A preparation method of sodium 3-diphenylphosphinobenzenesulfonate

Abstract

The invention discloses a method for preparing sodium 3-diphenylphosphinobenzenesulfonate, which belongs to the field of organic synthesis technology. Using triphenylphosphine as raw material, fluoroboric acid is added to 1,4-dioxane to obtain triphenylphosphine fluoroborate, which is then reacted with fuming sulfuric acid for monosulfonation, and sodium hydroxide is used to form a sodium salt to obtain sodium 3-diphenylphosphinobenzenesulfonate. This process has relatively few disulfonation by-products and the yield is increased to 73-78%, ensuring product purity and providing guarantee for large-scale production.

Description

Technical Field

[0001] The invention relates to a preparation method of sodium 3-diphenylphosphinobenzenesulfonate, belonging to the technical field of organic synthesis. Background Art

[0002] Sodium 3-diphenylphosphinobenzenesulfonate (TPPMS Na Sodium 3-(diphenyl phosphanyl)benzenesulfonate, CAS: 63995-75-5. Sodium 3-diphenylphosphinobenzenesulfonate is widely used as a water-soluble phosphorus ligand in homogeneous catalytic reactions and serves as an intermediate in the synthesis of a series of biologically active substances. For example, rhodium-catalyzed two-phase hydroformylation reactions can also be used in Wittig reactions. The resulting olefins generally do not require column chromatography purification to obtain high-purity products. TPPMS / CBr4 can be used as a highly efficient catalyst for the preparation of acetals from aldehydes.

[0003] Initial TPPMS Na In 1958, Chatt et al. obtained the product by direct sulfonation of triphenylphosphine with fuming sulfuric acid. They then used centrifugation to separate the water-soluble sodium 3-diphenylphosphinobenzenesulfonate. However, direct sulfonation was associated with polysulfonation and a small amount of oxidation, and the purification efficiency of centrifugation was limited, yielding only 32%.

[0004] The literature [European Journal of Inorganic Chemistry, 2010, #6, p.942-946] reported the optimization of triphenylphosphine sulfonation, which proposed a rapid phosphorus spectrum 31 The yield was increased to 59% by detecting P, quickly adding triphenylphosphine to reduce disulfonation to 22%, quickly adjusting the pH to 2-3 or neutral to reduce oxidation, and post-treatment using column chromatography without ethanol as an eluent. However, the disubstituted content was still high, and the amount of wastewater could not be reduced, making it unsuitable for large-scale production.

[0005] In view of the above method, in order to avoid the increase of by-products, the present invention selects triphenylphosphine to form a salt and then sulfonate it, so that the product quality is high and the yield is high. Under this premise, detailed optimization is carried out to make it suitable for factory production to meet the growing market demand. Summary of the Invention

[0006] In order to overcome the above technical defects, the present invention uses triphenylphosphine as a raw material, adds fluoroboric acid to 1,4-dioxane to obtain triphenylphosphine fluoroborate, then reacts with fuming sulfuric acid for monosulfonation, and forms a sodium salt with sodium hydroxide to obtain sodium 3-diphenylphosphinobenzenesulfonate. The process has relatively few disulfonation by-products and the yield is increased to 73-78%, thereby ensuring product purity and providing a guarantee for large-scale production.

[0007] The preparation method of sodium 3-diphenylphosphinobenzenesulfonate described in the present invention specifically comprises the following steps:

[0008]

[0009] Step S1: triphenylphosphine and 1,4-dioxane are mixed, and fluoroboric acid is added to react to obtain triphenylphosphine fluoroborate;

[0010] Step S2: triphenylphosphinofluoroborate and fuming sulfuric acid are mixed to react to obtain 3-diphenylphosphinobenzenesulfonic acid, followed by adding sodium hydroxide aqueous solution, and obtaining sodium 3-diphenylphosphinobenzenesulfonate through post-treatment.

[0011] Furthermore, in the above technical solution, the fluoroboric acid in step S1 is selected from a 48% fluoroboric acid aqueous solution.

[0012] Furthermore, in the above technical solution, the molar ratio of triphenylphosphine to fluoroboric acid in step S1 is 1:2.1-2.2.

[0013] Furthermore, in the above technical solution, the fuming sulfuric acid in step S2 is selected from 22% fuming sulfuric acid or 45% fuming sulfuric acid.

[0014] Furthermore, in the above technical solution, the molar ratio of triphenylphosphinofluoroborate to fuming sulfuric acid in step S2 is 1:2.5-3.5.

[0015] Furthermore, in the above technical solution, the post-treatment in step S2 is optimized at the kilogram level, and 3-diphenylphosphinobenzenesulfonate is obtained by dilution with water after cooling, extraction with triisobutyl phosphate, neutralization with aqueous sodium hydroxide solution, and recrystallization with deionized water.

[0016] Advantageous Effects of the Invention

[0017] The invention uses triphenylphosphine as a raw material and forms a salt with fluoroboric acid. The subsequent sulfonation can effectively reduce by-products such as disulfonation and improve the yield. The method of extracting tributyl phosphate is optimized to reduce the generation of wastewater, thereby reducing the salt content and avoiding the reduction in yield caused by multiple recrystallizations. Specific embodiments

[0018] The present invention will be further described below by way of specific examples. These embodiments should be understood to be merely illustrative of the present invention and not intended to limit the scope of protection of the present invention. After reading the contents described herein, those skilled in the art may make various changes or modifications to the present invention, and these equivalent variations and modifications also fall within the scope defined by the claims of the present invention.

[0019] Synthesis of Sodium 3-Diphenylphosphinobenzenesulfonate

[0020] Example 1

[0021]

[0022] At room temperature, 48% aqueous fluoroboric acid solution (80.5 g, 0.44 mol) was added dropwise to a reaction flask containing triphenylphosphine (52.5 g, 0.2 mol) and dioxane (380 mL). The reaction was carried out at room temperature for 10 minutes, heated to 75°C for 8 hours, and concentrated under reduced pressure to dryness. The resulting mixture was added with MTBE for pulping, filtered, rinsed with MTBE, and dried to obtain 67.7 g of triphenylphosphine fluoroborate as a white solid with a yield of 96.7% and an HPLC index of 99.8%. 1 HNMR(400MHz,DMSO-d6)δ:11.2(s,1H),7.77-7.70(m,9H),7.64-7.59(m,6H).

[0023] Example 2

[0024]

[0025] At room temperature, 22% fuming sulfuric acid (61.9g, 0.17mol) was added to a reaction flask, cooled to 0-5°C, and triphenylphosphine fluoroborate (17.5g, 0.05mol) was added at one time under rapid stirring. The temperature was subsequently raised to 15-20°C and the reaction was continued for 2 hours until the material dissolved. The temperature was subsequently raised to 25-30°C and the reaction was continued for 6 hours. Sampling was performed to detect that there was no raw material remaining, and the monosulfonation was 86%. The temperature was lowered to 0°C, 200g of water was added to dilute the mixture, and 10% aqueous sodium carbonate solution was slowly added dropwise and the pH was adjusted to 4.5-5.0. Then, 5% aqueous sodium hydroxide solution was slowly added dropwise and the pH was adjusted to 7.0-7.3. The mixture was stirred at room temperature overnight, filtered, and the filter cake was put back into the reaction flask. 90mL of water was added for recrystallization, and the mixture was dried to give 12.1g of sodium 3-diphenylphosphinobenzenesulfonate as a white solid. The yield was 66.6%, and the HPLC value was 99.8%. 1 HNMR(400MHz,D2O)δ:7.81-7.63(m,2H),7.13-6.94(m,12H).

[0026] Example 3

[0027]

[0028] At room temperature, 22% fuming sulfuric acid (61.9g, 0.17mol) was added to a reaction flask, cooled to 0-5°C, and triphenylphosphine fluoroborate (17.5g, 0.05mol) was added in six portions under rapid stirring. The mixture was subsequently heated to 15-20°C and reacted for 1 hour until the material dissolved. The mixture was subsequently heated to 25-30°C and reacted for 7 hours. Sampling and detection showed no residual raw material, resulting in a monosulfonation of 79%. The mixture was cooled to 0°C, diluted with 200g of water, and slowly added dropwise with 10% aqueous sodium carbonate solution to adjust the pH to 4.5-5.0. Subsequently, a 5% aqueous sodium hydroxide solution was slowly added dropwise and the pH was adjusted to 7.0-7.3. The mixture was stirred overnight at room temperature, filtered, and the filter cake was re-imported into a reaction flask. 90mL of water was added for recrystallization, and the mixture was dried to give 10.9g of sodium 3-diphenylphosphinobenzenesulfonate as a white solid. The yield was 59.7%, and the HPLC result was 99.7%.

[0029] Example 4

[0030]

[0031] Under a controlled temperature of 0-10°C, 40g of 98% sulfuric acid and triphenylphosphinofluoroborate (17.5g, 0.05mol) were added to a reaction flask, followed by the slow dropwise addition of 45% fuming sulfuric acid (26.7g, 0.15mol). After the addition was complete, the temperature was raised to 25-30°C and the reaction was allowed to proceed for 4 hours. After sampling to detect the presence of any residual starting material, the monosulfonation was 85%. The temperature was lowered to 0°C, diluted with 100g of water, and extracted with 100mL of tributyl phosphate twice. The organic phase was adjusted to a pH of 4.5-5.0 with a 5% aqueous sodium carbonate solution. Subsequently, a 5% aqueous sodium hydroxide solution was slowly added dropwise to adjust the pH to 7.0-7.3. The temperature was raised to 45°C and stirred for 1 hour. The stratification was allowed to proceed. The aqueous phase was cooled, filtered, and the filter cake was returned to the reaction flask. Recrystallization was performed by adding 70mL of water, and drying was performed to obtain 13.4g of sodium 3-diphenylphosphinobenzenesulfonate as a white solid with a yield of 73.4%, and an HPLC analysis of 99.9%.

[0032] Example 5

[0033]

[0034] At room temperature, 48% aqueous fluoroboric acid solution (737.6 g, 8.4 mol) was added dropwise to a 30 L reactor containing triphenylphosphine (1050 g, 4 mol) and dioxane (7.4 L). The reaction was stirred at room temperature for 10 minutes, slowly heated to 75 ° C and reacted overnight, concentrated under reduced pressure, replaced with MTBE and continued to concentrate under reduced pressure until no liquid was generated. MTBE was added for pulping, filtered, rinsed with MTBE, and dried to obtain 1370 g of triphenylphosphine fluoroborate as a white solid, HPLC 99.8%. At room temperature, 3.1 kg of 98% sulfuric acid and triphenylphosphine fluoroborate (1350 g, 3.856 mol) were added to a 10 L reactor, and 45% fuming sulfuric acid (1.77 kg, 9.95 mol) was slowly added dropwise at room temperature. After the addition was complete, the mixture was heated to 25-30 ° C and reacted for 4 hours. Sampling was performed to detect that no raw material remained, and the monosulfonation was 87%. The mixture was cooled to 5-10 ° C and added to 6.5 L of ice water, stirred and diluted, and extracted with 7 L of tributyl phosphate. The organic phase was 8 % sodium carbonate aqueous solution to adjust pH = 4.5-5.0, followed by slowly adding dropwise 5% sodium hydroxide aqueous solution and adjusting pH = 6.90-7.15, heating to 40 ° C and stirring for 1 hour, standing for stratification, retaining the aqueous phase, washing the organic phase with a small amount of water, combining the aqueous phases, cooling the aqueous phase and filtering, the filter cake was re-introduced into the reaction flask, adding 5.5L of water for recrystallization, and drying to obtain 1098g of sodium 3-diphenylphosphinobenzenesulfonate as a white solid, with a yield of 78.1%, HPLC99.5%.

[0035] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A method for preparing sodium 3-diphenylphosphinobenzenesulfonate, the specific technical scheme comprises the following steps: ； S1: triphenylphosphine and 1,4-dioxane are mixed, and fluoroboric acid is added to react to obtain triphenylphosphine fluoroborate; S2: triphenylphosphinofluoroborate and fuming sulfuric acid are mixed to react to obtain 3-diphenylphosphinobenzenesulfonic acid, followed by adding sodium hydroxide aqueous solution, and performing post-treatment to obtain sodium 3-diphenylphosphinobenzenesulfonate; the molar ratio of triphenylphosphinofluoroborate to fuming sulfuric acid is 1: 2.5-3.5; the post-treatment comprises dilution with water after cooling, extraction with triisobutyl phosphate, neutralization with sodium hydroxide aqueous solution, and recrystallization with deionized water to obtain sodium 3-diphenylphosphinobenzenesulfonate.

2. The method for preparing sodium 3-diphenylphosphinobenzenesulfonate according to claim 1, wherein: In step S1, the fluoroboric acid is selected from a 48% fluoroboric acid aqueous solution.

3. The method for preparing sodium 3-diphenylphosphinobenzenesulfonate according to claim 1, wherein: In step S1, the molar ratio of triphenylphosphine to fluoroboric acid is 1:2.1-2.

2.

4. The method for preparing sodium 3-diphenylphosphinobenzenesulfonate according to claim 1, wherein: In step S2, the fuming sulfuric acid is selected from 22% fuming sulfuric acid or 45% fuming sulfuric acid.

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