CN106631916A - Method for preparing dibenzenesulfonimide by solvent-free grinding method - Google Patents
Method for preparing dibenzenesulfonimide by solvent-free grinding method Download PDFInfo
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- CN106631916A CN106631916A CN201611010415.2A CN201611010415A CN106631916A CN 106631916 A CN106631916 A CN 106631916A CN 201611010415 A CN201611010415 A CN 201611010415A CN 106631916 A CN106631916 A CN 106631916A
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- dibenzenesulfonimide
- benzsulfamide
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- sulfonyl chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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Abstract
The invention relates to a method for preparing dibenzenesulfonimide by a solvent-free grinding method. According to the method, firstly, benzsulfamide and pure benzene sulfonyl chloride are put into a ball mill to be ground, so that the benzsulfamide and the benzene sulfonyl chloride are sufficiently and uniformly mixed at room temperature; then, solid NaOH is fed into the ball mill in different batches; the grinding is continuously performed; the temperature of a reactant is maintained to be lower than 60 DEG C; after the reaction is completed, the reactant is moved out from the ball mill; the reactants are dissolved by organic solvents; filtering is performed for removing generated NaCl; filter liquid is obtained; finally, the filter liquid is subjected to concentration crystallization, filtering and drying; a product is obtained. In the whole reaction process, the solvent is not needed; the environment pollution is reduced; the production cost is reduced. The atom utilization rate of the whole preparation process is high; the atom economic green and environment-friendly ideal is met; the method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of dibenzenesulfonimide, more particularly to a kind of double benzene of solvent-free polishing preparation
The method of sulfimide.
Background technology
Dibenzenesulfonimide（Abbreviation BBI）It is a kind of important organic chemical industry's nickel softening agent, resists miscellaneous dose.In electroplating industry
In, replace saccharin to make first brightener with it, consumption advantage less than saccharin good with leveling effect.In addition, in recent years with
Electrophilic fluorination reagent --- extensive application of the N- fluoro-diphenyl sulfimides in organic fluorination reaction, as preparation N- fluorine
For the primary raw material of dibenzenesulfonimide, the demand of BBI further increases.The side of the synthesis BBI for having reported for work in document at present
Method mainly has following several：
Chemical Engineer, report in 11 phases page 59 in 2009, with the benzsulfamide of benzene sulfonyl chloride and twice equivalent, twice equivalent
NaOH reacts in aqueous at 55 DEG C, and with 72% yield dibenzenesulfonimide is obtained.This method benzsulfamide and hydrogen-oxygen
The consumption for changing sodium is all larger, low yield.
Org. Lett., reports in 2009,11,1147, and benzene sulfonyl chloride and benzsulfamide exist in tetrahydrofuran
React in the presence of NaH, dibenzenesulfonimide can be obtained.NaH and tetrahydrofuran price all costly, are not suitable for industrial life in this method
Produce.
A kind of benzsulfamide and benzene sulfonyl chloride are reported in Chinese patent CN101671285A in sodium hydrate aqueous solution
The method that reaction prepares dibenzenesulfonimide, although yield is higher in the method, reacts required maximum temperature up to 100 ~ 105
DEG C, benzene sulfonyl chloride meets water very facile hydrolysis under high temperature.
Chem. Eur. J., report benzene sulfonyl chloride and benzsulfamide in 2013,19,16910, deposit in Et3N and DMAP
Under, reaction can be obtained dibenzenesulfonimide in dichloromethane, but Et3N used in reacting and DMAP are costly, no
Suitable industrial production dibenzenesulfonimide.
Report in WO2016009448A1 within 2016, with acetonitrile as solvents, benzene more than benzene sulfonyl chloride and twice equivalent
Sulfonamide reacts the dibenzenesulfonimide that can be made in the presence of Et3N, and benzsulfamide consumption is big in the method, acetonitrile and Et3N
All costly, industrial production is not suitable for.
The method of made as described above dibenzenesulfonimide, mostly using alkali costly or solvent, although some are used
Cheap NaOH is alkali, but will use water as solvent, causes benzene sulfonyl chloride to hydrolyze during the course of the reaction, is produced after the completion of reaction big
Amount waste water, causes environmental pollution.
It is well known that solvent-free organic synthesis do not use solvent because of it, it is to avoid solvent is to environment in course of reaction
Pollution, while and reducing production cost.In addition, due to the intervention without solvent, it has reacts not with conventional solution
Same molecule environment, thus there is a possibility that speed, selectivity and the conversion ratio of reaction are improved.This kind of reaction can be by grinding
The succinct technology such as mill, microwave, Ultrasonic Radiation, vibration and illumination is realizing.It is solvent-free to have based on above plurality of advantages
Machine synthetic reaction has obtained synthesizing the concern of chemist in recent years.
The content of the invention
The technical problem to be solved is to provide that a kind of easy to operate, atom utilization is high, environmental pollution is little, into
The method that this cheap solvent-free polishing prepares dibenzenesulfonimide.
To solve the above problems, the method that a kind of solvent-free polishing of the present invention prepares dibenzenesulfonimide, its
It is characterised by：First benzsulfamide is put into grinding in ball grinder with pure benzene sulfonyl chloride, makes benzsulfamide exist with benzene sulfonyl chloride
It is sufficiently mixed under room temperature uniform；Then put into solid NaOH in ball mill in batches to continue to grind, and keep the temperature of reactant
Less than 60 DEG C；Reaction removes reactant from the ball mill after terminating, and the reactant is organic molten with 3 ~ 15 times of its quality
Agent is dissolved, and is filtered to remove the NaCl of generation, obtains filtrate；Finally the concentrating filter liquor is crystallized, filter, be dried, obtain final product product
Product；The mol ratio of the benzsulfamide, the benzene sulfonyl chloride and the NaOH is 1：1~2：1~2.5.
The organic solvent is any one in methyl alcohol, ethanol, dichloromethane, ethyl acetate.
The condition of the drying refers to that temperature is 70 ~ 100 DEG C.
The present invention has compared with prior art advantages below：
1st, the reaction between benzsulfamide of the present invention, benzene sulfonyl chloride and solid NaOH is solvent-free griding reaction, in course of reaction
Solvent is not needed, the pollution to environment is reduced, while and reducing production cost.Reactional equation is as follows：
2nd, organic solvent used when present invention dissolving, purified product can be recycled repeatedly, thus reduce further production
Cost.
3rd, whole process of the present invention only produces a small amount of solid NaCl, and purity is higher, can be directly used as industrial
NaCl.Therefore, it is not only easy to operate, and whole preparation process atom utilization is high, meet atom economy and environmental protection
Theory, is adapted to industrialized production.
Description of the drawings
The specific embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the HPLC spectrograms of the products obtained therefrom of the embodiment of the present invention 1.
Specific embodiment
Described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited only to the following side of being preferable to carry out
Formula.On concept to the invention of those skilled in the art's here, around benzsulfamide and the solvent-free reaction of benzene sulfonyl chloride
The some improvement for preparing dibenzenesulfonimide are made, protection scope of the present invention is belonged to.
The method that a kind of solvent-free polishing of embodiment 1 prepares dibenzenesulfonimide, first by 500 grams（3.185 mol）
Benzsulfamide and 589 grams（3.344 mol）Pure benzene sulfonyl chloride is put into the stainless steel ball grinding machine that volume is 5 liters and grinds 5 minutes,
Benzsulfamide is set to be sufficiently mixed at room temperature uniformly with benzene sulfonyl chloride；Then divide 5 times and 140 grams are put into in stainless steel ball grinding machine
（3.5 mol）Solid NaOH, adds every time after NaOH and grinds material 3 ~ 7 minutes, and keeps the temperature of reactant less than 60 DEG C,
Continue to grind 15 minutes；Reaction from ball mill moves on to reactant after terminating in 5 liters of three-necked bottle, and in the reactant it is added
The methyl alcohol that 10 times of quality, loads onto condenser, heats, stirs, flows back 30 minutes, heat filtering, by the solids heat in funnel
Methyl alcohol is washed three times, is filtered to remove the NaCl of generation, merging filtrate；Finally filtrate is boiled off prior to heating distillation and concentration under normal pressure
After 2/3 solvent, by cooling, crystallization and filtration under leftover materials room temperature, thing is precipitated, the sediment is 70 DEG C of bars in temperature
It is dried under part, obtains final product 870 grams of dibenzenesulfonimide product, yield is 92%, and purity is 99.4%.
Products obtained therefrom is carried out respectively1H NMR and13C NMR detections, determine that its structure is correct：
1H NMR (600 MHz, CD3OD) 7.84 ~ 7.82 (m, 4H), 7.62~7.57 (m, 2H), 7.51~7.47
(m, 4H), 5.14 (br, 1H)。
13C NMR (150 MHz, CD3OD) δ 141.67 , 134.75 , 130.24 , 128.48 。
The purity of products obtained therefrom is detected with HPLC, as a result shows that its purity is 99.4%（Referring to Fig. 1）.
The method that a kind of solvent-free polishing of embodiment 2 prepares dibenzenesulfonimide, first by 500 grams（3.185 mol）
Benzsulfamide and 563 grams（3.185 mol）Pure benzene sulfonyl chloride is put into the stainless steel ball grinding machine that volume is 5 liters and grinds 5 minutes,
Benzsulfamide is set to be sufficiently mixed at room temperature uniformly with benzene sulfonyl chloride；Then divide 5 times and 127 grams are put into in stainless steel ball grinding machine
（3.185 mol）Solid NaOH, adds every time after NaOH and grinds material 3 ~ 7 minutes, and keeps the temperature of reactant to be less than 60
DEG C, continue to grind 15 minutes；Reaction from ball mill moves on to reactant after terminating in 5 liters of three-necked bottle, in the reactant plus
Enter the methyl alcohol of 3 times of its quality, load onto condenser, heat, stir, flow back 30 minutes, heat filtering, by the solids heat in funnel
Methyl alcohol wash three times, be filtered to remove the NaCl of generation, merging filtrate；Finally filtrate is steamed prior to heating distillation and concentration under normal pressure
After removing 2/3 solvent, by cooling, crystallization and filtration under leftover materials room temperature, thing is precipitated, the sediment is 100 in temperature
It is dried under the conditions of DEG C, obtains final product 643 grams of benzenesulfonimide product, yield is 68%, and purity is 97.5%.
The method that a kind of solvent-free polishing of embodiment 3 prepares dibenzenesulfonimide, first by 500 grams（3.185 mol）
Benzsulfamide and 729 grams（4.14 mol）Pure benzene sulfonyl chloride is put into the stainless steel ball grinding machine that volume is 5 liters and grinds 5 minutes,
Benzsulfamide is set to be sufficiently mixed at room temperature uniformly with benzene sulfonyl chloride；Then divide 5 times and 171 grams are put into in stainless steel ball grinding machine
（4.3 mol）Solid NaOH, adds every time after NaOH and grinds material 3 ~ 7 minutes, and keeps the temperature of reactant less than 60 DEG C,
Continue to grind 15 minutes；Reaction from ball mill moves on to reactant after terminating in 5 liters of three-necked bottle, and in the reactant it is added
The methyl alcohol that 5 times of quality, loads onto condenser, heats, stirs, flows back 30 minutes, heat filtering, by the first of the solids heat in funnel
Alcohol is washed three times, is filtered to remove the NaCl of generation, merging filtrate；Finally filtrate is boiled off into 2/3 prior to heating distillation and concentration under normal pressure
Solvent after, will under leftover materials room temperature cooling, crystallization and filtration, be precipitated thing, the sediment in temperature be 80 DEG C of conditions
Lower drying, obtains final product 872 grams of dibenzenesulfonimide product, and yield is 92.2%, and purity is 97.8%.
The method that a kind of solvent-free polishing of embodiment 4 prepares dibenzenesulfonimide, first by 500 grams（3.185 mol）
Benzsulfamide and 589 grams（3.344 mol）Pure benzene sulfonyl chloride is put into the stainless steel ball grinding machine that volume is 5 liters and grinds 5 minutes,
Benzsulfamide is set to be sufficiently mixed at room temperature uniformly with benzene sulfonyl chloride；Then divide 5 times and 196 grams are put into in stainless steel ball grinding machine
（4.9 mol）Solid NaOH, adds every time after NaOH and grinds material 3 ~ 7 minutes, and keeps the temperature of reactant less than 60 DEG C,
Continue to grind 15 minutes；Reaction from ball mill moves on to reactant after terminating in 5 liters of three-necked bottle, and in the reactant it is added
The methyl alcohol that 12 times of quality, loads onto condenser, heats, stirs, flows back 30 minutes, heat filtering, by the solids heat in funnel
Methyl alcohol is washed three times, is filtered to remove the NaCl of generation, merging filtrate；Finally filtrate is boiled off prior to heating distillation and concentration under normal pressure
After 2/3 solvent, by cooling, crystallization and filtration under leftover materials room temperature, thing is precipitated, the sediment is 90 DEG C of bars in temperature
It is dried under part, obtains final product 865 grams of dibenzenesulfonimide product, yield is 90%, and purity is 98.0%.
The method that a kind of solvent-free polishing of embodiment 5 prepares dibenzenesulfonimide, first by 500 grams（3.185 mol）
Benzsulfamide and 840 grams（4.775 mol）Pure benzene sulfonyl chloride is put into the stainless steel ball grinding machine that volume is 5 liters and grinds 5 minutes,
Benzsulfamide is set to be sufficiently mixed at room temperature uniformly with benzene sulfonyl chloride；Then divide 5 times and 204 grams are put into in stainless steel ball grinding machine
（5.096 mol）Solid NaOH, adds every time after NaOH and grinds material 3 ~ 7 minutes, and keeps the temperature of reactant to be less than 60
DEG C, continue to grind 15 minutes；Reaction from ball mill moves on to reactant after terminating in 5 liters of three-necked bottle, in the reactant plus
Enter the ethanol of 13 times of its quality, load onto condenser, heat, stir, flow back 30 minutes, heat filtering uses the solids in funnel
The ethanol of heat is washed three times, is filtered to remove the NaCl of generation, merging filtrate；Finally by filtrate prior to heating distillation and concentration under normal pressure,
After boiling off 2/3 solvent, by cooling, crystallization and filtration under leftover materials room temperature, thing is precipitated, the sediment is 75 in temperature
It is dried under the conditions of DEG C, obtains final product 869 grams of dibenzenesulfonimide product, yield is 92%, and purity is 98.0%.
The method that a kind of solvent-free polishing of embodiment 6 prepares dibenzenesulfonimide, first by 500 grams（3.185 mol）
Benzsulfamide and 1009 grams（5.733 mol）Pure benzene sulfonyl chloride is put into the stainless steel ball grinding machine that volume is 5 liters and grinds 5 points
Clock, makes benzsulfamide be sufficiently mixed at room temperature uniformly with benzene sulfonyl chloride；Then divide 5 times and put into 255 in stainless steel ball grinding machine
Gram（6.37 mol）Solid NaOH, adds every time after NaOH and grinds material 3 ~ 7 minutes, and keeps the temperature of reactant to be less than 60
DEG C, continue to grind 15 minutes；Reaction from ball mill moves on to reactant after terminating in 5 liters of three-necked bottle, in the reactant plus
Enter the dichloromethane of 10 times of its quality, load onto condenser, heat, stir, flow back 30 minutes, heat filtering, by the solid in funnel
The dichloromethane of thing heat is washed three times, is filtered to remove the NaCl of generation, merging filtrate；Finally filtrate is steamed prior to heating under normal pressure
Evaporate concentration, after boiling off 2/3 solvent, will under leftover materials room temperature cooling, crystallization and filtration, be precipitated thing, the sediment in
Temperature is dry under the conditions of 85 DEG C, obtains final product 879 grams of dibenzenesulfonimide product, and yield is 93%, and purity is 98.0%.
The method that a kind of solvent-free polishing of embodiment 7 prepares dibenzenesulfonimide, first by 500 grams（3.185 mol）
Benzsulfamide and 1121 grams（6.37 mol）Pure benzene sulfonyl chloride is put into the stainless steel ball grinding machine that volume is 5 liters and grinds 5 minutes,
Benzsulfamide is set to be sufficiently mixed at room temperature uniformly with benzene sulfonyl chloride；Then divide 5 times and 318.5 grams are put into in stainless steel ball grinding machine
（7.9625 mol）Solid NaOH, adds every time after NaOH and grinds material 3 ~ 7 minutes, and keeps the temperature of reactant to be less than 60
DEG C, continue to grind 15 minutes；Reaction from ball mill moves on to reactant after terminating in 5 liters of three-necked bottle, in the reactant plus
Enter the ethyl acetate of 15 times of its quality, load onto condenser, heat, stir, flow back 30 minutes, heat filtering, by the solid in funnel
The ethyl acetate of thing heat is washed three times, is filtered to remove the NaCl of generation, merging filtrate；Finally filtrate is steamed prior to heating under normal pressure
Evaporate concentration, after boiling off 2/3 solvent, will under leftover materials room temperature cooling, crystallization and filtration, be precipitated thing, the sediment in
Temperature is dry under the conditions of 95 DEG C, obtains final product 877 grams of dibenzenesulfonimide product, and yield is 92.8%, and purity is 98.2%.
In above-described embodiment 1 ~ 7, the container used by griding reaction is ball mill or its texturing machine.
Claims (3)
1. a kind of method that solvent-free polishing prepares dibenzenesulfonimide, it is characterised in that：First by benzsulfamide with it is pure
Benzene sulfonyl chloride is put into grinding in ball grinder, benzsulfamide is sufficiently mixed at room temperature uniformly with benzene sulfonyl chloride；Then in batches to
Solid NaOH is put into ball mill to continue to grind, and keeps the temperature of reactant to be less than 60 DEG C；Reaction terminate after by reactant from
Remove in the ball mill, the reactant organic solvent of 3 ~ 15 times of its quality dissolves, and is filtered to remove the NaCl of generation, obtains
Filtrate；Finally the concentrating filter liquor is crystallized, filter, be dried, obtain final product product；The benzsulfamide, the benzene sulfonyl chloride and
The mol ratio of the NaOH is 1：1~2：1~2.5.
2. the method that a kind of solvent-free polishing as claimed in claim 1 prepares dibenzenesulfonimide, it is characterised in that：It is described
Organic solvent is any one in methyl alcohol, ethanol, dichloromethane, ethyl acetate.
3. the method that a kind of solvent-free polishing as claimed in claim 1 prepares dibenzenesulfonimide, it is characterised in that：It is described
Dry condition refers to that temperature is 70 ~ 100 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110950783A (en) * | 2019-11-23 | 2020-04-03 | 苏州华道生物药业股份有限公司 | Solid phase synthesis method of N-butyl benzene sulfonamide |
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| JP2008266155A (en) * | 2007-04-17 | 2008-11-06 | Asahi Kasei Corp | Method for producing sulfonimide lithium salt |
| CN101671285A (en) * | 2009-09-29 | 2010-03-17 | 武汉风帆化工有限公司 | Preparation method of BBI |
| WO2016009448A1 (en) * | 2014-07-15 | 2016-01-21 | Srf Limited | Process for the preparation of dibenzenesulfonimide |
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2016
- 2016-11-17 CN CN201611010415.2A patent/CN106631916B/en active Active
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| JP2008266155A (en) * | 2007-04-17 | 2008-11-06 | Asahi Kasei Corp | Method for producing sulfonimide lithium salt |
| CN101671285A (en) * | 2009-09-29 | 2010-03-17 | 武汉风帆化工有限公司 | Preparation method of BBI |
| WO2016009448A1 (en) * | 2014-07-15 | 2016-01-21 | Srf Limited | Process for the preparation of dibenzenesulfonimide |
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| DYNESEN, EYLIF ET AL: "Electron-impact studies. XXI. The Mass spectra of sulfonamides and sulfonyl chlorides. The Formation of carbon-oxygen and carbon-nitrogen bonds upon electron impact", 《JOURNAL OF THE CHEMICAL SOCIETY [SECTION] B: PHYSICAL ORGANIC》 * |
| MANESH, ABBAS AMINI ET AL: "N-Bromo-(4-methylphenyl) sulfonimide: a mild and efficient reagent for oxidative deoximation of oximes under microwave irradiations", 《ASIAN JOURNAL OF CHEMISTRY》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110950783A (en) * | 2019-11-23 | 2020-04-03 | 苏州华道生物药业股份有限公司 | Solid phase synthesis method of N-butyl benzene sulfonamide |
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