CN105153048B - A kind of preparation method of 2,4 quinazoline diones class compound - Google Patents
A kind of preparation method of 2,4 quinazoline diones class compound Download PDFInfo
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- CN105153048B CN105153048B CN201510465483.7A CN201510465483A CN105153048B CN 105153048 B CN105153048 B CN 105153048B CN 201510465483 A CN201510465483 A CN 201510465483A CN 105153048 B CN105153048 B CN 105153048B
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- 0 C[C@@](*=C)C(C(N)=CC=C(C)*)=C Chemical compound C[C@@](*=C)C(C(N)=CC=C(C)*)=C 0.000 description 13
- GJCIRHGWDGKMHP-UHFFFAOYSA-N CNc1cc(Cl)ccc1N(C)I Chemical compound CNc1cc(Cl)ccc1N(C)I GJCIRHGWDGKMHP-UHFFFAOYSA-N 0.000 description 1
- CZZZABOKJQXEBO-UHFFFAOYSA-N Cc(cc1C)ccc1N Chemical compound Cc(cc1C)ccc1N CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 1
- HBTPEFKQWCXAMX-UHFFFAOYSA-N I[O]1CCCCC1 Chemical compound I[O]1CCCCC1 HBTPEFKQWCXAMX-UHFFFAOYSA-N 0.000 description 1
- PRIOKVMBFXTMRV-UHFFFAOYSA-N Nc(ccc(I)c1)c1C#N Chemical compound Nc(ccc(I)c1)c1C#N PRIOKVMBFXTMRV-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention belongs to organic chemistry filed, and in particular to a kind of preparation method of 2,4 quinazoline diones class compounds.The preparation method, using 2 aminobenzonitrile compounds and carbon dioxide as raw material, it is preferred that under amide groups bivalent rare earth metal aminate and DBU catalysis, 50 DEG C 150 DEG C, normal pressure, 4 40h are reacted in aprotic polar solvent, you can 2,4 quinazoline diones class compounds are made with higher yield.Not only reaction condition is gentle for this method, and catalyst amount is few, isolates and purifies simplicity, and yield is higher, and wide application range of substrates.
Description
Technical field
The invention belongs to organic chemistry filed, and in particular to the preparation method of one kind 2,4- quinazoline diones class compounds.
Background technology
2,4- quinazoline diones class compounds are the important dominance structure skeletons of a class, with extensive biological activity,
Such as, it can lead to as antibiotic, serum receptor antagonist, glutamate receptor antagonists, aldose reductase inhibitor, calcium ion
Road antagonist, acetylcholine receptor antagonists etc..
At present, preparing the method for 2,4- quinazoline diones class compounds has a lot.Wherein, important one kind is with titanium dioxide
Carbon and 2- aminobenzonitrile compounds are raw material, prepared in the presence of catalyst that the reaction is due to its atom economy
Property and receive much concern.
2002, Takumi Mizuno seminars disclosed the preparation method of one kind 2,4- quinazoline diones class compounds,
I.e. using 2- aminobenzonitrile compounds and carbon dioxide as raw material, under 3 equivalent DBU catalysis, using DMF as solvent, at 1
Atmospheric pressure, react 24h under the conditions of 20 DEG C, 2,4- quinazoline diones class compounds can be made with higher yield;When DBU consumption
, it is necessary under the conditions of 10 atmospheric pressure, 80 DEG C during for 0.1 equivalent, could be made 2,4- quinazoline diones classes compound (see
Tetrahedron 2002,58,3155-3158).2007, the seminar disclosed one kind 2,4- quinazoline diones class chemical combination
The preparation method of thing, i.e., using 2- aminobenzonitrile compounds and carbon dioxide as raw material, under 0.2-1 equivalents DBU catalysis,
React 4h under the conditions of 1 atmospheric pressure, 120-150 DEG C, can be made with higher yields 2,4- quinazoline diones classes compounds (see
Synthesis, 2007,16,2524-2428).
However, above-mentioned preparation method is present, catalyst amount is more, catalyst type is limited, severe reaction conditions, substrate are fitted
With scope it is narrower the shortcomings of.
Therefore, study that new reaction condition is gentle, catalyst amount is few and wide application range of substrates with 2- aminobenzenes
First nitrile compounds and carbon dioxide are significant for the method that raw material prepares 2,4- quinazoline diones class compounds.
The content of the invention
It is existing using 2- aminobenzonitrile compounds and carbon dioxide as raw material system therefore, to be solved by this invention
Method severe reaction conditions, the skill that catalyst amount is more, the substrate scope of application is narrower of standby 2,4- quinazoline diones class compounds
Art problem, so as to propose that a kind of reaction condition is gentle, catalyst amount is few and wide application range of substrates with 2- anthranilo nitriles
Class compound and carbon dioxide are the method that raw material prepares 2,4- quinazoline diones class compounds.
In order to solve the above technical problems, the present invention is achieved through the following technical solutions:
The present invention provides the preparation method of one kind 2,4- quinazoline diones class compounds, and reaction equation is as follows,
Comprise the following steps:Using 2- aminobenzonitrile compounds and carbon dioxide as raw material, in amide groups bivalent rare earth
Under metal aminate and DBU catalysis, reacted in aprotic polar solvent;
Wherein, R is selected from (C1-C10)-alkyl, OR3、CN、CF3、NO2, halogen, NR4R5、NHCOR6、COOR7;
R3Selected from H, (C1-C10)-alkyl, aryl;
R4、R5H, (C are selected from independently from each other1-C10)-alkyl, aryl;
R6、R7(C is selected from independently from each other1-C10)-alkyl, aryl;
X represents the number of the substituent on phenyl ring, selected from 0,1,2,3,4;
The amide groups bivalent rare earth metal aminate has the chemical structural formula shown in formula (I):
Wherein, R1、R2It is independently from each other hydrogen, methyl, isopropyl or the tert-butyl group;
M and n represent the number of benzene ring substituents, are independently from each other 0,1,2,3,4 or 5;
Ln is Eu or Yb;
The aprotic polar solvent is selected from least one of amide-type, sulfoxide type, ketone.
Preferably, in one embodiment of the invention, above-mentioned preparation method comprises the following steps:
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in the amide groups bivalent rare earth metal aminate and 3-10 molar parts shown in 1-15 molar parts formula (I)
Under DBU catalysis, 50 DEG C -150 DEG C, normal pressure reacts 4-40h in aprotic polar solvent.
It is further preferred that in another embodiment of the invention, above-mentioned preparation method comprises the following steps:
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in the amide groups bivalent rare earth metal aminate and 4-6 molar parts shown in 2-11 molar parts formula (I)
Under DBU catalysis, 70 DEG C -130 DEG C, normal pressure reacts 6-36h in aprotic polar solvent.
It is further preferred that in another embodiment of the invention, above-mentioned preparation method comprises the following steps:
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in the amide groups bivalent rare earth metal aminate and 5 molar part DBU shown in 2.5 molar part formulas (I)
Catalysis under, 100 DEG C, normal pressure reacts 6-36h in aprotic polar solvent;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in urging for the amide groups bivalent rare earth metal aminate shown in 5 molar part formulas (I) and 5 molar part DBU
Under change, 80 DEG C, normal pressure reacts 6-36h in aprotic polar solvent;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in urging for the amide groups bivalent rare earth metal aminate shown in 5 molar part formulas (I) and 5 molar part DBU
Under change, 100 DEG C, normal pressure reacts 6-36h in aprotic polar solvent;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in urging for the amide groups bivalent rare earth metal aminate shown in 5 molar part formulas (I) and 5 molar part DBU
Under change, 120 DEG C, normal pressure reacts 6-36h in aprotic polar solvent;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in the amide groups bivalent rare earth metal aminate shown in 10 molar part formulas (I) and 5 molar part DBU
Under catalysis, 100 DEG C, normal pressure reacts 6-36h in aprotic polar solvent.
Preferably, in one embodiment of the invention, above-mentioned preparation method,
R1For isopropyl or methyl, m is 2, R2For the tert-butyl group or hydrogen, n is 1 or 5, Ln are Eu or Yb.
It is highly preferred that in another embodiment of the invention, above-mentioned preparation method,
R1For isopropyl, m is 2, R2For the tert-butyl group, n is that 1, Ln is Eu;Or
R1For isopropyl, m is 2, R2For hydrogen, n is that 5, Ln is Eu;Or
R1For isopropyl, m is 2, R2For hydrogen, n is that 5, Ln is Yb;Or
R1For methyl, m is 2, R2For hydrogen, n is that 5, Ln is Yb.
It is further preferred that in another embodiment of the invention, above-mentioned preparation method,
Amide groups bivalent rare earth metal aminate shown in formula (I) is:
Preferably, in one embodiment of the invention, above-mentioned preparation method,
The aprotic polar solvent is selected from least one of DMF, dimethyl sulfoxide (DMSO), acetone.
It is further preferred that in another embodiment of the invention, above-mentioned preparation method comprises the following steps:
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in 2.5 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure,
Reacted in dimethyl sulfoxide (DMSO);Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and
Excess carbon dioxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 80 DEG C, normal pressure,
6-36h is reacted in dimethyl sulfoxide (DMSO);Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure,
6-36h is reacted in dimethyl sulfoxide (DMSO);Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure,
6-36h is reacted in N,N-dimethylformamide;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 120 DEG C, normal pressure,
6-36h is reacted in dimethyl sulfoxide (DMSO);Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and
Excess carbon dioxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C,
Normal pressure, reacts 6-36h in dimethyl sulfoxide (DMSO);Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure,
6-36h is reacted in dimethyl sulfoxide (DMSO);Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and mistake
Amount carbon dioxide is raw material, in 10 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure,
6-36h is reacted in dimethyl sulfoxide (DMSO).
Preferably, in one embodiment of the invention, above-mentioned preparation method,
R is selected from (C1-C4)-alkyl, OR3、F、Cl、Br、I、NR4R5、NHCOR6、COOR7;
R3Selected from (C1-C4)-alkyl;
R4、R5(C is selected from independently from each other1-C4)-alkyl;
R6、R7(C is selected from independently from each other1-C4)-alkyl.
It is further preferred that in another embodiment of the invention, above-mentioned preparation method,
The 2- aminobenzonitrile compounds are selected from
Preferably, in one embodiment of the invention, above-mentioned preparation method, in addition to the step of reaction is quenched with inorganic acid
Suddenly the step of separation and purification treatment is carried out to the 2,4- quinazoline diones class compound and using isolation and purification method.
It is further preferred that in another embodiment of the invention, above-mentioned preparation method, the acid is selected from hydrochloric acid, sulphur
At least one of acid, nitric acid, phosphoric acid, the isolation and purification method are selected from washing, filtering, extraction, recrystallization, distillation, post layer
At least one of analysis, thin-layer chromatography, freeze-drying.
The above-mentioned technical proposal of the present invention has advantages below compared with prior art:
The preparation method of the present invention 2,4- quinazoline diones class compounds, with 2- aminobenzonitrile compounds and titanium dioxide
Carbon is raw material, preferably under amide groups bivalent rare earth metal aminate and DBU catalysis, 50 DEG C -150 DEG C, normal pressure, non-proton
Property polar solvent in react 4-40h, you can 2,4- quinazoline diones class compounds are made with higher yield.This method is not only anti-
Answer mild condition (50 DEG C -150 DEG C, normal pressure, aprotic polar solvent), few (the amide groups bivalent rare earth metal of catalyst amount
The mol ratio of aminate and 2- aminobenzonitrile compounds is mole of 2-11%, DBU and 2- aminobenzonitrile compounds
Than for 4-6%), simplicity is isolated and purified, yield is higher (61-99%), and wide application range of substrates.
Brief description of the drawings
In order that present disclosure is more likely to be clearly understood, specific embodiment and combination below according to the present invention
Accompanying drawing, the present invention is further detailed explanation, wherein:
Fig. 1 is { L in the embodiment of the present invention 11Eu[N(SiMe3)2]·THF}2Mono-crystalline structures figure.
Embodiment
1st, term explanation
DBU represent for 1,8- diazabicyclos [5.4.0];
{L1Eu[N(SiMe3)2]·THF}2Represent be
{L2Eu[N(SiMe3)2]·THF}2Represent be
{L2Yb[N(SiMe3)2]·THF}2Represent be
L1What H was represented is
L2What H was represented is
5mol% { L2Eu[N(SiMe3)2]·THF}2Represent be:{L2Eu[N(SiMe3)2]·THF}2With substrate 2-
The mol ratio of aminobenzonitrile compounds is 5:100;
What 5mol% DBU was represented is:The mol ratio of DBU and substrate 2- aminobenzonitrile compounds is 5:100.
2nd, reagent and instrument explanation
Reagent and solvent used are commercially available product in following examples, and purity is pure for chemistry.
Rigaku Mercury four-circle diffractometers;The type NMR instrument of Bruker AscendTM 400.
3rd, experimental implementation explanation
Because amide groups rare-earth metal amide is all very sensitive to steam and air, therefore all operations are both needed to use
Schlenk technologies, are carried out under anhydrous, anaerobic and inert gas shielding.High temperature is obtained by oil bath heating.
Comparative example 15mol% DBU is catalyzed 2- anthranilo nitriles under 100 DEG C of normal pressures and carbon dioxide reaction prepares 2,
4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 11.2 μ L (7.5 × 10 are added in reaction bulb-5Mol) DBU, in titanium dioxide
Under the protection of carbon airbag, 2mL dimethyl sulfoxide (DMSO)s are added, 0.1771 gram (1.5 × 10 is added-3Mol) 2- anthranilo nitriles, 100
DEG C constant temperature bath in stirring reaction.After 24h, 5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, successively with 3 × 5mL salt
Acid, toluene and ether washing solid, extract residual solvent, dry solid, obtain product, yield is 45%.
Comparative example 25mol% { L2Eu[N(SiMe3)2]·THF}2Under 100 DEG C of normal pressures be catalyzed 2- anthranilo nitriles and
Carbon dioxide reaction prepares 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999 gram (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, carbon dioxide airbag protection under, add 2mL dimethyl sulfoxide (DMSO)s, add 0.1771 gram (1.5 ×
10-3Mol) 2- anthranilo nitriles, the stirring reaction in 100 DEG C of constant temperature bath.After 24h, 5mL 2mol/L salt is added, then is taken out
Filter, successively washs solid with 3 × 5mL hydrochloric acid, toluene and ether, extracts residual solvent, dries solid, obtains product, yield is
12%.
Embodiment 1{L1Eu[N(SiMe3)2]·THF}2Preparation
In the reaction bulb that anhydrous, anaerobic, argon gas are protected, Eu [N (SiMe are added3)2]2, dissolved with tetrahydrofuran;Another
One anhydrous, in the reaction bulb of anaerobic, argon gas protection, weighs and Eu [N (SiMe3)2]2Equimolar than ligand L1H, adds four
Hydrogen furans, Eu [N (SiMe are slowly added into by ligand solution3)2]2In the clear liquid of ether solvent, 4h is reacted, clear liquid is finally given.
After reaction terminates, solvent is drained, is washed with n-hexane, add tetrahydrofuran to whole dissolvings, centrifugation takes upper strata
Clear liquid drains solvent to crystallizing in bottle, with appropriate tetrahydrofuran-n-hexane dissolution, is stored at room temperature until separating out crystal, as
Amide groups bivalent rare earth aminate { L1Eu[N(SiMe3)2]·THF}2, yield is 75%.
{L1Eu[N(SiMe3)2]·THF}2Detailed transistor parameter be shown in Table 1, main bond distance, bond angle data are shown in Table 2, single
Crystal structure figure is shown in Fig. 1.
{ the L of table 11Eu[N(SiMe3)2]·THF}2Crystal parameterses
{ the L of table 21Eu[N(SiMe3)2]·THF}2Main bond distance and bond angle
Embodiment 2{L2Yb[N(SiMe3)2]·THF}2Preparation
In the reaction bulb that anhydrous, anaerobic, argon gas are protected, Yb [N (SiMe are added3)2]2, dissolved with tetrahydrofuran;Another
One anhydrous, weighs and Yb [N (SiMe in the reaction bulb of anaerobic, argon gas protection3)2]2Equimolar than ligand L2H, adds tetrahydrochysene
Furans, Yb [N (SiMe are slowly added into by ligand solution3)2]2In the clear liquid of ether solvent, 4h is reacted, clear liquid is finally given.
After reaction terminates, solvent is drained, is washed with n-hexane, add tetrahydrofuran to whole dissolvings, centrifugation takes upper strata
Clear liquid drains solvent to crystallizing in bottle, with appropriate tetrahydrofuran-n-hexane dissolution, is stored at room temperature until separating out crystal, as
Amide groups bivalent rare earth aminate { L2Yb[N(SiMe3)2]·THF}2, yield is 82%.
Implement 3{L2Eu[N(SiMe3)2]·THF}2Preparation
In the reaction bulb that anhydrous, anaerobic, argon gas are protected, Eu [N (SiMe are added3)2]2, dissolved with tetrahydrofuran;Another
One anhydrous, weighs and Eu [N (SiMe in the reaction bulb of anaerobic, argon gas protection3)2]2Equimolar than ligand L2H, adds tetrahydrochysene
Furans, Eu [N (SiMe are slowly added into by ligand solution3)2]2In the clear liquid of ether solvent, reaction 4h finally gives clear liquid.
After reaction terminates, solvent is drained, is washed with n-hexane, add tetrahydrofuran to whole dissolvings, centrifugation takes upper strata
Clear liquid drains solvent to crystallizing in bottle, with appropriate tetrahydrofuran-n-hexane dissolution, is stored at room temperature until separating out crystal, as
Amide groups bivalent rare earth aminate { L2Eu[N(SiMe3)2]·THF}2, yield is 78%.
Embodiment 45mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- anthranilo nitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.1771g (1.5 × 10-3Mol) 2- anthranilo nitriles, the stirring reaction in 100 DEG C of constant temperature bath.24h
Afterwards, 5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, successively solid is washed with 3 × 5mL hydrochloric acid, toluene and ether, takes out
Except residual solvent, solid is dried, product is obtained, yield is 91%.1HNMR (400MHz, DMSO-d6):11.29 (s, 1H, NH),
11.14 (s, 1H, NH), 7.89-7.91 (d, 1H, ArH), 7.62-7.66 (t, 1H, ArH), 7.17-7.20 (t, 2H, ArH).
Embodiment 55mol% { L1Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- anthranilo nitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.1083g (7.5 × 10 is added in reaction bulb-5mol){L1Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.1771g (1.5 × 10-3Mol) 2- anthranilo nitriles, the stirring reaction in 100 DEG C of constant temperature bath.24h
Afterwards, 5mL2mol/L hydrochloric acid reaction, then suction filtration are added, successively solid is washed with 3 × 5mL hydrochloric acid, toluene and ether, takes out
Except residual solvent, solid is dried, product is obtained, yield is 83%.
Embodiment 65mol% { L2Yb[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- anthranilo nitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.1030g (7.5 × 10 is added in reaction bulb-5mol){L2Yb[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.1771g (1.5 × 10-3Mol) 2- anthranilo nitriles, the stirring reaction in 100 DEG C of constant temperature bath.24h
Afterwards, 5mL2mol/L hydrochloric acid reaction, then suction filtration are added, successively solid is washed with 3 × 5mL hydrochloric acid, toluene and ether, takes out
Except residual solvent, solid is dried, product is obtained, yield is 61%.
Embodiment 72.5mol% { L2Eu[N(SiMe3)2]·THF}2Urged with 5mol% DBU under 100 DEG C of normal pressures
Change 2- anthranilo nitriles and carbon dioxide reaction prepares 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0499g (3.75 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.1771g (1.5 × 10-3Mol) 2- anthranilo nitriles, the stirring reaction in 100 DEG C of constant temperature bath.24h
Afterwards, 5mL2mol/L hydrochloric acid reaction, then suction filtration are added, successively solid is washed with 3 × 5mL hydrochloric acid, toluene and ether, takes out
Except residual solvent, solid is dried, product is obtained, yield is 78%.
Embodiment 810mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- anthranilo nitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.1998g (1.5 × 10 is added in reaction bulb-4mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.1771g (1.5 × 10-3Mol) 2- anthranilo nitriles, the stirring reaction in 100 DEG C of constant temperature bath.24h
Afterwards, 5mL2mol/L hydrochloric acid reaction, then suction filtration are added, successively solid is washed with 3 × 5mL hydrochloric acid, toluene and ether, takes out
Except residual solvent, solid is dried, product is obtained, yield is 73%.
Embodiment 95mol% { L2Eu[N(SiMe3)2]·THF}2With 5mol% DBU 2- is catalyzed under 80 DEG C of normal pressures
Anthranilo nitrile and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.1771g (1.5 × 10-3Mol) 2- anthranilo nitriles, the stirring reaction in 80 DEG C of constant temperature bath.After 24h,
5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, successively solid is washed with 3 × 5mL hydrochloric acid, toluene and ether, extracts
Residual solvent, dries solid, obtains product, yield is 63%.
Embodiment 105mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 120 DEG C of normal pressures
2- anthranilo nitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.1771g (1.5 × 10-3Mol) 2- anthranilo nitriles, the stirring reaction in 120 DEG C of constant temperature bath.24h
Afterwards, 5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, successively solid is washed with 3 × 5mL hydrochloric acid, toluene and ether, takes out
Except residual solvent, solid is dried, product is obtained, yield is 68%.
Embodiment 115mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
O-amino benzonitride and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.1771g (1.5 × 10-3Mol) 2- anthranilo nitriles, the stirring reaction in 100 DEG C of constant temperature bath.36h
Afterwards, 5mL2mol/L hydrochloric acid reaction, then suction filtration are added, successively solid is washed with 3 × 5mL hydrochloric acid, toluene and ether, takes out
Except residual solvent, solid is dried, product is obtained, yield is 92%.
Embodiment 125mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- amino -4,5- dimethoxybenzonitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.3333g (1.5 × 10-3Mol) 2- amino -4,5- dimethoxybenzonitrile, in 100 DEG C of constant temperature bath
Stirring reaction.After 24h, 5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, successively with 3 × 5mL hydrochloric acid, toluene and second
Ether washs solid, extracts residual solvent, dries solid, obtains product, yield is 99%.1HNMR (400MHz, DMSO-d6):
11.13 (s, 1H, NH), 10.95 (s, 1H, NH), 7.29 (s, 1H, ArH), 6.71 (s, 1H, ArH), 3.81-3.86 (d, 6H,
CH3)。
Embodiment 135mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- amino -5- methyl benzonitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.2643g (1.5 × 10-3Mol) 2- amino -5- methyl benzonitriles, stir anti-in 100 DEG C of constant temperature bath
Should.After 24h, 5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, is successively washed with 3 × 5mL hydrochloric acid, toluene and ether
Solid, extracts residual solvent, dries solid, obtains product, yield is 97%.1HNMR (400MHz, DMSO-d6):11.21 (s,
1H, NH), 11.04 (s, 1H, NH), 7.69 (s, 1H, ArH), 7.45-7.47 (d, 1H, ArH), 7.06-7.08 (d, 1H, ArH),
2.32 (s, 3H, CH3)。
Embodiment 145mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- amino -5- nitrobenzonitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.3107g (1.5 × 10-3Mol) 2- amino -5- nitrobenzonitriles, stir anti-in 100 DEG C of constant temperature bath
Should.After 24h, 5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, is successively washed with 3 × 5mL hydrochloric acid, toluene and ether
Solid, extracts residual solvent, dries solid, obtains product, yield is 81%.1HNMR (400MHz, DMSO-d6):11.73 (s,
1H, NH), 11.78 (s, 1H, NH), 8.59 (d, 1H, ArH), 8.44-8.47 (m, 1H, ArH), 7.32-7.34 (d, 1H, ArH).
Embodiment 155mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- amino -5- trifluoromethylbenzonitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.3452g (1.5 × 10-3Mol) 2- amino -5- trifluoromethylbenzonitriles, are stirred in 100 DEG C of constant temperature bath
Mix reaction.After 24h, 5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, successively with 3 × 5mL hydrochloric acid, toluene and ether
Solid is washed, residual solvent is extracted, solid is dried, obtains product, yield is 80%.1HNMR (400MHz, DMSO-d6):
11.55-11.60 (d, 2H, NH), 8.13 (d, 1H, ArH), 7.98-8.01 (m, 1H, ArH), 7.35-7.37 (d, 1H, ArH).
Embodiment 165mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- amino-5-fluorines benzonitrile and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.2702g (1.5 × 10-3Mol) 2- amino-5-fluorines benzonitrile, the stirring reaction in 100 DEG C of constant temperature bath.
After 24h, 5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, successively washs solid with 3 × 5mL hydrochloric acid, toluene and ether
Body, extracts residual solvent, dries solid, obtains product, yield is 97%.1HNMR (400MHz, DMSO-d6):11.44 (s, 1H,
NH), 11.23 (s, 1H, NH), 7.55-7.63 (m, 2H, ArH), 7.21-7.25 (m, 1H, ArH).
Embodiment 175mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- amino -5- chlorobenzonitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.2949g (1.5 × 10-3Mol) 2- amino -5- chlorobenzonitriles, the stirring reaction in 100 DEG C of constant temperature bath.
After 24h, 5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, successively washs solid with 3 × 5mL hydrochloric acid, toluene and ether
Body, extracts residual solvent, dries solid, obtains product, yield is 91%.1HNMR (400MHz, DMSO-d6):11.47 (s, 1H,
NH), 11.31 (s, 1HNH), 7.84 (d, 1H, ArH), 7.70-7.73 (m, 1H, ArH), 7.70-7.72 (d, 1H, ArH).
Embodiment 185mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- amino -5- bromobenzylcyanides and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.3616g (1.5 × 10-3Mol) 2- amino -5- bromobenzylcyanides, the stirring reaction in 100 DEG C of constant temperature bath.
After 24h, 5mL 2mol/L hydrochloric acid reaction, then suction filtration are added, successively washs solid with 3 × 5mL hydrochloric acid, toluene and ether
Body, extracts residual solvent, dries solid, obtains product, yield is 64%.1HNMR (400MHz, DMSO-d6):11.44 (s, 1H,
NH), 11.28 (s, 1H, NH), 7.94 (d, 1H, ArH), 7.78-7.81 (m, 1H, ArH), 7.11-7.13 (d, 1H, ArH).
Embodiment 195mol% { L2Eu[N(SiMe3)2]·THF}2It is catalyzed with 5mol% DBU under 100 DEG C of normal pressures
2- amino -4- chlorobenzonitriles and carbon dioxide reaction prepare 2,4- quinazoline diones class compounds
Under anhydrous, anaerobic, argon gas protection, 0.0999g (7.5 × 10 is added in reaction bulb-5mol){L2Eu[N
(SiMe3)2]·THF}2, add 11.2 μ L (7.5 × 10-5Mol) DBU, under the protection of carbon dioxide airbag, adds 2mL diformazans
Base sulfoxide, adds 0.2949g (1.5 × 10-3Mol) 2- amino -4- chlorobenzonitriles, the stirring reaction in 100 DEG C of constant temperature bath.
After 24h, 5mL2mol/L hydrochloric acid reaction, then suction filtration are added, successively solid is washed with 3 × 5mL hydrochloric acid, toluene and ether,
Residual solvent is extracted, solid is dried, obtains product, yield is 62%.1HNMR (400MHz, DMSO-d6):11.39 (s, 1H,
NH), 11.23 (s, 1H, NH);(7.87-7.89 d, 1H, ArH);(7.17-7.22 m, 2H, ArH).
The reaction substrate of various embodiments above, reaction condition and yield are as shown in table 3.
Reaction substrate, reaction condition and the yield of each embodiment of table 3
As shown in Table 3, using 2- aminobenzonitrile compounds and carbon dioxide as raw material, preferably in amide groups bivalent rare earth
Under metal aminate and DBU catalysis, 50 DEG C -150 DEG C, normal pressure reacts 4-40h in aprotic polar solvent, you can with
2,4- quinazoline diones class compounds are made in higher yield.This method not only reaction condition it is gentle (50 DEG C -150 DEG C, normal pressure,
Aprotic polar solvent), catalyst amount few (amide groups bivalent rare earth metal aminate and 2- aminobenzonitrile compounds
Mol ratio be that the mol ratios of 2-11%, DBU and 2- aminobenzonitrile compounds is 4-6%), isolate and purify simplicity, yield
Higher (61-99%), and wide application range of substrates.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. one kind 2, the preparation method of 4- quinazoline diones class compounds, it is characterised in that reaction equation is as follows,
Comprise the following steps:Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitriles
Compound and excess carbon dioxide are raw material, in the amide groups bivalent rare earth metal aminate shown in 1-15 molar parts formula (I) and
Under 3-10 molar parts DBU catalysis, 50 DEG C -150 DEG C, normal pressure reacts 4-40h in aprotic polar solvent;
Wherein, R is selected from (C1-C10)-alkyl, OR3、CF3、NO2, halogen, NR4R5;
R3Selected from H, (C1-C10)-alkyl;
R4、R5H, (C are selected from independently from each other1-C10)-alkyl;
X represents the number of the substituent on phenyl ring, selected from 0,1,2,3,4;
The amide groups bivalent rare earth metal aminate has the chemical structural formula shown in formula (I):
Wherein, R1、R2It is independently from each other hydrogen, methyl, isopropyl or the tert-butyl group;
M and n represent the number of benzene ring substituents, are independently from each other 0,1,2,3,4 or 5;
Ln is Eu or Yb;
The aprotic polar solvent is selected from least one of amide-type, sulfoxide type, ketone.
2. preparation method according to claim 1, it is characterised in that comprise the following steps:
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in the amide groups bivalent rare earth metal aminate shown in 2-11 molar parts formula (I) and 4-6 molar parts DBU
Under catalysis, 70 DEG C -130 DEG C, normal pressure reacts 6-36h in aprotic polar solvent.
3. preparation method according to claim 1 or 2, it is characterised in that comprise the following steps:
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in the catalysis of amide groups bivalent rare earth metal aminate and 5 molar part DBU shown in 2.5 molar part formulas (I)
Under, 100 DEG C, normal pressure reacts 6-36h in aprotic polar solvent;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in the catalysis of amide groups bivalent rare earth metal aminate and 5 molar part DBU shown in 5 molar part formulas (I)
Under, 80 DEG C, normal pressure reacts 6-36h in aprotic polar solvent;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in the catalysis of amide groups bivalent rare earth metal aminate and 5 molar part DBU shown in 5 molar part formulas (I)
Under, 100 DEG C, normal pressure reacts 6-36h in aprotic polar solvent;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in the catalysis of amide groups bivalent rare earth metal aminate and 5 molar part DBU shown in 5 molar part formulas (I)
Under, 120 DEG C, normal pressure reacts 6-36h in aprotic polar solvent;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in the catalysis of amide groups bivalent rare earth metal aminate and 5 molar part DBU shown in 10 molar part formulas (I)
Under, 100 DEG C, normal pressure reacts 6-36h in aprotic polar solvent.
4. preparation method according to claim 1 or 2, it is characterised in that
R1For isopropyl or methyl, m is 2, R2For the tert-butyl group or hydrogen, n is 1 or 5, Ln are Eu or Yb.
5. preparation method according to claim 1 or 2, it is characterised in that
R1For isopropyl, m is 2, R2For the tert-butyl group, n is that 1, Ln is Eu;Or
R1For isopropyl, m is 2, R2For hydrogen, n is that 5, Ln is Eu;Or
R1For isopropyl, m is 2, R2For hydrogen, n is that 5, Ln is Yb;Or
R1For methyl, m is 2, R2For hydrogen, n is that 5, Ln is Yb.
6. preparation method according to claim 1 or 2, it is characterised in that
Amide groups bivalent rare earth metal aminate shown in formula (I) is:
7. preparation method according to claim 1 or 2, it is characterised in that
The aprotic polar solvent is selected from least one of DMF, dimethyl sulfoxide (DMSO), acetone.
8. preparation method according to claim 1 or 2, it is characterised in that comprise the following steps:
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in 2.5 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure, two
Reacted in methyl sulfoxide;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 80 DEG C, normal pressure, in dimethyl
6-36h is reacted in sulfoxide;Or
Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure, in diformazan
6-36h is reacted in base sulfoxide;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure, in N, N-
6-36h is reacted in dimethylformamide;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 120 DEG C, normal pressure, in diformazan
6-36h is reacted in base sulfoxide;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure,
6-36h is reacted in dimethyl sulfoxide (DMSO);Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in 5 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure, in diformazan
6-36h is reacted in base sulfoxide;Or
Under conditions of anhydrous, anaerobic and using argon gas protection, with 100 molar part 2- aminobenzonitrile compounds and excessive two
Carbonoxide is raw material, in 10 molar partsUnder catalysis with 5 molar part DBU, 100 DEG C, normal pressure, in diformazan
6-36h is reacted in base sulfoxide.
9. preparation method according to claim 1 or 2, it is characterised in that
R is selected from (C1-C4)-alkyl, OR3、F、Cl、Br、I、NR4R5;
R3Selected from (C1-C4)-alkyl;
R4、R5(C is selected from independently from each other1-C4)-alkyl.
10. preparation method according to claim 1 or 2, it is characterised in that
The 2- aminobenzonitrile compounds are selected from
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