CN107082761B - Phenanthridinone or benzophenanthridinone derivative and synthesis method thereof - Google Patents
Phenanthridinone or benzophenanthridinone derivative and synthesis method thereof Download PDFInfo
- Publication number
- CN107082761B CN107082761B CN201710250419.6A CN201710250419A CN107082761B CN 107082761 B CN107082761 B CN 107082761B CN 201710250419 A CN201710250419 A CN 201710250419A CN 107082761 B CN107082761 B CN 107082761B
- Authority
- CN
- China
- Prior art keywords
- phenanthridinone
- methoxy
- benzophenanthridinone
- derivative
- follows
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- RZFVLEJOHSLEFR-UHFFFAOYSA-N phenanthridone Chemical compound C1=CC=C2C(O)=NC3=CC=CC=C3C2=C1 RZFVLEJOHSLEFR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- XIUUWMMLYLBRBH-UHFFFAOYSA-N 2h-benzo[k]phenanthridin-1-one Chemical class C1=CC=C2C3=C4C(=O)CC=CC4=NC=C3C=CC2=C1 XIUUWMMLYLBRBH-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000001257 hydrogen Chemical group 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000460 chlorine Chemical group 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical class [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 32
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 23
- -1 methoxy, methyl Chemical group 0.000 claims description 19
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical class [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- ZBIKORITPGTTGI-UHFFFAOYSA-N [acetyloxy(phenyl)-$l^{3}-iodanyl] acetate Chemical compound CC(=O)OI(OC(C)=O)C1=CC=CC=C1 ZBIKORITPGTTGI-UHFFFAOYSA-N 0.000 claims description 15
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical class [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 15
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical class [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 150000003936 benzamides Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- VLRKYJUEGKNWJF-UHFFFAOYSA-N acetic acid hydroiodide Chemical compound I.CC(O)=O.CC(O)=O VLRKYJUEGKNWJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- YRXICXUINRGLJP-UHFFFAOYSA-N hydroxy(dimethyl)silicon Chemical compound C[Si](C)O YRXICXUINRGLJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052763 palladium Inorganic materials 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 150000004395 organic heterocyclic compounds Chemical class 0.000 abstract description 2
- 238000011056 performance test Methods 0.000 abstract description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 56
- 238000005481 NMR spectroscopy Methods 0.000 description 28
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 17
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 4
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- BXUGEJAHPQFPGM-UHFFFAOYSA-N 4-chloro-n-methoxybenzamide Chemical compound CONC(=O)C1=CC=C(Cl)C=C1 BXUGEJAHPQFPGM-UHFFFAOYSA-N 0.000 description 2
- CFGLLQPCOXUMCS-UHFFFAOYSA-N 9-methoxy-5H-phenanthridin-6-one Chemical compound COC1=CC=C2C(NC=3C=CC=CC=3C2=C1)=O CFGLLQPCOXUMCS-UHFFFAOYSA-N 0.000 description 2
- 235000001258 Cinchona calisaya Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- JRAFKZKLACPZSS-UHFFFAOYSA-N n,4-dimethoxybenzamide Chemical compound CONC(=O)C1=CC=C(OC)C=C1 JRAFKZKLACPZSS-UHFFFAOYSA-N 0.000 description 2
- GBUZSFILMYQUFA-UHFFFAOYSA-N n-methoxy-4-methylbenzamide Chemical compound CONC(=O)C1=CC=C(C)C=C1 GBUZSFILMYQUFA-UHFFFAOYSA-N 0.000 description 2
- HIJYJXGWKHLZPA-UHFFFAOYSA-N n-methoxy-4-nitrobenzamide Chemical compound CONC(=O)C1=CC=C([N+]([O-])=O)C=C1 HIJYJXGWKHLZPA-UHFFFAOYSA-N 0.000 description 2
- PBQZQTQFQFYBNJ-UHFFFAOYSA-N n-methoxybenzamide Chemical compound CONC(=O)C1=CC=CC=C1 PBQZQTQFQFYBNJ-UHFFFAOYSA-N 0.000 description 2
- 229960000948 quinine Drugs 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- NHNAEZDWNCRWRW-UHFFFAOYSA-N 2-bromobenzamide Chemical compound NC(=O)C1=CC=CC=C1Br NHNAEZDWNCRWRW-UHFFFAOYSA-N 0.000 description 1
- RZPFVRFSYMUDJO-UHFFFAOYSA-N 2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)CC=CC2=C1 RZPFVRFSYMUDJO-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- 108700020129 Human immunodeficiency virus 1 p31 integrase Proteins 0.000 description 1
- 239000012661 PARP inhibitor Substances 0.000 description 1
- 229940121906 Poly ADP ribose polymerase inhibitor Drugs 0.000 description 1
- 238000006923 Schmidt rearrangement reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 229940124524 integrase inhibitor Drugs 0.000 description 1
- 239000002850 integrase inhibitor Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
Abstract
The invention relates to a phenanthridinone or benzophenanthridinone derivative and a synthesis method thereof. TheThe compounds have the following structure:
wherein R is methoxyl, methyl, hydrogen, chlorine and nitryl. Theoretically, the method is subjected to palladium catalytic coupling reaction, provides a new synthetic idea for constructing a phenanthridinone or benzophenanthridinone framework, and enriches the synthetic method of the organic heterocyclic compound. According to performance test analysis, the phenanthridinone or benzophenanthridinone derivative has certain photoelectric performance, and part of compounds have better quantum yield, so that the phenanthridinone or benzophenanthridinone derivative is an organic luminescent material with potential application value.
Description
Technical Field
The invention relates to a fused heterocyclic compound phenanthridinone or benzophenanthridinone derivative and a synthesis method thereof.
Background
Phenanthridinone is an important heterocyclic compound, and the structural unit of phenanthridinone widely exists in a plurality of natural products and bioactive medicine intermediates[1]The compounds have potential biological activity, including anticancer antibacterial, antiviral efficacy and anti-cytotoxicity[2]PARP inhibitor as anticancer agent[3]In addition, they can be used as HIV-1 integrase inhibitors[4]。
The traditional method for synthesizing phenanthridinone mainly comprises the steps of cyclization reaction of a biphenylcarbonyl nitro compound and Beckmann/Schmidt rearrangement of fluorenone[5]And the like. Recently, o-bromobenzamide is subjected to coupling reaction under palladium catalysis to synthesize phenanthridinone, and benzyne and benzamide derivatives are subjected to reaction under palladium catalysis to simultaneously construct C-C/C-N bond to phenanthridinone[6]. At present, we find that, under the catalysis of palladium, benzyne or naphtyne respectively reacts with N-methoxy-4-substituted benzamide derivatives through C-H/N-H bond activation and cyclization reaction to synthesize phenanthridinone or benzophenanthridinone derivatives.
Disclosure of Invention
The invention aims to provide a phenanthridinone or benzophenanthridinone derivative.
The second purpose of the invention is to provide a preparation method and photoelectric properties of the derivatives.
In order to achieve the purpose, the reaction process of the invention is as follows:
benzo-bis (oxydisilocene) (1) or oxydisilenaphthalene (7) reacts with iodobenzene diacetate and trifluoromethanesulfonic acid to generate phenyl [ o- (hydroxydimethylsilyl) oxydisilenyl fused phenyl]Triflic acid iodide (2) or phenyl [ o- (hydroxydimethylsilyl) naphthyl]Triflic acid iodide (8). Under reflux, N-methoxy-4-substituted benzamide 4a-e, cesium fluoride (CsF), palladium acetate (Pd (OAc))2) Tetrabutylammonium bromide (TBAB), copper acetate (Cu (OAc)2) Firstly, a benzyne intermediate 3 or a naphthylyne intermediate 9 is generated and immediately reacts with N-methoxy-4-substituted benzamide 4a-e to generate oxydisilicophenanthridinone derivatives 5a-e and dioxotrisilylphenanthridinone derivatives 6a-d, and the total yield is 48-70%; or benzophenanthridinone derivatives 10a-e, with a yield of 52-83%. The specific reaction equation is as follows:
according to the reaction mechanism, the invention adopts the following technical scheme:
a fused heterocyclic compound phenanthridinone or benzophenanthridinone derivative, characterized in that the compound has one of the following structures: (1)
(2)
wherein R is methoxy, methyl, hydrogen, chlorine or nitro;
a method for preparing the phenanthridinone or benzophenanthridinone derivative, characterized in that the method comprises the following steps:
a. under the protection of inert gas nitrogen and under the condition of ice-water bath, adding trifluoromethanesulfonic acid into a dichloromethane solution of iodobenzene diacetate, reacting for 0.5-1 hour in ice-water bath, and reacting for 1-2 hours at room temperature; adding the reaction solution into a cooled dichloromethane solution of benzo-bis (oxadisilylone) or oxadisilyl naphthalene under the condition of ice-water bath, continuing ice-water bath reaction for 0.5-1 hour, reacting at room temperature for 3-4 hours, extracting with dichloromethane, washing with water, drying and removing the solvent by spinning to obtain phenyl [ o- (hydroxy dimethyl silicon) oxadisilyl condensed phenyl]Triflic acid iodide or phenyl [ o- (hydroxydimethylsilyl) naphthyl)]Triflic acid iodide, the structural formula of which is respectively:
the structural formula of the iodobenzene diacetate is as follows: PhI (OAc)2；
The structural formula of the benzo-bis (oxydisilocene) is as follows:
the structural formula of the oxydisilyl naphthalene is as follows:
b. in N2Protecting the phenyl [ o- (hydroxydimethylsilyl) oxydisilyl condensed phenyl obtained in the step a]Triflic acid iodide or phenyl [ o- (hydroxydimethylsilyl) naphthyl)]Adding acetonitrile solution of triflurosulfonic acid iodide into acetonitrile solution of N-methoxy-4-substituted benzamide derivative, cesium fluoride, palladium acetate, copper acetate and tetrabutylammonium bromide in batches, carrying out reflux reaction for 2 hours, separating and purifying to obtain solid silicon oxide-based phenanthridinone, silicon dioxide trisilico phenanthridinone or benzophenanthridinone derivative, wherein the structural formulas of the solid silicon oxide-based phenanthridinone, the silicon dioxide-based phenanthridinone or the benzophenanthridinone derivative are respectively as follows:
said N-methoxy-4-substitutionThe structural formula of the benzamide derivative is as follows:
the molar ratio of the diacetate iodide salt, the trifluoromethanesulfonic acid, the benzobis (oxydisilocene) or the oxydisinylnaphthalene, the N-methoxy-4-substituted benzamide derivative, the cesium fluoride, the copper acetate, the tetrabutylammonium bromide and the palladium acetate is as follows: 1.0-1.5: 2.5-3.0: 1.0-1.2: 0.5: 2.5-3.0: 1.0-1.5: 0.5-1.0: 0.02-0.03.
The method takes benzobis (oxydisilocene) or oxydisinglianylene as an aryne precursor, forms benzyne and naphthone at room temperature, and further reacts with N-methoxy-4-substituted benzamide derivative to generate oxydisisilicyl phenanthridinone, dioxo-trisilylphenanthridinone or benzophenanthridinone derivative. The synthesis method has the advantages of high reaction speed, mild reaction conditions, environmental friendliness and the like.
Theoretically, the method is subjected to palladium catalytic coupling reaction, provides a new synthetic idea for constructing a phenanthridinone or benzophenanthridinone framework, and enriches the synthetic method of the organic heterocyclic compound.
According to performance test analysis, the phenanthridinone or benzophenanthridinone derivative has certain photoelectric properties (shown in figures 1-4 and tables 1-2), and a part of compounds have better quantum yield, so that the phenanthridinone or benzophenanthridinone derivative is an organic luminescent material with potential application value.
Drawings
FIG. 1 absorption spectra of compounds 5a-e in dichloromethane solvent;
FIG. 2 absorption spectra of compounds 10a-e in dichloromethane solvent;
FIG. 3 emission spectra of compounds 5a-e in dichloromethane solvent;
FIG. 4 emission spectra of compounds 10a-e in dichloromethane solvent.
Detailed Description
The first embodiment is as follows:
iodobenzene diacetate (1.0 to 1.5eq), trifluoromethanesulfonic acid (2.5 to 3.0eq), benzobis (oxydisilocene) (1,1.0 to 1.2eq), N-methoxy-4-methoxybenzamide (4a,0.5eq), cesium fluoride (2.5 to 3.0eq), copper acetate (1.0 to 1.5eq), tetrabutylammonium bromide (0.5 to 1.0eq), palladium acetate (0.02 to 0.03eq), and the obtained phenanthridinone derivative is: 2, 3-oxydisilyl-5, 9-methoxy-6-phenanthridinone (5a) and 2, 3-dioxotrisilyl-5, 9-dimethoxy-6-phenanthridinone (6a), in a total yield of 65% (5 a: 63%, 6a: 2%). The structure of the compound is as follows:
5a molecular formula: c19H23NO4Si2
Chinese naming: 2, 3-oxydisilyl-5, 9-dimethoxy-6-phenanthridinone
English naming: 2, 3-oxadiliole-5, 9-dimethoxy-6(5H) -phenylanthridinone
Molecular weight: 385.12
Melting point: 167 ℃ F. & 168 ℃ C. (R.)
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ0.45(s,12H,SiMe2),4.02(s,3H,OCH3),4.14(s,3H,OCH3),7.18(dd,J＝9.0,2.0Hz,1H,Ar-H),7.73(d,J＝2.0Hz,1H,Ar-H),7.82(s,1H,Ar-H),8.35(s,1H,Ar-H),8.49(d,J＝9.0Hz,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ1.0,1.3,55.7,62.7,105.3,114.6,115.8,119.1,120.0,125.5,130.7,134.9,136.8,141.4,150.5,157.2,163.2ppm.
6a molecular formula: c21H29NO5Si3
Chinese naming: 2, 3-dioxo-trisilyl-5, 9-dimethoxy-6-phenanthridinone
English naming: 2, 3-dioxaristolone-5, 9-dimethoxy-6(5H) -phenylanthridinone
Molecular weight: 459.14
Melting point: 163 ℃ 164-
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ0.15(s,6H,SiMe2),0.50(s,6H,SiMe2),0.51(s,6H,SiMe2),4.01(s,3H,OCH3),4.13(s,3H,OCH3),7.18(dd,J＝9.0,2.0Hz,1H,Ar-H),7.67(d,J＝2.0Hz,1H,Ar-H),7.81(s,1H,Ar-H),8.33(s,1H,Ar-H),8.50(d,J＝9.0Hz,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ0.7,1.9,2.1,55.6,62.7,105.5,115.2,117.5,117.9,120.2,128.6,130.9,135.6,139.3,148.7,152.7,157.2,163.1ppm.
example two:
iodobenzene diacetate (1.0 to 1.5eq), trifluoromethanesulfonic acid (2.5 to 3.0eq), benzobis (oxydisilocene) (1,1.0 to 1.2eq), N-methoxy-4-methylbenzamide (4b,0.5eq), cesium fluoride (2.5 to 3.0eq), copper acetate (1.0 to 1.5eq), tetrabutylammonium bromide (0.5 to 1.0eq), palladium acetate (0.02 to 0.03eq), and the obtained phenanthridinone derivative is: 2, 3-oxydisilyl-5-methoxy-9-methyl-6-phenanthridinone (5b) and 2, 3-dioxotrisilyl-5-methoxy-9-methyl-6-phenanthridinone (6b), in a total yield of 70% (5 b: 60%, 6b: 10%). The structure of the compound is as follows:
5b, molecular formula: c19H23NO3Si2
Chinese naming: 2, 3-oxydisilyl-5-methoxy-9-methyl-6-phenanthridinone
English naming: 2, 3-oxadilole-5-methoxy-9-methyl-6 (5H) -phenylanthridinone
Molecular weight: 369.12
Melting point: 161-162 deg.C
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ0.45(s,6H,SiMe2),0.46(s,6H,SiMe2),2.60(s,3H,CH3),4.15(s,3H,OCH3),7.43(dd,J＝8.0,0.5Hz,1H,Ar-H),7.83(s,1H,Ar-H),8.16(s,1H,Ar-H),8.44-8.45(m,2H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ1.0,1.3,22.1,62.7,114.5,119.3,122.0,124.1,
125.5,128.5,129.7,132.9,136.5,141.5,143.3,150.2,157.4ppm.
6b molecular formula: c21H29NO4Si3
Chinese naming: 2, 3-dioxo-trisilyl-5-methoxy-9-methyl-6-phenanthridinone
English naming: 2, 3-dioxaristolone-5-methoxy-9-methyl-6 (5H) -phenylanthridinone
Molecular weight: 443.14
Melting point: 158 ℃ to 159 DEG C
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ0.16(s,6H,SiMe2),0.51(s,6H,SiMe2),0.53(s,6H,SiMe2),2.59(s,3H,CH3),4.14(s,3H,OCH3),7.42(d,J＝8.0Hz,1H,Ar-H),7.82(s,1H,Ar-H),8.06(s,1H,Ar-H),8.40(s,1H,Ar-H),8.44(d,J＝8.0Hz,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ0.7,1.9,2.2,22.2,62.7,117.7,117.9,121.7,124.4,128.5,128.6,129.7,132.7,135.3,139.4,143.3,148.3,157.3ppm.
example three:
iodobenzene diacetate (1.0 to 1.5eq), trifluoromethanesulfonic acid (2.5 to 3.0eq), benzobis (oxydisilocene) (1,1.0 to 1.2eq), N-methoxybenzamide (4c,0.5eq), cesium fluoride (2.5 to 3.0eq), copper acetate (1.0 to 1.5eq), tetrabutylammonium bromide (0.5 to 1.0eq), palladium acetate (0.02 to 0.03eq), and the obtained phenanthridinone derivative is: 2, 3-oxydisilyl-5-methoxy-6-phenanthridinone (5c) and 2, 3-dioxotrisilyl-5-methoxy-6-phenanthridinone (6c) in a total yield of 60% (5 c: 50%, 6c: 10%). The structure of the compound is as follows:
5c, molecular formula: c18H21NO3Si2
Chinese naming: 2, 3-oxydisilyl-5-methoxy-6-phenanthridinone
English naming: 2, 3-oxadilole-5-methoxy-6 (5H) -phenylanthridinone
Molecular weight: 355.11
Melting point: 148 ℃ 149 DEG C
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ0.449(s,6H,SiMe2),0.454(s,6H,SiMe2),4.16(s,3H,OCH3),7.62(t,J＝7.5Hz,1H,Ar-H),7.80(t,J＝7.5Hz,1H,Ar-H),7.85(s,1H,Ar-H),8.40(d,J＝8.5Hz,1H,Ar-H),8.47(s,1H,Ar-H),8.57(d,J＝7.5Hz,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13CNMR(125MHz,CDCl3):δ1.0,1.3,62.7,114.5,119.4,122.0,125.6,126.4,128.3,128.6,132.6,133.0,136.4,141.6,150.4,157.3ppm.
6c, molecular formula: c20H27NO4Si3
Chinese naming: 2, 3-dioxo-trisilyl-5-methoxy-6-phenanthridinone
English naming: 2, 3-dioxaristolone-5-methoxy-6 (5H) -phenylanthridinone
Molecular weight: 429.12
Melting point: 150 ℃ 151-
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ0.16(s,6H,SiMe2),0.51(s,6H,SiMe2),0.53(s,6H,SiMe2),4.15(s,3H,OCH3),7.62(t,J＝7.5Hz,1H,Ar-H),7.80(t,J＝7.5Hz,1H,Ar-H),7.84(s,1H,Ar-H),8.32(d,J＝8.0Hz,1H,Ar-H),8.44(s,1H,Ar-H),8.56(d,J＝8.0Hz,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ0.7,1.9,2.1,62.7,117.8,117.9,121.8,126.6,128.3,128.60,128.61,132.7,135.2,138.2,139.7,148.5,157.3ppm.
example four:
iodobenzene diacetate (1.0 to 1.5eq), trifluoromethanesulfonic acid (2.5 to 3.0eq), benzobis (oxydisillocene) (1,1.0 to 1.2eq), N-methoxy-4-chlorobenzamide (4d,0.5eq), cesium fluoride (2.5 to 3.0eq), copper acetate (1.0 to 1.5eq), tetrabutylammonium bromide (0.5 to 1.0eq), palladium acetate (0.02 to 0.03eq), and the obtained phenanthridinone derivative is: 2, 3-oxydisilyl-5-methoxy-9-chloro-6-phenanthridinone (5d) and 2, 3-dioxotrisilyl-5-methoxy-9-chloro-6-phenanthridinone (6d), in a total yield of 52% (5 d: 48%, 6d: 4%). The structure of the compound is as follows:
5d, molecular formula: c18H20ClNO3Si2
Chinese naming: 2, 3-oxydisilyl-5-methoxy-9-chloro-6-phenanthridinone
English naming: 2, 3-oxadilole-5-methoxy-9-chloro-6 (5H) -phenylanthridinone
Molecular weight: 389.07
Melting point: 155 ℃ and 156 DEG C
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ0.46(s,12H,SiMe2),4.15(s,3H,OCH3),7.54(d,J＝8.0Hz,1H,Ar-H),7.84(s,1H,Ar-H),8.33(s,1H,Ar-H),8.36(s,1H,Ar-H),8.48(d,J＝7.5Hz,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ1.0,1.2,62.8,114.6,118.1,121.9,124.8,125.6,128.6,130.3,134.5,136.7,139.5,142.0,151.4,156.7ppm.
6d, molecular formula: c20H26ClNO4Si3
Chinese naming: 2, 3-dioxo-trisilyl-5-methoxy-9-chloro-6-phenanthridinone
English naming: 2, 3-dioxaristolone-5-methoxy-9-chloro-6 (5H) -phenylanthridinone
Molecular weight: 463.09
Melting point: 153 ℃ C. -
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ0.16(s,6H,SiMe2),0.51(s,6H,SiMe2),0.53(s,6H,SiMe2),4.14(s,3H,OCH3),7.56(dd,J＝8.5,1.5Hz,1H,Ar-H),7.83(s,1H,Ar-H),8.22(d,J＝1.5Hz,1H,Ar-H),8.31(s,1H,Ar-H),8.49(d,J＝8.5Hz,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ0.7,1.9,2.2,62.8,116.7,118.0,121.7,125.0,128.6,128.7,130.4,134.2,135.6,139.6,140.1,149.6,156.7ppm.
example five:
iodobenzene diacetate (1.0 to 1.5eq), trifluoromethanesulfonic acid (2.5 to 3.0eq), benzobis (oxydisillocene) (1,1.0 to 1.2eq), N-methoxy-4-nitrobenzamide (4e,0.5eq), cesium fluoride (2.5 to 3.0eq), copper acetate (1.0 to 1.5eq), tetrabutylammonium bromide (0.5 to 1.0eq), palladium acetate (0.02 to 0.03eq), and the obtained phenanthridinone derivative is: 2, 3-oxydisilyl-5-methoxy-9-nitro-6-phenanthridinone (5e), yield 48%. The structure of the compound is as follows:
5e molecular formula: c18H20N2O5Si2
Chinese naming: 2, 3-oxydisilyl-5-methoxy-9-nitro-6-phenanthridinone
English naming: 2, 3-oxadilole-5-methoxy-9-nitro-6 (5H) -phenylanthridinone
Molecular weight: 400.09
Melting point: 163 ℃ 164-
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ0.47(s,6H,SiMe2),0.49(s,6H,SiMe2),4.19(s,3H,OCH3),7.88(s,1H,Ar-H),8.39(dd,J＝9.0,2.0Hz,1H,Ar-H),8.50(s,1H,Ar-H),8.75(d,J＝9.0Hz,1H,Ar-H),9.23(d,J＝2.0Hz,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ1.0,1.3,62.9,114.8,117.9,118.0,121.9,126.0,130.4,130.7,134.3,136.8,142.8,150.5,152.6,155.9ppm.
example six:
iodobenzene diacetate (1.0 to 1.5eq), trifluoromethanesulfonic acid (2.5 to 3.0eq), oxydosilylnaphthalene (7,1.0 to 1.2eq), N-methoxy-4-methoxybenzamide (4a,0.5eq), cesium fluoride (2.5 to 3.0eq), copper acetate (1.0 to 1.5eq), tetrabutylammonium bromide (0.5 to 1.0eq), palladium acetate (0.02 to 0.03eq), and the obtained phenanthridinone derivative is: 2, 6-dimethoxy-5-benzophenanthridinone (10a), yield 60%. The structure of the compound is as follows:
10a molecular formula: c19H15NO3
Chinese naming: 2, 6-dimethoxybenzo-5-phenanthridinone
English naming: 2, 6-dimethoxybenzoic [ b ] phenonthridin-5 (6H) -one
Molecular weight: 305.11
Melting point: 170 ℃ C
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ4.04(s,3H,OCH3),4.19(s,3H,OCH3),7.16-7.18(m,1H,Ar-H),7.48(t,J＝7.5Hz,1H,Ar-H),7.56(t,J＝8.0Hz,1H,Ar-H),7.79(d,J＝1.5,1H,Ar-H),7.93(d,J＝8.0Hz,1H,Ar-H),7.97-7.99(m,2H,Ar-H),8.48(d,J＝9.0Hz,1H,Ar-H),8.66(s,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ55.7,62.5,105.7,108.6,115.8,119.1,119.7,123.0,125.2,127.3,127.5,128.2,129.3,130.9,133.9,134.0,134.7,157.2,163.2ppm.
example seven:
iodobenzene diacetate (1.0 to 1.5eq), trifluoromethanesulfonic acid (2.5 to 3.0eq), oxydosilylnaphthalene (7,1.0 to 1.2eq), N-methoxy-4-methylbenzamide (4b,0.5eq), cesium fluoride (2.5 to 3.0eq), copper acetate (1.0 to 1.5eq), tetrabutylammonium bromide (0.5 to 1.0eq), palladium acetate (0.02 to 0.03eq), and the obtained phenanthridinone derivative is: 2-methyl-6-methoxy-5-benzophenanthridinone (10b), yield 76%. The structure of the compound is as follows:
10b molecular formula: c19H15NO2
Chinese naming: 2-methyl-6-methoxy-5-benzophenanthridinone
English naming: 2-Methyl-6-methoxy benzob ] phenanthridin-5(6H) -one
Molecular weight: 289.11
Melting point: 189 deg.C, 191 deg.C
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ2.61(s,3H,CH3),4.20(s,3H,OCH3),7.44(d,J＝8.0Hz,1H,Ar-H),7.49(t,J＝8.0Hz,1H,Ar-H),7.56(t,J＝7.5Hz,1H,Ar-H),7.94(d,J＝8.0Hz,1H,Ar-H),7.98(d,J＝8.0Hz,1H,Ar-H),8.00(s,1H,Ar-H),8.23(s,1H,Ar-H),8.44(d,J＝8.5Hz,1H,Ar-H),8.74(s,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ22.2,62.5,108.6,119.3,122.4,122.9,123.9,125.2,127.3,127.4,128.2,128.7,129.4,129.8,132.8,133.7,133.8,143.4,157.4ppm.
example eight:
iodobenzene diacetate (1.0 to 1.5eq), trifluoromethanesulfonic acid (2.5 to 3.0eq), oxydosilylnaphthalene (7,1.0 to 1.2eq), N-methoxybenzamide (4c,0.5eq), cesium fluoride (2.5 to 3.0eq), copper acetate (1.0 to 1.5eq), tetrabutylammonium bromide (0.5 to 1.0eq), palladium acetate (0.02 to 0.03eq), and the obtained phenanthridinone derivative is: 6-methoxy-5-benzophenanthridinone (10c), yield 83%. The structure of the compound is as follows:
10c molecular formula: c18H13NO2
Chinese naming: 6-methoxy-5-benzophenanthridinone
English naming: 6-Methoxy benzol [ b ] phenoanthridin-5 (6H) -one
Molecular weight: 275.09
Melting point: 153 ℃ C. -
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ4.20(s,3H,OCH3),7.47-7.50(m,1H,Ar-H),7.54-7.57(m,1H,Ar-H),7.60-7.63(m,1H,Ar-H),7.78-7.81(m,1H,Ar-H),7.92(d,J＝8.5Hz,1H,Ar-H),7.96(d,J＝8.5Hz,1H,Ar-H),7.99(s,1H,Ar-H),8.41(d,J＝8.0Hz,1H,Ar-H),8.54-8.56(m,1H,Ar-H),8.71(s,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ62.5,108.6,119.3,122.2,123.0,125.3,126.2,127.3,127.5,128.2,128.4,128.7,129.4,132.7,132.8,133.6,133.7,157.3ppm.
example nine:
iodobenzene diacetate (1.0 to 1.5eq), trifluoromethanesulfonic acid (2.5 to 3.0eq), oxydosilylnaphthalene (7,1.0 to 1.2eq), N-methoxy-4-chlorobenzamide (4d,0.5eq), cesium fluoride (2.5 to 3.0eq), copper acetate (1.0 to 1.5eq), tetrabutylammonium bromide (0.5 to 1.0eq), palladium acetate (0.02 to 0.03eq), and the obtained phenanthridinone derivative is: 2-chloro-6-methoxy-5-benzophenanthridinone (10d), yield 63%. The structure of the compound is as follows:
10d, molecular formula: c18H12ClNO2
Chinese naming: 2-chloro-6-methoxy-5-benzophenanthridinone
English naming: 2-Chloro-6-methoxy-benzob ] phenanthridin-5(6H) -one
Molecular weight: 309.06
Melting point: 177 temperature 178 ℃ C
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ4.21(s,3H,OCH3),7.51(t,J＝7.5Hz,1H,Ar-H),7.56-7.61(m,2H,Ar-H),7.95(d,J＝8.0Hz,1H,Ar-H),7.99(d,J＝10.0Hz,1H,Ar-H),8.01(s,1H,Ar-H),8.39(d,J＝1.5Hz,1H,Ar-H),8.49(d,J＝8.5Hz,1H,Ar-H),8.68(s,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ62.6,108.9,118.1,122.2,123.4,124.6,125.6,127.4,127.9,128.3,128.8,129.4,130.5,133.7,134.1,134.4,139.6,156.7ppm.
example ten:
iodobenzene diacetate (1.0 to 1.5eq), trifluoromethanesulfonic acid (2.5 to 3.0eq), oxydosilylnaphthalene (7,1.0 to 1.2eq), N-methoxy-4-nitrobenzamide (4e,0.5eq), cesium fluoride (2.5 to 3.0eq), copper acetate (1.0 to 1.5eq), tetrabutylammonium bromide (0.5 to 1.0eq), palladium acetate (0.02 to 0.03eq), and the obtained phenanthridinone derivative is: 2-nitro-6-methoxy-5-benzophenanthridinone (10e), yield 52%. The structure of the compound is as follows:
10e molecular formula: c18H12N2O4
Chinese naming: 2-nitro-6-methoxy-5-benzophenanthridinone
English naming: 2-Nitro-6-methoxy benzob ] phenanthridin-5(6H) -one
Molecular weight: 320.08
Melting point: 201-
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3):δ4.23(s,3H,OCH3),7.55(t,J＝7.5Hz,1H,Ar-H),7.62(t,J＝8.0Hz,1H,Ar-H),7.95(d,J＝8.5Hz,1H,Ar-H),8.02(s,1H,Ar-H),8.03(s,1H,Ar-H),8.35(dd,J＝8.5,1.5Hz,1H,Ar-H),8.70(d,J＝8.5Hz,1H,Ar-H),8.78(s,1H,Ar-H),9.22(d,J＝1.5Hz,1H,Ar-H)ppm.
nuclear magnetic resonance carbon spectrum:13C NMR(125MHz,CDCl3):δ62.8,109.3,117.7,117.9,122.1,124.0,126.0,127.4,128.4,128.5,129.5,130.3,130.7,133.5,134.2,134.4,150.5,155.8ppm.
TABLE 1 photochemical Properties and thermal stabilities of Compounds 5a-e and 10a-e
[a]Measured in methylene chloride solvent.[b]The wavelength of maximum absorption.[c]The maximum emission wavelength.[d]1.0M H2SO4The quinine solution of (phi) is standard3130.48) test 5a-e with 0.1M H2SO4The quinine solution of (phi) is standard3650.54) tests 10 a-e.[e]The decomposition temperature was measured by thermogravimetric analysis with a heating rate of 10 ℃/min under nitrogen.
TABLE 2 electrochemical Properties of Compounds 5a-e and 10a-e
[a]Determination of the Oxidation potential (E) in acetonitrile solvent by Cyclic voltammetryox) The scanning speed is 100mV/s, E is calculated by taking ferrocene (vacuum dissociation energy-4.8 eV) as an external standard and taking a platinum electrode as a working electrode, a platinum wire as an auxiliary electrode, a Saturated Calomel Electrode (SCE) as a reference electrode, an agar salt bridge and 0.1M tetrabutyl ammonium hexafluorophosphate as an electrolyte1/2(Fc/Fc+)＝0.43V。[b]HOMO＝-[Eox–[E1/2(Fc/Fc+)]+4.8].[c]The energy level difference Eg is estimated from the uv absorption in dichloromethane.[d]LUMO＝HOMO+Optical band gap。
Claims (2)
1. A fused heterocyclic compound phenanthridinone or benzophenanthridinone derivative, wherein the compound has one of the following structures:
(1)
(2)
wherein R is methoxy, methyl, hydrogen, chlorine or nitro.
2. A process for the preparation of phenanthridinone or benzophenanthridinone derivatives according to claim 1, characterized in that it has the following steps:
a. under the protection of inert gas nitrogen and under the condition of ice-water bath, adding trifluoromethanesulfonic acid into a dichloromethane solution of iodobenzene diacetate, reacting for 0.5-1 hour in ice-water bath, and reacting for 1-2 hours at room temperature; adding the reaction solution into a cooled dichloromethane solution of benzo-bis (oxadisilylone) or oxadisilyl naphthalene under the condition of ice-water bath, continuing ice-water bath reaction for 0.5-1 hour, reacting at room temperature for 3-4 hours, extracting with dichloromethane, washing with water, drying and removing the solvent by spinning to obtain phenyl [ o- (hydroxy dimethyl silicon) oxadisilyl condensed phenyl]Triflic acid iodide or phenyl [ o- (hydroxydimethylsilyl) naphthyl)]Triflic acid iodide, the structural formula of which is respectively:
the structural formula of the iodobenzene diacetate is as follows: PhI (OAc)2；
The structural formula of the benzo-bis (oxydisilocene) is as follows:
the structural formula of the oxydisilyl naphthalene is as follows:
b. in N2Protecting the phenyl [ o- (hydroxydimethylsilyl) oxydisilyl condensed phenyl obtained in the step a]Triflic acid iodide or phenyl [ o- (hydroxydimethylsilyl) naphthyl)]Adding acetonitrile solution of triflurosulfonic acid iodide into acetonitrile solution of N-methoxy-4-substituted benzamide derivative, cesium fluoride, palladium acetate, copper acetate and tetrabutylammonium bromide in batches, carrying out reflux reaction for 2 hours, separating and purifying to obtain solid silicon oxide based phenanthridinone or benzophenanthridinone derivative, wherein the structural formulas are respectively as follows:
the structural formula of the N-methoxy-4-substituted benzamide derivative is as follows:
the molar ratio of the diacetate iodide salt, the trifluoromethanesulfonic acid, the benzobis (oxydisilocene) or the oxydisinylnaphthalene, the N-methoxy-4-substituted benzamide derivative, the cesium fluoride, the copper acetate, the tetrabutylammonium bromide and the palladium acetate is as follows: 1.0-1.5: 2.5-3.0: 1.0-1.2: 0.5: 2.5-3.0: 1.0-1.5: 0.5-1.0: 0.02-0.03.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710250419.6A CN107082761B (en) | 2017-04-17 | 2017-04-17 | Phenanthridinone or benzophenanthridinone derivative and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710250419.6A CN107082761B (en) | 2017-04-17 | 2017-04-17 | Phenanthridinone or benzophenanthridinone derivative and synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107082761A CN107082761A (en) | 2017-08-22 |
| CN107082761B true CN107082761B (en) | 2020-04-03 |
Family
ID=59612080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710250419.6A Expired - Fee Related CN107082761B (en) | 2017-04-17 | 2017-04-17 | Phenanthridinone or benzophenanthridinone derivative and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107082761B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320539A (en) * | 2018-04-23 | 2019-02-12 | 上海大学 | Spiral shell benzoxazine or spiral shell naphtho- oxazines and isoquinolin indolinone derivative and its synthetic method |
| CN110128459A (en) * | 2019-05-16 | 2019-08-16 | 上海大学 | Eight cyclic ketones of dibenzo thia or eight cyclic ketone derivative of benzo naphtho- thia and its synthetic method |
| CN113024462A (en) * | 2019-12-25 | 2021-06-25 | 清华大学 | Method for efficiently preparing phenanthridinone and derivatives thereof without metal participation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1356984A (en) * | 1999-04-19 | 2002-07-03 | 三共株式会社 | Neurotrophin protentiators |
| CN102812007A (en) * | 2010-02-01 | 2012-12-05 | 国立大学法人鹿儿岛大学 | Therapeutic agent for hepatitis C |
| CN104860883A (en) * | 2014-02-26 | 2015-08-26 | 三星显示有限公司 | Compound And Organic Light-emitting Device Including The Same |
| CN105131974A (en) * | 2015-07-28 | 2015-12-09 | 江苏和成新材料有限公司 | Phenanthridone-structure heterocyclic polymerizable liquid crystal compound and preparation method thereof |
-
2017
- 2017-04-17 CN CN201710250419.6A patent/CN107082761B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1356984A (en) * | 1999-04-19 | 2002-07-03 | 三共株式会社 | Neurotrophin protentiators |
| CN102812007A (en) * | 2010-02-01 | 2012-12-05 | 国立大学法人鹿儿岛大学 | Therapeutic agent for hepatitis C |
| CN104860883A (en) * | 2014-02-26 | 2015-08-26 | 三星显示有限公司 | Compound And Organic Light-emitting Device Including The Same |
| CN105131974A (en) * | 2015-07-28 | 2015-12-09 | 江苏和成新材料有限公司 | Phenanthridone-structure heterocyclic polymerizable liquid crystal compound and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107082761A (en) | 2017-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107082761B (en) | Phenanthridinone or benzophenanthridinone derivative and synthesis method thereof | |
| JP5940548B2 (en) | Novel spirobifluorene compounds | |
| CN109369629B (en) | β -lactam derivatives and process for their preparation | |
| US20110195947A1 (en) | Methods of synthesizing and isolating n-(bromoacetyl)-3,3-dinitroazetidine and a composition including the same | |
| Wang et al. | Selectivities in the reaction of vicinal diimines and acyl chlorides | |
| CN103951694A (en) | Acridine or benzacridine derivative and synthesis method thereof | |
| CN108341778B (en) | Synthetic method of phenanthridinone compound | |
| CN106432316B (en) | Indolizine and iso-indoles or benzindole piperazine and isoindole derivatives and its synthetic method | |
| Hall et al. | The synthesis of pyrido [4, 3-b] carbazoles from diphenylamine derivatives: alternative routes to and relay syntheses of ellipticines and olivacines | |
| Oparina et al. | Metal-and Solvent-free Synthesis of Functionalized Dihydrooxazolo [3, 2-a] indoles by One-Pot Tandem Assembly of 3H-Indoles and Propargylic Alcohols | |
| CN110407784A (en) | 2- sweet-smelling formacyl benzofuran derivatives or 2- sweet-smelling formacyl aphthofurans derivative and its synthetic method | |
| CN105669668B (en) | Pyrido indazole or benzo pyrido indazole derivative and its synthetic method | |
| RU2599987C1 (en) | Method of producing 3, 3', 4, 4'-tetramethyldiphenyl | |
| Jiang et al. | Design, synthesis, and anticancer activities of new compounds bearing the quinone–pyran–lactone tricyclic pharmacophore | |
| WO2014016338A1 (en) | New synthetic route for the preparation of 3-amino-piperidine compounds | |
| CN104592290A (en) | Phenanthridine derivatives and synthetic methods thereof | |
| Aly | Photochemical synthesis of [2.2](3, 8)-pyridazinophane and quinolinophane-2 (1H)-one as well as synthesis of [2](5, 8)-quinolinophanes and fused spiro-pyranoindanoparacyclophanes | |
| CN111704630A (en) | 3-arylformyl naphtho-isoxazole or 3-arylformyl anthraceno-isoxazole derivative and synthetic method thereof | |
| Kitamura et al. | Isoacenofuran: a novel quinoidal building block for efficient access to high-ordered polyacene derivatives | |
| CN113336784B (en) | 3-substituted benzofluorenone or 3-substituted naphthofluorenone derivatives and synthesis method thereof | |
| Shinkevich et al. | Synthesis of 1-substituted 1, 2, 3, 4-tetrahydrobenz [g] isoquinoline-5, 10-diones | |
| CN114716359A (en) | Preparation method of hydrogenated indole imine diastereoisomer | |
| Xie et al. | A base-promoted desalicyloylative dimerization of 3-(1-alkynyl) chromones: An unusual approach to 2-alkynyl xanthones | |
| CN105418499A (en) | Preparation method of acridine compound | |
| CN109265311B (en) | Phenyl fluorene derivative and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200403 |