CN116730944A - Saccharin preparation method - Google Patents

Saccharin preparation method Download PDF

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Publication number
CN116730944A
CN116730944A CN202310998345.XA CN202310998345A CN116730944A CN 116730944 A CN116730944 A CN 116730944A CN 202310998345 A CN202310998345 A CN 202310998345A CN 116730944 A CN116730944 A CN 116730944A
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formula
compound
saccharin
reaction
application
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CN116730944B (en
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陈厚凯
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Beijing Huiyu Lebang Environmental Protection Technology Co ltd
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Beijing Huiyu Lebang Environmental Protection Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom

Abstract

The application belongs to the technical field of chemical products, and particularly relates to a preparation method of saccharin. The preparation route disclosed by the application comprises the following steps: carrying out oxidation reaction on a compound of the following formula 2 and an oxidant to obtain a compound of the formula 1; acidifying the compound of formula 1 to obtain saccharin;

Description

Saccharin preparation method
Technical Field
The application belongs to the technical field of chemical products, and particularly relates to a preparation method of saccharin.
Background
The phthalimide is commonly called saccharin, which is white crystalline powder, is difficult to dissolve in water, has the sweetness 300-500 times that of sucrose, does not contain calories, has slight bitter taste and metallic taste after being eaten, and has sodium salt which is easy to dissolve in water. Saccharin is a chemical synthetic food additive with the lowest application cost and the widest application range in all high-power sweeteners so far, is mainly used for table, processing food and beverage, and is widely applied in the fields of medicine, daily chemical industry, electroplating, feed, pesticide and the like.
The mature process method for producing saccharin in the prior art comprises the following steps:
(1) A toluene process; and the final reaction step of synthesizing saccharin by toluene method process is as follows:
；
(2) Phthalic anhydride process; and the final reaction step of synthesizing saccharin by phthalic anhydride method is as follows:
；
(3) A sulfonamide process; and the final reaction step of synthesizing saccharin by the sulfonamide method is as follows:
；
(4) A catalytic oxidation process; and the reaction for synthesizing saccharin by a catalytic oxidation method is as follows:
；
the method (1) belongs to an early production process, and is low in total yield, large in three wastes and unstable in quality, so that few production enterprises use the method at present. The method (2) is the most common production process for enterprises at home and abroad at present, but the method has larger environmental protection problem: the ammonium salt wastewater is more, and the copper acid wastewater is large. The method (3) has the advantages that ammonium salt and water are not generated, but the stripped methanol is mixed with an inert solvent, so that the methanol and the inert solvent are difficult to separate, meanwhile, the saccharin also has a certain solubility in the methanol, and the source of the saccharin is obtained from the method (2), so that the cost of the saccharin is influenced.
The method (4) has high selectivity to the catalyst. And the production line is also longer, and the price is not low.
Finding new synthetic routes is a continuing technical problem to be solved by those skilled in the art for the production of saccharin.
Disclosure of Invention
The application provides a new synthetic route for producing saccharin, which is short in synthetic route and easy to realize, and the prepared saccharin has high yield and good quality.
The application provides a saccharin preparation method for realizing the technical effects, which comprises the following steps:
carrying out oxidation reaction on a compound shown in the following formula 2 and an oxidant to obtain a compound shown in the formula 1; acidifying the compound of the formula 1 to obtain saccharin;
；
in the formula 1, A contains any one of alkali metal cations and ammonium radicals.
The application adopts toluene chlorinated by-product o-chlorotoluene, and o-benzene sulfonate benzaldehyde is obtained by methods such as methyl chlorination hydrolysis or oxidation, and substitution, amination, oxidation and the like are carried out on the o-benzene sulfonate benzaldehyde as a reaction raw material to prepare saccharin. The application has the advantages of easy realization of the designed route, high yield and good quality of the prepared saccharin.
In some embodiments of the application, the oxidizing agent is a permanganate, such as potassium permanganate, sodium permanganate, calcium permanganate, and the like.
In some embodiments of the application, the oxidizing agent is potassium permanganate.
In some embodiments of the present application, the compound of formula 2 is obtained by reacting a compound of formula 3 with ammonia or aqueous ammonia:
；
the substituent R in the formula 3 comprises halogen; such as chlorine, bromine, iodine, etc.
In some embodiments of the application, substituent R in formula 3 is chloro.
In some embodiments of the present application, the compound of formula 3 is obtained by substitution reaction of a compound of formula 4:
；
and B in the formula 4 is any one of hydrogen and alkali metal cations.
In some embodiments of the present application, a in formula 1 and B in formula 4 are each independently selected from any one of hydrogen, sodium, potassium.
In some embodiments of the application, the halogenating agent comprises any one or a combination of two or more of thionyl halide, sulfuryl halide, halosulfonic acid, acetyl halide, phosphorus trihalide oxygen, phosphorus pentahalide, halogenated toluene;
preferably, the catalyst is any one of thionyl chloride, sulfuryl chloride, chlorosulfonic acid, acetyl chloride, phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride and trichlorotoluene.
In some embodiments of the present application, the substitution reaction temperature is 20 to 115 ℃, and the reaction temperature is affected by the type of halogenated agent.
In some embodiments of the application, the substitution reaction is performed in an organic solvent comprising any one or a combination of two or more of toluene, solvent oil, and n-hexane. Common mineral spirits include, but are not limited to, sulfonated kerosene.
The following explains and illustrates the nouns of the application:
the compounds provided by the present application may be named according to IUPAC (international union of pure and applied chemistry) or CAS (chemical abstract service, columbus, OH) naming system.
Definition of terms used in connection with the present application: unless otherwise indicated, the initial definitions provided for substituent groups or terms herein apply to the groups or terms throughout the specification; for terms not specifically defined herein, the meanings that one skilled in the art can impart based on the disclosure and the context.
"oxidation" refers to the process by which a molecule gets oxygen.
"substitution" refers to the process by which a hydrogen atom or other atom or molecule in a molecule is replaced.
"halogen" includes fluorine, chlorine, bromine or iodine.
The "alkali metal" includes the first main group element.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Detailed Description
Exemplary embodiments of the present application will be described in more detail below with reference to specific embodiments. While only exemplary embodiments of the application have been shown, it should be understood that the application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the application to those skilled in the art.
Preparation of intermediate 3:
；
in formula 4, B contains hydrogen and alkali metal cations such as any one of lithium ion, sodium ion and potassium ion, and sodium ion is selected for the following investigation.
According to the difference of halogenated agents, the method specifically comprises the following steps:
(1) The halogenating agent is thionyl chloride:
mixing sodium benzaldehyde o-sulfonate and thionyl chloride according to a molar ratio of 1 (1.2-2.4), dissolving into solvent toluene or solvent oil, wherein the mass of the solvent is 2-4 times that of the mixed materials, and controlling the reaction temperature to be 20-85 ℃ for 2-8 hours to obtain an organic solvent solution containing o-benzaldehyde sulfonyl chloride, wherein the specific synthetic route is as follows:
；
(2) The halogenated reagent is sulfuryl chloride:
mixing sodium benzaldehyde o-sulfonate and sulfonyl halide according to a molar ratio of 1 (1.2-2.0), dissolving into solvent n-hexane or sulfonated kerosene, wherein the mass of the solvent is 3 times that of the mixed materials, controlling the reaction temperature to be not higher than 65 ℃ for 2-6 hours, and performing post-treatment to obtain o-benzaldehyde sulfonyl chloride, wherein the specific synthetic route is as follows:
；
(3) The halogenated reagent is chlorosulfonic acid:
mixing sodium benzaldehyde o-sulfonate and chlorosulfonic acid according to a molar ratio of 1 (1.2-2.0), dissolving into solvent n-hexane or sulfonated kerosene, wherein the mass of the solvent is 3 times that of the mixed materials, controlling the reaction temperature to be not higher than 65 ℃ for 2-6 hours, and performing post-treatment to obtain o-benzaldehyde sulfonyl chloride, wherein the specific synthetic route is as follows:
；
(4) The halogenated reagent is acetyl chloride:
mixing sodium benzaldehyde o-sulfonate and acetyl chloride according to a molar ratio of 1 (1.5-2.0), dissolving into solvent toluene, wherein the mass of the solvent is 3-5 times of that of a mixed material, controlling the reaction temperature to be 30-80 ℃, reacting for 5-8 hours, and performing post-treatment to obtain o-benzaldehyde sulfonyl chloride, wherein the specific synthetic route is as follows:
；
(5) The halogenated reagent is phosphorus trichloride:
mixing sodium benzaldehyde o-sulfonate and phosphorus trichloride according to a molar ratio of 1 (1.2-2.0), dissolving into solvent toluene, wherein the mass of the solvent is 3-5 times that of the phosphorus trichloride, controlling the reaction temperature to be not higher than 80 ℃, reacting for 4-8 hours, and performing post-treatment to obtain o-benzaldehyde sulfonyl chloride, wherein the specific synthetic route is as follows:
；
(6) The halogenated reagent is phosphorus oxychloride:
mixing sodium benzaldehyde o-sulfonate and phosphorus oxychloride according to a molar ratio of 1 (1.2-2.0), dissolving into solvent toluene, wherein the mass of the solvent is 3-5 times that of the phosphorus oxychloride, controlling the reaction temperature to be not higher than 80 ℃, reacting for 4-8 hours, and performing post-treatment to obtain o-benzaldehyde sulfonyl chloride, wherein the specific synthetic route is as follows:
；
(7) The halogenated reagent is phosphorus pentachloride:
mixing sodium benzaldehyde o-sulfonate and phosphorus pentachloride according to a molar ratio of 1 (1.2-2.0), dissolving into solvent toluene, wherein the mass of the solvent is 3-5 times that of the phosphorus pentachloride, controlling the reaction temperature to be not higher than 80 ℃, reacting for 4-8 hours, and performing post-treatment to obtain o-benzaldehyde sulfonyl chloride, wherein the specific synthetic route is as follows:
；
(8) The halogenated reagent is trichlorotoluene (benzyl trichloride):
mixing sodium benzaldehyde o-sulfonate and phosphorus pentachloride according to a molar ratio of 1 (1.2-2.0), dissolving into solvent toluene, wherein the mass of the solvent is 3-5 times that of the phosphorus pentachloride, controlling the reaction temperature to be 80-115 ℃, reacting for 3-8 hours, and performing post-treatment to obtain o-benzaldehyde sulfonyl chloride, wherein the specific synthetic route is as follows:
；
preparation of intermediate 2:
；
in formula 3, the substituent R contains halogen, such as fluorine, chlorine, bromine or iodine, and the application selects chlorine for the following investigation. The amination reagent contains any one of ammonia gas and ammonia water, and the application selects the ammonia water for the following investigation.
The specific synthetic route comprises:
；
the specific reaction process is as follows:
and adding o-benzaldehyde sulfonyl chloride into ammonia water with the mass concentration of 8% -15% (the mass of the ammonia water is 1-2 times of that of the o-benzaldehyde sulfonyl chloride), rapidly stirring, controlling the temperature to be not higher than 45 ℃, detecting the pH value of a reaction system after the reaction is carried out for about 8 hours, supplementing ammonia water or blowing ammonia gas to continue the reaction if the pH value is less than 9, and if the pH value is more than or equal to 9, indicating that the reaction is complete, filtering, washing the filtered material until the filtered material is neutral to obtain o-sulfonamide benzaldehyde for later use. And collecting the filtrate, collecting ammonia water for recycling through distillation, and continuously evaporating residues after removing ammonium chloride to be sent to a biochemical treatment system for subsequent treatment.
Preparation of Compound 1:
；
in the formula 1, A contains any one of alkali metal cations and ammonium, wherein alkali metal contains any one of lithium ions, sodium ions and potassium ions, and sodium ions are selected for the following investigation.
The oxidant is permanganate, such as potassium permanganate, sodium permanganate, calcium permanganate, etc. Because of serious chromium damage of potassium dichromate, the corrosion and safety of nitric acid and the post-treatment are troublesome, and persulfate is expensive and difficult to thoroughly react. For this purpose, the present application selects the conventional permanganate (potassium) as the oxidizing agent.
The application selects potassium permanganate for the following investigation.
The specific synthetic route comprises:
；
the specific reaction process is as follows:
adding o-sulfonamide benzaldehyde into water which is 3-8 times of the o-sulfonamide benzaldehyde, stirring and pulping, slowly dripping a potassium permanganate aqueous solution with the mass concentration of about 20% when no caking phenomenon exists, controlling the temperature to be not higher than 35 ℃, detecting the reaction liquid through liquid chromatography after 5-8 hours, detecting the reaction liquid by using starch potassium iodide test paper when the o-sulfonamide benzaldehyde content is lower than 0.05%, if the reaction liquid can make the starch potassium iodide test paper develop color, stopping adding the potassium permanganate aqueous solution, otherwise, continuing adding the potassium permanganate, slowly adding the potassium permanganate test paper, continuously detecting by using the starch potassium iodide test paper until the reaction liquid makes the color development of the starch potassium iodide test paper maintain for more than 3 hours, and finishing the reaction. After the reaction is finished, stirring for 3-5 hours, and quenching the potassium permanganate of the reaction system by using a sodium sulfite or potassium sulfite aqueous solution with the mass concentration of 20 percent: sodium sulfite is added continuously by using starch potassium iodide test paper: if the starch potassium iodide test paper does not develop color after 1 hour, the potassium permanganate is eliminated, otherwise, sodium sulfite is continuously added. The converted amount (mol) of sodium sulfite is not higher than 0.1% of the amount of potassium permanganate. After the reaction is determined, filtering, transferring the filtrate to the next process, washing a manganese dioxide filter cake until no sulfate radical (the washing water and the barium chloride aqueous solution are clear, transparent and free from turbidity, the sulfate radical or the sulfite radical is derived from sodium sulfite of quenched potassium permanganate), combining the washing water for the next reaction, and collecting and packaging the manganese dioxide filter cake after simple drying, wherein the manganese dioxide filter cake can be used in a common grade (the content is not equal to 95-98.5, and impurities mainly comprise alkali insoluble substances such as calcium and magnesium in water).
Then, the compound shown in the formula 1 is acidified to pH=1 by conventional acidification reaction, such as adding sulfuric acid or hydrochloric acid, so as to obtain saccharin, wherein the calculated saccharin yield is more than 90% and the saccharin purity is more than 98.5%.
；
Examples 1 to 14
Discloses a saccharin preparation method, wherein reactants and specific reaction conditions are shown in a table 1:
TABLE 1 list of reaction conditions
Comparative examples 1 to 2
Comparative example 1 provides a process for the preparation of saccharin, which differs from example 4 in that the oxidizer used is potassium dichromate.
Comparative example 2 provides a process for the preparation of saccharin, which differs from example 1 in that the amination reagent selects an ammonium salt, such as ammonium sulfate.
The yields and purities of saccharin produced under the reaction conditions of the examples and comparative examples of the present application are shown in table 2;
TABLE 2 list of yields and purities
From the above list, the present application has been found to be advantageous in reducing the probability of occurrence of side reactions by selecting permanganate as a catalyst, and has been studied to obtain a suitable route for saccharin, which route is high in yield.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the application is subject to the protection scope of the claims.

Claims (10)

1. A method of preparing saccharin, the method comprising: carrying out oxidation reaction on the compound of the formula 2 and an oxidant to obtain a compound of the formula 1; acidifying the compound of the formula 1 to obtain saccharin;
；
and in formula 1, A contains any one of alkali metal cations and ammonium groups.
2. The method of claim 1, wherein the oxidizing agent is a permanganate.
3. The method according to claim 1 or 2, wherein the oxidizing agent is potassium permanganate.
4. The method according to claim 1 or 2, wherein the compound of formula 2 is obtained by reacting a compound of formula 3 with ammonia or ammonia gas:
；
wherein the substituent R in the formula 3 is halogen.
5. The method of claim 4, wherein the substituent R in formula 3 is chloro.
6. The method of claim 4, wherein the compound of formula 3 is a compound represented by formula 4, obtained by substitution reaction with a halogenated reagent:
；
wherein, in the formula 4, B is any one of hydrogen and alkali metal cations.
7. The method according to claim 6, wherein a in formula 1 and B in formula 4 are each independently selected from any one of hydrogen, sodium, and potassium.
8. The method according to claim 6 or 7, wherein the halogenating agent is any one or a combination of two or more of thionyl halide, sulfuryl halide, halosulfonic acid, acetyl halide, phosphorus trihalide, phosphorus pentahalide, halogenated toluene.
9. The method according to claim 6 or 7, wherein the substitution reaction temperature is 20-115 ℃.
10. The method according to claim 6 or 7, wherein the substitution reaction is performed in an organic solvent comprising any one or a combination of two or more of toluene, solvent oil, and n-hexane.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000016560A (en) * 1996-06-13 2000-03-25 하니 쥬니어, 리차드 에이. Substituted benzylidene indenyl formamides, acetamides and propionamides
CN101130524A (en) * 2006-08-23 2008-02-27 上海港福化工技术咨询有限公司 Method for producing saccharin
CN103373972A (en) * 2012-04-19 2013-10-30 张卫民 Production process for saccharin zinc
CN103709118A (en) * 2013-12-19 2014-04-09 中国平煤神马集团开封兴化精细化工有限公司 Method for producing sodium saccharin
CN108586381A (en) * 2018-04-16 2018-09-28 天津北方食品有限公司 A kind of preparation method of saccharin sodium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000016560A (en) * 1996-06-13 2000-03-25 하니 쥬니어, 리차드 에이. Substituted benzylidene indenyl formamides, acetamides and propionamides
CN101130524A (en) * 2006-08-23 2008-02-27 上海港福化工技术咨询有限公司 Method for producing saccharin
CN103373972A (en) * 2012-04-19 2013-10-30 张卫民 Production process for saccharin zinc
CN103709118A (en) * 2013-12-19 2014-04-09 中国平煤神马集团开封兴化精细化工有限公司 Method for producing sodium saccharin
CN108586381A (en) * 2018-04-16 2018-09-28 天津北方食品有限公司 A kind of preparation method of saccharin sodium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李善吉: "甜味剂糖精合成新工艺研究", 中国调味品, no. 6, pages 344 - 43 *

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