CN114082442B - Succinimidyl ionic liquid and method for synthesizing quinazoline-2, 4 (1H, 3H) -diketone by using same as catalyst - Google Patents
Succinimidyl ionic liquid and method for synthesizing quinazoline-2, 4 (1H, 3H) -diketone by using same as catalyst Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 19
- -1 Succinimidyl Chemical group 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 125000005594 diketone group Chemical group 0.000 claims abstract 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229960002317 succinimide Drugs 0.000 claims description 11
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical class NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002879 Lewis base Substances 0.000 claims description 7
- 150000007527 lewis bases Chemical class 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000006352 cycloaddition reaction Methods 0.000 claims description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical compound NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007363 ring formation reaction Methods 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 229910000071 diazene Inorganic materials 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 description 33
- 238000002474 experimental method Methods 0.000 description 29
- 238000001514 detection method Methods 0.000 description 25
- SDQJTWBNWQABLE-UHFFFAOYSA-N 1h-quinazoline-2,4-dione Chemical compound C1=CC=C2C(=O)NC(=O)NC2=C1 SDQJTWBNWQABLE-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000006473 carboxylation reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 description 1
- UZHALXIAWJOLLR-UHFFFAOYSA-N 2-amino-4-chlorobenzonitrile Chemical compound NC1=CC(Cl)=CC=C1C#N UZHALXIAWJOLLR-UHFFFAOYSA-N 0.000 description 1
- OATYCBHROMXWJO-UHFFFAOYSA-N 2-amino-5-bromobenzonitrile Chemical compound NC1=CC=C(Br)C=C1C#N OATYCBHROMXWJO-UHFFFAOYSA-N 0.000 description 1
- QYRDWARBHMCOAG-UHFFFAOYSA-N 2-amino-5-chlorobenzonitrile Chemical compound NC1=CC=C(Cl)C=C1C#N QYRDWARBHMCOAG-UHFFFAOYSA-N 0.000 description 1
- VFQDFQDXMNVDPW-UHFFFAOYSA-N 2-amino-5-fluorobenzonitrile Chemical compound NC1=CC=C(F)C=C1C#N VFQDFQDXMNVDPW-UHFFFAOYSA-N 0.000 description 1
- MGCGMYPNXAFGFA-UHFFFAOYSA-N 2-amino-5-nitrobenzonitrile Chemical compound NC1=CC=C([N+]([O-])=O)C=C1C#N MGCGMYPNXAFGFA-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940075419 choline hydroxide Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000008516 quinazoline-2,4(1H,3H)-diones Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- 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
- B01J31/0279—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 cationic portion being acyclic or nitrogen being a substituent on a ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
- C07D239/96—Two oxygen atoms
Abstract
The invention relates to a butyryl diimine ionic liquid and a method for synthesizing quinazoline-2, 4 (1) by catalyzing carbon dioxide and anthranilamide through a carboxyl cyclization reaction by using the butyryl diimine ionic liquidH,3H) -a diketone process. The invention aims to solve the problems of the prior synthesis of quinazoline-2, 4 (1) by using carbon dioxide and anthranilamideH,3H) The process of diketones has the problems of low catalyst activity, severe reaction conditions, the use of cocatalysts, etc. With succinimidyl ionic liquid as a catalyst, 100mol% of ionic liquid is used for catalyzing carbon dioxide and anthranile to synthesize quinazoline-2, 4 (1)H,3H) Diketones with a maximum yield of 98.8%.
Description
Technical Field
The invention belongs to the technical field of environment-friendly catalysis, and particularly relates to a succinimide ionic liquid, a preparation method and a method for synthesizing quinazoline-2, 4 (1H, 3H) -dione by catalyzing a reaction of carbon dioxide and anthranilamide by using the ionic liquid.
Background
Currently, CO 2 As the main greenhouse gas in the atmosphere, the method seriously affects the global environment and the social activities of human beings, but is also a cheap and rich C1 resource, can replace toxic CO or phosgene to synthesize a plurality of products with high added value, and has great environmental and economic significance. CO 2 The carboxylation reaction with anthranilate is a CO 2 One of the routes of conversion and the reaction has 100% atomic utilization. The product quinazoline-2, 4 (1H, 3H) -diketone has very high pharmaceutical activity and has wide application in the aspects of medicines, pesticides, organic synthesis and the like.
Because of the important economic value and wide application prospect of quinazoline-2, 4 (1H, 3H) -diketone, the performance of the catalyst needs to be further improved so as to improve the catalytic yield and reduce the cost. Among the various homogeneous and heterogeneous catalysts reported so far, ionic liquids are distinguished by their unique advantages among a wide variety of catalysts. In recent decades, imidazole, quaternary ammonium salt, quaternary phosphonium salt and other ionic liquids appear successively, but the ionic liquids generally have the defects of low catalytic activity, harsh catalytic conditions, low reusability and the like. Therefore, it is necessary to prepare a highly efficient ionic liquid capable of having excellent catalytic activity under mild conditions.
Disclosure of Invention
In order to solve the technical problems of low catalyst activity, harsh reaction conditions, organic solvent use and the like in the existing quinazoline-2, 4 (1H, 3H) -dione synthesis method, the invention aims to provide a succinimide-based ionic liquid and a method for catalyzing CO by using the succinimide-based ionic liquid 2 The method for synthesizing quinazoline-2, 4 (1H, 3H) -diketone can be carried out under normal pressure, has high catalytic activity and does not need any cocatalyst.
The invention also provides a preparation method of the succinimide-based ionic liquid.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a butanodiimide ionic liquid having any one of the structural formulas shown below:
the invention discloses a preparation method of the succinimide-based ionic liquid, which comprises the following steps:
reacting a methanol solution of Lewis base with succinimide for 10-24 hours at normal temperature, and performing post-treatment after the reaction is finished to obtain the catalyst;
the molar ratio of the Lewis base to the succinimide is 1:1-1.2;
the Lewis base is benzyltrimethylammonium hydroxide, choline hydroxide, 1, 3-tetramethylguanidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene or 1-methylimidazole.
The invention also provides a method for synthesizing quinazoline-2, 4 (1H, 3H) -diketone by utilizing the succinimidyl ionic liquid, which comprises the following steps:
adding succinimidyl ionic liquid and an o-aminobenzonitrile analogue into a reaction kettle with a digital display pressure gauge according to the mol ratio of 1-4:4, introducing carbon dioxide under the existence of a solvent to enable the pressure to be 0.1MPa, then performing cycloaddition reaction for 6-10 hours at a constant temperature and a constant pressure at 50-80 ℃, and after the reaction is finished, performing post-treatment to obtain quinazoline-2, 4 (1H, 3H) -dione.
Specifically, the anthranilate analogue is a compound with any one of the following structures:
further, the solvent may be Dimethylsulfoxide (DMSO), acetonitrile, tetrahydrofuran, N-dimethylformamide, water, or the like.
The invention provides a method for catalyzing CO by using a butanodiimide ionic liquid 2 And o-aminobenzeneA process for preparing quinazoline-2, 4 (1H, 3H) -dione from carbonitrile analog features that the succinimidyl ionic liquid is used as catalyst, and under mild condition, no cocatalyst is used to make CO 2 And synthesizing quinazoline-2, 4 (1H, 3H) -diketone by the carboxyl cyclization reaction of the anthranile nitrile. CO 2 The reaction equation for preparing quinazoline-2, 4 (1H, 3H) -dione from anthranilonitrile by the carbocyclization reaction is as follows:
wherein R is H, m-F, m-Cl, m-Br, m-NO 2 And p-Cl, etc.
The invention aims to solve the problems of low catalyst activity, harsh reaction conditions, cocatalyst use and the like in the existing method for synthesizing quinazoline-2, 4 (1H, 3H) -dione by utilizing carbon dioxide and anthranilamide. The succinimidyl ionic liquid is used as a catalyst, 100mol percent of ionic liquid is used for catalyzing carbon dioxide and anthranilamide to synthesize quinazoline-2, 4 (1H, 3H) -diketone under the condition of 70 ℃ and normal pressure, and the highest yield can reach 98.8 percent. Compared with the prior art, the invention has the following beneficial effects:
1) The succinimidyl ionic liquid provided by the invention can efficiently catalyze CO under the conditions of mild (normal pressure) and no cocatalyst 2 And anthranilonitrile to quinazoline-2, 4 (1H, 3H) -dione. The catalyst can catalyze different anthranilans and CO 2 Exhibits excellent universality by the carboxylation reaction of (a);
2) The succinimidyl ionic liquid of the invention catalyzes CO 2 And the anthranilamide can be recycled for a plurality of times, after the quinazoline-2, 4 (1H, 3H) -diketone is produced by catalysis, the quinazoline-2, 4 (1H, 3H) -diketone and unreacted anthranilamide can be separated out after water is added, the ionic liquid is dissolved in the water, and the solid ionic liquid can be obtained after the water is removed and dried, so that the recycling performance is good, and the cost is reduced. The catalyst catalyzes CO 2 The catalyst has high catalytic activity, mild reaction condition, no metal and safe operation in the carboxylation cyclization reaction with the anthranilateHigh integrity and good industrial application prospect.
Drawings
FIG. 1 is a block diagram of [ BzTMA ] prepared in example 1 + ][Suc - ]Nuclear magnetic resonance hydrogen spectrum of the catalyst;
FIG. 2 is a block diagram of [ BzTMA ] prepared in example 1 + ][Suc - ]Nuclear magnetic resonance carbon spectrum of the catalyst;
[BzTMA + ][Suc - ]the data for nuclear magnetic resonance hydrogen and carbon spectra are as follows: [ BzTMA + ][Suc - ]： 1 H NMR(400MHz,D 2 O)δ7.62-7.21(m,5H,-Ph),4.32(s,2H,-CH 2 -),2.95(s,9H,-CH 3 ),2.39-2.11(m,4H,-CH 2 -CH 2 -). 13 C NMR(101MHz,D 2 O)δ200.59,132.73,130.76,129.12,127.31,69.53,52.30,31.82.MS(ESI):[BzTMA + ]m/z 149.72,[Suc - ]m/z 98.39.Anal.Calcd for C 14 H 20 N 2 O 2 :C,67.82,N,11.28,H,8.12.found:C,67.71,N,10.89,H,8.33.
From fig. 1 and 2 and the corresponding nuclear magnetic data analysis, it can be seen that the synthesized catalyst is the target catalyst.
Detailed Description
The following describes the technical scheme of the present invention in further detail with reference to examples, but the scope of the present invention is not limited thereto.
Example 1
The structural formula of the succinimidyl ionic liquid catalyst prepared in the embodiment is as follows:
firstly, adding 5.94g (0.06 mol) of succinimide and 20.91g of 40% benzyl trimethyl ammonium hydroxide (0.05 mol) methanol solution into a 100mL single-neck flask, stirring at room temperature for reaction for 12 hours, and removing a methanol solvent by rotary evaporation after the reaction is finished; then adding 20mL cyclohexane as a water carrying agent, removing water generated in the reaction under the heating condition, finally washing and drying the residual substances by ethyl acetate,to give the product as a white solid [ BzTMA + ][Suc - ]。
[HMIm + ][Suc - ]And [ Ch ] + ][Suc - ]The method comprises the steps of reacting a substrate Lewis base and a substance with the ratio of succinimide being 1:1 in a methanol solvent for 12 hours, removing the methanol solvent by rotary evaporation after the reaction is finished, and drying to obtain a product.
[HDBU + ][Suc - ]And [ HTMG ] + ][Suc - ]According to document [1 ]]The literature information is synthesized as follows:
[1]Fusheng Liu,Ran Ping,Penghui Zhao,Yongqiang Gu,Jun Gao,Mengshuai Liu.Succinimide-Based Ionic Liquids:An Efficient and Versatile Platform for Transformation of CO 2 into Quinazoline-2,4(1H,3H)-diones under Mild and Solvent-Free Conditions[J].ACS Sustainable Chemistry&Engineering.2019,7:13517-13522。
example 2
By [ BzTMA ]][Suc-]Ionic liquid catalyzed CO 2 The reaction with anthranile is exemplified by the following:
0.248g (1 mmol) of [ BzTMA ]][Suc-]And 0.118g (1 mmol) of anthranilonitrile are respectively added into a 50mL reaction kettle equipped with a magnetic stirrer and a digital pressure gauge, 1mL of DMSO is added as a reaction solvent, and CO is slowly introduced 2 Discharging the residual air in the reaction kettle, and adjusting CO by observing a digital pressure gauge 2 The pressure was maintained at 0.1MPa. Heating the reaction kettle to 70 ℃ and 0.1MPa CO 2 The reaction was carried out under pressure for 10h. After the reaction, the yield of the product quinazoline-2, 4 (1H, 3H) -dione was 98.8% and the selectivity was > 99% by High Performance Liquid Chromatography (HPLC).
Example 3
The specific experimental process is the same as that of example 2, and the detection method is a separation method for measuring the catalytic yield, and comprises the following specific steps: after the reaction is finished, adding 10-15 mL of deionized water, transferring the mixture to a centrifuge tube, and washing the solid with the deionized water for 3 times by centrifugation, wherein 10-15 mL of deionized water is added each time; washing the solid with methyl tertiary butyl ether for 3 times, wherein 10-15 mL of the solid is used each time; the product is obtained after drying, the catalytic yield is 76.7% by weight and the selectivity is more than 99%.
Example 4
The experimental procedure and the detection method are the same as in example 2, except that the catalyst used is [ HTMG ] + ][Suc - ]The catalytic yield was measured to be 89.2% with a selectivity > 99%.
Example 5
The experimental procedure and the detection method are the same as in example 3, except that the catalyst used was [ HDBU ] + ][Suc - ]The catalytic yield was measured to be 78.1% with a selectivity > 99%.
Example 6
The experimental procedure and the detection method are the same as in example 2, except that the catalyst used is [ HMIm + ][Suc - ]The catalytic yield was measured to be 13.0% with a selectivity > 99%.
Example 7
The experimental procedure and the detection method are the same as in example 2, except that the catalyst used is [ Ch + ][Suc - ]The catalytic yield was found to be 80.3% with a selectivity > 99%.
Example 8
The experimental procedure and the detection method are the same as in example 2, except that acetonitrile (CH) 3 CN), the catalytic yield was determined to be 87.5% with selectivity > 99%.
Example 9
The procedure and the detection method are the same as in example 2, except that Tetrahydrofuran (THF) is used as solvent, and the catalytic yield is 87.5% and the selectivity is > 99%.
Example 10
The specific experimental procedure and the detection method are the same as in example 2, except that the solvent used is N, N-Dimethylformamide (DMF), and the catalytic yield is 81.4% and the selectivity is > 99%.
Example 11
The experimental procedure and the detection method are the same as in example 2, except that the solvent used is water (H 2 O), the catalytic yield was determined to be 36.7% with a selectivity > 99%.
Example 12
The specific experimental procedure and the detection method are the same as in example 2, except that the reaction temperature is 50 ℃, the catalytic yield is 34.2% and the selectivity is more than 99%.
Example 13
The specific experimental procedure and the detection method are the same as in example 2, except that the reaction temperature is 60 ℃, the catalytic yield is 74.8% and the selectivity is more than 99%.
Example 14
The specific experimental procedure and the detection method are the same as in example 2, except that the reaction temperature is 80 ℃, the catalytic yield is 99.1% and the selectivity is more than 99%.
Example 15
The specific experimental procedure and the detection method are the same as in example 2, except that the catalyst used represents 25mol% of the molar content of anthranilate, and the catalytic yield is 59.6% and the selectivity is > 99%.
Example 16
The specific experimental procedure and the detection method are the same as in example 2, except that the catalyst used represents 50mol% of the molar content of anthranilate, and the catalytic yield is measured to be 81.3% and the selectivity is greater than 99%.
Example 17
The specific experimental procedure and the detection method are the same as in example 2, except that the catalyst used represents 75mol% of the molar content of anthranilate, and the catalytic yield is 92.9% and the selectivity is > 99%.
Example 18
The specific experimental procedure and the detection method are the same as in example 2, except that the reaction time is 6h, and the catalytic yield is 86.2% and the selectivity is > 99%.
Example 19
The specific experimental procedure and the detection method are the same as in example 2, except that the reaction time is 7h, and the catalytic yield is 89.1% and the selectivity is > 99%.
Example 20
The specific experimental procedure and the detection method are the same as in example 2, except that the reaction time is 8h, the catalytic yield is 92.6% and the selectivity is > 99%.
Example 21
The specific experimental procedure and the detection method are the same as in example 2, except that the reaction time is 9h, and the catalytic yield is 95.6% and the selectivity is more than 99%.
Example 22
The specific experimental procedure and the detection method are the same as in example 2, except that the anthranilonitrile used is replaced by 2-amino-5-fluorobenzonitrile, and the catalytic yield is 98.6% and the selectivity is > 99%.
The reaction equation of this experiment is:
example 23
The specific experimental procedure and the detection method are the same as in example 2, except that the anthranilonitrile used is replaced by 2-amino-5-chlorobenzonitrile, and the catalytic yield is 99.8% and the selectivity is > 99%.
The reaction equation of this experiment is:
example 24
The specific experimental procedure and the detection method are the same as in example 2, except that the anthranilonitrile used is replaced by 2-amino-5-bromobenzonitrile, and the catalytic yield is 98.8% and the selectivity is > 99%.
The reaction equation of this experiment is:
example 25
The specific experimental procedure and the detection method are the same as in example 2, except that the anthranilonitrile used is replaced by 2-amino-4-chlorobenzonitrile, and the catalytic yield is 93.4% and the selectivity is > 99%.
The reaction equation of this experiment is:
example 26
The specific experimental procedure and the detection method are the same as in example 2, except that the anthranilonitrile used is replaced by 2-amino-5-nitrobenzonitrile, and the catalytic yield is 86.9% and the selectivity is > 99%.
The reaction equation of this experiment is:
examples 27 to 30
Specific experimental procedure and detection method the same as in example 2, except that the catalyst used was [ BzTMA recovered in example 2 + ][Suc - ]The catalyst is recovered by the following steps: after the reaction is finished, adding about 10mL of water, precipitating white solid, filtering, adding about 20mL of cyclohexane as a water carrying agent into the filtrate, heating at 110 ℃ for about 6 hours, removing water and DMSO, repeatedly washing the generated solid with ethyl acetate, and drying to obtain the recovered [ BzTMA ] + ][Suc - ]。
4 recycling experiments were performed under the same conditions, and the obtained results are shown in Table 1.
TABLE 1 EXAMPLES 27-30 catalyst recovery Using catalytic results
| Examples | Example 27 | Example 28 | Example 29 | Example 30 |
| Number of times of recovery | 1 | 2 | 3 | 4 |
| Product yield/% | 98.8 | 98.6 | 95.0 | 92.4 |
| Selectivity/% | >99 | >99 | >99 | >99 |
As can be seen from Table 1, [ BzTMA ] + ][Suc - ]After 4 times of recycling, the catalytic yield is only slightly reduced and still remains above 90%, which indicates that the catalyst has good recycling performance.
Claims (5)
1. Catalytic synthesis of quinazoline-2, 4 (1)H,3H) -a succinimidyl ionic liquid of a diketone, characterized by having the structural formula shown below:
。
2. the method for preparing the succinimidyl ionic liquid according to claim 1, which is characterized by comprising the following steps:
reacting a methanol solution of Lewis base with succinimide for 10-24 hours at normal temperature, and performing post-treatment after the reaction is finished to obtain the catalyst;
the molar ratio of the Lewis base to the succinimide is 1:1-1.2;
the Lewis base is benzyltrimethylammonium hydroxide.
3. Catalytic synthesis of quinazoline-2, 4 (1) using the succinimidyl ionic liquid of claim 1H,3H) -a process for diketoning comprising the steps of:
adding succinimidyl ionic liquid and an anthranilonitrile analogue into a reaction kettle with a digital display pressure gauge according to the mol ratio of 1:1, introducing carbon dioxide under the existence of a solvent to enable the pressure to be 0.1MPa, then performing cycloaddition reaction for 6-10 hours at a constant temperature and a constant pressure of 50-80 ℃, and after the reaction is finished, performing post treatment to obtain quinazoline-2, 4 (1)H,3H) -a diketone.
4. A succinimidyl ionic liquid catalyzed synthesis of quinazoline-2, 4 (1) according to claim 3H,3H) -a diketone process characterized in that said anthranilate analogue is a compound of any one of the following structures:，，/>。
5. a succinimidyl ionic liquid catalyzed synthesis of quinazoline-2, 4 (1) according to claim 3H,3H) -diketone process, characterized in that the solvent is dimethylSulfoxide, acetonitrile, tetrahydrofuran, N-dimethylformamide or water.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106722A (en) * | 1984-07-30 | 1987-03-25 | 默里尔多药物公司 | 1, the preparation of 3-dihydro-4-pyridine acyl-2H-imidazole-2-ketone compound |
| CN1683336A (en) * | 2005-03-10 | 2005-10-19 | 浙江工业大学 | Process for synthesizing acyl imidogen substituted cyclo compound |
| CN101492422A (en) * | 2009-03-06 | 2009-07-29 | 华东师范大学 | Alkyl imidazole succinimide ionic liquid and method for preparing the same |
| CN102030706A (en) * | 2010-12-22 | 2011-04-27 | 江苏食品职业技术学院 | Method for preparing 6-hydroxy-2(1H)-quinolone in ionic liquid by using one-pot method |
| CN102348675A (en) * | 2009-03-09 | 2012-02-08 | 巴斯夫欧洲公司 | Process for preparing substituted 2-nitrobiphenyls |
| CN103896952A (en) * | 2014-04-09 | 2014-07-02 | 中国科学院化学研究所 | Ionic liquid catalyst as well as preparation method and application of ionic liquid catalyst |
| CN106946800A (en) * | 2017-03-21 | 2017-07-14 | 华东师范大学 | A kind of synthetic method of (1H, the 3H) diketone of quinazoline 2,4 and its derivative |
| CN106946787A (en) * | 2017-03-22 | 2017-07-14 | 南京工业大学 | A kind of synthetic method of imidazoles acidic ion liquid |
| CN110105321A (en) * | 2019-04-25 | 2019-08-09 | 青岛科技大学 | A kind of method of eutectic ionic liquid catalysis carbon dioxide synthesizing annular carbonate |
| CN110711601A (en) * | 2019-10-30 | 2020-01-21 | 青岛科技大学 | In-situ conversion of CO2Process and catalyst for preparing quinazoline-2, 4(1H,3H) -diones and derivatives thereof |
| CN110746357A (en) * | 2019-10-28 | 2020-02-04 | 河南大学 | Imidazole diionic liquid and method for catalytic synthesis of cyclic carbonate by using same |
| KR20200071001A (en) * | 2018-12-10 | 2020-06-18 | 연세대학교 산학협력단 | Ionic thermoelectric materials and ionic thermoelectric devices comprising the same |
| CN111909094A (en) * | 2020-08-28 | 2020-11-10 | 河南大学 | Multi-active center ionic liquid, preparation method and method for catalytically synthesizing cyclic carbonate by using multi-active center ionic liquid |
| CN112409190A (en) * | 2020-11-05 | 2021-02-26 | 河南大学 | Method for efficiently synthesizing cyclic carbonate by using amine salt ionic liquid as catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10175557B2 (en) * | 2014-01-31 | 2019-01-08 | Nippon Kayaku Kabushikikaisha | Optical wavelength conversion element containing ionic liquid, and article equipped with said optical wavelength conversion element |
| CA2994403A1 (en) * | 2015-07-31 | 2017-02-09 | Novomer, Inc. | Production system/production process for acrylic acid and precursors thereof |
| MX2016008702A (en) * | 2016-06-30 | 2018-01-01 | Mexicano Inst Petrol | Catalysts supported in natural polymers for obtaining carbonates from co2. |
-
2021
- 2021-11-18 CN CN202111367649.3A patent/CN114082442B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106722A (en) * | 1984-07-30 | 1987-03-25 | 默里尔多药物公司 | 1, the preparation of 3-dihydro-4-pyridine acyl-2H-imidazole-2-ketone compound |
| CN1683336A (en) * | 2005-03-10 | 2005-10-19 | 浙江工业大学 | Process for synthesizing acyl imidogen substituted cyclo compound |
| CN101492422A (en) * | 2009-03-06 | 2009-07-29 | 华东师范大学 | Alkyl imidazole succinimide ionic liquid and method for preparing the same |
| CN102348675A (en) * | 2009-03-09 | 2012-02-08 | 巴斯夫欧洲公司 | Process for preparing substituted 2-nitrobiphenyls |
| CN102030706A (en) * | 2010-12-22 | 2011-04-27 | 江苏食品职业技术学院 | Method for preparing 6-hydroxy-2(1H)-quinolone in ionic liquid by using one-pot method |
| CN103896952A (en) * | 2014-04-09 | 2014-07-02 | 中国科学院化学研究所 | Ionic liquid catalyst as well as preparation method and application of ionic liquid catalyst |
| CN106946800A (en) * | 2017-03-21 | 2017-07-14 | 华东师范大学 | A kind of synthetic method of (1H, the 3H) diketone of quinazoline 2,4 and its derivative |
| CN106946787A (en) * | 2017-03-22 | 2017-07-14 | 南京工业大学 | A kind of synthetic method of imidazoles acidic ion liquid |
| KR20200071001A (en) * | 2018-12-10 | 2020-06-18 | 연세대학교 산학협력단 | Ionic thermoelectric materials and ionic thermoelectric devices comprising the same |
| CN110105321A (en) * | 2019-04-25 | 2019-08-09 | 青岛科技大学 | A kind of method of eutectic ionic liquid catalysis carbon dioxide synthesizing annular carbonate |
| CN110746357A (en) * | 2019-10-28 | 2020-02-04 | 河南大学 | Imidazole diionic liquid and method for catalytic synthesis of cyclic carbonate by using same |
| CN110711601A (en) * | 2019-10-30 | 2020-01-21 | 青岛科技大学 | In-situ conversion of CO2Process and catalyst for preparing quinazoline-2, 4(1H,3H) -diones and derivatives thereof |
| CN111909094A (en) * | 2020-08-28 | 2020-11-10 | 河南大学 | Multi-active center ionic liquid, preparation method and method for catalytically synthesizing cyclic carbonate by using multi-active center ionic liquid |
| CN112409190A (en) * | 2020-11-05 | 2021-02-26 | 河南大学 | Method for efficiently synthesizing cyclic carbonate by using amine salt ionic liquid as catalyst |
Non-Patent Citations (4)
| Title |
|---|
| Choline hydroxide promoted chemicalfixation of CO2 to quinazoline-2,4(1 H,3 H )-diones in water;Wenj ing Lu et.al;《RSC Advances》;第4卷;第50993 –50997页 * |
| Fusheng Liu et.al.Succinimide-Based Ionic Liquids: An Efficient and Versatile Platform for Transformation of CO2 into Quinazoline-2,4(1 H,3 H)‑diones under Mild and Solvent-Free Conditions.《ACS Sustainable Chemistry & Engineering》.2019,第7卷摘要、实验部分. * |
| High CO2 absorption capacity by chemisorption at cations and anions in choline-based ionic liquids;Shubhankar Bhattacharyya et.al;《Physical Chemistry Chemical Physics》;第19卷;摘要、图1 * |
| Succinimide-Based Ionic Liquids: An Efficient and Versatile Platform for Transformation of CO2 into Quinazoline-2,4(1 H,3 H)‑diones under Mild and Solvent-Free Conditions;Fusheng Liu et.al;《ACS Sustainable Chemistry & Engineering》;第7卷;摘要、实验部分 * |
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