Synthesis method of group IIIA organic metal halide derivative and Lewis base adduct thereof

Abstract

The invention discloses a group IIIA organic metal halide derivative and a synthesis method and application of a Lewis base adduct of the group IIIA organic metal halide derivative, and belongs to the field of organic metal chemistry. By optimizing reaction conditions and ligand selection, accurate control of the product structure is realized. The synthesized compound shows a unique M-C bond vibration characteristic in an infrared spectrum, and the function of the compound can be expanded through a derivatization reaction. The prepared product has wide application prospects in the fields of catalysis, material science and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organometallic chemistry, in particular to a synthesis method and application of a group IIIA organometallic halide derivative and its Lewis base adduct. BACKGROUND

[0002] The research of group IIIA organometallic halides lags behind other group III metals (such as tin, antimony). Among them, the known alkyl halides of aluminum, indium and gallium are mainly in the form of polymers, and the types of derivatives are limited, and the stereochemical properties have not been systematically explored. The existing synthesis method often faces problems such as multiple side reactions, difficult separation of products, etc.

[0003] The technical scheme for synthesizing dialkyl group IIIA metal halide in the prior art generally uses alkyl group IIIA metal and group IIIA metal halide as raw materials to generate disubstituted alkyl group IIIA metal halide (such as CN112409390A, etc.). It has the problems of high cost, complicated operation, and dangerous alkyl group IIIA metal as raw material, etc.

[0004] Therefore, it is an urgent problem for those skilled in the art to provide a method for efficiently preparing group IIIA organometallic halide and its derivative or adduct. SUMMARY

[0005] Therefore, the present application provides a synthesis method and application of a group IIIA organometallic halide derivative and its Lewis base adduct.

[0006] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] A synthesis method of a group IIIA organometallic halide derivative, comprising the following steps:

[0008] (1) mixing a nucleophile and a trihalide of group IIIA metal into a first organic solvent, heating and refluxing and stirring;

[0009] (2) removing the first organic solvent by reduced pressure distillation to obtain a group IIIA organometallic halide derivative.

[0010] Further, the nucleophile in step (1) is Grignard reagent or alkyl lithium reagent; the group IIIA metal is Al, In, Ga; and the halogen is any one of F, Cl, Br and I.

[0011] In the present application, the metal halide represented by formula (1), the organic metal reagent represented by formula (2) or formula (3) is prepared into the group IIIA organic metal halide represented by formula (4) through nucleophilic reaction. In formula 1 to 4, M is group IIIA metal; R1, R2 are independently hydrogen, (C1-C10) alkyl, (C1-C10) alkoxy, (C3-C12) cycloalkyl or (C3-C12) heterocycloalkyl; X is F, Cl, Br, I halogen; R1, R2 can be further substituted by one or more substituents such as halogen, trifluoromethyl, amino, cyano and hydroxyl.

[0012]

[0013] Further, the molar ratio of the trihalide of group IIIA metal to the nucleophilic reagent is 1:1-2.

[0014] Further, the first organic solvent in step (1) is diethyl ether.

[0015] The heating reflux temperature in step (1) is 60-110℃; the heating reflux reaction time is 0.5-48h, and the stirring speed is 130-160r / min.

[0016] The temperature of the reduced pressure distillation in step (2) is controlled at 40-60℃, and the reduced pressure distillation pressure is 0.5torr-1.5torr.

[0017] The present application also provides a synthesis method of the Lewis base adduct of the group IIIA organic metal halide derivative, comprising the following steps:

[0018] The group IIIA organic metal halide derivative and the Lewis base are mixed and added into the second organic solvent, heated and refluxed, and yellow crystals are precipitated after cooling, filtered and dried to obtain the Lewis base adduct of the group IIIA organic metal halide derivative.

[0019] Further, the Lewis base is pyridine or triphenylphosphine;

[0020] The molar ratio of the group IIIA organic metal halide derivative to the Lewis base is 1:1-2.

[0021] Further, the second organic solvent is toluene.

[0022] The Lewis base adduct of the group IIIA organic metal halide derivative prepared by the present application can be used as a catalyst and a precursor for C-C bond coupling reaction, and can also be applied in semiconductor electronic materials.

[0023] The group IIIA organic metal halide derivative prepared by the application can also be used for preparing functional group IIIA organic metal halide derivative by adding acetylacetate, 8-hydroxyquinoline acid salt and other reagents, and applied in catalysis, material science and other fields.

[0024] The application has the advantages of:

[0025] Controllability of reaction conditions: the application realizes the directional conversion of the product from the trialkyl IIIA metal compound to the disubstituted IIIA metal halide derivative by adjusting the reaction time and the type of ligand.

[0026] Structural diversity: the group IIIA organic metal halide synthesized by the application has a dimer structure (halogen bridging) in benzene solution, and the infrared spectrum confirms the M-C bond vibration characteristics (asymmetric stretching vibration frequency: 520-550 cm -1 , symmetric stretching vibration: 480-500 cm -1 ); M is Al, Ga or In.

[0027] Application potential: the Lewis base adduct of the group IIIA organic metal halide derivative prepared by the application can be used as a catalyst precursor or functional material, and is suitable for the fields of organic synthesis, semiconductor electronic material, and preparation of optoelectronic materials. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the application will be described below in a clear and complete manner. Obviously, the described embodiments are only some of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0029] Example 1: synthesis method of dimethyl aluminum (III) fluoride:

[0030] Methyl magnesium chloride (2 mmol) and AlCl3 (1 mmol) and BF3 were mixed in diethyl ether, heated to reflux for 12 h, and stirred at room temperature for 48 h. The solvent was removed by distillation under reduced pressure to obtain a white solid product with a yield of 85%.

[0031] Example 2: synthesis method of dimethyl aluminum (III) chloride:

[0032] Methyl lithium (2 mmol) and AlCl3 (1 mmol) were mixed in diethyl ether, heated to reflux and stirred for 48 h. The solvent was removed by distillation under reduced pressure to obtain a white solid product with a yield of 95%.

[0033] Table 1: proportion of reaction product of example 2 changing with time

[0034]

[0035] Example 3: Synthesis of dimethylaluminum(III) bromide:

[0036] Methylmagnesium chloride (2 mmol) was mixed with AlBr3(1 mmol) in diethyl ether and stirred at reflux for 48 h. The solvent was removed by distillation under reduced pressure to give the white solid product in 85% yield.

[0037] Example 4: Synthesis of dimethylaluminum(III) iodide:

[0038] Methyl lithium (2 mmol) was mixed with All3(1 mmol) in diethyl ether and stirred at room temperature for 48 h. The solvent was removed by distillation under reduced pressure to give the white solid product in 91% yield. The infrared spectrum showed the characteristic peak of Al-I bond (145 cm -1 ),

[0039] Example 5: Preparation of pyridine adduct of dimethylaluminum(III) iodide:

[0040] Al(CH3)2I (1 mmol) was reacted with pyridine (1 mmol) in toluene at reflux for 2 h. Yellow crystals were precipitated upon cooling and were filtered and dried. The yellow solid product was obtained in 85% yield.

[0041] Although the embodiments of the present application have been shown and described above, it is to be understood that the above-described embodiments are exemplary only, and that changes, modifications, substitutions and variations can be made by those skilled in the art without departing from the scope of the present application.

Claims

1. A method for synthesizing a Group IIIA organometallic halide derivative, characterized in that, Includes the following steps: (1) The alkylating nucleophile is mixed with the trihalide of a group IIIA metal and added to the first organic solvent. The mixture is heated to reflux and stirred to control the temperature. (2) The first organic solvent was removed by vacuum distillation to obtain a group IIIA organic IIIA metal halide.

2. The method for synthesizing a Group IIIA organometallic halide according to claim 1, characterized in that, The alkylating agent in step (1) is a Grignard reagent or an alkyl lithium reagent, and the IIIA metal is any one of Al, In, and Ga; the halogen is any one of F, Cl, Br, and I.

3. The method for synthesizing a Group IIIA organometallic halide derivative according to claim 2, characterized in that, The molar ratio of the alkylating agent to the trihalide is 1:1-2.

4. The method for synthesizing a Group IIIA organometallic halide derivative according to claim 1, characterized in that, In step (1), the first organic solvent is diethyl ether.

5. The method for synthesizing a Group IIIA organometallic halide derivative according to claim 1, characterized in that, The heating reflux temperature in step (1) is 60-110℃; the heating reflux reaction time is 0.5-48h; and the stirring speed is 130-160r / min.

6. The method for synthesizing a Group IIIA organometallic halide derivative according to claim 1, characterized in that, In step (2), the vacuum distillation temperature is controlled at 40-60℃ and the vacuum distillation pressure is 0.5 torr-1.5 torr.

7. A method for synthesizing Lewis base adducts of group IIIA organometallic halide derivatives prepared by the method according to any one of claims 1-6, characterized in that, Includes the following steps: A group IIIA organometal halide derivative was mixed with a Lewis base and added to a second organic solvent. The mixture was heated under reflux and reacted. After cooling, yellow crystals precipitated. The crystals were filtered and dried to obtain Lewis base adducts of group IIIA organometal halide derivatives.

8. The method for synthesizing a Lewis base adduct of a Group IIIA organometallic halide derivative according to claim 7, characterized in that, The Lewis base is pyridine or triphenylphosphine; The molar ratio of the group IIIA organometallic halide derivative to the Lewis base is [value missing].

9. The method for synthesizing a Lewis base adduct of a Group IIIA organometallic halide derivative according to claim 7, characterized in that, The second organic solvent is toluene.

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