Synthesis method of heterocyclic dithio alkyl sodium sulfonate

Abstract

The invention discloses a synthesis method of heterocyclic dithio alkyl sodium sulfonate, which comprises the following steps: adding 2-mercapto heterocycle and sodium hydroxide into a used solvent, adding sulfur into the mixed solution, refluxing and stirring for a period of time, cooling to room temperature, adding sultone, continuously stirring, separating out a large amount of faint yellow solid, and cooling to room temperature to obtain the heterocyclic dithio alkyl sodium sulfonate. And recrystallizing to obtain the heterocyclic dithio alkyl sodium sulfonate. According to the method, the heterocyclic dithio alkyl sodium sulfonate is synthesized by taking 2-sulfydryl heterocycle, sodium hydroxide, sulfur, sultone and the like as raw materials and adopting a one-pot method, so that the method is green and environment-friendly, the process is simple, the yield (greater than 85%) and the purity (greater than 98%) of the product are greatly improved, and amplified production is facilitated.

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing sodium heterocyclic disulfide alkyl sulfonate. Background Art

[0002] Sodium heterocyclic disulfide alkyl sulfonate, one of which is sodium thiazoline disulfide propane sulfonate (hereinafter referred to as SH-110), molecular formula: C6H 11 NO3S4, molecular weight: 273, CAS number: 8106-00-1, is a white to yellow solid powder, mainly used as a brightener for acid copper plating, and is an essential additive in copper plating. Its special feature is that it has both promoting groups and inhibiting groups in its molecular structure, which can play a role in leveling and refining grains during electroplating. This process is particularly suitable for the electroplating industry.

[0003] Patent CN117756740A discloses a method for efficiently preparing sodium thiazoline dithiopropane sulfonate (SH-110) and its application. The method adopts a one-pot synthesis method, by sequentially adding 1,3-propane sultone solution and hydrogen peroxide as an oxidant to a mixture containing 2-mercaptothiazoline, sodium hydrosulfide and a solvent at 5-25°C, then reacting at 20-35°C, and finally obtaining high-purity and high-yield SH-110 through a recrystallization step.

[0004] In the above patent, sodium hydrosulfide and 1,3-propane sultone are used as raw materials to react and obtain SH-110. This reaction not only requires the addition of a catalyst, hydrogen peroxide, but also has a low yield (80%) and average purity (95%). In addition, the raw material sodium hydrosulfide is highly toxic, which is not conducive to green synthesis.

[0005] Therefore, it is necessary to provide a green method for synthesizing sodium heterocyclic disulfide alkyl sulfonate with high yield and purity. Summary of the invention

[0006] In view of the shortcomings of the prior art, the present invention provides a method for synthesizing sodium heterocyclic disulfide alkyl sulfonate, which is used to solve the problem of how to obtain sodium heterocyclic disulfide alkyl sulfonate with high yield and purity through green synthesis.

[0007] To achieve the above objectives, the present invention includes the following technical solutions:

[0008] A method for synthesizing sodium heterocyclic disulfide alkyl sulfonate comprises the following steps:

[0009] 1) adding 2-mercaptoheterocycle and sodium hydroxide to an appropriate amount of solvent to form a mixed solution, adding sulfur to the mixed solution, heating under reflux and stirring for a period of time, and then cooling to room temperature;

[0010] 2) Add sultone and continue stirring until a large amount of light yellow solid is precipitated, and obtain sodium heterocyclic disulfide alkyl sulfonate after recrystallization.

[0011] Furthermore, in the above-mentioned method for synthesizing sodium heterocyclic disulfide alkylsulfonate, the molar ratio of the 2-mercapto heterocycle to sodium hydroxide is 1:1.2-2.5.

[0012] Furthermore, in the above-mentioned method for synthesizing sodium heterocyclic disulfide alkylsulfonate, the molar ratio of the 2-mercapto heterocycle to sulfur is 1:2-5.

[0013] Furthermore, in the above-mentioned method for synthesizing sodium heterocyclic disulfide alkylsulfonate, the molar ratio of the 2-mercapto heterocycle to sultone is 1:1.5-3.

[0014] Furthermore, in the above-mentioned method for synthesizing sodium heterocyclic disulfide alkylsulfonate, the solvent includes one or more of methanol, ethanol, isopropanol, n-butanol and tert-butanol.

[0015] Furthermore, in the above-mentioned method for synthesizing sodium heterocyclic disulfide alkylsulfonate, the solvent used for recrystallization includes one or more of water, methanol, ethanol, isopropanol, n-butanol and tert-butanol.

[0016] Furthermore, in the above-mentioned method for synthesizing sodium heterocyclic disulfide alkyl sulfonate, the recrystallization temperature is 50-60°C.

[0017] Furthermore, the total reaction time of the above-mentioned method for synthesizing sodium heterocyclic disulfide alkyl sulfonate is 5-6 hours.

[0018] The present invention also discloses a sodium heterocyclic disulfide alkyl sulfonate, which is synthesized by any of the above-mentioned methods.

[0019] Preferably, the above-mentioned sodium heterocyclic disulfide alkyl sulfonate includes one of imidazolinyl disulfide propane sulfonate, sodium thiazolinyl disulfide propane sulfonate, sodium oxazolinyl disulfide propane sulfonate, sodium imidazolinyl disulfide butane sulfonate, sodium thiazolinyl disulfide butane sulfonate, and sodium oxazolinyl disulfide butane sulfonate.

[0020] The invention also discloses the application of the heterocyclic sodium disulfide alkyl sulfonate in the additive for preparing electrolytic copper foil.

[0021] The invention also discloses an additive for electrolytic copper foil, comprising the above-mentioned sodium heterocyclic disulfide alkyl sulfonate.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The invention discloses a method for synthesizing sodium dithioalkyl sulfonate of heterocyclic group. The method adopts 2-mercapto heterocycle, sodium hydroxide, sulfur, sultone and other raw materials to synthesize the sodium dithioalkyl sulfonate of heterocyclic group by a one-pot method. The method is green and environmentally friendly, has a simple process, greatly improves the yield (greater than 85%) and purity (greater than 98%) of the product, and is conducive to large-scale production. The prepared sodium dithioalkyl sulfonate of heterocyclic group can be widely used in the electroplating industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is the overall reaction formula of the present invention. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] The present application provides a method for synthesizing sodium heterocyclic disulfide alkyl sulfonate, comprising the following steps:

[0027] 1) adding 2-mercaptoheterocycle and sodium hydroxide to an appropriate amount of solvent to form a mixed solution, adding sulfur to the mixed solution, heating under reflux and stirring for a period of time, and then cooling to room temperature;

[0028] 2) Add sultone and continue stirring until a large amount of light yellow solid is precipitated, and obtain sodium heterocyclic disulfide alkyl sulfonate after recrystallization.

[0029] Its reaction formula is Figure 1 shown.

[0030] Among them, a one-pot method is adopted to synthesize heterocyclic sodium disulfide alkyl sulfonate using thiol heterocycle, sodium hydroxide, sulfur and sultone as raw materials. This method is green and environmentally friendly, has a simple process and a high yield and purity.

[0031] The prepared heterocyclic sodium disulfide alkylsulfonate can be widely used in the electroplating industry.

[0032] Example 1

[0033] A method for preparing sodium imidazoline dithiopropane sulfonate comprises the following steps:

[0034] Add 180 mL of ethanol, 30 g (0.75 mol) of sodium hydroxide and 51 g (0.5 mol) of ethylene thiourea to a 1000 mL three-necked flask and stir evenly, slowly add 40 g (1.25 mol) of sulfur, heat and reflux until the reaction solution turns brown, cool to room temperature, slowly add 122 g (1 mol) of 1,3-propane sultone in 240 mL of ethanol solution, and control the dripping rate with a peristaltic pump. After the addition is complete, a large amount of light yellow solid is precipitated. After stirring for a period of time, remove the solvent with a rotary evaporator, recrystallize with a water-alcohol system, filter, and dry to obtain 109.1 g (yield 85.2%, purity 96.8%) of sodium imidazolyl dithiopropane sulfonate.

[0035] Example 2

[0036] A method for preparing sodium thiazoline dithiopropane sulfonate comprises the following steps:

[0037] Add 180 mL of ethanol, 30 g (0.75 mol) of sodium hydroxide and 59.5 g (0.5 mol) of 2-mercaptothiazoline into a 1000 mL three-necked flask and stir evenly. Slowly add 40 g (1.25 mol) of sulfur, heat and reflux until the reaction solution turns brown, cool to room temperature, slowly add 122 g (1 mol) of 1,3-propane sultone in 240 mL of ethanol solution, and control the dripping rate with a peristaltic pump. After the addition is complete, a large amount of light yellow solid is precipitated. After stirring for a period of time, remove the solvent with a rotary evaporator, recrystallize with a water-alcohol system, filter, and dry to obtain 118.2 g (yield 86.6%, purity 98.5%) of sodium thiazoline dithiopropane sulfonate.

[0038] Example 3

[0039] A method for preparing sodium oxazoline dithiopropane sulfonate comprises the following steps:

[0040] To a 1000mL three-necked flask, 180mL of ethanol, 30g (0.75mol) of sodium hydroxide and 51.5g (0.5mol) of 2-thiotetrahydro-1,3-oxazole were added and stirred evenly. 40g (1.25mol) of sulfur was slowly added, and the temperature was raised and refluxed until the reaction solution turned brown. After cooling to room temperature, 122g (1mol) of 1,3-propane sultone was slowly added in 240mL of ethanol solution. The dripping rate was controlled by a peristaltic pump. After the addition was completed, a large amount of light yellow solid was precipitated. After stirring for a period of time, the solvent was removed by a rotary evaporator, and the mixture was recrystallized with a water-alcohol system, filtered, and dried to obtain 106.9g (yield 83.2%, purity 97.3%) of sodium oxazolinyl dithiopropane sulfonate.

[0041] Example 4

[0042] A method for preparing sodium imidazoline dithiobutane sulfonate comprises the following steps:

[0043] Add 180 mL of ethanol, 30 g (0.75 mol) of sodium hydroxide and 51 g (0.5 mol) of ethylene thiourea to a 1000 mL three-necked flask and stir evenly, slowly add 40 g (1.25 mol) of sulfur, heat and reflux until the reaction solution turns brown, cool to room temperature, slowly add 136 g (1 mol) of 1,4-butane sultone in 240 mL of ethanol solution, and control the dripping rate with a peristaltic pump. After the addition is complete, a large amount of light yellow solid is precipitated. After stirring for a period of time, remove the solvent with a rotary evaporator, recrystallize with a water-alcohol system, filter, and dry to obtain 93.8 g (yield 69.5%, purity 83.5%) of sodium imidazolinyl dithiobutane sulfonate.

[0044] Example 5

[0045] A method for preparing sodium thiazolinyl dithiobutane sulfonate comprises the following steps:

[0046] Add 180 mL of ethanol, 30 g (0.75 mol) of sodium hydroxide and 59.5 g (0.5 mol) of 2-mercaptothiazoline to a 1000 mL three-necked flask and stir evenly. Slowly add 40 g (1.25 mol) of sulfur, heat and reflux until the reaction solution turns brown, cool to room temperature, slowly add 136 g (1 mol) of 1,4-butane sultone in 240 mL of ethanol solution, and control the dripping rate with a peristaltic pump. After the addition is complete, a large amount of light yellow solid is precipitated. After stirring for a period of time, remove the solvent with a rotary evaporator, recrystallize with a water-alcohol system, filter, and dry to obtain 102.2 g (yield 71.2%, purity 85.9%) of sodium thiazoline dithiobutane sulfonate.

[0047] Example 6

[0048] A method for preparing sodium oxazoline dithiobutane sulfonate comprises the following steps:

[0049] Add 180mL of ethanol, 30g (0.75mol) of sodium hydroxide and 51.5g (0.5mol) of 2-thiotetrahydro-1,3-oxazole to a 1000mL three-necked flask and stir evenly, slowly add 40g (1.25mol) of sulfur, heat and reflux until the reaction solution turns brown, cool to room temperature, slowly add 136g (1mol) of 1,4-butane sultone in 240mL of ethanol solution, control the dripping rate with a peristaltic pump, and a large amount of light yellow solid precipitates after the addition. After stirring for a period of time, remove the solvent with a rotary evaporator, recrystallize with a water-alcohol system, filter, and dry to obtain 89.8g (yield 66.3%, purity 81.2%) of sodium oxazolinyl dithiobutane sulfonate.

[0050] Test Case

[0051] The yield and purity of the reactions of Test Examples 1-6, wherein the yield formula is:

[0052] Yield = mass of product / theoretical mass x 100%;

[0053] Where: Theoretical mass = molar equivalent of heterocycle * molecular weight of product;

[0054] The purity is HPLC purity.

[0055] The results are shown in Table 1.

[0056] Table 1 Yield and purity

[0057] Group Yield purity Example 1 85.2 96.8 Example 2 86.6 98.5 Example 3 83.2 97.3 Example 4 69.5 83.5 Example 5 71.2 85.9 Example 6 66.3 81.2

[0058] As shown in Table 1, the yield and purity of the heterocyclic sodium dithioalkyl sulfonate synthesized from the five-membered ring sulfonic acid lactone are higher than those of the product synthesized from the six-membered ring sulfonic acid lactone, wherein the yield of sodium thiazolyl dithiopropane sulfonate in Example 2 is 86.6% and the purity is 98.5%, which is much higher than the yield of 80% and the purity of 95% in patent CN117756740A.

[0059] It can be seen from the above embodiments that the present invention discloses a method for synthesizing sodium dithioalkyl sulfonate of heterocyclic group. The method adopts 2-mercapto heterocycle, sodium hydroxide, sulfur, sultone and other raw materials to synthesize sodium dithioalkyl sulfonate in one pot, which is green and environmentally friendly, has a simple process, greatly improves the yield (greater than 85%) and purity (greater than 98%) of the product, and is conducive to scale-up production; the prepared sodium dithioalkyl sulfonate of heterocyclic group can be widely used in the electroplating industry.

[0060] The above are limited to several preferred embodiments of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the present invention. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A method for synthesizing sodium heterocyclic disulfide alkyl sulfonate, characterized in that: The following steps are involved: 1) adding 2-mercaptoheterocycle and sodium hydroxide to an appropriate amount of solvent to form a mixed solution, adding sulfur to the mixed solution, heating under reflux and stirring for a period of time, and then cooling to room temperature; 2) Add sultone and continue stirring until a large amount of light yellow solid is precipitated, and obtain sodium heterocyclic disulfide alkyl sulfonate after recrystallization.

2. The method for synthesizing sodium heterocyclic disulfide alkyl sulfonate according to claim 1, characterized in that: The molar ratio of the 2-mercapto heterocycle to sodium hydroxide is 1:1.2-2.

5.

3. The method for synthesizing sodium heterocyclic disulfide alkyl sulfonate according to claim 1, characterized in that: The molar ratio of the 2-mercapto heterocycle to sulfur is 1:2-5.

4. The method for synthesizing sodium heterocyclic disulfide alkyl sulfonate according to claim 1, characterized in that: The molar ratio of the 2-mercapto heterocycle to sultone is 1:1.5-3.

5. The method for synthesizing sodium heterocyclic disulfide alkyl sulfonate according to claim 1, characterized in that: The solvent in step 1) includes one or more of methanol, ethanol, isopropanol, n-butanol and tert-butanol.

6. The method for synthesizing sodium heterocyclic disulfide alkyl sulfonate according to claim 1, characterized in that: The solvent used for recrystallization in step 2) includes one or more of water, methanol, ethanol, isopropanol, n-butanol and tert-butanol.

7. The method for synthesizing sodium heterocyclic disulfide alkyl sulfonate according to claim 1, characterized in that: The recrystallization temperature is 50-60°C.

8. The method for synthesizing sodium heterocyclic disulfide alkyl sulfonate according to claim 1, characterized in that: The total reaction time is 5-6h.

9. A sodium heterocyclic disulfide alkyl sulfonate, characterized in that: The method is synthesized by any one of claims 1 to 8.

10. Use of the sodium heterocyclic disulfide alkylsulfonate as claimed in claim 9 in the additive for preparing electrolytic copper foil.

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