CN113185468B - Method for synthesizing quinazolinone through photocatalysis - Google Patents
Method for synthesizing quinazolinone through photocatalysis Download PDFInfo
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- CN113185468B CN113185468B CN202110477712.2A CN202110477712A CN113185468B CN 113185468 B CN113185468 B CN 113185468B CN 202110477712 A CN202110477712 A CN 202110477712A CN 113185468 B CN113185468 B CN 113185468B
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- quinazolinone
- anthranilamide
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- 238000000034 method Methods 0.000 title claims abstract description 31
- AVRPFRMDMNDIDH-UHFFFAOYSA-N 1h-quinazolin-2-one Chemical compound C1=CC=CC2=NC(O)=NC=C21 AVRPFRMDMNDIDH-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 8
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical compound NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 70
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000011941 photocatalyst Substances 0.000 claims abstract description 9
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 84
- 239000002904 solvent Substances 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- -1 3, 4-dimethylphenyl Chemical group 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 claims description 2
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000002541 furyl 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
- 125000005059 halophenyl group Chemical group 0.000 claims description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 120
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 84
- 239000007787 solid Substances 0.000 description 29
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 28
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 28
- 238000004440 column chromatography Methods 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 238000002844 melting Methods 0.000 description 28
- 230000008018 melting Effects 0.000 description 28
- 239000003208 petroleum Substances 0.000 description 28
- 239000011541 reaction mixture Substances 0.000 description 28
- 238000002390 rotary evaporation Methods 0.000 description 28
- 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 19
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IXMXCFSRQIHRHB-UHFFFAOYSA-N 2-(4-fluorophenyl)-1h-quinazolin-4-one Chemical compound C1=CC(F)=CC=C1C1=NC(=O)C2=CC=CC=C2N1 IXMXCFSRQIHRHB-UHFFFAOYSA-N 0.000 description 3
- FIEYHAAMDAPVCH-UHFFFAOYSA-N 2-methyl-1h-quinazolin-4-one Chemical compound C1=CC=C2NC(C)=NC(=O)C2=C1 FIEYHAAMDAPVCH-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- RSKPIJGOGQGETI-UHFFFAOYSA-N 2,3-diphenylquinazolin-4-one Chemical compound C=1C=CC=CC=1C1=NC2=CC=CC=C2C(=O)N1C1=CC=CC=C1 RSKPIJGOGQGETI-UHFFFAOYSA-N 0.000 description 2
- AUEZMLBIHNUTTI-UHFFFAOYSA-N 2-(2-phenylethyl)-1h-quinazolin-4-one Chemical compound N1C2=CC=CC=C2C(=O)N=C1CCC1=CC=CC=C1 AUEZMLBIHNUTTI-UHFFFAOYSA-N 0.000 description 2
- INWHPBGNSUYRME-UHFFFAOYSA-N 2-(3-bromophenyl)-1h-quinazolin-4-one Chemical compound BrC1=CC=CC(C=2NC(=O)C3=CC=CC=C3N=2)=C1 INWHPBGNSUYRME-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
- MEWDLKFIQDINLZ-UHFFFAOYSA-N 2-cyclohexyl-1h-quinazolin-4-one Chemical compound N1C2=CC=CC=C2C(=O)N=C1C1CCCCC1 MEWDLKFIQDINLZ-UHFFFAOYSA-N 0.000 description 2
- PWLHUQRFCZDOQK-UHFFFAOYSA-N 2-naphthalen-1-yl-1h-quinazolin-4-one Chemical compound C1=CC=C2C(C3=NC(C4=CC=CC=C4N3)=O)=CC=CC2=C1 PWLHUQRFCZDOQK-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
- FPQXJSZKSFDUFR-UHFFFAOYSA-N 3-methyl-2-phenylquinazolin-4-one Chemical compound N=1C2=CC=CC=C2C(=O)N(C)C=1C1=CC=CC=C1 FPQXJSZKSFDUFR-UHFFFAOYSA-N 0.000 description 2
- KINPFEIFSJMYNL-UHFFFAOYSA-N 4-(4-oxo-1h-quinazolin-2-yl)benzonitrile Chemical compound N1C2=CC=CC=C2C(=O)N=C1C1=CC=C(C#N)C=C1 KINPFEIFSJMYNL-UHFFFAOYSA-N 0.000 description 2
- YBGVJFZTKPJHFV-UHFFFAOYSA-N 6-fluoro-2-phenyl-1h-quinazolin-4-one Chemical compound N1C(=O)C2=CC(F)=CC=C2N=C1C1=CC=CC=C1 YBGVJFZTKPJHFV-UHFFFAOYSA-N 0.000 description 2
- DWSBXSUAJILPPH-UHFFFAOYSA-N 7-chloro-2-phenyl-1h-quinazolin-4-one Chemical compound C=1C(Cl)=CC=C(C(N=2)=O)C=1NC=2C1=CC=CC=C1 DWSBXSUAJILPPH-UHFFFAOYSA-N 0.000 description 2
- SQHDRGBPGNFYKA-UHFFFAOYSA-N 7-methyl-2-phenyl-1h-quinazolin-4-one Chemical compound C=1C(C)=CC=C(C(N2)=O)C=1N=C2C1=CC=CC=C1 SQHDRGBPGNFYKA-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- BEUXPBLZGPKLQT-UHFFFAOYSA-N C1(CC=CCC1)C1=NC2=CC=CC=C2C(N1)=O Chemical compound C1(CC=CCC1)C1=NC2=CC=CC=C2C(N1)=O BEUXPBLZGPKLQT-UHFFFAOYSA-N 0.000 description 2
- LQRUAMXCQHSABE-UHFFFAOYSA-N C1=CC=C2C(=O)NC(CCCCCCCCC)=NC2=C1 Chemical compound C1=CC=C2C(=O)NC(CCCCCCCCC)=NC2=C1 LQRUAMXCQHSABE-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- ZZFIIOFXVHZVGK-UHFFFAOYSA-N 2-(3,4-dimethylphenyl)-1h-quinazolin-4-one Chemical compound C1=C(C)C(C)=CC=C1C1=NC2=CC=CC=C2C(=O)N1 ZZFIIOFXVHZVGK-UHFFFAOYSA-N 0.000 description 1
- AKHUKZJZNGHOJU-UHFFFAOYSA-N 2-(4-chlorophenyl)-1h-quinazolin-4-one Chemical compound C1=CC(Cl)=CC=C1C1=NC(=O)C2=CC=CC=C2N1 AKHUKZJZNGHOJU-UHFFFAOYSA-N 0.000 description 1
- RUHKZVAPXHIWJH-UHFFFAOYSA-N 2-amino-4-methylbenzamide Chemical compound CC1=CC=C(C(N)=O)C(N)=C1 RUHKZVAPXHIWJH-UHFFFAOYSA-N 0.000 description 1
- REPZELLBLWMUAB-UHFFFAOYSA-N 2-amino-6-fluorobenzamide Chemical compound NC(=O)C1=C(N)C=CC=C1F REPZELLBLWMUAB-UHFFFAOYSA-N 0.000 description 1
- FDPVTENMNDHFNK-UHFFFAOYSA-N 2-amino-n-phenylbenzamide Chemical compound NC1=CC=CC=C1C(=O)NC1=CC=CC=C1 FDPVTENMNDHFNK-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 1
- IQVAERDLDAZARL-UHFFFAOYSA-N 2-phenylpropanal Chemical compound O=CC(C)C1=CC=CC=C1 IQVAERDLDAZARL-UHFFFAOYSA-N 0.000 description 1
- POQJHLBMLVTHAU-UHFFFAOYSA-N 3,4-Dimethylbenzaldehyde Chemical compound CC1=CC=C(C=O)C=C1C POQJHLBMLVTHAU-UHFFFAOYSA-N 0.000 description 1
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KIMWOULVHFLJIU-UHFFFAOYSA-N N-Methylanthranilamide Chemical compound CNC(=O)C1=CC=CC=C1N KIMWOULVHFLJIU-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000001773 anti-convulsant effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 229960003965 antiepileptics Drugs 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- DCFDVJPDXYGCOK-UHFFFAOYSA-N cyclohex-3-ene-1-carbaldehyde Chemical compound O=CC1CCC=CC1 DCFDVJPDXYGCOK-UHFFFAOYSA-N 0.000 description 1
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
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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
- C07D239/86—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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
- B01J31/0208—Ketones or ketals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C07D239/86—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in position 4
- C07D239/88—Oxygen atoms
-
- 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
- C07D239/86—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in position 4
- C07D239/88—Oxygen atoms
- C07D239/90—Oxygen atoms with acyclic radicals attached in position 2 or 3
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a method for synthesizing quinazolinone through photocatalysis, which takes anthranilamide and aldehyde as raw materials, takes fluorescein as a photocatalyst, takes p-toluenesulfonic acid as an auxiliary catalyst, and performs photocatalytic reaction under the irradiation of visible light to obtain quinazolinone. The invention uses the non-metal catalyst, thus reducing the reaction cost; the reaction conditions are mild, and the reaction can be completed at room temperature; simple operation, short reaction time, simple post-treatment, high product yield and more environmental protection. The method not only has higher academic value, but also has certain industrialization prospect.
Description
Technical Field
The invention relates to a method for synthesizing quinazolinone through photocatalysis, in particular to a method for synthesizing quinazolinone through photocatalysis, which is simple to operate and mild in reaction conditions, and belongs to the technical field of organic synthetic chemistry.
Background
Quinazolinone is an important nitrogen heterocyclic aromatic compound, and has wide biological activity and pharmacological activity, including antibacterial, antiviral, antiinflammatory, anticonvulsant and anticancer properties. In recent decades, various methods for synthesizing quinazolinones have been developed, but most classical methods still generate quinazolinones by oxidation of an intermediate formed by condensation of anthranilamide and an aldehyde. However, these methods for synthesizing quinazolinones require the use ofExcess harmful oxidant (KMnO) 4 CuCl, DDQ and MnO 2 Etc.) or under the combined action of a transition metal catalyst and an oxidant to synthesize the quinazolinone. Longer reaction times and higher reaction temperatures are often required in these synthesis processes. (a) I.Khan, A.Ibrar, N.Abbas and A.Saeed, Eur.J.Med.Chem.76 (2014) 193. K.K.Cook.L.L.Wilson-Lingard, L.M.Risen, T.A.Vickers, R.Ranken, L.B.Blyn, R.Wyatt, P.D.Cook.D.Cook.Ecker, J.Med.Chem.42 (1999) 4705. Buckner 4713, (c) N.J.Liverton, D.J.Armstrong, D.A.Claremmon, D.C.Remy, J.Baldwin, R.J.Lynch, G.Zhang, R.J.1998, Waorg.Saung, Waer, Q.W.M.J.Sch.Sch.R.J.Sy, Q.J.Sy.Z.W.T.T.T.K.L.K.Cook.Cook.Cook.K.K.Cook.K.K.K.K.Cook.K.K.K.Cook.K.K.Cook.K.K.K.K.K.Cook.K.K.K.K.K.Cook.L.L.K.K.K.K.K.K.K.K.Cook.K.K.K.K.K.K.Cook.K.K.K.K.K.K.K.K.K.K.K.K.K.Cook.K.K.K.Cook.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.Cook.K.K.K.K.K.K.Cook.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K., C.S. Quaglitato, W.J. Greenlee, A.A. Patchett, R.S.L. Chang, V.J. Lotti, T.B. Chen, S.A. Scheck, K.A. Faust, S.S. Kivlighn, T.S. Schorn, G.J. Zingaro, P.K.S. Siegl, J.Med. chem.36 (1993) 3207-membered canister 3210, (f) M.M. Aly, Y.A. Mohamed, K.A. El-Bauloki, W.M. Basyoni, S.Y. Abbas, Eur. J.Med.Chem.2010.45 (3373) S.Bayashi, M.ueki, R.Suzuki H. 930, Ishii.J. Cheng.H. Chen.H. Chen.S. Shi.H. Chen.H. Shi.H. Chen.H.103, T.A. Patchett, K.A. Kivli, T.S.S.S.S.S.S. Kivli. Kivli, K.S. Kivli, T.S. Chen, K.S. Kivli, K.S. Shi, J. Chen, J. 36 (H. 103, (7), (3, S. Shi, S. 3, S. Shi, S. Shi, S. 3, S. Shi. 3, S. 3, S. H. 3, S. H. S. H. 3, S. H. 3, S. Shi, S. Shi. Shi, S. Shi. H. Shi, S. H. Shi. H. 3, (7, S. H. S. H. S. H. 3, S. 3, (9, S. 3, S. 3, S. 3, S. H. 3, S. H. D. H. S. H. S. H. S. H. S. H. S. H. S. H., m, Ichikawa, A, Nakagawa, M, Tsuji, chem, phase, Bull, 23 (1975) 1910. 1916, (k) R.J. Abdel-Jalil, H.M. Aldoqum, M.T. Ayuub, W.Voelter, Heterocyles 65 (2005) 2061-, K. Ghandi, Q. Zeng, RSC Adv. 3 (2013) 9325−9329.）
In recent years, with the idea of green chemical atom economy, the use of transition metal catalysts to catalyze organic reactions has received much attention. Among them, the acceptor-free dehydrogenation reaction catalyzed by a transition metal catalyst is an important method for preparing quinazolinone. 2011, Zhou et al reported an iridium catalyst [ Cp IrCl ] 2 ] 2 A method for catalytically synthesizing quinazolinone. The method selects anthranilamide and primary alcohol as raw materials, quinazolinone is obtained with high yield under the action of a catalyst, and H is generated in the reaction process 2 And H 2 O is the only by-product. In 2015, the Li research group utilized a water-soluble catalyst [ Cp Ir (H) 2 O) 3 ][OTf] 2 The quinazolinone is successfully prepared in an aqueous phase by selecting anthranilamide and aldehyde as reactants. Compared with the report of Zhou et al, the method selects water as the solvent to replace the traditional organic solvent, and better meets the requirement of green chemistry. ((a) A. Corma, J. Navas, M.J. Sabat, chem. Rev.12 (2019) 3642-3644, (b) K.W. Dong, Z. Wang, K.L. Ding, J. Am. chem. Soc. 134 (2013) 12474-12477, (c) J.W. Liu, J. Yang, C. Schneider, R. Franke, R. Jackstell, M. Beller, Angel. chem. Int. Ed. 59 (2020) 9032-9040, (d) C.Gnaaparapakasam, D. Millin, Science 341 (2013) 1229712 e) F.Li, L. Lu, P.C. Liu, Org. Lett. 18) 2580-J. 2583, J. Zong, J. Cheg, 2011. J. Sabat, 2011, 7-Cheg, F.L. Lu. 779, (f.J. Sa. Ser. 26, J. Save. J. Save. 2015. 160, P.J. Val. mu. J. Val. Ser. 32-80, J. Val. mu. J. Val. 2015. mu. 35, J. D.32, J. D.D.D.
Although the synthesis of quinazolinones by transition metal catalyzed processes avoids the formation of by-products and improves the atom economy of the reaction, the use of transition metals is inevitably required. Transition metals such as Ir, Ru, and Rh are not only low in reserves on the earth but also expensive, and bring about a certain influence in the separation and purification of products.
Therefore, from the perspective of green organic synthesis, the development of a method for synthesizing quinazolinone under the catalysis of a nonmetal catalyst under mild conditions has important research value and scientific significance.
Disclosure of Invention
The invention aims to provide a method for synthesizing quinazolinone through photocatalysis, which synthesizes quinazolinone through photocatalysis, does not use nonmetal catalysis, has mild reaction conditions, simple operation and environmental protection, and provides a new idea for the synthesis of quinazolinone.
The invention is realized by the following technical scheme:
the quinazolinone provided by the invention has a structure shown in the following formula I:
the method for synthesizing the quinazolinone shown in the formula I comprises the step of obtaining the quinazolinone shown in the formula I through the photocatalytic reaction of anthranilamide shown in the formula II and aldehyde shown in the formula III; the reaction formula is as follows:
further, in the above formula I, formula II and formula III, R 1 Selected from hydrogen, methyl or halogen; r 2 Selected from phenyl, methylphenyl, 3, 4-dimethylphenyl, isopropylphenyl, methoxyphenyl, halophenyl, hydroxyphenyl, cyanophenyl, trifluoromethylphenyl, pyridyl, furyl, naphthyl, phenethyl, cinnamyl, cyclohexenyl, nonyl, cyclohexyl or methyl; r 3 Selected from hydrogen, methyl or phenyl.
Furthermore, the photocatalytic reaction refers to that anthranilamide and aldehyde are subjected to cyclization oxidation reaction under the induction of visible light to obtain quinazolinone. In the photocatalytic reaction, fluorescein is used as a photocatalyst, p-toluenesulfonic acid is used as an auxiliary catalyst, and the photocatalytic reaction is carried out under the irradiation of blue light. The structure of fluorescein is shown below:
further, the molar ratio of anthranilamide to aldehyde is 1: 1.
Further, the photocatalyst is used in an amount of 1 to 3mol%, preferably 2 to 3mol%, based on the anthranilamide.
Further, the p-toluenesulfonic acid is used in an amount of 10 to 30%, preferably 10%, based on the molar amount of anthranilamide.
Further, the blue light can be realized by a blue light lamp, and the power of the blue light lamp is 5-15 w.
Further, the photocatalytic reaction is carried out in the presence of a solvent. The solvent is used for providing a reaction environment, and organic solvents such as acetonitrile, toluene, tetrahydrofuran or ethanol can be selected. The choice of different solvents has an influence on the yield of the reaction, the preferred solvent being acetonitrile. The amount of the solvent may be adjusted as necessary.
Further, in the step (1), the reaction temperature is room temperature, and the reaction time is 2-3 h.
In one embodiment of the present invention, there is provided a specific process for the synthesis of quinazolinones, comprising the steps of: mixing anthranilamide, aldehyde, photocatalyst, p-toluenesulfonic acid and solvent, and reacting the obtained mixture under the irradiation of a 5-15W blue light lamp to obtain quinazolinone.
The invention selects fluorescein as a photocatalyst, and the quinazolinone is synthesized by the cyclization oxidation reaction of anthranilamide and aldehyde under the irradiation of blue light. Compared with the prior art, the method has the following remarkable advantages:
1) the nonmetal catalyst is used, so that the reaction cost is reduced;
2) the reaction conditions are mild, and the reaction can be completed at room temperature;
3) simple operation, short reaction time, simple post-treatment, high product yield and more environmental protection.
4) The method not only has higher academic value, but also has certain industrialization prospect.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the product of example 1.
FIG. 2 is a nuclear magnetic carbon spectrum of the product of example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not to be construed as limiting the scope of the invention. Many modifications, variations and changes in materials, methods and reaction conditions may be made simultaneously with respect to the disclosure herein. All such modifications, variations and changes are intended to fall within the spirit and scope of the present invention.
Example 1 2-phenyl-4-quinazolinone
2-Phenyl-4-quinazolinone
Anthranilamide (27.2 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as white solid (39.1 mg) with the melting point of 237-.
The nuclear magnetic spectrum of the product is shown in figures 1 and 2 and specifically as follows:
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.56 (br s, 1H), 8.19-8.15 (m, 3H), 7.84 (t, J = 7.5 Hz, 1H), 7.76 (d, J = 8.1 Hz, 1H), 7.59-7.51 (m, 4H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 162.3, 152.3, 148.8, 134.6, 131.4, 128.6, 127.8, 127.5, 126.6, 125.9, 121.0, 39.5.
example 2-phenyl-4-quinazolinone
2-Phenyl-4-quinazolinone
Anthranilamide (27.2 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (10.2 mg, 30 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as white solid (39.1 mg) with the melting point of 237-.
Example 3 2-phenyl-4-quinazolinone
2-Phenyl-4-quinazolinone
Anthranilamide (27.2 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (0.7 mg, 1 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as white solid (35.3 mg) with the melting point of 237-.
Example 4 2-phenyl-4-quinazolinone
2-Phenyl-4-quinazolinone
Anthranilamide (27.2 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (2.0 mg, 3 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as white solid (39.2 mg) with the melting point of 237-.
Example 5 2-phenyl-4-quinazolinone
2-Phenyl-4-quinazolinone
Anthranilamide (27.2 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 1 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (the volume ratio of developing agent to petroleum ether/ethyl acetate is =3: 1) as white solid (36.3 mg) with the melting point of 237-.
Example 6 2-phenyl-4-quinazolinone
2-Phenyl-4-quinazolinone
Anthranilamide (27.2 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture was reacted for 3h under the irradiation of a 10 w blue light lamp, after the reaction was completed, the solvent was removed by rotary evaporation, and then pure target compound was obtained as a white solid (39.2 mg) by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1), melting point 237-.
Example 7 2-phenyl-4-quinazolinone
2-Phenyl-4-quinazolinone
Anthranilamide (27.2 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and toluene (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as white solid (24.3 mg) with the melting point of 237-.
Example 8 2-phenyl-4-quinazolinone
2-Phenyl-4-quinazolinone
Anthranilamide (27.2 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and tetrahydrofuran (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as white solid (34.5 mg) with the melting point of 237-.
Example 9 2-phenyl-4-quinazolinone
2-Phenyl-4-quinazolinone
Anthranilamide (27.2 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and ethanol (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (a developing solvent: petroleum ether/ethyl acetate volume ratio is =3: 1) as a white solid (34.9 mg) with a melting point of 237-.
Example 10 2- (4-methylphenyl) -4- [3H ] quinazolinone
2-(p-Tolyl)quinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), 4-methylbenzaldehyde (24.0 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as white solid (42.8 mg) with the melting point of 243-.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.48 (br s, 1H), 8.15 (d, J = 7.8 Hz, 1H), 8.11 (d, J = 7.8 Hz, 2H), 7.82 (t, J = 7.5 Hz, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.50 (t, J = 7.5 Hz, 1H), 7.36 (d, J = 7.8 Hz, 2H), 2.39 (s, 3H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 162.3, 152.2, 148.9, 141.5, 134.6, 129.9, 129.2, 127.7, 127.5, 126.4, 125.9, 120.9, 21.0.
Example 112- (3, 4-dimethylphenyl) -4- [3H ] quinazolinone
2-(3,4-Dimethylphenyl)quinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), 3, 4-dimethylbenzaldehyde (26.8 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (a developing solvent: petroleum ether/ethyl acetate volume ratio is =3: 1) as a white solid (43.6 mg) with a melting point of 239-.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.41 (br s, 1H), 8.15 (d, J = 7.8 Hz, 1H), 8.00 (s, 1H), 7.93 (d, J = 7.8 Hz, 1H), 7.82 (t, J = 7.5 Hz, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.51 (t, J = 7.4 Hz, 1H), 7.30 (d, J = 7.8 Hz, 1H), 2.31 (d, J = 6.4 Hz, 6H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 162.3, 152.4, 148.9, 140.3, 136.6. 134.6, 130.2, 129.7, 128.6, 127.4, 126.4, 125.9, 125.2, 120.9, 19.46, 19.43.
Example 12 2- (4-methoxyphenyl) -4- [3H ] quinazolinone
2-(4-Methoxyphenyl)quinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), 4-methoxybenzaldehyde (27.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (the volume ratio of the developing agent to the petroleum ether to the ethyl acetate is =3: 1) as a white solid (44.8 mg) with the melting point of 246-247 ℃.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.43 (br s, 1H), 8.20 (d, J = 8.2 Hz, 2H), 8.14 (d, J = 7.7 Hz, 1H), 7.81 (t, J = 7.3 Hz, 1H), 7.71 (d, J = 8.0 Hz, 1H), 7.48 (t, J = 7.3 Hz, 1H), 7.10 (d, J = 8.2 Hz, 2H), 3.84 (s, 3H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 162.4, 161.9, 152.0, 148.8, 134.6, 129.5, 127.2, 126.2, 125.9, 124.8, 120.7, 114.0, 55.5.
Example 13 2- (4-fluorophenyl) -4- [3H ] quinazolinone
2-(4-Fluorophenyl)quinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), 4-fluorobenzaldehyde (24.8 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 hours under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (a developing agent: petroleum ether/ethyl acetate volume ratio is =3: 1) and is a white solid (39.2 mg) with a melting point of 258-.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.57 (br s, 1H), 8.25 (t, J = 6.7 Hz, 2H), 8.16 (d, J = 7.8 Hz, 1H), 7.84 (t, J = 7.6 Hz, 1H), 7.75 (d, J = 8.1 Hz, 1H), 7.52 (t, J = 7.4 Hz, 1H), 7.40 (t, J = 8.5 Hz, 2H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 165.3 (d, J C-F = 248.0 Hz), 162.3, 151.4, 148.7, 134.7, 130.5 (d, J C-F = 9.0 Hz), 129.3 (d, J C-F = 2.8 Hz), 127.5, 126.7, 125.9, 120.9, 115.8 (d, J C-F = 21.8 Hz).
Example 14 2- (4-chlorophenyl) -4- [3H ] quinazolinone
2-(4-Fluorophenyl)quinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), 4-chlorobenzaldehyde (28.1 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as white solid (43.7 mg) with melting point of 185-.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.65 (br s, 1H), 8.19 (d, J = 7.9 Hz, 1H), 7.86 (t, J = 7.6 Hz, 1H), 7.72 (d, J = 8.2 Hz, 1H), 7.68 (d, J = 7.5 Hz, 1H), 7.63-7.56 (m, 3H), 7.50 (t, J = 7.4 Hz, 1H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 161.4, 152.3, 148.6, 134.6, 133.8, 131.7, 131.5, 130.9, 129.6, 127.5, 127.3, 127.1, 125.9, 121.3.
Example 15 2- (3-bromophenyl) -4- [3H ] quinazolinone
2-(3-Bromophenyl)quinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), 3-bromobenzaldehyde (37.0 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added in that order to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as a white solid (53.2 mg) with a melting point of 296-297 ℃.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.62 (br s, 1H), 8.37 (s, 1H), 8.17 (t, J = 9.3 Hz, 2H), 7.85 (t, J = 7.6 Hz, 1H), 7.78 (t, J = 9.1 Hz, 2H), 7.56-7.50 (m, 2H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 162.2, 151.0, 148.5, 135.0, 134.8, 134.1, 130.8, 130.4, 127.7, 127.0, 126.8, 125.9, 121.9, 121.2.
Example 16 2- (4-cyanophenyl) -4- [3H ] quinazolinone
4-(4-Oxo-3,4-dihydroquinazolin-2-yl)benzonitrile
Anthranilamide (27.2 mg, 0.2 mmol), 4-cyanobenzaldehyde (26.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture was reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction was completed, the solvent was removed by rotary evaporation, and then pure target compound was obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as a white solid (44.8 mg) with a melting point of 281-.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.76 (br s, 1H), 8.34 (d, J = 8.0 Hz, 2H), 8.18 (d, J = 7.8 Hz, 1H), 8.05 (d, J = 8.0 Hz, 2H), 7.87 (t, J = 7.4 Hz, 1H), 7.79 (d, J = 8.0 Hz, 1H), 7.57 (t, J = 7.4 Hz, 1H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 162.2, 151.0, 148.3, 136.9, 134.8, 132.6, 128.7, 127.7, 127.3, 126.0, 121.2, 118.4, 113.6.
Example 17 2- (2-pyridinyl) -4- [3H ] quinazolinone
2-(Pyridin-2-yl)quinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), pyridine-2-carbaldehyde (21.4 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (a developing solvent: petroleum ether/ethyl acetate volume ratio is =3: 1) as a white solid (37.2 mg) with a melting point of 144-146 ℃.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 11.87 (br s, 1H), 8.77 (d, J = 4.5 Hz, 1H), 8.47 (d, J = 7.9 Hz, 1H), 8.20 (d, J = 7.8 Hz, 1H), 8.08 (t, J = 7.7 Hz, 1H), 7.88 (t, J = 7.5 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.67 (t, J = 6.0 Hz, 1H), 7.58 (t, J = 7.4 Hz, 1H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 160.8, 150.0, 149.0, 148.7, 148.5, 138.0, 134.8, 127.8, 127.3, 126.6, 126.1, 122.2, 122.0.
Example 18 2- (1-naphthyl) -4- [3H ] quinazolinone
2-(Naphthalen-1-yl)quinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), 1-naphthaldehyde (31.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (the volume ratio of developing agent: petroleum ether/ethyl acetate is =3: 1) as white solid (48.1 mg) with the melting point of 286-.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.70 (br s, 1H), 8.24-8.12 (m, 3H), 8.06 (d, J = 8.2 Hz, 1H), 7.87 (t, J = 7.6 Hz, 1H), 7.81 (d, J = 7.0 Hz, 1H), 7.75 (d, J = 8.1 Hz, 1H), 7.67-7.57 (m, 4H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 162.0, 153.8, 148.6, 134.6, 133.2, 131.7, 130.4, 130.3, 128.4, 127.7, 127.4, 127.1, 126.9, 126.4, 125.9, 125.3, 125.1, 121.2.
Example 19 2- (phenethyl) -4- [3H ] quinazolinone
2-Phenethylquinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), phenylpropanal (26.8 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (the volume ratio of the developing agent to the petroleum ether to the ethyl acetate is =3: 1) as a white solid (43.2 mg) with the melting point of 210-211 ℃.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.27 (br s, 1H), 8.09 (d, J = 7.8 Hz, 1H), 7.78 (t, J = 7.5 Hz, 1H), 7.63 (d, J = 8.1 Hz, 1H), 7.47 (t, J = 7.4 Hz, 1H), 7.28-7.19 (m, 5H), 3.05 (t, J = 7.8 Hz, 2H), 2.89 (t, J = 7.8 Hz, 2H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 161.8, 156.6, 148.9, 140.8, 134.4, 128.4, 128.4, 126.9, 126.1, 126.1, 125.7, 120.9, 36.4, 32.5.
Example 20 2- (3-cyclohexenyl) -4- [3H ] quinazolinone
2-(Cyclohex-3-en-1-yl)quinazolin-4(3H)-one
Anthranilamide (27 mg, 0.2 mmol), 1,2,3, 6-tetrahydrobenzaldehyde (22 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (the volume ratio of the developing agent to the petroleum ether to the ethyl acetate is =3: 1) as a white solid (38.5 mg) with the melting point of 236-238 ℃.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.18 (br s, 1H), 8.09 (d, J = 7.8 Hz, 1H), 7.77 (t, J = 7.6 Hz, 1H), 7.61 (d, J = 8.1 Hz, 1H), 7.46 (t, J = 7.5 Hz, 1H), 5.76-5.70 (m, 2H), 2.79-2.77 (m, 1H), 2.43-2.25 (m, 2H), 2.13-1.99 (m, 3H), 1.79-1.68 (m, 1H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 162.4, 160.9, 149.3, 134.8, 127.5, 127.0, 126.5, 126.2, 121.4, 29.1, 27.1, 25.2.
Example 21 2- (nonyl) -4- [3H ] quinazolinone
2-Nonylquinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), decanal (28.4 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (the volume ratio of developing agent to petroleum ether/ethyl acetate is =3: 1) as white solid (45.3 mg) with the melting point of 150-.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 121.17 (br s, 1H), 8.08 (d, J = 7.8 Hz, 1H), 7.76 (t, J = 7.6 Hz, 1H), 7.59 (d, J = 8.2 Hz, 1H), 7.44 (t, J = 7.5 Hz, 1H), 2.58 (t, J = 7.5 Hz, 2H), 1.72-1.67 (m, 2H), 1.28-1.22 (m, 12H), 0.83 (t, J = 5.9 Hz, 3H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 161.9, 157.5, 149.0, 134.3, 126.8, 128.9, 125.7, 120.8, 34.5, 31.3, 28.9, 28.8, 28.7, 28.6, 26.8, 22.1, 14.0.
Example 22 2- (cyclohexyl) -4- [3H ] quinazolinone
2-Cyclohexylquinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), cyclohexylformaldehyde (22.4 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (a developing agent: petroleum ether/ethyl acetate volume ratio is =3: 1) as a white solid (37.8 mg) with a melting point of 150-.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.09 (br s, 1H), 8.08 (d, J = 7.8 Hz, 1H), 7.75 (t, J = 7.6 Hz, 1H), 7.60 (d, J = 8.1 Hz, 1H), 7.44 (t, J = 7.4 Hz, 1H), 2.56 (t, J = 11.7 Hz, 1H), 1.91-1.88 (m, 4H), 1.65-1.53 (m, 3H), 1.34-1.19 (m, 3H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 162.0, 160.8, 149.0, 134.3, 127.0, 126.0, 125.7, 121.0, 42.9, 30.2, 25.6, 25.4.
Example 23 2- (methyl) -4- [3H ] quinazolinone
2-Methylquinazolin-4(3H)-one
Anthranilamide (27.2 mg, 0.2 mmol), aqueous acetaldehyde (40%) (22.0 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound is obtained by column chromatography (a developing solvent: petroleum ether/ethyl acetate volume ratio is =3: 1) as a white solid (27.1 mg) with a melting point of 238-.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.20 (br s, 1H), 8.07 (d, J = 7.6 Hz, 1H), 7.78-7.74 (m, 1H), 7.57 (d, J = 7.9 Hz, 1H),7.46-7.43 (m, 1H), 2.34 (s, 3H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 161.7, 154.3, 149.0, 134.3, 126.6, 125.9, 125.7, 120.7, 21.5.
Example 24 7-methyl-2-phenyl-4- [3H ] quinazolinone
7-Methyl-2-phenylquinazolin-4(3H)-one
2-amino-4-methylbenzamide (30.0 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-methylbenzenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were sequentially added to a 15 mL reaction tube. The reaction mixture is reacted for 2 hours under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (the volume ratio of the developing agent to the petroleum ether to the ethyl acetate is =3: 1) and is a white solid (39.3 mg) with the melting point of 205-207 ℃.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.46 (br s, 1H), 8.17 (d, J = 7.6 Hz, 2H), 8.04 (d, J = 8.0 Hz, 1H), 7.59-7.52 (m, 4H), 7.35 (d, J = 8.1 Hz, 1H), 2.47 (s, 3H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 162.1, 152.4, 148.9, 145.2, 132.8, 131.4, 128.7, 128.1, 127.8, 127.2, 125.8, 118.6, 21.4.
Example 25 6-fluoro-2-phenyl-4- [3H ] quinazolinone
6-Fluoro-2-phenylquinazolin-4(3H)-one
2-amino-6-fluorobenzamide (30.8 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added in this order to a 15 mL reaction tube. The reaction mixture is reacted for 2 hours under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (the volume ratio of developing agent to petroleum ether/ethyl acetate is =3: 1) as a white solid (41.6 mg) with the melting point of 277-.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.67 (br s, 1H), 8.17 (d, J = 7.6 Hz, 2H), 7.81 (m, 2H), 7.72 (t, J = 8.7 Hz, 1H), 7.59-7.53 (m, 3H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 161.7, 161.2 (d, J C-F = 240.0 Hz), 151.9, 145.7, 132.6, 131.5, 130.4 (d, J C-F = 8.2 Hz), 128.7, 127.8, 123.2 (d, J C-F = 23.9 Hz), 122.3 (d, J C-F = 8.3 Hz), 110.7 (d, J C-F = 23.2 Hz).
Example 26 7-chloro-2-phenyl-4- [3H ] quinazolinone
7-Chloro-2-phenylquinazolin-4(3H)-one
2-amino-7-chlorobenzamide (34.1 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture was reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction was completed, the solvent was removed by rotary evaporation, and then pure target compound was obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =3: 1) as a white solid (46.2 mg) with a melting point of 279-287 ℃.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 12.68 (br s, 1H), 8.17-8.12 (m, 3H), 7.77 (s, 1H), 8.60-8.52 (m, 4H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 161.7, 153.8, 149.9, 139.2, 132.4, 131.8, 128.7, 128.0, 128.0, 126.8, 126.6, 119.8.
Example 27 3-methyl-2-phenyl-4- [3H ] quinazolinone
3-Methyl-2-phenylquinazolin-4(3H)-one
2-amino-N-methylbenzamide (30.0 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-methylbenzenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were sequentially added to a 15 mL reaction tube. The reaction mixture is reacted for 2 hours under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (the volume ratio of the developing agent to the petroleum ether to the ethyl acetate is =3: 1) and is a white solid (41.3 mg) with the melting point of 112-114 ℃.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 8.20 (d, J = 7.5 Hz, 1H), 7.84 (t, J = 7.6 Hz, 1H), 7.69 (m, 3H), 7.56-7.55 (m, 4H), 3.36 (s, 3H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 161.7, 156.2, 147.1, 135.4, 134.4, 129.8, 128.4, 128.3, 127.2, 126.9, 126.1, 120.2, 33.9.
Example 28 diphenyl-4- [3H ] quinazolinone
2,3-diphenylquinazolin-4(3H)-one
2-amino-N-phenylbenzamide (42.4 mg, 0.2 mmol), benzaldehyde (21.2 mg, 0.2 mmol), fluorescein (1.3 mg, 2 mol%), p-toluenesulfonic acid (3.4 mg, 10 mol%) and acetonitrile (2 mL) were added sequentially to a 15 mL reaction tube. The reaction mixture is reacted for 2 h under the irradiation of a 10 w blue light lamp, after the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (the volume ratio of the developing agent to the petroleum ether to the ethyl acetate is =3: 1) as a white solid (52.8 mg) with the melting point of 158-159 ℃.
1 H NMR (400 MHz, [D 6 ]DMSO) δ 8.21 (d, J = 7.9 Hz, 1H), 7.90 (t, J = 7.6 Hz, 1H), 7.78 (d, J = 8.1 Hz, 1H), 7.61 (t, J = 7.5 Hz, 1H), 7.38-7.21 (m, 10H); 13 C NMR (100 MHz, [D 6 ]DMSO) δ 161.4, 155.2, 147.3, 137.9, 135.7, 134.9, 129.6, 128.9, 128.9, 128.6, 128.2, 127.5, 127.4, 127.2, 126.5, 120.8.
Comparative example 1
2-phenyl-4-quinazolinone was prepared in the manner of example 1, except that: p-toluenesulfonic acid was not used. At the end of the reaction, a white solid was obtained, weighing 6.9 mg.
Claims (8)
1. A method for synthesizing quinazolinone through photocatalysis is characterized in that: the method comprises the steps of carrying out a photocatalytic reaction on anthranilamide shown in a formula II and aldehyde shown in a formula III to obtain quinazolinone shown in a formula I;
in the formulae I, II and III, R 1 Selected from hydrogen, methyl or halogen; r 2 Selected from phenyl, methylphenyl, 3, 4-dimethylphenyl, isopropylphenyl, methoxyphenyl, halophenyl, hydroxyphenyl, cyanophenyl, trifluoromethylphenyl, pyridyl, furyl, naphthyl, phenethyl, cinnamyl, cyclohexenyl, nonyl, cyclohexyl or methyl; r 3 Selected from hydrogen, methyl or phenyl;
the fluorescein is used as a photocatalyst, and the p-toluenesulfonic acid is used as an auxiliary catalyst to perform photocatalytic reaction under the irradiation of blue light.
2. The method of claim 1, further comprising: the dosage of the photocatalyst is 1-3 mol% of anthranilamide; the dosage of the p-toluenesulfonic acid is 10 to 30 percent of the molar weight of the anthranilamide.
3. The method of claim 2, wherein: the amount of the photocatalyst is 2-3mol% of the anthranilamide.
4. The method of claim 1, further comprising: the power of the blue light is 5-15 w.
5. The method of claim 1, further comprising: the molar ratio of anthranilamide to aldehyde was 1: 1.
6. The method of claim 1, further comprising: the reaction is carried out in the presence of a solvent, which is acetonitrile, toluene, tetrahydrofuran or ethanol.
7. The method according to any of claims 1-6, characterized by the following specific steps: mixing anthranilamide, aldehyde, photocatalyst, p-toluenesulfonic acid and solvent, and reacting the obtained mixture under the irradiation of a 5-15W blue light lamp to obtain quinazolinone.
8. A method according to claim 1,2 or 3, characterized by: the reaction temperature is room temperature, and the reaction time is 1-3 h.
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