Preparation method of diisopropyl amino silane

Abstract

The invention relates to a preparation method of diisopropyl amino silane, and belongs to the technical field of organic synthesis. The preparation method comprises the following steps: in a protective atmosphere, S1, adding a solvent into phenylsilane to obtain a phenylsilane solution; s2, adding trifluoromethanesulfonic acid into the phenylsilane solution at the temperature of 50 DEG C below zero to 10 DEG C below zero, and stirring for reaction to obtain a reaction solution; s3, adding diisopropylamine and an acid-binding agent into the reaction solution at the temperature of 50 DEG C below zero to 10 DEG C below zero, and stirring to react to obtain a mixed solution; and S4, filtering the mixed solution, and distilling to obtain the diisopropyl amino silane. According to the preparation method, phenylsilane is adopted as a raw material to provide silyl, trifluoromethanesulfonic acid is used for replacing phenyl to obtain trifluoromethanesulfonic acid silyl, and diisopropyl amine is used for replacing trifluoromethanesulfonic acid to obtain diisopropyl amino silane. Unit point substitution is adopted, and the conversion rate is high; no oxidation-reduction reaction exists, only substitution reaction exists, and the safety is high.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing diisopropylaminosilane. Background Art

[0002] Silyl compounds are widely used in advanced processes. They are an important silicon-based precursor material for manufacturing thin film materials such as silicon oxide. The following are some key applications of silicon oxide in advanced processes: Gate dielectric layer: In transistor structures, silicon oxide is often used as a gate dielectric layer material. It is located between the gate and the semiconductor and plays an insulating role. Chemical mechanical polishing (CMP): In the wafer manufacturing process, CMP is a key process to achieve global wafer flatness. The silicon oxide layer is used as a polishing dielectric layer in CMP to ensure that the wafer surface reaches nanometer-level flatness. CMP technology is widely used in both front-end processing and back-end packaging. Silicon on insulator (SOI) technology: SOI technology uses silicon oxide as an insulating layer to isolate the top silicon film from the silicon substrate. This structure can reduce parasitic capacitance and leakage current and improve device performance. SOI technology is particularly important in high-performance logic and memory devices. Thermal oxide layer: The silicon dioxide layer formed on the silicon surface can be used as the gate dielectric of the device, the wafer surface passivation layer, the diffusion doping barrier layer, etc. The thickness and quality of the thermal oxide layer have a direct impact on device performance. Strained silicon technology: In strained silicon technology, the silicon oxide layer can be used to achieve strain in the silicon layer, thereby improving the electron mobility and performance of the transistor. Interconnect technology: In multi-layer interconnect technology, the silicon oxide layer is used as a dielectric material to achieve isolation between different metal layers. Packaging technology: In advanced packaging technology, the silicon oxide layer also plays an important role, such as in through silicon via (TSV) technology and 3D IC packaging.

[0003] The application of silyl compounds in advanced processes is multifaceted. It is not only the basic material for realizing device functions, but also the key factor in improving device performance and integration. Since the polarity of silyl compound molecules is higher than that of other silicon organic compounds, it has a wide range of application prospects in high aspect ratio device structures.

[0004] Organic aminosilanes containing silyl groups are desirable precursors for thin film materials such as silicon oxide. In the thin film deposition process, diisopropylaminosilane is usually used as a single source precursor for the preparation of thin film materials such as silicon oxide. The existing process for preparing diisopropylaminosilane uses chlorosilanes such as silicon tetrachloride, trichlorosilane, and dichlorodihydrosilane as raw materials. RSiCl is first obtained by substitution reaction. n H 3-nThen, it reacts with strong reducing agents such as lithium aluminum hydride and lithium hydride to obtain the target product. However, the multiple reaction sites of the raw materials cause many side reactions, resulting in low conversion rate and high purification cost. In addition, the reaction involves a relatively violent redox reaction, which poses safety hazards such as explosion and fire. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a method for preparing diisopropylaminosilane.

[0006] The object of the present invention is to provide a method for preparing diisopropylaminosilane, comprising the following steps: under a protective atmosphere,

[0007] S1: adding a solvent to phenylsilane to obtain a phenylsilane solution;

[0008] S2: adding trifluoromethanesulfonic acid to the phenylsilane solution described in S1 at -50°C to -10°C, stirring to react and obtaining a reaction solution;

[0009] S3: adding diisopropylamine and an acid binding agent to the reaction solution in S2 at -50°C to -10°C, stirring to react and obtaining a mixed solution;

[0010] S4: filtering and distilling the mixed solution described in S3 to obtain the diisopropylaminosilane.

[0011] In one embodiment of the present invention, in S1, the solvent is selected from one or more of toluene, tetrahydrofuran, diethyl ether, n-hexane and n-pentane.

[0012] In one embodiment of the present invention, in S1, the solvent is toluene.

[0013] In one embodiment of the present invention, in S2, the molar ratio of phenylsilane to trifluoromethanesulfonic acid is 1:(1-1.2).

[0014] In one embodiment of the present invention, in S2, the stirring reaction time is 1h-2h.

[0015] In one embodiment of the present invention, in S3, the molar ratio of phenylsilane to diisopropylamine is 1:(1-1.2).

[0016] In one embodiment of the present invention, in S3, the molar ratio of diisopropylamine to the acid binding agent is 1:(1-1.2).

[0017] In one embodiment of the present invention, in S3, the acid binding agent is selected from triethylamine and / or pyridine.

[0018] In one embodiment of the present invention, in S3, the acid binding agent is triethylamine.

[0019] In one embodiment of the present invention, the protective atmosphere is selected from a nitrogen atmosphere or an inert gas atmosphere.

[0020] The technical solution of the present invention has the following advantages over the prior art:

[0021] The preparation method of the present invention uses phenylsilane as a raw material to provide a silyl group, uses trifluoromethanesulfonic acid to replace the phenyl group to obtain trifluoromethanesulfonic acid silane, and uses diisopropylamine to replace the trifluoromethanesulfonic acid group to obtain diisopropylaminosilane. Single-point substitution is used, and the conversion rate is high; there is no redox reaction, only substitution reaction, and the safety is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein:

[0023] Figure 1 This is the NMR spectrum of diisopropylaminosilane prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0024] In order to solve the above technical problems, the present invention provides a method for preparing diisopropylaminosilane, which adopts phenylsilane as a raw material to provide a silyl group, uses trifluoromethanesulfonic acid to replace the phenyl group to obtain trifluoromethanesulfonic acid silane, and uses diisopropylamine to replace the trifluoromethanesulfonic acid group to obtain diisopropylaminosilane.

[0025] The object of the present invention is to provide a method for preparing diisopropylaminosilane, comprising the following steps: under a protective atmosphere,

[0026] S1: adding a solvent to phenylsilane to obtain a phenylsilane solution;

[0027] S2: adding trifluoromethanesulfonic acid to the phenylsilane solution described in S1 at -50°C to -10°C, stirring to react and obtaining a reaction solution;

[0028] S3: adding diisopropylamine and an acid binding agent to the reaction solution in S2 at -50°C to -10°C, stirring to react and obtaining a mixed solution;

[0029] S4: filtering and distilling the mixed solution described in S3 to obtain the diisopropylaminosilane.

[0030] In one embodiment of the present invention, in S1, the solvent is selected from one or more of toluene, tetrahydrofuran, diethyl ether, n-hexane and n-pentane.

[0031] In one embodiment of the present invention, in S1, the solvent is toluene.

[0032] In one embodiment of the present invention, in S2, the molar ratio of phenylsilane to trifluoromethanesulfonic acid is 1:(1-1.2), for example, it can be (1:1), (1:1.1), (1:1.2), for example, it can be (1:1), (1:1.1), (1:1.2), etc.

[0033] In one embodiment of the present invention, in S2, the stirring reaction time is 1h-2h, for example, it can be 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, etc.

[0034] In one embodiment of the present invention, in S2, the reaction temperature can be -50°C, -49°C, -48°C, -47°C, -46°C, -45°C, -44°C, -43°C, -42°C, -41°C, -40°C, -39°C, -38°C, -37°C, -36°C, -35°C, -34°C, -33°C, -32°C, -31°C, -30°C, -29°C, -28°C, -27°C, -26°C, -25°C, -24°C, -23°C, -22°C, -21°C, -20°C, -19°C, -18°C, -17°C, -16°C, -15°C, -14°C, -13°C, -12°C, -11°C, -10°C, etc.

[0035] In one embodiment of the present invention, in S3, the molar ratio of phenylsilane to diisopropylamine is 1:(1-1.2), for example, (1:1), (1:1.1), (1:1.2), etc.

[0036] In one embodiment of the present invention, in S3, the molar ratio of diisopropylamine to the acid binding agent is 1:(1-1.2), for example, it can be (1:1), (1:1.1), (1:1.2), etc.

[0037] In one embodiment of the present invention, in S3, the acid binding agent is selected from triethylamine and / or pyridine.

[0038] In one embodiment of the present invention, in S3, the acid binding agent is triethylamine.

[0039] In one embodiment of the present invention, in S3, the reaction temperature can be -50°C, -49°C, -48°C, -47°C, -46°C, -45°C, -44°C, -43°C, -42°C, -41°C, -40°C, -39°C, -38°C, -37°C, -36°C, -35°C, -34°C, -33°C, -32°C, -31°C, -30°C, -29°C, -28°C, -27°C, -26°C, -25°C, -24°C, -23°C, -22°C, -21°C, -20°C, -19°C, -18°C, -17°C, -16°C, -15°C, -14°C, -13°C, -12°C, -11°C, -10°C, etc.

[0040] In one embodiment of the present invention, the protective atmosphere is selected from a nitrogen atmosphere or an inert gas atmosphere.

[0041] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. It should be understood that the specific embodiments are only used to explain the present invention, but the embodiments are not intended to limit the present invention.

[0042] In the present invention, unless otherwise explained, technical and scientific terms used in the present invention have the same meanings as commonly understood by those skilled in the art to which the present invention belongs.

[0043] In the present invention, unless otherwise stated, the term "and / or" used in the present invention includes any and all combinations of one or more of the associated listed items.

[0044] In the present invention, unless otherwise stated, the experimental methods used in the embodiments of the present invention are conventional methods unless otherwise stated, and the materials, reagents, etc. used are all commercially available unless otherwise stated.

[0045] In the present invention, unless otherwise stated, when the terms "comprise" and / or "include" are used in the specification of the present invention, it indicates the existence of the described features, integers, steps, operations, raw materials or components, but does not exclude the existence or addition of one or more other features, integers, steps, operations, raw materials, components or their combinations.

[0046] Example 1

[0047] The preparation method of diisopropylaminosilane in this embodiment specifically comprises the following steps:

[0048] In a fume hood, replace the gas in the reaction bottle with nitrogen, transfer phenylsilane (8.87 g, 0.082 mol), transfer to toluene (600 mL) for dilution, add trifluoromethanesulfonic acid (12.31 g, 0.082 mol) at -30°C, stir for 1 hour, and slowly warm to -10°C. Lower the temperature to -50°C, add a mixture of diisopropylamine (8.3 g, 0.082 mol) and triethylamine (8.3 g, 0.082 mol) under stirring, slowly return to room temperature, filter to remove triethylamine trifluoromethanesulfonate, and distill the filtrate to obtain a colorless transparent liquid (8.6 g, 0.0656 mol) with a yield of 80%.

[0049] The reaction equation is as follows:

[0050] C6H5SiH3+CF3SO3H→CF3SO3SiH3;

[0051] CF3SO3SiH3+[(CH3)2CH]2NH→[(CH3)2CH]2NSiH3.

[0052] Example 2

[0053] The preparation method of diisopropylaminosilane in this embodiment specifically comprises the following steps:

[0054] In a fume hood, replace the gas in the reaction bottle with nitrogen, transfer phenylsilane (8.87 g, 0.082 mol), transfer to toluene (600 mL) for dilution, add trifluoromethanesulfonic acid (13.51 g, 0.090 mol) at -30°C, stir for 1 hour, and slowly warm to -10°C. Lower the temperature to -50°C, add a mixture of diisopropylamine (9.11 g, 0.090 mol) and triethylamine (9.11 g, 0.090 mol) under stirring, slowly return to room temperature, filter to remove triethylamine trifluoromethanesulfonate, and distill the filtrate to obtain a colorless transparent liquid (8.9 g, 0.068 mol) with a yield of 83%.

[0055] Example 3

[0056] The preparation method of diisopropylaminosilane in this embodiment specifically comprises the following steps:

[0057] In a fume hood, replace the gas in the reaction bottle with nitrogen, transfer phenylsilane (8.87 g, 0.082 mol), transfer to toluene (600 mL) for dilution, add trifluoromethanesulfonic acid (13.81 g, 0.092 mol) at -30°C, stir for 1 hour, and slowly warm to -10°C. Lower the temperature to -50°C, add a mixture of diisopropylamine (9.31 g, 0.092 mol) and triethylamine (9.31 g, 0.092 mol) under stirring, slowly return to room temperature, filter to remove triethylamine trifluoromethanesulfonate, and distill the filtrate to obtain a colorless transparent liquid (8.67 g, 0.066 mol) with a yield of 81%.

[0058] Example 4

[0059] The preparation method of diisopropylaminosilane in this embodiment specifically comprises the following steps:

[0060] In a fume hood, replace the gas in the reaction bottle with nitrogen, transfer phenylsilane (8.87 g, 0.082 mol), transfer tetrahydrofuran (600 mL) to dilute, add trifluoromethanesulfonic acid (12.31 g, 0.082 mol) at -30°C, stir for 1 hour, and slowly warm to -10°C. Lower the temperature to -50°C, add a mixture of diisopropylamine (8.3 g, 0.082 mol) and triethylamine (8.3 g, 0.082 mol) under stirring, slowly return to room temperature, filter to remove triethylamine trifluoromethanesulfonate, and distill the filtrate to obtain a colorless transparent liquid (8.4 g, 0.0643 mol) with a yield of 78%.

[0061] Example 5

[0062] The preparation method of diisopropylaminosilane in this embodiment specifically comprises the following steps:

[0063] In a fume hood, replace the gas in the reaction bottle with nitrogen, transfer phenylsilane (8.87 g, 0.082 mol), transfer n-hexane (600 mL) to dilute, add trifluoromethanesulfonic acid (12.31 g, 0.082 mol) at -30°C, stir for 1 hour, and slowly heat to -10°C. Lower the temperature to -50°C, add a mixture of diisopropylamine (8.3 g, 0.082 mol) and triethylamine (8.3 g, 0.082 mol) under stirring, slowly return to room temperature, filter to remove triethylamine trifluoromethanesulfonate, and distill the filtrate to obtain a colorless transparent liquid (8.7 g, 0.066 mol) with a yield of 80%.

[0064] Example 6

[0065] The preparation method of diisopropylaminosilane in this embodiment specifically comprises the following steps:

[0066] In a fume hood, replace the gas in the reaction bottle with nitrogen, transfer phenylsilane (8.87 g, 0.082 mol), transfer to toluene (600 mL) for dilution, add trifluoromethanesulfonic acid (12.31 g, 0.082 mol) at -40°C, stir for 1 hour, and slowly warm to -10°C. Lower the temperature to -50°C, add a mixture of diisopropylamine (8.3 g, 0.082 mol) and triethylamine (8.3 g, 0.082 mol) under stirring, slowly return to room temperature, filter to remove triethylamine trifluoromethanesulfonate, and distill the filtrate to obtain a colorless transparent liquid (8.7 g, 0.066 mol) with a yield of 80%.

[0067] Example 7

[0068] The preparation method of diisopropylaminosilane in this embodiment specifically comprises the following steps:

[0069] In a fume hood, replace the gas in the reaction bottle with nitrogen, transfer phenylsilane (8.87 g, 0.082 mol), transfer to toluene (600 mL) for dilution, add trifluoromethanesulfonic acid (12.31 g, 0.082 mol) at -50°C, stir for 1 hour, and slowly warm to -10°C. Lower the temperature to -50°C, add a mixture of diisopropylamine (8.3 g, 0.082 mol) and triethylamine (8.3 g, 0.082 mol) under stirring, slowly return to room temperature, filter to remove triethylamine trifluoromethanesulfonate, and distill the filtrate to obtain a colorless transparent liquid (8.8 g, 0.067 mol) with a yield of 82%.

[0070] Comparative Example 1

[0071] In a fume hood, the gas in the reaction bottle was replaced with nitrogen, phenylsilane (8.87 g, 0.082 mol) was added, and toluene (600 mL) was added for dilution. Diisopropylamine (8.3 g, 0.082 mol) was added at -30°C, and the temperature was slowly restored to room temperature. No product was obtained by distilling the reaction liquid.

[0072] Comparative Example 2

[0073] In the fume hood, replace the gas in the reaction bottle with nitrogen, transfer dichlorosilane (10.1g, 0.1mol), transfer to toluene (600mL) for dilution, add a mixture of diisopropylamine (10.12g, 0.1mol) and triethylamine (12.1g, 0.12mol) at -20℃, stir at room temperature for 1h, filter, remove most of the solvent under reduced pressure, add 600mL tetrahydrofuran to dissolve, and cool the reaction solution to -10℃. Add lithium aluminum hydride (3.8g, 0.1mol) to it, reflux for 2h, filter, and distill the filtrate to obtain a colorless transparent liquid (6056g, 0.05mol), with a yield of 50%. During the experiment, flames emerged from the tail gas end, which was the reaction and combustion of the silane produced by the reduction and air; when the filter residue was quenched, it was violently exothermic, which should be due to the residual lithium aluminum hydride, and the reaction was more dangerous.

[0074] Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims

1. A method for preparing diisopropylaminosilane, characterized in that: The following steps are involved: Under protective atmosphere, S1: adding a solvent to phenylsilane to obtain a phenylsilane solution; S2: adding trifluoromethanesulfonic acid to the phenylsilane solution described in S1 at -50°C to -10°C, stirring to react and obtaining a reaction solution; S3: adding diisopropylamine and an acid binding agent to the reaction solution in S2 at -50°C to -10°C, stirring to react and obtaining a mixed solution; S4: filtering and distilling the mixed solution described in S3 to obtain the diisopropylaminosilane.

2. The method for preparing diisopropylaminosilane according to claim 1, characterized in that: In S1, the solvent is selected from one or more of toluene, tetrahydrofuran, diethyl ether, n-hexane and n-pentane.

3. The method for preparing diisopropylaminosilane according to claim 2, characterized in that: In S1, the solvent is toluene.

4. The method for preparing diisopropylaminosilane according to claim 1, characterized in that: In S2, the molar ratio of phenylsilane to trifluoromethanesulfonic acid is 1:(1-1.2).

5. The method for preparing diisopropylaminosilane according to claim 1, characterized in that: In S2, the stirring reaction time is 1 h-2 h.

6. The method for preparing diisopropylaminosilane according to claim 1, characterized in that: In S3, the molar ratio of phenylsilane to diisopropylamine is 1:(1-1.2).

7. The method for preparing diisopropylaminosilane according to claim 1, characterized in that: In S3, the molar ratio of diisopropylamine to the acid binding agent is 1:(1-1.2).

8. The method for preparing diisopropylaminosilane according to claim 1, characterized in that: In S3, the acid binding agent is selected from triethylamine and / or pyridine.

9. The method for preparing diisopropylaminosilane according to claim 8, characterized in that: In S3, the acid binding agent is triethylamine.

10. The method for preparing diisopropylaminosilane according to claim 1, characterized in that: The protective atmosphere is selected from a nitrogen atmosphere or an inert gas atmosphere.

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