CN102190624B - Sulfur-containing/nitrogen-group-containing ionic liquid and preparation method thereof - Google Patents
Sulfur-containing/nitrogen-group-containing ionic liquid and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sulfur-containing/nitrogen-group-containing ionic liquid of which the structure is disclosed as Formula I, Formula II and Formula III. The preparation method provided by the invention is implemented by reacting a sulfur-containing/nitrogen-group-containing compound with an imidazole or pyridine compound. The ionic liquid prepared by the method provided by the invention can be used as a solvent or catalyst in an organic synthesis reaction, a desulfurizer in petrochemical industry, or the like.
Description
Technical field
The present invention relates to ionic liquid of a kind of sulfur-bearing and nitrogen-containing group and preparation method thereof.Can be used as the solvent in organic synthesis or catalyzer, the sweetening agent etc. in petrochemical complex.
Background technology
Ionic liquid is the green matter being subject to academia and industry member extensive concern in recent years, ionic liquid has the physicochemical property of many uniquenesses, as reused, the advantage such as steam forces down, the ability of stronger dissolved organic matter and inorganics, molten journey is long, polarity is adjustable, be widely used in organic synthesis now, and show huge application prospect at petrochemical complex, biomass energy, environment and Material Field.Existing ionic liquid mainly comprises imidazoles, pyridines, doped quaternary ammonium salt class and quaternary phosphine salt ionic liquid.People expect to develop more ionic liquid, apply more widely to obtain.
Summary of the invention
Object of the present invention provides ionic liquid of a kind of novel sulfur-bearing and nitrogen-containing group and preparation method thereof.
The object of the invention is to realize by the following technical solutions: the ionic liquid that the invention provides a kind of sulfur-bearing and nitrogen-containing group, its structure be formula I, shown in formula II and formula III:
Wherein radicals R=C
2h
4o, C
2h
4oC
2h
4s, C
2h
4, S, C
2h
4s, C
3h
6s, C
4h
8s or C
5h
10s,
Wherein radicals R=CH
3, CH
2cH
3or
Wherein radicals R=C
2h
4o, C
2h
4s, S or C
2h
4oC
2h
4s.
The ionic liquid of sulfur-bearing of the present invention and nitrogen-containing group comprises the ionic liquid of one of following chemical formula:
H1：a＝0，b＝0，c＝0，d＝0
H2：a＝2，b＝1，c＝0，d＝0
H3：a＝2，b＝1，c＝2，d＝1
H4：a＝2，b＝0，c＝0，d＝0
H5：a＝0，b＝0，c＝0，d＝1
H6：a＝3，b＝0，c＝0，d＝1
H7：a＝2，b＝0，c＝0，d＝1
H8：a＝4，b＝0，c＝0，d＝1
H9：a＝5，b＝0，c＝0，d＝1
The invention provides the preparation method of the ionic liquid of a kind of sulfur-bearing and nitrogen-containing group:
(1) described sulfur-bearing and nitrogen-containing group compound and imidazoles or pyridine compounds and their are protected in nitrogen; 12 ~ 72h is stirred under the reaction conditions that oil bath is 50 ~ 100 DEG C; with anhydrous alcohol solution; wash with anhydrous diethyl ether; vacuum-drying 20 ~ 30h obtains ionic liquid, obtains toxicity and greatly reduce and can utilize ionic liquid after vacuum-drying.
(2) described sulfur-bearing and nitrogen-containing group compound and imidazoles or pyridine compounds and their is protected in nitrogen, react 1 ~ 10min under single mold microwave power 30 ~ 100w condition; with anhydrous alcohol solution; wash with anhydrous diethyl ether; vacuum-drying 20 ~ 30h obtains ionic liquid, obtains toxicity and greatly reduce and can utilize ionic liquid after vacuum-drying.The reaction expression of the method is:
Sulfur-bearing of the present invention and nitrogen-containing group compound are mustard gas, 1-(2-chloroethene sulfenyl)-2-(2-chloroethoxy) ethane, two-(2-chloroethene sulphur ethyl) ether, 2-chloroethyl-4 '-chlorobutyl thioether, two-(2-chloroethyl) disulfide, 1, 3-pair-(2-chloroethene sulfenyl)-propane, 1, 2-pair-(2-chloroethene sulfenyl) ethane, 1, 4-pair-(2-chloroethene sulfenyl) butane, 1, 5-pair-(2-chloroethene sulfenyl) pentane, three-(2-chloroethyl) amine, N-methyl-N.N-two-(2-chloroethyl) amine, N-ethyl-N.N-two-(2-chloroethyl) amine or 2-chloroethyl-2 '-hydroxyethyl thioether.
Glyoxaline compound of the present invention is Methylimidazole, and pyridine compounds and their is pyridine.
Ionic liquid sulfur-bearing of the present invention and nitrogenous series compound structural regularity by force, study its character more representative, synthesize the ionic liquid obtained and possess adjustability of structure, can according to embody rule change structure.
And, have employed microwave technology in the present invention to prepare ionic liquid, shorten the reaction times, improve reaction efficiency, for the extensive Synthesis and applications of ionic liquid provides condition.
Embodiment
Embodiment 1
The synthesis of ionic liquid H1: get mustard gas (1.00g; 0.00633mol) with Methylimidazole (1.50g; 0.0183mol) be added in 50ml twoport flask; nitrogen protection, oil bath 70 DEG C backflow 20h, adds dehydrated alcohol (5.00ml) and dissolves after reaction terminates; add ether (20.0ml) washing; product recrystallized from acetonitrile, obtains 2.30g white solid H1, productive rate 113%.Fusing point 115 ~ 119 DEG C.1H?NMR(600MHz，D2O)：δ＝8.673(s，2H)，7.399(t，J＝1.8Hz，2H)，7.346(s，2H)，4.300(s，4H)，3.784(d，J＝1.8Hz，6H)，2.915～2.906(m，4H)。
Embodiment 2
The synthesis of ionic liquid H2: get 1-(2-chloroethene sulfenyl)-2-(2-chloroethoxy) ethane (1.58g, 0.00778mol) with Methylimidazole (2.38g, 00.0290mol) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 72h is reacted under magneton agitation condition, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10min, to incline desolventizing, obtain light yellow liquid, with ethyl acetate and ether repetitive scrubbing, dry 24h in vacuum drying oven under 70 DEG C of conditions, obtain 1.71g light yellow slightly thick liquid H2, productive rate 61.1%.1H?NMR(600MHz，D2O)：δ＝8.691(s，1H)，8.643(s，1H)，7.413(s，2H)，7.344(d，J＝7.2Hz，2H)，4.281(d，J＝2.4Hz，4H)，3.787(d，J＝7.2Hz，6H)，3.591(t，J＝4.8Hz，2H)，2.922～2.903(m，2H)，2.639～2.622(m，2H)。
Embodiment 3
The synthesis of ionic liquid H3: get two-(2-chloroethene sulphur ethyl) ether (1.50g, 0.00570mol) with Methylimidazole (2.36g, 0.0289mol) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 24h is reacted under magneton agitation condition, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10min, to incline desolventizing, obtain yellow liquid, with ethyl acetate and ether repetitive scrubbing, dry 24h in vacuum drying oven under 70 DEG C of conditions, obtain 1.54g yellow slightly thick liquid H3, productive rate 82.8%.1H?NMR(600MHz，D2O)：δ＝7.326(d，J＝1.2Hz，2H)，7.245(d，J＝1.8Hz，2H)，4.205(t，J＝6.6Hz，4H)，3.679(d，J＝7.8Hz，6H)，3.479(t，J＝6.0Hz，4H)，2.848(t，J＝6.6Hz，4H)，2.544(t，J＝6.0Hz，4H)。13C?NMR(150MHz，DMSO-d6)：δ＝136.275，123.728，122.578，69.507，48.806，35.904，31.665，30.862。
Embodiment 4
The synthesis of ionic liquid H4: get 2-chloroethyl-4 '-chlorobutyl thioether (0.970g, 0.00518mol) with Methylimidazole (2.46g, 0.0299) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 24h is reacted under magneton agitation condition, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, to incline desolventizing, stir 10min, obtain red thick liquid, with ethyl acetate and ether repetitive scrubbing, dry 24h in vacuum drying oven under 70 DEG C of conditions, obtain 1.44g red thick liquid H4, productive rate 82.3%.1H?NMR(600MHz，D2O)：δ＝8.740(s，1H)，8.666(d，J＝4.2Hz，1H)，7.456～7.366(m，4H)，4.343～4.322(m，2H)，4.174～4.129(m，2H)，3.849～3.814(m，6H)，2.942(t，J＝6.0Hz，2H)，2.517(t，J＝7.2Hz，2H)，1.986～1.825(m，2H)，1.527～1.514(m，2H)。
Embodiment 5
The synthesis of ionic liquid H5: get two-(2-chloroethyl) disulfide (0.890g, 0.00466mol) with Methylimidazole (1.91g, 0.0233mol) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 24h is reacted under magneton agitation condition, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10min, to incline desolventizing, obtain viscous brown liquid state, with ethyl acetate and ether repetitive scrubbing, dry 24h in vacuum drying oven under 70 DEG C of conditions, obtain 1.45g brown viscous liquid H5, productive rate 88.9%.1H?NMR(600MHz，D2O)：δ＝8.657(s，2H)，7.382(s，2H)，7.324(s，2H)，4.417(t，J＝6.0Hz，4H)，3.761(s，6H)，3.032(t，J＝6.0Hz，4H)。
Embodiment 6
The synthesis of ionic liquid H6: get 1, 3-pair-(2-chloroethene sulfenyl) propane (1.02g, 0.00437mol) with Methylimidazole (1.56g, 0.0190mol) in 50ml twoport flask, nitrogen protection, 24h is reacted under oil bath 70 DEG C of conditions, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10 minutes, obtain thick pale yellow solid, with ethyl acetate and ether repetitive scrubbing three times, dry 24h in vacuum drying oven under 70 DEG C of conditions, obtain 1.33g light yellow solid H6, productive rate 84.0%.1H?NMR(600MHz，D2O)：δ＝8.658(s，2H)，7.392～7.322(m，4H)，4.269(t，J＝6.0Hz，4H)，3.767(s，6H)，2.890(t，J＝6.0Hz，4H)，2.470(t，J＝7.2Hz，4H)，1.678(t，J＝7.2Hz，2H)。
Embodiment 7
The synthesis of ionic liquid H7: get 1, 2-pair-(2-chloroethene sulfenyl) ethane (1.41g, 0.00643mol) with Methylimidazole (3.30g, 0.0402mol) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 24h is reacted under magneton agitation condition, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10min, to incline desolventizing, obtain pale solid, with ethyl acetate and ether repetitive scrubbing, dry 24h in vacuum drying oven under 70 DEG C of conditions, obtain 1.98g pale solid H7, productive rate 80.8%.1H?NMR(600MHz，D2O)：δ＝8.662(s，2H)，7.395(s，2H)，7.326(s，2H)，4.279(t，J＝6.0Hz，4H)，2.924(t，J＝6.0Hz，4H)，2.644(d，J＝0.6Hz，4H)。
Embodiment 8
The synthesis of ionic liquid H8: get 1, 4-pair-(2-chloroethene sulfenyl) butane (1.06g, 0.00429mol) with Methylimidazole (1.63g, 0.0198mol) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 24h is reacted under magneton agitation condition, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10 minutes, to incline desolventizing, obtain reddish-brown thick liquid, with ethyl acetate and ether repetitive scrubbing three times, in vacuum drying oven under 70 DEG C of conditions dry 24h, obtain 1.60g reddish-brown thick liquid H8, productive rate 93.0%.1H?NMR(600MHz，D2O)：δ＝8.697(s，2H)，7.426(s，2H)，7.353(s，2H)，4.299(t，J＝6.0Hz，4H)，3.799(s，6H)，2.921(t，J＝6.0Hz，4H)，2.445(s，4H)，1.510(s，4H)。
Embodiment 9
The synthesis of ionic liquid H9: get 1, 5-pair-(2-chloroethene sulfenyl) pentane (1.01g, 0.00387mol) with Methylimidazole (1.63g, 0.0198mol) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 24h is reacted under magneton agitation condition, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10 minutes, to incline desolventizing, obtain light yellow viscous liquid, with ethyl acetate and ether repetitive scrubbing, dry 24h under 70 DEG C of conditions in vacuum drying oven, obtain 1.48g reddish-brown thick liquid H9, productive rate 91.9%.1H?NMR(600MHz，D2O)：δ＝8.779(s，2H)，7.492(s，2H)，7.419(s，2H)，4.345(t，J＝6.0Hz，4H)，3.846(s，6H)，2.956(t，J＝6.0Hz，4H)，2.469(dd，J＝7.2Hz，6.6Hz，4H)，1.491～1.422(m，4H)，1.351～1.312(m，2H)。
Embodiment 10
The synthesis of ionic liquid H10: get three-(2-chloroethyl) amine (1.53g, 0.00748mol) with Methylimidazole (3.64g, 0.0443mol) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 24h is reacted under magneton agitation condition, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10min, to incline desolventizing, obtain red thick liquid, with ethyl acetate and ether repetitive scrubbing, dry 24h in vacuum drying oven under 70 DEG C of conditions, obtain 1.65g red thick liquid H10, productive rate 48.9%.1H?NMR(600MHz，D2O)：δ＝8.635(s，3H)，7.343(d，J＝12.6Hz，6H)，4.153(t，J＝6.6Hz，6.0H)，3.791(s，9H)，3.022(t，J＝6.6Hz，6H)。13C?NMR(150MHz，DMSO-d6)：δ＝136.145，127.270，123.740，52.344，46.660，33.362。
Embodiment 11
The synthesis of ionic liquid H11: get N-methyl-N.N-two-(2-chloroethyl) amine (1.50g, 0.00961mol) with Methylimidazole (3.94g, 0.0480mol) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 24h is reacted under magneton agitation condition, after reaction terminates, add 1 dehydrated alcohol (5.00m) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10min, to incline desolventizing, obtain khaki color solid, with ethyl acetate and ether repetitive scrubbing, dry 24h in vacuum drying oven under 70 DEG C of conditions, obtain 2.16g khaki color solid H11, productive rate 71.6%.1H?NMR(600MHz，D2O)：δ＝8.611(s，2H)，7.339(d，J＝12.6Hz，4H)，4.211～4.191(t，J＝6.0Hz，4H)，3.796(s，6H)，2.843(t，J＝6.0Hz，4H)，2.273(s，3H)。
Embodiment 12
The synthesis of ionic liquid H12: get N-ethyl-N.N-two-(2-chloroethyl) amine (1.06g, 0.00623mol) with Methylimidazole (2.44g, 0.0297mol) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 24h is reacted under magneton agitation condition, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10min, to incline desolventizing, obtain khaki color solid, with ethyl acetate and ether repetitive scrubbing, dry 24h in vacuum drying oven under 70 DEG C of conditions, obtain 1.15g khaki color solid H12, productive rate 57.5%.1H?NMR(600MHz，D2O)：δ＝8.609(s，2H)，7.360(s，2H)，7.340(s，2H)，4.165(t，J＝6.0Hz，4H)，3.803(s，6H)，2.904(t，J＝6.0Hz，4H)，2.586(d，J＝7.8Hz，2H)，0.882(t，J＝7.8Hz，2H)。
Embodiment 13
The synthesis of ionic liquid H13: get 2-chloroethyl-2 '-hydroxyethyl thioether (1.00g, : 0.00711mol) and Methylimidazole (1.86g, 0.0226mol) in 50ml twoport flask, nitrogen protection, oil bath 70 DEG C, reflux condensation mode, 36h is reacted under magneton agitation condition, after reaction terminates, add dehydrated alcohol (5.00ml) vibration, pour in 100ml beaker, add anhydrous diethyl ether (20.0ml) washing, stir 10min, to incline desolventizing, obtain red thick liquid, with ethyl acetate and ether repetitive scrubbing, dry 24h under 70 DEG C of conditions in vacuum drying oven, obtain 1.55g red thick liquid H13, productive rate 95.6%.1H?NMR(600MHz，D2O)：δ＝8.763(s，1H)，7.481(s，1H)，7.399(s，1H)，4.349(t，J＝6.0Hz，2H)，3.835(s，3H)，3.628(t，J＝6.0Hz，2H)，2.977(t，J＝6.0Hz，2H)，2.626(t，J＝6.0Hz，2H)。
Embodiment 14
The synthesis of ionic liquid H2: get 1-(2-chloroethene sulfenyl)-2-(2-chloroethoxy) ethane (0.520g, 0.00256mol) with Methylimidazole (0.500g, 0.00609mol) in 10ml confined reaction test tube, be filled with nitrogen protection, impose a condition as temperature 70 C at U.S. CE M microwave reaction instrument (model: discover-s model:908860), power 40w, reaction times 2min, dynamic heat pattern, dehydrated alcohol (3.00ml) is added by reactants dissolved after reaction terminates, pour in 50ml small beaker, with ethyl acetate and ether repetitive scrubbing, put into vacuum drying oven dry 24h at 70 DEG C, obtain 0.560g weak yellow liquid H2, productive rate 60.2%.1HNMR(600MHz，DMSO-d6)：δ＝8.707(s，1H)，8.659(s，1H)，7.436(d，J＝7.8Hz，2H)，7.363(d，J＝9.0Hz，2H)，4.316～4.292(m，4H)，3.812～3.783(m，6H)，3.610(t，J＝6.0Hz，2H)，2.931(t，J＝6.0Hz，2H)，2.649(t，J＝6.0Hz，2H)。13C?NMR(150MHz，DMSO-d6)：δ＝136.647，136.517，123.915，123.714，122.773，122.539，69.614，68.424，49.279，48.779，36.018，35.958，31.673，30.918。
Embodiment 15
The synthesis of ionic liquid H14: get 1-(2-chloroethene sulfenyl)-2-(2-chloroethoxy) ethane (0.530g, 0.00261mol) with pyridine (1.08g, 0.0137mol) in 10ml confined reaction test tube, be filled with nitrogen protection, in U.S. CE M microwave reaction instrument (model: discover-s, model:908860) impose a condition as temperature 100 DEG C, power 50w, reaction times 5min, dynamic heat pattern, dehydrated alcohol (3.00ml) is added by reactants dissolved after reaction terminates, pour in 50ml small beaker, with ethyl acetate and ether repetitive scrubbing, put into vacuum drying oven dry 24h at 70 DEG C, obtain 0.230g light yellow viscous liquid H14, productive rate 24.5%.1H?NMR(600MHz，DMSO-d6)：δ＝8.749～8.730(m，4H)，8.494～8.445(m，2H)，7.990～7.947(m，4H)，4.700～4.636(m，4H)，3.920～3.877(m，2H)，3.562(t，J＝6.0Hz，2H)，3.016(t，J＝6.0Hz，2H)，2.585(t，J＝6.0Hz，2H)。13C?NMR(150MHz，DMSO-d6)：δ＝146.375，146.226，144.935，144.723，128.330，128.274，69.644，68.714，61.230，60.542，32.514，31.071。
Embodiment 16
The synthesis of ionic liquid H7: get 1, 2-pair-(2-chloroethene sulfenyl) ethane (0.300g, 0.00137mol) with Methylimidazole (0.440g, 0.00536mol) in 10ml confined reaction test tube, be filled with nitrogen protection, impose a condition as temperature 70 C at U.S. CE M microwave reaction instrument (model: discover-s model:908860), power 40w, reaction times 2min, dynamic heat pattern, dehydrated alcohol (3.00ml) is added by reactants dissolved after reaction terminates, pour in 50ml small beaker, with ethyl acetate and ether repetitive scrubbing, put into vacuum drying oven dry 24h at 70 DEG C, obtain 0.740g khaki color sticky solid H7, productive rate 142%, fusing point 119 DEG C.1H?NMR(600MHz，DMSO-d6)：δ＝8.690(s，2H)，7.421(s，2H)，7.349(s，2H)，4.305(dd，J＝6.0Hz，6.6Hz，4H)，3.792(s，6H)，2.950(dd，J＝6.0Hz，6.6Hz，4H)，2.669(s，4H)。13C?NMR(150MHz，DMSO-d6)：δ＝136.525，123.904，122.509，48.817，35.958，31.495，31.227。
Embodiment 17
The synthesis of ionic liquid H15: get 1, 2-pair-(2-chloroethene sulfenyl) ethane (0.300g, 0.00137mol) with pyridine (0.210g, 0.00266mol) in 10ml confined reaction test tube, be filled with nitrogen protection, impose a condition as temperature 90 DEG C at U.S. CE M microwave reaction instrument (model: discover-s model:908860), power 50w, reaction times 5min, dynamic heat pattern, dehydrated alcohol (3.00ml) is added by reactants dissolved after reaction terminates, pour in 50ml small beaker, with ethyl acetate and ether repetitive scrubbing, put into vacuum drying oven dry 24h at 70 DEG C, obtain 0.230g khaki color sticky solid H15, productive rate 44.2%, fusing point < 40 DEG C.1H?NMR(600MHz，DMSO-d6)：δ＝8.762(d，J＝6.0Hz，4H)，8.476(t，J＝7.8Hz，2H)，7.979(dd，J＝7.2Hz，6.6Hz，4H)，4.706～4.636(m，4H)，3.096(dd，J＝6.6Hz，6.0Hz，4H)，2.654(s，4H)。13C?NMR(150MHz，DMSO-d6)：δ＝146.360，144.730，128.330，60.598，32.339，31.309。
Embodiment 18
The synthesis of ionic liquid H5: get two-(2-chloroethyl) disulfide (0.300g, 0.00157mol) with Methylimidazole (0.340g, 0.00415mol) in 10ml confined reaction test tube, be filled with nitrogen protection, impose a condition as temperature 70 C at U.S. CE M microwave reaction instrument (model: discover-s model:908860), power 40w, reaction times 5min, dynamic heat pattern, dehydrated alcohol (3.00ml) is added by reactants dissolved after reaction terminates, pour in 50ml small beaker, with ethyl acetate and ether repetitive scrubbing, put into vacuum drying oven dry 24h at 70 DEG C, obtain 0.0800g yellowish red color viscous liquid H5, productive rate 14.5%.1H?NMR(600MHz，DMSO-d6)：δ＝8.657(s，2H)，7.382(s，2H)，7.324(s，2H)，4.417(t，J＝6.0Hz，4H)，3.761(s，6H)，3.032(t，J＝6.0Hz，4H)。
Embodiment 19
The synthesis of ionic liquid H17: get two-(2-chloroethyl) disulfide (0.320g, 0.00167mol) with pyridine (0.310g, 0.00392mol) in 10ml confined reaction test tube, be filled with nitrogen protection, impose a condition as temperature 90 DEG C at U.S. CE M microwave reaction instrument (model: discover-s model:908860), power 50w, reaction times 5min, dynamic heat pattern, dehydrated alcohol (3.00ml) is added by reactants dissolved after reaction terminates, pour in 50ml small beaker, with ethyl acetate and ether repetitive scrubbing, put into vacuum drying oven dry 24h at 70 DEG C, obtain 0.180g khaki color sticky solid H17, productive rate 32.6%.1H?NMR(600MHz，DMSO-d6)：δ＝8.769(d，J＝6.0Hz，4H)，8.498(dd，J＝7.2Hz，2H)，7.997(dd，J＝7.2Hz，6.6Hz，4H)，4.859(dd，J＝6.0Hz，6.6Hz，4H)，3.255(dd，J＝6.0Hz，6.6Hz，4H)。13CNMR(150MHz，DMSO-d6)：δ＝146.501，144.883，128.475，59.713，37.052。
Embodiment 20
The synthesis of ionic liquid H3: get two-(2-chloroethene sulphur ethyl) ether (0.310g, 0.00118mol) with Methylimidazole (0.420g, 0.00512mol) in 10ml confined reaction test tube, be filled with nitrogen protection, impose a condition as temperature 70 C at U.S. CE M microwave reaction instrument (model: discover-s model:908860), power 50w, reaction times 5min, dynamic heat pattern, dehydrated alcohol (3.00ml) is added by reactants dissolved after reaction terminates, pour in 50ml small beaker, with ethyl acetate and ether repetitive scrubbing, put into vacuum drying oven dry 24h at 70 DEG C, obtain the liquid H3 of 0.480g thick pale yellow, productive rate 100%.1H?NMR(600MHz，DMSO-d6)：δ＝8.690(s，2H)，7.420(s，2H)，7.347(s，2H)，4.307(dd，J＝6.0Hz，6.6Hz，4H)，3.792(s，6H)，3.583(t，J＝6.0Hz，4H)，2.956(dd，J＝6.0Hz，6.6Hz，4H)，2.649(t，J＝6.0Hz，4H)。13C?NMR(150MHz，DMSO-d6)：δ＝136.510，123.885，122.520，69.514，48.843，35.962，31.729，30.885。
Embodiment 21
The synthesis of ionic liquid H16: get two-(2-chloroethene sulphur ethyl) ether (0.300g, 0.00114mol) with pyridine (0.310g, 0.00392mol) in 10ml confined reaction test tube, be filled with nitrogen protection, in U.S. CE M microwave reaction instrument (model: discover-s, model:908860) impose a condition as temperature 110 DEG C, power 60w, reaction times 5min, dynamic heat pattern, dehydrated alcohol (3.00ml) is added by reactants dissolved after reaction terminates, pour in 50ml small beaker, with ethyl acetate and ether repetitive scrubbing, put into vacuum drying oven dry 24h at 70 DEG C, obtain 0.180g pale yellow viscous liquid H16, productive rate 37.5%.1H?NMR(600MHz，DMSO-d6)：δ＝8.765(d，J＝6Hz，4H)，8.472(t，J＝7.8Hz，1H)，7.977(dd，J＝6.6Hz，7.2Hz，4H)，4.702(dd，J＝6Hz，5.4Hz，4H)，3.564(dd，J＝6Hz，5.4Hz，4H)，3.109(dd，J＝6Hz，6.6Hz，4H)，2.640(dd，J＝6Hz，5.4Hz，4H)。13C?NMR(150MHz，DMSO-d6)：δ＝146.334，144.745，128.319，69.488，60.657，32.596，31.093。
Product H1 ~ the H17 of above-described embodiment synthesis is a series of new ionic liquids, and have steam and force down, can reuse, molten journey is wide, heterogeneous catalyst efficiency high.The solvent in organic synthesis or catalyzer can be used as, the sweetening agent etc. in petrochemical complex.
Claims (3)
1. an ionic liquid for sulfur-bearing, is characterized in that: the chemical formula of described ionic liquid is as follows:
2. the preparation method of the ionic liquid of a sulfur-bearing, it is characterized in that: the preparation method of described ionic liquid is as follows: a sulfocompound and glyoxaline compound are protected in nitrogen, 12 ~ 72h is stirred under the reaction conditions that oil bath is 50 ~ 100 DEG C, with anhydrous alcohol solution, wash with anhydrous diethyl ether, vacuum-drying 20 ~ 30h, obtains the ionic liquid of described sulfur-bearing;
Wherein, described sulfocompound is mustard gas, 1-(2-chloroethene sulfenyl)-2-(2-chloroethoxy) ethane, two-(2-chloroethene sulphur ethyl) ether, 2-chloroethyl-4 '-chlorobutyl thioether, two-(2-chloroethyl) disulfide, 1,3-pair-(2-chloroethene sulfenyl)-propane, 1,2-pair-(2-chloroethene sulfenyl) ethane, 1,4-pair-(2-chloroethene sulfenyl) butane, 1,5-pair-(2-chloroethene sulfenyl) pentane;
Described glyoxaline compound is Methylimidazole.
3. the preparation method of the ionic liquid of a sulfur-bearing, comprise the steps: a sulfocompound and glyoxaline compound to protect in nitrogen, react 1 ~ 10min under single mold microwave power 30 ~ 100w condition, with anhydrous alcohol solution, wash with anhydrous diethyl ether, vacuum-drying 20 ~ 30h, obtains the ionic liquid of described sulfur-bearing;
Wherein, described sulfocompound is mustard gas, 1-(2-chloroethene sulfenyl)-2-(2-chloroethoxy) ethane, two-(2-chloroethene sulphur ethyl) ether, 2-chloroethyl-4 '-chlorobutyl thioether, two-(2-chloroethyl) disulfide, 1,3-pair-(2-chloroethene sulfenyl)-propane, 1,2-pair-(2-chloroethene sulfenyl) ethane, 1,4-pair-(2-chloroethene sulfenyl) butane, 1,5-pair-(2-chloroethene sulfenyl) pentane;
Described glyoxaline compound is Methylimidazole.
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| CN101219995A (en) * | 2008-01-14 | 2008-07-16 | 华东理工大学 | Ion liquid based on heteropoly acid and synthesis thereof |
| CN101768120A (en) * | 2008-12-29 | 2010-07-07 | 吉化集团吉林市星云工贸有限公司 | Biphosphonate polyethoxy diimidazole salt compound as energy-saving antiwear agent and preparation method thereof |
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| CN101219995A (en) * | 2008-01-14 | 2008-07-16 | 华东理工大学 | Ion liquid based on heteropoly acid and synthesis thereof |
| CN101768120A (en) * | 2008-12-29 | 2010-07-07 | 吉化集团吉林市星云工贸有限公司 | Biphosphonate polyethoxy diimidazole salt compound as energy-saving antiwear agent and preparation method thereof |
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