Preparation method of 4-(thiazolidine-2-sulfydryl) butane sodium sulfonate

Abstract

The invention discloses a preparation method of 4-(thiazolidine-2-sulfydryl) butane sodium sulfonate, and relates to the field, and the preparation method comprises the following specific steps: S1, adding 1 mol of aziridine into 200 ml of anhydrous THF, and stirring with a stirring rod to obtain an ethanolamine hydrochloride solution; s2, adding 150ml of carbon disulfide into the ethanolamine hydrochloride solution to obtain a solution A; s3, refluxing the solution A in an oil bath at 80 DEG C to obtain a solution B; and S4, cooling the solution B to 36 DEG C, and then evaporating. Ethanolamine hydrochloride is selected as a raw material, carbon disulfide is used as a sulfur source, a thiazoline-2-thio compound intermediate product is firstly prepared, then 1, 4-butane sultone is used as a sulfonating agent to prepare 4-(thiazoline-2-sulfydryl) sodium butane sulfonate (TBS), the price of the raw material can be reduced, meanwhile, preparation is more convenient, and the method is suitable for industrial production. Meanwhile, the generated sulfonate containing N and S elements is used for preparing the high-elongation copper foil, so that the pollution to the environment is reduced.

Description

Technical Field

[0001] The present invention relates to the field of, specifically to a preparation method of sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate. Background Art

[0002] Thiazoline widely exists in various bioactive molecules and natural products. It is a five-membered compound with S and N heteroatoms at positions 1 and 3 respectively. Compared with the parent thiazole, thiazoline has two more hydrogens. Although the aromaticity of the structure disappears, its stability decreases, the structure is more easily degraded, the toxicity to the environment and humans decreases, and it has a wide range of applications in other fields such as functional materials, cosmetics, and food flavors; Currently, it is prepared by condensing an amino thiol with a carboxylic acid or its derivative in the presence of isobutylaluminum, and the yield is between 43% and 77%; Or cyclizing β-hydroxyamide with a thio reagent, thiohydroxyamide or β-mercaptoamide to synthesize thiazoline; Reacting aziridine with carbon disulfide to synthesize thiazoline-2-thio compounds; However, the above preparation methods have high raw material prices, relatively harsh reaction conditions, complex post-treatment, and the treated substances are not environmentally friendly. Summary of the Invention

[0003] Based on this, the purpose of the present invention is to provide a preparation method of sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate to solve the technical problems.

[0004] To achieve the above purpose, the present invention provides the following technical solution: A preparation method of sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate, the specific steps are as follows: S1: First, add 1 mole of ethanolamine hydrochloride solution to 200 ml of anhydrous THF, and add 1 mole of base.

[0005] S2: Add 150 ml of carbon disulfide to obtain solution A; S3: Reflux solution A in an oil bath at 80 °C to obtain solution B; S4: Cool solution B to 36 °C, and then evaporate to obtain intermediate product C; S5: Dissolve 1 mole of 1,4-butanesultone in 100 ml of methanol to obtain solution E; S6: Dissolve the obtained intermediate product C in a beaker containing 100 ml of organic solvent, and add 1 mole of base; S7: Dropwise add solution E into the beaker and react for 3 hours; S8: After that, the solution in the beaker is filtered to obtain a precipitate, which is washed with ethanol and diethyl ether to obtain a crude product. Recrystallization with ethanol can yield sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate.

[0006] The present invention is further configured such that the base used in S6 is one of Na2CO3, K2CO3, Cs2CO3, K3PO3, K2HPO3, NaOH, KOH, KOCH3.

[0007] The present invention is further configured such that the organic solvent used in S6 is one of ethanol, ether, acetonitrile, toluene, ether, tetrahydrofuran.

[0008] The present invention is further configured such that the oil bath time in S3 is 0.5 - 2 hours.

[0009] The present invention is further configured such that after cooling to 36 degrees Celsius in S4, the oil bath equipment needs to be depressurized to make it in an atmospheric pressure state.

[0010] In summary, the present invention mainly has the following beneficial effects: By selecting ethanolamine hydrochloride as the raw material and carbon disulfide as the sulfur source, the present invention first prepares an intermediate product of thiazoline-2-thione compound, and then uses 1,4-butanesultone as the sulfonating agent to prepare sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate (TBS), which can reduce the price of raw materials, make the preparation more convenient, and at the same time, the sulfonate containing N and S elements produced is used to prepare high-ductility copper foil, reducing environmental pollution. Description of the Drawings

[0011] Figure 1 is the synthesis flow chart provided by the present invention; Figure 2 is the 1H NMR spectrum of sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate provided by the present invention; Figure 3 is the 13C NMR spectrum of sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate provided by the present invention; Figure 4 is the infrared spectrum of sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate provided by the present invention. Detailed Embodiments

[0012] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. The embodiments described below by referring to the drawings are exemplary and are only used to explain the present invention, and should not be construed as a limitation to the present invention.

[0013] The embodiments of the present invention will be described below according to the overall structure of the present invention.

[0014] A preparation method of sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate comprises the following specific steps: S1: First, add 1 mole of ethanolamine hydrochloride solution to 200 ml of anhydrous THF, and then add 1 mole of base.

[0015] S2: Add 150 ml of carbon disulfide to obtain solution A. S3: Reflux solution A in an oil bath at 80 °C to obtain solution B. S4: Cool solution B to 36 °C, and then evaporate it to obtain intermediate product C. S5: Dissolve 1 mole of 1,4-butanesultone in 100 ml of methanol to obtain solution E. S6: Dissolve the obtained intermediate product C in a beaker containing 100 ml of organic solvent, and add 1 mole of base. S7: Dropwise add solution E into the beaker and react for 3 hours. S8: Then filter the solution in the beaker to obtain a precipitate, wash it with ethanol and diethyl ether to obtain a crude product, and recrystallize it with ethanol to obtain sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate. By selecting ethanolamine hydrochloride as the raw material and carbon disulfide as the sulfur source, the thiazoline-2-thione compound intermediate is first prepared, and then 1,4-butanesultone is used as the sulfonating agent to prepare sodium 4-(dihydrothiazole-2-mercapto)butanesulfonate (TBS), which can reduce the price of raw materials and make the preparation more convenient.

[0016] Please refer to the figure. The base used in S6 is one of Na2CO3, K2CO3, Cs2CO3, K3PO3, K2HPO3, NaOH, KOH, KOCH3, and the organic solvent used in S6 is one of ethanol, ether, acetonitrile, toluene, ether, and tetrahydrofuran.

[0017] It can be understood that by selecting Na2CO3, K2CO3, Cs2CO3, K3PO3, K2HPO3, NaOH, KOH, KOCH3 as the base, the usage cost can be reduced and the reaction conditions can be lowered; by selecting ethanol, ether, acetonitrile, toluene, ether, and tetrahydrofuran as the organic solution, it can better serve as the matrix solution, accelerate the dissolution efficiency, and reduce the production cost.

[0018] Please refer to the figure. The oil bath time in S3 is 0.5 - 2 hours. After cooling to 36 °C in S4, the oil bath equipment needs to be depressurized to make it in an atmospheric pressure state.

[0019] It should be noted that a 0.5 - 2 - hour oil bath can enable the solution worker to heat up the solution comprehensively, avoiding the phenomenon of uneven overall temperature of the solution. After cooling in S4, pressure relief is required to avoid production accidents caused by high pressure.

[0020] Although the embodiments of the present invention have been shown and described, the specific embodiments are only interpretations of the present invention and not limitations thereof. The specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. After reading this specification, those skilled in the art can, without departing from the principles and purposes of the present invention, make modifications, substitutions and variations that do not contribute creatively to the embodiments as needed. However, as long as they are within the scope of the claims of the present invention, they are protected by the patent law.

Claims

1. A method for preparing sodium 4-(dihydrothiazolidine-2-mercapto)butane sulfonate, characterized in that: The specific steps are as follows: S1: First, add 1 mol of ethanolamine hydrochloride solution to 200 ml of anhydrous THF, and then add 1 mol of base.

2. S2: Add 150 ml of carbon disulfide to obtain solution A; S3: Solution A is refluxed in an oil bath at 80 degrees Celsius to obtain solution B; S4: Cooling solution B to 36 degrees Celsius, and then evaporating to obtain intermediate product C; S5: dissolving 1 mol of 1,4-butane sultone in 100 ml of methanol to obtain solution E; S6: dissolving the obtained intermediate product C in a beaker containing 100 ml of an organic solvent, and adding 1 mol of a base; S7: Add solution E dropwise into the beaker and react for 3 hours; S8: The solution in the beaker is then filtered to obtain a precipitate, which is then washed with ethanol and diethyl ether to obtain a crude product, which is then recrystallized with ethanol to obtain sodium 4-(dihydrothiazolidine-2-mercapto)butane sulfonate.

3. The method for preparing sodium 4-(dihydrothiazolidine-2-mercapto)butane sulfonate according to claim 1, characterized in that: The base used in S1 is one of KOH, NaOH, and KOC4H9 (potassium tert-butoxide).

4. The method for preparing sodium 4-(dihydrothiazolidine-2-mercapto)butane sulfonate according to claim 1, characterized in that: The alkali used in S6 is one of Na2CO3, K2CO3, Cs2CO3, K3PO3, K2HPO3, NaOH, KOH, and KOCH3.

5. The method for preparing sodium 4-(dihydrothiazolidine-2-mercapto)butane sulfonate according to claim 1, characterized in that: The organic solvent used in S6 is one of ethanol, diethyl ether, acetonitrile toluene, diethyl ether and tetrahydrofuran.

6. The method for preparing sodium 4-(dihydrothiazolidine-2-mercapto)butane sulfonate according to claim 1, characterized in that: The oil bath time in S3 is 0.5-2 hours.

7. The method for preparing sodium 4-(dihydrothiazolidine-2-mercapto)butane sulfonate according to claim 1, characterized in that: After cooling to 36 degrees Celsius in S4, the oil bath equipment needs to be depressurized to be in a normal pressure state.

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