阅读说明：本技术 一种乙酰乙酰磺胺酸基三乙胺盐的制备方法 (Preparation method of acetoacetyl sulfanilamide triethylamine salt ) 是由 朱小刚 庆九 俞新南 刘芳 于 2021-07-05 设计创作，主要内容包括：本发明涉及化工领域,特别是涉及一种乙酰乙酰磺胺酸基三乙胺盐的制备方法。本发明通过在氨基磺酸与三乙胺中和反应过程中,调节氨基磺酸和三乙胺合成所得物的pH值,来改变乙酰乙酰磺胺酸基三乙胺盐的pH值,研制了一种乙酰乙酰磺胺酸基三乙胺盐的制备方法。通过该方法制备的乙酰乙酰磺胺酸基三乙胺盐用于环合反应,环合水解收率提高至95％以上。(The invention relates to the field of chemical industry, in particular to a preparation method of acetoacetyl sulfanilamide triethylamine salt. The invention develops a preparation method of acetoacetyl-sulfadoxyl triethylamine salt by adjusting the pH value of a product obtained by synthesizing sulfamic acid and triethylamine in the neutralization reaction process of sulfamic acid and triethylamine to change the pH value of the acetoacetyl-sulfadoxyl triethylamine salt. The acetoacetyl sulfanilamide triethylamine salt prepared by the method is used for cyclization reaction, and the cyclization hydrolysis yield is improved to more than 95%.)

1. A preparation method of acetoacetyl sulfanilamide triethylamine salt comprises the following steps: (1) performing neutralization reaction on sulfamic acid and triethylamine to obtain a product synthesized by sulfamic acid and triethylamine; (2) adding organic acid into a product obtained by synthesizing sulfamic acid and triethylamine to obtain a neutralization reaction solution, wherein the pH value of the neutralization reaction solution is 5.5-7.5 by adding the organic acid; (3) adding diketene into the neutralization reaction liquid for acylation reaction to obtain the acetoacetyl sulfanilamide triethylamine salt.

2. The process according to claim 1, wherein the molar ratio of the organic acid added in step (2) to the sulfamic acid in step (1) is 6 to 7.

3. The process of claim 1, wherein the molar ratio of the amount of organic acid added in step (2) to the amount of sulfamic acid in step (1) is from 1.9 to 3: 20.

4. the method according to claim 1, wherein the amount of the organic acid added is 1 to 15% by mass based on the mass of the sulfamic acid.

5. The method of claim 1, wherein the organic acid is selected from the group consisting of a mono-acid, a di-acid, and a tri-acid.

6. The method of claim 1, wherein the organic acid has 1 to 6 carbon atoms.

7. The method of claim 1, wherein the organic acid is selected from the group consisting of acetic acid, propionic acid, malonic acid, succinic acid.

8. An acetoacetamidotriethylamine salt prepared by the process of any of claims 1-7.

9. Use of the process according to any one of claims 1 to 7 or of the acetoacetamidotriethylamine salt according to claim 8 in the manufacture of acesulfame potassium.

10. A process for the production of acesulfame potassium comprising the method of any one of claims 1 to 7.

Technical Field

The invention relates to the field of chemical industry, in particular to a preparation method of acetoacetyl sulfanilamide triethylamine salt.

Background

AK sugar (acesufame-K) is known as 6-Methyl-1,2, 3-oxathiazine-4 (3H) -ketone-2, 2-potassium dioxide in Chinese culture, and is known as 6-Methyl-1,2,3-oxathiazin-4(3H) -one 2,2-dioxide potassium salt in English, which is commonly called Acesulfame potassium. Appearance properties: colorless crystals. Solubility: is easily dissolved in water, and the solubility is 270g/L at 20 ℃. CAS number 55589-62-3. The molecular formula is as follows: c₄H₄O₄KNS. Molecular weight: 201.24. melting Point (. degree. C.): 229-232. Relative density (water ═ 1): 1.81. pH value: the pH value is 5.5-7.5. Acesulfame potassium has the advantages of safety, no toxicity, stable property, sweet taste, no bad aftertaste, proper price and the like, is one of the sweeteners with the best stability in the world at present, and is used as a sweetener in the aspects of food, medicine and the like.

The synthesis process of acetyl sulfanilic acid and its potassium salt includes the following steps: (1) performing neutralization reaction on sulfamic acid and triethylamine solution, and performing acylation reaction on the neutralization reaction solution and diketene to obtain acetoacetyl sulfanilamide triethylamine salt; (2) reacting the acetoacetyl sulfanilamide triethylamine salt in the step (1) with sulfur trioxide, and hydrolyzing to obtain acetyl sulfanilic acid after ring closure; (3) performing neutralization reaction on the acesulfame and potassium hydroxide in the step (2) to obtain an acesulfame potassium water solution; (4) and (4) concentrating, refining, centrifuging and drying the potassium acetylsulfanilate aqueous solution in the step (3) to obtain the potassium acetylsulfanilate solid. However, the yield of cyclization hydrolysis needs to be improved.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a method for preparing acetoacetyl sulfanilamide triethylamine salt.

In order to achieve the above objects and other related objects, the present invention adopts the following technical solutions:

the invention provides a preparation method of acetoacetyl sulfanilamide triethylamine salt, which comprises the following steps:

(1) performing neutralization reaction on sulfamic acid and triethylamine to obtain a product synthesized by sulfamic acid and triethylamine;

(2) adding organic acid into a product obtained by synthesizing sulfamic acid and triethylamine to obtain a neutralization reaction solution;

(3) adding diketene into the neutralization reaction liquid for acylation reaction to obtain the acetoacetyl sulfanilamide triethylamine salt.

In a preferred embodiment, in the step (2), the organic acid is added so that the pH value of the neutralization reaction solution is in the range of 5.5 to 7.5. Further, the organic acid is added so that the pH value of the neutralization reaction liquid is 6-7.

In a preferred embodiment, the molar ratio of the amount of organic acid added in step (2) to the sulfamic acid in step (1) is from 1.9 to 3: 20. further, the molar ratio of the addition amount of the organic acid in the step (2) to the sulfamic acid in the step (1) is 1.94-2.425: 20.

in a preferred embodiment, the amount of the organic acid added is 1 to 15% by mass of the sulfamic acid.

In a preferred embodiment, the organic acid is selected from a monobasic acid, a dibasic acid or a tribasic acid.

In a preferred embodiment, the organic acid has 1 to 6 carbon atoms.

In a preferred embodiment, the organic acid is selected from the group consisting of acetic acid, propionic acid, malonic acid, succinic acid.

The invention also provides the acetoacetamide-N-sulfonate prepared by the method. The chroma of the acetoacetyl sulphamido triethylamine salt solution is less than 200 Hazen.

The invention also provides the application of the acetyl sulfacetamide triethylamine salt prepared by the method or the method in the production of the potassium sulfacetamide.

A process for producing acesulfame potassium, which comprises the preparation method of the acesulfame potassium triethylamine salt.

The preparation method of the acetoacetyl sulfanilamide triethylamine salt has the following beneficial effects:

the invention develops a preparation method of acetoacetyl-sulfadoxyl triethylamine salt by adjusting the pH value of a product obtained by synthesizing sulfamic acid and triethylamine in the neutralization reaction process of sulfamic acid and triethylamine to change the pH value of the acetoacetyl-sulfadoxyl triethylamine salt. The acetoacetyl sulfanilamide triethylamine salt prepared by the method is used for cyclization reaction, and the cyclization hydrolysis yield is improved to more than 95%.

Detailed Description

The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art. Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.

Example 1

97g (1.0mol) of sulfamic acid was added to 700g of a methylene chloride solvent, and 111g (1.097mol) of triethylamine was further added thereto to carry out a neutralization reaction; 5.9g (0.097mol) of acetic acid is added into a product obtained by synthesizing sulfamic acid and triethylamine, redundant triethylamine is neutralized, 90g (1.05mol) of diketene is added into a neutralization reaction liquid for acylation reaction by controlling the pH value of the neutralization reaction liquid to be 6, and 1003.9g of acetoacetylsulfamic acid triethylamine salt is obtained. The chroma of the acetyl sulfanilic acid triethylamine salt solution is 180 Hazen. The acetoacetyl sulfanilamide triethylamine salt prepared by the method is used for cyclization reaction, and the cyclization hydrolysis yield is over 95.2 percent.

Example 2

97g (1.0mol) of sulfamic acid was added to 700g of a methylene chloride solvent, and 112.4g (1.11mol) of triethylamine was further added thereto to carry out a neutralization reaction; adding 8.1g (0.11mol) of propionic acid into a product obtained by synthesizing sulfamic acid and triethylamine, neutralizing redundant triethylamine, and controlling the pH value of a neutralization reaction solution to be 5.5; 88.3g (1.03mol) of diketene was added to the neutralized reaction solution to conduct acylation reaction, whereby 1005.8g of acetoacetamidotriethylamine salt was obtained. The chroma of the acetyl sulfanilic acid triethylamine salt solution is 155 Hazen. The acetoacetyl sulfanilamide triethylamine salt prepared by the method is used for cyclization reaction, and the cyclization hydrolysis yield is over 95 percent.

Example 3

58.2g (0.6mol) of sulfamic acid was added to 500g of a methylene chloride solvent, and 66.8g (0.66mol) of triethylamine was further added thereto to conduct a neutralization reaction; adding 4.4g (0.06mol) of propionic acid into a product obtained by synthesizing sulfamic acid and triethylamine, neutralizing redundant triethylamine, and controlling the pH value of a neutralization reaction solution to be 6; 52.7g (0.615mol) of diketene was added to the neutralized reaction solution to conduct acylation reaction, whereby 682.1g of acetoacetamidotriethylamine salt was obtained. The chroma of the acetoacetamidogen triethylamine salt solution is 165 Hazen. The acetoacetyl sulfanilamide triethylamine salt prepared by the method is used for cyclization reaction, and the cyclization hydrolysis yield is over 95.3 percent.

Example 4

77.6g (0.8mol) of sulfamic acid was added to 600g of a methylene chloride solvent, and 97.3g (0.96mol) of triethylamine was further added thereto to carry out a neutralization reaction; adding 8.5g (0.08mol) of malonic acid into a product obtained by synthesizing sulfamic acid and triethylamine, neutralizing redundant triethylamine, and controlling the pH value of a neutralization reaction solution to be 7.2; 70.2g (0.82mol) of diketene was added to the neutralized reaction solution to conduct acylation reaction, whereby 853.6g of acetoacetamidotriethylamine salt was obtained. The chroma of the acetyl sulfanilic acid triethylamine salt solution is 185 Hazen. The acetoacetyl sulfanilamide triethylamine salt prepared by the method is used for cyclization reaction, and the cyclization hydrolysis yield is over 95.2 percent.

Example 5

126.1g (1.3mol) of sulfamic acid was added to 1100g of a methylene chloride solvent, and 162.6g (1.60mol) of triethylamine was further added thereto to carry out a neutralization reaction; adding 18.6g (0.15mol) of succinic acid into a product obtained by synthesizing sulfamic acid and triethylamine, neutralizing redundant triethylamine, and controlling the pH value of a neutralization reaction solution to be 6.2; 114g (1.33mol) of diketene was added to the neutralized reaction solution to conduct acylation reaction, whereby 1521.3g of acetoacetamidotriethylamine salt was obtained. The chroma of the acetyl sulfanilic triethylamine salt solution is 172 Hazen. The acetoacetyl sulfanilamide triethylamine salt prepared by the method is used for cyclization reaction, and the cyclization hydrolysis yield is over 95.3 percent.

Example 6

145.5g (1.5mol) of sulfamic acid was added to 1050g of a methylene chloride solvent, and 166g (1.64mol) of triethylamine was further added thereto to carry out a neutralization reaction; adding 8.6g (0.14mol) of acetic acid into a product obtained by synthesizing sulfamic acid and triethylamine, neutralizing redundant triethylamine, and controlling the pH value of a neutralization reaction solution to be 7.5; 135g (1.57mol) of diketene was added to the neutralized reaction solution to conduct acylation reaction, thereby obtaining 1505.1g of acetoacetylsulfonamido triethylamine salt. The chroma of the acetyl sulfanilic triethylamine salt solution is 192 Hazen. The acetoacetyl sulfanilamide triethylamine salt prepared by the method is used for cyclization reaction, and the cyclization hydrolysis yield is over 95.4 percent.

Example 7

194g (2.0mol) of sulfamic acid is added into 1400g of dichloromethane solvent, and 232.8g (2.3mol) of triethylamine is added into the mixture for neutralization reaction; adding 22.2g (0.3mol) of propionic acid into a product obtained by synthesizing sulfamic acid and triethylamine, neutralizing redundant triethylamine, and controlling the pH value of a neutralization reaction solution to be 7; 180g (2.1mol) of diketene was added to the neutralized reaction solution to conduct acylation reaction, whereby 2029g of acetoacetamidotriethylamine salt was obtained. The chroma of the acetyl sulfanilic acid triethylamine salt solution is 197 Hazen. The acetoacetyl sulfanilamide triethylamine salt prepared by the method is used for cyclization reaction, and the cyclization hydrolysis yield is over 95.3 percent.

In conclusion, the present invention effectively overcomes various disadvantages of the prior art and has high industrial utilization value.

The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.