CN104250231B - For the synthesis of the benzotriazole ionic liquid of toluencediamine base alkyl formate - Google Patents
For the synthesis of the benzotriazole ionic liquid of toluencediamine base alkyl formate Download PDFInfo
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- CN104250231B CN104250231B CN201410477927.4A CN201410477927A CN104250231B CN 104250231 B CN104250231 B CN 104250231B CN 201410477927 A CN201410477927 A CN 201410477927A CN 104250231 B CN104250231 B CN 104250231B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
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Abstract
The invention provides a kind of benzotriazole ionic liquid such as formula structure (I) Suo Shi and preparation method thereof and preparing the application in toluencediamine base alkyl formate, this application is for raw material with tolylene diamine and alkyl carbamate, the benzotriazole ionic liquid such as formula structure (I) Suo Shi is used to react as catalyzer, make that the yield of target product toluencediamine base alkyl formate is high, technique is simple and environmentally friendly, be suitable for suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of benzotriazole ionic liquid and its preparation method and application, belong to organic synthesis field.
Technical background
Toluencediamine base alkyl formate is an important intermediate of non-phosgene synthesis tolylene diisocyanate (TDI), toluencediamine base alkyl formate can obtain TDI after catalyse pyrolysis, and TDI is the important source material of producing urethane, its polyurethane products are widely used in the aspects such as urethanes, agricultural chemicals, coating and weaving, along with developing rapidly of polyurethane industrial, the demand for TDI constantly increases.
At present, the method for synthesizing toluencediamine base alkyl formate mainly contains Wyler's process and methylcarbonate method.Wherein, simple (the Ind.Eng.Chem.Res. of method synthetic route of tolylene dicarbamate is generated with urea, methyl alcohol and tolylene diamine direct reaction, 2011,50 (24), 13636-13641.), but face the shortcomings such as by product is many, productive rate is low, the difficult separation of product.The people such as king (Ind.Eng.Chem.Res.2007,46,6858-6864) report the method for a kind of methylcarbonate method synthesis toluencediamine base alkyl formate, but the higher price of methylcarbonate is the principal element that restriction the method is applied to suitability for industrialized production in the market.It should be noted that, alkyl carbamate can be obtained by urea and alkyl alcohol direct reaction, the route being synthesized toluencediamine base alkyl formate by alkyl carbamate and tolylene diamine had both solved the not high problem of Wyler's process selectivity, turn avoid the use of methylcarbonate, is the desirable route of synthesis toluencediamine base alkyl formate.American documentation literature US20140073811A1 discloses a kind of method of carbamate and tolylene diamine Reactive Synthesis toluencediamine base alkyl formate, the method with the metal-salt of Cu, Zn, Sn and Pb etc. for catalyzer, weak point is that catalyzer is difficult to reclaim, and the discharge of metal ion can cause environmental pollution.Therefore, for a person skilled in the art, find with low cost a, environmental protection, high yield toluencediamine base alkyl formate synthetic route to overcome above-mentioned deficiency of the prior art, be a technical barrier urgently to be resolved hurrily.
Summary of the invention
What the present invention solved is that the cost that toluencediamine base alkyl formate synthetic method of the prior art exists is high, yield is low, the problem of contaminate environment, and then provide that a kind of cost is low, yield is high, and the toluencediamine base alkyl formate synthetic method of environmental protection.
The technical scheme that the present invention solves the problems of the technologies described above is:
A kind of benzotriazole ionic liquid such as formula structure (I) Suo Shi,
Wherein, R represents at least one C
1~ C
4alkyl, X
-for Cl
-or Br
-.
At least one C described
1~ C
4alkyl be 4 '-methyl, 4 '-ethyl, 4 '-tertiary butyl, 3 ', 5 '-dimethyl or 2 ', any one in 4 ', 6 '-trimethylammonium.
Comprise the steps:
Under protection of inert gas, be dissolved completely in by benzotriazole in organic solvent, slowly add benzyl halide, the mol ratio of described benzotriazole and described benzyl halide is 1: (1 ~ 1.5); Stir under 50 ~ 110 DEG C of conditions and react, after having reacted, reaction solution is carried out purification process, namely obtain described benzotriazole ionic liquid;
Wherein said benzyl halide is C
1~ C
4the benzyl chloride that alkyl replaces or the bromotoluene that C1 ~ C4 alkyl replaces.
Described benzyl halide is any one in 4-methyl-benzyl bromine, 4-ethylbenzyl chloride, 4-t-butylbenzyl chlorine, 3,5-dimethyl benzyl bromines or 2,4,6-trimethyl benzyl bromine.
Described organic solvent is one or more in toluene, dimethylbenzene, acetonitrile or tetrahydrofuran (THF).
Reaction times is 12 ~ 24h.
Described purification process is: carry out underpressure distillation to described reaction solution, and namely residue obtains described benzotriazole ionic liquid through column chromatography for separation.
When carrying out described column chromatography for separation, elutriant used is volume ratio is (1 ~ 3): the methylene dichloride of 1 and the mixed solvent of sherwood oil.
Described benzotriazole ionic liquid is preparing the application in toluencediamine base alkyl formate.
Described benzotriazole ionic liquid prepares a method for toluencediamine base alkyl formate, comprises the steps:
Under protection of inert gas; in organic solvent, add mol ratio is 1: (2.5 ~ 3): the tolylene diamine of (0.001 ~ 0.005), alkyl carbamate and described benzotriazole ionic liquid; stir under 1 ~ 2MPa, the condition of 140 ~ 180 DEG C and react; after having reacted; purification process is carried out to reaction solution, namely obtains described toluencediamine base alkyl formate.
Described alkyl carbamate is any one in Urethylane, urethanum or butyl carbamate.
Described organic solvent is one or more in anhydrous methanol, dehydrated alcohol, Virahol, pyridine, benzene, toluene, chlorobenzene, dimethylbenzene, orthodichlorobenzene or tetramethylene sulfone; The mol ratio of described organic solvent and described tolylene diamine is (20 ~ 80): 1.
Described tolylene diamine is 2,4-tolylene diamine, 2,6-tolylene diamines or mass ratio are 2,4-tolylene diamines of 1 ~ (4: 1) and the mixture of 2,6-tolylene diamine.
Reaction times is 4 ~ 6 hours.
Described purification process is: carry out underpressure distillation to described reaction solution, and residue, through column chromatography for separation, namely obtains described toluencediamine base alkyl formate.
When carrying out described column chromatography for separation, elutriant used is volume ratio is the sherwood oil of 100: 1 and the mixed solvent of ethyl acetate.
The preparation method of toluencediamine base alkyl formate of the present invention; under protection of inert gas; in organic solvent, add mol ratio is 1: (2.5 ~ 3): the tolylene diamine of (0.001 ~ 0.005), alkyl carbamate and benzotriazole ionic liquid; why adopt this molar ratio; advantage is to make the transformation efficiency of tolylene diamine reach 99%, and the selectivity of target product is good, by product is few.
Compared with toluencediamine base alkyl formate synthetic method of the prior art, the advantage of the preparation method of toluencediamine base alkyl formate of the present invention is: the present invention uses benzotriazole ionic liquid as catalyzer, on the one hand the catalytic performance of benzotriazole ionic liquid good, be easy to removing and environmentally friendly; Avoid using metal catalyst of the prior art on the other hand, make reaction of the present invention not need harsh equipment material and operational condition, greatly reduce production cost, be suitable for industrial applications.
Accompanying drawing explanation
Fig. 1 is the liquid chromatogram of the reaction solution of embodiment 1;
Fig. 2 is the high resolution mass spectrum figure of 2-(4 '-methyl-benzyl) benzotriazole bromine ionic liquid.
Embodiment
Below in conjunction with specific embodiment, the preparation method to toluencediamine base alkyl formate provided by the invention is described in detail.
Embodiment 1
The preparation method of the tolylene dicarbamate described in the present embodiment, comprises the steps:
Under nitrogen protection; 2 are added successively in the autoclave of 1L; 4-tolylene diamine 12.2g, Urethylane 18.7g, 2-(4 '-methyl-benzyl) benzotriazole bromine salt 30.2mg and methyl alcohol 320mL; be heated to 140 DEG C; and keep reacting kettle inner pressure to be 2MPa, react under stirring.Follow the tracks of reaction process by liquid chromatography, after 6 hours, 2,4-tolylene diamines react completely, stopped reaction, and question response liquid is cooled to room temperature, discharge the residual ammonia in reactor; Through liquid-phase chromatographic analysis, in reaction solution, the productive rate of tolylene dicarbamate is 89.5%, and the liquid chromatogram of this reaction solution as shown in Figure 1; By above-mentioned reaction solution underpressure distillation removing methyl alcohol, be the sherwood oil of 100: 1 and the mixed solvent of ethyl acetate be that elutriant carries out column chromatography for separation to residue with volume ratio, namely obtain described tolylene dicarbamate, yield is 83.4%.
Utilize the structure of nucleus magnetic hydrogen spectrum to described tolylene dicarbamate to characterize, result is as follows:
1HNMR(400MHz，CDCl
3，TMS)：δ7.72(d，J＝7.2Hz，1H)，7.67(s，1H)，7.55(s，1H)，7.42(d，J＝6.8Hz，1H)，7.32(d，J＝7.6Hz，1H)，3.68(s，3H)，3.70(s，3H)，2.19(s，3H)ppm。
Wherein, the preparation method of 2-(4 '-methyl-benzyl) the benzotriazole bromine ionic liquid of the present embodiment use is as follows:
Under nitrogen protection, in the there-necked flask of 500mL, add benzotriazole 60g and toluene 100mL, stir until benzotriazole dissolves completely; The toluene solution 60mL being dissolved with 92.5g4-methyl-benzyl bromine is slowly dripped again in above-mentioned there-necked flask, 24h is reacted under 50 DEG C of conditions, after reaction terminates, concentrating under reduced pressure is carried out to reaction solution, be the methylene dichloride of 1: 1 and the mixed solvent of sherwood oil with volume ratio be that elutriant carries out column chromatography for separation to residue, namely obtain described 2-(4 '-methyl-benzyl) benzotriazole bromine ionic liquid, yield is 64.6%.
Utilize the structure of the analysis means such as high resolution mass spectrum, nucleus magnetic hydrogen spectrum to described 2-(4 '-methyl-benzyl) benzotriazole bromine ionic liquid to characterize, result is as follows:
HRMS(EI，m/z)：224.1193(M+H)
+；
1HNMR(400MHz，CDCl
3，TMS)：δ13.13(s，1H)，7.96(dd，J＝8.8Hz，2.4Hz，2H)，7.40(dd，J＝8.0，2.4Hz，2H)，7.17(d，J＝8.0Hz，2H)，7.00(d，J＝7.2Hz，2H)，3.98(d，J＝7.2Hz，2H)，2.19(s，3H)ppm。The high resolution mass spectrum figure of described 2-(4 '-methyl-benzyl) benzotriazole bromine ionic liquid as shown in Figure 2.
Embodiment 2
The preparation method of the tolylene dicarbamate described in the present embodiment, comprises the steps:
Under nitrogen protection; 2 are added successively in the autoclave of 1L; 6-tolylene diamine 24.4g, Urethylane 45.0g, 2-(3 '; 5 '-dimethyl benzyl) benzotriazole bromine salt 158.0mg and pyridine 1280mL; be heated to 160 DEG C; and keep reacting kettle inner pressure to be 1MPa, react under stirring.Follow the tracks of reaction process by liquid chromatography, after 4 hours, 2,6-tolylene diamines react completely, stopped reaction, and question response liquid is cooled to room temperature, discharge the residual ammonia in reactor; Through liquid-phase chromatographic analysis, in reaction solution, the productive rate of tolylene dicarbamate is 93.5%; By above-mentioned reaction solution underpressure distillation removing pyridine, be the sherwood oil of 100: 1 and the mixed solvent of ethyl acetate be that elutriant carries out column chromatography for separation to residue with volume ratio, namely obtain described tolylene dicarbamate, yield is 90.9%.
Wherein, the preparation method of 2-(3 ', 5 '-dimethyl benzyl) the benzotriazole bromine ionic liquid of the present embodiment use is as follows:
Under nitrogen protection, in the there-necked flask of 500mL, add benzotriazole 60g and toluene 100mL, stir until benzotriazole dissolves completely; Slowly drip in above-mentioned there-necked flask again and be dissolved with 150g3, the toluene solution 60mL of 5-dimethylbenzyl bromine, back flow reaction 12h under 110 DEG C of conditions, after reaction terminates, carrying out concentrating under reduced pressure to reaction solution, be the methylene dichloride of 1: 1 and the mixed solvent of sherwood oil is that elutriant carries out column chromatography for separation to residue with volume ratio, namely obtains described 2-(3 ', 5 '-dimethyl benzyl) benzotriazole bromine ionic liquid, yield is 79.5%.
Utilize the structure of nucleus magnetic hydrogen spectrum to described 2-(3 ', 5 '-dimethyl benzyl) benzotriazole bromine ionic liquid to characterize, result is as follows:
1HNMR(400MHz，CDCl
3，TMS)：δ13.19(s，1H)，7.97(dd，J＝8.8，2.4Hz，2H)，7.40(dd，J＝8.0，2.4Hz，2H)，7.24(d，J＝8.0Hz，1H)，6.72(s，2H)，3.89(d，J＝7.6Hz，2H)，2.27(s，6H)ppm。
Embodiment 3
The preparation method of the tolylene dicarbamate described in the present embodiment, comprises the steps:
Under nitrogen protection; 2 are added successively in the autoclave of 1L; 4-tolylene diamine 9.8g, 2; 6-tolylene diamine 2.4g, Urethylane 20.2g, 2-(2 '; 4 ', 6 '-trimethyl benzyl) benzotriazole bromine salt 166mg and orthodichlorobenzene 565mL, be heated to 180 DEG C; and keep reacting kettle inner pressure to be 1.5MPa, react under stirring.Follow the tracks of reaction process by liquid chromatography, after 5 hours, tolylene diamine reacts completely, stopped reaction, and question response liquid is cooled to room temperature, discharges the residual ammonia in reactor; Through liquid-phase chromatographic analysis, in reaction solution, the productive rate of tolylene dicarbamate is 99.0%; By above-mentioned reaction solution underpressure distillation removing orthodichlorobenzene, residue is through column chromatography for separation, and eluent is volume ratio is the sherwood oil of 100: 1 and the mixed solvent of ethyl acetate, namely obtains described tolylene dicarbamate, and yield is 94.2%.
Wherein, the preparation method of 2-(2 ', 4 ', 6 '-trimethyl benzyl) the benzotriazole bromine ionic liquid of the present embodiment use is as follows:
Under nitrogen protection, in the there-necked flask of 500mL, add benzotriazole 60g and p-Xylol 100mL, stir until benzotriazole dissolves completely; Slowly drip in above-mentioned there-necked flask again and be dissolved with 135g2, the p-Xylol solution 60mL of 4,6-trimethylammonium benzyl bromine, reacts 18h under 80 DEG C of conditions, after reaction terminates, carry out concentrating under reduced pressure to reaction solution, residue is again through column chromatography for separation, and elutriant is volume ratio is the methylene dichloride of 3: 1 and the mixed solvent of sherwood oil, namely described 2-(2 ' is obtained, 4 ', 6 '-trimethyl benzyl) benzotriazole bromine ionic liquid, yield is 50.5%.
Utilize the structure of nucleus magnetic hydrogen spectrum to described 2-(2 ', 4 ', 6 '-trimethyl benzyl) benzotriazole bromine ionic liquid to characterize, result is as follows:
1HNMR(400MHz，CDCl
3，TMS)：δ13.22(s，1H)，7.96(dd，J＝9.2，2.4Hz，2H)，7.40(dd，J＝8.4，2.4Hz，2H)，6.67(s，2H)，3.94(d，J＝7.6Hz，2H)，2.29(s，6H)，2.27(s，3H)ppm。
Embodiment 4
The preparation method of the toluencediamine base ethyl formate described in the present embodiment, comprises the steps:
Under nitrogen protection; 2 are added successively in the autoclave of 1L; 4-tolylene diamine 6.1g, 2; 6-tolylene diamine 6.1g, urethanum 24.9g, 2-(3 '; 5 '-dimethyl benzyl) benzotriazole bromine salt 0.95g and tetramethylene sulfone 190mL; be heated to 150 DEG C, and keep reacting kettle inner pressure to be 1.5MPa, react under stirring.Follow the tracks of reaction process by liquid chromatography, after 5.5 hours, tolylene diamine reacts completely, stopped reaction, and question response liquid is cooled to room temperature, discharges the residual ammonia in reactor; Through liquid-phase chromatographic analysis, in reaction solution, the productive rate of toluencediamine base ethyl formate is 98.2%; By above-mentioned reaction solution underpressure distillation removing tetramethylene sulfone, residue is through column chromatography for separation, and eluent is volume is the sherwood oil of 100: 1 and the mixed solvent of ethyl acetate, and namely obtain described toluencediamine base ethyl formate, yield is 92.5%.
Wherein, the preparation method of described 2-(3 ', 5 '-dimethyl benzyl) benzotriazole bromine ionic liquid is with embodiment 2.Utilize the structure of nucleus magnetic hydrogen spectrum to described toluencediamine base ethyl formate to characterize, result is as follows:
1HNMR(400MHz，CDCl
3，TMS)：δ7.70(d，J＝7.6Hz，1H)，7.66(s，1H)，7.50(s，1H)，7.39(d，J＝8.8Hz，1H)，7.28(d，J＝7.2Hz，1H)，4.15(dd，J＝7.6Hz，J＝4.0Hz，4H)，2.18(s，3H)，1.29(s，3H)，1.27(s，3H)ppm。
Embodiment 5
The preparation method of the toluencediamine base ethyl formate described in the present embodiment, comprises the steps:
Under nitrogen protection; 2 are added successively in the autoclave of 1L; 4-tolylene diamine 12.2g, urethanum 22.3g, 2-(4 '-Ethylbenzyl) benzotriazole villaumite 82mg and dehydrated alcohol 230mL; be heated to 140 DEG C; and keep reacting kettle inner pressure to be 1.5MPa, react under stirring.Follow the tracks of reaction process by liquid chromatography, after 5 hours, 2,4-tolylene diamines react completely, stopped reaction, and question response liquid is cooled to room temperature, discharge the residual ammonia in reactor; Through liquid-phase chromatographic analysis, in reaction solution, the productive rate of toluencediamine base ethyl formate is 93.6%; By above-mentioned reaction solution underpressure distillation removing ethanol, residue is through column chromatography for separation, and eluent is volume ratio is the sherwood oil of 100: 1 and the mixed solvent of ethyl acetate, and namely obtain described toluencediamine base ethyl formate, yield is 88.2%.
Wherein, the preparation method of 2-(4 '-Ethylbenzyl) the benzotriazole chloride salt ions liquid of the present embodiment use is as follows:
Under nitrogen protection, in the there-necked flask of 500mL, add benzotriazole 60g and acetonitrile 100mL, stir until benzotriazole dissolves completely; The acetonitrile solution 60mL being dissolved with 96g4-Ethyl Benzyl Chloride is slowly dripped again in above-mentioned there-necked flask, 20h is reacted under 85 DEG C of conditions, after reaction terminates, concentrating under reduced pressure is carried out to reaction solution, residue is through column chromatography for separation, elutriant is volume ratio is the methylene dichloride of 2: 1 and the mixed solvent of sherwood oil, and namely obtain described 2-(4 '-Ethylbenzyl) benzotriazole chloride salt ions liquid, yield is 68.7%.
Utilize the structure of nucleus magnetic hydrogen spectrum to described 2-(4 '-Ethylbenzyl) benzotriazole chloride salt ions liquid to characterize, result is as follows:
1HNMR(400MHz，CDCl
3，TMS)：δ13.10(s，1H)，7.89(dd，J＝8.4Hz，2.4Hz，2H)，7.36(dd，J＝7.6，2.4Hz，2H)，7.14(d，J＝7.2Hz，2H)，6.98(d，J＝7.6Hz，2H)，3.94(d，J＝7.2Hz，2H)，2.72(m，2H)，1.18(s，3H)ppm。
Embodiment 6
The preparation method of the toluene diamino butyl formate described in the present embodiment, comprises the steps:
Under nitrogen protection; 2 are added successively in the autoclave of 1L; 4-tolylene diamine 12.2g, butyl carbamate 23.4g, 2-(4 '-t-butylbenzyl) benzotriazole villaumite 54.6mg and chlorobenzene 610mL; be heated to 150 DEG C; and keep reacting kettle inner pressure to be 2MPa, react under stirring.Follow the tracks of reaction process by liquid chromatography, after 6 hours, 2,4-tolylene diamines react completely, stopped reaction, and question response liquid is cooled to room temperature, discharge the residual ammonia in reactor; Through liquid-phase chromatographic analysis, in reaction solution, the productive rate of toluene diamino butyl formate is 90.3%; By above-mentioned reaction solution underpressure distillation removing chlorobenzene, residue is through column chromatography for separation, and eluent is volume ratio is the sherwood oil of 100: 1 and the mixed solvent of ethyl acetate, namely obtains described toluene diamino butyl formate, and yield is 86.2%.
Utilize the structure of nucleus magnetic hydrogen spectrum to described toluene diamino butyl formate to characterize, result is as follows:
1HNMR(400MHz，CDCl
3，TMS)：δ7.84(d，J＝7.2Hz，1H)，7.77(s，1H)，7.63(s，1H)，7.49(d，J＝7.2Hz，1H)，7.38(d，J＝8.0Hz，1H)，3.90(t，J＝7.2Hz，4H)，2.19(s，3H)，1.49-1.40(m，4H)，1.29-1.19(m，4H)，0.90(t，J＝7.2Hz，6H)ppm。
Wherein, the preparation method of 2-(4 '-t-butylbenzyl) the benzotriazole chloride salt ions liquid of the present embodiment use is as follows:
Under nitrogen protection, in the there-necked flask of 500mL, add benzotriazole 60g and tetrahydrofuran (THF) 100mL, stir until benzotriazole dissolves completely; The tetrahydrofuran solution 60mL being dissolved with 109g4-tertiary butyl benzyl chlorine is slowly dripped again in above-mentioned there-necked flask, 24h is reacted under 70 DEG C of conditions, after reaction terminates, concentrating under reduced pressure is carried out to reaction solution, residue is through column chromatography for separation, elutriant is volume ratio is the methylene dichloride of 1: l and the mixed solvent of sherwood oil, and namely obtain described 2-(4 '-t-butylbenzyl) benzotriazole chloride salt ions liquid, yield is 63.8%.
Utilize the structure of nucleus magnetic hydrogen spectrum to described 2-(4 '-t-butylbenzyl) benzotriazole chloride salt ions liquid to characterize, result is as follows:
1HNMR(400MHz，CDCl
3，TMS)：δ13.19(s，1H)，7.99(dd，J＝8.8Hz，2.4Hz，2H)，7.43(d，J＝7.2Hz，2H)，7.18(d，J＝7.6Hz，2H)，7.08(d，J＝7.2Hz，2H)，4.04(d，J＝7.6Hz，2H)，1.13(s，9H)ppm。
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (14)
1. such as formula a benzotriazole ionic liquid for structure (I) Suo Shi,
Wherein, R is 4 '-methyl, 4 '-ethyl, 4 '-tertiary butyl, 3 ', 5 '-dimethyl or 2 ', any one in 4 ', 6 '-trimethylammonium, X
-for Cl
-or Br
-.
2. the preparation method of benzotriazole ionic liquid described in claim 1, is characterized in that, comprise the steps:
Under protection of inert gas, be dissolved completely in by benzotriazole in organic solvent, slowly add benzyl halide, the mol ratio of described benzotriazole and described benzyl halide is 1:(1 ~ 1.5); Stir under 50 ~ 110 DEG C of conditions and react, after having reacted, reaction solution is carried out purification process, namely obtain described benzotriazole ionic liquid;
Wherein said benzyl halide is any one in 4-methyl-benzyl bromine, 4-ethylbenzyl chloride, 4-t-butylbenzyl chlorine, 3,5-dimethyl benzyl bromines or 2,4,6-trimethyl benzyl bromine.
3. the preparation method of benzotriazole ionic liquid as claimed in claim 2, it is characterized in that, described organic solvent is one or more in toluene, dimethylbenzene, acetonitrile or tetrahydrofuran (THF).
4. the preparation method of benzotriazole ionic liquid as claimed in claim 2 or claim 3, it is characterized in that, the reaction times is 12 ~ 24h.
5. the preparation method of benzotriazole ionic liquid as claimed in claim 2 or claim 3, it is characterized in that, described purification process is: carry out underpressure distillation to described reaction solution, and namely residue obtains described benzotriazole ionic liquid through column chromatography for separation.
6. the preparation method of benzotriazole ionic liquid as claimed in claim 5, is characterized in that, when carrying out described column chromatography for separation, elutriant used is volume ratio is (1 ~ 3): the methylene dichloride of 1 and the mixed solvent of sherwood oil.
7. benzotriazole ionic liquid according to claim 1 is preparing the application in toluencediamine base alkyl formate.
8. use benzotriazole ionic liquid described in claim 1 to prepare a method for toluencediamine base alkyl formate, comprise the steps:
Under protection of inert gas; in organic solvent, add mol ratio is 1:(2.5 ~ 3): the tolylene diamine of (0.001 ~ 0.005), alkyl carbamate and described benzotriazole ionic liquid; stir under 1 ~ 2MPa, the condition of 140 ~ 180 DEG C and react; after having reacted; purification process is carried out to reaction solution, namely obtains described toluencediamine base alkyl formate.
9. prepare the method for toluencediamine base alkyl formate as claimed in claim 8, it is characterized in that, described alkyl carbamate is any one in Urethylane, urethanum or butyl carbamate.
10. prepare the method for toluencediamine base alkyl formate as claimed in claim 8, it is characterized in that, described organic solvent is one or more in anhydrous methanol, dehydrated alcohol, Virahol, pyridine, benzene, toluene, chlorobenzene, dimethylbenzene, orthodichlorobenzene or tetramethylene sulfone; The mol ratio of described organic solvent and described tolylene diamine is (20 ~ 80): 1.
11. methods preparing toluencediamine base alkyl formate as claimed in claim 8, it is characterized in that, described tolylene diamine is 2,4-tolylene diamine, 2,6-tolylene diamine or mass ratio are 2, the 4-tolylene diamines of 1 ~ (4:1) and the mixture of 2,6-tolylene diamine.
12. methods preparing toluencediamine base alkyl formate as described in any one of claim 8-11, it is characterized in that, the reaction times is 4 ~ 6 hours.
13. methods preparing toluencediamine base alkyl formate as described in any one of claim 8-11, it is characterized in that, described purification process is: carry out underpressure distillation to described reaction solution, and residue, through column chromatography for separation, namely obtains described toluencediamine base alkyl formate.
14. methods preparing toluencediamine base alkyl formate as claimed in claim 13, is characterized in that, when carrying out described column chromatography for separation, elutriant used is volume ratio is the sherwood oil of 100:1 and the mixed solvent of ethyl acetate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516128A (en) * | 2011-12-19 | 2012-06-27 | 河北工业大学 | Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis |
| CN102659635A (en) * | 2012-04-17 | 2012-09-12 | 河北工业大学 | Method for preparing toluene diamino butyl formate |
| CN102746279A (en) * | 2011-04-19 | 2012-10-24 | 中国科学院兰州化学物理研究所 | Benzotriazole group-containing ionic liquid and its preparation method and use |
| CN102933545A (en) * | 2010-07-07 | 2013-02-13 | 三井化学株式会社 | Method of producing toluene dicarbamate, method of producing toluene diisocyanate, and toluene dicarbamate |
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| CN102933545A (en) * | 2010-07-07 | 2013-02-13 | 三井化学株式会社 | Method of producing toluene dicarbamate, method of producing toluene diisocyanate, and toluene dicarbamate |
| CN102746279A (en) * | 2011-04-19 | 2012-10-24 | 中国科学院兰州化学物理研究所 | Benzotriazole group-containing ionic liquid and its preparation method and use |
| CN102516128A (en) * | 2011-12-19 | 2012-06-27 | 河北工业大学 | Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis |
| CN102659635A (en) * | 2012-04-17 | 2012-09-12 | 河北工业大学 | Method for preparing toluene diamino butyl formate |
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