CN107074753A - The manufacture method of (fluorine sulphonyl) perfluoro alkane sulfimide salt - Google Patents
The manufacture method of (fluorine sulphonyl) perfluoro alkane sulfimide salt Download PDFInfo
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- CN107074753A CN107074753A CN201580058448.1A CN201580058448A CN107074753A CN 107074753 A CN107074753 A CN 107074753A CN 201580058448 A CN201580058448 A CN 201580058448A CN 107074753 A CN107074753 A CN 107074753A
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
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Abstract
[problem] provides (fluorine sulphonyl) perfluoro alkane sulfimide salt with high selectivity and in high yield.[solution] passes through manufacture of such as getting off (fluorine sulphonyl) perfluoro alkane sulfimide salt：Perfluoro alkane sulfonic acid halide is reacted with ammonia in a solvent, thus obtain the solution (the 1st process) comprising perfluoro alkane sulfonamide ammonium salt and ammonium halide；Obtained solution is filtered out, thus separated ammonium halide contained in the solution except (the 2nd process)；Organic base is added to the obtained solution comprising perfluoro alkane sulfonamide ammonium salt, so as to be included the solution (the 3rd process) of " salt of perfluoro alkane sulfonamide and organic base " and ammonia；Vikane (the 4th process) is added into obtained solution.
Description
Technical field
The present invention relates to the manufacture method of (fluorine sulphonyl) perfluoro alkane sulfimide salt.
Background technology
(fluorine sulphonyl) perfluoro alkane sulfimide salt is used as cell electrolyte solvent, acid catalyst, ionic liquid, anti-quiet
Electric agent is useful material.
It is used as the manufacture method of (fluorine sulphonyl) perfluoro alkane sulfimide class, it is known that make perfluoro alkane sulfonamide and vikane
The method (patent document 1) of reaction, make perfluoro alkane sulfonamide and fluorosulfuric acid, the method (patent document 2) of sulfur trioxide reaction,
Make method (patent document 3) that perfluoro alkane sulfonamide and fluorosulfuric acid, thionyl chloride react or make perfluoro alkane isocyanates with
Sulfur trioxide, the method (patent document 4) of ammonium fluoride reaction.
Prior art literature
Patent document
Patent document 1：No. 5874616 specifications of U.S. Patent No.
Patent document 2：No. 2011/148961 publication of International Publication
Patent document 3：No. 2011/148958 publication of International Publication
Patent document 4：Japanese Unexamined Patent Publication 2012-162470 publications
The content of the invention
Problems to be solved by the invention
The method of patent document 1 is preferred method, but yield is as little as moderate (55%), is not necessarily efficient.
For the method for patent document 2, patent document 3, sulfuric acid, hydrochloric acid due to by-product, reaction solution is in acidity, (fluorine sulphur
Acyl) perfluoro alkane sulfimide has the possibility of decomposition, therefore can not be said to be preferred method.
It should be noted that the method for patent document 2, patent document 3 and patent document 4 is due to using the high fluorine of toxicity
The dangerous sulfur trioxide of sulfuric acid, processing, therefore be also difficult to be adopted as industrially preparing process.
The solution used to solve the problem
Therefore, the present inventor etc. have made intensive studies in view of the above problems, as a result find, by making to produce in reaction solution
Raw fluoroalkyl sulfonamides, accessory substance ammonium fluoride is removed, so as to get solution reacted with organic base and vikane, so as to close
Into (fluorine sulphonyl) perfluoro alkane sulfimide salt, so as to complete the present invention.
That is, the present invention provides the technical scheme described in following [technical scheme 1]-[technical scheme 6].
[technical scheme 1]
A kind of manufacture method of (fluorine sulphonyl) perfluoro alkane sulfimide salt, (fluorine sulphonyl) the perfluoro alkane sulfimide
Salt by formula [1] represent,
[in formula, RfThe perfluoroalkyl of the straight or branched of carbon number 1~6 is represented, B represents organic base]
The manufacture method is characterised by, including following process：
[the 1st process]
In the presence of the solvent, the perfluoro alkane sulfonic acid halide and ammonia (NH shown in formula [2] are made3) reaction, thus included
The process of the solution of perfluoro alkane sulfonamide ammonium salt and ammonium halide.
RfSO2X [2]
[in formula, RfThe perfluoroalkyl of the straight or branched of carbon number 1~6 is represented, X represents halogen atom]
[the 2nd process]
The solution obtained in 1st process is filtered out, thus ammonium halide contained in the solution is separated and removed, is obtained
The process of solution comprising perfluoro alkane sulfonamide ammonium salt.
[the 3rd process]
Organic base is added to the solution comprising perfluoro alkane sulfonamide ammonium salt obtained in the 2nd process, " perfluor is included
The solution of the salt of alkane sulfonamide and organic base " and ammonia, then separates ammonia the process removed from the solution.
[the 4th process]
In the presence of organic base, to obtained from ammonia separation is removed in the 3rd process comprising " perfluoro alkane sulfonamide with
The solution addition vikane of the salt of organic base ", so as to obtain the process of (fluorine sulphonyl) perfluoro alkane sulfimide salt.
[technical scheme 2]
Manufacture method according to technical scheme 1, wherein, in the 1st process, solvent is acetonitrile, propionitrile, dimethyl Asia
Sulfone, sultone, diethylene glycol dimethyl ether, tetrahydrofuran or dimethylformamide.
[technical scheme 3]
Manufacture method according to technical scheme 1 or 2, wherein, in the 1st process, reaction temperature is 0 DEG C~100 DEG C.
[technical scheme 4]
Manufacture method according to technical scheme 1, wherein, in the 2nd process, temperature when filtering out is 10 DEG C~80
℃。
[technical scheme 5]
Manufacture method according to technical scheme 1, it is characterised in that in the 3rd process, to including " perfluoro alkane sulphur
The solution of the salt of acid amides and organic base " and ammonia by ammonia separated from the solution except when, in 0.02MPa~0.1MPa pressure strip
Heated under part, at 20 DEG C~80 DEG C.
[technical scheme 6]
The manufacture method of (fluorine sulphonyl) perfluoro alkane sulfimide acid metal salt shown in formula [3], it is characterised in that pass through
Any one of technical scheme 1~5 manufactures (fluorine sulphonyl) perfluoro alkane sulfimide salt, then, makes (fluorine sulphonyl) the perfluor alkane
The hydroxide or carbonate reaction of the hydroxide or carbonate or alkaline-earth metal of hydrocarbon sulfimide salt and alkali metal,
[in formula [3], RfIt is identical with the formula [1] of technical scheme 1.M represents alkali metal or alkaline-earth metal.N is represented and the metal
The equal integer of valence mumber.]
The present invention especially has feature on the 2nd process is combined.Then carried out under conditions of it will not carry out the 2nd process
In the case of 3rd process and the 4th process, become in reaction system containing ammonium halide.Judge to carry out being used as this hair under this condition
During 4 process of bright final process, the double fluorine sulfimides of generation accessory substance, it is impossible to which purity is obtained as target product well
(fluorine sulphonyl) perfluoro alkane sulfimide salt (with reference to comparative example described later).
Therefore the present inventor etc. has found, by being filtered to the solution obtained in the 1st process, by contained by the solution
Ammonium halide is separated except organic base (the 3rd process) is added in (the 2nd process), the filtrate then obtained into the 2nd process, thus shape
Into " salt of perfluoro alkane sulfonamide and organic base ", itself and vikane reaction (the 4th process) are made to the salt that this is obtained, so that with height
Yield obtains (fluorine sulphonyl) perfluoro alkane sulfimide salt as target product.
In addition, also obtaining following opinion：By the hydroxide for making (fluorine sulphonyl) perfluoro alkane sulfimide salt and alkali metal
The hydroxide reaction of thing or alkaline-earth metal, can easily derive as (fluorine sulphonyl) perfluoro alkane sulphonyl Asia shown in formula [3]
Amino acid metal salt.
The inventive point of the present invention is that it is possible to the manufacturing objective product under not separation of intermediates perfluoro alkane sulfonamide
(fluorine sulphonyl) perfluoro alkane sulfimide salt；The organic solvent used in the 1st process and need not be removably can directly be used
Using until the 4th process etc., industrially preparing process is easily adopted as, it may be said that be extremely beneficial method.
The effect of invention
The present invention plays following effect：Can discarded object be few without the separation of the perfluoro alkane sulfonamide of each process
Favourable (fluorine sulphonyl) perfluoro alkane sulfimide salt in ground process industry.
Embodiment
Hereinafter, the present invention is explained.Embodiments of the present invention are illustrated below, but the present invention is not limited
In following embodiment, the general knowledge based on those skilled in the art it can fit in the range of do not damage the purport of the present invention
Preferably implement.
Manufacture method of the invention for (fluorine sulphonyl) perfluoro alkane sulfimide salt, including following process：Make perfluoro alkane
Sulfonic acid halide reacts with ammonia in a solvent, thus obtains the solution (the 1st process) comprising perfluoro alkane sulfonamide ammonium salt and ammonium halide；
Then the solution obtained in the 1st process is filtered out, thus ammonium halide contained in the solution is separated and removed, comprising
The solution (the 2nd process) of perfluoro alkane sulfonamide ammonium salt；Then perfluoro alkane sulfonamide ammonium salt is included to what is obtained in the 2nd process
Solution addition organic base, so that the solution of " salt of perfluoro alkane sulfonamide and organic base " and ammonia is included, then by ammonia
Separated from the solution except (the 3rd process)；Then in the presence of organic base, the solution obtained in the 3rd process is added
Vikane, so as to obtain (the 4th process) of (fluorine sulphonyl) perfluoro alkane sulfimide salt.
Also include following manufacture method：Then (fluorine sulphonyl) perfluoro alkane sulphur that the method by the 1st~4 process is manufactured is made
The hydroxide reaction of the hydroxide or alkaline-earth metal of imide salts and alkali metal, thus obtains (the fluorine sulphur shown in formula [3]
Acyl) perfluoro alkane sulfimide acid metal salt, illustrate in detail below.
<1st process>
First, the 1st process is illustrated.1st process is to make perfluoro alkane sulfonic acid halide and ammonia in the presence of the solvent
(NH3) reaction, thus obtain the process (circuit 1) of the solution comprising perfluoro alkane sulfonamide ammonium salt and ammonium halide.
Circuit 1
The perfluoro alkane sulfonic acid halide used in this process can use the perfluoro alkane sulphur of the straight or branched of carbon number 1~6
Carboxylic acid halides, preferably carbon number 1~4, particularly preferred carbon number 1 (trifluoromethyl).As specific compound, it can include：Fluoroform
Sulfuryl fluoride, pentafluoroethane sulfuryl fluoride, heptafluoro-propane sulfuryl fluoride, nine fluorine butane sulfuryl fluorides, trifluoromethanesulfonyl chloride, pentafluoroethane sulphur
Acyl chlorides, heptafluoro-propane sulfonic acid chloride, nine fluorine butane sulfonic acid chlorides, fluoroform sulfonic acid bromide, pentafluoroethane sulfonic acid bromide, heptafluoro-propane sulphonyl
Bromine, nine fluorine butane sulfonic acid bromides, fluoroform sulfonic acid iodide, pentafluoroethane sulfonic acid iodide, heptafluoro-propane sulfonic acid iodide, nine fluorine butane sulfonic acid iodides
Deng.
Wherein, preferably fluoroform sulfuryl fluoride, pentafluoroethane sulfuryl fluoride, heptafluoro-propane sulfuryl fluoride, trifluoromethanesulfonyl chloride,
Pentafluoroethane sulfonic acid chloride, heptafluoro-propane sulfonic acid chloride, fluoroform sulfonic acid bromide, pentafluoroethane sulfonic acid bromide, heptafluoro-propane sulfonic acid bromide, three
Fluoromethane sulfonic acid iodide, pentafluoroethane sulfonic acid iodide, heptafluoro-propane sulfonic acid iodide, particularly preferred fluoroform sulfuryl fluoride, pentafluoroethane sulphur
Acyl fluorides, trifluoromethanesulfonyl chloride, pentafluoroethane sulfonic acid chloride, fluoroform sulfonic acid bromide, pentafluoroethane sulfonic acid bromide, fluoroform sulphonyl
Iodine, pentafluoroethane sulfonic acid iodide (circuit 1).
For the consumption of the ammonia used in this process, relative to 1 mole of perfluoro alkane sulfonic acid halide, needed in stoichiometry for
3 moles, usually 3~10 moles, preferably suitably selected from 3~5 moles.If fewer than 3 moles, as reaction yield
The reason for reduction.Even if in addition, using more than 10 moles, the progress to reaction also has no problem, but reaction speed, yield,
Or the aspect of economy does not have special advantage.It should be noted that for the ammonia that is used in this process its own, monomer (NH3；
Anhydrous ammonia) or be dissolved in the material (ammoniacal liquor etc.) that water equal solvent obtains and can use.
The solvent used in this process is excellent usually using the polar solvent not reacted with ammonia, perfluoro alkane sulfonic acid halide
Select acetonitrile, propionitrile, dimethyl sulfoxide (DMSO), sultone, diethylene glycol dimethyl ether, tetrahydrofuran, dimethylformamide, particularly preferred second
The nitrile series solvents such as nitrile, propionitrile.
As the consumption of solvent, it is not particularly limited, as long as relative to 1 mole of use 0.1L (liter) of perfluoro alkane sulfonic acid halide
More than, it is usually preferred to 0.1~20L, particularly more preferably 0.1~10L.
As temperature conditionss, it is not particularly limited, as long as the scope at -50~200 DEG C is carried out.Generally preferable 0~
100 DEG C, particularly more preferably 0~70 DEG C.
If the temperature less than -50 DEG C, then reaction speed is slack-off, if the temperature more than 200 DEG C, then also send out sometimes
Produce decomposition of thing etc..
As pressure condition, it is not particularly limited, as long as being 0.02MPa~3MPa (absolute for example under decompression~pressurization
Pressure.It is same as below.) scope carry out, in such a situation it is preferred to 0.02MPa~2MPa, particularly more preferably
0.02MPa~1MPa.
As the reaction vessel used in reaction, monel metal, Hastelloy, nickel or with this can be included
The fluororesin such as a little metal, polytetrafluoroethylene (PTFE), PFPE resins are pressure-resistant reaction vessel of lining etc..
As the reaction time, it is not particularly limited, as long as the scope at 0.1~24 hour is carried out, due to because of matrix
And reaction condition and it is different, therefore preferably by analysis means such as gas-chromatography, liquid chromatogram, NMR, the carry out situation to reaction is entered
Row is followed the trail of, and terminal is used as at the time of the perfluoro alkane sulfonic acid halide as raw material is disappeared substantially.
In this process, due to while perfluoro alkane sulfonamide ammonium salt is generated, ammonium halide is also generated in reaction system
(NH4X), therefore after reaction obtained in the form of comprising the solution as the ammonium salt, ammonium halide and solvent of target product
Arrive.The raw material of the 2nd process is directly used as separating target product not from the solution in this process, from the sight of productivity ratio
It is also one of preferred mode that point, which sets out,.
<2nd process>
Then, the 2nd process is illustrated.2nd process is that the solution obtained in the 1st process is filtered out, and thus will
Contained ammonium halide, which is separated, in the solution removes, and obtains the process (circuit 2) of the solution comprising perfluoro alkane sulfonamide ammonium salt.
Circuit 2
As the embodiment for implementing to filter out and (also referred to as filter), it is not particularly limited, with the common behaviour of organic chemistry
Carry out.For example preferably centrifuge, be filtered under diminished pressure, pressure filtration, particularly preferably centrifuge, pressure filtration.
Implement preferred 10-80 DEG C, particularly preferred 30-60 DEG C of the temperature conditionss of filtering.If temperature is less than 10 DEG C, perfluor alkane
Hydrocarbon sulfonamide ammonium salt is also separated out, yield can be reduced.If in addition, the temperature more than 80 DEG C, then ammonium halide in a solvent also can be molten
Solution, it becomes difficult to separate, also as the reason for the selection rate of target product, yield can be reduced in the 4th process described later.
After this process, obtain ammonium halide and be separated the solution for including perfluoro alkane sulfonamide ammonium salt removed, but can be
The stage does not carry out purification process to the solution, and is directly used as the raw material of the 3rd process.
<3rd process>
Then, the 3rd process is illustrated.3rd process is to include perfluoro alkane sulfonamide ammonium to what is obtained in the 2nd process
The solution addition organic base of salt, so as to be included the solution of " salt of perfluoro alkane sulfonamide and organic base " and ammonia, then will
Ammonia separates the process (circuit 3) removed from the solution.
Circuit 3
The organic base used in the present invention can be included：Methylamine, dimethylamine, ethamine, diethylamine, n-propylamine, di-n-propylamine,
Isopropylamine, diisopropylamine, n-butylamine, di-n-butylamine, sec-butylamine, di-sec-butylamine, tert-butylamine, two tert-butylamines, aniline, diphenylamines etc.
Primary amine or secondary amine,
Tertiary amine shown in following formula
NR1R2R3
[in formula, R1、R2、R3It is identical or different, represent alkyl, the cycloalkanes of carbon number 3~8 of the straight or branched of carbon number 1~8
Base or aryl (part or all of the hydrogen atom of aryl can by halogen (fluorine, chlorine, bromine, iodine), the alkyl of carbon number 1~10,
Haloalkyl, the cycloalkyl of carbon number 3~8, amino, nitro, acetyl group, cyano group or the hydroxyl substitution of carbon number 1~10.).]、
Pyridine, 2,4,6- trimethylpyridines, 4-dimethylaminopyridine, lutidines (Lutidine), pyrimidine, rattle away
Piperazine, pyrazine, oxazole, isoxazole, thiazole, isothiazole, imidazoles, DMIZ 1,2 dimethylimidazole, 3- (dimethylamino) propyl imidazole, pyrrole
Azoles, furazan, quinoline, isoquinolin, purine, 1H- indazoles, quinazoline, cinnolines, quinoxaline, phthalazines, pyridine of talking endlessly, phenanthridines, the tertiary fourths of 2,6- bis-
Yl pyridines, 2,2'- bipyridyls, 4,4'- dimethyl -2,2'- bipyridyls, 4,4'- dimethyl -2,2'- bipyridyls, 5,5'- diformazans
The adjacent diaza of base -2,2'- bipyridyls, the 6,6'- tert-butyl group -2,2'- bipyridyls, 4,4'- diphenyl -2,2'- bipyridyls, 1,10-
Phenanthrene, 2,7- dimethyl -1,10- phenanthrolenes, 5,6- dimethyl -1,10- phenanthrolenes, 4,7- diphenyl -1,10- neighbours two
The nitrogenous heteroaromatic formula compound such as aza-phenanthrenes,
The imines systems such as the carbon -7- alkene of 1,8- diazabicylos [5.4.0] 11,1,5- diazabicylos [4.3.0] nonyl- 5- alkene
Alkali.
The specific example of foregoing tertiary amine be trimethylamine, triethylamine, N- ethyl diisopropylamines, Tri-n-Propylamine, tri-isopropyl amine,
Tri-n-butylamine, trioctylamine, tridecylamine, triphenylamine, tribenzylamine, tris-(2-ethylhexyl)amine, N, N- dimethyldodecyl amides, N- benzyls two
Methylamine, N- normal-butyls dimethylamine, N, N- dimethylcyclohexylam,nes, N, N, N ', N '-tetramethylethylenediamine, N, accelerine,
N, N- diethylaniline, 1,4- diazabicylos [2.2.2] octane, N- crassitudes, N- methyl piperidines, N-methylmorpholine,
N-ethylmorpholine, N, N '-lupetazin, N- methyl pipecoline (N-methylpipecoline), 1-METHYLPYRROLIDONE, N-
Vinyl-pyrrolidinone, double (2- dimethylarnino-ethyls) ethers, N, N, N, N', N "-five methyl diethylentriamine, three ethanol
Amine, tripropanol amine, dimethylethanolamine, dimethyl amino ethoxy ethanol, N, N- dimethylaminopropyls amine, N, N, N', N',
N "-pentamethyldipropylenetriamine, three (3- dimethylaminopropyls) amine, tetramethyl imino group-bis- (propyl group amine), N- diethyl
Monoethanolamine etc..
Among these, preferably dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diphenylamines, trimethylamine,
Triethylamine, diisopropylethylamine, three n-propyl amine, tri-n-butylamine, pyridine, 2,4,6- trimethylpyridines, 4- dimethylamino pyrroles
Pyridine, lutidines, pyrimidine, pyridazine, pyrazine, the more preferably carbon -7- alkene of 1,8- diazabicylos [5.4.0] 11, diethylamine, three
Ethamine, diisopropylethylamine, tri-n-butylamine, pyridine.
The consumption of the organic base used in this process be commonly angled relative to 1 mole of perfluoro alkane sulfonamide ammonium salt be 1 mole with
On.In order that this process is successfully carried out, relative to 1 mole of perfluoro alkane sulfonamide ammonium salt, organic base is needed in stoichiometry
To be 1 mole, be also for the 4th process described later, be reacted making " salt of perfluoro alkane sulfonamide and organic base " with vikane
When, relative to 1 mole of the salt, organic base is necessary for 1 mole.Therefore in this process, it can be assumed that the 4th process described later, phase
For the organic base of 1 mole of perfluoro alkane sulfonamide ammonium salt, more than 2 moles of use.
It should be noted that if organic base is fewer than 1 mole, free, the removal of ammonia sometimes can not be carried out fully.In addition,
If using organic base more than stoichiometry, reaction speed accelerates, may shorten the time of the 3rd process, if but beyond required
Ground is excessively used, then is economically disadvantageous.Therefore, as the consumption of organic base, relative to perfluoro alkane sulfonamide ammonium salt 1
Mole, preferably 2 moles~10 moles, more preferably 2.5~5 moles.
Due to adding after organic base as reaction is carried out, ammonia is produced in reaction system, therefore in this process, for example may be used
Include and reacted in the reaction vessel with cooler, with cooler by the recovery ammonia produced together with the carrying out of reaction
Method.Its method is not particularly limited, those skilled in the art can suitably adjust.
It should be noted that when reclaiming ammonia, can be high by using reaction condition described later (temperature conditionss, pressure condition)
Reclaim ammonia in effect ground.
Reaction temperature is usually 20~80 DEG C, preferably 25~60 DEG C.If reaction temperature is less than 20 DEG C, ammonia it is free,
Removal can not be carried out fully, and the time needed for process can be elongated.On the other hand, if in the situation of the reaction temperature more than 80 DEG C
Under, then there is the worry that solvent, organic base disperse.
Pressure condition is usually 0.02MPa~0.1MPa, preferably 0.04MPa~0.08MPa.If more than the scope
Implement under reduced pressure, then can efficiency preferably remove, therefore be preferred, if but degree of decompression is excessive, solvent, organic base
It can disperse, be economically disadvantageous.
In this process, to including " salt of perfluoro alkane sulfonamide and organic base " and ammonia (NH3) solution ammonia is molten from this
Separated in liquid except when, by under 0.02MPa~0.1MPa pressure condition, heated and carried out at 20 DEG C~80 DEG C
It is one of preferred mode.
As the reaction time, it is not particularly limited, as long as the scope at 0.1~24 hour is carried out, due to because of matrix
And reaction condition and it is different, therefore preferably by analysis means such as gas-chromatography, liquid chromatogram, chromatography of ions, NMR, to reaction
Carry out situation is tracked, and terminal is used as at the time of perfluoro alkane sulfonamide ammonium salt is disappeared substantially.
In the 4th process, when the ammonium salt reacts in the state of a large amount of remain in reaction solution with vikane, pair can be caused
The yield of target product in reaction, the 4th process can be reduced, therefore the few person of unreacted perfluoro alkane sulfonamide ammonium salt is preferred
's.
As the reaction vessel used in reaction, monel metal, Hastelloy, nickel or with this can be included
The fluororesin such as a little metal, polytetrafluoroethylene (PTFE), PFPE resins are pressure-resistant reaction vessel of lining etc..
So, by this process by perfluoro alkane sulfonamide ammonium salt (RfSO2NH2·NH3) it is converted into perfluoro alkane sulfonamide
With the salt of organic base, by applying specific reaction condition, energy efficiency removes ammonia well.
It should be noted that for molten comprising " salt of perfluoro alkane sulfonamide and organic base " by what is obtained in this process
Liquid is directly used as the raw material of the 4th process, is also one of preferred mode from the viewpoint of productivity ratio.
<4th process>
Then, the 4th process is illustrated.4th process is to including for being obtained in the 3rd process in the presence of organic base
The solution addition vikane of " salt of perfluoro alkane sulfonamide and organic base ", synthesis (fluorine sulphonyl) perfluoro alkane sulfimide salt
Process (circuit 4).
Circuit 4
Because the consumption of vikane that is used in this process is relative to 1 mole of " salt of perfluoro alkane sulfonamide and organic base "
Needed in stoichiometry for 1 mole, therefore usually using more than 1 mole.But it is actual from 1 mole~10 moles, it is excellent
Select and suitably selected in 1~5 mole.
If fewer than 1 mole, the reason for being reduced as reaction yield.Even if in addition, 10 moles are used more than, to reaction
Progress also have no problem, but there is no special advantage in terms of reaction speed, yield or economy.
On organic base, can also it is possible to additionally incorporate in this process with used in the 3rd process it is same kind of organic
Alkali.For the consumption of organic base, relative to 1 mole of " salt of perfluoro alkane sulfonamide and organic base ", in terms of stoichiometry generally
It is (specific using the situation of organic base more than stoichiometry in the 3rd process for 1 mole, but described in the 3rd process as in the previous
For be relative to 1 mole of perfluoro alkane sulfonamide ammonium salt, more than 2 moles of use situation) under, in this process, in preceding process
The organic base used is remained in reaction system.It therefore, it can the addition of the organic base according to preceding process, subtract in this process
Lack the amount of organic base or newly add the desired amount of organic base.But, if using more than the amount of stoichiometry for organic base,
Then reaction speed accelerates, and may shorten the time of the 3rd process, on the other hand, if beyond being excessively used as needed, economically
It is unfavorable.Therefore, as the consumption of organic base, relative to 1 mole of perfluoro alkane sulfonamide ammonium salt, preferably 2 moles~10
Mole, more preferably 2.5~5 moles.It should be noted that if organic base is fewer than 1 mole, the free of ammonia, removal sometimes is not
Can fully it carry out.
The reaction dissolvent used in this process can use the solvent identical solvent with being used in the 1st process.Need
It is bright, for the present invention, it can be come by the process of foregoing 1st process~the 4th not carrying out replacement operator of solvent etc. especially
Implement this process.
It should be noted that in this process in addition addition solvent when solvent species and consumption, can use with
Same condition described in 1st process, does not repeat especially to record in this process.
As temperature conditionss, it is not particularly limited, as long as the scope at -50~200 DEG C is carried out.Generally preferable 0~
100 DEG C, particularly more preferably 0~70 DEG C.If the temperature less than -50 DEG C, then reaction speed is slack-off, if more than 200
DEG C temperature, then decomposition etc. of product also occurs sometimes.
As pressure condition, it is not particularly limited, as long as being 0.02MPa~3MPa scope for example under decompression~pressurization
Progress, in such a situation it is preferred to 0.02MPa~2MPa, particularly more preferably 0.02MPa~1MPa.
As the reaction vessel used in reaction, monel metal, Hastelloy, nickel or with this can be included
The fluororesin such as a little metal, polytetrafluoroethylene (PTFE), PFPE resins are pressure-resistant reaction vessel of lining etc..
As the reaction time, it is not particularly limited, as long as the scope at 0.1~24 hour is carried out, due to because of matrix
And reaction condition and it is different, therefore preferably by analysis means such as gas-chromatography, liquid chromatogram, chromatography of ions, NMR, to reaction
Carry out situation is tracked, and terminal is used as at the time of when raw material is disappeared substantially.
More than, by the way that by the process of the 1st process~the 4th, (fluorine sulphonyl) can be manufactured with industrial favourable manufacture method
Perfluoro alkane sulfimide salt.
Then, to make to obtain (fluorine sulphonyl) perfluoro alkane sulfimide salt and the hydroxide or carbonate of alkali metal,
Or the hydroxide or carbonate reaction of alkaline-earth metal, obtain (fluorine sulphonyl) perfluoro alkane sulfimidic acid gold shown in formula [3]
The method of category salt is illustrated.
Herein, in formula [3], " M " represents alkali metal or alkaline-earth metal, its hydroxide or carbonic acid with alkali metal described later
Alkali metal, alkaline-earth metal in the hydroxide or carbonate of salt or alkaline-earth metal is corresponding.And then, in formula [3], " n " is represented
The integer equal with the valence mumber of the metal.
As the hydroxide of the alkali metal used, lithium hydroxide (LiOH), sodium hydroxide (NaOH), hydrogen-oxygen can be included
Change potassium (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH)；As the carbonate of alkali metal, lithium carbonate can be included
(Li2CO3), sodium carbonate (Na2CO3), potassium carbonate (K2CO3), rubidium carbonate (Rb2CO3), cesium carbonate (Cs2CO3)；It is used as alkaline-earth metal
Hydroxide, magnesium hydroxide (Mg (OH) can be included2), calcium hydroxide (Ca (OH)2), barium hydroxide (Ba (OH)2), hydrogen-oxygen
Change strontium (Sr (OH)2)；As the carbonate of alkaline-earth metal, magnesium carbonate (MgCO can be included3), calcium carbonate (CaCO3), barium carbonate
(BaCO3), strontium carbonate (SrCO3), can preferably include lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH),
Rubidium hydroxide (RbOH), cesium hydroxide (CsOH), magnesium hydroxide (Mg (OH)2), calcium hydroxide (Ca (OH)2), barium hydroxide (Ba
(OH)2), strontium hydroxide (Sr (OH)2)。
In addition, the hydroxide or carbonate of these alkali metal or the hydroxide or carbonate of alkaline-earth metal can also
It is applied in combination one kind or two or more.During using two or more, the hydroxide and carbonate of same alkali metal are preferably used (for example
Potassium hydroxide and potassium carbonate) combination or same alkaline-earth metal hydroxide and carbonate (such as magnesium hydroxide and carbonic acid
Magnesium) combination.
The hydroxide or the consumption of carbonate of hydroxide or carbonate or alkaline-earth metal for alkali metal, relatively
In 1 mole of (fluorine sulphonyl) perfluoro alkane sulfimide salt, preferably 1 mole~5 moles, more preferably 1 mole~3 moles.
In the case of making amount more than 5 moles i.e. excessive alkali reaction, although reaction is carried out, sometimes foregoing (fluorine sulphonyl) perfluoro alkane
Sulfimide salt etc. " salt or complex compound that are formed by imidic acid and organic base " can be decomposed, and yield can be reduced.On the other hand, if than
1 mole few, then conversion ratio is reduced sometimes.
Make alkali metal hydroxide or carbonate or alkaline-earth metal hydroxide or carbonate reaction when, can make
Use solvent.In the case of for example using water as solvent, the mass % of 10 mass %~70, preferably 20 matter are generally turned into concentration
The mass % of amount %~60 mass %, more preferably 30 mass %~60 mode is added water and is advisable.If the amount of water is very few, reactant
Stirring in system becomes difficult, in addition in the case of excessive, and reacted processing becomes miscellaneous, it is necessary to bigger more anti-than usual
Answer container.
It should be noted that organic solvent than water can also be used.Ether, dioxanes, tetrahydrochysene furan can be used
Mutter, the solvent of the ethers such as ethylene glycol dimethyl ether etc..Used alternatively, it is also possible to be combined together with water.As the consumption of solvent,
Relative to (fluorine sulphonyl) perfluoro alkane sulfimide salt, generally enter from 0.5~10 times of capacity, the scope of preferably 1~7 times capacity
The suitable selection of row.But, even if organic molten using than water because using water, reaction also can be carried out fully, therefore specially
The advantage of agent is few.
Reaction temperature is not particularly limited, is usually -10 DEG C~110 DEG C, is preferably 25~80 DEG C.If less than -10 DEG C,
Following problem is then produced sometimes：Reaction will not be carried out fully, and the reason for being reduced as yield is economically disadvantageous, or instead
Speed reduction is answered to need long-time etc. untill reaction terminates.On the other hand, if more than 110 DEG C, easily producing by-product
Thing.The energy efficiency of excessive heating is poor in addition.
As the reaction time, it is not particularly limited, as long as the scope generally within 24 hours is carried out, preferably passes through
The analysis means such as chromatography of ions, NMR are tracked to the carry out situation of reaction, and end is used as at the time of stock substrate is disappeared substantially
Point.
The reactor used in this process can use the metal systems such as stainless steel, Hastelloy, monel metal
Container；By tetrafluoroethylene resin, daiflon, pvdf resin, PFA resins, acrylic resin, polyethylene tree
Fat and glass etc. internally do the reactor that container of lining etc. can fully be reacted under normal pressure or pressurization.
[embodiment]
The present invention will be described in detail by the following examples, but is not limited to these embodiments.
Embodiment 1
1st process：
Acetonitrile 300g is added in 500ml stainless steel autoclave reactor, reactor is cooled down, 5 are changed into liquid temperature
To being de-gassed in reactor after below DEG C.After degassing, anhydrous ammonia 24.7g (1.45mol) is added, then, warm 0 in the holding of side~
5 DEG C of sides are slowly added to fluoroform sulfuryl fluoride 66.3g (0.436mol).The importing of fluoroform sulfuryl fluoride terminate after with former state after
Continuous stirring 13 hours.After 13 hours, pass through19F NMR are quantified to reaction solution, and as a result trifluoromethanesulfonamide ammonium salt is
0.415mol (yield 95.1%).
2nd process：
The reaction solution obtained in 1st process is heated to after 40 DEG C, implements to be filtered under diminished pressure using paulownia mountain funnel.After filtering,
The content of the ammonium fluoride in filtrate is confirmed by chromatography of ions, is as a result 0.0046mol, it is thus identified that 99% can be removed.
3rd process：
The solution obtained in 2nd process is moved to and is provided with the reactor of Di Muluo condenser pipes, triethylamine 126g is added
(1.25mol), is heated 12 hours under 0.064~0.068MPa decompression, at 50~55 DEG C, ammonia is dissociated.After reaction, lead to
The content that chromatography of ions confirms ammonium ion is crossed, results verification from 0.42mol is reduced to 0.0007mol (slip 99.8%).
4th process：
The solution obtained in 3rd process is put into 1000ml stainless steel autoclave reactor, reactor is cooled down,
To being de-gassed in reactor after liquid temperature is changed into below 5 DEG C.After degassing, vikane is slowly added to when keeping interior warm 0~5 DEG C
63.15g(0.623mol).After the importing of vikane terminates, continue to stir 17 hours with its former state.After 17 hours, pass through19F
NMR is quantified to reaction solution, as a result obtains the second ammonium of target product three (fluorine sulphonyl) fluoroform sulphonyl with 92.3% yield
Inferior amine salt 0.404mol.
Embodiment 2
1st process：
Acetonitrile 300g is added in 500ml stainless steel autoclave reactor, reactor is cooled down, 5 are changed into liquid temperature
To being de-gassed in reactor after below DEG C.After degassing, anhydrous ammonia 24.7g (1.45mol) is added, then, warm 0 in the holding of side~
5 DEG C of sides are slowly added to pentafluoroethane sulfuryl fluoride 88.1g (0.436mol).The importing of pentafluoroethane sulfuryl fluoride terminate after with its former state
Continue to stir 69 hours.After 69 hours, pass through19F NMR are quantified to reaction solution, and as a result trifluoromethanesulfonamide ammonium salt is
0.369mol (yield 84.7%).
The process of 2nd process~the 4th：
For the 2nd process and after, reacted by method similarly to Example 1.As a result, with 77.3% receipts
Rate obtains second ammonium (fluorine sulphonyl) the pentafluoroethane sulfimide salt of target product three 0.337mol.
Embodiment 3
1st process：
Acetonitrile 200g is added in 500ml stainless steel autoclave reactor, reactor is cooled down, 5 are changed into liquid temperature
To being de-gassed in reactor after below DEG C.After degassing, anhydrous ammonia 12.3g (0.725mol) is added, then, side keeps interior temperature 0
~5 DEG C of sides are slowly added to nine fluorine butane sulfuryl fluoride 65.9g (0.218mol).The importing of nine fluorine butane sulfuryl fluorides is former with it after terminating
Sample continues to stir 22 hours.After 22 hours, pass through19F NMR are quantified to reaction solution, and as a result nine fluorine butane sulfonamide ammonium salts are
0.177mol (yield 81.2%).
The process of 2nd process~the 4th：
For the 2nd process and after, reacted by method similarly to Example 1.As a result, with 72.3% receipts
Rate obtains the fluorine butane sulfimide salt 0.157mol of the second ammonium of target product three (fluorine sulphonyl) nine.
Embodiment 4
1st process：
Acetonitrile 300g is added in 500ml stainless steel autoclave reactor, reactor is cooled down, 5 are changed into liquid temperature
To being de-gassed in reactor after below DEG C.After degassing, anhydrous ammonia 24.7g (1.45mol) is added, then, warm 0 in the holding of side~
5 DEG C of sides are slowly added to fluoroform sulfuryl fluoride 66.3g (0.436mol).The importing of fluoroform sulfuryl fluoride terminate after with its former state
Continue to stir 18 hours.After 18 hours, pass through19F NMR are quantified to reaction solution, and as a result trifluoromethanesulfonamide ammonium salt is
0.415mol (yield 95.1%).
2nd process：
To the reaction solution obtained in the 1st process, implement to be filtered under diminished pressure at room temperature, using paulownia mountain funnel, obtain filtrate
400g.Pass through19F NMR are quantified, trifluoromethanesulfonamide containing 0.415mol in the filtered filtrate of results verification
Ammonium salt.It is as a result 0.0112mol in addition, confirming the content of the ammonium fluoride in filtered filtrate by chromatography of ions, it is thus identified that
97% can be removed.
The process of 3rd process~the 4th：
For the 3rd process and after, except using diethylamine 91.4g (1.25mol) replace triethylamine in addition to, by with reality
Apply the same method of example 1 to be reacted, target product diethyl ammonium (fluorine sulphonyl) fluoroform is thus obtained with 86.2% yield
Sulfimide salt 0.376mol.
Embodiment 5
1st process：
Acetonitrile 300g is added in 500ml stainless steel autoclave reactor, reactor is cooled down, 5 are changed into liquid temperature
To being de-gassed in reactor after below DEG C.After degassing, anhydrous ammonia 24.7g (1.45mol) is added, then, warm 0 in the holding of side~
5 DEG C of sides are slowly added to fluoroform sulfuryl fluoride 66.3g (0.436mol).The importing of fluoroform sulfuryl fluoride terminate after with its former state
Continue to stir 15 hours.After 15 hours, pass through19F NMR are quantified to reaction solution, and as a result trifluoromethanesulfonamide ammonium salt is
0.415mol (yield 95.1%).
2nd process：
The reaction solution that obtains in 1st process is implemented at room temperature, with paulownia mountain funnel to be filtered under diminished pressure, filtrate 400g is obtained.
Pass through19F NMR are quantified, trifluoromethanesulfonamide ammonium salt containing 0.415mol in the filtered filtrate of results verification.
It is as a result 0.0112mol, it is thus identified that can in addition, confirming the content of the ammonium fluoride in filtered filtrate by chromatography of ions
Remove 97%.
The process of 3rd process~the 4th：
For the 3rd process and after, except using pyridine 98.8g (1.25mol) replace triethylamine in addition to, by with implementation
The same method of example 1 is reacted, and thus obtains target product pyridine (fluorine sulphonyl) fluoroform sulphonyl with 82.1% yield
Inferior amine salt 0.358mol.
[comparative example 1]
1st process：
Acetonitrile 300g is added in 500ml stainless steel autoclave reactor, reactor is cooled down, 5 are changed into liquid temperature
To being de-gassed in reactor after below DEG C.After degassing, anhydrous ammonia 24.7g (1.45mol) is added, then, warm 0 in the holding of side~
5 DEG C of sides are slowly added to fluoroform sulfuryl fluoride 66.3g (0.436mol).The importing of fluoroform sulfuryl fluoride terminate after with its former state
Continue to stir 15 hours.After 15 hours, pass through19F NMR are quantified to reaction solution, and as a result trifluoromethanesulfonamide ammonium salt is
0.415mol (yield 95.1%).
Then, in addition to the solution addition triethylamine 162g (1.60mol) obtained in the 1st process, with embodiment 1
The same method of 3rd process, the 4th process is reacted, and thus obtains second ammonium (the fluorine sulphur of target product three with 60.6% yield
Acyl) trifluoromethanesulfonimide salt 0.264mol.
Understand, in the case where carrying out the 3rd process and the 4th process without the 2nd process, (fluorine sulphonyl) perfluoro alkane
The yield of sulfimide salt is significantly reduced.It is the presence of a large amount of ammonium cations in reaction system to speculate this, so as to easily occur secondary
Reaction.
Embodiment 6
Then, by three second ammoniums (fluorine sulphonyl) the trifluoromethanesulfonimide salt 0.404mol obtained in embodiment 1
(134.2g) and the aqueous solution comprising potassium hydroxide 24.9g are mixed at room temperature, are stirred 1 hour.After stirring, by reactant mixture
In contained triethylamine and water distillation remove, obtain (fluorine sulphonyl) trifluoromethanesulfonimide potassium.And then add acetonitrile thereto,
Undissolved composition is filtered out, acetonitrile is distilled and removed, (the fluorine sulphonyl) three of purity more than 99% is obtained with 80% yield
Fluoromethane sulfimide potassium 87.0g.
Embodiment 7
Then, except triethyl ammonium (fluorine sulphonyl) the pentafluoroethane sulfimide salt 0.337mol that will be obtained in embodiment 2
Beyond (128.8g) and the aqueous solution comprising lithium hydroxide 8.9g are mixed at room temperature, operation similarly to Example 6 is carried out.Its
As a result, (fluorine sulphonyl) five fluoromethane sulfimide lithium 75.5g of purity 99% is obtained with 78% yield.
Industrial applicability
In the present invention centre of medicine, agricultural chemicals is may be used as (fluorine sulphonyl) perfluoro alkane sulfimide salt of object
Body, cell electrolyte and acid catalyst.
Claims (6)
1. it is a kind of（Fluorine sulphonyl）The manufacture method of perfluoro alkane sulfimide salt, it is described（Fluorine sulphonyl）Perfluoro alkane sulfimide salt
Represented by formula [1],
In formula [1], RfThe perfluoroalkyl of the straight or branched of carbon number 1~6 is represented, B represents organic base,
The manufacture method is characterised by, including following process：
[the 1st process]
In the presence of the solvent, the perfluoro alkane sulfonic acid halide and ammonia shown in formula [2] are made（NH3）Reaction, thus obtains including perfluor alkane
The process of the solution of hydrocarbon sulfonamide ammonium salt and ammonium halide,
RfSO2X [2]
In formula [2], RfThe perfluoroalkyl of the straight or branched of carbon number 1~6 is represented, X represents halogen atom；
[the 2nd process]
The solution obtained in 1st process is filtered out, thus ammonium halide contained in the solution is separated and removed, comprising
The process of the solution of perfluoro alkane sulfonamide ammonium salt；
[the 3rd process]
Organic base is added to the solution comprising perfluoro alkane sulfonamide ammonium salt obtained in the 2nd process, " perfluoro alkane is included
The solution of the salt of sulfonamide and organic base " and ammonia, then separates ammonia the process removed from the solution；
[the 4th process]
In the presence of organic base, to obtained from ammonia separation is removed in the 3rd process comprising " perfluoro alkane sulfonamide with it is organic
The solution addition vikane of the salt of alkali ", so as to obtain（Fluorine sulphonyl）The process of perfluoro alkane sulfimide salt.
2. manufacture method according to claim 1, wherein, in the 1st process, solvent is acetonitrile, propionitrile, dimethyl Asia
Sulfone, sultone, diethylene glycol dimethyl ether, tetrahydrofuran or dimethylformamide.
3. manufacture method according to claim 1 or 2, wherein, in the 1st process, reaction temperature is 0 DEG C~100 DEG C.
4. manufacture method according to claim 1, wherein, in the 2nd process, temperature when filtering out is 10 DEG C~80 DEG C.
5. manufacture method according to claim 1, it is characterised in that in the 3rd process, to including " perfluoro alkane sulphonyl
The solution of the salt of amine and organic base " and ammonia, by ammonia separated from the solution except when, in 0.02MPa~0.1MPa pressure strip
Heated under part, at 20 DEG C~80 DEG C.
6. shown in formula [3]（Fluorine sulphonyl）The manufacture method of perfluoro alkane sulfimide acid metal salt, it is characterised in that pass through power
Profit requires any one of 1~5 manufacture（Fluorine sulphonyl）Perfluoro alkane sulfimide salt, then, makes this（Fluorine sulphonyl）Perfluoro alkane
The hydroxide or carbonate reaction of the hydroxide or carbonate or alkaline-earth metal of sulfimide salt and alkali metal,
In formula [3], RfIdentical with the formula [1] of claim 1, M represents alkali metal or alkaline-earth metal, and n represents the valence mumber with the metal
Equal integer.
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| PCT/JP2015/082231 WO2016080384A1 (en) | 2014-11-20 | 2015-11-17 | Method for producing (fluorosulfonyl)perfluoroalkanesulfonylimide salt |
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|---|---|---|---|---|
| CN108422127A (en) * | 2017-11-13 | 2018-08-21 | 天能集团（河南）能源科技有限公司 | A kind of aqueous scaling powder of lead-acid accumulator |
| CN115490619A (en) * | 2022-09-02 | 2022-12-20 | 衢州市九洲化工有限公司 | Preparation method of bis (trifluoromethylsulfonyl) imide salt |
| CN115784945A (en) * | 2022-11-25 | 2023-03-14 | 九江天赐高新材料有限公司 | Preparation method of bi-per-fluoroalkyl sulfimide salt |
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| CN109803952B (en) | 2016-10-19 | 2022-10-04 | 魁北克电力公司 | Sulfamic acid derivatives and process for preparing same |
| WO2021031430A1 (en) | 2019-08-22 | 2021-02-25 | Fujian Yongjing Technology Co., Ltd | New process for the synthesis of fluorinated conductive salts for lithium ion batteries |
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| JPWO2016080384A1 (en) | 2017-08-31 |
| KR20170058994A (en) | 2017-05-29 |
| JP6631534B2 (en) | 2020-01-15 |
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| CN107074753B (en) | 2019-09-06 |
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