CN108117522A - A kind of synthetic method of dicarboxylic acids imidazole salts - Google Patents
A kind of synthetic method of dicarboxylic acids imidazole salts Download PDFInfo
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Abstract
A kind of synthetic method of dicarboxylic acids imidazole salts of the present invention; with 2; 6 diisopropyl anilines are raw material; 4 iodine 2 are generated with Iod R; 6 diisopropyl anilines (A); A adds in catalyst reaction generation 3,5 diisopropyl, 4 aminobenzene methyl acrylate (B) with methyl acrylate under the conditions of inert gas shielding.Compound B generates 1,4 pairs of 1,3 butadiene (C) of [(4 methoxycarbonylvinyl, 2,6 diisopropyl) phenyl] 1,4 diaza with glyoxal reaction.Compound C generates compound 1,3 pairs [(4 methoxycarbonylvinyl, 2,6 diisopropyl) phenyl] imidazolium chloride salt (D) with paraformaldehyde through catalytic reaction.Compound D is through hydrolysis generation target compound E：1,3 pairs of [(4 carboxy vinyl, 2,6 diisopropyl) phenyl] imidazolium chloride salts.The present invention synthesis one there is no literature reported on the miscellaneous carbene precursor dicarboxylic acids imidazole salts of N, have synthetic method it is simple, synthesis it is at low cost, yield is high, product purity is high the advantages of.Target compound E such as following formulas：
Description
Technical field
The present invention relates to a kind of synthetic methods of dicarboxylic acids imidazole salts.
Background technology
Metal-organic framework (metal-organic frameworks, MOFs) refers to metal ion (or metal ion
Cluster) and organic ligand is under prescribed conditions, in multicomponent system between different component (constructing module), passes through coordinate bond, oversubscription
The guiding of son effect etc., the polymer of the periodic network structure for the three-dimensional structure for carrying out self assembly and being formed are otherwise known as and match somebody with somebody
Position polymer.Why prosperous always the ligand of class containing carboxyl is does not wane by being determined the characteristics of its own with advantage：(1) carboxyl
Coordination ability is very strong, can be coordinated to form coordination polymer with various metals.(2) carboxyl has abundant coordination mode, substantially may be used
It is divided into three classes, i.e. monodentate ligand, chelating ligands and bridging coordination.(3) difference of carboxyl deprotonation can form different structures.
There are two in ortho position, meta or para position due to tool by aromatic dicarboxylic acids' (such as phthalic acid class, biphenyl acid class and naphthalene diacid)
Carboxyl, spatially with preferable expansion, and bridge ligand supporting network is can be used as with the dicarboxylic acids of rigid structure
Network structure, thus it is frequently used to design, synthesize the structure of the organic topology of metal.If Yaghi Yaghi seminar is with to benzene two
Formic acid (1,4-BDC) is that ligand has synthesized aperture and isMOF-5, (Zn O4(BDC)3·(DMF)8·C6H5Cl), it is real
Impressive progress of the crystalline microporous material to crystalline-state mesoporous material is showed.MOF-5 has CaB6Topological structure is with octahedra secondary
Structural unit (ZnO4(CO2)6Cluster) node (node) as 6- connections, Isosorbide-5-Nitrae-BDC ligands are as link (linker) by node
The three-dimensional cubic network structure that bridging is formed together.MOF-5 can be stabilized in air to 300 DEG C, complete in guest molecule
After full removing, crystal still is able to remain intact.French scientist F é rey reports are with terephthalic acid (TPA) and cadmium nitrate and hydrofluoric acid
Raw material hydrothermal synthesis MIL-101, Cr3F(H2O)2O[(O2C)-C6H4-(CO2)]3·nH2O(n-25).MIL-101 be with
The molecular sieve analog in the super large hole of MTN topological classifications, unit-cell volume differenceThe structure of compound is all built upon
The octahedra building unit of three core Cr clusters (Cr-SBU) is connected with terephthalic acid (TPA), four Cr-SBU and six in MIL-101
Terephthalic acid (TPA) connects into a super tetrahedron, then is formed simultaneously pentagon and the cage on six sides by common vertex.It is worth mentioning
It is that MIL-101 structures can be to be stabilized to 275 DEG C in air, its skeleton still keeps original completeness after object is lost.Simultaneously
The specific surface area of MIL-101 is up to 5900m2g-1, there is stronger adsorption capacity.
Extended rigidity dicarboxylic acids ligand usually leads to more micropore MOFs materials of structure novel, large specific surface area,
And microcellular structure can be changed, electronic environment in its micropore is made to obtain optimizing to improve above application performance, therefore, design synthesis
The extension dicarboxylic acids ligand of structure novel has simultaneously become one of hot spot studied now applied to MOFs materials.So
And large-sized rigid dicarboxylic acid compound's synthesis is relatively difficult, it particularly can be as the dicarboxylic acids of the miscellaneous carbene precursors of N-
Imidazole salt compound, therefore double [(4- carboxy vinyl -2, the 6- diisopropyls of 1,3- of structure novel involved in the present invention
Base) phenyl] imidazolium chloride salt is a kind of organic ligand with huge potential using value.There is no literature reported on the changes at present
Close object.
The content of the invention
Double [(the 4- carboxylics of new 1,3- at low cost, yield is high, product purity is high are synthesized the object of the present invention is to provide a kind of
Base vinyl -2,6- diisopropyls) phenyl] imidazolium chloride salt synthetic method.
A kind of synthetic method of dicarboxylic acids imidazole salts of the present invention, synthesis step are：
(i) using 2,6-DIPA as raw material, a certain amount of sodium acid carbonate is added in, methanol is added in as solvent, adds in
The dichloromethane solution of iodine, molar ratio 2,6-DIPA：Iodine：Sodium acid carbonate is 1:1.1~1.5:2.5~3.5,2,6-
The amount ratio of diisopropyl aniline and methanol is 1 mmoles：3~6 milliliters, the amount ratio of 2,6-DIPA and dichloromethane
It is 1 mmoles：1.5~2.5 milliliters.After adding when 20~30 DEG C of reactions 10~15 are small, reaction terminates to filter solid, adds dichloro
Methane washes solid, is concentrated in vacuo filtrate, add 50~80mL saturated sodium thiosulfate solution continue stirring 2 it is small when, add methylene chloride
It extracts (30~60mL × 3), merges organic phase, anhydrous magnesium sulfate drying is filtered, and vacuum decompression filtrate obtains compound A：4-
Iodo- 2,6- diisopropyl anilines；
(II) argon gas or nitrogen protection under, be separately added into 250mL there-necked flasks the iodo- 2,6-DIPAs of 4-,
Methyl acrylate, potassium carbonate, triphenylphosphine, tetrabutylammonium bromide and a certain amount of solvent DMF, iodo- 2, the 6- bis- of molar ratio 4- are different
Propyl aniline：Methyl acrylate：Potassium carbonate：Triphenylphosphine：Tetrabutylammonium bromide is 1:5.0~7.0：2.0~4.0：0.1~
0.3：The ratio of the iodo- 2,6-DIPA of 4~6,4- and solvent is 1 mmoles：5.0~15.0 milliliters.Add in a certain amount of palladium
Salt when 90 DEG C of reactions 30~50 are small, pour into precipitation is precipitated in 50mL ice water after reaction, add a small amount of hydrochloric acid as catalyst
Catalyst is quenched, suction filtration obtains a large amount of white solids, and 20~40mL water is added to dilute, and dichloromethane extraction (40~70mL × 3) is received
Collection organic phase simultaneously it is carried out with anhydrous sodium sulfite to remove water process, filter, steam dichloromethane solvent and obtain crude product, finally with
Dichloromethane and petroleum ether are 10 by volume:0.8~1.2 mixed solvent is obtained for eluant, eluent with column chromatography separating-purifying
Compound B：3,5- diisopropyls -4- amino-cinnamic acid methyl esters；
(III) 3,5- diisopropyls -4- amino-cinnamic acid methyl esters, glyoxal and acetic acid in molar ratio 1:0.48~
0.52：It is dissolved in after 0.08~0.12 mixing in certain solvent, 3,5- diisopropyl -4- amino-cinnamic acid methyl esters and solvent
Amount ratio is 1 mmoles：It 8.0~15.0 milliliters, when 20~30 DEG C of reactions 20~30 are small, filters after reaction, crude product is used
10~30mL absolute methanols recrystallization purifying 3 times, filtering, dry compound C：1,4- pairs [(4- methoxycarbonylvinyl -2,
6- diisopropyls) phenyl] -1,4- diaza -1,3- butadiene；
(IV) is separately added into double [(4- methoxycarbonylvinyl -2,6- diisopropyls) benzene of 1,4- in 250mL there-necked flasks
Base]-Isosorbide-5-Nitrae-diaza -1,3-butadiene, anhydrous zinc chloride, paraformaldehyde and a certain amount of hydrochloric acid, molar ratio Isosorbide-5-Nitrae-bis- [(4-
Methoxycarbonylvinyl -2,6- diisopropyls) phenyl] -1,4- diaza -1,3- butadiene：Anhydrous zinc chloride：Paraformaldehyde：
Hydrochloric acid is 1:0.8~1.2：2.5~4.0:1~2, Isosorbide-5-Nitrae-bis- [(4- methoxycarbonylvinyls -2,6- diisopropyl) phenyl] -1,
4- diaza -1,3- butadiene and the ratio of solvents tetrahydrofurane are 1 mmoles：20.0~40.0 milliliters.When 70 DEG C of reactions 4~8 are small,
Reaction terminates to steam tetrahydrofuran, adds the mixed solvent of 20~40mL ethyl acetate and water (volume ratio 1:1), until generating big
Solid is measured, filtering washs crude product with cold ethyl acetate, obtains pure compound D：1,3- pairs [(4- methoxycarbonylvinyls-
2,6- diisopropyls) phenyl] imidazolium chloride salt；
(V) double [(4- methoxycarbonylvinyl -2,6- diisopropyls) phenyl] imidazolium chloride salts of 1,3- and LiOH are pressed
Molar ratio 1:10~30 add in the in the mixed solvent of Isosorbide-5-Nitrae-dioxane and water, the volume ratio of Isosorbide-5-Nitrae-dioxane and water for 3~
5:When 1,95 DEG C of reflux 8~12 is small, excessive Isosorbide-5-Nitrae-dioxane is evaporated off, is diluted with water, adds in excessive dilute HCl and is acidified to pH=
1, white solid is precipitated, is dried in vacuo to obtain final compound E：1,3- is double [(4- carboxy vinyl -2,6- diisopropyls) phenyl]
Imidazolium chloride salt.
A kind of synthetic method of the dicarboxylic acids imidazole salts, it is characterised in that：When preparing A, molar ratio 2,6- bis-
Isopropyl aniline：Iodine：Sodium acid carbonate is 1:1.1~1.5:2.5~3.5.
A kind of synthetic method of the dicarboxylic acids imidazole salts, it is characterised in that：A is prepared with methanol and dichloromethane
For mixed solvent, the amount ratio of 2,6-DIPA and methanol is 1 mmoles：3~6 milliliters, 2,6-DIPA with
The amount ratio of dichloromethane is 1 mmoles：1.5~2.5 milliliters.When 20~30 DEG C of reactions 10~15 are small.
A kind of synthetic method of the dicarboxylic acids imidazole salts, it is characterised in that：During prepare compound A, crude product
It is middle addition 50~80mL saturated sodium thiosulfate solution continue stirring 2 it is small when, add methylene chloride extraction (30~60mL × 3), conjunction
And organic phase, anhydrous magnesium sulfate drying.
A kind of synthetic method of the dicarboxylic acids imidazole salts, it is characterised in that：During prepare compound B, molar ratio
A：Methyl acrylate：Potassium carbonate：Triphenylphosphine：Tetrabutylammonium bromide is 1:5.0~7.0：2.0~4.0：0.1~0.3：4~6.
150mL DMF need to be added to make solvent.It is 10 by volume to purify B dichloromethane and petroleum ether:0.8~1.2 mixed solvent is
Eluant, eluent.
A kind of synthetic method of the dicarboxylic acids imidazole salts, it is characterised in that：The catalysis that prepare compound B is used
Agent is palladium, and dosage is the 3~7% of the amount of the substance of B, and reaction need to carry out under anaerobic.
A kind of synthetic method of the dicarboxylic acids imidazole salts, it is characterised in that：During prepare compound C, molar ratio
B：Glyoxal：Acetic acid is 1:0.48~0.52：The amount ratio of 0.08~0.12, B and solvent is 1 mmoles：5.0~15.0 milliliters.
A kind of synthetic method of the dicarboxylic acids imidazole salts, it is characterised in that：During prepare compound C, purifying C is used
10~30mL absolute methanols recrystallize 3 times.
A kind of synthetic method of the dicarboxylic acids imidazole salts, it is characterised in that：During prepare compound D, molar ratio
C：Anhydrous zinc chloride：Paraformaldehyde：Hydrochloric acid is 1:0.8~1.2:2.5~4.0:1~2.The ratio of C and solvent is 1 mmoles：20.0
~40.0 milliliters.When 70 DEG C of reactions 4~8 are small.
A kind of synthetic method of the dicarboxylic acids imidazole salts, it is characterised in that：During prepare compound D, add 20~
The mixed solvent of 40mL ethyl acetate and water (volume ratio 1:1) D is purified.
A kind of synthetic method of the dicarboxylic acids imidazole salts, it is characterised in that：During prepare compound E, D and LiOH
In molar ratio 1:50~70, the in the mixed solvent of solvent Isosorbide-5-Nitrae-dioxane and water, volume ratio is 2~4:1, it is acidified to pH=1.
With double [(4- carboxy vinyl -2,6- diisopropyls) phenyl] imidazolitm chlorides of the novel 1,3- of this method composite structure
The advantageous effect of salt is：Extended rigidity dicarboxylic acids class ligand is widely used in the synthesis of MOFs materials, this kind of material
Usually have orderly pore passage structure, big specific surface area, make this kind of material gaseous storage with separating, chemical sensitisation, catalysis
And the different fields such as medicament slow release have potential application.Extended rigidity dicarboxylic acids corresponding imidazolium salts usually lead to structure
Novel, more micropore MOFs materials of large specific surface area, and microcellular structure can be changed, make in its stomata electronic environment obtain optimizing from
And improve above application performance.Since double [(4- carboxy vinyl -2,6- diisopropyls) phenyl] imidazolium chloride salts of 1,3- can
As the precursor of the miscellaneous Cabbeens of N-, the MOFs materials synthesized using the ligand can prepare the miscellaneous card containing N- by the method for rear synthetic modification
Guest and the MOFs materials of the miscellaneous carbine metal complexs of N-, this kind of material will be generated and be more widely applied, particularly non-equal
Phase catalytic field.Therefore, the novel extension dicarboxylic acids corresponding imidazolium salts of composite structure are designed and applied to MOFs materials
One of hot spot studied now is become.However, large-sized rigidity dicarboxylic acids imidazole salts synthesis is relatively difficult.Cause
This, with double [(4- carboxy vinyls -2, the 6- diisopropyl) phenyl] imidazolium chloride salts of novel 1, the 3- of this method composite structure
It is a kind of dicarboxylic acids corresponding imidazolium salts with huge potential using value.
Description of the drawings
The structural formula schematic diagram of target compound E in Fig. 1 present invention.
The synthesis schematic diagram of compound A and B in Fig. 2 present invention.
The synthesis schematic diagram of compound C in Fig. 3 present invention.
The synthesis schematic diagram of compound D in Fig. 4 present invention.
The synthesis schematic diagram of compound E in Fig. 5 present invention.
Specific embodiment
The synthesis side of double [(4- carboxy vinyl -2,6- diisopropyls) phenyl] imidazolium chloride salts of the 1,3- of the present invention
Method, synthesis step are：
With 2,6-DIPA, iodine generates the iodo- 2,6-DIPAs of 4- for raw material through iodide reaction
(A), A with methyl acrylate with, through Heck coupling reactions generation 3,5- diisopropyls -4- amino-cinnamic acid methyl esters (B), synthesizing
Route is as shown in Figure 2.B is generated 1,4- pairs [(4- methoxycarbonylvinyl -2,6- diisopropyls) with glyoxal under acetic acid catalysis
Phenyl]-Isosorbide-5-Nitrae-diaza -1,3-butadiene (C), synthetic route is as shown in Figure 3.C is with paraformaldehyde in anhydrous zinc chloride and salt
Double [(4- methoxycarbonylvinyls -2, the 6- diisopropyl) phenyl] imidazolium chloride salts (D) of 1,3- of cyclisation generation, are closed under acid catalysis
It is as shown in Figure 4 into route.D finally hydrolysis obtains double [(4- carboxy vinyl -2,6- diisopropyls) benzene of target compound 1,3-
Base] imidazolium chloride salt (E), synthetic route is as shown in Figure 5.
Specific embodiment is as follows：
(i) as shown in Figure 2：2,6-DIPA (10mL, 53mmol), carbon are sequentially added in 500mL round-bottomed flasks
Sour hydrogen sodium (13.4g, 110mmol) and methanol (200mL).Then add in the dichloromethane solution of iodine (14.8g, 58mmol)
(150mL), be stirred at room temperature 12 it is small when.Then solid is filtered, dichloromethane washing filter cake is concentrated in vacuo filtrate and obtains darkorange oil
Shape crude product adds in 60mL sodium thiosulfate saturated solutions, 2h is stirred at room temperature.Dichloromethane extracts 3 times (40mL × 3), merges
Organic layer, anhydrous MgSO4Dry, be concentrated under reduced pressure to obtain brown oil A (14g), yield 88%.
Compound A nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data：1H NMR(400MHz,CDCl3)δ7.31(s,
2H), 3.79 (s, 2H), 2.86 (sept, J=6.8Hz, 2H), 1.27 (d, J=6.8Hz, 12H)13C NMR(101MHz,
CDCl3)δ140.10,135.02,131.72,81.18,27.92,22.31。HRMS(ESI),C12H18IN, measured value (calculate
Value), m/z:304.1829[M+H]+(304.1825)。
(II) is as shown in Figure 2：Compound A (7.2g, 24mmol), methyl acrylate are separately added into 250mL there-necked flasks
(12g,36eq)、K2CO3(9g,66mmol)、PPh3(0.8g, 3mmol) and tetrabutylammonium bromide (36g, 120mmol) adds in
The DMF of 150mL after being passed through Ar 10min, adds Pd (OAc) as solvent2(0.12g, 5.0mmol%), 120 DEG C of reaction 48h, instead
It being poured into after answering and precipitation is precipitated in 150mL ice water, add a small amount of hydrochloric acid catalyst, suction filtration obtains a large amount of yellow solids,
30mL water is added to dilute, dichloromethane extraction (60mL × 3) collected organic layer, anhydrous Na2SO3Dry, filtering, steams dichloromethane
Solvent obtains crude product, through silica gel column chromatography (eluant, eluent after drying:Dichloromethane/petroleum ether=10:1) purify, obtain light white toner
Last B (5.6g), yield 90%.Fusing point：115-116℃.
Compound B nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data：1H NMR(400MHz,CDCl3)δ7.66(d,J
=15.8Hz, 1H), 7.24 (s, 2H), 6.29 (dd, J=15.9,1.0Hz, 1H), 3.79 (d, J=1.0Hz, 3H), 2.89
(dt, J=13.5,6.7Hz, 2H), 1.29 (dd, J=6.8,0.9Hz, 12H)13C NMR(101MHz,CDCl3)δ168.22,
146.25,142.97,132.21,124.32,123.52,112.62,51.38,27.87,22.24。HRMS(ESI),
C16H23NO2, measured value (calculated value), m/z:262.3587[M+H]+(262.3593)。
(III) is as shown in Figure 3：Compound B (3.6g, 14mmol), glyoxal are sequentially added in 250mL round-bottomed flasks
(40%, 0.8mL, 7mmol), acetic acid (0.08mL) and 150mL methanol, are stirred for 24 hours at room temperature, are separated by filtration solid, 20 milliliters
Cold methanol washs filter cake, and crude product recrystallizes 3 times to obtain yellow crystals C (3.2g), yield 85% with 20 absolute methanols.Fusing point：
187-189℃。
Compound C nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data：1H NMR(400MHz,CDCl3)δ8.08(s,
2H), 7.71 (d, J=16.0Hz, 2H), 7.35 (s, 4H), 6.44 (d, J=16.0Hz, 2H), 3.82 (s, 6H), 2.92 (dt, J
=13.5,6.7Hz, 4H), 1.22 (d, J=6.8Hz, 24H)13C NMR(101MHz,CDCl3)δ167.58,162.74,
149.85,145.12,137.38,131.28,123.38,116.38,51.61,28.08,23.20。HRMS(ESI),
C34H44N2O4, measured value (calculated value), m/z:545.7248[M+H]+(545.7242)。
(IV) is as shown in Figure 4：Compound C (2.7g, 4mmol), anhydrous zinc chloride are sequentially added in 250mL round-bottomed flasks
(593mg, 4mmol) and 100mL tetrahydrofurans stir 5min at 70 DEG C, paraformaldehyde (393mg, 13mmol) are added dropwise
Hydrochloric acid solution (4M in dioxane, 1.65mL, 6.5mmol) continues to react 5h at 70 DEG C, concentrates filtrate, add 30mL acetic acid
Ethyl ester and water (v/v=1:1) mixed liquor is until there is solid precipitation, filtering, dry white powder D (2g), yield 88%.It is molten
Point：264-265℃.
Compound D nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data：1H NMR(400MHz,DMSO-d6)δ10.30
(s, 1H), 8.58 (s, 2H), 7.89 (s, 4H), 7.78 (d, J=16.1Hz, 2H), 6.97 (d, J=16.1Hz, 2H), 3.75
(s, 6H), 2.32 (dt, J=13.5,6.7Hz, 4H), 1.28 (d, J=6.7Hz, 12H), 1.17 (d, J=6.8Hz, 12H)13C
NMR(101MHz,DMSO-d6)δ166.94,146.02,143.59,139.68,137.86,131.51,126.64,125.05,
120.98,52.09,29.20,24.38,23.36.HRMS (ESI), C35H45ClN2O4[M+H]+, measured value (calculated value), m/z:
594.1951(594.1958)。
(V) as shown in Figure 5：Compound D (1.0g, 1.7mmol), LiOH are sequentially added in the round-bottomed flask of 250mL
(5.0g, 208mmol), adds in 60mL Isosorbide-5-Nitraes-dioxane and 20mL water, and 95 DEG C of reaction 12h steam Isosorbide-5-Nitrae-dioxane, add
Enter suitable water dissolution carboxylic acid sodium salt, filter, in filtrate plus dilute HCl is acidified to pH=1, and precipitation is precipitated, stands, it is clear to topple over upper strata
Liquid filters, washing and drying obtains white powder E (0.9g), yield 98%.Fusing point：>300℃.
Compound E nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data：：1H NMR(400MHz,DMSO-d6)δ12.20
(s, 2H), 10.31 (s, 1H), 8.56 (s, 2H), 7.88 (s, 4H), 7.76 (d, J=16.1Hz, 2H), 6.98 (d, J=
16.1Hz, 2H), 2.34 (dt, J=13.5,6.7Hz, 4H), 1.26 (d, J=6.7Hz, 12H), 1.18 (d, J=6.8Hz,
12H).13C NMR(101MHz,DMSO-d6)δ166.95,146.04,143.57,139.66,137.88,131.54,126.62,
125.07,120.96,29.20,24.38,23.36.HRMS (ESI), C33H41ClN2O4[M-H]+, measured value (calculated value), m/
z:564.1429(564.1426)。
The above described is only a preferred embodiment of the present invention, not making limitation in any form to the present invention, appoint
Without departing from technical solution of the present invention content, technical spirit according to the invention any is simply repaiied to what above example was made for what
Change, equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (10)
1. a kind of synthetic method of dicarboxylic acids imidazole salts, which is characterized in that synthesis step is：
(i) using 2,6-DIPA as raw material, a certain amount of sodium acid carbonate is added in, methanol is added in as solvent, adds in iodine
Dichloromethane solution, molar ratio 2,6-DIPA：Iodine：Sodium acid carbonate is 1:1.1~1.5:2.5~3.5,2,6- bis- is different
The amount ratio of propyl aniline and methanol is 1 mmoles：3~6 milliliters, the amount ratio of 2,6-DIPA and dichloromethane is 1
Mmoles：1.5~2.5 milliliters.After adding when 20~30 DEG C of reactions 10~15 are small, reaction terminates to filter solid, adds dichloromethane
Alkane washes solid, is concentrated in vacuo filtrate, add 50~80mL saturated sodium thiosulfate solution continue stirring 2 it is small when, add methylene chloride extraction
It takes (30~60mL × 3), merges organic phase, anhydrous magnesium sulfate drying is filtered, and vacuum decompression filtrate obtains compound A：4- is iodo-
2,6- diisopropyl anilines；
(II) is separately added into the iodo- 2,6-DIPAs of 4-, propylene under argon gas or nitrogen protection in 250mL there-necked flasks
Sour methyl esters, potassium carbonate, triphenylphosphine, tetrabutylammonium bromide and a certain amount of solvent DMF, iodo- 2, the 6- diisopropyls of molar ratio 4-
Aniline：Methyl acrylate：Potassium carbonate：Triphenylphosphine：Tetrabutylammonium bromide is 1:5.0~7.0：2.0~4.0：0.1~0.3：4
The ratio of the iodo- 2,6-DIPA of~6,4- and solvent is 1 mmoles：5.0~15.0 milliliters.Add in a certain amount of palladium salt conduct
Catalyst when 90 DEG C of reactions 30~50 are small, pour into precipitation is precipitated in 50mL ice water after reaction, a small amount of hydrochloric acid is added to urge
Agent, suction filtration obtain a large amount of white solids, and 20~40mL water is added to dilute, and dichloromethane extraction (40~70mL × 3) is collected organic
Mutually and it is carried out with anhydrous sodium sulfite to remove water process, filter, steam dichloromethane solvent and obtain crude product, finally with dichloromethane
Alkane and petroleum ether are 10 by volume:0.8~1.2 mixed solvent obtains compound for eluant, eluent with column chromatography separating-purifying
B：3,5- diisopropyls -4- amino-cinnamic acid methyl esters；
(III) 3,5- diisopropyls -4- amino-cinnamic acid methyl esters, glyoxal and acetic acid in molar ratio 1:0.48~0.52：
It is dissolved in after 0.08~0.12 mixing in certain solvent, the amount ratio of 3,5- diisopropyl -4- amino-cinnamic acid methyl esters and solvent
It is 1 mmoles：8.0~15.0 milliliters, when 20~30 DEG C of reactions 20~30 are small, filter after reaction, crude product with 10~
30mL absolute methanols recrystallization purifying 3 times, filtering, dry compound C：The double [(4- methoxycarbonylvinyls -2,6- two of 1,4-
Isopropyl) phenyl] -1,4- diaza -1,3- butadiene；
(IV) is separately added into double [(4- methoxycarbonylvinyl -2,6- diisopropyls) phenyl] -1 of 1,4- in 250mL there-necked flasks,
4- diazas -1,3-butadiene, anhydrous zinc chloride, paraformaldehyde and a certain amount of hydrochloric acid, molar ratio Isosorbide-5-Nitrae-bis- [(4- methoxy carbonyls
Base vinyl -2,6- diisopropyls) phenyl] -1,4- diaza -1,3- butadiene：Anhydrous zinc chloride：Paraformaldehyde：Hydrochloric acid is
1:0.8~1.2：2.5~4.0:1~2, Isosorbide-5-Nitrae-bis- [(4- methoxycarbonylvinyls -2,6- diisopropyl) phenyl]-Isosorbide-5-Nitrae-phenodiazine
Miscellaneous -1,3- butadiene and the ratio of solvents tetrahydrofurane are 1 mmoles：20.0~40.0 milliliters.When 70 DEG C of reactions 4~8 are small, reaction knot
Beam steams tetrahydrofuran, adds the mixed solvent of 20~40mL ethyl acetate and water (volume ratio 1:1), until generating a large amount of solid
Body, filtering, washs crude product with cold ethyl acetate, obtains pure compound D：The double [(4- methoxycarbonylvinyls -2,6- of 1,3-
Diisopropyl) phenyl] imidazolium chloride salt；
(V) by double [(4- methoxycarbonylvinyl -2,6- diisopropyls) phenyl] imidazolium chloride salts of 1,3- and LiOH by mole
Than 1:The volume ratio of the in the mixed solvent of 10~30 addition Isosorbide-5-Nitrae-dioxane and water, Isosorbide-5-Nitrae-dioxane and water is 3~5:1,
When 95 DEG C of reflux 8~12 are small, excessive Isosorbide-5-Nitrae-dioxane is evaporated off, is diluted with water, adds in excessive dilute HCl and is acidified to pH=1, analyse
Go out white solid, be dried in vacuo to obtain final compound E：Double [(4- carboxy vinyl -2,6- diisopropyls) phenyl] chlorinations of 1,3-
Imidazole salts, its chemical structural formula are：
2. a kind of synthetic method of dicarboxylic acids imidazole salts according to claim 1, it is characterised in that：When preparing A, rub
You are than 2,6- diisopropyl aniline：Iodine：Sodium acid carbonate is 1:1.1~1.5:2.5~3.5.
3. a kind of synthetic method of dicarboxylic acids imidazole salts according to claim 1, it is characterised in that：A is prepared with first
Alcohol and dichloromethane are mixed solvent, and the amount ratio of 2,6-DIPA and methanol is 1 mmoles：3~6 milliliters, 2,6- bis-
The amount ratio of isopropyl aniline and dichloromethane is 1 mmoles：1.5~2.5 milliliters.When 20~30 DEG C of reactions 10~15 are small.
4. a kind of synthetic method of dicarboxylic acids imidazole salts according to claim 1, it is characterised in that：Prepare compound
During A, in crude product add in 50~80mL saturated sodium thiosulfate solution continue stirring 2 it is small when, the extraction that adds methylene chloride (30~
60mL × 3), merge organic phase, anhydrous magnesium sulfate drying.
5. a kind of synthetic method of dicarboxylic acids imidazole salts according to claim 1, it is characterised in that：Prepare compound
During B, molar ratio A：Methyl acrylate：Potassium carbonate：Triphenylphosphine：Tetrabutylammonium bromide is 1:5.0~7.0：2.0~4.0：0.1
~0.3：4~6.150mL DMF need to be added to make solvent.It is 10 by volume to purify B dichloromethane and petroleum ether:0.8~1.2
Mixed solvent is eluant, eluent.
6. a kind of synthetic method of dicarboxylic acids imidazole salts according to claim 1, it is characterised in that：Prepare compound
The catalyst that B is used is palladium, and dosage is the 3~7% of the amount of the substance of B, and reaction need to carry out under anaerobic.
7. a kind of synthetic method of dicarboxylic acids imidazole salts according to claim 1, it is characterised in that：Prepare compound
During C, molar ratio B：Glyoxal：Acetic acid is 1:0.48~0.52：The amount ratio of 0.08~0.12, B and solvent is 1 mmoles：5.0~
15.0 milliliters.
8. a kind of synthetic method of dicarboxylic acids imidazole salts according to claim 1, it is characterised in that：Prepare compound
During C, purifying C is recrystallized 3 times with 10~30mL absolute methanols.
9. a kind of synthetic method of dicarboxylic acids imidazole salts according to claim 1, it is characterised in that：Prepare compound
During D, molar ratio C：Anhydrous zinc chloride：Paraformaldehyde：Hydrochloric acid is 1:0.8~1.2：2.5~4.0:1~2.The ratio of C and solvent is 1
Mmoles：20.0~40.0 milliliters.When 70 DEG C of reactions 4~8 are small；During prepare compound D, add the mixed of 20~40mL ethyl acetate and water
Bonding solvent (volume ratio 1:1) D is purified.
10. a kind of synthetic method of dicarboxylic acids imidazole salts according to claim 1, it is characterised in that：Prepare chemical combination
During object E, D and LiOH in molar ratio 1:50~70, the in the mixed solvent of solvent Isosorbide-5-Nitrae-dioxane and water, volume ratio is 2~4:
1, it is acidified to pH=1.
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| CN113336721A (en) * | 2021-06-28 | 2021-09-03 | 成都大学 | Chiral N-heterocyclic carbene catalyst and preparation method and application thereof |
| CN115322154A (en) * | 2022-07-21 | 2022-11-11 | 上海师范大学 | Synthesis method of 1, 3-bis (4-carboxyphenyl-2, 6-diisopropyl) imidazolium chloride |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109503492A (en) * | 2019-01-08 | 2019-03-22 | 遵义医学院 | A kind of synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- |
| CN113336721A (en) * | 2021-06-28 | 2021-09-03 | 成都大学 | Chiral N-heterocyclic carbene catalyst and preparation method and application thereof |
| CN113336721B (en) * | 2021-06-28 | 2023-03-21 | 成都大学 | Chiral N-heterocyclic carbene catalyst and preparation method and application thereof |
| CN115322154A (en) * | 2022-07-21 | 2022-11-11 | 上海师范大学 | Synthesis method of 1, 3-bis (4-carboxyphenyl-2, 6-diisopropyl) imidazolium chloride |
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