CN106631916B - A kind of method that solvent-free polishing prepares dibenzenesulfonimide - Google Patents
A kind of method that solvent-free polishing prepares dibenzenesulfonimide Download PDFInfo
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- CN106631916B CN106631916B CN201611010415.2A CN201611010415A CN106631916B CN 106631916 B CN106631916 B CN 106631916B CN 201611010415 A CN201611010415 A CN 201611010415A CN 106631916 B CN106631916 B CN 106631916B
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- benzsulfamide
- benzene sulfonyl
- dibenzenesulfonimide
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- 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 present invention relates to a kind of methods that solvent-free polishing prepares dibenzenesulfonimide, are put into ball mill benzsulfamide with pure benzene sulfonyl chloride grind first, are sufficiently mixed benzsulfamide and benzene sulfonyl chloride at room temperature uniformly；Then solid NaOH is put into ball mill in batches to continue to grind, and keep the temperature of reactant lower than 60 DEG C；Reactant is removed from the ball mill after reaction, which is dissolved with organic solvent, is filtered to remove the NaCl of generation, is obtained filtrate；Finally by concentrating filter liquor crystallization, filtering, drying to get product.Solvent is not needed in the entire reaction process of the present invention, the pollution to environment is reduced, reduces production cost.Whole preparation process atom utilization is high, meets atom economy and environmentally protective theory, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation methods of dibenzenesulfonimide more particularly to a kind of solvent-free polishing to prepare double benzene
The method of sulfimide.
Background technique
Dibenzenesulfonimide (abbreviation BBI) is the important organic chemical industry's nickel softening agent of one kind, resists miscellaneous dose.In electroplating industry
In, it replaces saccharin to make first brightener with it, has and flatten the advantages of effect is good, and consumption is less than saccharin.In addition, in recent years with
Electrophilic fluorination reagent --- N- fluoro-diphenyl sulfimide organic fluorination reaction in extensive use, as preparation N- fluorine
For the primary raw material of dibenzenesulfonimide, the demand of BBI is further increased.The side of the synthesis BBI to have registered in document at present
Method mainly include the following types:
Chemical Engineer reports in 11 phases page 59 in 2009, with the benzsulfamide of benzene sulfonyl chloride and twice of equivalent, works as twice
The sodium hydroxide of amount reacts at 55 DEG C in aqueous solution, obtains dibenzenesulfonimide with 72% yield.This method benzsulfamide and
The dosage of sodium hydroxide is all larger, low yield.
Org. Lett. is reported in 2009,11,1147, benzene sulfonyl chloride and benzsulfamide is existed in tetrahydrofuran
It is reacted in the presence of NaH, dibenzenesulfonimide can be obtained.NaH and tetrahydrofuran price are all more expensive in this method, and it is raw to be not suitable for industry
It produces.
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 reacts required maximum temperature up to 100 ~ 105 although yield is higher in the method
DEG C, benzene sulfonyl chloride meets water very facile hydrolysis under high temperature.
Chem. Eur. J. reports benzene sulfonyl chloride and benzsulfamide in 2013,19,16910, deposits in Et3N and DMAP
Under, dibenzenesulfonimide can be made in reaction in methylene chloride, but Et3N and DMAP used in reaction is more expensive, no
It is suitble to industrial production dibenzenesulfonimide.
It is reported in WO2016009448A1 within 2016, the benzene with acetonitrile as solvents, more than benzene sulfonyl chloride and twice of equivalent
Sulfonamide reacts the dibenzenesulfonimide that can be made under the action of Et3N, and benzsulfamide dosage is big in the method, acetonitrile and Et3N
It is all more expensive, be not suitable for industrial production.
The method of made as described above dibenzenesulfonimide, mostly using alkali or solvent costly, although some are used
Cheap NaOH is alkali, but will use water as solvent, and benzene sulfonyl chloride is caused to hydrolyze during the reaction, is generated after the reaction was completed big
Waste water is measured, environmental pollution is caused.
It is well known that solvent-free organic synthesis avoids in reaction process solvent to environment because it does not use solvent
Pollution, while reducing production cost again.In addition, due to the intervention of not no solvent, it has reacts not with conventional solution
Same molecule environment, thus there is a possibility that rate, selectivity and the conversion ratio of reaction are improved.This kind of reaction can be by grinding
The succinct technology such as mill, microwave radiation, Ultrasonic Radiation, oscillation and illumination is realized.It is solvent-free to have based on the above plurality of advantages
Machine synthetic reaction has obtained the concern of synthesis chemist in recent years.
Summary of the invention
Technical problem to be solved by the invention is to provide it is a kind of it is easy to operate, atom utilization is high, environmental pollution is small, at
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,
It is characterized in that: benzsulfamide being put into ball mill with pure benzene sulfonyl chloride grind first, benzsulfamide and benzene sulfonyl chloride is made to exist
It is sufficiently mixed at room temperature uniformly；Then solid NaOH is put into ball mill in batches to continue to grind, and keep the temperature of reactant
Lower than 60 DEG C；Reactant is removed from the ball mill after reaction, the reactant is organic molten with 3 ~ 15 times of its quality
Agent dissolution, is filtered to remove the NaCl of generation, obtains filtrate；Finally by concentrating filter liquor crystallization, filtering, drying to get production
Product；The molar ratio of the benzsulfamide, the benzene sulfonyl chloride and the NaOH is 1:1 ~ 2:1 ~ 2.5.
The organic solvent is methanol, ethyl alcohol, methylene chloride, any one in ethyl acetate.
The condition of the drying refers to that temperature is 70 ~ 100 DEG C.
Compared with the prior art, the present invention has the following advantages:
1, the reaction between benzsulfamide of the present invention, benzene sulfonyl chloride and solid NaOH is solvent-free griding reaction, is reacted
Solvent is not needed in journey, reduces the pollution to environment, while reducing production cost again.Reactional equation is as follows:
2, organic solvent used when present invention dissolution, purified product can recycle repeatedly, thus further reduced
Production cost.
3, whole process of the present invention only generates a small amount of solid NaCl, and purity is higher, can be directly used as industrial
NaCl.Therefore, not only easy to operate, and whole preparation process atom utilization is high, meet atom economy and environmentally protective
Theory is suitble to industrialized production.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is the HPLC spectrogram of 1 products obtained therefrom of the embodiment of the present invention.
Specific embodiment
The following is a preferred embodiment of the present invention, and what the present invention was protected is not limited only to following preferred implementation side
Formula.To those skilled in the art on the concept of the invention, around the solvent-free reaction of benzsulfamide and benzene sulfonyl chloride
Several improvement for preparing dibenzenesulfonimide are made, protection scope of the present invention is belonged to.
A kind of method that solvent-free polishing prepares dibenzenesulfonimide of embodiment 1, first by 500 grams (3.185 mol)
Benzsulfamide and 589 grams of (3.344 mol) pure benzene sulfonyl chlorides are put into the stainless steel ball grinding machine that volume is 5 liters and grind 5 minutes,
It is sufficiently mixed benzsulfamide and benzene sulfonyl chloride at room temperature uniformly；Then divide 5 times and put into 140 grams into stainless steel ball grinding machine
Material is ground 3 ~ 7 minutes after NaOH is added every time, and keeps the temperature of reactant lower than 60 DEG C by (3.5 mol) solid NaOH,
Continue grinding 15 minutes；After reaction by reactant from the three-necked bottle for moving on to 5 liters in ball mill, it is added in the reactant
The methanol that 10 times of quality loads onto condenser, heating, stirring, reflux 30 minutes, heat filtering, by the solids heat in funnel
Methanol washes the NaCl for being filtered to remove generation three times, merging filtrate；Finally filtrate is boiled off prior to heating distillation and concentration under normal pressure
After 2/3 solvent, by surplus material, cooling at room temperature, crystallization and filtration, obtains sediment, which is 70 DEG C of items in temperature
It is dried under part to get 870 grams of dibenzenesulfonimide product, yield 92%, purity 99.4%.
Products obtained therefrom is carried out respectively1H NMR and13C NMR detection, determines 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, the results showed that its purity is 99.4%(referring to Fig. 1).
A kind of method that solvent-free polishing prepares dibenzenesulfonimide of embodiment 2, first by 500 grams (3.185 mol)
Benzsulfamide and 563 grams of (3.185 mol) pure benzene sulfonyl chlorides are put into the stainless steel ball grinding machine that volume is 5 liters and grind 5 minutes,
It is sufficiently mixed benzsulfamide and benzene sulfonyl chloride at room temperature uniformly；Then divide 5 times and put into 127 grams into stainless steel ball grinding machine
Material is ground 3 ~ 7 minutes after NaOH is added every time, and keeps the temperature of reactant lower than 60 by (3.185 mol) solid NaOH
DEG C, continue grinding 15 minutes；After reaction by reactant from the three-necked bottle for moving on to 5 liters in ball mill, add in the reactant
The methanol for entering 3 times of its quality loads onto condenser, heating, stirring, reflux 30 minutes, heat filtering, by the solids heat in funnel
Methanol wash the NaCl for being filtered to remove generation three times, merging filtrate；Finally filtrate is steamed prior to heating distillation and concentration under normal pressure
After removing 2/3 solvent, by surplus material, cooling at room temperature, crystallization and filtration, obtains sediment, which is 100 in temperature
It is dried under the conditions of DEG C to get 643 grams of benzenesulfonimide product, yield 68%, purity 97.5%.
A kind of method that solvent-free polishing prepares dibenzenesulfonimide of embodiment 3, first by 500 grams (3.185 mol)
Benzsulfamide and 729 grams of (4.14 mol) pure benzene sulfonyl chlorides are put into the stainless steel ball grinding machine that volume is 5 liters and grind 5 minutes,
It is sufficiently mixed benzsulfamide and benzene sulfonyl chloride at room temperature uniformly；Then divide 5 times and put into 171 grams into stainless steel ball grinding machine
Material is ground 3 ~ 7 minutes after NaOH is added every time, and keeps the temperature of reactant lower than 60 DEG C by (4.3 mol) solid NaOH,
Continue grinding 15 minutes；After reaction by reactant from the three-necked bottle for moving on to 5 liters in ball mill, it is added in the reactant
The methanol that 5 times of quality loads onto condenser, heating, stirring, reflux 30 minutes, heat filtering, by the first of the solids heat in funnel
Alcohol washes the NaCl for being filtered to remove generation three times, merging filtrate；Filtrate is finally boiled off 2/3 prior to heating distillation and concentration under normal pressure
Solvent after, by surplus material cooling, crystallization and filtration at room temperature, obtain sediment, which is 80 DEG C of conditions in temperature
Lower drying is to get 872 grams of dibenzenesulfonimide product, yield 92.2%, purity 97.8%.
A kind of method that solvent-free polishing prepares dibenzenesulfonimide of embodiment 4, first by 500 grams (3.185 mol)
Benzsulfamide and 589 grams of (3.344 mol) pure benzene sulfonyl chlorides are put into the stainless steel ball grinding machine that volume is 5 liters and grind 5 minutes,
It is sufficiently mixed benzsulfamide and benzene sulfonyl chloride at room temperature uniformly；Then divide 5 times and put into 196 grams into stainless steel ball grinding machine
Material is ground 3 ~ 7 minutes after NaOH is added every time, and keeps the temperature of reactant lower than 60 DEG C by (4.9 mol) solid NaOH,
Continue grinding 15 minutes；After reaction by reactant from the three-necked bottle for moving on to 5 liters in ball mill, it is added in the reactant
The methanol that 12 times of quality loads onto condenser, heating, stirring, reflux 30 minutes, heat filtering, by the solids heat in funnel
Methanol washes the NaCl for being filtered to remove generation three times, merging filtrate；Finally filtrate is boiled off prior to heating distillation and concentration under normal pressure
After 2/3 solvent, by surplus material, cooling at room temperature, crystallization and filtration, obtains sediment, which is 90 DEG C of items in temperature
It is dried under part to get 865 grams of dibenzenesulfonimide product, yield 90%, purity 98.0%.
A kind of method that solvent-free polishing prepares dibenzenesulfonimide of embodiment 5, first by 500 grams (3.185 mol)
Benzsulfamide and 840 grams of (4.775 mol) pure benzene sulfonyl chlorides are put into the stainless steel ball grinding machine that volume is 5 liters and grind 5 minutes,
It is sufficiently mixed benzsulfamide and benzene sulfonyl chloride at room temperature uniformly；Then divide 5 times and put into 204 grams into stainless steel ball grinding machine
Material is ground 3 ~ 7 minutes after NaOH is added every time, and keeps the temperature of reactant lower than 60 by (5.096 mol) solid NaOH
DEG C, continue grinding 15 minutes；After reaction by reactant from the three-necked bottle for moving on to 5 liters in ball mill, add in the reactant
The ethyl alcohol for entering 13 times of its quality loads onto condenser, and heating, stirring, reflux 30 minutes, heat filtering uses the solids in funnel
The ethyl alcohol of heat washes the NaCl for being filtered to remove generation three times, merging filtrate；Finally by filtrate prior to heating distillation and concentration under normal pressure,
After boiling off 2/3 solvent, by surplus material, cooling at room temperature, crystallization and filtration, obtains sediment, which is 75 in temperature
It is dried under the conditions of DEG C to get 869 grams of dibenzenesulfonimide product, yield 92%, purity 98.0%.
A kind of method that solvent-free polishing prepares dibenzenesulfonimide of embodiment 6, first by 500 grams (3.185 mol)
Benzsulfamide and 1009 grams of (5.733 mol) pure benzene sulfonyl chlorides, which are put into the stainless steel ball grinding machine that volume is 5 liters, grinds 5 points
Clock is sufficiently mixed benzsulfamide and benzene sulfonyl chloride at room temperature uniformly；Then divide 5 times and put into 255 into stainless steel ball grinding machine
Material is ground 3 ~ 7 minutes after NaOH is added every time, and keeps the temperature of reactant lower than 60 by gram (6.37 mol) solid NaOH
DEG C, continue grinding 15 minutes；After reaction by reactant from the three-necked bottle for moving on to 5 liters in ball mill, add in the reactant
The methylene chloride for entering 10 times of its quality loads onto condenser, heating, stirring, reflux 30 minutes, heat filtering, by the solid in funnel
The methylene chloride of object heat washes the NaCl for being filtered to remove generation three times, merging filtrate；Finally filtrate is steamed prior to heating under normal pressure
Evaporate concentration, after boiling off 2/3 solvent, by surplus material cooling, crystallization and filtration at room temperature, obtain sediment, the sediment in
Temperature is dried under the conditions of being 85 DEG C to get 879 grams of dibenzenesulfonimide product, yield 93%, purity 98.0%.
A kind of method that solvent-free polishing prepares dibenzenesulfonimide of embodiment 7, first by 500 grams (3.185 mol)
Benzsulfamide and 1121 grams of (6.37 mol) pure benzene sulfonyl chlorides are put into the stainless steel ball grinding machine that volume is 5 liters and grind 5 minutes,
It is sufficiently mixed benzsulfamide and benzene sulfonyl chloride at room temperature uniformly；Then divide 5 times and put into 318.5 grams into stainless steel ball grinding machine
Material is ground 3 ~ 7 minutes after NaOH is added every time, and keeps the temperature of reactant lower than 60 by (7.9625 mol) solid NaOH
DEG C, continue grinding 15 minutes；After reaction by reactant from the three-necked bottle for moving on to 5 liters in ball mill, add in the reactant
The ethyl acetate for entering 15 times of its quality loads onto condenser, heating, stirring, reflux 30 minutes, heat filtering, by the solid in funnel
The ethyl acetate of object heat washes the NaCl for being filtered to remove generation three times, merging filtrate；Finally filtrate is steamed prior to heating under normal pressure
Evaporate concentration, after boiling off 2/3 solvent, by surplus material cooling, crystallization and filtration at room temperature, obtain sediment, the sediment in
Temperature is dried under the conditions of being 95 DEG C to get 877 grams of dibenzenesulfonimide product, yield 92.8%, purity 98.2%.
In above-described embodiment 1 ~ 7, container used in griding reaction is ball mill or its texturing machine.
Claims (1)
1. a kind of method that solvent-free polishing prepares dibenzenesulfonimide, it is characterised in that: first by benzsulfamide and pure
Benzene sulfonyl chloride is put into ball mill and grinds, and is sufficiently mixed benzsulfamide and benzene sulfonyl chloride at room temperature uniformly；Then in batches to
Solid NaOH is put into ball mill to continue to grind, and keeps the temperature of reactant lower than 60 DEG C；After reaction by reactant from
It is removed in the ball mill, which is dissolved with 3 ~ 15 times of its quality of organic solvent, is filtered to remove the NaCl of generation, is obtained
Filtrate；Finally by concentrating filter liquor crystallization, filtering, drying to get product；The benzsulfamide, the benzene sulfonyl chloride and
The molar ratio of the NaOH is 1:1 ~ 2:1 ~ 2.5；The organic solvent is methanol, ethyl alcohol, methylene chloride, appointing in ethyl acetate
It anticipates one kind；The condition of the drying refers to that temperature is 70 ~ 100 DEG C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| JP2008266155A (en) * | 2007-04-17 | 2008-11-06 | Asahi Kasei Corp | Method for producing sulfonimide lithium salt |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Electron-impact studies. XXI. The Mass spectra of sulfonamides and sulfonyl chlorides. The Formation of carbon-oxygen and carbon-nitrogen bonds upon electron impact;Dynesen, Eylif et al;《Journal of the Chemical Society [Section] B: Physical Organic》;19681231(第1期);15-21 |
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