Preparation and raw material recovery method of tin triphenyl p-toluenesulfonate

Abstract

The invention discloses a preparation and raw material recovery method of triphenyl p-toluenesulfonic acid tin. The method comprises the following steps: taking raw materials of triphenyl tin chloride, sodium methoxide and water to react in an ethanol solvent, and then treating to obtain triphenyl tin hydroxide. Under optimal conditions, the preparation yield of the triphenyltin hydroxide in the first step reaches 99.5%. And reacting the synthesized triphenyl tin hydroxide with p-toluenesulfonic acid in the presence of ethanol serving as a solvent to obtain triphenyl p-toluenesulfonic acid tin. Under preferable conditions, the one-way yield of the tin triphenyl p-toluenesulfonate prepared by the second-step reaction reaches 92.35%, and the comprehensive yield can reach 97.54%. The synthesis and separation methods are simple, and the prepared triphenyl p-toluenesulfonic acid tin is used as an organic Lewis acid and is widely used as a ligand and a (co-) catalyst.

Description

Technical Field

[0001] The invention relates to the field of organic synthesis, and in particular to a method for preparing triphenyltin p-toluenesulfonate and recovering raw materials. Background Art

[0002] Adiponitrile is widely used, mainly in the production of nylon 66. However, the production technology of adiponitrile is in the hands of a few large companies abroad, which monopolize the supply of adiponitrile raw materials in my country, seriously affecting the economic benefits and international market competitiveness of my country's nylon industry. In the process of synthesizing adiponitrile by butadiene method, by adding Lewis acid as a co-catalyst, the reaction rate, catalyst life and product linearity can be improved; it can be strongly coordinated with the lone electron pair of the nickel intermediate nitrogen during the reaction of hydrocyanation to form HNiL3CN-Lewis acid complex; it can increase the concentration of nickel in the catalytic cycle species, accelerate the carbon-carbon coupling to form alkyl nitrile, and is conducive to the formation of linear intermediates with less steric hindrance. At present, inorganic Lewis acid is mainly used as a co-catalyst (such as AlCl3, FeCl3, ZnCl2, etc.), which has very low solubility in organic reaction systems. The triphenyltin p-toluenesulfonate synthesized by the present invention is used as an organic Lewis acid as a co-catalyst with high solubility in the system and can better play its role.

[0003] There are many reports on the synthesis method of triphenyltin sulfonate analogs. For example, Diop, CAK et al. recorded in the document Main Group Metal Chemistry, 1997, 20, 681-686 and Main Group Metal Chemistry, 2002, 25, 683-690 that triphenyltin sulfonic acid derivatives were prepared by reaction in anhydrous ethanol using organic sulfonic acid or sulfonate and triphenyltin hydroxide as raw materials, the document only recorded the reaction route, and did not mention the yield of the product, and in the subsequent separation and purification, methanol was used as a solvent for recrystallization, and the recrystallization operation was relatively cumbersome and the product loss was large. In addition, the route did not actually realize the recovery of raw materials. McKinney, RJ et al. reported in the literature Organometallics 1989, 8, 2871-2875 that triphenyltin trifluoromethanesulfonate was prepared from triphenyltin cyanide and trifluoromethanesulfonic acid. This route requires the use of hydrocyanic acid as a raw material for preparing triphenyltin cyanide. HCN toxic gas is released during the reaction of triphenyltin cyanide and trifluoromethanesulfonic acid, posing a major safety hazard.

[0004] The analog of triphenyltin p-toluenesulfonate is triphenyltin carboxylate derivative, and its synthesis method is also based on many reports. For example, Molloy, KC et al. reported in the document Journal of the Chemical Society, Dalton Transactions, 1987, 101-106 that triphenyltin hydroxide and formic acid were used as raw materials to prepare triphenyltin formate by azeotropic dehydration under toluene reflux conditions, and triphenyltin acetate was prepared by double decomposition reaction of triphenyltin chloride and sodium acetate in water. Ford, BFE et al. recorded in the document Journal of Organometallic Chemistry, 1969, 19, 53-65 that triphenyltin formate and triphenyltin propionate were prepared in ether / water mixture using triphenyltin chloride and sodium formate or sodium propionate as raw materials. Yin Handong introduced in the document Organic Chemistry, 1998, 18, 352-355 that trialkyltin heterocyclic carboxylates were prepared by reaction in benzene solvent using triphenyltin chloride and carboxylates of heterocyclic compounds as raw materials. However, there are almost the same problems in the above reports, the experimental details are not disclosed enough and the repeatability is poor, the recovery of raw materials is not achieved, and the post-processing purification generally adopts recrystallization, which has a long cycle, consumes a large amount of solvent and has a large product loss. Chinese patent CN113816988A also discloses a method for synthesizing triphenyltin acetate in water in a one-step method using sodium acetate and triphenyltin chloride as raw materials. However, this method does not purify the product, and the content of triphenyltin acetate in the obtained product is only about 66%. Summary of the invention

[0005] In order to solve the above problems, the present invention adopts the following technical solutions:

[0006] A method for preparing triphenyltin p-toluenesulfonate and recovering raw materials, wherein the synthetic route is as follows Figure 2 It is characterized by comprising the following steps:

[0007] (1) Triphenyltin chloride, sodium methoxide and water are heated in ethanol for reaction, cooled to room temperature and then the solvent is removed by rotary evaporation, and then the mixture is washed with water three times and dried to obtain triphenyltin hydroxide.

[0008] (2) Triphenyltin hydroxide and p-toluenesulfonic acid are heated in ethanol for reaction under a nitrogen atmosphere, and the solvent is removed by rotary evaporation after cooling to room temperature, and a low-polarity solvent is added. After heating and stirring, the crude product triphenyltin p-toluenesulfonate is obtained by filtering, washing, and drying.

[0009] (3) Adding crude triphenyltin p-toluenesulfonate to water, stirring, washing, filtering, and drying to obtain the target product triphenyltin p-toluenesulfonate.

[0010] (4) The low polarity filtrate in (2) is dried by spin drying to obtain recovered triphenyltin hydroxide.

[0011] Wherein, in step (2), triphenyltin hydroxide needs to be freshly prepared.

[0012] Furthermore, in the step (1), the molar ratio of triphenyltin chloride to sodium methoxide is 1:1.5-1:1.

[0013] Furthermore, in the step (1), the water and ethanol are added to form a solution having an ethanol content of 85%-95%.

[0014] Furthermore, in the step (1), the reaction temperature is 40-80°C.

[0015] Furthermore, in the step (2), the p-toluenesulfonic acid is anhydrous p-toluenesulfonic acid.

[0016] Furthermore, in the step (2), the molar ratio of the added triphenyltin hydroxide to p-toluenesulfonic acid is 1:1.5-1.5:1.

[0017] Furthermore, in the step (2), the reaction temperature is 60-80°C.

[0018] Furthermore, the low polarity solvent in step (2) is an alkane solvent such as petroleum ether, cyclohexane, n-hexane, etc.

[0019] Beneficial effects of the present invention:

[0020] The experimental conditions are simple, and the reaction can be carried out at a relatively low temperature and normal pressure; no toxic or corrosive products are generated during the reaction process, and the production process is safe; the recovery of raw materials and the purification of products can be achieved without adopting a recrystallization method in the post-reaction treatment, that is, triphenyltin hydroxide is recovered by a low-polarity solvent, and p-toluenesulfonic acid is removed by water. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The invention discloses a process flow diagram of a method for preparing triphenyltin p-toluenesulfonate and recovering raw materials.

[0022] Figure 2 This is a synthetic route for triphenyltin p-toluenesulfonate.

[0023] Figure 3 The raw material is triphenyltin chloride 1 H NMR spectra.

[0024] Figure 4 The raw material is p-toluenesulfonic acid 1 H NMR spectra.

[0025] Figure 5 Triphenyltin hydroxide is purchased 1 H NMR spectra.

[0026] Figure 6 It is freshly prepared triphenyltin hydroxide 1 H NMR spectra.

[0027] Figure 7 It is the preparation of triphenyltin p-toluenesulfonate 1 H NMR spectra.

[0028] Figure 8 It is used to recover triphenyltin hydroxide 1 H NMR spectra. DETAILED DESCRIPTION

[0029] The embodiments of the present invention will be described in detail below with reference to examples.

[0030] The structure of the compound is determined by NMR ( 1 H NMR).

[0031] Embodiment 1:

[0032] The preparation method of triphenyltin p-toluenesulfonate and the raw material recovery method comprise the following steps:

[0033] (1) 5.67 g of sodium methoxide, 100 mL of water, 1900 mL of ethanol, and 38.55 g of triphenyltin chloride were placed in a 3 L flask; the mixture was stirred at 40° C. for 24 h, cooled to room temperature, and the solvent was removed by rotary evaporation, then washed with water three times, and the filter cake was dried to obtain 36.12 g of triphenyltin hydroxide, with a yield of 98.4%.

[0034] (2) Under a nitrogen atmosphere, 19.38 g of triphenyltin hydroxide, 7.54 g of anhydrous p-toluenesulfonic acid, and 400 mL of ethanol were placed in a 500 mL flask and reacted at 80° C. for 24 h; the solvent was removed by rotary evaporation, and 50 mL of toluene was vortexed twice at 65° C. to obtain an off-white solid, 150 mL of petroleum ether was added, and the mixture was stirred at 45° C. for 30 min, then filtered, washed with a small amount of petroleum ether, and the filter cake was dried to obtain a crude product of triphenyltin p-toluenesulfonate.

[0035] (3) The crude triphenyltin p-toluenesulfonate was added to 60 mL of water and stirred for 30 min, filtered, washed with a small amount of water, and the filter cake was dried to obtain a white solid, namely triphenyltin p-toluenesulfonate, with a mass of 21.18 g and a yield of 92.35%.

[0036] (4) The filtrate of the petroleum ether in (2) was dried by rotary evaporation to obtain 4.09 g of triphenyltin hydroxide, with a recovery rate of 91.58%. After deducting the recovered triphenyltin hydroxide, the comprehensive yield of triphenyltin p-toluenesulfonate was 97.54%.

[0037] Embodiment 2:

[0038] The preparation method of triphenyltin p-toluenesulfonate and the raw material recovery method comprise the following steps:

[0039] (1) 5.67 g of sodium methoxide, 100 mL of water, 2000 mL of ethanol, and 38.55 g of triphenyltin chloride were placed in a 3 L flask; the mixture was stirred at 60° C. for 24 h, cooled to room temperature, and the solvent was removed by rotary evaporation, then washed with water three times, and the filter cake was dried to obtain 36.53 g of triphenyltin hydroxide, with a yield of 99.5%.

[0040] (2) Under a nitrogen atmosphere, 11.01 g of triphenyltin hydroxide, 5.17 g of anhydrous p-toluenesulfonic acid, and 300 mL of ethanol were placed in a 500 mL flask and reacted at 65° C. for 24 h; the solvent was removed by rotary evaporation, and 50 mL of toluene was vortexed twice at 65° C. to obtain an off-white solid, 150 mL of n-hexane was added, and stirred at 45° C. for 30 min, then filtered, washed with a small amount of n-hexane, and the filter cake was dried to obtain a crude product of triphenyltin p-toluenesulfonate.

[0041] (3) The crude triphenyltin p-toluenesulfonate was added to 100 mL of water and stirred for 30 min, filtered, washed with a small amount of water, and the filter cake was dried to obtain a white solid, namely triphenyltin p-toluenesulfonate, with a mass of 11.3 g and a yield of 72.26%.

[0042] (4) The filtrate of the petroleum ether in (2) was dried by rotary evaporation to obtain 2.76 g of triphenyltin hydroxide, with a recovery rate of 90.40%. After deducting the recovered triphenyltin hydroxide, the comprehensive yield of triphenyltin p-toluenesulfonate was 96.45%.

[0043] Embodiment 3:

[0044] The preparation method of triphenyltin p-toluenesulfonate and the raw material recovery method comprise the following steps:

[0045] (1) 11.34 g of sodium methoxide, 50 mL of water, 950 mL of ethanol, and 77.1 g of triphenyltin chloride were placed in a 2 L flask; the mixture was stirred at 80° C. for 24 h, cooled to room temperature, and the solvent was removed by rotary evaporation, then washed with water three times, and the filter cake was dried to obtain 72.91 g of triphenyltin hydroxide, with a yield of 99.3%.

[0046] (2) Under a nitrogen atmosphere, 11.01 g of triphenyltin hydroxide, 6.20 g of p-toluenesulfonic acid, and 300 mL of ethanol were placed in a 500 mL flask and reacted at 70° C. for 24 h; the solvent was removed by rotary evaporation, and 50 mL of toluene was vortexed twice at 65° C. to obtain an off-white solid, 150 mL of cyclohexane was added, and the mixture was stirred at 45° C. for 30 min, then filtered, washed with a small amount of cyclohexane, and the filter cake was dried to obtain a crude product of triphenyltin p-toluenesulfonate.

[0047] (3) The crude triphenyltin p-toluenesulfonate was added with 60 mL of water, filtered, washed with a small amount of water, and the filter cake was dried to obtain a white solid, namely triphenyltin p-toluenesulfonate, with a mass of 10.32 g and a yield of 66.00%.

[0048] (4) The filtrate of the petroleum ether in (2) was dried by rotary evaporation to obtain 3.01 g of triphenyltin hydroxide, with a recovery rate of 80.42%. After deducting the recovered triphenyltin hydroxide, the comprehensive yield of triphenyltin p-toluenesulfonate was 90.84%.

[0049] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the embodiments of the present invention may have various modifications and variations. Any modification, equivalent replacement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing triphenyltin p-toluenesulfonate and recovering raw materials, characterized in that: The steps include: (1) Triphenyltin chloride, sodium methoxide and water are heated in ethanol for reaction, cooled to room temperature and then the solvent is removed by rotary evaporation, and then the mixture is washed with water three times and dried to obtain triphenyltin hydroxide. (2) Triphenyltin hydroxide and p-toluenesulfonic acid are heated in ethanol for reaction under a nitrogen atmosphere, and after cooling to room temperature, the solvent is removed by reduced pressure, a low-polarity solvent is added, and after heating and stirring, the mixture is filtered, washed, and dried to obtain a crude product of triphenyltin p-toluenesulfonate. (3) Adding crude triphenyltin p-toluenesulfonate to water, stirring, washing, filtering, and drying to obtain the target product triphenyltin p-toluenesulfonate. (4) The low polarity solvent filtrate in (2) is spin-dried to obtain recovered triphenyltin hydroxide.

2. The method for preparing triphenyltin p-toluenesulfonate and recovering raw materials according to claim 1, characterized in that The triphenyltin hydroxide in step (2) needs to be freshly prepared.

3. The method for preparing triphenyltin p-toluenesulfonate and recovering raw materials according to claim 1, characterized in that In the step (1), when preparing triphenyltin hydroxide, the molar ratio of triphenyltin chloride to sodium methoxide is 1:1.5-1:

1.

4. The method for preparing triphenyltin p-toluenesulfonate and recovering raw materials according to claim 1, characterized in that: In the step (1), the water and ethanol are added to form a solution having an ethanol content of 85%-95%.

5. The method for preparing triphenyltin p-toluenesulfonate and recovering raw materials according to claim 1, characterized in that: In the step (1), the reaction temperature is 40-80°C.

6. The method for preparing triphenyltin p-toluenesulfonate and recovering raw materials according to claim 1, characterized in that: In the step (2), the p-toluenesulfonic acid is anhydrous p-toluenesulfonic acid.

7. The method for preparing triphenyltin p-toluenesulfonate and recovering raw materials according to claim 1, characterized in that: In the step (2), the molar ratio of the added triphenyltin hydroxide to p-toluenesulfonic acid is 1:1.5-1.5:

1.

8. The method for preparing triphenyltin p-toluenesulfonate and recovering raw materials according to claim 1, characterized in that: In the step (2), the reaction temperature is 60-80°C.

9. The method for preparing triphenyltin p-toluenesulfonate and recovering raw materials according to claim 1, characterized in that: The low polarity solvent in step (2) is an alkane solvent such as petroleum ether, cyclohexane, n-hexane, etc.

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