CN1974547A

CN1974547A - Ionic liquid of alkyl guanidine salt and its prepn process

Info

Publication number: CN1974547A
Application number: CN 200610015314
Authority: CN
Inventors: 赵新强; 刘择收; 王延吉
Original assignee: Hebei University of Technology
Current assignee: Hebei University of Technology
Priority date: 2006-08-11
Filing date: 2006-08-11
Publication date: 2007-06-06
Anticipated expiration: 2026-08-11
Also published as: CN100528839C

Abstract

Alkylguanidine salt ionic liquid of the present invention and preparation method thereof belong to guanidine compound, have following general formula: Its synthetic steps are as follows: (1) the synthesis of pentaalkylguanidine; Carry out (2) pentaalkylguanidine again on this basis Synthesis of salt ionic liquid; or (3) synthesis of hexaalkylguanidine salt ionic liquid. In the organic synthesis reaction, the alkylguanidine salt ionic liquid is used as the catalyst, the reaction process is relatively simple, easy to operate, high catalytic activity, good repeatability, easy to separate from the product, and the post-reaction treatment is simple, which is beneficial to obtain a product with higher purity.

Description

Alkyl guanidine salt ionic liquid and preparation method thereof

Technical Field

The invention belongs to guanidine compounds, and particularly relates to alkyl guanidine salt ionic liquid and a preparation method thereof.

Background

Guanidine compounds are a strong class of organic bases (PKa ═ 13.6). In recent years, guanidine compounds can be utilized to efficiently catalyze a plurality of reactions, such as Strecker reaction, silanization reaction, Henry reaction, Michael addition reaction, Baylis-Hillman reaction, Wittig and Horner-Wadsworth-Emmons reaction, ester synthesis reaction, decarboxylation reaction and epoxy reaction; the ionic liquid has the advantages of low melting point, strong dissolving capacity, almost no vapor pressure, good thermal stability and chemical stability, and has become a hot point of domestic and foreign research. At present, the ionic liquid is mostly composed of alkyl pyridine and dialkyl imidazole quaternary ammonium cations and anions such as chloroaluminate, fluoroborate and fluorophosphates. Organic guanidine salt ionic liquids are novel members of the ionic liquid family, and their use as catalysts for chemical reactions has many advantages. However, the information about the organic guanidine salt ionic liquid is not reported in the same type or related documents at present.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: alkyl guanidine salt ionic liquids and methods of making the same are provided. The alkyl guanidine salt ionic liquid can efficiently catalyze a plurality of reactions, is easy to separate when used as a catalyst, has simple post-reaction treatment, and is beneficial to obtaining products with higher purity.

The technical scheme adopted by the invention for solving the technical problem is as follows:

the alkyl guanidine salt ionic liquid has the following general formula:

wherein

The substituent R is methyl, the substituent R 'is n-butyl, the substituent R' is H, and Y is trifluoromethyl acetate anion, trifluoromethyl sulfonate anion, lactate anion, methylsulfonate anion, formate anion, or tetrafluoroborate anion;

or substituent R is methyl, substituent R 'is cyclohexyl, n-octyl, or phenyl, substituent R' is H, Y is acetate anion, trifluoromethylacetate anion, trifluoromethylsulfonate anion, lactate anion, methylsulfonate anion, formate anion, tetrafluoroborate anion, or hexafluorophosphate anion;

or the substituent R is methyl, the substituent R 'is cyclohexyl, n-octyl or phenyl, the substituent R' is methyl, and Y is iodide anion;

or the substituent R is methyl, the substituent R 'is n-butyl, cyclohexyl, n-octyl, or phenyl, the substituent R' is methyl, and Y is acetate anion, trifluoromethylacetate anion, trifluoromethylsulfonate anion, lactate anion, methylsulfonate anion, tetrafluoroborate anion, or hexafluorophosphate anion.

The preparation method of the alkyl guanidine salt ionic liquid disclosed by the invention and shown by the general formula comprises the following synthetic steps:

(1) synthesizing the pentaalkylguanidine by either one of the following two methods

① dissolving 0.30mol of tetramethylurea in 30-100 mL of toluene, and adding 0.30-0.33 mol of newly steamed POCl dropwise under the protection of nitrogen and stirring₃Reacting at 60 ℃ for 15-72 hours, and then using 150-200 mL of CH at 0-5 DEG C₂Cl₂Diluting the reaction system, and slowly dripping 1.20-1.35 mol of mono-substituted amine R' NH₂Wherein R' is n-butyl, cyclohexyl, n-octyl or phenyl, the mixture is heated to 50 to 60 ℃, then refluxed for 12 to 48 hours, 35 percent by mass of NaOH solution is dripped into themixture under the cooling of an ice bath until the system is neutral, and 150 to 200mL of CH is used for a reaction mixture₂Cl₂Extracting, mixing organic phases, and adding anhydrous Na₂SO₄Drying for 24-72 hours, filtering, evaporating to remove the solvent, and distilling the residual liquid under reduced pressure to obtain 0.15-0.27 mol of pentaalkylguanidine;

② dissolving 0.30mol of tetramethylurea in 150-200 mL of toluene, and adding 0.30-0.33 mol of newly steamed POCl dropwise under the protection of nitrogen and stirring conditions₃Reacting for 2-10 hours at room temperature, and then dropwise adding 0.66-0.75 mol of mono-substituted amine R' NH₂Wherein R' is n-butyl, cyclohexyl, n-octyl or phenyl, stirring at room temperature for 20-48 hours after the reaction is finished, diluting the reaction system with 150-200 mL of water, vigorously stirring for 5-30 minutes, taking the lower layer solution, adding solid NaOH to make the system alkaline, then separating the solution into two layers, filtering out the solid, separating the filtrate into layers, taking the upper layer solution, dissolving the upper layer solution in diethyl ether, and then using anhydrous Na₂CO₃Drying, filtering, evaporating to remove the solvent, and distilling the residual liquid under reduced pressure to obtain 0.06-0.18 mol of pentaalkylguanidine;

(2) synthesizing the pentaalkyl guanidine salt ionic liquid by selecting one of the following two methods according to requirements

①, neutralizing 0.30mol of pentaalkylguanidine with N ' -substituent R ' prepared in step (1) as N-butyl with 0.30-0.31 mol of trifluoroacetic acid, trifluoromethanesulfonic acid, lactic acid, methanesulfonic acid, formic acid, or tetrafluoroboric acid to obtain 0.21-0.30 mol of pentaalkylguanidine salt ionic liquid, wherein N-and N ' -substituent R in the pentaalkylguanidine salt ionic liquid product is methyl, N ' -substituent R ' is N-butyl, N ' -substituent R ' is H, Y is trifluoromethylacetate anion, trifluoromethylsulfonate anion, lactate anion, methylsulfonate anion, formate anion, or tetrafluoroborate anion;

②, 0.30mol of pentaalkylguanidine of which the N ' -substituent R ' prepared in the step (1) is cyclohexyl, N-octyl or phenyl is neutralized with 0.30 to 0.31mol of acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, lactic acid, methanesulfonic acid, formic acid, tetrafluoroboric acid or hexafluorophosphoric acid to prepare 0.24 to 0.30mol of pentaalkylguanidine salt ionic liquid, wherein N-and N ' -substituent R in the pentaalkylguanidine salt ionic liquid product is methyl, N ' -substituent R ' is phenyl, cyclohexyl or N-octyl, N ' -substituent R ' is H, Y is acetate anion, trifluoromethylacetate anion, trifluoromethylsulfonate anion, lactate anion, methylsulfonate anion, formate anion, tetrafluoroborate anion or hexafluorophosphate anion;

(3) synthesizing hexaalkylguanidinium ionic liquid by one of the following three methods according to requirements

① dissolving 0.30mol of the N '-pentaalkylguanidine compound with the substituent R' being cyclohexyl, N-octyl or phenyl prepared in the step (1) in 20-100 mL of refined acetonitrile, dripping a newly steamed mixed solution of 0.30-0.33 mol of methyl monoiodide and 20-100 mL of acetonitrile under ice water bath cooling and nitrogen protection, continuing stirring and reacting for 12-48 hours after the temperature of the system is recovered to room temperature, evaporating the acetonitrile in the reaction system, washing residual liquid with ethyl acetate for 2-5 times, and vacuumizing the ethyl acetate in the system to prepare 0.12-0.30 mol of hexaalkylguanidine iodide ionic liquid, wherein the hexaalkylguanidine iodide ionic liquid is prepared by the steps ofN '-substituent R' in the hexaalkylguanidinium iodide ionic liquid product is cyclohexyl, N-octyl or phenyl, and N '-substituent R' is CH₃Y is I;

② dissolving 0.30mol of the N '-substituted group R' prepared in step (1) in 20-100 mL of refined acetonitrile, dripping a newly evaporated mixture of 0.30-0.33 mol of methyl monoiodide and 20-100 mL of acetonitrile under ice-water bath cooling and nitrogen protection, continuing to stir for 12-48 hours after the temperature of the system returns to room temperature, evaporating off the acetonitrile in the reaction system, washing the residual liquid with ethyl acetate for 2-5 times, vacuum pumping off the ethyl acetate in the system to obtain 0.12-0.30 mol of hexaalkylguanidinium iodide ionic liquid, dissolving 0.30mol of the hexaalkylguanidinium iodide ionic liquid prepared in 20-100 mL of distilled water, dripping 50mL of an aqueous solution containing 0.30-0.31 mol of sodium tetrafluoroborate or potassium hexafluorophosphate under stirring, stirring for 1-10 hours at room temperature, separating out an oil layer, dissolving the oil layer in 40-100 mL of CH₂Cl₂Washing with 40-100 mL of distilled water, and using anhydrous Na as an organic phase₂SO₄Drying, and distilling off the solvent CH at normal pressure₂Cl₂Obtaining 0.12-0.30 mol of hexaalkylguanidinium ionic liquid, wherein N '-substituent R' in the hexaalkylguanidinium ionic liquid product is N-butyl, cyclohexyl, N-octyl or phenyl, and N '-substituent R' is CH₃Y is tetrafluoroborate anion or hexafluorophosphate anion;

③ dissolving 0.30mol of hexaalkylguanidinium iodide ionic liquid prepared in step (3) ② in 20-100 mL of distilled water, slowly dropwise adding 60mL of aqueous solution containing 0.30-0.31 mol of lead salt of acetic acid, trifluoromethyl sulfonic acid, lactic acid or methyl sulfonic acid while stirring to quickly generate yellow precipitate,strongly stirring at room temperature for 1-2 hours, carrying out vacuum filtration to remove yellow solid, removing water in filtrate to obtain 0.15-0.27 mol of hexaalkylguanidinium ionic liquid, wherein N '-substituent R' in the hexaalkylguanidinium ionic liquid product is N-butyl, cyclohexyl, N-octyl or phenyl, and N '-substituent R' is CH₃Y is acetate anion, trifluoromethyl sulfonate anion, milkAcid anion, or methylsulfonate anion;

according to actual needs, the required amount of the alkyl guanidine salt ionic liquid is prepared by proportionally changing the amounts of the reactants and the solvent in the preparation method.

The invention has the beneficial effects that: in the organic synthesis reaction, the alkyl guanidine salt ionic liquid is used as a catalyst, the reaction process is simple, the operation is easy, the catalyst has high activity and good repeatability, and the industrial amplification is easy to realize; in the synthesis reaction of diethylene glycol bis allyl carbonate, the absorption capacity of the alkyl guanidine salt ionic liquid to carbon dioxide is large, which is beneficial to improving the concentration of carbon dioxide in a reaction liquid phase, thereby promoting the reaction; the alkyl guanidine salt ionic liquid is easy to separate as a catalyst, and the post-reaction treatment is simple, so that a product with higher purity can be obtained;

the preparation method of the alkyl guanidine salt ionic liquid has the following characteristics: in the synthesis step, tetramethylurea is used as a raw material, N' -pentaalkylguanidine with different substituents is synthesized by two different methods, and then a series of pentaalkylguanidine salt ionic liquids with different anions are synthesized; and the hexaalkylguanidine halide salt is synthesized by taking the pentaalkylguanidine as a raw material, and then a series of hexaalkylguanidine saltionic liquids with different anions are synthesized. The method uses single raw material, and can synthesize various alkyl guanidine salt ionic liquid products on one reaction line according to requirements.

Detailed Description

Example 1

Synthesis of N, N, N ', N' -tetramethyl-N "-butylguanidine (ButMG), optionally by one of the following two methods

① dissolving 0.30mol tetramethylurea in 60mL toluene, and adding 0.32mol POCl under nitrogen protection and stirring₃After 20 hours at 60 ℃ with 170mL CH at 3 ℃₂Cl₂Diluting the reaction system, slowly dripping 1.27mol of n-butylamine into the reaction system, heating the reaction system to 55 ℃, refluxing the reaction system for 30 hours, dripping 35 percent NaOH solution by mass into the reaction system under the cooling of an ice bath until the reaction system is neutral, and using 170 parts of NaOH solution to react with the reaction mixturemL CH₂Cl₂Extracting, mixing organic phases, and adding anhydrous Na₂SO₄After drying for 48 hours, filtering, evaporating the solvent, and distilling the residual liquid under reduced pressure to obtain 0.17mol of target product. FTIR (KBr): upsilon is_max：2927，2870，1625，1494，1454，1363，1145cm^-1。

② dissolving 0.30mol tetramethylurea in 150mL toluene, and adding 0.30mol POCl under nitrogen protection and stirring₃Reacting for 5 hours at room temperature, dropwise adding 0.66mol of n-butylamine, stirring for 20 hours at room temperature after the reaction is finished, diluting the reaction system with 150mL of water, vigorously stirring for 10 minutes, taking the lower layer solution, adding solid NaOH into the lower layer solution until the system is alkaline, then separating the solution into two layers, filtering out the solid, separating the filtrate, taking the upper layer solution, dissolving the upper layer solution in diethyl ether, and then using anhydrous Na₂CO₃After drying, filtering, evaporating the solvent, and distilling the residual liquid under reduced pressure to obtain 0.09mol of target product. FTIR (KBr): upsilon is_max：2927，2870，1625，1494，1454，1363，1145cm^-1。

Example 2

Synthesis of N, N, N ', N ' -tetramethyl-N ' -cyclohexylguanidine (CyTMG)

0.30mol of tetramethylurea is dissolved in 200mL of toluene, and freshly distilled 0.33mol of POCl is added dropwise under the protection of nitrogen and with stirring₃Reacting for 2 hours at room temperature, dropwise adding 0.75mol of cyclohexylamine, stirring for 48 hours at room temperature after the reaction is finished, diluting a reaction system by 200mL of water, vigorously stirring for 5 minutes, taking a lower-layer solution, adding solid NaOH into the lower-layer solution until the system is alkaline, separating the solution into two layers, filtering out solids, separating the filtrate, taking an upper-layer solution, dissolving the upper-layer solution in diethyl ether, and then using anhydrous Na₂CO₃After drying, filtering, evaporating the solvent, and distilling the residual liquid under reduced pressure to obtain 0.11mol of target product. FTIR (KBr): upsilon is_max：2926，2852，1625，1494，1450，1361，1145，1124，796，752cm^-1。

Example 3

Synthesis of N, N, N ', N' -tetramethyl-N "-octylguanidine (OctTMG)

Taking 0.30mol of tetramethylDissolving urea in 175mL of toluene, and adding newly distilled 0.31mol of POCl dropwise under the protection of nitrogen and stirring₃Reacting for 10 hoursat room temperature, dropwise adding 0.70mol of n-octylamine, stirring for 34 hours at room temperature after reaction, diluting a reaction system by 175mL of water, vigorously stirring for 30 minutes, taking a lower layer solution, adding solid NaOH into the lower layer solution until the system shows alkalinity, then separating the solution into two layers, filtering out solids, separating the filtrate into layers, taking an upper layer solution, dissolving the upper layer solution in diethyl ether, and then using anhydrous Na₂CO₃After drying, filtering, evaporating the solvent, and distilling the residual liquid under reduced pressure to obtain 0.10mol of target product. FTIR (KBr): upsilon is_max：2922，2852，1611，1477，1430，1383，1142cm^-1。

Example 4

Synthesis of N, N, N ', N' -tetramethyl-N "-phenylguanidine (PhTMG)

0.30mol of tetramethylurea is dissolved in 70mL of toluene, and freshly distilled 0.32mol of POCl is added dropwise under the protection of nitrogen and with stirring₃After 30 hours at 60 ℃ with 180mL CH at 0 ℃₂Cl₂Diluting the reaction system, slowly dripping 1.30mol of aniline, heating to 51 ℃, refluxing for 28 hours, dripping 35 percent NaOH solution by mass under the cooling of an ice bath until the system is neutral, and using 200mL of CH for the reaction mixture₂Cl₂Extracting, mixing organic phases, and adding anhydrous Na₂SO₄After drying for 54 hours, filtering, evaporating the solvent, and distilling the residual liquid under reduced pressure to obtain 0.24mol of target product. FTIR (KBr): upsilon is_max：3071，3006，2925，2886，1605，1575，1505，1487，1377，1140，1018，782，695cm^-1。

Example 5

Synthesis of N, N, N ', N' -tetramethyl-N "-methyl-N" -butylguanidinium iodide ([ MBuTMG]I)

Pentaalkylguanidine BuTMG was synthesized as in example 1. Dissolving 0.30mol of BuTMG in 20mL of refined acetonitrile, dripping a newly distilled mixed solution of 0.30mol of methyl iodide and 20mL of acetonitrile into the solution under the cooling of ice water bath and the protection of nitrogen, continuing stirring the solution to react for 12 hours after the temperature of the system is recovered to room temperature, distilling off the acetonitrile in the reaction system, and using acetic acid to carry out residual liquidWashing with ethyl ester for 2 times, and vacuum-pumping out ethyl acetate from the system to obtain 0.24mol of target product. FTIR (KBr): upsilon is_max：2956，2873，1586，1470，1408，1255，1155，900cm^-1。

Example 6

Synthesis of N, N, N ', N' -tetramethyl-N 'methyl-N' -cyclohexylguanidinium iodide ([ MCyTMG]I)

Pentaalkylguanidine CyTMG was synthesized as in example 2. Dissolving 0.30mol of CyTMG in refined 60mL of acetonitrile, dripping a newly distilled mixed solution of 0.32mol of methyl iodide and 60mL of acetonitrile under the cooling of ice-water bath and the protection of nitrogen, continuing stirring for reaction for 30 hours after the temperature of the system is recovered, distilling off the acetonitrile in the reaction system, washing residual liquid for 3 times by using ethyl acetate, and vacuumizing the ethyl acetate in the system to obtain 0.13mol of target product. FTIR (KBr): upsilon is_max：2930，2857，1598，1470，1450，1407，1257，1151，898cm^-1。

Example 7

Synthesis of N, N, N ', N' -tetramethyl-N "-methyl-N" -octylguanidinium iodide ([ MOctTMG]I)

Pentaalkylguanidine OctTMG was synthesized as in example 3. Dissolving 0.30mol of OctTMG in 100mL of refined acetonitrile, dripping a newly distilled mixed solution of 0.33mol of methyl iodide and 100mL of acetonitrile under the cooling of ice-water bath and the protection of nitrogen, continuing stirring for reaction for 48 hours after the temperature of the system is recovered to room temperature, distilling off the acetonitrile in the reaction system, washing residual liquid with ethyl acetate for 5 times, and vacuumizing the ethyl acetate in the system to obtain 0.19mol of target product. FTIR (KBr): upsilon is_max：2922，2852，1651，1513，1498，1392，1255，1156，900cm^-1。

Example 8

Synthesis of N, N, N ', N' -tetramethyl-N "-methyl-N" -phenylguanidinium iodide ([ MPhTMG]I)

Pentaalkylguanidine PhTMG was synthesized as in example 4. Dissolving 0.30mol PhTMG in 20mL refined acetonitrile, dripping a newly distilled mixed solution of 0.32mol methyl iodide and 20mL acetonitrile under the cooling of ice water bath and the protection of nitrogen, continuing stirring for reaction for 15 hours after the temperature of the system is recovered to room temperature, distilling off the acetonitrile in the reaction system, and washing residual liquid with ethyl acetateAnd (2) vacuumizing ethyl acetate in the system to obtain 0.22mol of target product. FTIR (KBr): upsilon is_max：3091，3115，2940，2898，1646，1618，1580，1536，1520，1500，1498，1377，1258，1156，1026，900，792，716cm^-1。

Example 9

N, N, N ', N' -tetramethyl-N '-methyl-N' -butyl guanidine tetrafluoroborate ionic liquid ([ MBTMG]]BF₄) Synthesis of (2)

Synthesis of hexaalkylguanidinium iodide [ MBTMG]as in example 5]I. 0.30mol of [ MBTMG]is taken]I is dissolved in 50mL of distilled water, and 50mL of solution containing 0.30mol of NaBF is added dropwise with stirring₄The aqueous solution of (1) was stirred at room temperature for 1 hour. The oil layer was separated and dissolved in 100mL of CH₂Cl₂In (1), the mixture was washed with 100mL of distilled water and then with anhydrous Na₂SO₄The organic phase is dried and the solvent is distilled off to obtain 0.27mol of the target product. FTIR (KBr): upsilon is_max：2958，2873，1582，1468，1408，1255，1155，1084，900cm^-1。

Example 10

N, N, N ', N' -tetramethyl-N "-methyl-N" -cyclohexylguanidinium tetrafluoroborate ([ MCyTMG)]BF₄) Synthesis of ionic liquids

Synthesis of hexaalkylguanidinium iodide [ MCyTMG]as in example 6]I. Taking 0.30mol of [ MCyTMG]I is dissolved in 20mL of distilled water, and 50mL of solution containing 0.30mol of NaBF is added dropwise with stirring₄Stirring the resulting solution at room temperature for 1 hour, separating an oil layer, and dissolving the oil layer in 40mL of CH₂Cl₂In (1), the mixture was washed with 40mL of distilled water and then with anhydrous Na₂SO₄The organic phase is dried, and the solvent is distilled off under normal pressure, thus obtaining 0.28mol of target product. FTIR (KBr): upsilon is_max：2932，2858，1597，1469，1453，1408，1257，1148，1084，899cm^-1。

Example 11

N, N, N ', N' -tetramethyl-N '-methyl-N' -octylguanidine tetrafluoroborate ionic liquid ([ MOctTMG)]BF₄) Synthesis of (2)

Synthesis of hexaalkylguanidinium iodide [ MOctTMG]as in example 7]I. Taking 0.30mol of [ MOctTMG]]I is dissolved in 50mL of distilled water and added dropwise with stirring50mL of a solution containing 0.31mol of NaBF₄Stirring the resulting solution at room temperature for 5 hours, separating an oil layer, and dissolving the oil layer in 70mL of CH₂Cl₂In (1), the mixture was washed with 70mL of distilled water and then with anhydrous Na₂SO₄The organic phase is dried, and the solvent is distilled off under normal pressure, thus obtaining 0.23mol of target product. FTIR (KBr): upsilon is_max：2922，2852，1648，1513，1498，1392，1255，1156，1084，900cm^-1。

Example 12

N, N, N ', N' -tetramethyl-N '-methyl-N' -phenylguanidine tetrafluoroborate ionic liquid ([ MPhTMG)]BF₄) Synthesis of (2)

Synthesis of hexaalkylguanidinium iodide [ MPhTMG]as in example 8]I. Taking 0.30mol [ MPhTMG]I is dissolved in 100mL of distilled water, and 50mL of solution containing 0.31mol of NaBF is added dropwise with stirring₄Stirring the resulting solution at room temperature for 10 hours, separating an oil layer, and dissolving the oil layer in 100mL of CH₂Cl₂In (1), the mixture was washed with 100mL of distilled water and then with anhydrous Na₂SO₄And drying the organic phase, and evaporating the solvent at normal pressure to obtain 0.24mol of a target product. FTIR (KBr): upsilon is_max：3100，3118，2946，2898，1640，1618，1580，1536，1520，1500，1498，1377，1258，1156，1084，1026，900，792，716cm^-1。

Example 13

N, N, N ', N' -tetramethyl-N '-methyl-N' -butyl guanidine hexafluorophosphate ionic liquid ([ MBTMG]]PF₆) Synthesis of (2)

Synthesis of hexaalkylguanidinium iodide [ MBTMG]as in example 5]I. 0.30mol of [ MBTMG]is taken]I dissolved in 50mL of distilled waterIn (1), 50mL of a solution containing 0.30mol of KPF was added dropwise with stirring₆Stirring the resulting solution at room temperature for 2 hours, separating an oil layer, and dissolving the oil layer in 100mL of CH₂Cl₂In (1), the mixture was washed with 100mL of distilled water and then with anhydrous Na₂SO₄The organic phase is dried, and the solvent is distilled off under normal pressure, thus obtaining 0.22mol of target product. FTIR (KBr): upsilon is_max：2969，2883，1587，1476，1412，1254，1151，899，840cm^-1。

Example 14

N, N, N ', N' -tetramethyl-N 'methyl-N'-cyclohexyl guanidine hexafluorophosphate Ionic liquid ([ MCyTMG)]PF₆) Synthesis of (2)

Synthesis of hexaalkylguanidinium iodide [ MCyTMG]as in example 6]I. Taking 0.30mol of [ MCyTMG]I is dissolved in 50mL of distilled water and 50mL of a solution containing 0.30mol of KPF is added dropwise with stirring₆Stirring the aqueous solution at room temperature for 2 hours, separating an oil layer, and dissolving the oil layer in 100mL of CH₂Cl₂In (1), the mixture was washed with 100mL of distilled water and then with anhydrous Na₂SO₄And drying the organic phase, and evaporating the solvent at normal pressure to obtain 0.17mol of a target product. FTIR (KBr): upsilon is_max：2933，2862，1596，1476，1457，1411，1259，1150，898，840cm^-1。

Example 15

N, N, N ', N' -tetramethyl-N '-methyl-N' -octylguanidinium hexafluorophosphate ionic liquid ([ MOctTMG)]PF₆) Synthesis of (2)

Synthesis of hexaalkylguanidinium iodide [ MOctTMG]as in example 7]I. Taking 0.30mol of [ MOctTMG]]I is dissolved in 50mL of distilled water and 50mL of a solution containing 0.30mol of KPF is added dropwise with stirring₆Stirring the resulting solution at room temperature for 2 hours, separating an oil layer, and dissolving the oil layer in 100mL of CH₂Cl₂In (1), the mixture was washed with 100mL of distilled water and then with anhydrous Na₂SO₄Drying the organic phase, and evaporating the solvent under normal pressure to obtain 0.20mol of the target product. FTIR (KBr): upsilon is_max：2936，2856，1652，1513，1498，1392，1254，1155，900，840cm^-1。

Example 16

N, N, N ', N' -tetramethyl-N '-methyl-N' -phenylguanidinium hexafluorophosphate ionic liquid ([ MPhTMG)]PF₆) Synthesis of (2)

Synthesis of hexaalkylguanidinium iodide [ MPhTMG]as in example 8]I. Taking 0.30mol [ MPhTMG]I is dissolved in 50mL of distilled water and 50mL of a solution containing 0.30mol of KPF is added dropwise with stirring₆Stirring the resulting solution at room temperature for 2 hours, separating an oil layer, and dissolving the oil layer in 100mL of CH₂Cl₂In (1), the mixture was washed with 100mL of distilled water and then with anhydrous Na₂SO₄And drying the organic phase, and evaporating the solvent at normal pressure to obtain 0.24mol of a target product. FTIR (KBr): upsilon is_max：3092，3115，2942，2900，1648，1618，1580，1536，1520，1500，1498，1377，1256，1158，1028，899，840，792，716cm^-1。

Example 17

N, N, N ', N' -tetramethyl-N '-methyl-N' -butyl guanidine acetate ionic liquid ([ MBTMG]]CH₃COO) synthesis

Synthesis of hexaalkylguanidinium iodide [ MBTMG]as in example 5]I. 0.30mol of [ MBTMG]is taken]I was dissolved in 20mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was slowly added dropwise with stirring₃COO)₂The water solution of (2) quicklygenerates yellow precipitate, the mixture is intensively stirred for 1 hour at room temperature, yellow solid is removed by suction filtration under reduced pressure, and 0.27mol of target product is prepared after water in the filtrate is removed. FTIR (KBr): upsilon is_max：2963，2877，1694，1581，1469，1409，1255，1171，899，801cm^-1。

Example 18

N, N, N ', N' -tetramethyl-N '-methyl-N' -cyclohexyl guanidine acetate ionic liquid ([ MCyTMG)]CH₃COO) in a hydrocarbonBecome into

Synthesis of hexaalkylguanidinium iodide [ MCyTMG]as in example 6]I. Taking 0.30mol of [ MCyTMG]I was dissolved in 60mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃COO)₂The aqueous solution of (2) quickly generates yellow precipitate, the mixture is intensively stirred for 1.5 hours at room temperature, yellow solid is removed by vacuum filtration, and 0.26mol of target product is prepared after water in filtrate is removed. FTIR (KBr): upsilon is_max：2930，2857，1702，1598，1470，1450，1407，1257，1151，898，822cm^-1。

Example 19

N, N, N ', N' -tetramethyl-N 'methyl-N' -octyl guanidine acetate ionic liquid ([ MOctTMG)]CH₃COO) synthesis

Synthesis of hexaalkylguanidinium iodide [ MOctTMG]as in example 7]I. Taking 0.30mol of [ MOctTMG]]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃COO)₂The water solution of (2) quickly generates yellow precipitate, the mixture is intensively stirred for 2 hours at room temperature, yellow solid is removed by vacuum filtration, and 0.24mol of target product is prepared after water in the filtrate is removed. FTIR (KBr): upsilon is_max：2922，2852，1726，1651，1513，1498，1392，1255，1156，900，826cm^-1。

Example 20

N, N, N ', N' -tetramethyl-N 'methyl-N' -phenylguanidine acetate ionic liquid ([ MPhTMG)]CH₃COO) Synthesis of hexaalkylguanidinium iodide [ MPhTMG]Synthesis as in example 8]I. Taking 0.30mol [ MPhTMG]I was dissolved in 50mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃COO)₂The water solution of (2) quickly generates yellow precipitate, the mixture is intensively stirred for 1 hour at room temperature, yellow solid is removed by suction filtration under reduced pressure, and 0.23mol of target product is prepared after water in the filtrate is removed. FTIR (KBr): upsilon is_max：3091，3115，2940，2898，1728，1646，1618，1580，1536，1520，1500，1498，1377，1258，1156，1026，900，828，792，716cm^-1。

Example 21

N, N, N ', N' -tetramethyl-N 'methyl-N' -butyl guanidine trifluoromethyl acetate ionic liquid ([ MBTMG]]CF₃COO) synthesis

0.15mol of yellow lead oxide and 50mL of distilled water are mixed in a 100mL beaker and stirred, and 0.30mol of trifluoromethyl acetic acid is slowly added into the yellow lead oxide, and the lead oxide is dissolved immediately to react as follows:

synthesis of hexaalkylguanidinium iodide [ MBTMG]as in example 5]I. 0.30mol of [ MBTMG]is taken]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CF) was added dropwise with stirring₃COO)₂The water solution of (2) quickly generates precipitate, the solution is intensively stirred for 1 hour at room temperature, yellow solid is removed by suction filtration under reduced pressure, and 0.18mol of target product is prepared after water in the filtrate is removed. FTIR (KBr): upsilon is_max：2961，2875，1694，1579，1470，1408，1256，1201，1171，1125，1065，1036，899，640cm^-1。

Example 22

N, N, N ', N' -tetramethyl-N 'methyl-N' -cyclohexyl guanidine trifluoromethyl acetate ionic liquid ([ MCyTMG)]CF₃COO) synthesis

Synthesis of Pb (CF) as in example 21₃COO)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MCyTMG]as in example 6]I。Taking 0.30mol of [ MCyTMG]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CF) was added dropwise with stirring₃COO)₂The water solution of (2) quickly generates precipitate, the solution is intensively stirred for 1 hour at room temperature, yellow solid is removed by suction filtration under reduced pressure, and 0.21mol of target product is prepared after water in the filtrate is removed. FTIR (KBr): upsilon is_max：2930，2857，1702，1598，1470，1450，1407，1257，1176，1151，1038，898，642cm^-1。

Example 23

N, N, N ', N' -tetramethyl-N '-methyl-N' -octyl guanidine trifluoromethyl acetate ionic liquid ([ MOctTMG)]CF₃COO) synthesis

Synthesis of Pb (CF) as in example 21₃COO)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MOctTMG]as in example 7]I. Taking 0.30mol of [ MOctTMG]]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CF) was added dropwise with stirring₃COO)₂The water solution of (2) quickly generates precipitate, thesolution is intensively stirred for 1 hour at room temperature, yellow solid is removed by suction filtration under reduced pressure, and 0.17mol of target product is prepared after water in the filtrate is removed. FTIR (KBr): upsilon is_max：2922，2852，1706，1651，1513，1498，1392，1255，1178，1156，1037，900，644cm^-1。

Example 24

N, N, N ', N' -tetramethyl-N 'methyl-N' -phenylguanidine trifluoromethyl acetate ionic liquid ([ MPhTMG)]CF₃COO) synthesis

Synthesis of Pb (CF) as in example 21₃COO)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MPhTMG]as in example 8]I. Taking 0.30mol [ MPhTMG]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CF) was added dropwise with stirring₃COO)₂The water solution of (2) quickly generates precipitate, the solution is intensively stirred for 1 hour at room temperature, yellow solid is removed by suction filtration under reduced pressure, and 0.20mol of target product is prepared after water in the filtrate is removed. FTIR (KBr): upsilon is_max：3089，3116，2942，2889，1710，1644，1620，1584，1536，1520，1500，1498，1377，1258，1176，1156，1038，1026，900，792，716，645cm^-1。

Example 25

N, N, N ', N' -tetramethyl-N 'methyl-N' -butyl guanidine trifluoromethyl sulfonate ionic liquid ([ MBTMG]]CF₃SO₃) Synthesis of (2)

0.15mol of yellow lead oxide and 50mL of distilled water are mixed in a 100mL beaker and stirred, and then 0.30mol of trifluoromethyl sulfonic acid is slowly added into the yellow lead oxide, and the lead oxide is dissolved immediately to generate the following reaction:

synthesis of hexaalkylguanidinium iodide [ MBTMG]as in example 5]I. 0.30mol of [ MBTMG]is taken]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CF) was added dropwise with stirring₃SO₃)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.16mol of target product. FTIR (KBr): upsilon is_max：2881，2972，1600，1581，1475，1458，1409，1265，1156，1031，889，639cm^-1。

Example 26

N, N, N ', N' -tetramethyl-N 'methyl-N' -cyclohexylguanidine trifluoromethanesulfonate ionic liquid ([ MCyTMG)]CF₃SO₃) Synthesis of (2)

Synthesis of Pb (CF) as in example 25₃SO₃)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MCyTMG]as in example 6]I. Taking 0.30mol of [ MCyTMG]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CF) was added dropwise with stirring₃SO₃)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.18mol of target product. FTIR (KBr): upsilon is_max：2930，2857，1620，1598，1470，1450，1407，1257，1151，1036，898，640cm^-1。

Example 27

N, N, N ', N' -tetramethyl-N '-methyl-N' -octyl guanidine trifluoromethyl sulphonate ionic liquid ([ MOctTMG)]CF₃SO₃) Synthesis of (2)

Synthesis of Pb (CF) as in example 25₃SO₃)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MOctTMG]as in example 7]I. Taking 0.30mol of [ MOctTMG]]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CF) was added dropwise with stirring₃SO₃)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.22mol of target product. FTIR (KBr): upsilon is_max：2922，2852，1651，1624，1513，1498，1392，1255，1156，1042，900，642cm^-1。

Example 28

N, N, N ', N' -tetramethyl-N '-methyl-N' -phenyl guanidine trifluoromethyl sulfonate ionic liquid ([ MPhTMG)]CF₃SO₃) Synthesis of (2)

Synthesis of Pb (CF) as in example 25₃SO₃)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MPhTMG]as in example 8]I. Taking 0.30mol [ MPhTMG]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CF) was added dropwise with stirring₃SO₃)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.24mol of target product. FTIR (KBr): upsilon is_max：3091，3115，2940，2898，1646，1620，1580，1536，1520，1500，1498，1377，1258，1156，1036，1026，900，792，716，636cm^-1。

Example 29

N, N, N ', N' -tetramethyl-N 'methyl-N' -butyl guanidine lactate ionic liquid ([ MBTMG]]CH₃CHOHCO) synthesis

0.15mol of yellow lead oxide and 50mL of distilled water are mixed in a 100mL beaker and stirred, and 0.30mol of lactic acid is slowly added into the yellow lead oxide, so that the lead oxide is dissolved immediately and reacts as follows:

synthesis of hexaalkylguanidinium iodide [ MBTMG]as in example 5]I. 0.30mol of [ MBTMG]is taken]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃CHOHCOO)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.16mol of target product. FTIR (KBr): upsilon is_max：2929，2868，1587，1462，1416，1402，1246，1153，1058，895cm^-1。

Example 30

N, N, N ', N' -tetramethyl-N 'methyl-N' -cyclohexylguanidine lactate ionic liquid: ([MCyTMG]CH₃CHOHCO) synthesis

Synthesis of Pb (CH) as in example 29₃CHOHCOO)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MCyTMG]as in example 6]I. Taking 0.30mol of [ MCyTMG]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃CHOHCOO)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.18mol of target product. FTIR (KBr): upsilon is_max：2930，2857，1598，1470，1450，1418，1407，1257，1248，1151，1056，898cm^-1。

Example 31

N, N, N ', N' -tetramethyl-N 'methyl-N' -octyl guanidine lactate ionic liquid ([ MOctTMG)]CH₃CHOHCO) synthesis

Synthesis of Pb (CH) as in example 29₃CHOHCOO)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MOctTMG]as in example 7]I。0.30mol[MOctTMG]I was dissolved in 100mL of distilled water and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃CHOHCOO)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.20mol of target product. FTIR (KBr): upsilon is_max：2922，2852，1651，1513，1498，1418，1392，1255，1244，1156，1052，900cm^-1。

Example 32

N, N, N ', N' -tetramethyl-N 'methyl-N' -phenylguanidine lactate ionic liquid ([ MPhTMG)]CH₃CHOHCO) synthesis

Synthesis of Pb (CH) as in example 29₃CHOHCOO)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MPhTMG]as in example 8]I. Taking 0.30mol [ MPhTMG]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃CHOHCOO)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.19mol of target product. FTIR (KBr): upsilon is_max：3096，3116，2941，2896，1645，1619，1582，1536，1520，1500，1498，1418，1377，1258，1248，1156，1055，1026，900，794，718cm^-1。

Example 33

N, N, N ', N' -tetramethyl-N '-methyl-N' -butyl guanidine methyl sulfonate ionic liquid ([ MBTMG]]CH₃SO₃) Synthesis of (2)

0.15mol of yellow lead oxide was mixed with 50mL of distilled water and stirred in a 100mL beaker. 0.30mol of methyl sulfonic acid is slowly added into the lead oxide, and the lead oxide is immediately dissolved to react as follows:

synthesis of hexaalkylguanidinium iodide [ MBTMG]as in example 5]I. 0.30mol of [ MBTMG]is taken]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃SO₃)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.23mol of target product. FTIR (KBr): upsilon is_max：2882，2974，1600，1581，1475，1458，1409，1268，1154，889cm^-1。

Example 34

N, N, N ', N' -tetramethyl-N 'methyl-N' -cyclohexyl guanidine methyl sulfonate ionic liquidBody ([ MCyTMG)]CH₃SO₃) Is/are as followsSynthesis of

Synthesis of Pb (CH) as in example 33₃SO₃)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MCyTMG]as in example 6]I. Taking 0.30mol of [ MCyTMG]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃SO₃)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.21mol of target product. FTIR (KBr): upsilon is_max：2934，2856，1622，1598，1470，1450，1407，1258，1151，898cm^-1。

Example 35

N, N, N ', N' -tetramethyl-N '-methyl-N' -octyl guanidine methyl sulfonate ionic liquid ([ MOctTMG)]CH₃SO₃) Synthesis of (2)

Synthesis of Pb (CH) as in example 33₃SO₃)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MOctTMG]as in example 7]I. Taking 0.30mol of [ MOctTMG]]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃SO₃)₂The water solution of (2) quickly generates precipitate, the stirring is continued for 1 hour at room temperature, the yellow solid is removed by vacuum filtration, and the water in the filtrate is removed to obtain 0.24mol of target product. FTIR (KBr): upsilon is_max：2926，2858，1651，1628，1513，1498，1392，1256，1154，900cm^-1。

Example 36

N, N, N ', N' -tetramethyl-N 'methyl-N' -phenyl guanidine methyl sulfonate ionic liquid ([ MPhTMG)]CH₃SO₃) Synthesis of (2)

Synthesis of Pb (CH) as in example 33₃SO₃)₂An aqueous solution of (a); synthesis of hexaalkylguanidinium iodide [ MPhTMG]as in example 8]I. Taking 0.30mol [ MPhTMG]I was dissolved in 100mL of distilled water, and 60mL of a solution containing 0.15mol of Pb (CH) was added dropwise with stirring₃SO₃)₂Quickly generating precipitate, continuously stirring at room temperature for 1 hr, vacuum filtering to remove yellow solid, and removing water from filtrate to obtain 019mol of the target product. FTIR (KBr): upsilon is_max：3096，3118，2942，2898，1646，1620，1580，1536，1520，1500，1498，1377，1258，1156，1026，900，792，716cm^-1。

Example 37

N, N, N ', N' -tetramethyl-N "-butylguanidinium tetrafluoroborate ([ HBTMG MG]]BF₄) Synthesis of ionic liquids

Pentaalkylguanidine BuTMG was synthesized as in example 1, taking 0.30mol of BuTMG and 0.30mol of HBF₄Carrying out neutralization reaction to obtain 0.24mol of target product. FTIR (KBr): upsilon is_max：2956，2875，1580，1466，1407，1254，1156，1084cm^-1。

Example 38

N, N, N ', N ' -tetramethyl-N ' -butyl guanidine trifluoromethyl acetate ionic liquid ([ HBTMG MG]]CF₃COO) synthesis

Pentaalkylguanidine BuTMG was synthesized as in example 1. Taking 0.30mol of BuTMG and 0.30mol of CF₃And performing neutralization reaction on COOH to obtain 0.23mol of target product. FTIR (KBr): upsilon is_max：2962，2878，1694，1580，1472，1406，1255，1201，1172，1125，1065cm^-1。

Example 39

N, N, N ', N ' -tetramethyl-N ' -butyl guanidine trifluoromethyl sulfonate ionic liquid ([ HBTMG MG]]CF₃SO₃) Synthesis of (2)

Pentaalkylguanidine BuTMG was synthesized as in example 1. Taking 0.30mol of BuTMG and 0.30mol of CF₃SO₃H is subjected to neutralization reaction to obtain 0.22mol of target product. FTIR (KBr): upsilon is_max：2882，2974，1602，1584，1468，1452，1406，1264，1155，1031，639cm^-1。

Example 40

N, N, N ', N ' -tetramethyl-N ' -butyl guanidine lactate ionic liquid ([ HBTMG MG]]CH₃CHOHCO) synthesis

Pentaalkylguanidine BuTMG was synthesized as in example 1. Taking 0.30mol of BuTMG and 0.30mol of CH₃CHOHCOOH is subjected to neutralization reaction to obtain 0.26mol of target product. FTIR (KB)r)：υ_max：2930，2872，1589，1464，1416，1402，1246，1156，1058cm^-1。

EXAMPLE 41

N, N, N ', N ' -tetramethyl-N ' -butyl guanidine methyl sulfonate ionic liquid ([ HBTMG MG]]CH₃SO₃) Synthesis of (2)

Pentaalkylguanidine BuTMG was synthesized as in example 1. Taking 0.30mol of BuTMG and 0.30mol of CH₃SO₃H is subjected to neutralization reaction to obtain 0.28mol of target product. FTIR (KBr): upsilon is_max：2882，2974，1600，1576，1475，1456，1409，1265，1156cm^-1。

Example 42

Synthesis of N, N, N ', N ' -tetramethyl-N ' -butyl guanidine formate ionic liquid ([ HBTMG]HCOO)

Pentaalkylguanidine BuTMG was synthesized as in example 1. 0.30mol of ButMG and 0.31mol of HCOOH are taken to carry out neutralization reaction, and 0.27mol of target product is prepared. FTIR (KBr): upsilon is_max：2961，2875，1694，1579，1470，1408，1256，1201，1171，1125，1065cm^-1。

Example 43

N, N, N ', N ' -tetramethyl-N ' -cyclohexylguanidinium tetrafluoroborate ([ HCyTMG)]BF₄) Synthesis of ionic liquids

Pentaalkylguanidine CyTMG was synthesized as in example 2. Taking 0.30mol of CyTMG and 0.30mol of HBF₄Carrying out neutralization reaction to obtain 0.29mol of target product. FTIR (KBr): upsilon is_max：2932，2858，1598，1472，1456，1412，1255，1148，1084cm^-1。

Example 44

N, N, N ', N ' -tetramethyl-N ' -cyclohexylguanidinium hexafluorophosphate ionic liquid ([ HCyTMG)]PF₆) Synthesis of (2)

Pentaalkylguanidine CyTMG was synthesized as in example 2. Taking 0.30mol of CyTMG and 0.30mol of HPF₆Carrying out neutralization reaction to obtain 0.27mol of target product. FTIR (KBr): upsilon is_max：2932，2866，1572，1478，1456，1411，1262，1154，840cm^-1。

Example 45

N, N, N ', N ' -tetramethyl-N ' -cyclohexyl guanidine acetate ionic liquid ([ HCyTMG)]CH₃COO) synthesis

Pentaalkylguanidine CyTMG was synthesized as in example 2. Taking 0.30mol of CyTMG and 0.30mol of CH₃And performing neutralization reaction on COOH to obtain 0.28mol of target product. FTIR (KBr): upsilon is_max：2932，2856，1704，1586，1468，1452，1416，1256，1151，822cm^-1。

Example 46

N, N, N ', N ' -tetramethyl-N ' -cyclohexyl guanidine trifluoromethyl acetate ionic liquid ([ HCyTMG)]CF₃COO) in a hydrocarbonBecome into

Pentaalkylguanidine CyTMG was synthesized as in example 2. Taking 0.30mol CyTMG and 0.30mol CF₃And performing neutralization reaction on COOH to obtain 0.22mol of target product. FTIR (KBr): upsilon is_max：2962，2878，1688，1572，1468，1406，1255，1201，1171，1124，1065，1036，640cm^-1。

Example 47

N, N, N ', N ' -tetramethyl-N ' -cyclohexyl guanidine trifluoromethyl sulfonate ionic liquid ([ HCyTMG)]CF₃SO₃) Synthesis of (2)

Pentaalkylguanidine CyTMG was synthesized as in example 2. Taking 0.30mol CyTMG and 0.30mol CF₃SO₃H is subjected to neutralization reaction to obtain 0.23mol of target product. FTIR (KBr): upsilon is_max：2932，2854，1622，1587，1476，1450，1407，1256，1152，1036，640cm^-1。

Example 48

N, N, N ', N ' -tetramethyl-N ' -cyclohexylguanidine lactate ionic liquid ([ HCyTMG)]CH₃CHOHCO) synthesis

Pentaalkylguanidine CyTMG was synthesized as in example 2. Taking 0.30mol of CyTMG and 0.30mol of CH₃CHOHCOOH is subjected to neutralization reaction to obtain 0.22mol of target product. FTIR (KBr): upsilon is_max：2928，2854，1589，1468，1450，1418，1407，1254，1246，1155，1056cm^-1。

Example 49

N, N, N ', N' -tetramethyl-N"-Cyclohexylguanidine methanesulfonate Ionic liquid ([ HCyTMG)]CH₃SO₃) Synthesis of (2)

Pentaalkylguanidine CyTMG was synthesized as in example 2. Taking 0.30mol of CyTMG and 0.30mol of CH₃SO₃H is subjected to neutralization reaction to obtain 0.25mol of target product. FTIR (KBr): upsilon is_max：2928，2848，1623，1596，1470，1450，1407，1256，1152cm^-1。

EXAMPLE 50

Synthesis of N, N, N ', N ' -tetramethyl-N ' -cyclohexyl guanidine formate ionic liquid ([ HCyTMG]HCOO)

Pentaalkylguanidine CyTMG was synthesized as in example 2. 0.30mol of CyTMG and 0.30mol of HCOOH are taken to carry out neutralization reaction, and 0.26mol of target product is prepared. FTIR (KBr): upsilon is_max：2968，2876，1686，1572，1466，1406，1254，1201，1171，1125，1065cm^-1。

Example 51

N, N, N ', N' -tetramethyl-N "-octylguanidinium tetrafluoroborate ([ HOctTMG]]BF₄) Synthesis of ionic liquids

Pentaalkylguanidine OctTMG was synthesized as in example 3. Taking 0.30mol of OctTMG and 0.30mol of HBF₄Carrying out neutralization reaction to obtain 0.26mol of target product. FTIR (KBr): upsilon is_max：2920，2850，1646，1512，1488，1387，1254，1155，1084cm^-1。

Example 52

N, N, N ', N ' -tetramethyl-N ' -octylguanidinium hexafluorophosphate ionic liquid ([ HOctTMG)]PF₆) Synthesis of (2)

Pentaalkylguanidine OctTMG was synthesized as in example 3. Taking 0.30mol of OctTMG and 0.30mol of HPF₆Carrying out neutralization reaction to obtain 0.27mol of target product. FTIR (KBr): upsilon is_max：2934，2852，1650，1512，1489，1388，1255，1156，840cm^-1。

Example 53

N, N, N ', N ' -tetramethyl-N ' -octylguanidine acetate ionic liquid ([ HOctTMG]]CH₃COO) synthesis

Pentaalkyl was synthesized as in example 3Guanidine OctTMG. Taking 0.30mol of OctTMG and 0.30mol of CH₃And performing neutralization reaction on COOH to obtain 0.26mol of target product. FTIR (KBr): upsilon is_max：2920，2854，1724，1650，1513，1498，1392，1254，1154，826cm^-1。

Example 54

N, N, N ', N ' -tetramethyl-N ' -octylguanidine trifluoromethyl acetate ionic liquid ([ HOctTMG]]CF₃COO) synthesis

Pentaalkylguanidine OctTMG was synthesized as in example 3. Taking 0.30mol of OctTMG and 0.30mol of CF₃And performing neutralization reaction on COOHto obtain 0.24mol of target product. FTIR (KBr): upsilon is_max：2929，2857，1706，1652，1513，1497，1394，1256，1178，1154，1037，644cm^-1。

Example 54

N, N, N ', N ' -tetramethyl-N ' -octyl guanidine trifluoromethyl sulfonate ionic liquid ([ HOctTMG]]CF₃SO₃) Synthesis of (2)

Pentaalkylguanidine OctTMG was synthesized as in example 3. Taking 0.30mol of OctTMG and 0.30mol of CF₃SO₃H is subjected to neutralization reaction to obtain 0.23mol of target product. FTIR (KBr): upsilon is_max：2938，2862，1624，1589，1469，1450，1407，1256，1152，1034，898，642cm^-1。

Example 56

N, N, N ', N ' -tetramethyl-N ' -octylguanidine lactate ionic liquid ([ HOctTMG]]CH₃CHOHCO) synthesis

Pentaalkylguanidine OctTMG was synthesized as in example 3. Taking 0.30mol of OctTMG and 0.30mol of CH₃CHOHCOOH is subjected to neutralization reaction to obtain 0.25mol of target product. FTIR (KBr): upsilon is_max：2930，2856，1652，1516，1492，1420，1392，1254，1246，1154，1052cm^-1。

Example 57

N, N, N ', N ' -tetramethyl-N ' -octylguanidine methyl sulfonate ionic liquid ([ HOctTMG]]CH₃SO₃) Synthesis of (2)

Pentaalkylguanidine OctTMG was synthesized as in example 3. Taking 0.30mol of OctTMG and 0.30mol of CH₃SO₃H is subjected to neutralization reaction to obtain 0.26mol of target product. FTIR (KBr): upsilon is_max：2936，2856，1652，1626，1513，1496，1392，1255，1152cm^-1。

Example 58

Synthesis of N, N, N ', N ' -tetramethyl-N' -octylguanidinecarboxylate ionic liquid ([ HOctTMG]HCOO)

Pentaalkylguanidine OctTMG was synthesized as in example 3. 0.30mol of OctTMG and 0.30mol of HCOOH are taken to carry out neutralization reaction, and 0.24mol of target product is prepared. FTIR (KBr): upsilon is_max：2926，2854，1705，1656，1514，1496，1394，1256，1178，1154cm^-1。

Example 59

N, N, N ', N' -tetramethyl-N "-phenylguanidinium tetrafluoroborate ([ HPhTMG]BF₄) Synthesis of ionic liquids

Pentaalkylguanidine PhTMG was synthesized as in example 4. Taking 0.30mol PhTMG and 0.30mol HBF₄Carrying out neutralization reaction to obtain 0.23mol of target product. FTIR (KBr): upsilon is_max：3098，3116，2944，2888，1642，1616，1574，1532，1516，1500，1498，1377，1258，1154，1084，1025，799，718cm^-1。

Example 60

N, N, N ', N ' -tetramethyl-N ' -phenylguanidinium hexafluorophosphate ionic liquid ([ HPhTMG]PF₆) Synthesis of (2)

Pentaalkylguanidine PhTMG was synthesized as in example 4. Taking 0.30mol PhTMG and 0.30mol HPF₆Carrying out neutralization reaction to obtain 0.25mol of target product. FTIR (KBr): upsilon is_max：3096，3118，2944，2906，1646，1620，1576，1534，1521，1502，1496，1376，1254，1156，1027，840，792，716cm^-1。

Example 61

N, N, N ', N ' -tetramethyl-N ' -phenylguanidine acetate ionic liquid ([ HPhTMG)]CH₃COO) synthesis

Pentaalkylguanidine PhTMG was synthesized as in example 4. Taking 0.30mol PhTMG and 0.30mol CH₃The COOH is subjected to neutralization reaction to obtain 0.26And (5) mol of the target product. FTIR (KBr): upsilon is_max：3092，3118，2936，2887，1726，1647，1616，1582，1536，1520，1502，1496，1377，1256，1154，1027，829，794，714cm^-1。

Example 62

N, N, N ', N ' -tetramethyl-N ' -phenylguanidine trifluoromethyl acetate ionic liquid ([ HPhTMG)]CF₃COO) synthesis

Pentaalkylguanidine PhTMG was synthesized as in example 4. Taking 0.30mol PhTMG and 0.30mol CF₃And performing neutralization reaction on COOH to obtain 0.22mol of target product. FTIR (KBr): upsilon is_max：3088，3106，2942，2889，1706，1642，1616，1579，1534，1520，1500，1498，1376，1257，1176，1154，1038，1026，792，716，645cm^-1。

Example 63

N, N, N ', N ' -tetramethyl-N ' -phenylguanidine triflate ionic liquid ([ HPhTMG]]CF₃SO₃) Synthesis of (2)

Pentaalkylguanidine PhTMG was synthesized as in example 4. Taking 0.30mol PhTMG and 0.30mol CF₃SO₃H is subjected to neutralization reaction to obtain 0.23mol of target product. FTIR (KBr): upsilon is_max：3094，3110，2940，2896，1646，1620，1580，1536，1520，1500，1498，1377，1258，1156，1036，1024，794，718，636cm^-1。

Example 64

N, N, N ', N ' -tetramethyl-N ' -phenylguanidine lactate ionic liquid ([ HPhTMG)]CH₃CHOHCO) synthesis

Pentaalkylguanidine PhTMG was synthesized as in example 4. Taking 0.30mol PhTMG and 0.30mol CH₃CHOHCOOH is subjected to neutralization reaction to obtain 0.26mol of target product. FTIR (KBr): upsilon is_max：3095，3112，2941，2895，1646，1619，1582，1536，1520，1500，1498，1418，1377，1258，1248，1157，1054，1026，794，718cm^-1。

Example 65

N, N, N ', N ' -tetramethyl-N ' -phenyl guanidine methyl sulfonate ionic liquid ([ HPhTMG]CH₃SO₃) Synthesis of (2)

Pentaalkylguanidine PhTMG was synthesized as in example 4. Taking 0.30mol PhTMG and 0.30mol CH₃SO₃H is subjected to neutralization reaction to obtain 0.27mol of target product. FTIR (KBr): upsilon is_max：3099，3116，2940，2887，1645，1622，1582，1533，1520，1500，1498，1377，1258，1156，1026，792，718cm^-1。

Example 66

Synthesis of N, N, N ', N ' -tetramethyl-N ' -phenylguanidinecarboxylate ionic liquid ([ HPhTMG]HCOO)

Pentaalkylguanidine PhTMG was synthesized as in example 4. 0.30mol of PhTMG and 0.30mol of HCOOH are neutralizedThe target product of 0.25mol is obtained after the reaction. FTIR (KBr): upsilon is_max：3092，3106，2942，2889，1706，1642，1616，1579，1534，1520，1500，1498，1376，1257，1176，1154，1026，792，716cm^-1。

Claims

1. An alkylguanidinium ionic liquid having the formula:

wherein

2. The preparation method of the alkyl guanidine salt ionic liquid shown in the general formula of claim 1 is characterized by comprising the following synthesis steps:

① dissolving 0.30mol of tetramethylurea in 30-100 mL of toluene, and adding 0.30-0.33 mol of newly steamed POCl dropwise under the protection of nitrogen and stirring₃Reacting at 60 ℃ for 15-72 hours, and then using 150-200 mL of CH at 0-5 DEG C₂Cl₂Diluting the reaction system, and slowly dripping 1.20-1.35 mol of mono-substituted amine R' NH₂Wherein R' is n-butyl, cyclohexyl, n-octyl or phenyl, the mixture is heated to 50 to 60 ℃, then refluxed for 12 to 48 hours, 35 percent by mass of NaOH solution is dripped into the mixture under the cooling of an ice bath until the system is neutral, and 150 to 200mL of CH is used for a reaction mixture₂Cl₂Extracting, mixing organic phases, and adding anhydrous Na₂SO₄Drying for 24-72 hours, filtering, evaporating to remove the solvent, and distilling the residual liquid under reduced pressure to obtain 0.15-0.27 mol of pentaalkylguanidine;

② dissolving 0.30mol of tetramethylurea in 150-200 mL of toluene, and adding 0.30-0.33 mol of newly steamed POCl dropwise under the protection of nitrogen and stirring conditions₃Reacting for 2-10 hours at room temperature, and then dropwise adding 0.66-0.75 mol of mono-substituted amine R' NH₂Wherein R' is n-butyl, cyclohexyl, n-octyl or phenyl, stirring at room temperature for 20-48 hours after the reaction is finished, diluting the reaction system with 150-200 mL of water, vigorously stirring for 5-30 minutes, taking the lower layer solution, adding solid NaOH to make the system alkaline, then separating the solution into two layers, filtering out the solid, separating the filtrate into layers, taking the upper layer solution, dissolving the upper layer solution in diethyl ether, and then using anhydrous Na₂CO₃Drying, filtering, evaporating to remove solvent and residueDistilling the solution under reduced pressure to obtain 0.06-0.18 mol of pentaalkylguanidine;

②, 0.30mol of pentaalkylguanidine of which the N ' -substituent R ' prepared in the step(1) is cyclohexyl, N-octyl or phenyl is neutralized with 0.30 to 0.31mol of acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, lactic acid, methanesulfonic acid, formic acid, tetrafluoroboric acid or hexafluorophosphoric acid to prepare 0.24 to 0.30mol of pentaalkylguanidine salt ionic liquid, wherein N-and N ' -substituent R in the pentaalkylguanidine salt ionic liquid product is methyl, N ' -substituent R ' is phenyl, cyclohexyl or N-octyl, N ' -substituent R ' is H, Y is acetate anion, trifluoromethylacetate anion, trifluoromethylsulfonate anion, lactate anion, methylsulfonate anion, formate anion, tetrafluoroborate anion or hexafluorophosphate anion;

① dissolving 0.30mol of the N '-pentaalkylguanidine compound with the substituent R' being cyclohexyl, N-octyl or phenyl prepared in the step (1) in 20-100 mL of refined acetonitrile, dripping a newly distilled mixed solution of 0.30-0.33 mol of methyl monoiodide and 20-100 mL of acetonitrile under the ice water bath cooling and nitrogen protection, continuing stirring and reacting for 12-48 hours after the temperature of the system returns to room temperature, distilling off the acetonitrile in the reaction system, and washing the residual liquid with ethyl acetate for 2-2 hoursAnd (5) vacuum pumping off ethyl acetate in the system to obtain 0.12-0.30 mol of hexaalkylguanidinium iodide ionic liquid, wherein N '-substituent R' in the hexaalkylguanidinium iodide ionic liquid product is cyclohexyl, N-octyl or phenyl, and N '-substituent R' is CH₃Y is I;

③ dissolving 0.30mol of hexaalkylguanidinium iodide ionic liquid prepared in step (3) ② in 20-100 mL of distilled water, slowly dropwise adding 60mL of aqueous solution containing 0.30-0.31 mol of acetic acid, trifluoromethyl sulfonic acid, lactic acid or methyl sulfonic acid in lead salt under stirring to rapidly generate yellow precipitate, strongly stirring at room temperature for 1-2 hours, and pumping under reduced pressureFiltering to remove yellow solid, removing water in the filtrate to obtain 0.15-0.27 mol of hexaalkylguanidinium ionic liquid, wherein N ' -substituent R ' in the hexaalkylguanidinium ionic liquid product is N-butyl, cyclohexyl, N-octyl or phenyl, and N ' -is takenThe substituent R' is CH₃Y is an acetate anion, a trifluoromethylacetate anion, atrifluoromethylsulfonate anion, a lactate anion, or a methylsulfonate anion;