CN1743320A - Saccharin anion ion liquid and its preparing method - Google Patents
Saccharin anion ion liquid and its preparing method Download PDFInfo
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- CN1743320A CN1743320A CN 200510086526 CN200510086526A CN1743320A CN 1743320 A CN1743320 A CN 1743320A CN 200510086526 CN200510086526 CN 200510086526 CN 200510086526 A CN200510086526 A CN 200510086526A CN 1743320 A CN1743320 A CN 1743320A
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Abstract
This invention provides a new saccharin-anion solution and its preparation method. In this ion solution, the cation part is quaternary ammonium cation or amino acid ester cation; the anion part is saccharin-anion and. The preparation method is as follow. First, enable quaternary ammonium cation halogenide or amino acid ester salt and sodium saccharin to react in organic solvent; then, filter the solution after reaction, evaporate the filtrate to remove the solvent to acquire the saccharin-anion solution. Advantages: the invented ion solution not only has the ion solution characteristic but also has the characteristic of chiral substance and the acidity of Bmsted acid. Besides, it is harmless to the environment, low in cost, simple in production and high in purity.
Description
Technical field
The present invention relates to class ionic liquid and preparation method thereof, especially novel saccharin anion ion liquid and this kind preparation method of ionic liquid of a class belongs to new chemical material and preparing technical field thereof.
Background technology
Ionic liquid is a kind of watery fusion salt, near (＜150 ℃) under the room temperature condition, is the low-viscosity (mobile) liquid that is made of ion fully, and ionic liquid generally is made of organic cation and inorganic or organic anion.Ionic liquid is a kind of good ionogen, to 20th century the mid-80, it is found that ionic liquid can also be as a kind of novel dissolvent and brand-new catalytic material, have organic solvent commonly used and traditional catalyst incomparable character.In the catalyticing research field; ionic liquid replaces traditional catalyzer and organic solvent; improved the chemical reaction process that many people know, as Diels-Alder reaction, Friedel-Crafts reaction, Heck reaction, hydrogenation and hydroformylation of olefin etc.Particularly national governments have greatly promoted the development of Green Chemistry to the attention of environment in recent years, and ion liquid research promptly has been subjected to the promotion energetically of Green Chemistry.The advantages such as thermostability that ionic liquid has is non-volatile, polarity is adjustable, higher can provide non-water surrounding, are easy to recycle, and have the incomparable special performance of a lot of molecular solvent, are considered to the green solvent of alternative volatilization organic solvent commonly used.Studies show that ionic liquid replaces traditional catalyzer and organic solvent, can greatly improve reactive behavior.Rise the eighties, and the research institutions such as IFP of Britain BP company and France begin systematically to explore the possibility of ionic liquid as solvent and catalyzer.The nineties, the ion liquid successfully synthetic of a series of stable performances makes its applied research in catalysis and organic synthesis field active gradually.Existing ion liquid positively charged ion is by quaternary ammonium alkyl positively charged ion or the cation composition of Wan Ji quaternary phosphine, and wherein modal is N, and N-dialkylimidazolium positively charged ion, N-alkyl pyridine positively charged ion, negatively charged ion often are Cl
-, Br
-, AlCl
4 -, BF
4 -, PF
6 -, NO
3 -, (CF
38O
2)
2N
-, CF
3COO
-Deng univalent anion.It is all variant on physical properties and chemical property to utilize different zwitterions to make up the ionic liquid that obtains mutually, and the ionic liquid change of properties after the discussion combination and the mutual relationship of its structural changes are the important contents of ionic liquid applied research.In recent years, new synthetic ion liquid kind increases sharply, domestic relevant research is also being carried out rapidly, particularly the degradable green ionic liquid of self toxicological harmless more is subjected to people's expectation, described cationic ionic liquid of amino acid ester and preparation method thereof as patent document CN1621152, CN1631539 has described amino acid salts ionic liquid and preparation method thereof.But relevant saccharin anion ion liquid involved in the present invention does not have report so far as yet, and the preparation method of this class saccharin anion ion liquid also is that the present invention mentions first.
Summary of the invention
The saccharin anion ion liquid that provides a class novel is provided the object of the invention, and this class preparation method of ionic liquid is provided.
Saccharin anion ion liquid provided by the invention, its cationic moiety are quaternary ammonium cation or amino acid ester positively charged ion, and anionicsite is the asccharin negatively charged ion, and described asccharin anion structure formula is as follows:
The structural formula of above-mentioned quaternary ammonium cation is:
[NR
1R
2R
3R
4]
+
Wherein, R
1, R
2, R
3, R
4Be the lower alkyl or the aryl of identical or different had suitable substituent, as: methyl, ethyl, propyl group, butyl, the tertiary butyl, octyl group, benzyl, allyl group etc.
The cationic structural formula of above-mentioned amino acid ester is:
[HACOOR
5]
+
Wherein, A is the part except that carboxyl in the amino acid molecular, the amino acid that is suitable for includes but not limited to: glycine (Gly), D-, L-, DL-L-Ala (Ala), D-, L-, DL-valine (Val), D-, L-, DL-leucine (Leu), D-, L-, DL-Isoleucine (Ile), D-, L-, DL-phenylalanine (Phe), D-, L-, DL-cysteine (Cys), D-, L-, DL-Gelucystine (Cys), D-, L-, DL-Threonine (Thr), D-, L-, DL-L-glutamic acid (Glu), D-, L-, DL-glutamine (Gln), D-, L-, DL-aspartic acid (Asp), D-, L-, DL-l-asparagine (Asn), D-, L-, DL-methionine (Met), D-, L-, DL-serine (Ser), D-, L-, DL-proline(Pro) (Pro), D-, L-, DL-tyrosine (Tyr), D-, L-, DL-tryptophane (Try), D-, L-, DL-Methionin (Lys), D-, L-, DL-arginine (Arg), D-, L-, DL-histidine (His), D-, L-, DL-ornithine (Orn), Beta-alanine, 2,3,4-amino (different) butyric acid, 2,3,4,5-amino (different) valeric acid, 2,3,4,5,6-amino (different) caproic acid, o-, p-, m-amino-benzene ethylformic acid etc.; R
5Be the lower alkyl or the aryl that can have suitable substituent, as: methyl, ethyl, propyl group, butyl, the tertiary butyl, octyl group, benzyl, allyl group etc.
The preparation method of the above-mentioned saccharin anion ion liquid that the present invention also provides comprises the steps:
(1) quaternary ammonium cation halogenide or amino-acid ester salt and soluble saccharin are reacted in organic solvent;
(2) will be via the liquid filtering of (1) gained;
(3) volatilization eliminates the organic solvent in the filtrate, promptly gets the product saccharin anion ion liquid.
The halid structural formula of quaternary ammonium cation described in the above-mentioned preparation method is:
[NR
1R
2R
3R
4]X
Wherein, R
1, R
2, R
3, R
4Be the lower alkyl or the aryl of identical or different had suitable substituent, as: methyl, ethyl, propyl group, butyl, the tertiary butyl, octyl group, benzyl, allyl group etc.; X is a halogen.
The structural formula of the amino-acid ester salt described in the above-mentioned preparation method is:
[HACOOR
5]X
Wherein, A is the part except that carboxyl in the amino acid molecular, the amino acid that is suitable for includes but not limited to: glycine (Gly), D-, L-, DL-L-Ala (Ala), D-, L-, DL-valine (Val), D-, L-, DL-leucine (Leu), D-, L-, DL-Isoleucine (Ile), D-, L-, DL-phenylalanine (Phe), D-, L-, DL-cysteine (Cys), D-, L-, DL-Gelucystine (Cys), D-, L-, DL-Threonine (Thr), D-, L-, DL-L-glutamic acid (Glu), D-, L-, DL-glutamine (Gln), D-, L-, DL-aspartic acid (Asp), D-, L-, DL-l-asparagine (Asn), D-, L-, DL-methionine (Met), D-, L-, DL-serine (Ser), D-, L-, DL-proline(Pro) (Pro), D-, L-, DL-tyrosine (Tyr), D-, L-, DL-tryptophane (Try), D-, L-, DL-Methionin (Lys), D-, L-, DL-arginine (Arg), D-, L-, DL-histidine (His), D-, L-, DL-ornithine (Orn), Beta-alanine, 2,3,4-amino (different) butyric acid, 2,3,4,5-amino (different) valeric acid, 2,3,4,5,6-amino (different) caproic acid, o-, p-, m-amino-benzene ethylformic acid etc.; R
5Be the lower alkyl or the aryl that can have suitable substituent, as: methyl, ethyl, propyl group, butyl, the tertiary butyl, octyl group, benzyl, allyl group etc.; X is a halogen.
Saccharin anion ion liquid provided by the invention specifically mainly contains: tetramethylammonium saccharin salt ionic liquid, Tetrylammonium saccharin salt ionic liquid, tetrabutylammonium saccharin salt ionic liquid, benzyltrimethylammon.um saccharin salt ionic liquid, triethyl octyl group sucramin salt ion liquid, glycine methyl ester saccharin salt ionic liquid, L-alanine methyl ester saccharin salt ionic liquid, D-alanine methyl ester saccharin salt ionic liquid, DL-alanine methyl ester saccharin salt ionic liquid, L-L-Ala allyl ester saccharin salt ionic liquid, L-alanine benzyl ester saccharin salt ionic liquid, L-valine methyl ester saccharin salt ionic liquid, L-leucine methyl esters saccharin salt ionic liquid, L-Isoleucine methyl esters saccharin salt ionic liquid, L-Threonine methyl esters saccharin salt ionic liquid, L-proline methyl ester saccharin salt ionic liquid, L-ethyl prolinate saccharin salt ionic liquid, L-proline(Pro) propyl ester saccharin salt ionic liquid, L-proline(Pro) butyl ester saccharin salt ionic liquid, L-proline(Pro) tert-butyl ester saccharin salt ionic liquid, 6-aminocaprolc acid methyl esters saccharin salt ionic liquid.
Saccharin anion ion liquid provided by the invention and preparation thereof compared with prior art have following unusual effect:
1, the present invention is to provide the novel green ionic liquid of a class, developed ion liquid new variety;
The feature that can have chiral material when 2, saccharin anion ion liquid provided by the invention has the ionic liquid characteristic: as characteristic of chiral separation, chiral catalysis and chiral solvent etc.;
It is acid to have Br nsted acid when 3, saccharin anion ion liquid provided by the invention has the ionic liquid characteristic, and alternative solid acid is as acid material;
4, the zwitterion of saccharin anion ion liquid provided by the invention constitutes by the degradable ion of toxicological harmless, has green completely ion liquid feature;
5, the preparation raw material of product provided by the invention more easily obtains, and price is also cheaper, so preparation cost is low;
6, preparation method provided by the invention is easy and simple to handle, and required equipment is simple, and suitable for mass production is used.
Embodiment
Further specify the present invention below by preferred embodiment.
Embodiment 1: tetramethylammonium saccharin salt ionic liquid
2.19g (0.020mol) tetramethyl ammonium chloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is tetramethylammonium saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 88%.Reaction formula is:
Embodiment 2: Tetrylammonium saccharin salt ionic liquid
3.31g (0.020mol) etamon chloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is Tetrylammonium saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 86%.Reaction formula is:
Embodiment 3: tetrabutylammonium saccharin salt ionic liquid
5.56g (0.020mol) tetrabutylammonium chloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains light yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is tetrabutylammonium saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 85%.Reaction formula is:
Embodiment 4: benzyltrimethylammon.um saccharin salt ionic liquid
3.73g (0.020mol) benzyl trimethyl ammonium chloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains light yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is benzyltrimethylammon.um saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 78%.Reaction formula is:
Embodiment 5: triethyl octyl group sucramin salt ion liquid
5.00g (0.020mol) triethyl octyl group ammonium chloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains light yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is triethyl octyl group sucramin salt ion liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 82%.Reaction formula is:
Embodiment 6: glycine methyl ester saccharin salt ionic liquid
2.51g (0.020mol) glycine methyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains light yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is glycine methyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 86%.Reaction formula is:
Embodiment 7:L-alanine methyl ester saccharin salt ionic liquid
2.79g (0.020mol) L-alanine methyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains colourless transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-alanine methyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 89%.Reaction formula is:
Embodiment 8:D-alanine methyl ester saccharin salt ionic liquid
2.79g (0.020mol) D-alanine methyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains colourless transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is D-alanine methyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 89%.Reaction formula is:
Embodiment 9:DL-alanine methyl ester saccharin salt ionic liquid
2.79g (0.020mol) DL-alanine methyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains colourless transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is DL-alanine methyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 90%.Reaction formula is:
Embodiment 10:L-L-Ala allyl ester saccharin salt ionic liquid
3.31g (0.020mol) L-L-Ala allyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains colourless transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-L-Ala allyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 87%.Reaction formula is:
Embodiment 11:L-alanine benzyl ester saccharin salt ionic liquid
4.31g (0.020mol) L-alanine benzyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains light yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-alanine benzyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 83%.Reaction formula is:
Embodiment 12:L-valine methyl ester saccharin salt ionic liquid
3.35g (0.020mol) L-valine methyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains colourless transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-valine methyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 89%.Reaction formula is:
Embodiment 13:L-leucine methyl esters saccharin salt ionic liquid
3.63g (0.020mol) L-leucine methyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 48 hours, filter.Filtrate obtains yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-leucine methyl esters saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 87%.Reaction formula is:
Embodiment 14:L-Isoleucine methyl esters saccharin salt ionic liquid
3.63g (0.020mol) L-Isoleucine methyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 48 hours, filter.Filtrate obtains yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-Isoleucine methyl esters saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 77%.Reaction formula is:
Embodiment 15:L-Threonine methyl esters saccharin salt ionic liquid
3.37g (0.020mol) L-threonine methyl ester hydrochloric salt is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 72 hours, filter.Filtrate obtains colourless transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-Threonine methyl esters saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 79%.Reaction formula is:
Embodiment 16:L-proline methyl ester saccharin salt ionic liquid
3.31g (0.020mol) L-proline methyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains light yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-proline methyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 92%.Reaction formula is:
Embodiment 17:L-ethyl prolinate saccharin salt ionic liquid
3.59g (0.020mol) L-ethyl prolinate hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains light yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-ethyl prolinate saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 88%.Reaction formula is:
Embodiment 18:L-proline(Pro) propyl ester saccharin salt ionic liquid
3.87g (0.020mol) L-proline(Pro) propyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains light yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-proline(Pro) propyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 85%.Reaction formula is:
Embodiment 19:L-proline(Pro) butyl ester saccharin salt ionic liquid
4.16g (0.020mol) L-proline(Pro) butyl ester hydrochloride is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains light yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-proline(Pro) butyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 84%.Reaction formula is:
Embodiment 20:L-proline(Pro) tert-butyl ester saccharin salt ionic liquid
4.16g (0.020mol) L-proline hydrochloride tert-butyl is mixed in the 50mL acetonitrile solution with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains light yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is L-proline(Pro) tert-butyl ester saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 84%.Reaction formula is:
Embodiment 21:6-amino methyl cyclohexyl saccharin salt ionic liquid
6.56g (0.05mol) 6-aminocaprolc acid methyl esters is mixed in the 50mL acetone soln with 5.79g (0.024mol) soluble saccharin, two solution were mixed abundant stirring reaction 24 hours, filter.Filtrate obtains yellow transparent liquid with 60 ℃ of rotary evaporation solvent evaporated, is 6-aminocaprolc acid methyl esters saccharin salt ionic liquid.Temperature of reaction is 24 ℃ of room temperatures, productive rate: 86%.Reaction formula is:
Claims (13)
1, a class saccharin anion ion liquid is characterized in that, described ion liquid cationic moiety is quaternary ammonium cation or amino acid ester positively charged ion, and anionicsite is the asccharin negatively charged ion, and described asccharin anion structure formula is as follows:
2, ionic liquid as claimed in claim 1 is characterized in that, the structural formula of described quaternary ammonium cation is: [NR
1R
2R
3R
4]
+, R wherein
1, R
2, R
3, R
4Be identical or different substituent lower alkyl or the aryl of not having, perhaps be identical or different lower alkyl that has suitable substituent or aryl.
3, ionic liquid as claimed in claim 2 is characterized in that, described R
1, R
2, R
3, R
4Be selected from: methyl, ethyl, propyl group, butyl, the tertiary butyl, octyl group, benzyl, allyl group.
4, ionic liquid as claimed in claim 1 is characterized in that, the cationic structural formula of described amino acid ester is: [HACOOR
5]
+, wherein: A is the part except that carboxyl in the amino acid molecular; R
5For not having substituent lower alkyl or aryl, perhaps for having the lower alkyl or the aryl of suitable substituent.
5, ionic liquid as claimed in claim 4 is characterized in that, described A is selected from: glycine, D-, L-, the DL-L-Ala, D-, L-, DL-valine, D-, L-, the DL-leucine, D-, L-, the DL-Isoleucine, D-, L-, the DL-phenylalanine, D-, L-, DL-cysteine, D-, L-, the DL-Gelucystine, D-, L-, the DL-Threonine, D-, L-, DL-L-glutamic acid, D-, L-, the DL-glutamine, D-, L-, the DL-aspartic acid, D-, L-, the DL-l-asparagine, D-, L-, DL-methionine, D-, L-, DL-serine, D-, L-, the DL-proline(Pro), D-, L-, DL-tyrosine, D-, L-, the DL-tryptophane, D-, L-, DL-Methionin, D-, L-, the DL-arginine, D-, L-, DL-histidine, D-, L-, the DL-ornithine, Beta-alanine, 2,3,4-amino (different) butyric acid, 2,3,4,5-amino (different) valeric acid, 2,3,4,5,6-amino (different) caproic acid, o-, p-, the m-amino-benzene ethylformic acid.
6, as claim 4 or 5 described ionic liquids, it is characterized in that described R
5Be selected from: methyl, ethyl, propyl group, butyl, the tertiary butyl, octyl group, benzyl, allyl group.
7, a kind of preparation method of saccharin anion ion liquid comprises the steps: that (1) react quaternary ammonium cation halogenide or amino-acid ester salt and soluble saccharin in organic solvent; (2) will be via the liquid filtering of (1) gained; (3) volatilization eliminates the organic solvent in the filtrate, obtains saccharin anion ion liquid.
8, preparation method as claimed in claim 7 is characterized in that, the halid structural formula of described quaternary ammonium cation is: [NR
1R
2R
3R
4] X, wherein: R
1, R
2, R
3, R
4Be identical or different substituent lower alkyl or the aryl of not having, perhaps be identical or different lower alkyl that has suitable substituent or aryl; X is a halogen.
9, preparation method as claimed in claim 8 is characterized in that, described R
1, R
2, R
3, R
4Be selected from: methyl, ethyl, propyl group, butyl, the tertiary butyl, octyl group, benzyl, allyl group.
10, preparation method as claimed in claim 7 is characterized in that, the structural formula of described amino-acid ester salt is: [HACOOR
5] X, wherein: A is the part except that carboxyl in the amino acid molecular; R
5For not having substituent lower alkyl or aryl, perhaps for having the lower alkyl or the aryl of suitable substituent; X is a halogen.
11, preparation method as claimed in claim 10 is characterized in that, described A is selected from: glycine, D-, L-, the DL-L-Ala, D-, L-, DL-valine, D-, L-, the DL-leucine, D-, L-, the DL-Isoleucine, D-, L-, the DL-phenylalanine, D-, L-, DL-cysteine, D-, L-, the DL-Gelucystine, D-, L-, the DL-Threonine, D-, L-, DL-L-glutamic acid, D-, L-, the DL-glutamine, D-, L-, the DL-aspartic acid, D-, L-, the DL-l-asparagine, D-, L-, DL-methionine, D-, L-, DL-serine, D-, L-, the DL-proline(Pro), D-, L-, DL-tyrosine, D-, L-, the DL-tryptophane, D-, L-, DL-Methionin, D-, L-, the DL-arginine, D-, L-, DL-histidine, D-, L-, the DL-ornithine, Beta-alanine, 2,3,4-amino (different) butyric acid, 2,3,4,5-amino (different) valeric acid, 2,3,4,5,6-amino (different) caproic acid, o-, p-, the m-amino-benzene ethylformic acid.
12, preparation method as claimed in claim 10 is characterized in that, described R
5Be selected from: methyl, ethyl, propyl group, butyl, the tertiary butyl, octyl group, benzyl, allyl group.
As the described preparation method of each claim of claim 7～12, it is characterized in that 13, described organic solvent is acetonitrile or acetone.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102195091A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院过程工程研究所 | Ionic liquid electrolyte for lithium secondary battery |
| JP2020094009A (en) * | 2018-12-14 | 2020-06-18 | 日清紡ホールディングス株式会社 | Ammonium salt having saccharin anion |
-
2005
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102195091A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院过程工程研究所 | Ionic liquid electrolyte for lithium secondary battery |
| JP2020094009A (en) * | 2018-12-14 | 2020-06-18 | 日清紡ホールディングス株式会社 | Ammonium salt having saccharin anion |
| WO2020121667A1 (en) * | 2018-12-14 | 2020-06-18 | 日清紡ホールディングス株式会社 | Ammonium salt having saccharin anion |
| CN113227042A (en) * | 2018-12-14 | 2021-08-06 | 日清纺控股株式会社 | Ammonium salts with saccharin anion |
| US11512061B2 (en) | 2018-12-14 | 2022-11-29 | Nisshinbo Holdings Inc. | Ammonium salt having saccharin anion |
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| Publication number | Publication date |
|---|---|
| CN1321988C (en) | 2007-06-20 |
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