CN113735826A - Preparation method of 3-benzylidene-2, 3-dihydroquinolone compound - Google Patents
Preparation method of 3-benzylidene-2, 3-dihydroquinolone compound Download PDFInfo
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- CN113735826A CN113735826A CN202011213486.9A CN202011213486A CN113735826A CN 113735826 A CN113735826 A CN 113735826A CN 202011213486 A CN202011213486 A CN 202011213486A CN 113735826 A CN113735826 A CN 113735826A
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- benzylidene
- dihydroquinolone
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- -1 3-benzylidene-2, 3-dihydroquinolone compound Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
- 150000001361 allenes Chemical class 0.000 claims abstract description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- AVSDZXVDJKQVAD-UHFFFAOYSA-N S(=O)(=O)=NC1=C(C=CC=C1)I Chemical compound S(=O)(=O)=NC1=C(C=CC=C1)I AVSDZXVDJKQVAD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract 4
- 230000000996 additive effect Effects 0.000 claims abstract 4
- 239000003446 ligand Substances 0.000 claims abstract 4
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- FISAALNIXQMBDR-UHFFFAOYSA-N N-(2-iodophenyl)pyridine-2-sulfonamide Chemical compound C1=CC=C(C(=C1)NS(=O)(=O)C2=CC=CC=N2)I FISAALNIXQMBDR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 229950002475 mesilate Drugs 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 4
- CFPBYGKISUKURJ-UHFFFAOYSA-N 3h-quinolin-2-one Chemical class C1=CC=CC2=NC(=O)CC=C21 CFPBYGKISUKURJ-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- YNUJADNRNHJXDT-UHFFFAOYSA-N palladium;pentane-2,4-dione Chemical compound [Pd].CC(=O)CC(C)=O.CC(=O)CC(C)=O YNUJADNRNHJXDT-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BFSXRDGLHYCLHL-UHFFFAOYSA-N 1,3,5-trimethyl-5-(1,3,5-trimethylcyclohexa-2,4-dien-1-yl)oxycyclohexa-1,3-diene Chemical compound C1C(C)=CC(C)=CC1(C)OC1(C)C=C(C)C=C(C)C1 BFSXRDGLHYCLHL-UHFFFAOYSA-N 0.000 description 1
- UBPDKIDWEADHPP-UHFFFAOYSA-N 2-iodoaniline Chemical compound NC1=CC=CC=C1I UBPDKIDWEADHPP-UHFFFAOYSA-N 0.000 description 1
- CCBQXYXZWHVRCM-UHFFFAOYSA-N C(C1=CC=CC=C1)=C1C(N=C2C=CC=CC2=C1)=O Chemical class C(C1=CC=CC=C1)=C1C(N=C2C=CC=CC2=C1)=O CCBQXYXZWHVRCM-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 239000002062 molecular scaffold Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 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
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IAUBZYYUBMBVPI-UHFFFAOYSA-N pyridine;sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O.C1=CC=NC=C1 IAUBZYYUBMBVPI-UHFFFAOYSA-N 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
- C07D401/12—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 linked by a chain containing hetero atoms as chain links
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a 3-benzylidene-2, 3-dihydroquinolone compound, which comprises the following steps: adding a palladium catalyst, a ligand, a carbon monoxide substitute, an additive, N-pyridine sulfonyl-o-iodoaniline and allene into an organic solvent, reacting for 24-48 hours at 80-100 ℃, and after the reaction is completed, carrying out post-treatment to obtain the 3-benzylidene-2, 3-dihydroquinolone compound. The preparation method has the advantages of simple operation, cheap and easily obtained starting raw materials, high reaction efficiency and good substrate compatibility, can be used for quickly preparing the 3-benzylidene-2, 3-dihydroquinolone compound, and has stronger practicability.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a 3-benzylidene-2, 3-dihydroquinolone compound.
Background
2, 3-dihydroquinolone compounds are important carbonyl-containing six-membered nitrogen heterocycles and are widely present in various molecular scaffolds with important biological activities, such as compound A (J.Med.chem.1965,8, 566-.
Based on the importance of 2, 3-dihydroquinolone skeleton, a large number of synthetic methods have been reported in the literature (chem.2019,5, 1059-1011). However, few reports of synthesizing 2, 3-dihydroquinolone compounds through carbonylation reaction exist, and the application is not wide at present, so that the method has a wide application prospect.
Based on this, we developed a process for efficiently synthesizing 3-benzylidene-2, 3-dihydroquinolone compounds by a palladium-catalyzed carbonylation reaction using N-pyridylsulfonyl-o-iodoaniline and a allene as starting materials.
Disclosure of Invention
The invention provides a preparation method of a 3-benzylidene-2, 3-dihydroquinolone compound, which has simple steps, can be compatible with various functional groups, has good reaction applicability, can be expanded to gram level, and provides possibility for industrial large-scale production and application.
A process for preparing a 3-benzylidene-2, 3-dihydroquinolone compound, comprising the steps of: adding bis (acetylacetone) palladium, 1, 3-bis (diphenylphosphino) propane, triethylamine, 1,3, 5-mesitylene phenol ester, N-pyridine sulfonyl-o-iodoaniline and allene into an organic solvent, reacting for 24-48 hours at 80-100 ℃, and after the reaction is completed, carrying out post-treatment to obtain the 3-benzylidene-2, 3-dihydroquinolone compound;
the structure of the N-pyridine sulfonyl-o-iodoaniline is shown as a formula (II):
the structure of the allene is shown as a formula (III):
the structure of the 3-benzylidene-2, 3-dihydroquinolone compound is shown as the formula (I):
in formulas (I) to (III), R is substituted or unsubstituted aryl;
the substituent on the aryl is selected from one or more of methyl, tert-butyl, methoxy and halogen; the substitution position may be ortho, para or meta.
Further, the aryl group is preferably a phenyl group or a naphthyl group.
The molar ratio of the bis (acetylacetone) palladium to the 1, 3-bis (diphenylphosphino) propane to the 1,3, 5-mesic acid phenol ester is 0.1:0.1: 1;
the reaction formula is as follows:
during the reaction, palladium is inserted into the carbon-nitrogen bond of N-pyridine sulfonyl-o-iodoaniline to form aryl palladium intermediate, and carbon monoxide released from 1,3, 5-trimesic acid phenol ester is inserted into the aryl palladium intermediate to form acyl palladium intermediate. Subsequently, the allene coordinates and inserts with the acyl palladium intermediate to obtain the alkyl palladium intermediate. Finally, reductive elimination takes place to give the 3-benzylidene-2, 3-dihydroquinolone compound.
In the present invention, the optional post-processing procedure includes: filtering, mixing the sample with silica gel, and finally purifying by column chromatography to obtain the corresponding 3-benzylidene-2, 3-dihydroquinolone compound, wherein the purification by column chromatography is a technical means commonly used in the field.
Preferably, R is substituted or unsubstituted phenyl, and the substituent on the phenyl is selected from one or more of methyl, tert-butyl, methoxy, F, Cl and Br, so that the reaction yield is high.
Preferably, the reaction time is 24-48 hours, and the reaction time is short and is difficult to ensure the completeness of the reaction.
In the present invention, the organic solvent is preferably toluene, in which case various raw materials can be converted into products at a high conversion rate.
The dosage of the organic solvent can be only needed to dissolve the raw material well, and the dosage of the organic solvent used by 1mmol of the N-pyridine sulfonyl-o-iodoaniline is about 5 mL.
Preferably, the catalyst is palladium bis (acetylacetonate), and the reaction efficiency is higher in a plurality of palladium catalysts.
As a further preference, the 3-benzylidene-2, 3-dihydroquinolone compound is one of compounds represented by formula (I-1) to formula (I-5):
in the above preparation method, the bis (acetylacetonato) palladium and the 1, 3-bis (diphenylphosphino) propane are generally commercially available products, and can be conveniently obtained from the market; the N-pyridine sulfonyl-o-iodoaniline can be quickly synthesized from corresponding o-iodoaniline and pyridine sulfonyl chloride; the allenes can be obtained by quickly synthesizing corresponding olefins.
Compared with the prior art, the invention has the beneficial effects that: the preparation method is easy to operate, and the post-treatment is simple and convenient; the method has the advantages of cheap and easily-obtained reaction starting raw materials, strong designability of the substrate, wide tolerance range of substrate functional groups, high reaction efficiency, capability of quickly synthesizing the 3-benzylidene-2, 3-dihydroquinolone compound and strong practicability.
Detailed Description
The invention is further described with reference to specific examples.
Adding palladium bis (acetylacetonate), 1, 3-bis (diphenylphosphino) propane, triethylamine (1mmol), 1,3, 5-mesityloxide, N-pyridinesulfonyl-o-iodoaniline (II), allene (III) and 2.5mL of an organic solvent into a 35mL Schlenk tube according to the raw material ratio shown in Table 1, uniformly mixing and stirring, reacting for 24 hours according to the reaction conditions shown in Table 2, filtering, stirring by silica gel, and purifying by column chromatography to obtain the corresponding 3-benzylidene-2, 3-dihydroquinolone compound (I), wherein the reaction process is shown as the following formula:
TABLE 1 raw material addition amounts of examples 1 to 15
TABLE 2
In tables 1 and 2, T is the reaction temperature, T is the reaction time, Ph is phenyl, Me is methyl, OMe is methoxy, T-Bu is T-butyl, tolumene is toluene.
Structure confirmation data of the compounds prepared in examples 1 to 5:
nuclear magnetic resonance of 3-benzylidene-2, 3-dihydrocarbostyril compound (I-1) prepared in example 1: (1H NMR、13C NMR) and High Resolution (HRMS) detection data:
1H NMR(400MHz,CDCl3)δ8.36–8.35(m,1H),7.95(dd,J＝7.8,1.5Hz,1H),7.75(dd,J＝8.2,0.5Hz,1H),7.63–7.55(m,2H),7.48(d,J＝7.8Hz,1H),7.44(s,1H),7.36–7.32(m,2H),7.26–7.23(m,2H),7.18(d,J＝8.1Hz,2H),5.09(d,J＝1.4Hz,2H),2.39(s,3H).
13C NMR(100MHz,CDCl3)δ183.0,156.1,150.1,141.6,140.3,137.9,137.8,137.7,134.0,131.3,130.2,129.7,129.5,128.8,128.2,126.9,126.2,122.7,48.3,21.5.
HRMS(ESI-TOF)Calcd.for C22H19N2O3S+[M+H]+:391.1111；found:391.1115.
nuclear magnetic resonance of 3-benzylidene-2, 3-dihydrocarbostyril compound (I-2) obtained in example 2: (1H NMR、13C NMR) and High Resolution (HRMS) detection data:
1H NMR(400MHz,CDCl3)δ8.39(dd,J＝4.6,0.6Hz,1H),7.96(dd,J＝7.8,1.4Hz,1H),7.76(d,J＝7.8Hz,1H),7.65(td,J＝7.8,1.7Hz,1H),7.60–7.56(m,1H),7.53(d,J＝7.8Hz,1H),7.47(s,1H),7.36(ddd,J＝13.6,9.2,4.3Hz,3H),6.96–6.93(m,1H),6.88(d,J＝7.7Hz,2H),5.10(d,J＝1.4Hz,2H),3.84(s,3H).
13C NMR(100MHz,CDCl3)δ183.0,159.8,156.1,150.1,141.7,138.0,137.6,135.4,134.2,130.6,130.0,128.7,128.3,127.0,126.9,126.1,122.8,122.3,115.4,115.3,55.4,48.3.
HRMS(ESI-TOF)Calcd.for C22H19N2O4S+[M+H]+:407.1060；found:407.1064.
nuclear magnetic resonance of 3-benzylidene-2, 3-dihydroquinolone Compound (I-3) prepared in example 3: (1H NMR、13C NMR) and High Resolution (HRMS) detection data:
1H NMR(400MHz,CDCl3)δ8.44(dd,J＝4.6,0.7Hz,1H),7.97(dd,J＝7.8,1.5Hz,1H),7.78(d,J＝8.2Hz,1H),7.72(td,J＝7.8,1.7Hz,1H),7.68(s,1H),7.64(dd,J＝8.0,0.8Hz,1H),7.61–7.55(m,2H),7.41–7.36(m,2H),7.34–7.31(m,2H),7.28–7.23(m,1H),5.01(d,J＝1.6Hz,2H).
13C NMR(100MHz,CDCl3)δ182.5,155.8,150.1,141.6,138.2,136.6,134.3,133.4,131.5,130.9,130.2,128.6,128.4,127.7,127.3,127.0,126.0,125.7,122.6,48.4.
HRMS(ESI-TOF)Calcd.for C21H16BrN2O3S+[M+H]+:455.0060；found:455.0052.
nuclear magnetic resonance of 3-benzylidene-2, 3-dihydrocarbostyril compound (I-4) prepared in example 4: (1H NMR、13C NMR) and High Resolution (HRMS) detection data:
1H NMR(400MHz,CDCl3)δ8.42(dd,J＝4.6,0.7Hz,1H),7.99(dd,J＝7.8,1.4Hz,1H),7.79–7.77(m,1H),7.72–7.67(m,2H),7.61–7.55(m,2H),7.38(ddd,J＝7.7,4.8,1.1Hz,1H),7.34(td,J＝7.8,1.0Hz,1H),7.11(s,2H),6.98(s,1H),5.02(d,J＝1.6Hz,2H),2.34(s,3H),2.15(s,3H).
13C NMR(100MHz,CDCl3)δ183.1,156.4,150.0,149.9,141.8,137.9,137.0,136.9,135.6,134.8,134.1,133.0,130.5,129.2,128.8,128.4,127.0,126.8,125.8,122.7,48.5,21.1,19.5.
HRMS(ESI-TOF)Calcd.for C23H21N2O3S+[M+H]+:405.1267；found:405.1273.
nuclear magnetic resonance of 3-benzylidene-2, 3-dihydrocarbostyril compound (I-5) obtained in example 5: (1H NMR、13C NMR) and High Resolution (HRMS) detection data:
1H NMR(400MHz,CDCl3)δ8.39(d,J＝4.0Hz,1H),8.01(dd,J＝7.8,1.4Hz,1H),7.90–7.85(m,3H),7.80–7.77(m,2H),7.65(s,1H),7.63–7.59(m,2H),7.58–7.53(m,2H),7.48(d,J＝7.8Hz,1H),7.39–7.34(m,3H),5.20(d,J＝1.3Hz,2H).
13C NMR(100MHz,CDCl3)δ183.0,156.2,150.1,141.7,137.9,137.7,134.2,133.6,133.1,131.7,130.5,130.4,128.8,128.7,128.6,128.3,127.9,127.6,127.0,126.9,126.7,126.2,122.8,48.4.
HRMS(ESI-TOF)Calcd.for C25H18N2O3SNa+[M+Na]+:449.0930；found:449.0931.
Claims (9)
1. a process for preparing a 3-benzylidene-2, 3-dihydroquinolone compound comprising the steps of: adding a palladium catalyst, a ligand, a carbon monoxide substitute, an additive, N-pyridine sulfonyl-o-iodoaniline and allene into an organic solvent, reacting for 24-48 hours at 80-100 ℃, and after the reaction is completed, carrying out post-treatment to obtain the 3-benzylidene-2, 3-dihydroquinolone compound;
the structure of the N-pyridine sulfonyl-o-iodoaniline is shown as a formula (II):
the structure of the allene is shown as a formula (III):
the structure of the 3-benzylidene-2, 3-dihydroquinolone compound is shown as the formula (I):
in formulas (I) to (III), R is substituted or unsubstituted aryl;
the substituents on the aryl are selected from C1～C6Alkyl radical, C1～C6One or more of alkoxy or halogen.
2. The process for producing a 3-benzylidene-2, 3-dihydroquinolone compound according to claim 1, wherein R is a substituted or unsubstituted phenyl group;
and the substituent on the phenyl is selected from one or more of methyl, tert-butyl, methoxy, F, Cl and Br.
3. The process for producing a 3-benzylidene-2, 3-dihydroquinolone compound according to claim 1, wherein the molar amount of N-pyridinesulfonyl-o-iodoaniline: allene: additive: palladium catalyst: ligand: carbon monoxide substitute ═ 1:2.5:2:0.1:0.1: 1.
4. The process for preparing a 3-benzylidene-2, 3-dihydroquinolone compound according to claim 1, wherein the organic solvent is toluene.
5. The process for preparing a 3-benzylidene-2, 3-dihydroquinolone compound according to claim 1, wherein the palladium catalyst is palladium bis (acetylacetonate).
6. The process for producing a 3-benzylidene-2, 3-dihydroquinolone compound according to claim 1, wherein the ligand is 1, 3-bis (diphenylphosphino) propane.
7. The process for preparing a 3-benzylidene-2, 3-dihydroquinolone compound according to claim 1, wherein the additive is triethylamine.
8. The method of claim 1, wherein the carbon monoxide substitute is phenol 1,3, 5-mesilate.
9. The process for producing a 3-benzylidene-2, 3-dihydroquinolone compound according to claim 1, wherein the 3-benzylidene-2, 3-dihydroquinolone compound is one of compounds represented by the formula (I-1) to the formula (I-5):
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104995190A (en) * | 2012-12-20 | 2015-10-21 | 拜耳医药股份有限公司 | Bet-protein-inhibiting dihydroquinoxalinones |
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| CN104995190A (en) * | 2012-12-20 | 2015-10-21 | 拜耳医药股份有限公司 | Bet-protein-inhibiting dihydroquinoxalinones |
Non-Patent Citations (4)
| Title |
|---|
| FANGGUO YE AND HOWARD ALPER: "Ionic-Liquid-Promoted Palladium-Catalyzed Multicomponent Cyclocarbonylation of o-Iodoanilines and Allenes To Form Methylene-2,3-dihydro-1H-quinolin-4-ones", J. ORG. CHEM. * |
| LARISA POLITANSKAYA等: "p-Toluenesulfonic acid mediated one-pot cascade synthesis and cytotoxicity evaluation of polyfluorinated 2-aryl-2,3-dihydroquinolin-4-ones and their derivatives", JOURNAL OF FLUORINE CHEMISTRY * |
| M. S. ATWAL等: "ANALGESICS. SOME SUBSTITUTED 2，3-DIHYDRO-4-QUINOLONES", J .MED .CHEM . * |
| RONALD GRIGG等: "Synthesis of quinol-4-ones and chroman-4-ones via a palladium-catalysed cascade carbonylation–allene insertion", TETRAHEDRON LETTERS * |
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