CN109503492A - A kind of synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- - Google Patents
A kind of synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- Download PDFInfo
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
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Abstract
A kind of synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N-; with 2; 6- diisopropyl aniline is raw material; 4- iodo- 2 is generated with Iod R; 6- diisopropyl aniline (A); catalyst reaction is added under the conditions of inert gas shielding and generates 4 '-amino -3 ', 5 '-diisopropyls-(1,1 '-xenyl) -4- methyl formate (B) for A and 4- methoxycarbonyl group phenyl boric acid.Compound B and glyoxal reaction generate bis- [(4- methoxycarbonyl group -3 ', 5 '-diisopropyls) the xenyl] -1,4- diaza -1,3- butadiene (C) of 1,4-.Compound C, which is reacted with paraformaldehyde through catalysis, generates bis- [(4- methoxycarbonyl group -3 ', the 5 '-diisopropyls) xenyl] imidazolium chloride salts (D) of compound 1,3-.Compound D generates bis- [(4- carboxyl -3 ', the 5 '-diisopropyls) xenyl] imidazolium chloride salts of target compound E:1,3- through hydrolysis.
Description
Technical field
The present invention relates to a kind of synthetic methods of miscellaneous carbene precursor of dicarboxylic acids N-.
Background technique
Metal organic frame (Metal-organic frameworks) is to be passed through by organic bridge ligand with metal ion
Coordinate bond or be aided with other weak forces and formed with height is regular and the coordination compound of infinite expanding structure, this
Class compound is also sometimes referred to as coordination polymer (Coordination polymers).Aromatic dicarboxylic acids are due to having two
A carboxyl in ortho position, meta or para position, spatially has preferable expansion, and there is rigid structure can be used as bridging
Ligand supporting network structure, thus it is frequently used to the structure of design, the synthesis organic topology of metal.As Yaghi seminar reports
MOF-5, utilize ZnO (CO2)6Four core zinc clusters are SBU, are connected with terephthalic acid (TPA) and constructHole,
Surface area is 2900m2g-1, realize impressive progress of the crystalline microporous material to crystalline-state mesoporous material.French scientist F é rey report
Road terephthalic acid (TPA) and cadmium nitrate and hydrofluoric acid are raw material hydrothermal synthesis MIL-101, Cr3F(H2O)2O[(O2C)-C6H4-
(CO2)]3·nH2O(n-25).MIL-101 is the molecular sieve analog in the super large hole with MTN topological classification, and unit-cell volume is The structure of compound is the octahedral structure unit and terephthalic acid (TPA) phase by three core Cr clusters (Cr-SBU)
It connects, four Cr-SBU and six terephthalic acid (TPA)s connect into a super tetrahedron in MIL-101, then pass through total vertex shape simultaneously
At the cage of pentagon and six sides.It is worth mentioning that MIL-101 structure can be to be stabilized to 275 DEG C, after losing object in air
Its skeleton still keeps original integrality.The specific surface area of MIL-101 is up to 5900m simultaneously2g-1, there is stronger adsorption energy
Power.Extended rigidity dicarboxylic acids ligand usually leads to more micropore MOFs materials of structure novel, large specific surface area, and can change
Become microcellular structure, so that electronic environment in its micropore is obtained optimization to improve above-mentioned application performance, therefore, design composite structure is new
The extensions dicarboxylic acids ligand of grain husk simultaneously has become one of the hot spot studied now applied to the synthesis of MOFs material.However, big ruler
Very little rigid dicarboxylic acid compound synthesis is relatively difficult, especially can be used as the dicarboxylic acids imidazole salts of the miscellaneous carbene precursor of N-
Compound, therefore bis- [(4- carboxyl -3 ', the 5 '-diisopropyls) xenyl] chlorine of 1,3- of structure novel involved in the present invention
Changing imidazole salts is a kind of organic ligand with huge potential using value.There is no literature reported on the compounds at present.
Summary of the invention
A kind of the object of the present invention is to provide synthesis costs bis- [(4- carboxylics of novel 1,3- low, that yield is high, product purity is high
Base -3 ', 5 '-diisopropyls) xenyl] imidazolium chloride salt synthetic method.
A kind of synthetic method of miscellaneous carbene precursor of dicarboxylic acids N- of the invention, synthesis step are as follows:
Step 1: using 2,6-DIPA as raw material, being added sodium bicarbonate, methanol is added as solvent, addition contains
There is the dichloromethane solution of iodine, molar ratio 2,6-DIPA: iodine: sodium bicarbonate 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 methylene chloride
It is 1 mmoles: 1.5-2.5 milliliters；After adding 20-30 DEG C reaction 10-15 hours, reaction terminate to filter solid, add dichloromethane
Alkane washes solid, is concentrated in vacuo filtrate, adds 50-80mL saturated sodium thiosulfate solution to continue stirring 2 hours, add methylene chloride extraction
30-60mL × 3 merge organic phase, and anhydrous magnesium sulfate dries, filters, and vacuum decompression filtrate obtains iodo- 2, the 6- bis- of compound A:4-
Isopropyl aniline；
Step 2: under argon gas or nitrogen protection, iodo- 2, the 6- diisopropyl benzene of 4- is separately added into 250mL there-necked flask
Amine, 4- methoxycarbonyl group phenyl boric acid, potassium carbonate and dioxane, the iodo- 2,6-DIPA of molar ratio 4-: 4- methoxycarbonyl phenyl
Boric acid: the ratio of the iodo- 2,6-DIPA of potassium carbonate 1:1-1.2:3.0-5.0,4- and solvent is 1 mmoles: 4.0-6.0 milli
It rises；Be added palladium salt be used as catalyst, 90 DEG C reaction 24-48 hours, react end steam Isosorbide-5-Nitrae-dioxane, add 20-40mL water
Dilution, methylene chloride extract 30-60mL × 3, collect organic phase and are carried out removing water process to it with anhydrous magnesium sulfate, filter, steam
Dichloromethane solvent obtains crude product out, is finally for the mixed solvent of 20:0.8-1.2 by volume with petroleum ether and methylene chloride
Eluant, eluent obtains compound B:4 '-amino -3 ', 5 '-diisopropyls-(1,1 '-xenyl) -4- first with column chromatography separating-purifying
Sour methyl esters；
Step 3: 4 '-amino -3 ', 5 '-diisopropyls-(1,1 '-xenyl) -4- methyl formate, glyoxal and acetic acid are pressed
It is dissolved in solvent after molar ratio 1:0.48-0.52:0.08-0.12 mixing, 4 '-amino -3 ', 5 '-diisopropyls-(1,1 '-biphenyl
Base) amount ratio of -4- methyl formate and solvent is 1 mmoles: 8.0-15.0 milliliters, 20-30 DEG C reaction 20-30 hours, reaction
After filter, crude product is with 10-30mL anhydrous methanol recrystallization purifying 3 times, filtering, dry the bis- [(4- of compound C:1,4-
Methoxycarbonyl group -3 ', 5 '-diisopropyls) xenyl] -1,4- diaza -1,3- butadiene；
Step 4: bis- [(4- methoxycarbonyl group -3 ', the 5 '-diisopropyls) biphenyl of 1,4- are separately added into 250mL there-necked flask
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-
Methoxycarbonyl group -3 ', 5 '-diisopropyls) xenyl] -1,4- diaza -1,3- butadiene: anhydrous zinc chloride: paraformaldehyde: salt
Acid is 1:0.8-1.2:2.5-4.0:1-2, bis- [(4- methoxycarbonyl group -3 ', the 5 '-diisopropyls) xenyl]-Isosorbide-5-Nitrae-phenodiazines of Isosorbide-5-Nitrae -
Miscellaneous -1,3- butadiene and the ratio of solvents tetrahydrofurane are 1 mmoles: 40.0-60.0 milliliters；70 DEG C reaction 4-8 hours, reaction terminates
Tetrahydrofuran is steamed, the mixed solvent (volume ratio 1:1) of 20-40mL ethyl acetate and water is added, until generating a large amount of solids, mistake
Filter, washs crude product with cold ethyl acetate, obtains pure compound D:1,3- bis- [(4- methoxycarbonyl group -3 ', 5 '-diisopropyls)
Xenyl] imidazolium chloride salt；
Step 5: by bis- [(4- methoxycarbonyl group -3 ', the 5 '-diisopropyls) xenyl] imidazolium chloride salts of 1,3- and NaOH
The volume ratio of the in the mixed solvent of 1:10-30 addition in molar ratio Isosorbide-5-Nitrae-dioxane and water, Isosorbide-5-Nitrae-dioxane and water is 3-
5:1,95 DEG C reflux 8-12 hours, excessive Isosorbide-5-Nitrae-dioxane is evaporated off, is diluted with water, excessive dilute HCl is added and is acidified to pH=
1, white solid is precipitated, is dried in vacuo to obtain bis- [(4- carboxyl -3 ', the 5 '-diisopropyls) xenyl] chlorine of final compound E:1,3-
Change imidazole salts, its chemical structural formula are as follows:
When the prepare compound A, molar ratio 2,6-DIPA: iodine: sodium bicarbonate 1:1.1-1.5:2.5-
3.5；Using methanol and methylene chloride as mixed solvent, the amount ratio of 2,6-DIPA and methanol is 1 mmoles: 3-6 milliliters,
The amount ratio of 2,6- diisopropyl aniline and methylene chloride is 1 mmoles: 1.5-2.5 milliliters；20-30 DEG C reaction 10-15 hours.
50-80mL saturated sodium thiosulfate solution is added when the prepare compound A, in crude product and continues stirring 2 hours,
Add methylene chloride extraction (30-60mL × 3), merges organic phase, and anhydrous magnesium sulfate is dry.
When the prepare compound B, molar ratio A:4- methoxycarbonyl group phenyl boric acid: potassium carbonate 1:1-1.2:3.0-5.0, A
Amount ratio with solvent is 1 mmoles: 4.0-6.0 milliliters；It purifies B petroleum ether and methylene chloride is 20:0.8-1.2 by volume
Mixed solvent be eluant, eluent.
The catalyst that the prepare compound B is used is tetrakis triphenylphosphine palladium, and dosage is the 1-4% of the amount of the substance of A,
Reaction need to carry out under anaerobic.
When the prepare compound C, molar ratio B: glyoxal: acetic acid 1:0.48-0.52:0.08-0.12, B and solvent
Amount ratio be 1 mmoles: 8.0-15.0 milliliters.
When the prepare compound C, purifying C is recrystallized 3 times with 10-30mL anhydrous methanol.When the prepare compound D,
Molar ratio C: anhydrous zinc chloride: paraformaldehyde: hydrochloric acid 1:0.8-1.2:2.5-4.0:1-2；The ratio of C and solvent is 1 mmoles:
40.0-60.0 milliliters；70 DEG C reaction 4-8 hours.
When the prepare compound D, add the mixed solvent of 20-40mL ethyl acetate and water, volume ratio 1:1 purifies D.
When the prepare compound E, 1:10-30, the mixing of solvent Isosorbide-5-Nitrae-dioxane and water are molten in molar ratio by D and NaOH
In agent, volume ratio 3-5:1, hydrochloric acid is acidified to pH=1.Beneficial effect by adopting the above technical scheme is:
With bis- [(4- carboxyl -3 ', the 5 '-diisopropyls) xenyl] imidazolitm chlorides of the novel 1,3- of composite structure of the present invention
The beneficial effect of salt is: extended rigidity dicarboxylic acids class ligand is widely used in the synthesis of MOFs material, and this kind of material is logical
Often with orderly cellular structure, big specific surface area, make this kind of material gaseous storage with separate, chemical sensitisation, catalysis and
The different fields such as medicament slow release have potential application.It is new that extended rigidity dicarboxylic acids corresponding imidazolium salts usually lead to structure
More micropore MOFs materials of grain husk, large specific surface area, and can change microcellular structure, make in its stomata electronic environment obtain optimization to
Improve above-mentioned application performance.Since bis- [(4- carboxyl -3 ', the 5 '-diisopropyls) xenyl] imidazolium chloride salts of 1,3- can be used as
The precursor of the miscellaneous Cabbeen of N-, the MOFs material synthesized using the ligand can be prepared by the method for rear synthetic modification containing the miscellaneous Cabbeen of N- and
The MOFs material of the miscellaneous carbine metal complex of N-, this kind of material will be generated and are more widely applied, especially urge heterogeneous
Change field.Therefore, the novel synthesis for extending dicarboxylic acids corresponding imidazolium salts and being applied to MOFs material of design composite structure
Have become one of the hot spot studied now.However, large-sized rigidity dicarboxylic acids imidazole salts synthesis is relatively difficult.Therefore,
It is a kind of with bis- [(4- carboxyl -3 ', the 5 '-diisopropyls) xenyl] imidazolium chloride salts of the novel 1,3- of this method composite structure
Dicarboxylic acids corresponding imidazolium salts with huge potential using value.
Detailed description of the invention
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 synthetic method of bis- [(4- carboxyl -3 ', the 5 '-diisopropyls) xenyl] imidazolium chloride salts of 1,3- of the invention,
Synthesis step are as follows:
With 2,6-DIPA, iodine is raw material through the iodide reaction generation iodo- 2,6-DIPA of 4-
(A), A generates 4 '-amino -3 ', 5 '-diisopropyls-(1,1 '-biphenyl through Suzuki coupling reaction with to methoxycarbonyl group phenyl boric acid
Base) -4- methyl formate (B), synthetic route is as shown in Figure 2.B and glyoxal generate bis- [(the 4- methoxy carbonyls of 1,4- under acetic acid catalysis
Base -3 ', 5 '-diisopropyls) xenyl]-Isosorbide-5-Nitrae-diaza -1,3-butadiene (C), synthetic route is as shown in Figure 3.C and poly
It is bis- [(4- methoxycarbonyl group -3 ', 5 '-diisopropyls) xenyl] that formaldehyde is cyclized generation 1,3- under anhydrous zinc chloride and hydrochloric acid catalysis
Imidazolium chloride salt (D), synthetic route is as shown in Figure 4.D finally hydrolyze obtain target compound 1,3- it is bis- [(4- carboxyl -3 ',
5 '-diisopropyls) xenyl] imidazolium chloride salt (E), synthetic route is as shown in Figure 5.
Specific embodiment is as follows:
(I) is as shown in Figure 2: 1000mL round-bottomed flask sequentially add 2,6-DIPA (20mL, 106mmol),
Sodium bicarbonate (26.8g, 219mmol) and methanol (400mL).The methylene chloride that iodine (29.6g, 116.5mmol) is then added is molten
Liquid (200mL) is stirred at room temperature 12 hours.Then solid is filtered, methylene chloride washs filter cake, and vacuum concentration filtrate obtains darkorange
Oily crude product is added 60mL saturated solution sodium thiosulfate and 2h is stirred at room temperature.40mL methane extracts 3 times, merges organic layer, nothing
Water MgSO4It is dry, brown oil A (28.3 grams), yield 88% is concentrated under reduced pressure to obtain.
Compound A nuclear-magnetism1H 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: be separately added into 500mL there-necked flask the iodo- 2,6- diisopropyl aniline of 4- (23.2g,
76.52mmol), 4- methoxycarbonyl group phenyl boric acid (15.1g, 84.17mmol), potassium carbonate (34.8g, 253mmol), 360mL 1,4-
Dioxane/water (3/1) and tetrakis triphenylphosphine palladium (1.77g, 2mol%), after replacing argon gas three times, lower 90 DEG C of argon gas protection
48h is reacted, reaction terminates to steam Isosorbide-5-Nitrae-dioxane, and 40mL water is added to dilute, and methylene chloride extracts (60mL × 3), collects organic
Layer, anhydrous magnesium sulfate is dry, filters, and steams methylene chloride and obtains reacting coarse product, through silica gel column chromatography (eluant, eluent: stone after drying
Oily ether/methylene chloride=20/1) purifying, obtain white powder B (24.2g), yield 65%.Fusing point: 136-137 DEG C.
Compound B nuclear-magnetism1H NMR、13C NMR and high resolution mass spectrum data:1H NMR(400MHz,CDCl3)δ8.07(d,J
=8.5Hz, 2H), 7.63 (d, J=8.5Hz, 2H), 7.33 (s, 2H), 3.93 (s, 3H), 2.99 (sept, J=6.8Hz, 2H),
(1.34 d, J=6.8Hz, 12H)13C NMR(101MHz,CDCl3)δ167.23,146.64,132.85,130.20,129.98,
127.52,127.25,126.26,121.93,52.02,28.10,22.47。HRMS(ESI),C20H25NO2, measured value (calculating
Value), m/z:312.4175 [M+H]+(312.4182)。
(iii) as shown in Figure 3: sequentially adding compound B (8.8g, 28.2mmol), glyoxal in 500mL round-bottomed flask
(40%, 1.5mL, 13.5mmol), acetic acid (0.16mL, 2826mmol) and 250mL methanol, stir for 24 hours at room temperature, are separated by filtration
Solid, 20 milliliters of cold methanols wash filter cake, and crude product recrystallizes 3 times to obtain yellow crystals C (7.6g) with 20 anhydrous methanols, yield
83%.Fusing point: 175-177 DEG C.
Compound C nuclear-magnetism1H NMR、13C NMR and high resolution mass spectrum data:1H NMR(400MHz,CDCl3)δ8.18(s,
2H), 8.13 (d, J=7.9Hz, 4H), 7.70 (d, J=7.9Hz, 4H), 7.45 (s, 4H), 3.96 (s, 6H), 3.02 (sept, J
=6.7Hz, 4H), 1.29 (d, J=6.7Hz, 24H)13C NMR(101MHz,CDCl3)δ167.06,163.13,148.10,
145.97,137.47,136.83,130.07,128.58,126.88,122.34,52.13,28.26,23.42。HRMS(ESI),
C42H48N2O4, measured value (calculated value), m/z:645.8519 [M+H]+(645.8515)。
(IV) is as shown in Figure 4: sequentially adding compound C (2.8g, 4mmol), anhydrous zinc chloride in 500mL round-bottomed flask
Paraformaldehyde (393mg, 13mmol) is added dropwise in 70 DEG C of stirring 5min in (593mg, 4mmol) and 200mL tetrahydrofuran
Hydrochloric acid solution (4M in dioxane, 1.65mL, 6.5mmol) continues in 70 DEG C of reaction 5h, and concentration filtrate adds 30mL acetic acid
The mixed liquor of ethyl ester and water (v/v=1:1) is until there is a solid precipitation, filtering, dry white powder D (2.6g), yield 87%.
Fusing point: 254-255 DEG C.
Compound D nuclear-magnetism1H NMR、13C NMR and high resolution mass spectrum data:1H NMR(400MHz,DMSO-d6)δ10.24
(s, 1H), 8.59 (d, J=10.8Hz, 2H), 8.08 (d, J=7.7Hz, 4H), 7.96 (d, J=7.8Hz, 4H), 7.80 (s,
4H), 3.88 (s, 6H), 2.41 (sept, J=6.4Hz, 4H), 1.33 (d, J=6.4Hz, 12H), 1.22 (d, J=6.4Hz,
12H).13C NMR(101MHz,DMSO-d6)δ166.48,146.16,144.01,142.94,130.46,130.29,130.08,
129.70,128.13,126.76,123.79,52.76,29.39,24.43,23.44.HRMS (ESI), C43H49ClN2O4[M+H]+,
Measured value (calculated value), m/z:694.3127 (694.3132).
(V) as shown in Figure 5: compound D (1.0g, 1.4mmol), NaOH are sequentially added in the round-bottomed flask of 250mL
(1.0g, 25mmol), 60mL Isosorbide-5-Nitrae-dioxane and 20mL water, 95 DEG C of reaction 10h steam Isosorbide-5-Nitrae-dioxane, are added appropriate
Water dissolve carboxylic acid sodium salt, filtering, in filtrate plus dilute HCl to be acidified to pH be 1 or so, precipitating is precipitated, stands, it is clear to topple over upper layer
Liquid filters, washing and drying obtains white powder E (0.94g), yield 98%.Fusing point: > 300 DEG C.
Compound E nuclear-magnetism1H NMR、13C NMR and high resolution mass spectrum data:1H NMR(400MHz,DMSO-d6)δ10.22
(s, 1H), 8.58 (d, J=10.8Hz, 2H), 8.06 (d, J=7.7Hz, 4H), 7.94 (d, J=7.8Hz, 4H), 7.81 (s,
4H), 2.42 (sept, J=6.8Hz, 4H), 1.35 (d, J=6.8Hz, 12H), 1.24 (d, J=6.8Hz, 12H)13C NMR
(101MHz,DMSO-d6)δ166.44,146.11,144.01,142.98,130.44,130.27,130.10,129.72,
128.12,126.74,123.78,29.36,24.47,23.48.HRMS (ESI), C41H45ClN2O4[M-H]+, measured value (calculating
Value), m/z:664.2606 (664.2601).
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form, appoint
What is to the above embodiments according to the technical essence of the invention any simply to repair without departing from technical solution of the present invention content
Change, equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N-, it is characterised in that: synthesis step are as follows:
Step 1: using 2,6-DIPA as raw material, being added sodium bicarbonate, methanol is added as solvent, addition contains iodine
Dichloromethane solution, molar ratio 2,6-DIPA: iodine: sodium bicarbonate 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 methylene chloride is 1 milli
It rubs: 1.5-2.5 milliliters；After adding 20-30 DEG C reaction 10-15 hours, reaction terminates to filter solid, and adding methylene chloride, it is solid to wash
Body is concentrated in vacuo filtrate, adds 50-80mL saturated sodium thiosulfate solution to continue stirring 2 hours, adds methylene chloride and extract 30-
60mL × 3 merge organic phase, and anhydrous magnesium sulfate dries, filters, and it is different that vacuum decompression filtrate obtains iodo- 2, the 6- bis- of compound A:4-
Propyl aniline；
Step 2: under argon gas or nitrogen protection, the iodo- 2,6-DIPA of 4-, 4- are separately added into 250mL there-necked flask
Methoxycarbonyl group phenyl boric acid, potassium carbonate and dioxane, the iodo- 2,6-DIPA of molar ratio 4-: 4- methoxycarbonyl group phenyl boric acid:
Potassium carbonate is 1:1-1.2:3.0-5.0, and the ratio of the iodo- 2,6-DIPA of 4- and solvent is 1 mmoles: 4.0-6.0 milliliters；Add
Enter palladium salt as catalyst, 90 DEG C reaction 24-48 hours, reaction terminates to steam Isosorbide-5-Nitrae-dioxane, add 20-40mL water to dilute,
Methylene chloride extracts 30-60mL × 3, collects organic phase and is carried out removing water process to it with anhydrous magnesium sulfate, filters, steam dichloro
Methane solvent obtains crude product, is by volume finally the mixed solvent of 20:0.8-1.2 using petroleum ether and methylene chloride as eluant, eluent
Compound B:4 '-amino -3 ', 5 '-diisopropyls-(1,1 '-xenyl) -4- formic acid first are obtained with column chromatography separating-purifying
Ester；
Step 3: 4 '-amino -3 ', 5 '-diisopropyls-(1,1 '-xenyl) -4- methyl formate, glyoxal and acetic acid by mole
Than being dissolved in solvent after 1:0.48-0.52:0.08-0.12 mixing, 4 '-amino -3 ', 5 '-diisopropyls-(1,1 '-xenyl) -
The amount ratio of 4- methyl formate and solvent is 1 mmoles: 8.0-15.0 milliliters, 20-30 DEG C reaction 20-30 hours, reaction terminates
After filter, crude product is with 10-30mL anhydrous methanol recrystallization purifying 3 times, filtering, dry bis- [(the 4- methoxies of compound C:1,4-
Carbonyl -3 ', 5 '-diisopropyls) xenyl] -1,4- diaza -1,3- butadiene；
Step 4: 1,4- bis- [(4- methoxycarbonyl group -3 ', 5 '-diisopropyls) xenyls]-is separately added into 250mL there-necked flask
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- methoxy
Carbonyl -3 ', 5 '-diisopropyls) xenyl] -1,4- diaza -1,3- butadiene: anhydrous zinc chloride: paraformaldehyde: hydrochloric acid is
1:0.8-1.2:2.5-4.0:1-2, bis- [(4- methoxycarbonyl group -3 ', the 5 '-diisopropyls) xenyl]-Isosorbide-5-Nitrae-diazas -1 of Isosorbide-5-Nitrae -,
3- butadiene and the ratio of solvents tetrahydrofurane are 1 mmoles: 40.0-60.0 milliliters；70 DEG C reaction 4-8 hours, reaction terminate steam
Tetrahydrofuran adds the mixed solvent (volume ratio 1:1) of 20-40mL ethyl acetate and water, until a large amount of solids are generated, filtering,
Crude product is washed with cold ethyl acetate, obtains bis- [(4- methoxycarbonyl group -3 ', the 5 '-diisopropyls) biphenyl of pure compound D:1,3-
Base] imidazolium chloride salt；
Step 5: bis- [(4- methoxycarbonyl group -3 ', the 5 '-diisopropyls) xenyl] imidazolium chloride salts of 1,3- and NaOH are massaged
The in the mixed solvent of Isosorbide-5-Nitrae-dioxane and water is added than 1:10-30 for you, and the volume ratio of Isosorbide-5-Nitrae-dioxane and water is 3-5:1,
95 DEG C reflux 8-12 hours, excessive Isosorbide-5-Nitrae-dioxane is evaporated off, is diluted with water, excessive dilute HCl is added and is acidified to pH=1, analyses
White solid out is dried in vacuo to obtain bis- [(4- carboxyl -3 ', 5 '-diisopropyls) xenyl] the chlorination miaows of final compound E:1,3-
Azoles salt, its chemical structural formula are as follows:
2. the synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- according to claim 1, it is characterised in that: described to prepare chemical combination
When object A, molar ratio 2,6-DIPA: iodine: sodium bicarbonate 1:1.1-1.5:2.5-3.5；With methanol and methylene chloride
For mixed solvent, the amount ratio of 2,6-DIPA and methanol is 1 mmoles: 3-6 milliliters, 2,6-DIPA and two
The amount ratio of chloromethanes is 1 mmoles: 1.5-2.5 milliliters；20-30 DEG C reaction 10-15 hours.
3. the synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- according to claim 1, it is characterised in that: described to prepare chemical combination
50-80mL saturated sodium thiosulfate solution is added when object A, in crude product and continues stirring 2 hours, add methylene chloride extraction (30-
60mL × 3), merge organic phase, anhydrous magnesium sulfate is dry.
4. the synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- according to claim 1, it is characterised in that: described to prepare chemical combination
When object B, molar ratio A:4- methoxycarbonyl group phenyl boric acid: the amount ratio of potassium carbonate 1:1-1.2:3.0-5.0, A and solvent is 1 milli
It rubs: 4.0-6.0 milliliters；Purifying B petroleum ether and methylene chloride are that the mixed solvent of 20:0.8-1.2 is eluant, eluent by volume.
5. the synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- according to claim 1, it is characterised in that: described to prepare chemical combination
The catalyst that object B is used be tetrakis triphenylphosphine palladium, dosage be A substance amount 1-4%, reaction need under anaerobic into
Row.
6. the synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- according to claim 1, it is characterised in that: described to prepare chemical combination
When object C, molar ratio B: glyoxal: the amount ratio of acetic acid 1:0.48-0.52:0.08-0.12, B and solvent is 1 mmoles: 8.0-
15.0 milliliters.
7. the synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- according to claim 1, it is characterised in that: described to prepare chemical combination
When object C, purifying C is recrystallized 3 times with 10-30mL anhydrous methanol.
8. the synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- according to claim 1, it is characterised in that: described to prepare chemical combination
When object D, molar ratio C: anhydrous zinc chloride: paraformaldehyde: hydrochloric acid 1:0.8-1.2:2.5-4.0:1-2；The ratio of C and solvent is 1
Mmoles: 40.0-60.0 milliliters；70 DEG C reaction 4-8 hours.
9. the synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- according to claim 1, it is characterised in that: described to prepare chemical combination
When object D, add the mixed solvent of 20-40mL ethyl acetate and water, volume ratio 1:1 purifies D.
10. the synthetic method of the miscellaneous carbene precursor of dicarboxylic acids N- according to claim 1, it is characterised in that: the preparationization
When closing object E, D and NaOH 1:10-30 in molar ratio, solvent Isosorbide-5-Nitrae-dioxane and water in the mixed solvent, volume ratio 3-5:
1, hydrochloric acid is acidified to pH=1.
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| 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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| CN108117522A (en) * | 2018-02-08 | 2018-06-05 | 遵义医学院 | A kind of synthetic method of dicarboxylic acids imidazole salts |
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| AUDREY HOSPITAL等: "Access to functionalised silver(I) and gold(I) N-heterocyclic carbenes by [2+3] dipolar cycloadditions", 《DALTON TRANS.》 * |
| JISEUL CHUN等: "Concomitant Formation of N-Heterocyclic Carbene-Copper Complexes within a Supramolecular Network in the Self-Assembly of Imidazolium Dicarboxylate with Metal Ions", 《INORG. CHEM.》 * |
| TUYET JEFFERY: "Heck-type Reactions in Water", 《TETRAHEDRON LETTERS》 * |
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| 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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