CN100528839C - Ionic liquid of alkyl guanidine salt and its preparation process - Google Patents
Ionic liquid of alkyl guanidine salt and its preparation process Download PDFInfo
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- CN100528839C CN100528839C CNB2006100153144A CN200610015314A CN100528839C CN 100528839 C CN100528839 C CN 100528839C CN B2006100153144 A CNB2006100153144 A CN B2006100153144A CN 200610015314 A CN200610015314 A CN 200610015314A CN 100528839 C CN100528839 C CN 100528839C
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Abstract
The present invention is ionic liquid of alkyl guanidine salt and its preparation process. The guanidine compound has the general expression as shown, and is synthesized through the following steps: synthesizing pentalkyl guanidine, and synthesizing ionic liquid of pentalkyl guanidine salt or hexalkyl guanidine salt. The ionic liquid of alkyl guanidine salt is used as catalyst in organic synthesis reaction, and has the advantages of simple reaction course, easy operation, high catalytic activity, high repeatability, easy separation from production, simple treatment after reaction and being favorable to obtaining high purity product.
Description
Technical field
The invention belongs to guanidine compound, specifically ionic liquid of alkyl guanidine salt and preparation method thereof.
Background technology
Guanidine compound is the strong organic bases of a class (PKa=13.6).In recent years, utilize guanidine compound much to react by efficient catalytic, as building-up reactions, decarboxylic reaction and the epoxy reaction of Strecker reaction, Silanization reaction, Henry reaction, Michael addition reaction, Bayis-Hillman reaction, Wittig and Horner-Wadsworth-Emmons reaction, ester; Fusing point is low, dissolving power by force, does not almost have the good advantage of vapour pressure, thermostability and chemical stability owing to having for ionic liquid, has become the focus of domestic and international research.Present ionic liquid is many to be made of alkyl pyridine and di-alkyl-imidazole quaternary ammonium cation and negatively charged ion such as chlorine aluminate, fluoroboric acid root and hexafluorophosphoric acid root.Organic guanidinium ionic liquid is the newcomer in the ionic liquid family, and the catalyzer that it is used as chemical reaction has many advantages.But the information of relevant organic guanidinium ionic liquid has had not yet to see similar or the pertinent literature report.
Summary of the invention
Technical problem to be solved by this invention is: ionic liquid of alkyl guanidine salt and preparation method thereof is provided.Ionic liquid of alkyl guanidine salt can much react by efficient catalytic, and it is easy to separate as catalyzer, and post-reaction treatment is simple, helps obtaining the purity high product.
The present invention solves this technical problem the technical scheme that is adopted:
Ionic liquid of alkyl guanidine salt of the present invention has following general formula:
Wherein
Substituent R is a methyl, substituent R ' be normal-butyl, substituent R " be H, Y is trifluoromethyl acetic acid anion, trifluoromethane sulfonic acid root negatively charged ion, lactic acid anion, methylsulphonic acid root negatively charged ion, formate anion or tetrafluoroborate negatively charged ion;
Or substituent R is a methyl, substituent R ' be cyclohexyl, n-octyl or phenyl, substituent R " be H, Y is acetic acid anion, trifluoromethyl acetic acid anion, trifluoromethane sulfonic acid root negatively charged ion, lactic acid anion, methylsulphonic acid root negatively charged ion, formate anion, tetrafluoroborate negatively charged ion or hexafluoro-phosphate radical negatively charged ion;
Or substituent R is methyl, substituent R ' be cyclohexyl, n-octyl or phenyl, substituent R " be methyl, Y is the iodine negatively charged ion;
Or substituent R is a methyl, substituent R ' be normal-butyl, cyclohexyl, n-octyl or phenyl, substituent R " be methyl, Y is acetic acid anion, trifluoromethyl acetic acid anion, trifluoromethane sulfonic acid root negatively charged ion, lactic acid anion, methylsulphonic acid root negatively charged ion, tetrafluoroborate negatively charged ion or hexafluoro-phosphate radical negatively charged ion.
The preparation method of ionic liquid of alkyl guanidine salt of the present invention shown in the above-mentioned general formula, its synthesis step is as follows:
(1) five alkyl guanidine synthetic selected in following two kinds of methods any one for use
1. get the 0.30mol tetramethyl-urea and be dissolved in 30～100mL toluene, under nitrogen protection and agitation condition, splash into 0.30～0.33mol POCl of new steaming
3, following to 150～200mL CH after 15～72 hours at 0～5 ℃ in 60 ℃ of following reactions
2Cl
2The diluting reaction system slowly splashes into the single amine R ' NH that replaces of 1.20～1.35mol
2, R ' is normal-butyl, cyclohexyl, n-octyl or phenyl here, refluxes 12～48 hours after being warming up to 50～60 ℃, and it is neutral to system is shown to splash into mass percent and be 35% NaOH solution under the ice bath cooling, and reaction mixture is with 150～200mL CH
2Cl
2Extraction merges organic phase, uses anhydrous Na
2SO
4Dry 24～72 hours after-filtration, steaming desolventizes, and raffinate gets 0.15～0.27mol, five alkyl guanidines through underpressure distillation;
2. get the 0.30mol tetramethyl-urea and be dissolved in 150～200mL toluene, under nitrogen protection and agitation condition, splash into 0.30～0.33mol POCl of new steaming
3, after room temperature condition reacts 2～10 hours down, drip the single amine R ' NH that replaces of 0.66～0.75mol
2, R ' is normal-butyl, cyclohexyl, n-octyl or phenyl here, at room temperature stirs after finishing 20～48 hours, after 150～200mL water diluting reaction system, vigorous stirring 5～30 minutes is taken off a layer solution, toward wherein adding solid NaOH to making system show alkalescence, then solution divides two-layer, solid filtering is fallen, after the filtrate layering, get upper solution, it is dissolved in the ether, uses anhydrous Na then
2CO
aDry after-filtration, steaming desolventizes, and raffinate gets 0.06～0.18mol, five alkyl guanidines through underpressure distillation;
(2) five ionic liquid of alkyl guanidine salt synthetic selected a kind of in following two kinds of methods as required
1. get 0.30mol by the N that makes of (1) step "-substituent R ' be five alkyl guanidines of normal-butyl and 0.30～0.31mol trifluoromethyl acetate; trifluoromethane sulfonic acid; lactic acid; methylsulphonic acid; formic acid; or Tetrafluoroboric acid carries out neutralization reaction and promptly makes 0.21～0.30mol, five ionic liquid of alkyl guanidine salt, N-and N '-substituent R are methyl in this five ionic liquid of alkyl guanidine salt product; N "-substituent R ' be normal-butyl; N "-substituent R " be H, Y is the trifluoromethyl acetic acid anion; trifluoromethane sulfonic acid root negatively charged ion; lactic acid anion; methylsulphonic acid root negatively charged ion; formate anion; or the tetrafluoroborate negatively charged ion;
2. get the N that 0.30mol was made by (1) step "-substituent R ' be cyclohexyl; n-octyl; or five alkyl guanidines of phenyl and 0.30～0.31mol acetate; trifluoromethyl acetate; trifluoromethane sulfonic acid; lactic acid, methylsulphonic acid, formic acid, Tetrafluoroboric acid, or phosphofluoric acid carries out neutralization reaction and promptly makes 0.24～0.30mol, five ionic liquid of alkyl guanidine salt, N-and N '-substituent R are methyl in this five ionic liquid of alkyl guanidine salt product; N "-substituent R ' be phenyl, cyclohexyl, or n-octyl; N "-substituent R " be H, Y is an acetic acid anion; the trifluoromethyl acetic acid anion; trifluoromethane sulfonic acid root negatively charged ion; lactic acid anion; methylsulphonic acid root negatively charged ion; formate anion, the tetrafluoroborate negatively charged ion, or hexafluoro-phosphate radical negatively charged ion;
(3) hexaalkylguanidium salts is ion liquid synthetic, selects a kind of in following three kinds of methods as required for use
1. get the N that 0.30mol was made by (1) step "-substituent R ' be cyclohexyl; n-octyl; or five alkyl guanidine compounds of phenyl are dissolved in 20～100mL purified acetonitrile; under ice-water bath cooling and nitrogen protection; splash into the single methyl iodide of 0.30～0.33mol of new steaming and the mixed solution of 20～100mL acetonitrile; treat to continue stirring reaction 12～48 hours after system temperature returns to room temperature; steam the acetonitrile that removes in the reaction system; raffinate washs 2～5 times with ethyl acetate; the ethyl acetate that vacuum is taken out in the system promptly makes 0.12～0.30mol, six alkyl guanidine metal iodide ions liquid; N in this six alkyl guanidines metal iodide ions product liquid "-substituent R ' be cyclohexyl; n-octyl; or phenyl, N "-substituent R " be CH
3, Y is I;
2. get the N that 0.30mol was made by (1) step "-substituent R ' be normal-butyl; cyclohexyl; n-octyl; or five alkyl guanidine compounds of phenyl are dissolved in 20～100mL purified acetonitrile; under ice-water bath cooling and nitrogen protection; splash into the single methyl iodide of 0.30～0.33mol of new steaming and the mixed solution of 20～100mL acetonitrile; treat to continue stirring reaction 12～48 hours after system temperature returns to room temperature; steam the acetonitrile that removes in the reaction system; raffinate washs 2～5 times with ethyl acetate; the ethyl acetate that vacuum is taken out in the system promptly makes 0.12～0.30mol, six alkyl guanidine metal iodide ions liquid; getting the six alkyl guanidine metal iodide ions liquid that 0.30mol makes thus is dissolved in 20～100mL distilled water; stirring down, Dropwise 5 0mL is dissolved with 0.30～0.31mol sodium tetrafluoroborate; or the aqueous solution of Potassium Hexafluorophosphate; in stirring at room 1～10 hour; divide oil-yielding stratum, it is dissolved in the CH of 40～100mL
2Cl
2In, with 40～100mL distilled water wash, the organic phase anhydrous Na
2SO
4Drying, normal pressure are steamed and are desolventized CH
2Cl
2, promptly make 0.12～0.30mol hexaalkylguanidium salts ionic liquid, N in this hexaalkylguanidium salts ionic liquid product "-substituent R ' be normal-butyl, cyclohexyl, n-octyl or phenyl, N "-substituent R " be CH
3, Y is tetrafluoroborate negatively charged ion or hexafluoro-phosphate radical negatively charged ion;
3. getting 0.30mol 2. goes on foot the six alkyl guanidine metal iodide ions liquid that make by (3) and is dissolved in 20～100mL distilled water, stir the slow down 60mL of dropping and be dissolved with 0.30～0.31mol acetate, trifluoromethyl acetate, trifluoromethane sulfonic acid, lactic acid, or the aqueous solution of the lead salt of methylsulphonic acid, produce yellow mercury oxide rapidly, violent stirring is 1～2 hour under room temperature, decompress filter is removed yellow solid, promptly make 0.15～0.27mol hexaalkylguanidium salts ionic liquid after water in the filtrate removed, N in this hexaalkylguanidium salts ionic liquid product "-substituent R ' be normal-butyl; cyclohexyl; n-octyl; or phenyl, N "-substituent R " be CH
3, Y is acetic acid anion, trifluoromethyl acetic acid anion, trifluoromethane sulfonic acid root negatively charged ion, lactic acid anion or methylsulphonic acid root negatively charged ion;
Change the consumption of reactant and solvent among the above-mentioned preparation method according to actual needs in proportion, promptly make the ionic liquid of alkyl guanidine salt of aequum.
Beneficial effect of the present invention is: be catalyzer with ionic liquid of alkyl guanidine salt of the present invention in organic synthesis, reaction process is simpler, and easy handling, and catalyst activity height, good reproducibility realize that easily industry amplifies; Ionic liquid of alkyl guanidine salt is big to carbon dioxide adsorption in the building-up reactions of diethylene glycol bis-allyl carbonate, helps improving the concentration of carbonic acid gas in the reaction liquid phase, thereby promotes the carrying out of reaction; Ionic liquid of alkyl guanidine salt is easy to separate as catalyzer, and post-reaction treatment is simple, helps obtaining the purity high product;
The preparation method of alkyl guanidine salt ionic liquid of the present invention has following characteristics: in synthesis step, with the tetramethyl-urea is raw material, adopted the synthetic N of two kinds of diverse ways "-five alkyl guanidines of different substituents, and then synthesized five ionic liquid of alkyl guanidine salt of a series of different anions; Be that raw material has synthesized six alkyl guanidine halogens with five alkyl guanidines again, and then the hexaalkylguanidium salts ionic liquid of a series of different anions of resynthesis.This method is raw materials used single, as required, can synthesize multiple ionic liquid of alkyl guanidine salt product on a response line.
Embodiment
Embodiment 1
N, N, N ', N '-tetramethyl--N "-butyl guanidine (BuTMG) synthetic, a kind of in optional following two kinds of methods
1. get the 0.30mol tetramethyl-urea and be dissolved in the 60mL toluene, under nitrogen protection and agitation condition, splash into the 0.32mol POCl of new steaming
3, use 170mL CH down at 3 ℃ after 20 hours in reaction under 60 ℃
2Cl
2The diluting reaction system slowly splashes into the 1.27mol n-Butyl Amine 99, refluxes 30 hours after being warming up to 55 ℃, and it is neutral to system is shown to splash into mass percent and be 35% NaOH solution under the ice bath cooling, reaction mixture 170mL CH
2Cl
2Extraction merges organic phase, uses anhydrous Na
2SO
4Dry 48 hours after-filtration, steaming desolventizes, and raffinate gets the 0.17mol target product through underpressure distillation.FTIR(KBr)：υ
max：2927，2870，1625，1494，1454，1363，1145cm
-1。
2. get the 0.30mol tetramethyl-urea and be dissolved in the 150mL toluene, under nitrogen protection and agitation condition, splash into the 0.30mol POCl of new steaming
3, after reacting 5 hours down, room temperature condition drips the 0.66mol n-Butyl Amine 99, at room temperature stirred after finishing 20 hours, after 150mL water diluting reaction system, vigorous stirring 10 minutes is taken off a layer solution, toward wherein adding solid NaOH to making system show alkalescence, then solution divides two-layer, solid filtering is fallen, after the filtrate layering, get upper solution, it is dissolved in the ether, uses anhydrous Na then
2CO
3Dry after-filtration, steaming desolventizes, and raffinate gets the 0.09mol target product through underpressure distillation.FTIR(KBr)：υ
max：2927，2870，1625，1494，1454，1363，1145cm
-1。
Embodiment 2
N, N, N ', N '-tetramethyl--N "-cyclohexyl guanidine (CyTMG) synthetic
Get the 0.30mol tetramethyl-urea and be dissolved in the 200mL toluene, under nitrogen protection and agitation condition, splash into the 0.33mol POCl of new steaming
3, after reacting 2 hours down, room temperature condition drips the 0.75mol hexahydroaniline, at room temperature stirred after finishing 48 hours, after 200mL water diluting reaction system, vigorous stirring 5 minutes is taken off a layer solution, toward wherein adding solid NaOH to making system show alkalescence, then solution divides two-layer, solid filtering is fallen, after the filtrate layering, get upper solution, it is dissolved in the ether, uses anhydrous Na then
2CO
3Dry after-filtration, steaming desolventizes, and raffinate gets the 0.11mol target product through underpressure distillation.FTIR(KBr)：υ
max：2926，2852，1625，1494，1450，1361，1145，1124，796，752cm
-1。
Embodiment 3
N, N, N ', N '-tetramethyl--N "-octyl group guanidine (OctTMG) synthetic
Get the 0.30mol tetramethyl-urea and be dissolved in the 175mL toluene, under nitrogen protection and agitation condition, splash into the 0.31mol POCl of new steaming
3, after reacting 10 hours down, room temperature condition drips the 0.70mol n-octyl amine, at room temperature stirred after finishing 34 hours, after 175mL water diluting reaction system, vigorous stirring 30 minutes is taken off a layer solution, toward wherein adding solid NaOH to making system show alkalescence, then solution divides two-layer, solid filtering is fallen, after the filtrate layering, get upper solution, it is dissolved in the ether, uses anhydrous Na then
2CO
3Dry after-filtration, steaming desolventizes, and raffinate gets the 0.10mol target product through underpressure distillation.FTIR(KBr)：υ
max：2922，2852，1611，1477，1430，1383，1142cm
-1。
Embodiment 4
N, N, N ', N '-tetramethyl--N "-benzene guanidine (PhTMG) synthetic
Get the 0.30mol tetramethyl-urea and be dissolved in the 70mL toluene, under nitrogen protection and agitation condition, splash into the 0.32molPOCl of new steaming
3, use 180mL CH down at 0 ℃ after 30 hours in reaction under 60 ℃
2Cl
2The diluting reaction system slowly splashes into 1.30mol aniline, refluxes 28 hours after being warming up to 51 ℃, and it is neutral to system is shown to splash into mass percent and be 35% NaOH solution under the ice bath cooling, reaction mixture 200mL CH
2Cl
2Extraction merges organic phase, uses anhydrous Na
2SO
4Dry 54 hours after-filtration, steaming desolventizes, and raffinate gets the 0.24mol target product through underpressure distillation.FTIR(KBr)：υ
max：3071，3006，2925，2886，1605，1575，1505，1487，1377，1140，1018，782，695cm
-1。
Embodiment 5
N, N, N ', N '-tetramethyl--N "-methyl-N "-butyl guanidine salt compounded of iodine ([MBuTMG] I) synthetic
Press embodiment 1 synthetic five alkyl guanidine BuTMG.Getting 0.30mol BuTMG is dissolved in the purified 20mL acetonitrile; under ice-water bath cooling and nitrogen protection; splash into the 0.30mol methyl iodide and the 20mL acetonitrile mixed solution of new steaming; treat to continue stirring reaction 12 hours after system temperature returns to room temperature; steam the acetonitrile that removes in the reaction system; raffinate is with ethyl acetate washing 2 times, and vacuum promptly makes the 0.24mol target product after taking out ethyl acetate in the system.FTIR(KBr)：υ
max：2956，2873，1586，1470，1408，1255，1155，900cm
-1。
Embodiment 6
N, N, N ', N-' tetramethyl--N "-methyl-N "-cyclohexyl guanidine salt compounded of iodine ([MCyTMG] I) synthetic
Press embodiment 2 synthetic five alkyl guanidine CyTMG.Getting 0.30mol CyTMG is dissolved in the purified 60mL acetonitrile; under ice-water bath cooling and nitrogen protection; splash into the 0.32mol methyl iodide and the 60mL acetonitrile mixed solution of new steaming; treat that system temperature recovers the back and continued stirring reaction 30 hours; steam the acetonitrile that removes in the reaction system; raffinate washs 3 times with ethyl acetate, and the ethyl acetate that vacuum is taken out in the system promptly makes the 0.13mol target product.FTIR(KBr)：υ
max：2930，2857，1598，1470，1450，1407，1257，1151，898cm
-1。
Embodiment 7
N, N, N ', N '-tetramethyl--N "-methyl-N "-octyl group guanidine salt compounded of iodine ([MOctTMG] I) synthetic
Press embodiment 3 synthetic five alkyl guanidine OctTMG.Get 0.30mol OctTMG and be dissolved in purified 100mL acetonitrile; under ice-water bath cooling and nitrogen protection; splash into the 0.33mol methyl iodide and the 100mL acetonitrile mixed solution of new steaming; treat to continue stirring reaction 48 hours after system temperature returns to room temperature; steam the acetonitrile that removes in the reaction system; raffinate washs 5 times with ethyl acetate, and the ethyl acetate that vacuum is taken out in the system promptly makes the 0.19mol target product.FTIR(KBr)：υ
max：2922，2852，1651，1513，1498，1392，1255，1156，900cm
-1。
Embodiment 8
N, N, N ', N '-tetramethyl--N "-methyl-N "-guanidines salt compounded of iodine ([MPhTMG] I) synthetic
Press embodiment 4 synthetic five alkyl guanidine PhTMG.Get 0.30mol PhTMG and be dissolved in purified 20mL acetonitrile; under ice-water bath cooling and nitrogen protection; splash into the 0.32mol methyl iodide and the 20mL acetonitrile mixed solution of new steaming; treat to continue stirring reaction 15 hours after system temperature returns to room temperature; steam the acetonitrile that removes in the reaction system; raffinate washs 2 times with ethyl acetate, and the ethyl acetate that vacuum is taken out in the system promptly makes the 0.22mol target product.FTIR(KBr)：υ
max：3091，3115，2940，2898，1646，1618，1580，1536，1520，1500，1498，1377，1258，1156，1026，900，792，716cm
-1。
Embodiment 9
N, N, N ', N '-tetramethyl--N "-methyl-N "-butyl guanidine tetrafluoroborate ion liquid ([MBTMG] BF
4) synthetic
Press embodiment 5 synthetic six alkyl guanidine salt compounded of iodine [MBTMG] I.Getting 0.30mol[MBTMG] I is dissolved in the 50mL distilled water, and stirring down, Dropwise 5 0mL contains 0.30mol NaBF
4The aqueous solution, in stirring at room 1 hour.Divide oil-yielding stratum, it is dissolved in 100mL CH
2Cl
2In, use the 100mL distilled water wash, use anhydrous Na
2SO
4Dry organic phase, steaming desolventizes and promptly gets the 0.27mol target product.FTIR(KBr)：υ
max：2958，2873，1582，1468，1408，1255，1155，1084，900cm
-1。
Embodiment 10
N, N, N ', N '-tetramethyl--N "-methyl-N "-cyclohexyl guanidine a tetrafluoro borate ([MCyTMG] BF
4) ion liquid synthetic
Press embodiment 6 synthetic six alkyl guanidine salt compounded of iodine [MCyTMG] I.Getting 0.30mol[MCyTMG] I is dissolved in the 20mL distilled water, and stirring down, Dropwise 5 0mL contains 0.30mol NaBF
4The aqueous solution, in stirring at room 1 hour, divide oil-yielding stratum, it is dissolved in 40mL CH
2Cl
2In, use the 40mL distilled water wash, use anhydrous Na
2SO
4Dry organic phase, normal pressure are steamed and are desolventized, and promptly make the 0.28mol target product.FTIR(KBr)：υ
max：2932，2858，1597，1469，1453，1408，1257，1148，1084，899cm
-1。
Embodiment 11
N, N, N ', N '-tetramethyl--N "-methyl-N "-octyl group guanidine tetrafluoroborate ion liquid ([MOctTMG] BF
4) synthetic
Press embodiment 7 synthetic six alkyl guanidine salt compounded of iodine [MOctTMG] I.Getting 0.30mol[MOctTMG] I is dissolved in the 50mL distilled water, and stirring down, Dropwise 5 0mL contains 0.31mol NaBF
4The aqueous solution, in stirring at room 5 hours, divide oil-yielding stratum, it is dissolved in 70mL CH
2Cl
2In, use the 70mL distilled water wash, use anhydrous Na
2SO
4Dry organic phase, normal pressure are steamed and are desolventized, and promptly make the 0.23mol target product.FTIR(KBr)：υ
max：2922，2852，1648，1513，1498，1392，1255，1156，1084，900cm
-1。
Embodiment 12
N, N, N ', N '-tetramethyl--N "-methyl-N "-guanidines tetrafluoroborate ion liquid ([MPhTMG] BF
4) synthetic
Press embodiment 8 synthetic six alkyl guanidine salt compounded of iodine [MPhTMG] I.Getting 0.30mol[MPhTMG] I is dissolved in the 100mL distilled water, and stirring down, Dropwise 5 0mL contains 0.31mol NaBF
4The aqueous solution, in stirring at room 10 hours, divide oil-yielding stratum, it is dissolved in 100mL CH
2Cl
2In, use the 100mL distilled water wash, use anhydrous Na
2SO
4Dry organic phase, normal pressure are steamed and are desolventized, and promptly make the 0.24mol target product.FTIR(KBr)：υ
max：3100，3118，2946，2898，1640，1618，1580，1536，1520，1500，1498，1377，1258，1156，1084，1026，900，792，716cm
-1。
Embodiment 13
N, N, N ', N '-tetramethyl--N "-methyl-N "-butyl guanidine hexafluorophosphate ionic liquid ([MBTMG] PF
6) synthetic
Press embodiment 5 synthetic six alkyl guanidine salt compounded of iodine [MBTMG] I.Getting 0.30mol[MBTMG] I is dissolved in the 50mL distilled water, and stirring down, Dropwise 5 0mL contains 0.30mol KPF
6The aqueous solution, in stirring at room 2 hours, divide oil-yielding stratum, it is dissolved in 100mL CH
2Cl
2In, use the 100mL distilled water wash, use anhydrous Na
2SO
4Dry organic phase, normal pressure are steamed and are desolventized, and promptly make the 0.22mol target product.FTIR(KBr)：υ
max：2969，2883，1587，1476，1412，1254，1151，899，840cm
-1。
Embodiment 14
N, N, N ', N '-tetramethyl--N "-methyl-N "-cyclohexyl guanidine hexafluorophosphate ionic liquid ([MCyTMG] PF
6) synthetic
Press embodiment 6 synthetic six alkyl guanidine salt compounded of iodine [MCyTMG] I.Getting 0.30mol[MCyTMG] I is dissolved in the 50mL distilled water, and stirring down, Dropwise 5 0mL contains 0.30mol KPF
6The aqueous solution, in stirring at room 2 hours, divide oil-yielding stratum, it is dissolved in 100mLCH
2Cl
2In, use the 100mL distilled water wash, use anhydrous Na
2SO
4Dry organic phase, normal pressure are steamed and are desolventized, and promptly make the 0.17mol target product.FTIR(KBr)：υ
max：2933，2862，1596，1476，1457，1411，1259，1150，898，840cm
-1。
Embodiment 15
N, N, N ', N '-tetramethyl--N "-methyl-N "-octyl group guanidine hexafluorophosphate ionic liquid ([MOctTMG] PF
6) synthetic
Press embodiment 7 synthetic six alkyl guanidine salt compounded of iodine [MOctTMG] I.Getting 0.30mol[MOctTMG] I is dissolved in the 50mL distilled water, and stirring down, Dropwise 5 0mL contains 0.30mol KPF
6The aqueous solution, in stirring at room 2 hours, divide oil-yielding stratum, it is dissolved in 100mL CH
2Cl
2In, use the 100mL distilled water wash, use anhydrous Na
2SO
4Dry organic phase, normal pressure are steamed and are desolventized, and promptly make the 0.20mol target product.FTIR(KBr)：υ
max：2936，2856，1652，1513，1498，1392，1254，1155，900，840cm
-1。
Embodiment 16
N, N, N ', N '-tetramethyl--N "-methyl-N "-guanidines hexafluorophosphate ionic liquid ([MPhTMG] PF
6) synthetic
Press embodiment 8 synthetic six alkyl guanidine salt compounded of iodine [MPhTMG] I.Getting 0.30mol[MPhTMG] I is dissolved in the 50mL distilled water, and stirring down, Dropwise 5 0mL contains 0.30mol KPF
6The aqueous solution, in stirring at room 2 hours, divide oil-yielding stratum, it is dissolved in 100mL CH
2Cl
2In, use the 100mL distilled water wash, use anhydrous Na
2SO
4Dry organic phase, normal pressure are steamed and are desolventized, and promptly make the 0.24mol target product.FTIR(KBr)：υ
max：3092，3115，2942，2900，1648，1618，1580，1536，1520，1500，1498，1377，1256，1158，1028，899，840，792，716cm
-1。
Embodiment 17
N, N, N ', N '-tetramethyl--N "-methyl-N "-butyl glucocyamine salt ion liquid ([MBTMG] CH
3Synthesizing COO)
Press embodiment 5 synthetic six alkyl guanidine salt compounded of iodine [MBTMG] I.Getting 0.30mol[MBTMG] I is dissolved in the 20mL distilled water, stirs slowly to drip 60mL down and contain 0.15mol Pb (CH
3COO)
2The aqueous solution, produce yellow mercury oxide rapidly, violent stirring is 1 hour under room temperature, decompress filter is removed yellow solid, promptly makes the 0.27mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2963，2877，1694，1581，1469，1409，1255，1171，899，801cm
-1。
Embodiment 18
N, N, N ', N '-tetramethyl--N "-methyl-N "-cyclohexyl glucocyamine salt ion liquid ([MCyTMG] CH
3Synthesizing COO)
Press embodiment 6 synthetic six alkyl guanidine salt compounded of iodine [MCyTMG] I.Getting 0.30mol[MCyTMG] I is dissolved in the 60mL distilled water, stirs to drip 60mL down and contain 0.15mol Pb (CH
3COO)
2The aqueous solution, produce yellow mercury oxide rapidly, violent stirring is 1.5 hours under room temperature, decompress filter is removed yellow solid, promptly makes the 0.26mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2930，2857，1702，1598，1470，1450，1407，1257，1151，898，822cm
-1。
Embodiment 19
N, N, N ', N '-tetramethyl--N "-methyl-N "-octyl group glucocyamine salt ion liquid ([MOctTMG] CH
3Synthesizing COO)
Press embodiment 7 synthetic six alkyl guanidine salt compounded of iodine [MOctTMG] I.Getting 0.30mol[MOctTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15mol Pb (CH
3COO)
2The aqueous solution, produce yellow mercury oxide rapidly, violent stirring is 2 hours under room temperature, decompress filter is removed yellow solid, promptly makes the 0.24mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2922，2852，1726，1651，1513，1498，1392，1255，1156，900，826cm
-1。
Embodiment 20
N, N, N ', N '-tetramethyl--N "-methyl-N "-guanidines acetate ions liquid ([MPhTMG] CH
3Synthesizing COO)
Press embodiment 8 synthetic six alkyl guanidine salt compounded of iodine [MPhTMG] I.Getting 0.30mol[MPhTMG] I is dissolved in the 50mL distilled water, stirs to drip 60mL down and contain 0.15mol Pb (CH
3COO)
2The aqueous solution, produce yellow mercury oxide rapidly, violent stirring is 1 hour under room temperature, decompress filter is removed yellow solid, promptly makes the 0.23mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：3091，3115，2940，2898，1728，1646，1618，1580，1536，1520，1500，1498，1377，1258，1156，1026，900，828，792，716cm
-1。
Embodiment 21
N, N, N ', N '-tetramethyl--N "-methyl-N "-butyl guanidine trifluoromethyl acetate ions liquid ([MBTMG] CF
3Synthesizing COO)
Get 0.15mol yellow lead oxide and 50mL distilled water and be mixed in the 100mL beaker and stir, get 0.30mol trifluoromethyl acetate again and slowly add wherein, plumbous oxide dissolves immediately, and following reaction takes place:
PbO+2CF
3COOH→Pb(CF
3COO)
2+H
2O
Press embodiment 5 synthetic six alkyl guanidine salt compounded of iodine [MBTMG] I.Getting 0.30mol[MBTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15mol Pb (CF
3COO)
2The aqueous solution, produce rapidly precipitation, violent stirring is 1 hour under room temperature, decompress filter is removed yellow solid, promptly makes the 0.18mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2961，2875，1694，1579，1470，1408，1256，1201，1171，1125，1065，1036，899，640cm
-1。
Embodiment 22
N, N, N ', N '-tetramethyl--N "-methyl-N "-cyclohexyl guanidine trifluoromethyl acetate ions liquid ([MCyTMG] CF
3Synthesizing COO)
Press embodiment 21 synthetic Pb (CF
3COO)
2The aqueous solution; Press embodiment 6 synthetic six alkyl guanidine salt compounded of iodine [MCyTMG] I.Getting 0.30mol[MCyTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15molPb (CF
3COO)
2The aqueous solution, produce rapidly precipitation, violent stirring is 1 hour under room temperature, decompress filter is removed yellow solid, promptly makes the 0.21mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2930，2857，1702，1598，1470，1450，1407，1257，1176，1151，1038，898，642cm
-1。
Embodiment 23
N, N, N ', N '-tetramethyl--N "-methyl-N "-octyl group guanidine trifluoromethyl acetate ions liquid ([MOctTMG] CF
3Synthesizing COO)
Press embodiment 21 synthetic Pb (CF
3COO)
2The aqueous solution; Press embodiment 7 synthetic six alkyl guanidine salt compounded of iodine [MOctTMG] I.Get 0.30mol [MOctTMG] I and be dissolved in the 100mL distilled water, stirring down, dropping 60mL contains 0.15molPb (CF
3COO)
2The aqueous solution, produce rapidly precipitation, violent stirring is 1 hour under room temperature, decompress filter is removed yellow solid, promptly makes the 0.17mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2922，2852，1706，1651，1513，1498，1392，1255，1178，1156，1037，900，644cm
-1。
Embodiment 24
N, N, N ', N '-tetramethyl--N "-methyl-N "-guanidines trifluoromethyl acetate ions liquid ([MPhTMG] CF
3Synthesizing COO)
Press embodiment 21 synthetic Pb (CF
3COO)
2The aqueous solution; Press embodiment 8 synthetic six alkyl guanidine salt compounded of iodine [MPhTMG] I.Getting 0.30mol[MPhTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15molPb (CF
3COO)
2The aqueous solution, produce rapidly precipitation, violent stirring is 1 hour under room temperature, decompress filter is removed yellow solid, promptly makes the 0.20mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：3089，3116，2942，2889，1710，1644，1620，1584，1536，1520，1500，1498，1377，1258，1176，1156，1038，1026，900，792，716，645cm
-1。
Embodiment 25
N, N, N ', N '-tetramethyl--N "-methyl-N "-butyl guanidine trifluoromethyl sulfonic acid ionic liquid ([MBTMG] CF
3SO
3) synthetic
Get 0.15mol yellow lead oxide and 50mL distilled water and be mixed in the 100mL beaker and stir, get the 0.30mol trifluoromethane sulfonic acid again and slowly add wherein, plumbous oxide dissolves immediately, and following reaction takes place:
PbO+2CF
3SO
3H→Pb(CF
3SO
3)
2+H
2O
Press embodiment 5 synthetic six alkyl guanidine salt compounded of iodine [MBTMG] I.Getting 0.30mol[MBTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15mol Pb (CF
3SO
3)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.16mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2881，2972，1600，1581，1475，1458，1409，1265，1156，1031，889，639cm
-1。
Embodiment 26
N, N, N ', N '-tetramethyl--N "-methyl-N "-cyclohexyl guanidine trifluoromethyl sulfonic acid ionic liquid ([MCyTMG] CF
3SO
3) synthetic
Press embodiment 25 synthetic Pb (CF
3SO
3)
2The aqueous solution; Press embodiment 6 synthetic six alkyl guanidine salt compounded of iodine [MCyTMG] I.Getting 0.30mol[MCyTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15molPb (CF
3SO
3)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.18mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2930，2857，1620，1598，1470，1450，1407，1257，1151，1036，898，640cm
-1。
Embodiment 27
N, N, N ', N '-tetramethyl--N "-methyl-N "-octyl group guanidine trifluoromethyl sulfonic acid ionic liquid ([MOctTMG] CF
3SO
3) synthetic
Press embodiment 25 synthetic Pb (CF
3SO
3)
2The aqueous solution; Press embodiment 7 synthetic six alkyl guanidine salt compounded of iodine [MOctTMG] I.Getting 0.30mol[MOctTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15molPb (CF
3SO
3)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.22mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2922，2852，1651，1624，1513，1498，1392，1255，1156，1042，900，642cm
-1。
Embodiment 28
N, N, N ', N '-tetramethyl--N "-methyl-N "-guanidines trifluoromethyl sulfonic acid ionic liquid ([MPhTMG] CF
3SO
3) synthetic
Press embodiment 25 synthetic Pb (CF
3SO
3)
2The aqueous solution; Press embodiment 8 synthetic six alkyl guanidine salt compounded of iodine [MPhTMG] I.Getting 0.30mol[MPhTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15molPb (CF
3SO
3)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.24mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：3091，3115，2940，2898，1646，1620，1580，1536，1520，1500，1498，1377，1258，1156，1036，1026，900，792，716，636cm
-1。
Embodiment 29
N, N, N ', N '-tetramethyl--N "-methyl-N "-butyl guanidine lactate ions liquid ([MBTMG] CH
3Synthesizing CHOHCOO)
Get 0.15mol yellow lead oxide and 50mL distilled water and be mixed in the 100mL beaker and stir, get 0.30mol lactic acid again and slowly add wherein, plumbous oxide dissolves immediately, and following reaction takes place:
Press embodiment 5 synthetic six alkyl guanidine salt compounded of iodine [MBTMG] I.Getting 0.30mol[MBTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15mol Pb (CH
3CHOHCOO)
2The aqueous solution, produce rapidly precipitation, continue under seed cell's temperature to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.16mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2929，2868，1587，1462，1416，1402，1246，1153，1058，895cm
-1。
Embodiment 30
N, N, N ', N '-tetramethyl--N "-methyl-N "-cyclohexyl guanidine lactate ions liquid ([MCyTMG] CH
3Synthesizing CHOHCOO)
Press embodiment 29 synthetic Pb (CH
3CHOHCOO)
2The aqueous solution; Press embodiment 6 synthetic six alkyl guanidine salt compounded of iodine [MCyTMG] I.Getting 0.30mol[MCyTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15mol Pb (CH
3CHOHCOO)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.18mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2930，2857，1598，1470，1450，1418，1407，1257，1248，1151，1056，898cm
-1。
Embodiment 31
N, N, N ', N '-tetramethyl--N "-methyl-N "-octyl group guanidine lactate ions liquid ([MOctTMG] CH
3Synthesizing CHOHCOO)
Press embodiment 29 synthetic Pb (CH
3CHOHCOO)
2The aqueous solution; Press embodiment 7 synthetic six alkyl guanidine salt compounded of iodine [MOctTMG] I.0.30mol[MOctTMG] I is dissolved in the 100mL distilled water stirring and drips 60mL down and contain 0.15molPb (CH
3CHOHCOO)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.20mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2922，2852，1651，1513，1498，1418，1392，1255，1244，1156，1052，900cm
-1。
Embodiment 32
N, N, N ', N '-tetramethyl--N "-methyl-N "-guanidines lactate ions liquid ([MPhTMG] CH
3Synthesizing CHOHCOO)
Press embodiment 29 synthetic Pb (CH
3CHOHCOO)
2The aqueous solution; Press embodiment 8 synthetic six alkyl guanidine salt compounded of iodine [MPhTMG] I.Getting 0.30mol[MPhTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15mol Pb (CH
3CHOHCOO)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.19mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：3096，3116，2941，2896，1645，1619，1582，1536，1520，1500，1498，1418，1377，1258，1248，1156，1055，1026，900，794，718cm
-1。
Embodiment 33
N, N, N ', N '-tetramethyl--N "-methyl-N "-butyl guanidine metilsulfate ionic liquid ([MBTMG] CH
3SO
3) synthetic
Getting 0.15mol yellow lead oxide and 50mL distilled water is mixed in the 100mL beaker and stirs.Get the 0.30mol methylsulphonic acid and slowly add wherein, plumbous oxide dissolves immediately, and following reaction takes place:
PbO+2CH
3SO
3H→Pb(CH
3SO
3)
2+H
2O
Press embodiment 5 synthetic six alkyl guanidine salt compounded of iodine [MBTMG] I.Getting 0.30mol[MBTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15mol Pb (CH
3SO
3)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.23mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2882，2974，1600，1581，1475，1458，1409，1268，1154，889cm
-1。
Embodiment 34
N, N, N ', N '-tetramethyl--N "-methyl-N "-cyclohexyl guanidine metilsulfate ionic liquid ([MCyTMG] CH
3SO
3) synthetic
Press embodiment 33 synthetic Pb (CH
3SO
3)
2The aqueous solution; Press embodiment 6 synthetic six alkyl guanidine salt compounded of iodine [MCyTMG] I.Getting 0.30mol[MCyTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15molPb (CH
3SO
3)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.21mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2934，2856，1622，1598，1470，1450，1407，1258，1151，898cm
-1。
Embodiment 35
N, N, N ', N '-tetramethyl--N "-methyl-N "-octyl group guanidine metilsulfate ionic liquid ([MOctTMG] CH
3SO
3) synthetic
Press embodiment 33 synthetic Pb (CH
3SO
3)
2The aqueous solution; Press embodiment 7 synthetic six alkyl guanidine salt compounded of iodine [MOctTMG] I.Getting 0.30mol[MOctTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15molPb (CH
3SO
3)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.24mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：2926，2858，1651，1628，1513，1498，1392，1256，1154，900cm
-1。
Embodiment 36
N, N, N ', N '-tetramethyl--N "-methyl-N "-guanidines metilsulfate ionic liquid ([MPhTMG] CH
3SO
3) synthetic
Press embodiment 33 synthetic Pb (CH
3SO
3)
2The aqueous solution; Press embodiment 8 synthetic six alkyl guanidine salt compounded of iodine [MPhTMG] I.Getting 0.30mol[MPhTMG] I is dissolved in the 100mL distilled water, stirs to drip 60mL down and contain 0.15molPb (CH
3SO
3)
2The aqueous solution, produce rapidly precipitation, under room temperature, continue to stir 1 hour, decompress filter is removed yellow solid, promptly makes the 0.19mol target product after the water in the filtrate is removed.FTIR(KBr)：υ
max：3096，3118，2942，2898，1646，1620，1580，1536，1520，1500，1498，1377，1258，1156，1026，900，792，716cm
-1。
Embodiment 37
N, N, N ', N '-tetramethyl--N "-butyl guanidine a tetrafluoro borate ([HBTMG] BF
4) ion liquid synthetic
Press embodiment 1 synthetic five alkyl guanidine BuTMG, get 0.30mol BuTMG and 0.30mol HBF
4Carry out neutralization reaction and promptly make the 0.24mol target product.FTIR(KBr)：υ
max：2956，2875，1580，1466，1407，1254，1156，1084cm
-1。
Embodiment 38
N, N, N ', N '-tetramethyl--N "-butyl guanidine trifluoromethyl acetate ions liquid ([HBTMG] CF
3Synthesizing COO)
Press embodiment 1 synthetic five alkyl guanidine BuTMG.Get 0.30mol BuTMG and 0.30mol CF
3COOH carries out neutralization reaction and promptly makes the 0.23mol target product.FTIR(KBr)：υ
max：2962，2878，1694，1580，1472，1406，1255，1201，1172，1125，1065cm
-1。
Embodiment 39
N, N, N ', N '-tetramethyl--N "-butyl guanidine trifluoromethyl sulfonic acid ionic liquid ([HBTMG] CF
3SO
3) synthetic
Press embodiment 1 synthetic five alkyl guanidine BuTMG.Get 0.30mol BuTMG and 0.30mol CF
3SO
3H carries out neutralization reaction and promptly makes the 0.22mol target product.FTIR(KBr)：υ
max：2882，2974，1602，1584，1468，1452，1406，1264，1155，1031，639cm
-1。
Embodiment 40
N, N, N ', N '-tetramethyl--N "-butyl guanidine lactate ions liquid ([HBTMG] CH
3Synthesizing CHOHCOO)
Press embodiment 1 synthetic five alkyl guanidine BuTMG.Get 0.30mol BuTMG and 0.30mol CH
3CHOHCOOH carries out neutralization reaction and promptly makes the 0.26mol target product.FTIR(KBr)：υ
max：2930，2872，1589，1464，1416，1402，1246，1156，1058cm
-1。
Embodiment 41
N, N, N ', N '-tetramethyl--N "-butyl guanidine metilsulfate ionic liquid ([HBTMG] CH
3SO
3) synthetic
Press embodiment 1 synthetic five alkyl guanidine BuTMG.Get 0.30mol BuTMG and 0.30mol CH
3SO
3H carries out neutralization reaction and promptly makes the 0.28mol target product.FTIR(KBr)：υ
max：2882，2974，1600，1576，1475，1456，1409，1265，1156cm
-1。
Embodiment 42
N, N, N ', N '-tetramethyl--N "-butyl guanidine formate ionic liquid ([HBTMG] HCOO) synthetic
Press embodiment 1 synthetic five alkyl guanidine BuTMG.Getting 0.30mol BuTMG and 0.31mol HCOOH carries out neutralization reaction and promptly makes the 0.27mol target product.FTIR(KBr)：υ
max：2961，2875，1694，1579，1470，1408，1256，1201，1171，1125，1065cm
-1。
Embodiment 43
N, N, N ', N '-tetramethyl--N "-cyclohexyl guanidine a tetrafluoro borate ([HCyTMG] BF
4) ion liquid synthetic
Press embodiment 2 synthetic five alkyl guanidine CyTMG.Get 0.30mol CyTMG and 0.30mol HBF
4Carry out neutralization reaction and promptly make the 0.29mol target product.FTIR(KBr)：υ
max：2932，2858，1598，1472，1456，1412，1255，1148，1084cm
-1。
Embodiment 44
N, N, N ', N '-tetramethyl--N "-cyclohexyl guanidine hexafluorophosphate ionic liquid ([HCyTMG] PF
6) synthetic
Press embodiment 2 synthetic five alkyl guanidine CyTMG.Get 0.30mol CyTMG and 0.30mol HPF
6Carry out neutralization reaction and promptly make the 0.27mol target product.FTIR(KBr)：υ
max：2932，2866，1572，1478，1456，1411，1262，1154，840cm
-1。
Embodiment 45
N, N, N ', N '-tetramethyl--N "-cyclohexyl glucocyamine salt ion liquid ([HCyTMG] CH
3Synthesizing COO)
Press embodiment 2 synthetic five alkyl guanidine CyTMG.Get 0.30mol CyTMG and 0.30mol CH
3COOH carries out neutralization reaction and promptly makes the 0.28mol target product.FTIR(KBr)：υ
max：2932，2856，1704，1586，1468，1452，1416，1256，1151，822cm
-1。
Embodiment 46
N, N, N ', N '-tetramethyl--N "-cyclohexyl guanidine trifluoromethyl acetate ions liquid ([HCyTMG] CF
3Synthesizing COO)
Press embodiment 2 synthetic five alkyl guanidine CyTMG.Get 0.30mol CyTMG and 0.30mol CF
3COOH carries out neutralization reaction and promptly makes the 0.22mol target product.FTIR(KBr)：υ
max：2962，2878，1688，1572，1468，1406，1255，1201，1171，1124，1065，1036，640cm
-1。
Embodiment 47
N, N, N ', N '-tetramethyl--N "-cyclohexyl guanidine trifluoromethyl sulfonic acid ionic liquid ([HCyTMG] CF
3SO
3) synthetic
Press embodiment 2 synthetic five alkyl guanidine CyTMG.Get 0.30mol CyTMG and 0.30mol CF
3SO
3H carries out neutralization reaction and promptly makes the 0.23mol target product.FTIR(KBr)：υ
max：2932，2854，1622，1587，1476，1450，1407，1256，1152，1036，640cm
-1。
Embodiment 48
N, N, N ', N '-tetramethyl--N "-cyclohexyl guanidine lactate ions liquid ([HCyTMG] CH
3Synthesizing CHOHCOO)
Press embodiment 2 synthetic five alkyl guanidine CyTMG.Get 0.30mol CyTMG and 0.30mol CH
3CHOHCOOH carries out neutralization reaction and promptly makes the 0.22mol target product.FTIR(KBr)：υ
max：2928，2854，1589，1468，1450，1418，1407，1254，1246，1155，1056cm
-1。
Embodiment 49
N, N, N ', N '-tetramethyl--N "-cyclohexyl guanidine metilsulfate ionic liquid ([HCyTMG] CH
3SO
3) synthetic
Press example 2 synthetic five alkyl guanidine CyTMG.Get 0.30mol CyTMG and 0.30mol CH
3SO
3H carries out neutralization reaction and promptly makes the 0.25mol target product.FTIR(KBr)：υ
max：2928，2848，1623，1596，1470，1450，1407，1256，1152cm
-1。
Example 50 is executed in enforcement
N, N, N ', N '-tetramethyl--N "-cyclohexyl guanidine formate ionic liquid ([HCyTMG] HCOO) synthetic
Press example 2 synthetic five alkyl guanidine CyTMG.Getting 0.30mol CyTMG and 0.30mol HCOOH carries out neutralization reaction and promptly makes the 0.26mol target product.FTIR(KBr)：υ
max：2968，2876，1686，1572，1466，1406，1254，1201，1171，1125，1065cm
-1。
Embodiment 51
N, N, N ', N '-tetramethyl--N "-octyl group guanidine a tetrafluoro borate ([HOctTMG] BF
4) ion liquid synthetic
Press embodiment 3 synthetic five alkyl guanidine OctTMG.Get 0.30mol OctTMG and 0.30mol HBF
4Carry out neutralization reaction and promptly make the 0.26mol target product.FTIR(KBr)：υ
max：2920，2850，1646，1512，1488，1387，1254，1155，1084cm
-1。
Embodiment 52
N, N, N ', N '-tetramethyl--N "-octyl group guanidine hexafluorophosphate ionic liquid ([HOctTMG] PF
6) synthetic
Press embodiment 3 synthetic five alkyl guanidine OctTMG.Get 0.30mol OctTMG and 0.30mol HPF
6Carry out neutralization reaction and promptly make the 0.27mol target product.FTIR(KBr)：υ
max：2934，2852，1650，1512，1489，1388，1255，1156，840cm
-1。
Embodiment 53
N, N, N ', N '-tetramethyl--N "-octyl group glucocyamine salt ion liquid ([HOctTMG] CH
3Synthesizing COO)
Press embodiment 3 synthetic five alkyl guanidine OctTMG.Get 0.30mol OctTMG and 0.30mol CH
3COOH carries out neutralization reaction and promptly makes the 0.26mol target product.FTIR(KBr)：υ
max：2920，2854，1724，1650，1513，1498，1392，1254，1154，826cm
-1。
Embodiment 54
N, N, N ', N '-tetramethyl--N "-octyl group guanidine trifluoromethyl acetate ions liquid ([HOctTMG] CF
3COO) the synthetic embodiment 3 synthetic five alkyl guanidine OctTMG that press.Get 0.30mol OctTMG and 0.30mol CF
3COOH carries out neutralization reaction and promptly makes the 0.24mol target product.FTIR(KBr)：υ
max：2929，2857，1706，1652，1513，1497，1394，1256，1178，1154，1037，644cm
-1。
Embodiment 54
N, N, N ', N '-tetramethyl--N "-octyl group guanidine trifluoromethyl sulfonic acid ionic liquid ([HOctTMG] CF
3SO
3) synthetic
Press embodiment 3 synthetic five alkyl guanidine OctTMG.Get 0.30mol OctTMG and 0.30mol CF
3SO
3H carries out neutralization reaction and promptly makes the 0.23mol target product.FTIR(KBr)：υ
max：2938，2862，1624，1589，1469，1450，1407，1256，1152，1034，898，642cm
-1。
Embodiment 56
N, N, N ', N '-tetramethyl--N "-octyl group guanidine lactate ions liquid ([HOctTMG] CH
3Synthesizing CHOHCOO)
Press embodiment 3 synthetic five alkyl guanidine OctTMG.Get 0.30mol OctTMG and 0.30mol CH
3CHOHCOOH carries out neutralization reaction and promptly makes the 0.25mol target product.FTIR(KBr)：υ
max：2930，2856，1652，1516，1492，1420，1392，1254，1246，1154，1052cm
-1。
Embodiment 57
N, N, N ', N '-tetramethyl--N "-octyl group guanidine metilsulfate ionic liquid ([HOctTMG] CH
3SO
3) synthetic
Press embodiment 3 synthetic five alkyl guanidine OctTMG.Get 0.30mol OctTMG and 0.30mol CH
3SO
3H carries out neutralization reaction and promptly makes the 0.26mol target product.FTIR(KBr)：υ
max：2936，2856，1652，1626，1513，1496，1392，1255，1152cm
-1。
Embodiment 58
N, N, N ', N '-tetramethyl--N "-octyl group guanidine formate ionic liquid ([HOctTMG] HCOO) synthetic
Press embodiment 3 synthetic five alkyl guanidine OctTMG.Getting 0.30mol OctTMG and 0.30mol HCOOH carries out neutralization reaction and promptly makes the 0.24mol target product.FTIR(KBr)：υ
max：2926，2854，1705，1656，1514，1496，1394，1256，1178，1154cm
-1。
Embodiment 59
N, N, N ', N '-tetramethyl--N "-guanidines a tetrafluoro borate ([HPhTMG] BF
4) ion liquid synthetic
Press embodiment 4 synthetic five alkyl guanidine PhTMG.Get 0.30mol PhTMG and 0.30mol HBF
4Carry out neutralization reaction and promptly make the 0.23mol target product.FTIR(KBr)：υ
max：3098，3116，2944，2888，1642，1616，1574，1532，1516，1500，1498，1377，1258，1154，1084，1025，799，718cm
-1。
Embodiment 60
N, N, N ', N '-tetramethyl--N "-guanidines hexafluorophosphate ionic liquid ([HPhTMG] PF
6) synthetic
Press embodiment 4 synthetic five alkyl guanidine PhTMG.Get 0.30mol PhTMG and 0.30mol HPF
6Carry out neutralization reaction and promptly make the 0.25mol target product.FTIR(KBr)：υ
max：3096，3118，2944，2906，1646，1620，1576，1534，1521，1502，1496，1376，1254，1156，1027，840，792，716cm
-1。
Embodiment 61
N, N, N ', N '-tetramethyl--N "-guanidines acetate ions liquid ([HPhTMG] CH
3Synthesizing COO)
Press embodiment 4 synthetic five alkyl guanidine PhTMG.Get 0.30mol PhTMG and 0.30mol CH
3COOH carries out neutralization reaction and promptly makes the 0.26mol target product.FTIR(KBr)：υ
max：3092，3118，2936，2887，1726，1647，1616，1582，1536，1520，1502，1496，1377，1256，1154，1027，829，794，714cm
-1。
Embodiment 62
N, N, N ', N '-tetramethyl--N "-guanidines trifluoromethyl acetate ions liquid ([HPhTMG] CF
3Synthesizing COO)
Press embodiment 4 synthetic five alkyl guanidine PhTMG.Get 0.30mol PhTMG and 0.30mol CF
3COOH carries out neutralization reaction and promptly makes the 0.22mol target product.FTIR(KBr)：υ
max：3088，3106，2942，2889，1706，1642，1616，1579，1534，1520，1500，1498，1376，1257，1176，1154，1038，1026，792，716，645cm
-1。
Embodiment 63
N, N, N ', N '-tetramethyl--N "-guanidines trifluoromethyl sulfonic acid ionic liquid ([HPhTMG] CF
3SO
3) the synthetic embodiment 4 that press synthesize five alkyl guanidine PhTMG.Get 0.30mol PhTMG and 0.30mol CF
3SO
3H carries out neutralization reaction and promptly makes the 0.23mol target product.FTIR(KBr)：υ
max：3094，3110，2940，2896，1646，1620，1580，1536，1520，1500，1498，1377，1258，1156，1036，1024，794，718，636cm
-1。
Embodiment 64
N, N, N ', N '-tetramethyl--N "-guanidines lactate ions liquid ([HPhTMG] CH
3Synthesizing CHOHCOO)
Press embodiment 4 synthetic five alkyl guanidine PhTMG.Get 0.30mol PhTMG and 0.30mol CH
3CHOHCOOH carries out neutralization reaction and promptly makes the 0.26mol target product.FTIR(KBr)：υ
max：3095，3112，2941，2895，1646，1619，1582，1536，1520，1500，1498，1418，1377，1258，1248，1157，1054，1026，794，718cm
-1。
Embodiment 65
N, N, N ', N '-tetramethyl--N "-guanidines metilsulfate ionic liquid ([HPhTMG] CH
3SO
3) the synthetic embodiment 4 that press synthesize five alkyl guanidine PhTMG.Get 0.30mol PhTMG and 0.30mol CH
3SO
3H carries out neutralization reaction and promptly makes the 0.27mol target product.FTIR(KBr)：υ
max：3099，3116，2940，2887，1645，1622，1582，1533，1520，1500，1498，1377，1258，1156，1026，792，718cm
-1。
Embodiment 66
N, N, N ', N '-tetramethyl--N "-guanidines formate ionic liquid ([HPhTMG] HCOO) synthetic
Press embodiment 4 synthetic five alkyl guanidine PhTMG.Getting 0.30mol PhTMG and 0.30mol HCOOH carries out neutralization reaction and promptly makes the 0.25mol target product.FTIR(KBr)：υ
max：3092，3106，2942，2889，1706，1642，1616，1579，1534，1520，1500，1498，1376，1257，1176，1154，1026，792，716cm
-1。
Claims (1)
1. the preparation method of an ionic liquid of alkyl guanidine salt, this ionic liquid of alkyl guanidine salt has following general formula:
Wherein substituent R is a methyl, substituent R ' be cyclohexyl or phenyl, substituent R " be H, Y is acetic acid anion, trifluoromethyl acetic acid anion, trifluoromethane sulfonic acid root negatively charged ion, lactic acid anion, methylsulphonic acid root negatively charged ion, formate anion, tetrafluoroborate negatively charged ion or hexafluoro-phosphate radical negatively charged ion;
Or substituent R is methyl, substituent R ' be cyclohexyl or phenyl, substituent R " be methyl, Y is the iodine negatively charged ion;
Or substituent R is methyl, substituent R ' be cyclohexyl or phenyl, substituent R " be methyl, Y is acetic acid anion, trifluoromethyl acetic acid anion, trifluoromethane sulfonic acid root negatively charged ion, lactic acid anion or methylsulphonic acid root negatively charged ion;
It is characterized in that synthesis step is as follows:
Synthesizing of (1) five alkyl guanidine
Get the 0.30mol tetramethyl-urea and be dissolved in 150～200mL toluene, under nitrogen protection and agitation condition, splash into 0.30～0.33mol POCl of new steaming
3, after room temperature condition reacts 2～10 hours down, drip the single amine R ' NH that replaces of 0.66～0.75mol
2, R ' is cyclohexyl or phenyl here, at room temperature stirs after finishing 20～48 hours, after 150～200mL water diluting reaction system, vigorous stirring 5～30 minutes is taken off a layer solution, toward wherein adding solid NaOH to making system show alkalescence, then solution divides two-layer, solid filtering is fallen, after the filtrate layering, get upper solution, it is dissolved in the ether, uses anhydrous Na then
2CO
3Dry after-filtration, steaming desolventizes, and raffinate gets 0.06～0.18mol, five alkyl guanidines through underpressure distillation;
Synthesizing of (2) five ionic liquid of alkyl guanidine salt,
1. get the N that 0.30mol was made by (1) step "-substituent R ' be five alkyl guanidines and 0.30～0.31mol acetate of cyclohexyl or phenyl; trifluoromethyl acetate; trifluoromethane sulfonic acid; lactic acid; methylsulphonic acid; formic acid, Tetrafluoroboric acid or phosphofluoric acid carry out neutralization reaction and promptly make 0.24～0.30mol, five ionic liquid of alkyl guanidine salt, N-and N '-substituent R are methyl in this five ionic liquid of alkyl guanidine salt product; N "-substituent R ' be cyclohexyl or phenyl; N "-substituent R " be H, Y is an acetic acid anion; the trifluoromethyl acetic acid anion; trifluoromethane sulfonic acid root negatively charged ion; lactic acid anion; methylsulphonic acid root negatively charged ion; formate anion, tetrafluoroborate negatively charged ion or hexafluoro-phosphate radical negatively charged ion;
(3) hexaalkylguanidium salts is ion liquid synthetic, selects a kind of in following two kinds of methods as required
1. get the N that 0.30mol was made by (1) step "-substituent R ' be cyclohexyl; or five alkyl guanidine compounds of phenyl are dissolved in 20～100mL purified acetonitrile; under ice-water bath cooling and nitrogen protection; splash into the single methyl iodide of 0.30～0.33mol of new steaming and the mixed solution of 20～100mL acetonitrile; treat to continue stirring reaction 12～48 hours after system temperature returns to room temperature; steam except that the acetonitrile in the reaction system; raffinate washs 2～5 times with ethyl acetate; the ethyl acetate that vacuum is taken out in the system promptly makes 0.12～0.30mol, six alkyl guanidine metal iodide ions liquid; N in this six alkyl guanidines metal iodide ions product liquid "-substituent R ' be cyclohexyl or phenyl, N "-substituent R " be CH
3, Y is I;
2. getting 0.30mol 1. goes on foot the six alkyl guanidine metal iodide ions liquid that make by (3) and is dissolved in 20～100mL distilled water, stir the slow down 60mL of dropping and be dissolved with 0.30～0.31mol acetate, trifluoromethyl acetate, trifluoromethane sulfonic acid, lactic acid, or the aqueous solution of the lead salt of methylsulphonic acid, produce yellow mercury oxide rapidly, violent stirring is 1～2 hour under room temperature, decompress filter is removed yellow solid, promptly make 0.15～0.27mol hexaalkylguanidium salts ionic liquid after water in the filtrate removed, N in this hexaalkylguanidium salts ionic liquid product "-substituent R ' be cyclohexyl or phenyl, N "-substituent R " be CH
3, Y is acetic acid anion, trifluoromethyl acetic acid anion, trifluoromethane sulfonic acid root negatively charged ion, lactic acid anion or methylsulphonic acid root negatively charged ion;
Change the consumption of reactant and solvent among the above-mentioned preparation method according to actual needs in proportion, promptly make the ionic liquid of alkyl guanidine salt of aequum.
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| CN102531967B (en) * | 2011-12-17 | 2013-12-18 | 常州花山化工有限公司 | Method for preparing and purifying hexaalkylguanidine chloride |
| CN105732437B (en) * | 2016-03-07 | 2017-09-12 | 四川大学 | The synthetic method of a kind of guanidine organic magnetic ionic liquid and its for building magnetic double-aqueous phase system |
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| CN110563614A (en) * | 2019-09-10 | 2019-12-13 | 河北工业大学 | Guanidine salt ionic liquid and preparation method and application thereof |
| CN110804198B (en) * | 2019-11-19 | 2022-08-26 | 石家庄学院 | Preparation method of antibacterial cellulose degradable composite membrane |
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