CN103896952B - Ionic-liquid catalyst and preparation method thereof and application - Google Patents
Ionic-liquid catalyst and preparation method thereof and application 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- 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
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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 a kind of ionic-liquid catalyst and preparation method thereof and application.This ionic liquid, is made up of any one in positively charged ion shown in negatively charged ion shown in formula II and formula Ia to formula Ic.This ionic-liquid catalyst is applicable to CO under catalysis normal temperature and pressure
2with the reaction system of a series of Gas chromatography compounds Reactive Synthesis quinazoline-2,4 (1H, 3H)-cyclohexadione compounds; This ionic-liquid catalyst is easy to synthesis, green, efficient and be easy to reclaim, and has stronger using value.
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 being 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, carbonic acid gas and Gas chromatography compounds is utilized to react to generate quinazoline-2,4 (1H, 3H)-cyclohexadione compounds to be successful one of important channel 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
2with Gas chromatography compounds Reactive Synthesis quinazoline-2; 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, magnesia-zirconia, ionic liquid ([Bmim] OH and [Bmim] Ac), N-methyl tetrahydropyridine and tetrabutyl ammonium tungstate; N.Okamoto, T.ItoandT.Miyata, TetrahedronLett.2000; 41,1051; Y.P.Patil, P.J.Tambade, S.R.JagtapandB.M.Bhanage, GreenChem.Lett.Rev.2008,1,127; Y.P.Patil, P.J.Tambade, K.D.Parghi, R.V.JayaramandB.M.Bhanage, Catal.Lett.2009,133,201; Y.P.Patil, P.J.Tambade, K.M.DeshmukhandB.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, GreenChem.2014,16,221; D.NagaiandT.Endo, J.Polym.Sci.PartA:Polym.Chem.2009,47,653; J.Gao, L.N.He, C.X.MiaoandS.Chanfreau, Tetrahedron2010,66,4063; T.Kimura, H.Sunaba, K.Kamataand, N.Mizuno, Inorg.Chem.2012,51,13001).But above-mentioned catalyst system usually 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 any one in positively charged ion shown in negatively charged ion shown in formula II and formula Ia to formula Ic:
The method of the described ionic liquid of preparation provided by the invention, comprises the steps:
In an inert atmosphere, shown for formula II ' compound and any one in the shown compound of formula Ia ' to formula Ic ' are mixed backflow and carries out neutralization reaction, react complete drying and obtain described ionic liquid;
Wherein, the shown compound of formula II ' is referred to as TFE;
The shown compound of formula Ia ' is referred to as DBU;
The shown compound of formula Ib ' is referred to as TMG;
The shown compound of formula Ic ' 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.
In the shown compound of described formula II ' and the shown compound of formula Ia ' to formula Ic ', any one molar ratio is 1:0.5-1, is specially 1:1;
Described inert atmosphere is nitrogen or argon gas atmosphere.
In addition, present invention also offers above-mentioned ionic liquid and prepare the application in compound shown in formula III:
In described formula III, R is-H ,-CH
3,-OMe ,-F, at least one in-Cl and-Br.
The method preparing compound shown in formula III provided by the invention, comprise the steps: at aforementioned ionic liquid provided by the invention as under the condition of catalyzer, the compounds of Gas chromatography shown in carbonic acid gas and formula IV is carried out addition reaction, reacts complete and obtain compound shown in described formula III;
In described formula III and formula IV, R is all selected from-H ,-CH
3,-OMe ,-F, at least one in-Cl and-Br.
In aforesaid method, the compounds of Gas chromatography shown in formula IV is specially 2-aminobenzonitrile, 2-amino-4,5-dimethoxy cyanophenyls, 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, be 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;
The molar ratio of Gas chromatography compounds and described catalyzer shown in described formula IV 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 be easily separated from reaction system; 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 Ar gas shielded, at 50 DEG C, neutralization reaction 24h is carried out in condensing reflux stirring, and gained ionic liquid is [HDBU after vacuum-drying
+] [TFE
-].
Nuclear magnetic data:
1hNMR (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, be slowly added drop-wise to by TFE (5.00g, 50mmol) in TMG (5.76g, 50mmol), then under Ar gas shielded, 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:
1hNMR (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, be slowly added drop-wise to by TFE (5.00g, 50mmol) in DBN (6.21g, 50mmol), then under Ar gas shielded, 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:
1hNMR (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 embodiment 1 gained ionic liquid [HDBU successively
+] [TFE
-] as catalyzer (756mg, 3mmol) and the 2-aminobenzonitrile (118mg, 1mmol) belonging to formula IV, use CO
2displacement air wherein; Then CO is kept
2vacuum tightness is 0.1MPa, and 30 DEG C of stirrings carry out addition reaction 24 hours.After question response terminates, 6ml deionized water is added in reaction system, produce a large amount of water-fast white precipitate, this white precipitate of collected by centrifugation, wash three times by water and t-butyl methyl ether respectively, after 90 DEG C of dry 12h, weigh and determine quinazoline-2,4 (1H, 3H)-diketone yield is 97%.Reaction product is used
1h and
13c nuclear magnetic spectrogram determines its structure.
1HNMR(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).
13CNMR(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 change 504mg(2mmol into), the yield obtaining quinazoline-2,4 (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 change 252mg(1mmol into), all the other are with embodiment 1, and the yield obtaining quinazoline-2,4 (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 the reaction times will change 3h into, the yield obtaining quinazoline-2,4 (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 the reaction times will change 6h into, the yield obtaining quinazoline-2,4 (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 the reaction times will change 12h into, the yield obtaining quinazoline-2,4 (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 the reaction times will change 20h into, the yield obtaining quinazoline-2,4 (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 embodiment 2 gained ionic liquid [HTMG
+] [TFE
-] (675mg, 3mmol), the yield obtaining quinazoline-2,4 (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 embodiment 3 gained ionic liquid [HDBN
+] [TFE
-] (672mg, 3mmol), the yield obtaining quinazoline-2,4 (1H, 3H)-diketone is 97%.
Embodiment 13, CO
2generation 6,7-dimethoxyquinazoline-2,4 (1H, 3H)-diketone is reacted with amino-4, the 5-dimethoxy cyanophenyls of 2-
Adopt and the identical reaction conditions of embodiment 1 and detection method, only the 2-aminobenzonitrile of ownership formula IV is replaced with 2-amino-4,5-dimethoxy cyanophenyl (178mg, 1mmol), [HDBU
+] [TFE
-] consumption replaces with 1.51g(6mmol), the yield obtaining 6,7-dimethoxyquinazoline-2,4 (1H, 3H)-diketone is 92%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram determines its structure.
1HNMR(DMSO-d
6,400MHz,)δ11.02(s,2H),7.26(s,1H),6.68(s,1H),3.83(d,3H),3.78(s,3H)
13CNMR(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-methylquinazolin-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 2-amino-4-methyl cyanophenyl (147mg, 1mmol), [HDBU
+] [TFE
-] consumption replaces with 1.51g(6mmol), the yield that Liquid Detection obtains 7-methylquinazolin-2,4 (1H, 3H)-diketone is 68%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram determines its structure.
1HNMR(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).
13CNMR(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-methylquinazolin-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 2-amino-5-fluorine cyanophenyl (136mg, 1mmol), [HDBU
+] [TFE
-] consumption replaces with 1.51g(6mmol), the yield that Liquid Detection obtains 6-fluquinconazole quinoline-2,4 (1H, 3H)-diketone is 96%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram determines its structure.
1HNMR(DMSO-d
6,400MHz,)δ11.29(s,2H),7.60-7.52(m,2H),7.21-7.18(q,1H).
13CNMR(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 2-amino-5-6-chlorophenyl nitrile (152mg, 1mmol), [HDBU
+] [TFE
-] consumption replaces with 1.51g(6mmol), the yield obtaining 6-chloro-quinazoline-2,4 (1H, 3H)-diketone is 92%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram determines its structure.
1HNMR(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).
13CNMR(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 2-amino-4-6-chlorophenyl nitrile (152mg, 1mmol), [HDBU
+] [TFE
-] consumption replaces with 1.51g(6mmol), the yield obtaining 7-chloro-quinazoline-2,4 (1H, 3H)-diketone is 90%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram determines its structure.
1HNMR(DMSO-d
6,400MHz,)δ11.30(s,2H),7.87-7.84(d,1H),7.19-7.15(m,2H).
13CNMR(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 2-amino-5-bromoxynil (196mg, 1mmol), [HDBU
+] [TFE
-] consumption is 1.51g(6mmol), the yield obtaining 6-bromine quinazoline-2,4 (1H, 3H)-diketone is 95%.
Reaction product is used
1h and
13c nuclear magnetic spectrogram determines its structure.
1HNMR(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).
13CNMR(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 (13)
1. an ionic liquid, by cation composition shown in negatively charged ion and formula Ic shown in formula II:
2. prepare a method for ionic liquid described in claim 1, comprise the steps:
In an inert atmosphere, shown for formula II ' compound and any one in the shown compound of formula Ic ' are mixed backflow and carries out neutralization reaction, react complete drying and obtain described ionic liquid;
3. method according to claim 2, is characterized in that: in described neutralization reaction step, and the time is 24-72 hour;
Temperature is 25-60 DEG C.
4. method according to claim 3, is characterized in that: in described neutralization reaction step, and the time is 48 hours;
Temperature is 50 DEG C.
5., according to described method arbitrary in claim 2-4, it is characterized in that: the molar ratio of the shown compound of described formula II ' and the shown compound of formula Ic ' is 1:0.5-1;
Described inert atmosphere is nitrogen or argon gas atmosphere.
6. method according to claim 5, is characterized in that: the molar ratio of the shown compound of described formula II ' and the shown compound of formula Ic ' is 1:1.
7. ionic liquid described in claim 1 is preparing the application in compound shown in formula III:
In described formula III, R is-H ,-CH
3,-OMe ,-F, any one in-Cl and-Br.
8. prepare the method for compound shown in formula III for one kind, comprise the steps: that ionic liquid is as under the condition of catalyzer described in claim 1, the compounds of Gas chromatography shown in carbonic acid gas and formula IV is carried out addition reaction, reacts complete and obtain compound shown in described formula III;
In described formula III and formula IV, R is selected from-H ,-CH
3,-OMe ,-F, any one in-Cl and-Br.
9. method according to claim 8, is characterized in that: Gas chromatography compounds shown in described formula IV is 2-aminobenzonitrile, 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;
Vacuum tightness is 0.1-1MPa;
The molar ratio of Gas chromatography compounds and described catalyzer shown in described formula IV is 1:1-6.
10. method according to claim 9, is characterized in that: in described addition reaction step, and temperature is 30 DEG C;
Vacuum tightness is 0.1MPa;
The molar ratio of Gas chromatography compounds and described catalyzer shown in described formula IV is 1:3.
Prepare 6 for 11. 1 kinds, 7-dimethoxyquinazoline-2, the method of 4 (1H, 3H)-diketone, comprises the steps: that ionic liquid is as under the condition of catalyzer described in claim 1, by carbonic acid gas and 2-amino-4,5-dimethoxy cyanophenyl carries out addition reaction, reacts complete and obtains described 6,7-dimethoxyquinazolines-2,4 (1H, 3H)-diketone.
12. methods according to claim 11, is characterized in that: in described addition reaction step, and the time is 3-24 hour; Temperature is 20-50 DEG C;
Vacuum tightness is 0.1-1MPa;
The molar ratio of amino-4, the 5-dimethoxy cyanophenyls of described 2-and described catalyzer is 1:1-6.
13. methods according to claim 12, is characterized in that: in described addition reaction step, and temperature is 30 DEG C;
Vacuum tightness is 0.1MPa;
The molar ratio of amino-4, the 5-dimethoxy cyanophenyls of described 2-and described catalyzer is 1:3.
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| CN113121455A (en) * | 2021-04-20 | 2021-07-16 | 廊坊师范学院 | Method for efficiently catalyzing and converting carbon dioxide into quinazoline diketone compound by utilizing eutectic solvent under normal temperature and pressure conditions |
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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 |
| 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 |
| CN111454222B (en) * | 2020-02-28 | 2023-05-23 | 南京工业大学 | Synthesis method of 2,4- (1H, 3H) -quinazolinedione and derivatives thereof |
| CN114437018B (en) * | 2020-11-05 | 2023-06-20 | 中国科学院化学研究所 | Method for preparing 1, 4-dioxane compound by dehydration cyclization of diol compound |
| CN112778219A (en) * | 2021-01-27 | 2021-05-11 | 浙江外国语学院 | Method for preparing 2,4- (1H,3H) -quinazoline diketone compound |
| CN113666933A (en) * | 2021-07-21 | 2021-11-19 | 厦门大学 | Proton type ionic liquid (HDBN) (2-PyOH), and preparation and application thereof |
| 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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| CN113121455A (en) * | 2021-04-20 | 2021-07-16 | 廊坊师范学院 | Method for efficiently catalyzing and converting carbon dioxide into quinazoline diketone compound by utilizing eutectic solvent under normal temperature and pressure conditions |
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