CN112778219A - Method for preparing 2,4- (1H,3H) -quinazoline diketone compound - Google Patents
Method for preparing 2,4- (1H,3H) -quinazoline diketone compound Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 36
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 4
- GBENMCWJFZFRHG-UHFFFAOYSA-N [C-]#N.NC1=CC=CC=C1 Chemical class [C-]#N.NC1=CC=CC=C1 GBENMCWJFZFRHG-UHFFFAOYSA-N 0.000 claims abstract 2
- SDQJTWBNWQABLE-UHFFFAOYSA-N 1h-quinazoline-2,4-dione Chemical class C1=CC=C2C(=O)NC(=O)NC2=C1 SDQJTWBNWQABLE-UHFFFAOYSA-N 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- -1 2-aminobenzoic cyanide compound Chemical class 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000007789 gas Substances 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 16
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- 241000973497 Siphonognathus argyrophanes Species 0.000 description 12
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical compound NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- UNISSOLHERSZOW-UHFFFAOYSA-N 2-amino-3-fluorobenzonitrile Chemical compound NC1=C(F)C=CC=C1C#N UNISSOLHERSZOW-UHFFFAOYSA-N 0.000 description 1
- ZLCIALUBLCAXPL-UHFFFAOYSA-N 2-amino-5-(trifluoromethyl)benzonitrile Chemical compound NC1=CC=C(C(F)(F)F)C=C1C#N ZLCIALUBLCAXPL-UHFFFAOYSA-N 0.000 description 1
- OATYCBHROMXWJO-UHFFFAOYSA-N 2-amino-5-bromobenzonitrile Chemical compound NC1=CC=C(Br)C=C1C#N OATYCBHROMXWJO-UHFFFAOYSA-N 0.000 description 1
- SRWMPAZUWXLIPG-UHFFFAOYSA-N 2-amino-5-methoxybenzonitrile Chemical compound COC1=CC=C(N)C(C#N)=C1 SRWMPAZUWXLIPG-UHFFFAOYSA-N 0.000 description 1
- OZLMBXPYRDASTP-UHFFFAOYSA-N 2-amino-5-methylbenzonitrile Chemical compound CC1=CC=C(N)C(C#N)=C1 OZLMBXPYRDASTP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 2,4- (1H,3H) -quinazoline diketone compounds, which takes 2-aminobenzene cyanide compounds shown in a formula (1) and carbon dioxide as raw materials to react in 2-hydroxypyridine ionic liquid to obtain 2,4- (1H,3H) -quinazoline diketone compounds shown in a formula (II), and the reaction formula is as follows:
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing 2,4- (1H,3H) -quinazoline diketone compounds.
Background
Carbon dioxide is a main greenhouse gas and is a C1 synthon with a good application prospect, and has attracted extensive attention in the field of organic synthesis. Due to the thermodynamic stability and kinetic inertness of carbon dioxide, it is crucial to develop an effective carbon dioxide activation and subsequent conversion strategy. The ionic liquid has the characteristics of high adjustability, high stability, low vapor pressure, high polarity and low melting point, shows great potential in the aspects of absorbing and activating carbon dioxide, and becomes an ideal organic solvent and catalyst in carbon dioxide conversion.
The 2,4- (1H,3H) -quinazoline diketone derivative is a heterocyclic compound which has important application in the fields of medicines and pesticide chemicals. The traditional synthesis mode is to synthesize the material by using anthranilic acid and urea or anthranilamide and phosgene. In recent years, there are successively reports of methods for synthesizing 2,4- (1H,3H) -quinazolinedione by using ionic liquid to catalyze carbon dioxide and 2-aminobenzonitrile (Angew. chem. int. Ed.,2014,53: 5922-. However, most of these ionic liquid systems require high temperature and high pressure to achieve good yield, or the ionic liquid synthesis is complicated and needs further improvement.
Disclosure of Invention
Aiming at the technical problems in the preparation process of 2,4- (1H,3H) -quinazoline diketone in the prior art, the invention provides a method for synthesizing the compound by using 2-hydroxypyridine type ionic liquid and taking carbon dioxide and 2-aminobenzonitrile as raw materials under normal pressure.
The method for preparing the 2,4- (1H,3H) -quinazoline diketone compound is characterized in that the 2-aminobenzene cyanide compound shown in the formula (1) and carbon dioxide are used as raw materials and react in 2-hydroxypyridine ionic liquid to obtain the 2,4- (1H,3H) -quinazoline diketone compound shown in the formula (II), and the reaction formula is as follows:
in the formula (1) and the formula (II), x represents the number of substituent groups R on a benzene ring, and x is 1-4; the substituent R at different substitution positions on the benzene ring is the same or different; the substituent R is selected from H, C1-C4 alkyl, halogen, C1-C4 alkoxy or trifluoromethyl.
The method for preparing the 2,4- (1H,3H) -quinazoline diketone compound is characterized in that the structural formula of the 2-hydroxypyridine type ionic liquid is selected from one of the following:
the method for preparing the 2,4- (1H,3H) -quinazoline diketone compound is characterized in that the molar ratio of the 2-aminobenzene cyanide compound shown in the formula (1) to the 2-hydroxypyridine ionic liquid is 1: 1-10, and preferably 1: 2-4.
The method for preparing the 2,4- (1H,3H) -quinazoline diketone compound is characterized in that the reaction temperature is 30-150 ℃, and the reaction time is 2-48 hours.
The method for preparing the 2,4- (1H,3H) -quinazoline diketone compound is characterized in that CO is generated during reaction2The pressure is 0.1MPa to 2 MPa.
Compared with the prior art, the invention has the advantages that: the ionic liquid used in the invention has a simpler synthesis method, and can be prepared by stirring 2-hydroxypyridine and organic base in an ethanol solvent at room temperature. When the ionic liquid is applied to the reaction for preparing the 2,4- (1H,3H) -quinazoline diketone compound, the reaction condition is mild, the separation and purification process of the product is simple, the product yield is high, and the application range of the substrate is wide.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
In example 1, the 2-hydroxypyridine ionic liquids used in the present invention are all prepared by stirring 2-hydroxypyridine and organic base in ethanol, and the specific steps are as follows:
experiment one: weighing 2-hydroxypyridine (1mol) and 1, 8-diazabicycloundecen-7-ene (DBU, 3mol), adding into a 50mL flask, adding 20mL absolute ethyl alcohol, stirring at room temperature for 24 hours, evaporating and concentrating to remove an ethanol solvent to obtain [ HDBU ] [2-OP ], a yellow liquid and a yield of 100%.
Experiment two: weighing 2-hydroxypyridine (1mol) and tetramethylammonium hydroxide (25% aqueous solution, 3mol), adding into a 50mL flask, adding 20mL absolute ethyl alcohol, stirring at room temperature for 24 hours, evaporating, concentrating and removing an ethanol solvent to obtain [ N ]1111][2-OP]Yellow liquid, yield 100%.
Experiment three: weighing 2-hydroxypyridine (1mol) and tetramethylguanidine (3mol), adding into a 50mL flask, adding 20mL absolute ethyl alcohol, stirring at room temperature for 24 hours, evaporating, concentrating and removing an ethanol solvent to obtain [ HTMG ] [2-OP ], a yellow liquid and a yield of 100%.
Experiment four: weighing 2-hydroxypyridine (1mol) and choline (48-50% aqueous solution, 3mol) and adding into a 50mL flask, adding 20mL absolute ethyl alcohol, stirring at room temperature for 24 hours, and evaporating and concentrating to remove an ethanol solvent to obtain [ Ch ] [2-OP ] as a yellow liquid with the yield of 100%.
Experiment five: weighing 2-hydroxypyridine (1mol) and tetrabutylammonium hydroxide (50% aqueous solution, 3mol), adding into a 50mL flask, adding 20mL anhydrous ethanol, stirring at room temperature for 24 hours, evaporating and concentrating to remove ethanol solvent to obtain [ N ]4444][2-OP]Yellow liquid, yield 100%.
Example 2:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
weighing 2-aminobenzonitrile (1mmol) and [ HDBU ]][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 8 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the objective product in a yield of 77.8%,1H NMR(400MHz,DMSO-d6)δ:11.23(s,1H, NH),11.17(s,1H,NH),7.89(dd,1H,Ar-H),7.65-7.62(m,1H,Ar-H),7.19-7.16(m, 2H,Ar-H)。
example 3:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
weighing 2-aminobenzonitrile (1mmol) and [ N ]1111][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the objective product in 62.6% yield.
Example 4:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
weighing 2-aminobenzonitrile (1mmol) and [ N ]4444][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the objective product in a yield of 76.3%.
Example 5:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
weighing 2-aminobenzonitrile (1mmol) and [ HTMG ]][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the objective product in a yield of 72.8%.
Example 6:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
weighing 2-aminobenzonitrile (1mmol) and [ Ch][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the objective product in 89.5% yield.
Example 7:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
weighing 2-aminobenzonitrile (1mmol) and [ Ch][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 60 ℃ for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the objective product in a yield of 61.9%.
Example 8:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
weighing 2-aminobenzonitrile (1mmol) and [ Ch][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), reaction at 100 ℃ for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the objective product in 82.2% yield.
Example 9:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
weighing 2-aminobenzonitrile (1mmol) and [ Ch][2-OP](3mmol) to a 20mL reaction tube, the mouth of the reaction tube is connected with carbon dioxideUnder the protection of carbon dioxide gas bag (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the objective product in 89.1% yield.
Example 10:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
weighing 2-aminobenzonitrile (1mmol) and [ Ch][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 9 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the objective product in 92.3% yield.
Example 11:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
5-methoxy-2-aminobenzonitrile (1mmol) and [ HDBU ] were weighed][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 8 hours. After the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), dried to obtain the desired product in 85.9% yield,1H NMR(400MHz,DMSO-d6) δ:11.28(s,1H,NH),11.03(s,1H,NH),7.33-7.27(m,2H,Ar-H),7.12(d,1H,Ar-H), 3.79(s,3H,CH3)。
example 12:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
5-trifluoromethyl-2-aminobenzonitrile (1mmol) and [ HDBU ] were weighed][2-OP](3mmol) to a 20mL reaction tube, the mouth of which is connectedConnecting with a gas bag filled with carbon dioxide under the protection of the gas bag (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 8 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the desired product in 83.2% yield,1HNMR(500MHz, DMSO-d6)δ:11.49(s,2H,NH),8.10(d,1H,Ar-H),7.97(dd,1H,Ar-H),7.33(d,1H, Ar-H)。
example 13:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
5-methyl-2-aminobenzonitrile (1mmol) and [ HDBU ] were weighed][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 8 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), and dried to obtain the desired product in a yield of 75.8%,1H NMR(400MHz,DMSO-d6) δ:11.15(s,2H,NH),7.69(s,1H,Ar-H),7.46(dd,1H,Ar-H),7.07(d,1H,Ar-H), 2.32(s,3H,CH3)。
example 14:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
3-fluoro-2-aminobenzonitrile (1mmol) and [ HDBU ] were weighed][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 8 hours. After the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), dried to obtain the desired product in a yield of 70.1%,1H NMR(400MHz,DMSO-d6) δ:11.44(s,1H,NH),11.29(s,1H,NH),7.73(d,1H,Ar-H),7.59-7.55(m,1H,Ar-H), 7.19-7.15(m,1H,Ar-H)。
example 15:
this example provides a method for preparing 2,4- (1H,3H) -quinazolinedione compounds, which includes the following steps:
5-bromo-2-aminobenzonitrile (1mmol) and [ HDBU ] were weighed][2-OP](3mmol) to 20mL reaction tube, the tube mouth of the reaction tube is connected with a gas bag filled with carbon dioxide, and the reaction tube is protected by the gas bag of carbon dioxide (CO in the reaction process)2Pressure about 0.1MPa), and reaction at 80 ℃ for 8 hours. After the reaction, the reaction mixture was cooled to room temperature, 10mL of water was added to precipitate a white solid, which was filtered, washed with water (10 mL. times.3), washed with methyl t-butyl ether (10 mL. times.3), dried to obtain the desired product in a yield of 70.5%,1H NMR(400MHz,DMSO-d6) δ:11.27(s,2H,NH),7.94(d,1H,Ar-H),7.79(dd,1H,Ar-H),7.12(d,1H,Ar-H)。
the reactants and reaction products described in examples 2-15 have the following structures:
the statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (5)
1. A method for preparing 2,4- (1H,3H) -quinazoline diketone compounds is characterized in that 2-aminobenzene cyanide compounds shown in a formula (1) and carbon dioxide are used as raw materials and react in 2-hydroxypyridine ionic liquid to obtain 2,4- (1H,3H) -quinazoline diketone compounds shown in a formula (II), and the reaction formula is as follows:
in the formula (1) and the formula (II), x represents the number of substituent groups R on a benzene ring, and x is 1-4; the substituent R at different substitution positions on the benzene ring is the same or different; the substituent R is selected from H, C1-C4 alkyl, halogen, C1-C4 alkoxy or trifluoromethyl.
2. The method of claim 1, wherein the 2-hydroxypyridine ionic liquid has a structural formula selected from the group consisting of:
3. the method for preparing 2,4- (1H,3H) -quinazoline dione compounds according to claim 1, wherein the molar ratio of the 2-aminobenzoic cyanide compound shown in formula (1) to the 2-hydroxypyridine ionic liquid is 1: 1-10, preferably 1: 2-4.
4. The process for preparing 2,4- (1H,3H) -quinazolinediones according to claim 1, wherein the reaction temperature is 30 ℃ to 150 ℃ and the reaction time is 2 hours to 48 hours.
5. The process for preparing 2,4- (1H,3H) -quinazolinediones according to claim 1, wherein the CO is present during the reaction2The pressure is 0.1MPa to 2 MPa.
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| CN116574226A (en) * | 2023-07-06 | 2023-08-11 | 珠海华大浩宏新材料有限公司 | Bio-based acidic color fixing agent and preparation method and application thereof |
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| CN116574226B (en) * | 2023-07-06 | 2023-09-05 | 珠海华大浩宏新材料有限公司 | Bio-based acidic color fixing agent and preparation method and application thereof |
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