CN112876427B - Preparation method of acesulfame potassium - Google Patents
Preparation method of acesulfame potassium Download PDFInfo
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- CN112876427B CN112876427B CN202110059891.8A CN202110059891A CN112876427B CN 112876427 B CN112876427 B CN 112876427B CN 202110059891 A CN202110059891 A CN 202110059891A CN 112876427 B CN112876427 B CN 112876427B
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Abstract
The invention relates to a preparation method of acesulfame potassium. The method comprises the following steps: (1) preparation of acetoacetamido-N-sulfonyl methyl ester: dissolving methyl sulfamate in chlorohydrocarbon solvent under the catalysis of strong-alkaline macroporous resinReacting with diketene to generate an intermediate acetoacetamido-N-sulfonyl methyl ester; (2) preparing acesulfame potassium: performing cyclization reaction on acetoacetamido-N-sulfonyl methyl ester under the action of a copper-pyridine complex catalyst, and removing a byproduct methanol by reactive distillation; then obtaining the acesulfame potassium by KOH treatment. Compared with the existing production technology, the copper-pyridine complex is used for replacing a strong acid catalyst in the cyclization process, so that the occurrence of polymerization side reactions of intermediates is remarkably reduced, and the product yield is improved. While avoiding the use of triethylamine and SO3Greatly reducing the generation of waste acid and waste water.
Description
Technical Field
The invention relates to a preparation method of a sweetener, in particular to a preparation method of acesulfame potassium.
Background
Acesulfame K, also known as the A-K sugar, was approved as a low calorie sweetener since 1988. The sweetener is an artificial synthetic sweetener, has the taste similar to that of cane sugar, has the sweetness 200 times that of cane sugar, and has a synergistic sweetening effect when being used with other sweeteners. It has fast sweetening effect, good heat stability, and no change in taste and calorie, and can be excreted via human digestive system.
The synthetic route of acesulfame potassium can be divided into an acetoacetamide method and a divinyl ketone method according to different starting materials, and the latter method has relatively low price and cost advantage.
In the existing acesulfame-K production process, most manufacturers adopt a diketene-sulfur trioxide method, sulfamic acid and diketene are used as initial raw materials to generate acetyl sulfanilic acid triethylamine salt under the catalysis of equivalent triethylamine, and SO is used for the production of acesulfame-K at low temperature3Cyclizing to obtain acetyl sulfanilic acid ASH, and salifying with KOH to prepare acesulfame potassium. The raw materials of the route are easy to obtain, but the route has remarkable defects: 1) the cyclization process requires the use of excess SO3Large amount of waste acid is generated after hydrolysis20 tons of waste acid is generated in one ton of products, and the environmental protection pressure is high; 2) SO (SO)3Strong acid, which causes the polymerization of the double bond of the intermediate during the catalytic cyclization, thus leading to a reaction yield of less than 82% (document Yan Fuan et al, science and technology of food industry, No. 5 2003, 74-76); 3) in the reaction process, the same amount of triethylamine is used as a sulfonic acid group protective agent, so that the cost of raw materials is increased, although patent (CN101157666A) reports that triethylamine can be recovered by a distillation and rectification mode, the energy consumption cost and treatment equipment are increased, and the odor of triethylamine in the recovery process is difficult to control. The production route is as follows:
the sulfamoyl fluoride-bisvinyl ketone method is reported in the literature (Guangxi chemical 1997 (3): 10), in which sulfamoyl fluoride is reacted with bisvinyl ketone to generate potassium salt of acetoacetylamino-N-sulfonyl fluoride as an intermediate, and the potassium salt is stirred with methanol-KOH solution to be cyclized to obtain acesulfame potassium. The route avoids triethylamine and SO3However, the raw material of the sulfonamide fluoride is difficult to prepare, expensive and difficult to control the cost, and waste water and waste gas generated by fluoride are difficult to treat. The synthetic route for preparing acesulfame by the sulfamide fluoride method is as follows:
patent CN1092066A reports that substituted phenyl sulfamate is used instead of sulfonyl fluoride, but the synthesis of substituted phenyl sulfamate as raw material requires sodium amide or azide, and the process is complicated and has great safety hazard, which makes the route liquid difficult to be industrialized. The synthesis route for preparing acesulfame by the phenyl sulfamate method is as follows:
therefore, the development of the acesulfame potassium preparation process which is easy to prepare and has low raw material cost and little three-waste pollution is of great significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of acesulfame potassium. According to the method, methyl sulfamate is used as a raw material and reacts with diketene to generate an intermediate acetoacetamido-N-sulfonyl methyl ester. Then preparing acetylsulfanilic acid by reaction rectification under the condition of a copper-pyridine complex catalyst, and then preparing acesulfame potassium by salifying the acetylsulfanilic acid with KOH. The selectivity of the acetyl sulfanilic acid is improved. Avoiding the use of SO3And the polymerization of the intermediate acetyl sulfanilic acid is avoided by using the strong acid, the reaction yield is improved to more than 94 percent, and the generation of waste acid is greatly reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of acesulfame potassium comprises the following steps:
(1) preparation of acetoacetamido-N-sulfonyl methyl ester: dissolving methyl sulfamate in a chlorohydrocarbon solvent, and reacting with diketene under the catalysis of strongly basic macroporous resin to generate an intermediate acetoacetamino-N-sulfonyl methyl ester;
(2) preparing acesulfame potassium: performing cyclization reaction on acetoacetamido-N-sulfonyl methyl ester under the action of a copper-pyridine complex catalyst, and removing a byproduct methanol by reactive distillation; then obtaining the acesulfame potassium by KOH treatment.
The reaction equation of step (1) of the present invention is as follows:
the chlorinated hydrocarbon solvent in the step (1) is one or more of chlorobenzene, dichlorobenzene and trichloroethane, and the dosage of the chlorinated hydrocarbon solvent is 3-5 times of the mass of the methyl sulfamate.
The strongly basic macroporous resin in the step (1) is preferably spherical styrene Cl-type strongly basic macroporous resin D201, and the using amount of the strongly basic macroporous resin D201 is 5-10% of the mass of the methyl sulfamate.
The reaction temperature in the step (1) is-10 ℃.
The molar ratio of the methyl sulfamate to the diketene in the step (1) is 1: (1.0-1.1).
Preferably, step (1) of the present invention is performed according to the following steps: slowly dropwise adding diketene at-10 ℃ for 15-30min into a chlorohydrocarbon solvent containing methyl sulfamate and a strong basic macroporous resin catalyst, keeping the temperature and stirring for 30-60min after dropwise adding is finished, and directly carrying out the next reaction after the obtained solution is filtered and the catalyst is recovered.
The reaction equation of step (2) of the present invention is as follows:
the step (2) is carried out by reactive distillation in the presence of a copper-pyridine complex catalyst.
The copper-pyridine complex in the step (2) is a mixture of copper salt and pyridine or derivatives thereof, and the dosage of the catalyst is 0.1-0.5% of the mass of methyl sulfamate.
The copper salt of the present invention comprises CuCl2、CuBr2、CuF2、Cu(AcO)2One or more of (a).
The pyridine or the derivatives thereof comprise one or more of pyridine, 2-bipyridine and a, a, a-terpyridine.
The molar ratio of the copper salt to the pyridine or the derivative thereof is 1: 2-1: 5.
the temperature of the reaction rectifying tower in the step (2) is 60-70 ℃, and the pressure is negative pressure.
Preferably, step (2) of the present invention is performed according to the following steps: adding the solution prepared in the reaction (1) into a rectifying tower kettle filled with a copper-pyridine complex catalyst, controlling the kettle temperature to be 60-70 ℃, and controlling the reflux ratio at the top of the tower to be 5: 1-15: 1, sampling and analyzing, and stopping the reaction when no methanol is extracted from the top of the tower. After the reaction is finished, the reaction solution is subjected to desolventizing, suction filtration and drying to obtain ASH, then the ASH is neutralized to pH6.8-7.2 by using methanol-KOH solution, and the ASK is obtained by cooling, crystallization, suction filtration and drying. The chemical purity is more than or equal to 99.0 percent.
The invention has the advantages that: 1) methyl sulfamate is used for replacing sulfamic acid, strong basic resin is used as a catalyst, triethylamine is not used, and the raw material cost is reduced. 2) In the cyclization step, a copper-pyridine complex is used for catalyzing the conversion of acetoacetamido-N-sulfonyl methyl ester from keto form to enol form, the enol and methyl sulfonate are subjected to ester exchange to generate acetyl sulfanilic acid, and a byproduct methanol is removed through reaction rectification, so that the selectivity of the acetyl sulfanilic acid is further improved. Avoiding the use of SO3And the polymerization of the intermediate acetyl sulfanilic acid is avoided by using the strong acid, the reaction yield is improved to more than 94 percent from 82 percent in the prior art, and the generation of waste acid is greatly reduced.
Detailed Description
The main raw materials of the methyl sulfamate are purchased from Bailingwei science and technology Limited, the diketene, the copper salt and the pyridine or the derivatives thereof are purchased from Sigma-Aldrich, and the spherical styrene Cl-type strong-base macroporous resin D201 is purchased from Shanghai Kai resin Limited.
Example 1
(1) Preparation of acetoacetamido-N-sulfonyl methyl ester
In N2Under the protection of gas, 50g of chlorobenzene, 16.65g of methyl sulfamate and 0.83g of D201 resin are added into a reaction kettle, and the temperature is reduced to-10 ℃. Under the condition of stirring, 13.0g of diketene is slowly dripped for 15min, and the temperature is kept for 30min after the dripping is finished. The obtained solution can be directly used for the next reaction after being filtered and the catalyst is recovered.
(2) Synthesis of acesulfame K (ASK)
Adding the solution prepared in the reaction (1) into a rectifying tower kettle, and adding 4.2mg of CuCl2And 12mg of pyridine, heating to 60 ℃, opening a vacuum system to control the pressure to be 5Kpa, and controlling the reflux of the rectifying tower to be 5: 1, sampling and analyzing, and stopping the reaction when no methanol is extracted from the top of the tower. Cooling to room temperature after reaction, concentrating the filtrate to 15mL (tower kettle 60 deg.C, vacuum 5Kpa), cooling to room temperature, precipitating a large amount of solid, vacuum filtering, and drying to obtain acesulfame (A), (B), (C) and (C) a (B) a substantial amount of precipitating a large amount of separating a large amount of solid separating a large amount of solid separating a large amount of a solid separating a large amount of solid separating a solid separating out after cooling to obtain a large amount of a solid after cooling to obtain a large amount of a solid after cooling to obtain a large amount of a solid after cooling to obtain a substance, and a large amount of a substance, and a, to obtain a large amount of a, to obtain aASH), cyclization selectivity 95%. Mixing ASH and 20% methanol-KOH solution, stirring to pH7.0, vacuum filtering, and oven drying to obtain white solid, i.e. acesulfame potassium (ASK). The purity is 99.0 percent, and the total yield is 94 percent.
Example 2
(1) Preparation of acetoacetamido-N-sulfonyl methyl ester
In N2Under the protection of gas, 83g of dichlorobenzene, 16.65g of methyl sulfamate and 1.25g of D201 resin are added into the reaction kettle, and the temperature is reduced to 0 ℃. Under the condition of stirring, 13.7g of diketene is slowly dripped for 20min, and the temperature is kept for 40min after the dripping is finished. The obtained solution can be directly used for the next reaction after being filtered and the catalyst is recovered.
(2) Synthesis of ASK
Adding the solution prepared in the reaction (1) into a rectifying tower kettle, adding 10.7mg of CuBr2 and 22.5mg of 2, 2-bipyridine, heating to 65 ℃, opening a vacuum system to control the pressure to be 1Kpa, and controlling the reflux of the rectifying tower to be 10: 1, sampling and analyzing, and stopping the reaction when no methanol is extracted from the top of the tower. And (3) cooling to room temperature after the reaction is finished, concentrating the filtrate to 20mL (the temperature of a tower kettle is 75 ℃, and the vacuum is 1Kpa), separating out a large amount of solids after the filtrate is cooled to the room temperature, performing suction filtration, and drying to obtain the Acesulfame (ASH), wherein the cyclization selectivity is 98%. Mixing ASH and 20% methanol-KOH solution, stirring to pH6.8, vacuum filtering, and oven drying to obtain white solid, i.e. acesulfame potassium (ASK). The purity is 99.5 percent, and the total yield is 97 percent.
Example 3
(1) Preparation of acetoacetamido-N-sulfonyl methyl ester
In N2Under the protection of gas, 67g of trichloroethane, 16.65g of methyl sulfamate and 1.67g of D201 resin are added into the reaction kettle, and the temperature is reduced to 10 ℃. Under the condition of stirring, slowly dropwise adding 14.0g of diketene for 30min, and preserving heat for 60min after dropwise adding. The obtained solution can be directly used for the next reaction after being filtered and the catalyst is recovered.
(2) Synthesis of ASK
Adding the solution prepared in the reaction (1) into a rectifying tower kettle, adding 20.1mg of Cu (AcO)2 and 63mg of a, a, a-terpyridine, heating to 70 ℃, opening a vacuum system to control the pressure to be 60Kpa, and controlling the reflux of the rectifying tower to be 15: 1, sampling and analyzing, and stopping the reaction when no methanol is extracted from the top of the tower. And (3) cooling to room temperature after the reaction is finished, concentrating the filtrate to 25mL (tower kettle 70 ℃, vacuum 60Kpa) through reduced pressure distillation, separating out a large amount of solids after the filtrate is cooled to room temperature, performing suction filtration, and drying to obtain the Acesulfame (ASH), wherein the cyclization selectivity is 97%. Mixing ASH and 20% methanol-KOH solution, stirring to pH7.2, vacuum filtering, and oven drying to obtain white solid, i.e. acesulfame potassium (ASK). The purity is 99.2 percent, and the total yield is 96 percent.
The cyclization selectivity of the examples 2 and 3 is slightly higher than that of the example 1, mainly because the enol structure of the acetoacetamido-N-sulfonyl methyl ester and the copper salt of 2, 2-bipyridine or the copper salt of a, a, a-terpyridine can form a more stable complex transition state, which is beneficial to the cyclization reaction.
Comparative example 1 (cyclization process copper free pyridine catalyst)
(1) Preparation of acetoacetamido-N-sulfonyl methyl ester
In N2Under the protection of gas, 50g of chlorobenzene, 16.65g of methyl sulfamate and 0.83g of D201 resin are added into a reaction kettle, and the temperature is reduced to-10 ℃. Under the condition of stirring, 13.0g of diketene is slowly dripped for 15min, and the temperature is kept for 30min after the dripping is finished. The obtained solution can be directly used for the next reaction after being filtered and the catalyst is recovered.
(2) Synthesis of acesulfame K (ASK)
Adding the solution prepared in the reaction (1) into a rectifying tower kettle, heating to 60 ℃, opening a vacuum system to control the pressure to be 5Kpa, and controlling the reflux of the rectifying tower to be 5: 1, stirring for 5 hours, and then extracting no methanol from the tower top. Indicating that the cyclization reaction did not proceed without the addition of the copper pyridine catalyst.
Comparative example 2 (cyclization process pyridine only, no copper ion)
(1) Preparation of acetoacetamido-N-sulfonyl methyl ester
In N2Under the protection of gas, 50g of chlorobenzene, 16.65g of methyl sulfamate and 0.83g of D201 resin are added into a reaction kettle, and the temperature is reduced to-10 ℃. Under the condition of stirring, 13.0g of diketene is slowly dripped for 15min, and the temperature is kept for 30min after the dripping is finished. The obtained solution can be directly used after being filtered and recycledThe next reaction was carried out.
(2) Synthesis of acesulfame K (ASK)
Adding the solution prepared in the reaction (1) into a rectifying tower kettle, heating to 60 ℃, opening a vacuum system to control the pressure to be 5Kpa, and controlling the reflux of the rectifying tower to be 5: 1, stirring for 5 hours, and extracting a small amount of methanol from the tower top. Through liquid phase analysis, only 5% of the acetoacetamido-N-sulfonyl methyl ester in the reaction liquid is converted into the acetyl sulfanilic acid, and the rest is not reacted. Indicating that the pyridine system without copper ions can not effectively catalyze the cyclization reaction.
Claims (7)
1. A preparation method of acesulfame potassium comprises the following steps:
(1) preparation of acetoacetamido-N-sulfonyl methyl ester: dissolving methyl sulfamate in a chlorohydrocarbon solvent, and reacting with diketene under the catalysis of strongly basic macroporous resin to generate an intermediate acetoacetamino-N-sulfonyl methyl ester;
(2) preparing acesulfame potassium: performing cyclization reaction on acetoacetamido-N-sulfonyl methyl ester under the action of a copper-pyridine complex catalyst, and removing a byproduct methanol by reactive rectification; then obtaining acesulfame potassium by KOH treatment; the strong basic macroporous resin in the step (1) is spherical styrene Cl-type strong basic macroporous resin D201; the copper-pyridine complex in the step (2) is a mixture of copper salt and pyridine or derivatives thereof; the copper salt is selected from CuCl2、CuBr2、CuF2、Cu(AcO)2One or more of; the pyridine or the derivatives thereof are selected from one or more of pyridine, 2-bipyridine and a, a, a-terpyridine.
2. The method as claimed in claim 1, wherein the strongly basic macroporous resin is used in an amount of 5-10% by mass of the methyl sulfamate.
3. The method according to claim 1, wherein the reaction temperature in the step (1) is-10 to 10 ℃.
4. The method according to claim 1, wherein the amount of the copper pyridine complex catalyst used in the step (2) is 0.1-0.5% by mass of the methyl sulfamate.
5. The process according to claim 1, wherein the molar ratio of the copper salt to the pyridine or the derivative thereof is 1: 2-1: 5.
6. the method of claim 1, wherein step (2) is performed according to the steps of: adding the solution prepared in the reaction (1) into a rectifying tower kettle filled with a copper-pyridine complex catalyst, controlling the kettle temperature to be 60-70 ℃, and controlling the reflux ratio at the top of the tower to be 5: 1-15: 1.
7. the method as claimed in claim 1, wherein the temperature of the reaction distillation tower bottom in the step (2) is 60-70 ℃, and the pressure is negative pressure.
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