CN111777564B - 一种在水相中光催化醇氧化合成喹唑啉酮化合物的方法 - Google Patents
一种在水相中光催化醇氧化合成喹唑啉酮化合物的方法 Download PDFInfo
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- -1 quinazolinone compound Chemical class 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 14
- 239000008346 aqueous phase Substances 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 6
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 3
- ZYHQGITXIJDDKC-UHFFFAOYSA-N 2-[2-(2-aminophenyl)ethyl]aniline Chemical group NC1=CC=CC=C1CCC1=CC=CC=C1N ZYHQGITXIJDDKC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 36
- 239000007787 solid Substances 0.000 description 33
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical compound NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- VDULOAUXSMYUMG-UHFFFAOYSA-N 2-phenyl-1h-quinazolin-4-one Chemical compound N=1C2=CC=CC=C2C(O)=NC=1C1=CC=CC=C1 VDULOAUXSMYUMG-UHFFFAOYSA-N 0.000 description 11
- AVRPFRMDMNDIDH-UHFFFAOYSA-N 1h-quinazolin-2-one Chemical class C1=CC=CC2=NC(O)=NC=C21 AVRPFRMDMNDIDH-UHFFFAOYSA-N 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 235000019445 benzyl alcohol Nutrition 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 6
- QMNUDYFKZYBWQX-UHFFFAOYSA-N 1H-quinazolin-4-one Chemical class C1=CC=C2C(=O)N=CNC2=C1 QMNUDYFKZYBWQX-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 4
- NWZIAOBMRQYTTD-UHFFFAOYSA-N 2-amino-5-methoxybenzamide Chemical compound COC1=CC=C(N)C(C(N)=O)=C1 NWZIAOBMRQYTTD-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
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- 239000012071 phase Substances 0.000 description 3
- MDRBCQOOJMXHOC-UHFFFAOYSA-N 2-(2-aminophenyl)-1h-quinazolin-4-one Chemical compound NC1=CC=CC=C1C1=NC(=O)C2=CC=CC=C2N1 MDRBCQOOJMXHOC-UHFFFAOYSA-N 0.000 description 2
- QACWURALMROYCA-UHFFFAOYSA-N 2-(4-ethylphenyl)-1h-quinazolin-4-one Chemical compound C1=CC(CC)=CC=C1C1=NC2=CC=CC=C2C(=O)N1 QACWURALMROYCA-UHFFFAOYSA-N 0.000 description 2
- HETSSARHFAGODR-UHFFFAOYSA-N 2-(4-methoxyphenyl)-1H-quinazolin-4-one Chemical compound C1=CC(OC)=CC=C1C1=NC(=O)C2=CC=CC=C2N1 HETSSARHFAGODR-UHFFFAOYSA-N 0.000 description 2
- UTEHUKGJDLVHIH-UHFFFAOYSA-N 2-(4-methylphenyl)-1h-quinazolin-4-one Chemical compound C1=CC(C)=CC=C1C1=NC(=O)C2=CC=CC=C2N1 UTEHUKGJDLVHIH-UHFFFAOYSA-N 0.000 description 2
- PDSXUXCWTDUVSZ-UHFFFAOYSA-N 2-(4-nitrophenyl)-1h-quinazolin-4-one Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1=NC(=O)C2=CC=CC=C2N1 PDSXUXCWTDUVSZ-UHFFFAOYSA-N 0.000 description 2
- UNZNFBNEWJIFGH-UHFFFAOYSA-N 2-(5-methylfuran-2-yl)-1h-quinazolin-4-one Chemical compound O1C(C)=CC=C1C1=NC(=O)C2=CC=CC=C2N1 UNZNFBNEWJIFGH-UHFFFAOYSA-N 0.000 description 2
- LHAJKJQNMKXZSZ-UHFFFAOYSA-N 2-amino-5-bromobenzamide Chemical compound NC(=O)C1=CC(Br)=CC=C1N LHAJKJQNMKXZSZ-UHFFFAOYSA-N 0.000 description 2
- QLWDRAMFFJADEJ-UHFFFAOYSA-N 2-pyridin-2-yl-1h-quinazolin-4-one Chemical compound N1C2=CC=CC=C2C(=O)N=C1C1=CC=CC=N1 QLWDRAMFFJADEJ-UHFFFAOYSA-N 0.000 description 2
- SVVNZCGMBNAQFW-UHFFFAOYSA-N 2-thiophen-2-yl-1h-quinazolin-4-one Chemical compound N1C2=CC=CC=C2C(=O)N=C1C1=CC=CS1 SVVNZCGMBNAQFW-UHFFFAOYSA-N 0.000 description 2
- OVEISJPVPHWEHR-UHFFFAOYSA-N 6-bromo-1h-quinazolin-4-one Chemical compound N1C=NC(=O)C2=CC(Br)=CC=C21 OVEISJPVPHWEHR-UHFFFAOYSA-N 0.000 description 2
- NXSZVAPNPHKIKA-UHFFFAOYSA-N 6-bromo-2-phenyl-1h-quinazolin-4-one Chemical compound N1C(=O)C2=CC(Br)=CC=C2N=C1C1=CC=CC=C1 NXSZVAPNPHKIKA-UHFFFAOYSA-N 0.000 description 2
- NOFVNLZQAOGUIT-UHFFFAOYSA-N 6-methoxy-1h-quinazolin-4-one Chemical compound N1=CNC(=O)C2=CC(OC)=CC=C21 NOFVNLZQAOGUIT-UHFFFAOYSA-N 0.000 description 2
- SRHTXPWEIWVHEE-UHFFFAOYSA-N 6-methoxy-2-(4-methoxyphenyl)-1h-quinazolin-4-one Chemical compound C1=CC(OC)=CC=C1C1=NC(=O)C2=CC(OC)=CC=C2N1 SRHTXPWEIWVHEE-UHFFFAOYSA-N 0.000 description 2
- UHSQXWSTFPABAF-UHFFFAOYSA-N 6-methoxy-2-phenyl-1h-quinazolin-4-one Chemical compound N=1C(=O)C2=CC(OC)=CC=C2NC=1C1=CC=CC=C1 UHSQXWSTFPABAF-UHFFFAOYSA-N 0.000 description 2
- MOBNCKURXDGQCB-UHFFFAOYSA-N 6-nitro-1h-quinazolin-4-one Chemical compound N1C=NC(=O)C2=CC([N+](=O)[O-])=CC=C21 MOBNCKURXDGQCB-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
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- YSLBFFIVJGJBSA-UHFFFAOYSA-N (4-ethylphenyl)methanol Chemical compound CCC1=CC=C(CO)C=C1 YSLBFFIVJGJBSA-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
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- SOBQOVZAFJDEJI-UHFFFAOYSA-N 2-amino-5-nitrobenzamide Chemical compound NC(=O)C1=CC([N+]([O-])=O)=CC=C1N SOBQOVZAFJDEJI-UHFFFAOYSA-N 0.000 description 1
- ONQBUHWENXKHHP-UHFFFAOYSA-N 2-phenyl-3,4-dihydro-1h-isoquinoline Chemical compound C1CC2=CC=CC=C2CN1C1=CC=CC=C1 ONQBUHWENXKHHP-UHFFFAOYSA-N 0.000 description 1
- PBCURFNSKTTYGF-UHFFFAOYSA-N 3-amino-6-bromopyrazine-2-carboxamide Chemical compound NC(=O)C1=NC(Br)=CN=C1N PBCURFNSKTTYGF-UHFFFAOYSA-N 0.000 description 1
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 1
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 description 1
- FNEJQOIAGPBETK-UHFFFAOYSA-N 5-methylfuran-2-ol Chemical compound CC1=CC=C(O)O1 FNEJQOIAGPBETK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- QJQYPZZUKLQGGT-UHFFFAOYSA-N methyl hypobromite Chemical compound COBr QJQYPZZUKLQGGT-UHFFFAOYSA-N 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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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
- C07D239/86—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in position 4
- C07D239/88—Oxygen atoms
- C07D239/91—Oxygen atoms with aryl or aralkyl radicals attached in position 2 or 3
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D475/00—Heterocyclic compounds containing pteridine ring systems
- C07D475/02—Heterocyclic compounds containing pteridine ring systems with an oxygen atom directly attached in position 4
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
Description
技术领域
本发明属于喹唑啉酮化合物合成技术领域,具体涉及一种在水相中光催化醇氧化合成喹唑啉酮化合物的方法。
背景技术
喹唑啉酮类化合物是一类十分重要含氮苯并杂环化合物,其广泛存在于自然界和生物体中,并且在化学、生物学和工业方面有广泛应用,很多天然化合物以及医药、农药和一些重要的化工产品都具有喹唑啉酮类化合物骨架。此外其在医药方面已经显示出巨大的应用价值。由于喹唑啉酮化合物结构的多样性,所以喹唑啉酮化合物具有非常广阔的应用前景,是当前药物研发中的热点。特别是对4(3H)喹唑啉酮类衍生物的结构合成和修饰。建立简单、高效的合成喹唑啉酮衍生物的方法显得十分必要,目前报道的喹唑啉酮类化合物的合成方法较多,这些方法各有优缺点。在化学计量或使用大量强氧化剂 (如KMnO4、MnO2、DDQ或t-BuOOH等)条件下的邻氨基苯甲酰胺与醛/酮直接环合是最常见的合成喹唑啉酮类化合物的方法,但是在大多数情况下,反应通常在高温下进行,这不利于工业化生产。另一个策略是使用更温和和易得的醇作为起始原料。该反应通过两步氧化途径进行,首先将醇氧化为醛,然后与2-氨基苯甲酰胺偶联形成胺类衍生物,最终氧化为喹唑啉酮。此催化体系下需要高活性和高选择性的催化剂,因为该反应涉及在一锅中同时脱氢C-H和N-H键。尽管这些方法导致了产物的良好形成,但反应涉及到贵金属催化剂的高负载、有毒溶剂、危险副产物或操作的复杂性。因此,从可持续化学的观点出发,开发一种环境友好条件下合成喹唑啉酮的新策略是非常必要的。
可见光催化体系具有反应条件温和、高效绿色、能耗低,产物选择性高以及避免使用一些强氧化剂和还原性物质的优点,其不仅可以解决日益严重的能源问题,也更符合现代绿色化学合成理念,为有机合成注入新活力。在大多数的C—N键活化反应中,通常使用有毒的有机溶剂,而水作为一种廉价、无毒、蕴藏丰富的介质来代替毒性大、价格昂贵的有机溶剂,是符合当今倡导的“绿色”化学理念,由于反应底物和催化剂的水溶性,对水的敏感性,以及产物的分离纯化等问题,探索水相中光照条件下的可控C—N键的功能化反应,发展绿色、高效的合成方法,符合当今绿色化学主题,在理论和实际应用上更具有重要的科学意义。可见光催化在药物合成和功能分子结构修饰等方面显示出了较高的应用价值。2014年,Wu课题组通过使用钴肟催化剂[Co(dmgH)2Cl2]代替了贵金属催化剂G-RuO2,以eosin Y为光敏催化剂成功实现了均相体系的N-苯基四氢异喹啉和吲哚的交叉偶联反应,产物收率最高达98%。研究表明有机溶剂和水对反应的进行都很重要。尽管这一领域已取得了一些进展,但是目前并没有可见光催化醇氧化制备喹唑啉酮化合物的相关研究。
发明内容
发明目的:针对上述技术问题,本发明提供了一种在水相中光催化醇氧化合成喹唑啉酮化合物的方法。
技术方案:为了达到上述发明目的,本发明所采用的技术方案如下:
一种在水相中光催化醇氧化合成喹唑啉酮化合物的方法,包括如下步骤:以式(I)化合物和式(II)化合物为原料,以水作为溶剂,加入可见光催化剂,在碱和可见光条件下进行反应,得到所述喹唑啉酮化合物(III);
其中,R1为H、C1-C4烷氧基、卤素或硝基;R2为H、取代或非取代的苯基、2- 吡啶基、2-噻吩基或5-甲基呋喃基;
所述取代的苯基是被氨基、硝基、C1-C4烷基或C1-C4烷氧基取代的苯基。
优选,所述R1位于苯环上氨基的对位。
作为本发明的优选方案,所述R1为氨基对位的H、甲氧基、溴或硝基;R2为H、苯基、2-氨基苯基、对硝基苯基、对甲基苯基、对甲氧基苯、对乙基苯基、2-吡啶基、 2-噻吩基或5-甲基呋喃基。
作为本发明的优选方案,所述可见光催化剂选自KI。
作为本发明的优选方案,所述碱选自无机碱或有机碱,优选无机碱;所述无机碱选自氢氧化钠、碳酸铯、磷酸钾、氢氧化钾,优选氢氧化钠;
作为本发明的优选方案,所述可见光的光源选自LED或者CFL光源,优选40W LED光源。
作为本发明的优选方案,所述式(I)化合物与式(II)化合物的摩尔比为1∶(1-10)。
作为本发明的优选方案,所述式(I)化合物与可见光催化剂的摩尔比为1∶(0.01-0.5),优选1∶0.2;所述式(I)化合物与碱的摩尔比为1∶(1-10),优选1∶4。
作为本发明的优选方案,所述式(I)化合物的浓度选自0.1至0.9mol/L,优选为0.3至0.4mol/L。
作为本发明的优选方案,所述反应的温度为20-200℃,优选20-30℃;反应的时间为10-24小时,优选12小时。
在本发明方法中,作为溶剂的水,其用量可在宽的范围内变化。
本发明最优选的反应流程如下所示:
R1为氨基对位的H、甲氧基、溴或硝基。R2为H、苯基、2-氨基苯基、对硝基苯基、对甲基苯基、对甲氧基苯、对乙基苯基、2-吡啶基、2-噻吩基或5-甲基呋喃基。
本发明是在温和的可见光催化体系中,以2-氨基苯甲酰胺和醇为原料,在水相中高效合成一系列喹唑啉酮衍生物的反应,为喹唑啉酮类化合物的合成提供了一种简便经济的方法。
技术效果:本发明是一种环境友好,操作简便,安全便宜,高效的制备喹唑啉酮化合物的方法。与现有技术相比,此方法不但能够适用大量的官能团,产率高,副产物少,而且操作简单,安全,成本低廉,环保。
附图说明
图1为本发明实施例1中2-苯基喹唑啉-4(3H)-酮的1H NMR图;
图2为本发明实施例1中2-苯基喹唑啉-4(3H)-酮的13C NMR图;
具体实施方式
以下通过实例对本发明做进一步详细阐述。
实施例1:
2-苯基喹唑啉-4(3H)-酮:
在10mL的圆底烧瓶中加入2-氨基苯甲酰胺(0.5mmol),苯甲醇(0.6mmol),KI(0.2equiv.),NaOH(2mmol)和溶剂H2O(2mL)。反应液在一个40W的白光LED灯下(距离反应瓶5cm)室温在光反应器内搅拌12h,应用TLC检测。反应完全后,减压蒸馏,粗产品通过柱层析分离纯化[V(乙酸乙酯):V(石油醚)=1:3]得到目标产物,产率91%.目标产物通过1H NMR,13CNMR和质谱进行结构表征。2-苯基喹唑啉-4(3H)-酮:白色固体; m.p.232-234℃;1H NMR(500MHz,DMSO-d6)δ12.56(s,1H),8.24–8.11(m,3H),7.83 (t,J=7.3Hz,1H),7.75(d,J=8.0Hz,1H),7.55(ddd,J=21.1,13.9,7.1Hz,4H).13C NMR (125MHz,DMSO-d6)δ162.77,152.81,149.13,135.06,133.17,131.85,129.07,128.22, 127.89,127.04,126.32,121.41.MS(EI,m/z):222[M+]。
实施例2:
2-(4-硝基苯基)喹唑啉-4(3H)-酮:制备方法同实施例1,加入4-硝基苯甲醇(0.6mmol),得黄色固体,产率82%。2-(4-硝基苯基)喹唑啉-4(3H)-酮:黄色固体;m.p.>300℃;1H NMR(400MHz,DMSO-d6)δ8.07(dd,J=8.0,1.1Hz,2H),7.86(dd,J=7.7,1.6Hz,2H),7.60(td,J=7.7,1.1Hz,2H),7.46(td,J=7.8,1.6Hz,2H).13C NMR(100MHz,DMSO-d6) δ147.2,145.4,139.8,135.1,135.1,129.2,123.0,120.1,119.6,109.8,109.1,100.5.MS(EI, m/z):267[M+].
实施例3:
2-(2-吡啶基)喹唑啉-4(3H)-酮:制备方法同实施例1,加入2-羟甲基吡啶(0.6mmol),得无色固体,产率78%。2-(2-吡啶基)喹唑啉-4(3H)-酮:无色固体;m.p.167-170℃;1H NMR(400MHz,CDCl3)δ10.93(s,1H),8.60(dd,J=33.8,6.0Hz,2H),8.33(d,J=7.8Hz, 1H),7.90-7.74(m,3H),7.51-7.43(m,2H).13C NMR(100MHz,CDCl3)δ161.5,149.2,149.0,148.8,148.5,137.6,134.6,128.1,127.4,126.8,126.3,122.6,122.1.MS(EI,m/z):223 [M+].
实施例4:
2-(4-甲氧基苯基)喹唑啉-4(3H)-酮:制备方法同实施例1,加入4-甲氧基苯甲醇(0.6 mmol),得黄色固体,产率84%。2-(4-甲氧基苯基)喹唑啉-4(3H)-酮:黄色固体;m.p.248-250℃;1H NMR(400MHz,DMSO-d6)δ12.42(s,1H),8.20-8.18(m,2H),8.14-8.12 (m,1H),7.83-7.79(m,1H),7.71-7.69(m,1H),7.50-7.46(m,1H),7.09(d,J=9.0Hz,2H), 3.85(s,3H).13C NMR(100MHz,DMSO-d6)δ162.3,161.9,151.8,148.9,134.5,129.5, 127.3,126.1,125.8,124.8,120.7 114.1,55.6.MS(EI,m/z):252[M+].
实施例5:
2-(2-氨基苯基)喹唑啉-4(3H)-酮:制备方法同实施例1,加入2-氨基苯甲醇(0.6mmol),得白色固体,产率72%。2-(2-氨基苯基)喹唑啉-4(3H)-酮:白色固体;m.p.225-227℃;1H NMR(400MHz,DMSO-d6)δ7.73(s,1H),7.53(dd,J=8.0,1.6Hz,1H),7.13(ddd,J=8.4,7.0,1.5Hz,1H),7.07(s,1H),6.68(dd,J=8.3,1.2Hz,1H),6.57(s,2H),6.50-6.43(m,1H).13C NMR(100MHz,DMSO-d6)δ184.0,181.9,171.8,162.2,158.6,150.65,143.4, 137.6,132.4,129.2,124.8,116.9,114.8,114.1.MS(EI,m/z):237[M+].
实施例6:
2-(4-甲基苯基)喹唑啉-4(3H)-酮:制备方法同实施例1,加入4-甲基苯甲醇(0.6mmol),得白色固体,产率91%。2-(4-甲基苯基)喹唑啉-4(3H)-酮:白色固体;m.p.263-265℃;1H NMR(400MHz,DMSO-d6)δ12.45(s,1H),8.11(dd,J=20.7,8.0Hz,3H),7.81(t,J=7.4Hz,1H),7.71(d,J=8.2Hz,1H),7.49(t,J=7.6Hz,1H),7.34(d,J=7.9Hz,2H),2.37(s,3H).13C NMR(100MHz,DMSO-d6)δ162.3,152.3,148.7,141.4,134.5,129.9,129.2,127.7,127.3,126.4,125.8,120.9,21.0.MS(EI,m/z):236[M+].
实施例7:
喹唑啉-4(3H)-酮:制备方法同实施例1,加入甲醇(0.6mmol),得白色固体,产率84%。喹唑啉-4(3H)-酮:白色固体;m.p.214-216℃;1H NMR(500MHz,CDCl3)δ12.12 (s,1H),8.27(dd,J=7.9,1.0Hz,1H),8.03(s,1H),7.78-7.74(m,2H),7.45-7.42(m,1H).13C NMR(125MHz,CDCl3)δ162.5,148.8,144.7 135.1,127.4,127.0,126.6,122.8.MS(EI, m/z):146[M+].
实施例8:
6-溴喹唑啉-4(3H)-酮:制备方法同实施例1,加入2-氨基-5-溴苯甲酰胺(0.5mmol),甲醇(0.6mmol),得白色固体,产率71%。6-溴喹唑啉-4(3H)-酮:白色固体;m.p.271-273 ℃;1H NMR(400MHz,CDCl3)δ7.22(dd,J=8.6,7.3Hz,2H),6.78-6.71(m,1H),6.68-6.61(m,2H).13C NMR(100MHz,CDCl3)δ161.0,148.4,143.2,139.6,129.3,129.0,117.3,112.9.MS(EI,m/z):224[M+].
实施例9:
6-溴蝶啶-4(3H)-酮:制备方法同实施例1,加入3-氨基-6-溴吡嗪-2-甲酰胺(0.5mmol),甲醇(0.6mmol),得白色固体,产率68%。6-溴蝶啶-4(3H)-酮:白色固体;m.p.254-255℃;1H NMR(400MHz,DMSO-d6)δ13.00(s,1H),9.16(s,1H),8.41(s,1H).13C NMR(100 MHz,DMSO-d6)δ159.38,154.35,152.76,149.71,137.67,134.7.MS(EI,m/z):226[M+].
实施例10:
2-(2-噻酚基)喹唑啉-4(3H)-酮:制备方法同实施例1,加入2-羟甲基噻吩(0.6mmol),得白色固体,产率80%。2-(2-噻酚基)喹唑啉-4(3H)-酮:白色固体;m.p.223-225℃;1H NMR(400MHz,DMSO-d6)δ8.70(t,J=2.0Hz,1H),8.47-8.22(m,4H),7.79-7.74(m,2H). 13C NMR(100MHz,DMSO-d6)δ166.2,161.2,148.3,138.1,136.2,134.3,130.6,126.4,124.7,122.7,119.2,107.2.MS(EI,m/z):228[M+].
实施例11:
6-甲氧基喹唑啉-4(3H)-酮:制备方法同实施例1,加入2-氨基-5-甲氧基苯甲酰胺(0.5 mmol),甲醇(0.6mmol),得白色固体,产率84%。6-甲氧基喹唑啉-4(3H)-酮:白色固体; m.p.242-243℃;1H NMR(400MHz,DMSO-d6)δ12.19(s,1H),7.98(s,1H),7.62(d,J=8.9Hz,1H),7.50(d,J=2.9Hz,1H),7.41(dd,J=8.9,3.0Hz,1H),3.87(s,3H).13C NMR(100MHz,DMSO-d6)δ160.6,157.7,149.3,143.1,129.0,123.7,123.4,106.0,55.6.MS(EI,m/z):176[M+].
实施例12:
6-硝基喹唑啉-4(3H)-酮:制备方法同实施例1,加入2-氨基-5-硝基苯甲酰胺(0.5mmol),甲醇(0.6mmol),得黄色固体,产率74%。6-硝基喹唑啉-4(3H)-酮:黄色固体;m.p.283-285℃;1H NMR(400MHz,DMSO-d6)δ8.58(s,1H),8.05(d,J=8.8Hz,1H), 7.85(s,2H),6.86(d,J=9.2Hz,1H).13C NMR(100MHz,DMSO-d6)δ168.1,156.1,135.7, 128.7,128.7,116.5,108.5.MS(EI,m/z):191[M+].
实施例13:
2-(4-甲氧基苯基)-6-甲氧基喹唑啉-4(3H)-酮:制备方法同实施例1,加入2-氨基-5- 甲氧基苯甲酰胺(0.5mmol),4-甲氧基苯甲醇(0.6mmol),得白色固体,产率89%。2-(4- 甲氧基苯基)-6-甲氧基喹唑啉-4(3H)-酮:白色固体;m.p.257-259℃;1H NMR(400MHz,DMSO-d6)δ12.36(br,1H),8.16(d,J=6.4Hz,2H),7.70(d,J=8.9Hz,1H),7.52(d,J=7.6Hz,2H),7.39(d,J=7.8Hz,1H),7.17(d,J=7.8Hz,1H),3.90(s,3H),3.80(s,3H).13C NMR(100MHz,DMSO-d6)δ162.1,157.8,150.1,143.2,132.8,131.0,129.6,128.6,127.5,124.1,121.5,118.8,113.9,105.9,55.6,55.2.MS(EI,m/z):282[M+].
实施例14:
2-苯基-6-溴喹唑啉-4(3H)-酮:制备方法同实施例1,加入2-氨基-5-溴苯甲酰胺(0.5 mmol),得白色固体,产率78%。2-苯基-6-溴喹唑啉-4(3H)-酮:白色固体;m.p.286-288 ℃;1H NMR(400MHz,DMSO-d6)δ12.73(s,1H),8.23(d,J=2.3Hz,1H),8.21-8.14(m,2H),7.98(dd,J=8.7,2.4Hz,1H),7.69(d,J=8.7Hz,1H),7.58(m,3H).13C NMR(100 MHz,DMSO-d6)δ165.4,150.6,147.8,137.4,132.6,131.60 130.85,128.6,128.0,127.8,122.7,119.9.MS(EI,m/z):300[M+].
实施例15:
2-苯基-6-甲氧基喹唑啉-4(3H)-酮:制备方法同实施例1,加入2-氨基-5-甲氧基苯甲酰胺(0.5mmol),得白色固体,产率87%。2-苯基-6-甲氧基喹唑啉-4(3H)-酮:白色固体; m.p.246-248℃;1H NMR(400MHz,DMSO-d6)δ12.52(s,1H),8.16(d,J=6.4Hz,2H), 7.70(d,J=8.9Hz,1H),7.56-7.51(m,4H),7.39(d,J=7.8Hz,1H),3.90(s,3H).13C NMR(100MHz,DMSO-d6)δ161.8,158.4,149.8,142.6,132.1,129.8,128.9,128.2,127.1,122.1,121.6,105.7,55.6.MS(EI,m/z):252[M+].
实施例16:
2-(4-乙基苯基)喹唑啉-4(3H)-酮:制备方法同实施例1,加入4-乙基苯甲醇(0.6mmol),得白色固体,产率90%。2-(4-乙基苯基)喹唑啉-4(3H)-酮:白色固体;m.p.282-283℃;1H NMR(400MHz,DMSO-d6)δ12.47(s,1H),8.18-8.10(m,3H),7.83(ddd,J=8.5,7.2,1.5Hz,1H),7.73(d,J=7.6Hz,1H),7.55-7.48(m,1H),7.39(d,J=8.3Hz,2H),2.70(q,J=7.6Hz,2H),1.23(t,J=7.6Hz,3H).13C NMR(100MHz,DMSO-d6)δ162.7,152.7,149.3,148.1,135.1,130.6,128.5,128.3,127.9,126.9,126.3,121.4,28.5,15.8.MS(EI,m/z):250 [M+].
实施例17:
2-(5-甲基呋喃基)喹唑啉-4(3H)-酮:制备方法同实施例1,加入5-甲基-2-羟基呋喃(0.6 mmol),得白色固体,产率81%。2-(5-甲基呋喃基)喹唑啉-4(3H)-酮:白色固体;m.p. 273-276℃;1H NMR(400MHz,DMSO-d6)δ12.37(s,1H),8.11(dd,J=7.9,1.2Hz,1H),7.80(ddd,J=8.5,7.2,1.6Hz,1H),7.69(d,J=7.7Hz,1H),7.56(d,J=3.4Hz,1H),7.50–7.44(m,1H),6.38(dd,J=3.4,0.9Hz,1H),2.41(s,3H).13C NMR(100MHz,DMSO-d6)δ 162.1,156.6,149.3,144.9,144.4,135.1,127.6,126.7,126.4,121.5,116.3,109.4,14.0.MS(EI,m/z):226[M+].
实施例18:
2-苯基喹唑啉-4(3H)-酮:在10mL的圆底烧瓶中加入2-氨基苯甲酰胺(0.5mmol),苯甲醇(0.6mmol),KI(0.2equiv.),KOH(2mmol)和溶剂H2O(2mL)。反应液在一个40 W的白光LED灯下(距离反应瓶5cm)室温在光反应器内搅拌12h,应用TLC检测。反应完全后,减压蒸馏,粗产品通过柱层析分离纯化[V(乙酸乙酯):V(石油醚)=1:3]得到目标产物,产率80%.
实施例19:
2-苯基喹唑啉-4(3H)-酮:在10mL的圆底烧瓶中加入2-氨基苯甲酰胺(0.5mmol),苯甲醇(0.6mmol),KI(0.2equiv.),Cs2CO3(2mmol)和溶剂H2O(2mL)。反应液在一个 40W的白光LED灯下(距离反应瓶5cm)室温在光反应器内搅拌12h,应用TLC检测。反应完全后,减压蒸馏,粗产品通过柱层析分离纯化[V(乙酸乙酯):V(石油醚)=1:3]得到目标产物,产率80%.
实施例20:
2-苯基喹唑啉-4(3H)-酮:在10mL的圆底烧瓶中加入2-氨基苯甲酰胺(0.5mmol),苯甲醇(0.6mmol),KI(0.2equiv.),K3PO4(2mmol)和溶剂H2O(2mL)。反应液在一个 40W的白光LED灯下(距离反应瓶5cm)室温在光反应器内搅拌12h,应用TLC检测。反应完全后,减压蒸馏,粗产品通过柱层析分离纯化[V(乙酸乙酯):V(石油醚)=1:3]得到目标产物,产率62%.
实施例21:
2-苯基喹唑啉-4(3H)-酮:在10mL的圆底烧瓶中加入2-氨基苯甲酰胺(0.5mmol),苯甲醇(0.6mmol),KI(0.2equiv.),NaOH(2mmol)和溶剂H2O(2mL)。反应液在一个 40W的白光CFL灯下(距离反应瓶5cm)室温在光反应器内搅拌12h,应用TLC检测。反应完全后,减压蒸馏,粗产品通过柱层析分离纯化[V(乙酸乙酯):V(石油醚)=1:3]得到目标产物,产率73%.
实施例22:
2-苯基喹唑啉-4(3H)-酮:在10mL的圆底烧瓶中加入2-氨基苯甲酰胺(0.5mmol),苯甲醇(0.6mmol),KI(0.2equiv.),NaOH(2mmol)和溶剂H2O(2mL)。反应液在一个 40W的白光LED灯下(距离反应瓶5cm)室温在光反应器内搅拌10h,应用TLC检测。反应完全后,减压蒸馏,粗产品通过柱层析分离纯化[V(乙酸乙酯):V(石油醚)=1:3]得到目标产物,产率78%.
实施例23:
2-苯基喹唑啉-4(3H)-酮:在10mL的圆底烧瓶中加入2-氨基苯甲酰胺(0.5mmol),苯甲醇(0.6mmol),KI(0.2equiv.),NaOH(2mmol)和溶剂H2O(2mL)。反应液在一个 40W的白光LED灯下(距离反应瓶5cm)室温在光反应器内搅拌14h,应用TLC检测。反应完全后,减压蒸馏,粗产品通过柱层析分离纯化[V(乙酸乙酯):V(石油醚)=1:3]得到目标产物,产率90%.
实施例24:
2-苯基喹唑啉-4(3H)-酮:在10mL的圆底烧瓶中加入2-氨基苯甲酰胺(0.5mmol),苯甲醇(0.6mmol),KI(0.2equiv.),NaOH(2mmol)和溶剂H2O(2mL)。反应液在一个 40W的白光LED灯下(距离反应瓶5cm)30℃在光反应器内搅拌12h,应用TLC检测。反应完全后,减压蒸馏,粗产品通过柱层析分离纯化[V(乙酸乙酯):V(石油醚)=1:3]得到目标产物,产率88%。
Claims (8)
2.根据权利要求1所述的在水相中光催化醇氧化合成喹唑啉酮化合物的方法,其特征在于,所述R1位于苯环上氨基的对位。
3.根据权利要求1所述的在水相中光催化醇氧化合成喹唑啉酮化合物的方法,其特征在于,所述R1为氨基对位的H、甲氧基、溴或硝基;R2为H、苯基、2-氨基苯基、对硝基苯基、对甲基苯基、对甲氧基苯、对乙基苯基、2-吡啶基、2-噻吩基或5-甲基呋喃基。
4.根据权利要求1所述的在水相中光催化醇氧化合成喹唑啉酮化合物的方法,其特征在于,所述可见光的光源选自LED或者CFL光源。
5.根据权利要求1所述的在水相中光催化醇氧化合成喹唑啉酮化合物的方法,其特征在于,所述式(I)化合物与式(II)化合物的摩尔比为1:(1-10)。
6.根据权利要求1所述的在水相中光催化醇氧化合成喹唑啉酮化合物的方法,其特征在于,所述式(I)化合物与可见光催化剂的摩尔比为1:(0.01-0.5);所述式(I)化合物与碱的摩尔比为1:(1-10)。
7.根据权利要求1所述的在水相中光催化醇氧化合成喹唑啉酮化合物的方法,其特征在于,所述式(I)化合物的浓度选自0.1至0.9mol/L。
8.根据权利要求1所述的在水相中光催化醇氧化合成喹唑啉酮化合物的方法,其特征在于,所述反应的时间为10-24小时。
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