CN103896952A - Ionic liquid catalyst as well as preparation method and application of ionic liquid catalyst - Google Patents
Ionic liquid catalyst as well as preparation method and application of ionic liquid catalyst Download PDFInfo
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J31/0282—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 of an aliphatic ring, e.g. morpholinium
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- 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
- B01J31/0285—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 also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C07—ORGANIC CHEMISTRY
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- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
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- C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C279/04—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton
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- 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
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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Abstract
The invention discloses an ionic liquid catalyst as well as a preparation method and an application of the ionic liquid catalyst. The ionic liquid catalyst is composed of negative ions as shown in a formula II and any one of positive ions as shown in formulas Ia to Ic. The ionic liquid catalyst is applicable to catalyzing a reaction system in which CO2 reacts with a series of aminobenzonitrile compounds to synthesize quinazoline-2,4(1H, 3H)-diketone compounds at a normal temperature and under normal pressure; the ionic liquid catalyst is easy to synthesize, green, efficient and easy to recovery, and also has high application value. The formulas are shown in the specification.
Description
Technical field
The present invention relates to a kind of ionic-liquid catalyst and preparation method thereof and application.
Background technology
As a kind of C1 resource, CO2 is cheap and easy to get, green non-poisonous, renewable, and the research that is translated into high valuable chemicals is the research topic (M.Y.He that people very pay attention to always, Y.H.Sun, B.X.Han, Angew.Chem.Int.Ed., 2013,52,9620).Wherein, utilize carbonic acid gas to react with Gas chromatography compounds and generate quinazoline-2,4 (1H, 3H)-cyclohexadione compounds is one of important channel successfully utilizing carbonic acid gas.Quinazoline-2,4 (1H, 3H)-cyclohexadione compounds is the important medicine intermediate (T.P.Tran of a class; E.L.Ellsworth, M.A.Stier, J.M.Domagala; H.D.H.Showalter; S.J.Gracheck, M.A.Shapiro, T.E.Joannides; R.Singh; Bioorg.Med.Chem.Lett.2004,14,4405; E.Mounetou, J.Legault, J.Lacroix, R.C.Gaudreault, J.Med.Chem.2001,44,694; M.B.Andrus, S.N.Mettath, C.Song, J.Org.Chem.2002,67,8284).That has reported at present passes through CO
2react synthetic quinazoline-2 with Gas chromatography compounds; 4 (1H; the catalyzer of 3H)-cyclohexadione compounds mainly contains: 1; (the T.Mizuno such as 8-diazabicylo 11 carbon-7-alkene (DBU), guanidine (TMG), cesium carbonate, magnesium oxide-zirconium white, ionic liquid ([Bmim] OH and [Bmim] Ac), N-methyl tetrahydropyridine and tetrabutyl ammonium tungstate; N.Okamoto, T.Ito and T.Miyata, Tetrahedron Lett.2000; 41,1051; Y.P.Patil, P.J.Tambade, S.R.Jagtap and B.M.Bhanage, Green Chem.Lett.Rev.2008,1,127; Y.P.Patil, P.J.Tambade, K.D.Parghi, R.V.Jayaram and B.M.Bhanage, Catal.Lett.2009,133,201; Y.P.Patil, P.J.Tambade, K.M.Deshmukh and B.M.Bhanage, Catal.Today2009,148,355; W.J.Lu, J.Ma, J.Y.Hu, J.L.Song, Z.F.Zhang, G.Y.Yang, B.X.Han, Green Chem.2014,16,221; D.Nagai and T.Endo, J.Polym.Sci.Part A:Polym.Chem.2009,47,653; J.Gao, L.N.He, C.X.Miao and S.Chanfreau, Tetrahedron2010,66,4063; T.Kimura, H.Sunaba, K.Kamataand, N.Mizuno, Inorg.Chem.2012,51,13001).But above-mentioned catalyst system conventionally needs High Temperature High Pressure or adds poisonous organic solvent etc.Therefore, exploitation gentle (normal temperature and pressure), green catalyst system remain the core of this repercussion study.
Summary of the invention
The object of this invention is to provide a kind of ionic-liquid catalyst and preparation method thereof and application.
Ionic liquid provided by the invention, is made up of to any one in positively charged ion shown in formula Ic negatively charged ion shown in formula II and formula Ia:
The method of the described ionic liquid of preparation provided by the invention, comprises the steps:
In inert atmosphere, compound shown in formula II ' and formula Ia ' are mixed to reflux to any one in compound shown in formula Ic ' and carry out neutralization reaction, react the complete dry described ionic liquid that obtains;
Wherein, compound shown in formula II ' is referred to as TFE;
Shown in formula Ia ', compound is referred to as DBU;
Shown in formula Ib ', compound is referred to as TMG;
Shown in formula Ic ', compound is referred to as DBN;
In the neutralization reaction step of aforesaid method, the time is 24-72 hour, is specially 48 hours;
Temperature is 25-60 DEG C, is specially 50 DEG C.
Compound shown in described formula II ' and formula Ia ' to any one molar ratio in compound shown in formula Ic ' be 1:0.5-1, be specially 1:1;
Described inert atmosphere is nitrogen or argon gas atmosphere.
In addition, the present invention also provides above-mentioned ionic liquid preparing the application in compound shown in formula III:
In described formula III, R is-H ,-CH
3,-OMe ,-F ,-Cl and-at least one in Br.
The method of preparing compound shown in formula III provided by the invention, comprise the steps: at aforementioned ionic liquid provided by the invention under the condition as catalyzer, Gas chromatography compounds shown in carbonic acid gas and formula IV is carried out to addition reaction, react the complete compound shown in described formula III that obtains;
In described formula III and formula IV, be all selected from-H of R ,-CH
3,-OMe ,-F ,-Cl and-at least one in Br.
In aforesaid method, the compounds of Gas chromatography shown in formula IV is specially 2-aminobenzonitrile, 2-amino-4,5-dimethoxy cyanophenyl, 2-amino-4-methyl cyanophenyl, 2-amino-5-6-chlorophenyl nitrile, 2-amino-4-6-chlorophenyl nitrile, 2-amino-5-bromoxynil or 2-amino-5-fluorine cyanophenyl;
In described addition reaction step, the time is 3-24 hour, is specially 3,6,12,20,24,3-20,3-12,6-24,6-20,12-24 or 20-24h; Temperature is 20-50 DEG C, is specially 30 DEG C;
Vacuum tightness is 0.1-1MPa, is specially 0.1MPa;
Shown in described formula IV, the molar ratio of Gas chromatography compounds and described catalyzer is 1:1-6, is specially 1:1,1:2,1:3,1:6,1:1-3,1:1-2,1:3-6 or 1:2-6.
Ionic-liquid catalyst synthetic method provided by the invention is simple, have higher catalytic activity and easily from reaction system, separate; This catalyst system is widely applicable, can be used for CO under normal temperature and pressure
2with multiple Gas chromatography compou nd synthesis quinazoline-2,4 (1H, 3H)-cyclohexadione compounds; There is stronger using value.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
Embodiment 1, prepare ionic liquid [HDBU
+] [TFE
-]
Under ice bath, by TFE(5.00g, 50mmol) be slowly added drop-wise to DBU(7.60g, 50mmol) in, then under the protection of Ar gas, at 50 DEG C, condensing reflux stirs and carries out neutralization reaction 24h, and gained ionic liquid is [HDBU after vacuum-drying
+] [TFE
-].
Nuclear magnetic data:
1h NMR (CDCl
3, 400MHz): δ 3.79-3.86 (q, 2H), 3.22-3.15 (m, 6H), 2.38-2.32 (m, 2H), 1.79-1.73 (m, 2H) 1.67-1.51 (m, 6H)
As from the foregoing, this product structure is correct, is ionic liquid [HDBU
+] [TFE
-].
Embodiment 2, prepare ionic liquid [HTMG
+] [TFE
-]
Under ice bath, TFE (5.00g, 50mmol) is slowly added drop-wise in TMG (5.76g, 50mmol), then under the protection of Ar gas, at 50 DEG C, neutralization reaction 24h is carried out in condensing reflux stirring, and gained ionic liquid is [HTMG after vacuum-drying
+] [TFE
-].
Nuclear magnetic data:
1h NMR (DMSO-d
6, 400MHz): δ 5.94 (s, 2H), 3.90-3.82 (q, 2H), 2.62 (s, 12H)
As from the foregoing, this product structure is correct, is ionic liquid [HTMG
+] [TFE
-].
Embodiment 3, prepare ionic liquid [HDBN
+] [TFE
-]
Under ice bath, TFE (5.00g, 50mmol) is slowly added drop-wise in DBN (6.21g, 50mmol), then under the protection of Ar gas, at 50 DEG C, neutralization reaction 24h is carried out in condensing reflux stirring, and gained ionic liquid is [HDBN after vacuum-drying
+] [TFE
-].
Nuclear magnetic data:
1h NMR (CDCl
3, 400MHz): δ 3.85-3.78 (q, 2H), 3.28-3.21 (m, 4H), 3.17-3.14 (t, 2H), 2.43-2.39 (t, 2H) 1.94-1.86 (m, 2H) 1.78-1.71 (m, 2H)
As from the foregoing, this product structure is correct, is ionic liquid [HDBN
+] [TFE
-].
Embodiment 4, CO
2react with 2-aminobenzonitrile and generate quinazoline-2,4 (1H, 3H)-diketone
In the single port bottle of 10 milliliters, add successively embodiment 1 gained ionic liquid [HDBU
+] [TFE
-] as the 2-aminobenzonitrile (118mg, 1mmol) of catalyzer (756mg, 3mmol) and ownership formula IV, use CO
2displacement air wherein; Then keep CO
2vacuum tightness is 0.1MPa, and 30 DEG C of stirrings are carried out addition reaction 24 hours.After question response finishes, in reaction system, add 6ml deionized water, produce a large amount of water-fast white precipitates, this white precipitate of centrifugal collection, water and t-butyl methyl ether washing three times respectively, after 90 DEG C of dry 12h, definite quinazoline-2 of weighing, 4 (1H, 3H)-diketone yield is 97%.Reaction product is used
1h and
13c nuclear magnetic spectrogram is determined its structure.
1H?NMR(DMSO-d6,400MHz,)δ11.19(s,2H),7.89-7.87(m,1H),7.63-7.59(m,1H),7.17-7.14(m,2H).
13C?NMR(DMSO-d
6,100MHz)δ162.82,150.30,140.87,134.90,126.93,122.28,115.31,114.33.
As from the foregoing, this product structure is correct, is quinazoline-2,4 (1H, 3H)-diketone.
Embodiment 5, CO
2react with Gas chromatography and generate quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only by [HDBU
+] [TFE
-] amount changes 504mg(2mmol into), obtaining quinazoline-2, the yield of 4 (1H, 3H)-diketone is 85%.
Embodiment 6, CO
2react with Gas chromatography and generate quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only by [HDBU
+] [TFE
-] amount changes 252mg(1mmol into), all the other,, with embodiment 1, obtain quinazoline-2, and the yield of 4 (1H, 3H)-diketone is 70%.
Embodiment 7, CO
2react with Gas chromatography and generate quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only will the reaction times change 3h into, obtain quinazoline-2, the yield of 4 (1H, 3H)-diketone is 47%.
Embodiment 8, CO
2react with Gas chromatography and generate quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only will the reaction times change 6h into, obtain quinazoline-2, the yield of 4 (1H, 3H)-diketone is 73%.
Embodiment 9, CO
2react with Gas chromatography and generate quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only will the reaction times change 12h into, obtain quinazoline-2, the yield of 4 (1H, 3H)-diketone is 86%.
Embodiment 10, CO
2react with Gas chromatography and generate quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only will the reaction times change 20h into, obtain quinazoline-2, the yield of 4 (1H, 3H)-diketone is 94%.
Embodiment 11, CO
2react with Gas chromatography and generate quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only catalyzer is replaced with to embodiment 2 gained ionic liquid [HTMG
+] [TFE
-] (675mg, 3mmol), obtaining quinazoline-2, the yield of 4 (1H, 3H)-diketone is 67%.
Embodiment 12, CO
2react with Gas chromatography and generate quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only catalyzer is become to embodiment 3 gained ionic liquid [HDBN
+] [TFE
-] (672mg, 3mmol), obtaining quinazoline-2, the yield of 4 (1H, 3H)-diketone is 97%.
Embodiment 13, CO
2with 2-amino-4, the reaction of 5-dimethoxy cyanophenyl generates 6,7-dimethoxyquinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only the 2-aminobenzonitrile of ownership formula IV is replaced with to 2-amino-4,5-dimethoxy cyanophenyl (178mg, 1mmol), [HDBU
+] [TFE
-] consumption replaces with 1.51g(6mmol), obtaining 6,7-dimethoxyquinazoline-2, the yield of 4 (1H, 3H)-diketone is 92%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram is determined its structure.
1H?NMR(DMSO-d
6,400MHz,)δ11.02(s,2H),7.26(s,1H),6.68(s,1H),3.83(d,3H),3.78(s,3H)
13C?NMR(DMSO-d
6,100MHz)δ162.39,154.88,150.37,145.00,136.52,107.14,106.17,97.74,55.78,55.69.
As from the foregoing, this product structure is correct, is 6,7-dimethoxyquinazoline-2,4 (1H, 3H)-diketone.
Embodiment 14, CO
2react with 2-amino-4-methyl cyanophenyl and generate 7-methyl quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1, only the 2-aminobenzonitrile of ownership formula IV is replaced with to 2-amino-4-methyl cyanophenyl (147mg, 1mmol), [HDBU
+] [TFE
-] consumption replaces with 1.51g(6mmol), Liquid Detection obtains 7-methyl quinazoline-2, and the yield of 4 (1H, 3H)-diketone is 68%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram is determined its structure.
1H?NMR(DMSO-d6,400MHz,)δ11.12(s,2H),7.78-7.76(d,1H),7.01-6.99(d,1H),6.95(s,1H),2.36(s,3H).
13C?NMR(DMSO-d
6,100MHz)δ162.67,150.43,145.56,140.92,126.88,123.62,115.03,112.03,21.41.
As from the foregoing, this product structure is correct, is 7-methyl quinazoline-2,4 (1H, 3H)-diketone.
Embodiment 15, CO
2react with 2-amino-5-fluorine cyanophenyl and generate 6-fluquinconazole quinoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1, only the 2-aminobenzonitrile of ownership formula IV is replaced with to 2-amino-5-fluorine cyanophenyl (136mg, 1mmol), [HDBU
+] [TFE
-] consumption replaces with 1.51g(6mmol), Liquid Detection obtains 6-fluquinconazole quinoline-2, and the yield of 4 (1H, 3H)-diketone is 96%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram is determined its structure.
1H?NMR(DMSO-d
6,400MHz,)δ11.29(s,2H),7.60-7.52(m,2H),7.21-7.18(q,1H).
13C?NMR(DMSO-d
6,100MHz)δ162.12,162.09,158.45,156.07,150.06,137.58,123.00,122.77,117.61,117.53,115.42,115.34,112.06,111.83.
As from the foregoing, this product structure is correct, is 6-fluquinconazole quinoline-2,4 (1H, 3H)-diketone.
Embodiment 16, CO
2react with 2-amino-5-6-chlorophenyl nitrile and generate 6-chloro-quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only the 2-aminobenzonitrile of ownership formula IV is replaced with to 2-amino-5-6-chlorophenyl nitrile (152mg, 1mmol), [HDBU
+] [TFE
-] consumption replaces with 1.51g(6mmol), obtaining 6-chloro-quinazoline-2, the yield of 4 (1H, 3H)-diketone is 92%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram is determined its structure.
1H?NMR(DMSO-d
6,400MHz,)δ11.33(s,2H),7.81-7.80(d,1H),7.69-7.66(q,1H),7.19-7.16(d,1H).
13C?NMR(DMSO-d
6,100MHz)δ161.85,150.12,139.85,134.73,126.21,125.88,117.56,115.78.
As from the foregoing, this product structure is correct, is 6-chloro-quinazoline-2,4 (1H, 3H)-diketone.
Embodiment 17, CO
2react with 2-amino-4-6-chlorophenyl nitrile and generate 7-chloro-quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only the 2-aminobenzonitrile of ownership formula IV is replaced with to 2-amino-4-6-chlorophenyl nitrile (152mg, 1mmol), [HDBU
+] [TFE
-] consumption replaces with 1.51g(6mmol), obtaining 7-chloro-quinazoline-2, the yield of 4 (1H, 3H)-diketone is 90%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram is determined its structure.
1H?NMR(DMSO-d
6,400MHz,)δ11.30(s,2H),7.87-7.84(d,1H),7.19-7.15(m,2H).
13C?NMR(DMSO-d
6,100MHz)δ162.07,150.18,141.95,139.28,128.99,122.43,114.68,113.31.
As from the foregoing, this product structure is correct, is 7-chloro-quinazoline-2,4 (1H, 3H)-diketone.
Embodiment 18, CO
2react with 2-amino-5-bromoxynil and generate 6-bromine quinazoline-2,4 (1H, 3H)-diketone
Adopt and the identical reaction conditions of embodiment 1 and detection method, only the 2-aminobenzonitrile of ownership formula IV is replaced with to 2-amino-5-bromoxynil (196mg, 1mmol), [HDBU
+] [TFE
-] consumption is 1.51g(6mmol), obtaining 6-bromine quinazoline-2, the yield of 4 (1H, 3H)-diketone is 95%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram is determined its structure.
1H?NMR(DMSO-d
6,400MHz,)δ11.35(s,2H),7.94-7.93(d,1H),7.81-7.78(q,1H),7.13-7.11(d,1H).
13C?NMR(DMSO-d
6,100MHz)δ161.71,150.05,140.08,137.43,128.90,117.76,116.19,113.80.
As from the foregoing, this product structure is correct, is 6-bromine quinazoline-2,4 (1H, 3H)-diketone.
Claims (7)
1. an ionic liquid, is made up of to any one in positively charged ion shown in formula Ic negatively charged ion shown in formula II and formula Ia:
2. a method of preparing ionic liquid described in claim 1, comprises the steps:
In inert atmosphere, compound shown in formula II ' and formula Ia ' are mixed to reflux to any one in compound shown in formula Ic ' and carry out neutralization reaction, react the complete dry described ionic liquid that obtains;
3. method according to claim 2, is characterized in that: in described neutralization reaction step, the time is 24-72 hour, is specially 48 hours;
Temperature is 25-60 DEG C, is specially 50 DEG C.
4. according to the method in claim 2 or 3, it is characterized in that: compound shown in described formula II ' and formula Ia ' to any one molar ratio in compound shown in formula Ic ' be 1:0.5-1, be specially 1:1;
Described inert atmosphere is nitrogen or argon gas atmosphere.
Described in claim 1 ionic liquid preparing the application in compound shown in formula III:
In described formula III, R is-H ,-CH3 ,-OMe ,-F ,-Cl and-at least one in Br.
6. prepare the method for compound shown in formula III for one kind, comprise the steps: at ionic liquid described in claim 1 under the condition as catalyzer, Gas chromatography compounds shown in carbonic acid gas and formula IV is carried out to addition reaction, react the complete compound shown in described formula III that obtains;
In described formula III and formula IV, be selected from-H of R ,-CH
3,-OMe ,-F ,-Cl and-at least one in Br.
7. method according to claim 6, it is characterized in that: Gas chromatography compounds shown in described formula IV is 2-aminobenzonitrile, 2-amino-4 5-dimethoxy cyanophenyl, 2-amino-4-methyl cyanophenyl, 2-amino-5-6-chlorophenyl nitrile, 2-amino-4-6-chlorophenyl nitrile, 2-amino-5-bromoxynil or 2-amino-5-fluorine cyanophenyl;
In described addition reaction step, the time is 3-24 hour; Temperature is 20-50 DEG C, is specially 30 DEG C;
Vacuum tightness is 0.1-1MPa, is specially 0.1MPa;
Shown in described formula IV, the molar ratio of Gas chromatography compounds and described catalyzer is 1:1-6, is specially 1:3.
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| CN106883151A (en) * | 2017-02-16 | 2017-06-23 | 华东师范大学 | A kind of five alkyl guanidine ionic liquids and its preparation and application |
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| CN107698587A (en) * | 2017-11-08 | 2018-02-16 | 贵州医科大学 | Heterocycle and hybar X class compounds process for production thereof |
| 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 |
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| CN114082442A (en) * | 2021-11-18 | 2022-02-25 | 河南大学 | Succinimidyl ionic liquid and method for catalytically synthesizing quinazoline-2, 4(1H,3H) -diketone by using same |
| CN114082442B (en) * | 2021-11-18 | 2024-01-19 | 河南大学 | Succinimidyl ionic liquid and method for synthesizing quinazoline-2, 4 (1H, 3H) -diketone by using same as catalyst |
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| CN105107545B (en) | 2017-07-14 |
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