Method of manufacturing isopropyl tris(dimethylamido)tin

Abstract

The present disclosure relates to a method for producing isopropyl tris(dimethylamido) tin (iPrSn(NMe2)3) which is useful as a precursor for depositing high-purity tin oxide thin films. The method exhibits excellent reaction efficiency even under mild reaction conditions and suppresses the generation of reaction by-products, thereby enabling the production of iPrSn(NMe2)3 with high purity and high yield.

Description

Technology Field

[0001] The present disclosure relates to the synthesis of organotin compounds, and more specifically to isopropyl tris(dimethylamido) tin ( i This relates to a method for manufacturing PrSn(NMe2)3). Background Technology

[0002] Isopropyl tris(dimethylamido) tin ( i PrSn(NMe2)3) is a typical RSn(NR'2)3 type organotin compound having a structure in which an isopropyl group and three dimethylamino groups are bonded to a tin atom, and it is highly utilized as a volatile precursor for thin film formation. In particular, high-purity tin oxide (SnO2) is used in thin film deposition processes such as extreme ultraviolet (EUV) lithography, chemical vapor deposition (CVD), and atomic layer deposition (ALD). x It is attracting attention as a precursor for film formation.

[0003] High-purity, high-volatility organotin precursors are utilized as hard mask materials or inkjet patterning precursors in the manufacture of microelectronic devices, and i PrSn(NMe2)3 is a compound with high industrial utility as a liquid precursor due to its characteristics such as thermal stability, appropriate vapor pressure, and purification potential.

[0004] However, the existing i The synthesis method of PrSn(NMe2)3 has the following problems.

[0005] Generally, for high-purity synthesis, isopropyl tin trichloride (SnCl3) i A method is used in which Pr)) is reacted with lithium dimethylamide (LiNMe2) and a purity of over 99% is obtained through a precise fractional distillation process. However, this process has the disadvantages of using an excessive amount of expensive reagents, being very sensitive to reaction and purification conditions, and requiring complex multi-stage filtration and device configuration.

[0006] In addition, in various synthesis methods for organotin compounds, desired precursors are prepared by reacting alkyltin salts, dialkylamines, lithium amides, etc., but in conventional technologies such as Korean Patent Publication KR10-2020-0058572, although examples of using pyridine or pyridine-based basic solvents exist, only functions such as additives, catalysts, or coordination are specified, and there is no consideration for the use of reaction solvents, and solvent optimization for controlling reactivity or improving purification efficiency has not been sufficiently achieved.

[0007] In particular, when the difference in boiling points between monoalkyl tin amide and dialkyl tin amide among the products is small, the problem arises that purification by distillation is very difficult, but no specific solution to improve this has been proposed.

[0008] Therefore, by simplifying reaction conditions while suppressing the generation of reaction by-products, high purity and high yield i There is a great technical need for a new manufacturing method that can efficiently produce PrSn(NMe2)3 and reduce the burden of purification. Prior art literature

[0009] (Patent Document 0001) KR 2020-0094658 A(Patent Document 0002) KR 2023-0053617 A(Patent Document 0003) KR 2025-0019125 A(Patent Document 0004) KR 2023-0131941 A(Patent Document 0005) KR 2023-0132582 A The problem to be solved

[0010] One embodiment is isopropyl tris(dimethylamido) tin ( i A method for manufacturing PrSn(NMe2)3) is provided. means of solving the problem

[0011] One embodiment is tetrakis(dimethylamido)tin (Sn(NMe2)4) in isopropylmagnesium chloride ( iReact with PrMgCl) to isopropyl tris(dimethylamido) tin ( i isopropyl tris(dimethylamido) tin (including the step of manufacturing PrSn(NMe2)3) i A method for manufacturing PrSn(NMe2)3) is provided.

[0012] The above pyridine solvent may further contain triethylamine.

[0013] The volume ratio of the mixture of pyridine and triethylamine may be 1:0.5 to 1:2.

[0014] The above Sn(NMe2)4 may be present in a pyridine solution at a concentration of 0.1 M to 0.5 M.

[0015] The above i PrMgCl may be used in an amount of 1 to 1.5 equivalents relative to the 1 equivalent of Sn(NMe2)4.

[0016] The above reaction may be carried out at a temperature of 20°C to 60°C.

[0017] The above-mentioned manufactured i It may further include a step of purifying PrSn(NMe2)3.

[0018] The above purification may be a distillation purification.

[0019] The above distillation purification may be performed at a pressure of 0.4 to 30 torr and a temperature of 50 to 150 ℃. Effects of the invention

[0020] According to one mode i The manufacturing method of PrSn(NMe2)3 is a simple process i PrSn(NMe2)3 can be provided with excellent yield and high purity. Specifically, according to one embodiment, the manufacturing method uses a pyridine solvent as a reaction solvent, thereby using Sn(NMe2)4, a tin precursor, and Grignard reagent iBy increasing the reaction efficiency between PrMgCl and suppressing the generation of reaction by-products, it is possible to simultaneously achieve simplification of the purification process and secure the purity and physical property stability of the product.

[0021] In particular, by using pyridine anhydride or a mixed solvent of pyridine anhydride and triethylamine anhydride as the reaction solvent, a balance between the stability and reactivity of Sn(NMe2)4 during the reaction can be secured, and i The reaction selectivity is enhanced during the drop reaction of PrMgCl, which can significantly suppress the formation of byproducts. This solvent composition also improves thermal stability during the purification step after the reaction is complete, enabling the acquisition of a high-purity product through simple fractional distillation under reduced pressure conditions.

[0022] Manufactured according to one embodiment i PrSn(NMe2)3 can reliably ensure high yield and high purity, and maintains similar reactivity and purification characteristics even during repeated manufacturing, resulting in excellent process reproducibility.

[0023] According to one mode i The method for manufacturing PrSn(NMe2)3 has simple reaction and purification conditions and does not require expensive reagents or precision equipment, making it highly applicable in actual industrial settings. Specific details for implementing the invention

[0024] Unless otherwise defined in this specification, all technical and scientific terms have the same meaning as generally understood by those skilled in the art to which the present invention pertains. The terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention.

[0025] The singular form used in this specification is intended to include the plural form unless specifically indicated otherwise in the context.

[0026] Throughout this specification, the terms “comprising,” “having,” “containing,” or “having” any component mean that, unless specifically stated otherwise, other components are not excluded but may be included, and do not exclude elements, materials, or processes not additionally listed.

[0027] The numerical ranges used herein include lower and upper limits and all values ​​within the range, increments logically derived from the form and width of the defined range, all of which are limited, and all possible combinations of upper and lower limits of the numerical range defined in different forms. Unless otherwise specifically defined in this specification, values ​​outside the numerical range that may occur due to experimental error or rounding are also included in the defined numerical range.

[0028] Unless otherwise specifically defined in this specification, “about” may be considered to be a value within 30%, 25%, 20%, 15%, 10%, or 5% of the specified value.

[0029] The present disclosure will be described in detail below. However, this is merely illustrative and the present disclosure is not limited to the specific embodiments described illustratively.

[0030] One embodiment is capable of simultaneously satisfying the simplification of the manufacturing process, improvement of yield, and productivity. i A method for manufacturing PrSn(NMe2)3 is provided.

[0031] Specifically, according to one mode i The method for preparing PrSn(NMe2)3 involves Sn(NMe2)4 in a pyridine solvent. i react with PrMgCl i It may include a step of manufacturing PrSn(NMe2)3.

[0032] conventional iThe method for manufacturing PrSn(NMe2)3 is difficult to expand and apply to industrial processes because it requires expensive precursors or reagents, and the reaction control and purification conditions are demanding. It is also difficult to ensure reproducibility during repeated manufacturing. In addition, dialkyl tin amide and other impurities are generated during the reaction process, making it difficult to stably obtain a high-purity product during the purification step, and there are problems with limited efficiency and yield of the purification process.

[0033] For example, in a diethyl ether solvent t -React BuMgCl with Sn(NMe2)4 t Although a technique for manufacturing -BuSn(NMe2)3 is known, in this case, together with the product t-BuSn(NMe2)3 ( t -Bu)2Sn(NMe2)2 and residual Sn(NMe2)4 coexist as impurities, and since they cannot be removed by simple distillation purification, complex purification processes such as fractional distillation or the addition of a chelating agent (TREN) are required. In addition, by introducing known technology i When reacting PrMgCl with Sn(NMe2)4, the target product is i PrSn(NMe2)3 and byproduct ( i Since Pr)2Sn(NMe2)2 coexist, they cannot be removed by simple distillation purification, and the low yield results in poor economic feasibility.

[0034] Furthermore, conventionally, only aprotic organic solvents such as THF, hexane, and toluene have generally been used as reaction solvents, and compositions using basic solvents such as pyridine, particularly pyridine, as a reaction solvent have not been considered at all.

[0035] In contrast, a manufacturing method according to one embodiment involves Sn(NMe2)4 in a pyridine solvent i By reacting with PrMgCl, the reaction efficiency is improved, and ( iThe formation of dialkyl tin byproducts such as Pr)2Sn(NMe2)2) is substantially suppressed, and the purification process is simplified to simple fractional distillation under reduced pressure, thereby producing the target compound i PrSn(NMe2)3 can be stably manufactured with high purity and high yield.

[0036] The above pyridine solvent may further include triethylamine, and the pyridine solvent may be pyridine alone or a mixed solvent of pyridine and triethylamine, specifically, anhydrous pyridine or a mixed solvent of anhydrous pyridine and anhydrous triethylamine.

[0037] The above-mentioned volume ratio of pyridine and triethylamine can be used as 1:0.5 to 1:2, or 1:1 to 1:2, or 1:0.5 to 1:1.5, or 1:1 to 1:1.5, or 1:1.5 to 1:2, and by adjusting the mixing ratio of pyridine and triethylamine within this range, the reaction efficiency and purification performance can be further improved.

[0038] The above Sn(NMe2)4 may be present in a pyridine solution at a concentration of 0.1 M to 0.5 M, or 0.2 M to 0.5 M, or 0.25 M to 0.5 M, or 0.25 M to 0.45 M, or 0.3 M to 0.5 M, or 0.3 M to 0.45 M, and within the above concentration ranges, the reaction efficiency can be optimized, the generation of reaction byproducts can be suppressed, and the purification process can be simplified.

[0039] The above i PrMgCl can be used in an amount of 1 to 1.5 equivalents, or 1 to 1.4 equivalents, or 1 to 1.3 equivalents, or 1 to 1.2 equivalents, or 1 to 1.1 equivalents with respect to the 41 equivalents of Sn(NMe2)4, and within the above-mentioned equivalent range, reaction efficiency can be optimized, byproduct formation can be suppressed, and reaction selectivity can be improved.

[0040] The above iPrMgCl may be in the form of a solution diluted in an ether-based solvent at a concentration of 1.5 M to 2.5 M, or 1.5 M to 2.0 M, or 2.0 M to 2.5 M.

[0041] A manufacturing method according to one embodiment optimizes reaction efficiency even under mild reaction conditions, suppresses byproduct generation, and improves reaction selectivity, i PrSn(NMe2)3 can be produced in high yield. For example, the reaction can be carried out for at least one hour, specifically 2 to 24 hours, 3 to 18 hours, or 3 to 15 hours, under temperature conditions of 20°C to 60°C, or 20°C to 50°C, or 30°C to 50°C.

[0042] The manufacturing method according to one embodiment is, as needed, the above-manufactured i The method may further include a step of purifying PrSn(NMe2)3, and the purity can be improved through additional purification.

[0043] The above purification may be distillation purification, and the distillation purification may be performed at a pressure of 0.4 to 30 torr and 50 to 150 ℃, specifically at a pressure of 0.5 to 25 torr and 50 to 140 ℃, more specifically at 1 to 25 torr and 80 to 140 ℃, more specifically at 10 to 20 torr and 120 to 130 ℃.

[0044] A manufacturing method according to one embodiment is under mild conditions i PrSn(NMe2)3 can be manufactured with high purity and high yield, enabling mass production and making it more advantageous for commercialization.

[0045] Manufactured according to one embodiment i PrSn(NMe2)3 can be used for various purposes, and due to its high purity, it is particularly useful as a material for semiconductor processes, especially photoresists that require high purity.

[0046] The above-described embodiment will be explained in more detail below through examples. However, the following examples are for illustrative purposes only and do not limit the scope of the claims.

[0047] [Example 1] i Preparation of PrSn(NMe2)3

[0048]

[0049] A 1 L 2-neck round-bottom flask was connected to a Schlenk line, and the inside of the flask was evacuated to a nitrogen atmosphere. Under a nitrogen atmosphere, Sn(NMe2)4 (50.0 g, 170 mmol) was added to the flask, and anhydrous pyridine (400 mL) was added. Subsequently, the flask was heated using a 1 L heating mantle to maintain the internal temperature between 30°C and 50°C. 2.0 M diluted in THF (tetrahydrofuran) was added to the heated flask. i PrMgCl (93.2 mL, 186 mmol) was added dropwise over 3 hours. After the addition was complete, the reaction mixture was cooled to room temperature and stirred overnight. After the reaction was complete, the solvent was removed under reduced pressure, and anhydrous hexane was added. n 400 mL of (-hexane) was added. The resulting solid was filtered using a Celite filter and washed once with anhydrous hexane (100 mL). The filtrate was dried under reduced pressure to obtain a crude product, which was observed to be yellow. The obtained crude product was transferred to a 100 mL 2-neck round-bottom flask and purified by distillation (20 torr, 120°C to 130°C) using a distillation apparatus equipped with a 20 cm long column. High-purity i PrSn(NMe2)3 was obtained in high yield.

[0050] 1 H NMR (C6D6): δ 1.26 (d, 6Η), 1.60 (m, 1Η), 2.83 (s, 18H)

[0051] [Example 2] i Preparation of PrSn(NMe2)3

[0052]

[0053] The procedure was carried out in the same manner as in Example 1 above, except that a mixed solvent of anhydrous triethylamine (TEA) (300 mL) and anhydrous pyridine (200 mL) was used instead of anhydrous pyridine (400 mL). High purity i PrSn(NMe2)3 was obtained in high yield.

[0054] 1 H NMR (C6D6): δ 1.26 (d, 6Η), 1.60 (m, 1Η), 2.83 (s, 18H)

[0055] [Comparative Example 1]

[0056] The procedure was carried out in the same manner as Example 1 above, except that diethyl ether (400 mL) was used instead of pyridine anhydrous (400 mL). After the reaction, numerous impurities were present in the product, and it was difficult to separate the high-purity product. In particular, the pure separation of the target compound was not smooth with simple distillation purification, and the complexity of the purification process and the decrease in yield were confirmed.

[0057] [Comparative Example 2]

[0058] The procedure was carried out in the same manner as Example 1 above, except that anhydrous triethylamine (600 mL) was used instead of anhydrous pyridine (400 mL). After the reaction, numerous impurities were present in the product, and it was difficult to separate the high-purity product. In particular, the pure separation of the target compound was not smooth with simple distillation purification, and the complexity of the purification process and the decrease in yield were confirmed.

[0059] As described above, the present invention has been explained by specific details and limited embodiments; however, this is provided merely to aid in a more comprehensive understanding of the invention, and the invention is not limited to the above embodiments. Those skilled in the art can make various modifications and variations from this description.

Claims

Claim 1 Sn(NMe2)4 in pyridine solvent i react with PrMgCl i The method comprising the step of manufacturing PrSn(NMe2)3 i Method for manufacturing PrSn(NMe2)3. Claim 2 In claim 1, the pyridine solvent further comprises triethylamine. i Method for manufacturing PrSn(NMe2)3. Claim 3 In paragraph 2, the mixing volume ratio of the pyridine and triethylamine is 1:0.5 to 1:2, i Method for manufacturing PrSn(NMe2)3. Claim 4 In claim 1, the Sn(NMe2)4 is present in a pyridine solution at a concentration of 0.1 M to 0.5 M. i Method for manufacturing PrSn(NMe2)3. Claim 5 In paragraph 1, the above i PrMgCl is used in an amount of 1 to 1.5 equivalents relative to the 41 equivalents of Sn(NMe2)4, i Method for manufacturing PrSn(NMe2)3. Claim 6 In claim 1, the reaction is carried out at a temperature of 20°C to 60°C, i Method for manufacturing PrSn(NMe2)3. Claim 7 In claim 1, the above-mentioned manufactured i A step of further including a step of purifying PrSn(NMe2)3, i Method for manufacturing PrSn(NMe2)3. Claim 8 In paragraph 7, the above-mentioned purification is a distillation purification, i Method for manufacturing PrSn(NMe2)3. Claim 9 In claim 8, the distillation purification is performed at a pressure of 0.4 to 30 torr and a temperature of 50 to 150 ℃, i Method for manufacturing PrSn(NMe2)3.

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