CN102229579A - Preparation method of novel Br phi nsted acid ionic liquid with 1, 3-thiazole-2-thioketone cation - Google Patents
Preparation method of novel Br phi nsted acid ionic liquid with 1, 3-thiazole-2-thioketone cation Download PDFInfo
- Publication number
- CN102229579A CN102229579A CN2011100880756A CN201110088075A CN102229579A CN 102229579 A CN102229579 A CN 102229579A CN 2011100880756 A CN2011100880756 A CN 2011100880756A CN 201110088075 A CN201110088075 A CN 201110088075A CN 102229579 A CN102229579 A CN 102229579A
- Authority
- CN
- China
- Prior art keywords
- thioketones
- thiazoles
- acid
- carbonatoms
- straight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to a preparation method of a novel acid ionic liquid based on 1, 3-thiazole-2-thioketone cation. The cation of the ionic liquid is 1, 3-thiazole-2-thioketone derivative, and the anion of the liquid is acid anion. 3 positions of cation thiazole thioketone is substituted by one of all C1-C16 straight-chain or branched alkyl groups, all C1-C16 partially fluorinated or perfluorinated straight-chain or branched alkyl groups, C3-C4 alkyl sulfonic acid and all C2-C10 straight-chain or branched alkyl groups containing ether, hydroxyl, carboxyl, nitrile group. The anion is one of chlorine, bromine, iodine, fluoroborate, fluorophosphate, sulfate, sodium bisulfate, dihydrogen phosphate, phosphate, nitrate, para-toluenesulfonate, trifluoroacetate, trifluoromethansulfonate, lactate, chloroacetate, formate, acetate, propionate and mesylate.
Description
Technical field
The present invention relates to a kind of novel based on 1,3-thiazoles-2-thioketones cationoid
The preparation method of acidic ion liquid.
Technical background
Ionic liquid (ILs) is meant the liquid of all being made up of ion.Ionic liquid is called ionic liquid at room temperature, room temperature melting salt, organic ion liquid etc. again.Ionic liquid generally be by the asymmetric organic cation of the relatively large structure of specific volume relative with volume less inorganic or organic anion constitutes, in room temperature or be bordering on the material that is in a liquid state under the room temperature.In recent years, ionic liquid has been brought into play unique effect as a kind of " green " solvent or catalyzer in organic synthesis.At first, ionic liquid provides the environment that is different from traditional molecular solvent as solvent for chemical reaction, and it can change the mechanism of reaction, makes that activity of such catalysts and stability are better, selectivity and transformation efficiency be higher; Secondly, be dissolved in the catalyzer in the ionic liquid, have homogeneous catalysis efficient height, the segregative advantage of heterogeneous catalyst, the separation of product can be used methods such as decant, extraction and distillation; Moreover because of ionic liquid does not have vapour pressure, the liquidus temperature wide ranges makes to separate to be easy to carry out.Therefore, relevant ion liquid applied research is being subjected to people's attention more and more.
People mainly concentrate on the ionic liquid that positively charged ion is quaternary ammonium salt ion, quaternary alkylphosphonium salt ion, imidazole salts ion and pyridinium salt ion etc. about ion liquid research in recent years.1914, people such as Walden reported first ionic liquid on The Journal of Organic Chemistry (1929,1291).After this ion liquid synthetic reaching used like rain back spring bamboo, especially functionalized ion liquid, is widely used in a lot of fields.People such as Cole in 2002 Journal of the American Chemical Society (2002,124:5962-5963) reported first to have strong Bronsted tart ion liquid synthetic.He Mingyuan etc. Green Chemistry (2003,5:38-39) reported [HMIM] BF
4([HMIM] is 1-Methylimidazole positively charged ion) ion liquid synthetic and application.2003, Deng have congruent people Catalysis Communications (2003,4:597-601) reported the imidazoles acidic ion liquid of two kinds of sulfonic functionals, find in the polyreaction of alkene, to have good reactive behavior and selectivity.So far, do not see that as yet positively charged ion is the ion liquid study on the synthesis report of 1,3-thiazoles-2-thioketones.Have advantages such as Adjustable structure, good stability in view of the thiazole thione ring, the present invention relates to a kind of novel based on 1,3-thiazoles-2-thioketones cationoid
The synthetic method of acidic ion liquid.
Summary of the invention
Ionic liquid of the prior art mainly concentrates on the ionic liquid that positively charged ion is quaternary ammonium salt ion, quaternary alkylphosphonium salt ion, imidazole salts ion and pyridinium salt ion etc., does not see the ion liquid research report that has based on 1,3-thiazoles-2-thioketones cationoid.At the still abundant problem of existing ionic liquid cation type, the invention provides a kind of preparation method based on the novel ion liquid of 1,3-thiazoles-2-thioketones cationoid with advantages such as Adjustable structure, good stabilities.
The technical solution used in the present invention: a kind of general structure is novel based on 1,3-thiazoles-2-thioketones cationoid of (I)
The preparation method of acidic ion liquid, wherein R
1Base contains one of them of straight or branched alkyl that ether, hydroxyl, carboxyl, itrile group functional group and carbonatoms are 2-10 for the alkylsulphonic acid of partially fluorinated or fluoridized all straight or branched alkyl of all straight or branched alkyl of representative carbonatoms 1-16, carbonatoms 1-16, carbonatoms 3-4 and all; X
-Be in chlorine, bromine, iodine, fluoroboric acid root, hexafluorophosphoric acid root, sulfate radical, bisulfate ion, dihydrogen phosphate, phosphate radical, nitrate radical, tosic acid root, trifluoroacetic acid root, trifluoromethanesulfonic acid root, lactate, chloroacetate root, formate, acetate moiety, propionate, the methanesulfonate one of them, it is characterized in that comprising the steps:
(1) with 1,3-thiazole-2-thioketones and haloalkane add in the reactor according to 1: 1 ratio of mol ratio, add phase-transfer catalyst Tetrabutyl amonium bromide and 30%NaOH solution then, stir, be heated to 80 ℃-90 ℃, reaction 8-12h after the cooling layering, tells organic phase, being washed with distilled water to does not have the precipitation generation after aqueous phase adds silver nitrate solution, pressure reducing and steaming solvent, vacuum-drying obtain 3-alkyl-1,3-thiazoles-2-thioketones.
(2) with in (1) 1,3-thiazole-2-thioketones is respectively with 1,3-propane sultone, 1,4-butane sultones adds in the reactor according to 1: 1 ratio of mol ratio, the adding ethyl acetate is a solvent, be heated to 80 ℃-90 ℃, reaction 8-12h solidifies, and leaches solid, with ether and ethyl acetate washing leaching cake, drying is used the agate mortar porphyrize, adds the heating of an amount of acetonitrile and ethyl acetate mixed solution then, filtered while hot is removed residual raw material, filtration cakes torrefaction obtains purified 3-alkylsulphonic acid-1,3-thiazoles-2-thioketones inner salt, white powder.
(3) with the 3-alkyl-1,3-thiazoles in (2), (3)-2-thioketones and 3-alkylsulphonic acid-1,3-thiazoles-2-thioketones inner salt and
Acid adds in the reaction flask according to 1: 1 ratio of mol ratio, be heated to 80 ℃-90 ℃ under solvent-free, 12-24h is to reaction solution homogeneous stopped reaction in reaction, after the cooling product is washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly get corresponding ionic liquid then.
Description of drawings
Fig. 1 is the ion liquid nucleus magnetic hydrogen spectrum spectrogram of 3-butyl-1,3-thiazoles-2-thioketones hydrosulfate.
Fig. 2 is the ion liquid nucleus magnetic hydrogen spectrum spectrogram of 3-butyl-1,3-thiazoles-2-thioketones tosilate.
Fig. 3 is the ion liquid nucleus magnetic hydrogen spectrum spectrogram of 3-butyl-1,3-thiazoles-2-thioketones fluoroform sulphonate.
Fig. 4 is the ion liquid nucleus magnetic hydrogen spectrum spectrogram of 3-butyl-1,3-thiazoles-2-thioketones trifluoroacetate.
Fig. 5 is 3-butyl sulfonic acid-1,3-thiazoles-2-thioketones hydrosulfate ionic liquid nucleus magnetic hydrogen spectrum spectrogram.
Fig. 6 is 3-butyl sulfonic acid-1,3-thiazoles-2-thioketones fluoroform sulphonate ionic liquid nucleus magnetic hydrogen spectrum spectrogram.
Fig. 7 is 3-butyl sulfonic acid-1,3-thiazoles-2-thioketones trifluoroacetate ionic liquid nucleus magnetic hydrogen spectrum spectrogram.
Fig. 8 is 3-propyl sulfonic acid-1,3-thiazoles-2-thioketones tosilate ionic liquid nucleus magnetic hydrogen spectrum spectrogram.
Fig. 9 is 3-propyl sulfonic acid-1,3-thiazoles-2-thion-phosphoric acid dihydric salt ionic liquid nucleus magnetic hydrogen spectrum spectrogram.
Figure 10 is 3-propyl sulfonic acid-1,3-thiazoles-2-thioketones fluoroform sulphonate ionic liquid nucleus magnetic hydrogen spectrum spectrogram.
Figure 11 is 3-propyl sulfonic acid-1,3-thiazoles-2-thioketones trifluoroacetate ionic liquid nucleus magnetic hydrogen spectrum spectrogram.
Embodiment
In order to make technique means of the present invention, creation characteristic, to reach purpose and effect and be easy to understand and understand, the present invention is explained in further detail below by specific embodiment:
The embodiment 1:3-butyl-1,3-thiazoles-ion liquid preparation of 2-thioketones hydrosulfate
In the 25mL round-bottomed flask, add 3-butyl-1,3-thiazoles-2-thioketones (20mmol), drip 95-98%H
2SO
4(20mmol), be warming up to 90 ℃, keep this thermotonus 12h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product then, pale brown look liquid.Adopt nuclear magnetic resonance analyser and mass spectrograph to detect, the parameter of products obtained therefrom is
1H NMR (400MHz, CDCl
3): δ 0.90 (t, 3H, CH
3), 1.27-1.37 (m, 2H, CH
2), 1.59-1.68 (m, 2H, CH
2), 3.09 (s, 2H, CH
2), 3.35 (t, 2H, CH
2), 4.42 (t, 2H, CH
2); ESI-MS:m/z=176[M
+], m/z=97[M
-].
The embodiment 2:3-butyl-1,3-thiazoles-ion liquid preparation of 2-thioketones tosilate
In the 25mL round-bottomed flask, add 3-butyl-1,3-thiazoles-2-thioketones (20mmol), add tosic acid (20mmol), be warming up to 90 ℃, keep this temperature 24h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product then, pale brown look liquid.Adopt nuclear magnetic resonance analyser and mass spectrometric detection, the parameter of products obtained therefrom is
1H NMR (400MHz, D
2O): δ 0.90 (t, 3H, CH
3), 1.18-1.76 (m, 4H, 2 * CH
2), 2.37 (s, 3H, CH
3), 3.07 (t, 2H, CH
2), 3.71 (t, 2H, CH
2), 4.25 (t, 2H, CH
2), 7.33-7.68 (dd, 4H, Ar); ESI-MS:m/z=176[M
+], m/z=171[M
-].
The embodiment 3:3-butyl-1,3-thiazoles-ion liquid preparation of 2-thioketones fluoroform sulphonate
In the 25mL round-bottomed flask, add 3-butyl-1,3-thiazoles-2-thioketones (20mmol), add trifluoromethanesulfonic acid (20mmol), be warming up to 85 ℃, keep this temperature 12h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product then, pale brown look liquid.Adopt nuclear magnetic resonance analyser and mass spectrometric detection, the parameter of products obtained therefrom is
1H NMR (400MHz, CDCl
3): δ 0.97 (t, 3H, CH
3), 1.44-1.53 (m, 2H, CH
2), 1.74-1.82 (m, 2H, CH
2), 3.35 (t, 2H, CH
2), 3.82 (t, 2H, CH
2), 4.48 (t, 2H, CH
2); ESI-MS:m/z=176[M
+], m/z=149[M
-].
The embodiment 4:3-butyl-1,3-thiazoles-ion liquid preparation of 2-thioketones trifluoroacetate
In the 25mL round-bottomed flask, add 3-butyl-1,3-thiazoles-2-thioketones (10mmol), drip trifluoroacetic acid (10mmol), be warming up to 85 ℃, keep this thermotonus 12h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product then, pale brown look liquid.The employing nuclear magnetic resonance analyser detects, and the parameter of products obtained therefrom is
1H NMR (400MHz, DMSO-d
6): δ 0.87 (t, 3H, CH
3), 1.25-1.40 (m, 2H, CH
2), 1.53-1.66 (m, 2H, CH
2), 3.13 (t, 2H, CH
2), 3.46 (t, 2H, CH
2), 4.16 (t, 2H, CH
2), (b, 1H, NH); ESI-MS:m/z=176[M
+], m/z=113[M
-].
The embodiment 5:3-butyl sulfonic acid-1,3-thiazoles-ion liquid preparation of 2-thioketones hydrosulfate
In the 25mL round-bottomed flask, add 3-butyl sulfonic acid-1,3-thiazoles-2-thioketones inner salt (10mmol), drip 95-98%H
2SO
4(20mmol), be warming up to 90 ℃, keep this temperature 24h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product then.Adopt nuclear magnetic resonance analyser and mass spectrograph to detect, the parameter of products obtained therefrom is
1H NMR (400MHz, D
2O): 1.69-2.01 (m, 4H, 2CH
2), 2.80 (t, 2H, CH
2), 3.22 (t, 2H, CH
2), 3.65 (t, 2H, CH
2), 4.20 (t, 2H, CH
2); ESI-MS:m/z=256[M
+], m/z=97[M
-].
The embodiment 6:3-butyl sulfonic acid-1,3-thiazoles-ion liquid preparation of 2-thioketones fluoroform sulphonate
In the 25mL round-bottomed flask, add 3-butyl sulfonic acid base-1,3-thiazoles-2-thioketones (20mmol), add trifluoromethanesulfonic acid (20mmol), be warming up to 80 ℃, keep this temperature 12h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product, weak yellow liquid then.Adopt nuclear magnetic resonance analyser and mass spectrograph to detect, the parameter of products obtained therefrom is
1H NMR (400MHz, D
2O): δ 1.70-1.86 (m, 4H, 2CH
2), 2.81 (t, 2H, CH
2), 3.23 (t, 2H, CH
2), 3.67 (t, 2H, CH
2), 4.21 (t, 2H, CH
2); ESI-MS:m/z=256[M
+], m/z=149[M
-].
The embodiment 7:3-butyl sulfonic acid-1,3-thiazoles-ion liquid preparation of 2-thioketones trifluoroacetate
In the 25mL round-bottomed flask, add 3-butyl sulfonic acid-1,3-thiazoles-2-thioketones inner salt (10mmol), drip trifluoroacetic acid (10mmol), be warming up to 90 ℃, keep this thermotonus 24h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product, weak yellow liquid then.Adopt nuclear magnetic resonance analyser and mass spectrograph to detect, the parameter of products obtained therefrom is
1H NMR (400MHz, D
2O): δ 1.70-1.85 (m, 4H, 2CH
2), 2.79 (t, 2H, CH
2), 3.23 (t, 2H, CH
2), 3.66 (t, 2H, CH
2), 4.20 (t, 2H, CH
2); Mass spectrum ESI-MS:m/z=256[M
+], m/z=113[M
-].
The embodiment 8:3-propyl sulfonic acid-1,3-thiazoles-ion liquid preparation of 2-thioketones tosilate
In the 25mL round-bottomed flask, add 3-propyl sulfonic acid-1,3-thiazoles-2-thioketones inner salt (10mmol), add tosic acid (10mmol), be warming up to 90 ℃, keep this temperature 24h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product, weak yellow liquid then.Adopt nuclear magnetic resonance analyser and mass spectrograph to detect, the parameter of products obtained therefrom is
1H NMR (400MHz, D
2O): δ 2.10-2.17 (m, 2H, CH
2), 2.29 (s, 3H, CH
3), 2.94 (t, 2H, CH
2), 3.33 (t, 2H, CH
2), 3.66 (t, 2H, CH
2), 4.20 (t, 2H, CH
2), 7.25-7.60 (dd, J=8.2Hz, 4H, ArH); ESI-MS:m/z=242[M
+], m/z=171[M
-].
The embodiment 9:3-propyl sulfonic acid-1,3-thiazoles-ion liquid preparation of 2-thion-phosphoric acid dihydric salt
In the 25mL round-bottomed flask, add 3-propyl sulfonic acid-1,3-thiazoles-2-thioketones (10mmol), add phosphoric acid (10mmol), be warming up to 90 ℃, keep this temperature backflow 24h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product, weak yellow liquid then.Adopt nuclear magnetic resonance analyser and mass spectrograph to detect, the parameter of products obtained therefrom is
1H NMR (400MHz, D
2O): δ 2.16-2.23 (m, 2H, CH
2), 2.93 (t, 2H, CH
2), 3.42 (t, 2H, CH
2), 3.76 (t, 2H, CH
2), 4.30 (t, 2H, CH
2); ESI-MS:m/z=242[M
+], m/z=97[M
-].
The embodiment 10:3-propanesulfonic acid base-1,3-thiazoles-ion liquid preparation of 2-thioketones fluoroform sulphonate
In the 25mL round-bottomed flask, add 3-propyl sulfonic acid-1,3-thiazoles-2-thioketones (20mmol), add trifluoromethanesulfonic acid (20mmol), be warming up to 90 ℃, keep this temperature 12h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product, weak yellow liquid then.Adopt nuclear magnetic resonance analyser and mass spectrograph to detect, the parameter of products obtained therefrom is
1H NMR (400MHz, D
2O): δ 2.12-2.18 (m, 2H, CH
2), 2.94 (t, 2H, CH
2), 3.37 (t, 2H, CH
2), 3.71 (t, 2H, CH
2), 4.24 (t, 2H, CH
2); ESI-MS:m/z=242[M
+], m/z=149[M
-].
The embodiment 11:3-propyl sulfonic acid-1,3-thiazoles-ion liquid preparation of 2-thioketones trifluoroacetate
In the 25mL round-bottomed flask, add 3-N-morpholinopropanesulfonic acid base-1,3-thiazoles-2-thioketones inner salt (10mmol), drip trifluoroacetic acid (10mmol), be warming up to 90 ℃, keep this thermotonus 12h.Reacted product has been washed three times with ether, pressure reducing and steaming ether and a spot of moisture, 100 ℃ of dry 10h of vacuum promptly obtain product, weak yellow liquid then.Adopt nuclear magnetic resonance analyser and mass spectrograph to detect, the parameter of products obtained therefrom is
1H NMR (400MHz, D
2O): δ 2.12-2.27 (m, 2H, CH
2), 3.03 (t, 2H, CH
2), 3.46 (t, 2H, CH
2), 3.79 (t, 2H, CH
2), 4.33 (t, 2H, CH
2); Mass spectrum ESI-MS:m/z=242[M
+], m/z=149[M
-].
Claims (4)
1. a general structure is the cationic novel based on 1,3-thiazoles-2-thioketones of (I)
The preparation method of acidic ion liquid, wherein R
1For the alkylsulphonic acid of partially fluorinated or fluoridized all straight or branched alkyl of all straight or branched alkyl of representing carbonatoms 1-16, carbonatoms 1-16, carbonatoms 3-4 and all contain in the straight or branched alkyl that ether, hydroxyl, carboxyl, itrile group functional group and carbonatoms are 2-10 one of them; X
-Be in chlorine, bromine, iodine, fluoroboric acid root, hexafluorophosphoric acid root, sulfate radical, bisulfate ion, dihydrogen phosphate, phosphate radical, nitrate radical, tosic acid root, trifluoroacetic acid root, trifluoromethanesulfonic acid root, lactate, chloroacetate root, formate, acetate moiety, propionate, the methanesulfonate one of them:
2. 1,3-thiazoles according to claim 1-2-thioketones is cationic novel
Acidic ion liquid is characterized in that described R
1For the alkylsulphonic acid of partially fluorinated or fluoridized all straight or branched alkyl of all straight or branched alkyl of representing carbonatoms 1-16, carbonatoms 1-16, carbonatoms 3-4 and all contain in the straight or branched alkyl that ether, hydroxyl, carboxyl, itrile group functional group and carbonatoms are 2-10 one of them.
3. 1,3-thiazoles according to claim 1-2-thioketones is cationic novel
Acidic ion liquid is characterized in that described X
-Be in chlorine, bromine, iodine, fluoroboric acid root, hexafluorophosphoric acid root, sulfate radical, bisulfate ion, dihydrogen phosphate, phosphate radical, nitrate radical, tosic acid root, trifluoroacetic acid root, trifluoromethanesulfonic acid root, lactate, chloroacetate root, formate, acetate moiety, propionate, the methanesulfonate one of them.
One kind cationic novel based on 1,3-thiazoles-2-thioketones
The preparation method of acidic ion liquid comprises the steps:
(1) 1,3-thiazoles-2-thioketones and haloalkane are obtained 3-alkyl-1,3-thiazoles-2-thioketones according to certain molar ratio in the certain condition reaction.
(2) 1,3-thiazoles-2-thioketones and alkylsulphonic acid lactone are reacted under certain conditions according to certain molar ratio obtain 3-alkylsulphonic acid-1,3-thiazoles-2-thioketones inner salt.
(3) with the 3-alkyl-1,3-thiazoles in right (1), (2)-2-thioketones or 3-alkylsulphonic acid-1,3-thiazoles-2-thioketones inner salt and
Acid adds in the reaction flask according to mol ratio at 1: 1, and under condition of no solvent, the reaction regular hour handles and promptly obtains product.
(4) right 4 (1), (2) described preparation method is characterized in that reaction medium is respectively water, ethyl acetate.Right 4 (3) described preparation methods is characterized in that described reaction is a solvent-free reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110088075.6A CN102229579B (en) | 2011-04-08 | 2011-04-08 | A kind of cation is the preparation method of the Br φ nsted acidic ion liquid of 1,3-thiazoles-2-thiones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110088075.6A CN102229579B (en) | 2011-04-08 | 2011-04-08 | A kind of cation is the preparation method of the Br φ nsted acidic ion liquid of 1,3-thiazoles-2-thiones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102229579A true CN102229579A (en) | 2011-11-02 |
| CN102229579B CN102229579B (en) | 2016-08-03 |
Family
ID=44842199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110088075.6A Expired - Fee Related CN102229579B (en) | 2011-04-08 | 2011-04-08 | A kind of cation is the preparation method of the Br φ nsted acidic ion liquid of 1,3-thiazoles-2-thiones |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102229579B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108570019A (en) * | 2018-05-31 | 2018-09-25 | 大连理工大学 | A kind of novel acid ionic liquid and its catalytic applications |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2953573A (en) * | 1957-01-23 | 1960-09-20 | Diamond Alkali Co | Certain thiazolidine-thione alkhalides and process |
| JP2006315963A (en) * | 2005-05-10 | 2006-11-24 | Kanto Denka Kogyo Co Ltd | Cyclic ionic liquid containing s or o and method for producing the same |
| CN101747290A (en) * | 2009-12-30 | 2010-06-23 | 山东师范大学 | N-substituent thiazolone derivative and preparation method and applications thereof |
-
2011
- 2011-04-08 CN CN201110088075.6A patent/CN102229579B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2953573A (en) * | 1957-01-23 | 1960-09-20 | Diamond Alkali Co | Certain thiazolidine-thione alkhalides and process |
| JP2006315963A (en) * | 2005-05-10 | 2006-11-24 | Kanto Denka Kogyo Co Ltd | Cyclic ionic liquid containing s or o and method for producing the same |
| CN101747290A (en) * | 2009-12-30 | 2010-06-23 | 山东师范大学 | N-substituent thiazolone derivative and preparation method and applications thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108570019A (en) * | 2018-05-31 | 2018-09-25 | 大连理工大学 | A kind of novel acid ionic liquid and its catalytic applications |
| CN108570019B (en) * | 2018-05-31 | 2021-02-26 | 大连理工大学 | Acidic ionic liquid and catalytic application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102229579B (en) | 2016-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102120728B (en) | Sulfonic- functionalized caprolactam acidic ion liquid and preparation method thereof | |
| CN102516128B (en) | Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis | |
| CN104072471B (en) | A kind of green catalysis prepares the method for 14-aryl-14H-dibenzo [a, j] oxa anthracenes derivative | |
| CN102295603A (en) | Peroxy heteropoly acid based ionic liquid and preparation method thereof | |
| CN107790178B (en) | Based on three (2,4,6- trimethoxyphenyl) phosphine ionic-liquid catalysts and preparation method thereof | |
| CN102060738A (en) | Ionic liquid combining B acid site and L acid site as well as preparation method and application thereof | |
| CN103521263B (en) | Morpholine salt ionic-liquid catalyst, Its Preparation Method And Use | |
| CN101168493A (en) | Preparation method for fluorochlorobenzene | |
| CN105618139A (en) | Method for degrading lignocellulose based on molybdenum polyoxometallate | |
| CN101747311B (en) | Method for synthesizing glycerol formal through reaction of glycerol and formaldehyde | |
| CN102659542A (en) | Method for preparing methyl acrolein by catalyzing condensation of formaldehyde and propionaldehyde by utilizing ionic liquid | |
| CN101153018A (en) | Br*nsted acidity ion liquid containing N-alkyl pyrrolidone group, producing method and use of the same | |
| CN105017150B (en) | A kind of method of the outer amine of the amine asymmetric hydrogenation synthesis of chiral ring of palladium chtalyst quinoline 3 | |
| CN102229579A (en) | Preparation method of novel Br phi nsted acid ionic liquid with 1, 3-thiazole-2-thioketone cation | |
| CN103880769B (en) | Heteropoly tridemorph quaternary ammonium salt as well as preparation method and application of quaternary ammonium salt | |
| CN111001440A (en) | Polyacid site ionic liquid catalyst and preparation method and application thereof | |
| CN102775311B (en) | Preparation method of isooctyl salicylate | |
| CN103936697B (en) | A kind of method catalyzing and synthesizing tetrahydrofuran (THF) | |
| CN103936677B (en) | A kind of sulfonic acid funtionalized ionic liquid based on perfluoro alkyl sulfonic acid root anion and preparation method thereof | |
| CN102040487B (en) | Method for preparing 3,4-dimethoxy toluene under catalysis | |
| CN102229569A (en) | Method for preparing Br[phi]nsted acidic ionic liquid based on benzimidazole cations | |
| CN105032484A (en) | Solid acid catalysts with dual-center ionic liquid structures and preparation method and application thereof | |
| CN104151283A (en) | Method for catalytically synthesizing 12-aryl-8,9,10,12-tetrahydrobenzo[alpha]xanthenes-11-one derivative | |
| CN103193727A (en) | Preparation method based on (R)-4-phenyl-1,3-thiazolidine-2-sulfur ketone chiral ionic liquid | |
| CN102911793B (en) | Functionalized alkaline ionic liquid and application thereof in preparation of biodiesel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160803 Termination date: 20210408 |