Industry Co., Ltd., purity 98%). The analysis results of the obtained composition are shown in Table 1.

[0060] Example 11 The procedure was the same as in Example 1, except that the type of additive used was 1-methylimidazole (manufactured by Fujifilm Wako Pure Chemical Industries, 98% purity). The analysis results of the obtained composition are shown in Table 1.

[0061] Example 12 The procedure was the same as in Example 1, except that the type of additive used was N,N-dimethylaniline (manufactured by Fujifilm Wako Pure Chemical Industries, 99% purity). The analysis results of the obtained composition are shown in Table 1.

[0062] Reference example 1 In accordance with Japanese Patent Publication No. 2011-74069, the procedure was carried out in the same manner as in Example 1, except that the type of additive used was α-methylstyrene (manufactured by Fujifilm Wako Pure Chemical Industries, 98% purity), but the amount of diethylzinc hydride in the reaction composition did not decrease. The analysis results are shown in Table 1. The invention described in Japanese Patent Publication No. 2011-74069 aims to improve the stability of organozinc compounds under heating and suppress the generation of metallic zinc by thermal decomposition, and does not aim to reduce the content of dialkylzinc hydride.

[0063] Reference example 2 In accordance with U.S. Patent No. 4,385,003, the procedure was carried out in the same manner as in Example 1, except that the type of additive was changed to anthracene (manufactured by Fujifilm Wako Pure Chemical Industries, 96% purity) that had been preheat-dried. However, the amount of diethylzinc hydride in the reaction composition did not decrease. The analysis results are shown in Table 1. The invention described in U.S. Patent No. 4,385,003 also aims to improve the stability of organozinc compounds under heating and suppress the generation of metallic zinc by thermal decomposition, and does not aim to reduce the content of dialkylzinc hydride.

[0064] Example 13 In a 1L autoclave equipped with a SUS stirrer and purged with nitrogen, 270g (2.18mol) of diethylzinc, a raw material containing 68ppm (18.3mg) of diethylzinc hydride (based on hydrogen atomic mass), and 2.72g (14.9mmol, manufactured by Fujifilm Wako Pure Chemical Industries, 98% purity, 1wt% relative to diethylzinc), which had been preheat-dried, were added and stirred at room temperature for 5 hours. An analysis of 18g of this reaction mixture revealed that the amount of diethylzinc hydride had decreased to 21ppm (70% reduction) (based on hydrogen atomic mass). Subsequently, the remaining 252g of the reaction mixture was distilled in a glass distillation column connected to the autoclave and packed with 10 theoretical plates (Sulzer EX Lab Packing, manufactured by Sulzer) under conditions of 3kPaA, 38°C, and reflux ratio 3. After removing the initial fraction of 38 g (0.290 mol), 169 g (1.37 mol, yield 67%) of diethylzinc, containing 14 ppm (79% reduction rate) of diethylzinc hydride in terms of hydrogen atom mass, was obtained as the main fraction. The analytical results are shown in Table 1.

[0065] Reference example 3 Without adding or mixing benzophenone, the raw material diethylzinc was distilled directly under the same conditions as in Example 13. The obtained main fraction of diethylzinc contained 39 ppm (43% reduction) of diethylzinc hydride in terms of hydrogen atom mass.

[0066] [Table 1] [Industrial applicability]

[0067] This invention is useful in the technical field relating to dialkylzinc.

Claims

1. A method for producing a dialkylzinc-containing composition, comprising mixing a dialkylzinc hydride, a mixture containing dialkylzinc, and an additive to obtain a composition containing dialkylzinc in which the content of the dialkylzinc hydride is lower than that of the mixture, The manufacturing method wherein the additive is at least one compound selected from the group consisting of a ketone compound represented by the following general formula (1), an ester compound represented by the following general formula (2), an aromatic amine compound represented by the following general formula (3), and a nitrogen-containing unsaturated cyclic hydrocarbon compound represented by the following general formulas (4) to (9). 【Chemistry 1】 (In general formula (1), R2 and R3 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted linear or branched alkenyl group having 1 to 15 carbon atoms, a substituted or unsubstituted linear or branched alkynyl group having 1 to 15 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, or R2 and R3 are cross-linked to a substituted or unsubstituted cycloalkyl group having 5 to 15 carbon atoms or a substituted or unsubstituted cycloalkenyl group having 5 to 15 carbon atoms.) 【Chemistry 2】 (In general formula (2), R4 and R5 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted linear or branched alkenyl group having 1 to 15 carbon atoms, a substituted or unsubstituted linear or branched alkynyl group having 1 to 15 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group. 【Transformation 3】 (In the above general formula, R6, R7, R14, and R16 are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted linear or branched alkenyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted linear or branched alkynyl group having 1 to 10 carbon atoms. R8 to R13 and R15 are each independently a hydrogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted linear or branched alkenyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted linear or branched alkynyl group having 1 to 10 carbon atoms. However, one, two, or three R8s may exist in general formula (3), one, two, or three R9s may exist in general formula (4), one, two, or three R10s may exist in general formula (5), one, two, or three R11s may exist in general formula (6), one, two, or three R12s may exist in general formula (7), one, two, or three R13s may exist in general formula (8), and one, two, or three R15s may exist in general formula (9).

2. The manufacturing method according to claim 1, further comprising subjecting the obtained composition to distillation to obtain a composition containing dialkylzinc in which the content of the dialkylzinc hydride is lower than that of the aforementioned composition.

3. The manufacturing method according to claim 1 or 2, wherein the alkyl group contained in the dialkylzinc and the dialkylzinc hydrogenate is a methyl group or an ethyl group.

4. The method for producing a carbon-neutral compound according to claim 1 or 2, wherein the ketone compound is a hydrocarbon compound having 5 to 25 carbon atoms.

5. The method for producing the ketone compound according to claim 1 or 2, wherein the ketone compound is cyclohexanone, acetophenone, or benzophenone.

6. The manufacturing method according to claim 1 or 2, wherein the ester compound is a hydrocarbon compound having 6 to 25 carbon atoms.

7. The production method according to claim 1 or 2, wherein the ester compound is methyl benzoate or benzyl benzoate.

8. The method for producing an aromatic amine compound and a nitrogen-containing unsaturated cyclic hydrocarbon compound, wherein the total number of carbon atoms and nitrogen atoms is 5 or more and 20 or less.

9. The production method according to claim 1 or 2, wherein the aromatic amine compound is N,N-dimethylaniline, and the nitrogen-containing unsaturated cyclic hydrocarbon compound is 1-methylimidazole, 2,4,6-collidine, or pyridine.

Images