CN106432316B - Indolizine and iso-indoles or benzindole piperazine and isoindole derivatives and its synthetic method - Google Patents
Indolizine and iso-indoles or benzindole piperazine and isoindole derivatives and its synthetic method Download PDFInfo
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- CN106432316B CN106432316B CN201610845730.0A CN201610845730A CN106432316B CN 106432316 B CN106432316 B CN 106432316B CN 201610845730 A CN201610845730 A CN 201610845730A CN 106432316 B CN106432316 B CN 106432316B
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- silicon substrate
- indolizine
- piperazine
- indoles
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- KKEMBOKJAXOEOD-UHFFFAOYSA-N N1CCNCC1.N1C=CC2=CC=C3C(=C12)C=CC=C3 Chemical compound N1CCNCC1.N1C=CC2=CC=C3C(=C12)C=CC=C3 KKEMBOKJAXOEOD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 125000000904 isoindolyl group Chemical class C=1(NC=C2C=CC=CC12)* 0.000 title claims abstract 11
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 title abstract description 49
- 238000010189 synthetic method Methods 0.000 title abstract description 9
- -1 methoxyl group Chemical group 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000460 chlorine Chemical group 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 58
- 239000010703 silicon Substances 0.000 claims description 58
- 239000000758 substrate Substances 0.000 claims description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000001301 oxygen Substances 0.000 claims description 48
- 229910052760 oxygen Inorganic materials 0.000 claims description 48
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 44
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- XEFCWBLINXJUIV-UHFFFAOYSA-N acetic acid;iodobenzene Chemical compound CC(O)=O.CC(O)=O.IC1=CC=CC=C1 XEFCWBLINXJUIV-UHFFFAOYSA-N 0.000 claims description 16
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 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 14
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 11
- YRXICXUINRGLJP-UHFFFAOYSA-N hydroxy(dimethyl)silicon Chemical compound C[Si](C)O YRXICXUINRGLJP-UHFFFAOYSA-N 0.000 claims description 11
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 4
- ZVVKQMKHETZPRR-UHFFFAOYSA-N acetonitrile;hydroiodide Chemical compound I.CC#N ZVVKQMKHETZPRR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims 1
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 7
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 5
- 239000001257 hydrogen Chemical group 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract description 2
- 238000011056 performance test Methods 0.000 abstract description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 150000002518 isoindoles Chemical class 0.000 description 77
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 58
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 241000790917 Dioxys <bee> Species 0.000 description 13
- 125000005605 benzo group Chemical group 0.000 description 12
- VAYJLUJYQADPLB-UHFFFAOYSA-N 15-azatetracyclo[6.6.1.02,7.011,15]pentadeca-1(14),2,4,6,8,10,12-heptaene Chemical compound C1=CC=C2C=CC3=C(C=CC=C4)C4=C1N32 VAYJLUJYQADPLB-UHFFFAOYSA-N 0.000 description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- 150000002475 indoles Chemical class 0.000 description 6
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- ZFKIEMWXMVCZHP-UHFFFAOYSA-N 1h-indole;piperazine Chemical compound C1CNCCN1.C1=CC=C2NC=CC2=C1 ZFKIEMWXMVCZHP-UHFFFAOYSA-N 0.000 description 2
- MUMVZZLEJULVAE-UHFFFAOYSA-N 2-(4-methoxyphenyl)indolizine Chemical compound C1=CC(OC)=CC=C1C1=CN2C=CC=CC2=C1 MUMVZZLEJULVAE-UHFFFAOYSA-N 0.000 description 2
- DCLHWYSXBSMRRM-UHFFFAOYSA-N 2-(4-methylphenyl)indolizine Chemical compound C1=CC(C)=CC=C1C1=CN2C=CC=CC2=C1 DCLHWYSXBSMRRM-UHFFFAOYSA-N 0.000 description 2
- CCRXTYXEWWXCOM-UHFFFAOYSA-N 2-(4-nitrophenyl)indolizine Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1=CN2C=CC=CC2=C1 CCRXTYXEWWXCOM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- HBMUMVMGBLMQJT-UHFFFAOYSA-N pyrrolo[2,1-a]isoquinoline Chemical compound C12=CC=CC=C2C=CN2C1=CC=C2 HBMUMVMGBLMQJT-UHFFFAOYSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- XBHPFCIWRHJDCP-UHFFFAOYSA-N (2-trimethylsilylphenyl) trifluoromethanesulfonate Chemical compound C[Si](C)(C)C1=CC=CC=C1OS(=O)(=O)C(F)(F)F XBHPFCIWRHJDCP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229940054051 antipsychotic indole derivative Drugs 0.000 description 1
- DYJFXZAVYGPICR-UHFFFAOYSA-N benzene;silicon Chemical compound [Si].C1=CC=CC=C1 DYJFXZAVYGPICR-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 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
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000284 extract Substances 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
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/16—Peri-condensed systems
-
- 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 Table
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The present invention relates to a kind of indolizine and iso-indoles or benzindole piperazine and isoindole derivatives and its synthetic methods.The compound has the following structure:Wherein, R is methoxyl group, methyl, hydrogen, chlorine, nitro.It theoretically analyzes, this method experienced [8+2] cycloaddition reaction, which successfully constructs indolizine simultaneously iso-indoles or benzindole piperazine and iso-indoles molecular skeleton, enrich the synthetic method of organic fused heterocyclic compound.It is analyzed from performance test, simultaneously isoindole derivatives have certain photoelectric properties, part of compounds quantum yield with higher for indolizine and iso-indoles or benzindole piperazine.These compounds show stronger blue or green fluorescence, are the luminous organic materials with potential using value.
Description
Technical field
The invention belongs to field of heterocyclic compound in organic chemistry, it is related to a kind of fused heterocyclic compound indolizine and iso-indoles
Or benzindole piperazine and isoindole derivatives and its synthetic method.
Background technique
Simultaneously isoindole derivatives have extraordinary fluorescence and high quantum production rate to indolizine, therefore in luminescent material and sensing
Device etc. is with potential application prospect, therefore, synthesis of indole piperazine and isoindole derivatives cause everybody interest.[8+
2] cycloaddition reaction is the important reaction of one kind of synthesizing heterocyclic compound, has the characteristics that Atom economy, and modern organic
Synthesis chemistry one of hot spot of interest.The synthesis of indolizine and isoindole derivatives is it has been reported that document report in 2007
Road forms benzyne under fluorine reagent effect using o-trimethylsilylphenyl triflate as aryne precursor, derivative with indolizine
Object reaction, synthesis obtain indolizine and isoindole derivatives, and method is easier.Currently, we have studied with the bis- (oxygen two of benzo
Silicon cyclopentadienyl) it is aryne precursor, two silicon benzyne of oxygen is formed at room temperature, and [8+2] cycloaddition reaction occurs with indole derivative,
Simplicity synthesis obtains two silicon indolizine of oxygen simultaneously isoindole derivatives and three silicon substrate indolizine of dioxy and isoindole derivatives.While I
Had found for the first time using two silicon substrate naphthalene of oxygen as naphthalyne precursor, form naphthalyne at room temperature, with indole derivative occur [8+
2] cycloaddition reaction, synthesis obtain new condensed hetero ring benzindole piperazine and isoindole derivatives, simple synthetic method, condition temperature
With.And have studied two silicon indolizine of oxygen and the photoelectric properties of isoindole derivatives and benzindole piperazine and isoindole derivatives.
Summary of the invention:
One of the objects of the present invention is to provide a new class of two silicon substrate indolizine of oxygen and isoindole derivatives, three silicon of dioxy
Base indolizine and isoindole derivatives or benzindole piperazine and isoindole derivatives.
The second object of the present invention is to provide the preparation method of these derivatives.
In order to achieve the above objectives, reaction process of the invention are as follows:
Benzo bis- (two silicon of oxygen cyclopentadienyl) (1) or two silicon substrate naphthalene (7) of oxygen are reacted with iodobenzene diacetate salt, trifluoromethanesulfonic acid, are generated
Phenyl [adjacent (two silicon substrate fused phenyl of hydroxyl dimethyl silicon substrate oxygen)] three fluosulfonic acid iodide (2) or phenyl [adjacent (hydroxyl dimethyl
Silicon substrate) naphthalene] three fluosulfonic acid iodide (8).At room temperature, 2- (hetero) aryl indole oxazine derivatives 4a-e, cesium fluoride are sequentially added
(CsF), benzyne intermediate 3 or naphthalyne intermediate 9 are first generated, [8+ occurs with 2- (hetero) aryl indole oxazine derivatives 4a-e immediately
2] cycloaddition reaction generates two silicon substrate indolizine of oxygen simultaneously isoindole derivatives 5a-e and three silicon substrate indolizine of dioxy and iso-indoles
Derivative 6a-e, total yield 42-63%；Or benzindole piperazine and isoindole derivatives 10a-e, yield 42-72%.
According to above-mentioned reaction mechanism, the present invention adopts the following technical scheme:
A kind of indolizine and iso-indoles or benzindole piperazine and isoindole derivatives, it is characterised in that the compound has such as
One of flowering structure:
、Or
Wherein, R is methoxyl group, methyl, hydrogen, chlorine or nitro.
A method of preparing above-mentioned indolizine simultaneously iso-indoles or benzindole piperazine and isoindole derivatives, feature
It is that this method has following steps:
A. under the protection of inert gas, trifluoromethanesulfonic acid is added to the dichloro of iodobenzene diacetate salt by ice-water bath condition
In dichloromethane, ice-water bath reacts 0.5~1 hour, reacts at room temperature 1~2 hour；The reaction solution is added under the conditions of ice-water bath
Into benzo bis- (two silicon of oxygen cyclopentadienyls) or the dichloromethane solution of two silicon substrate naphthalene of oxygen, continues ice-water bath and react 0.5~1 hour, room temperature
Reaction 3~4 hours extracts phenyl [adjacent (two silicon substrate fused phenyl of hydroxyl dimethyl silicon substrate oxygen)] three fluosulfonic acid iodine with methylene chloride
Compound or phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthalene] three fluosulfonic acid iodide, washing, drying simultaneously revolve solvent；
B. under inert gas protection, by phenyl obtained by step a, [adjacent (two silicon substrate of hydroxyl dimethyl silicon substrate oxygen condenses benzene
Base)] dichloromethane solutions of three fluosulfonic acid iodide or phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthalene] three fluosulfonic acid iodide
Acetonitrile solution be added portionwise in the dichloromethane solution or acetonitrile solution of 2- (hetero) aryl indole oxazine derivatives and cesium fluoride, flow back
1~1.5 hour, through separating-purifying, obtain final product indolizine simultaneously iso-indoles or benzindole piperazine and isoindole derivatives；
The structural formula of the iodobenzene diacetate salt are as follows: PhI (OAc)2；
The structural formula of the benzo bis- (two silicon of oxygen cyclopentadienyls) are as follows:；
The structural formula of the two silicon substrate naphthalene of oxygen are as follows:；
Three fluosulfonic acid iodide its structural formula of the phenyl [adjacent (two silicon substrate fused phenyl of hydroxyl dimethyl silicon substrate oxygen)]
Are as follows:；
Three fluosulfonic acid iodide its structural formula of the phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthalene] are as follows:；
The structural formula of the 2- (hetero) aryl indole oxazine derivatives are as follows:, wherein R be methoxyl group,
Methyl, hydrogen, chlorine or nitro；
The oxalic acid salt compounded of iodine, trifluoromethanesulfonic acid, benzo bis- (two silicon of oxygen cyclopentadienyls) or two silicon substrate naphthalene of oxygen, 2- (hetero) aryl indole
The molar ratio of oxazine derivatives, cesium fluoride (CsF) are as follows: 1.0~1.5: 2.5~3.0: 1.0 ~ 1.2: 0.5: 9.5~
10.0。
The method of the present invention is using benzo bis- (two silicon of oxygen cyclopentadienyls) or two silicon substrate naphthalene of oxygen as benzyne or naphthalyne precursor, at room temperature
Benzyne and naphthalyne are formed, is further reacted with indole derivative, two silicon substrate indolizine of oxygen and isoindole derivatives and two are generated
Three silicon substrate indolizine of oxygen and isoindole derivatives or benzindole piperazine and isoindole derivatives.The synthetic method has reaction speed
Fastly, reaction condition is mild, advantages of environment protection.
The invention discloses a kind of synthesis of indole piperazine and isoindole derivatives or benzindole piperazine and isoindole derivatives
Method is to form benzyne or naphthalene under mild conditions with benzo bis- (two silicon of oxygen cyclopentadienyls) or two silicon substrate naphthalene of oxygen for new aryne precursor
Alkynes, occurs [8+2] cycloaddition reaction with 2- (hetero) aryl indole oxazine derivatives respectively, synthesis obtain indolizine and isoindole derivatives or
Benzindole piperazine and isoindole derivatives.The synthetic method reaction speed is fast, and reaction condition is mild, has the spies such as Atom economy
Point.
It theoretically analyzes, this method experienced [8+2] cycloaddition reaction, which successfully constructs indolizine and different
Indoles or benzindole piperazine and iso-indoles molecular skeleton, enrich the synthetic method of organic fused heterocyclic compound.
It is analyzed from performance test, simultaneously isoindole derivatives have photo electric for indolizine and iso-indoles or benzindole piperazine
Can, see Fig. 1-4, table 1-2, part of compounds quantum yield with higher.These compounds show it is stronger blue or
Green fluorescence is the luminous organic material with potential using value.
Detailed description of the invention
Absorption spectrum of Fig. 1 compound 5a-5e in dichloromethane solvent；
Absorption spectrum of Fig. 2 compound 10a-10e in dichloromethane solvent；
Emission spectrum of Fig. 3 compound 5a-e in dichloromethane solvent；
Emission spectrum of Fig. 4 compound 10a-e in dichloromethane solvent.
Specific embodiment
Embodiment one: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), the bis- (oxygen of benzo
Two silicon cyclopentadienyl) (1,1.0 ~ 1.2 eq), 2- p-methoxyphenyl indolizine (4a, 0.5 eq), cesium fluoride (9.5~10.0 eq),
Gained indolizine and isoindole derivatives are as follows: two silicon substrate indolizine of 1- p-methoxyphenyl -7,8- oxygen simultaneously [3,4,5-ab] different Yin
Diindyl (5a) and three silicon substrate indolizine of 1- p-methoxyphenyl -7,8- dioxy simultaneously [3,4,5-ab] iso-indoles (6a), total yield 54%.
The structure of the compound are as follows:
With
5a: molecular formula: C25H25NO2Si2
Chinese name: two silicon substrate indolizine of 1- p-methoxyphenyl -7,8- oxygen simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Methoxyphenyl-7,8-oxadisilole indolizino[3,4,5-ab]
isoindole
Molecular weight: 427.14
Fusing point: 158-160 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 0.48 (s, 6H, SiMe2), 0.50 (s,
6H, SiMe2), 3.95 (s, 3H, OCH3), 7.17 (d, J = 8.5 Hz, 2H, Ar-H), 7.24 (s, 1H,
Ar-H), 7.72 (t, J = 8.0 Hz, 1H, Ar-H), 8.01 (d, J = 9.0 Hz, 2H, Ar-H), 8.03
(d, J = 8.0 Hz, 1H, Ar-H), 8.12 (d, J = 7.5 Hz, 1H, Ar-H), 8.53 (s, 1H, Ar-
H), 8.68 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ 1.3, 1.5, 55.4, 103.8, 107.7,
114.6, 115.0, 118.8, 120.0, 121.8, 125.3, 127.9, 128.8, 128.9, 129.7, 130.2,
131.3, 131.6, 140.4, 147.3, 159.3 ppm。
: molecular formula: C27H31NO3Si3
Chinese name: three silicon substrate indolizine of 1- p-methoxyphenyl -7,8- dioxy simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Methoxyphenyl-7,8-dioxatrisilole indolizino[3,4,5-ab]
isoindole
Molecular weight: 501.16
Fusing point: 176-177 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 0.17 (s, 6H, SiMe2), 0.55 (s,
6H, SiMe2), 0.57 (s, 6H, SiMe2), 3.95 (s, 3H, OCH3), 7.15 (d, J = 8.5 Hz, 2H,
Ar-H), 7.264 (s, 1H, Ar-H), 7.73 (t, J = 8.0 Hz, 1H, Ar-H), 8.02-8.04 (m, 3H,
Ar-H), 8.14 (d, J = 7.0 Hz, 1H, Ar-H), 8.66 (s, 1H, Ar-H), 8.67 (s, 1H, Ar-H)
ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 0.8,2.2,2.4,55.5,103.7,
108.1, 114.5, 115.0, 119.0, 120.1, 125.5, 127.8, 128.2, 128.3, 128.6, 128.8,
129.1, 129.7, 131.7, 138.4, 145.1, 159.3 ppm。
Embodiment two: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), the bis- (oxygen of benzo
Two silicon cyclopentadienyl) (1,1.0 ~ 1.2 eq), 2- p-methylphenyl indolizine (4b, 0.5 eq), cesium fluoride (9.5~10.0 eq), institute
Indolizine and isoindole derivatives are as follows: two silicon substrate indolizine of 1- p-methylphenyl -7,8- oxygen simultaneously [3,4,5-ab] iso-indoles
(5b) and three silicon substrate indolizine of 1- p-methylphenyl -7,8- dioxy simultaneously [3,4,5-ab] iso-indoles (6b), total yield 47%.The change
Close the structure of object are as follows:
With
5b: molecular formula: C25H25NOSi2
Chinese name: two silicon substrate indolizine of 1- p-methylphenyl -7,8- oxygen simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Methylphenyl-7,8-oxadisilole indolizino[3,4,5-ab]
isoindole
Molecular weight: 411.15
Fusing point: 167-169 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3): δ 0.50 (s, 6H, SiMe2), 0.51 (s,
6H, SiMe2), 2.52 (s, 3H, CH3), 7.29 (s, 1H, Ar-H), 7.45 (d, J = 8.0 Hz, 2H,
Ar-H), 7.72 (t, J = 8.0 Hz, 1H, Ar-H), 7.99 (d, J = 8.0 Hz, 2H, Ar-H), 8.04
(d, J = 8.0 Hz, 1H, Ar-H), 8.13 (d, J = 7.5 Hz, 1H, Ar-H), 8.57 (s, 1H, Ar-
H), 8.69 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ1.3,1.4, 21.3, 104.1, 107.8,
115.1, 120.0, 122.0, 125.3, 128.0, 128.5, 128.9, 129.8, 129.9, 130.3, 131.8,
133.3, 135.0, 137.3, 140.5, 147.4 ppm。
: molecular formula: C27H31NO2Si3
Chinese name: three silicon substrate indolizine of 1- p-methylphenyl -7,8- dioxy simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Methylphenyl-7,8-dioxatrisilole indolizino[3,4,5-ab]
isoindole
Molecular weight: 485.17
Fusing point: 157-159 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 0.16 (s, 6H, SiMe2), 0.55 (s,
6H, SiMe2), 0.57 (s, 6H, SiMe2), 2.50 (s, 3H, CH3), 7.31 (s, 1H, Ar-H), 7.42
(d, J = 8.0 Hz, 2H, Ar-H), 7.73 (t, J = 8.0 Hz, 1H, Ar-H), 8.00 (d, J = 8.0
Hz, 2H, Ar-H), 8.04 (d, J = 8.5 Hz, 1H, Ar-H), 8.14 (d, J = 7.5 Hz, 1H, Ar-
H), 8.66 (s, 1H, Ar-H), 8.70 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ0.8, 2.2, 2.4, 21.4, 104.0,
108.2, 115.2, 119.1, 120.1, 125.7, 127.9, 128.26, 128.32, 128.4, 129.1,
129.7, 129.9, 131.9, 133.1, 137.5, 138.5, 145.2 ppm。
Embodiment three: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), the bis- (oxygen of benzo
Two silicon cyclopentadienyl) (1,1.0 ~ 1.2 eq), 2-phenylindone piperazine (4c, 0.5 eq), cesium fluoride (9.5~10.0 eq), gained indoles
Piperazine and isoindole derivatives are as follows: two silicon substrate indolizine of 1- phenyl -7,8- oxygen simultaneously [3,4,5-ab] iso-indoles (5c) and phenyl -7 1-,
Three silicon substrate indolizine of 8- dioxy simultaneously [3,4,5-ab] iso-indoles (6c), total yield 63%.The structure of the compound are as follows:
With
5c: molecular formula: C24H23NOSi2
Chinese name: two silicon substrate indolizine of 1- phenyl -7,8- oxygen simultaneously [3,4,5-ab] iso-indoles
English name: 1-Phenyl-7,8-oxadisilole indolizino [3,4,5-ab]isoindole
Molecular weight: 397.13
Fusing point: 173-175 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 0.50 (s, 6H, SiMe2), 0.52 (s,
6H, SiMe2), 7.31 (s, 1H, Ar-H), 7.48 (t, J = 7.5 Hz, 1H, Ar-H), 7.64 (t, J =
7.5 Hz, 2H, Ar-H), 7.73 (t, J = 8.0 Hz, 1H, Ar-H), 8.06 (d, J = 8.5 Hz, 1H,
Ar-H), 8.10 (d, J = 7.5 Hz, 2H, Ar-H), 8.14 (d, J = 7.5 Hz, 1H, Ar-H), 8.57
(s, 1H, Ar-H), 8.70 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ 1.3, 1.4, 104.4, 107.9, 115.3,
119.0, 120.1, 122.0, 125.3, 127.4, 128.1, 128.6, 128.8, 129.1, 130.0, 130.3,
131.7, 136.3, 140.7, 147.5 ppm。
: molecular formula: C26H29NO2Si3
Chinese name: three silicon substrate indolizine of 1- phenyl -7,8- dioxy simultaneously [3,4,5-ab] iso-indoles
English name: 1-Phenyl-7,8-dioxatrisilole indolizino [3,4,5-ab]isoindole
Molecular weight: 471.15
Fusing point: 186-188 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 0.18 (s, 6H, SiMe2), 0.56 (s,
6H, SiMe2), 0.59 (s, 6H, SiMe2), 7.34 (s, 1H, Ar-H), 7.46 (t, J = 7.5 Hz, 1H,
Ar-H), 7.62 (t, J = 8.0 Hz, 2H, Ar-H), 7.74 (t, J = 8.0 Hz, 1H, Ar-H), 8.06
(d, J = 8.5 Hz, 1H, Ar-H), 8.11 (d, J = 7.5 Hz, 2H, Ar-H), 8.16 (d, J = 7.0
Hz, 1H, Ar-H), 8.68 (s, 1H, Ar-H), 8.71 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3):δ 0.8, 2.1, 2.4, 104.2, 108.3,
115.3, 119.2, 120.2, 121.7, 125.6, 127.6, 127.9, 128.3, 128.6, 128.8, 129.0,
131.8, 133.0, 136.1, 138.7, 145.2 ppm。
Example IV:
Iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), benzo bis- (two silicon of oxygen cyclopentadienyls) (1,
1.0 ~ 1.2 eq), 2- rubigan indolizine (4d, 0.5 eq), cesium fluoride (9.5~10.0 eq), gained indolizine is simultaneously different
Indole derivatives are as follows: two silicon substrate indolizine of 1- rubigan -7,8- oxygen simultaneously [3,4,5-ab] iso-indoles (5d) and 1- rubigan-
Three silicon substrate indolizine of 7,8- dioxy simultaneously [3,4,5-ab] iso-indoles (6d), yield 42%.The structure of the compound are as follows:
With
5d: molecular formula: C24H22ClNOSi2
Chinese name: two silicon substrate indolizine of 1- rubigan -7,8- oxygen simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Chlorophenyl-7,8-oxadisilole indolizino[3,4,5-ab]
isoindole
Molecular weight: 431.09
Fusing point: 192-193 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, DMSO):δ 0.45 (s, 6H, SiMe2), 0.46 (s,
6H, SiMe2), 7.51 (s, 1H, Ar-H), 7.74 (d, J = 8.5 Hz, 2H, Ar-H), 7.87 (t, J =
8.0 Hz, 1H, Ar-H), 8.11 (d, J = 8.5 Hz, 2H, Ar-H), 8.25 (d, J = 8.0 Hz, 1H,
Ar-H), 8.44 (d, J = 7.5 Hz, 1H, Ar-H), 8.59 (s, 1H, Ar-H), 8.99 (s, 1H, Ar-H)
ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 1.3, 1.4, 104.3, 108.2,
115.4, 118.9, 120.3, 121.7, 125.3, 128.2, 128.8, 129.2, 129.8, 130.0, 130.1,
130.2, 133.3, 134.8, 140.9, 147.7 ppm。
: molecular formula: C26H28ClNO2Si3
Chinese name: three silicon substrate indolizine of 1- rubigan -7,8- dioxy simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Chlorophenyl-7,8-dioxatrisilole indolizino[3,4,5-ab]
isoindole
Molecular weight: 505.11
Fusing point: 179-181 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 0.17 (s, 6H, SiMe2), 0.55 (s,
6H, SiMe2), 0.58 (s, 6H, SiMe2), 7.29 (s, 1H, Ar-H), 7.57 (d, J = 8.0 Hz, 2H,
Ar-H), 7.74 (t, J = 8.0 Hz, 1H, Ar-H), 8.01 (d, J = 8.5 Hz, 2H, Ar-H), 8.06
(d, J = 8.5 Hz, 1H, Ar-H), 8.16 (d, J = 7.5 Hz, 1H, Ar-H), 8.62 (s, 1H, Ar-
H), 8.66 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ0.8, 2.2, 2.4, 104.2, 108.5,
115.5, 118.5, 119.1, 120.4, 125.3, 128.0, 128.4, 128.7, 129.0, 129.2, 129.7,
130.3, 133.4, 134.6, 139.0, 145.5 ppm。
Embodiment five: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), the bis- (oxygen of benzo
Two silicon cyclopentadienyl) (1,1.0 ~ 1.2 eq), 2- p-nitrophenyl indolizine (4e, 0.5 eq), cesium fluoride (9.5~10.0 eq), institute
Indolizine and isoindole derivatives are as follows: two silicon substrate indolizine of 1- p-nitrophenyl -7,8- oxygen simultaneously [3,4,5-ab] iso-indoles
(5e) and three silicon substrate indolizine of 1- p-nitrophenyl -7,8- dioxy simultaneously [3,4,5-ab] iso-indoles (6e), total yield 58%.The change
Close the structure of object are as follows:
With
5e: molecular formula: C24H22N2O3Si2
Chinese name: two silicon substrate indolizine of 1- p-nitrophenyl -7,8- oxygen simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Nitrophenyl-7,8-oxadisilole indolizino[3,4,5-ab]
isoindole
Molecular weight: 442.12
Fusing point: 212-213 DEG C
Appearance: red powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 0.497 (s, 6H, SiMe2), 0.504 (s,
6H, SiMe2), 7.35 (s, 1H, Ar-H), 7.75-7.79 (m, 1H, Ar-H), 8.10 (d, J = 8.5 Hz,
1H, Ar-H), 8.17 (d, J = 7.5 Hz, 1H, Ar-H), 8.20 (d, J = 8.5 Hz, 2H, Ar-H),
8.47 (s, 1H, Ar-H), 8.48 (d, J=7.5 Hz, 2H, Ar-H), 8.69 (d,J = 1.0 Hz, 1H,
Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 1.3, 1.4, 104.9, 108.8,
116.1, 119.4, 120.8, 121.6, 124.5, 125.5, 128.5, 128.6, 128.8, 128.9, 130.0,
130.3, 141.8, 143.1, 146.8, 148.3 ppm。
: molecular formula: C26H28N2O4Si3
Chinese name: three silicon substrate indolizine of 1- p-nitrophenyl -7,8- dioxy simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Nitrophenyl-7,8-dioxatrisilole indolizino[3,4,5-ab]
isoindole
Molecular weight: 516.14
Fusing point: 188-190 DEG C
Appearance: red powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3):δ 0.17 (s, 6H, SiMe2), 0.56 (s,
6H, SiMe2), 0.58 (s, 6H, SiMe2), 7.38 (s, 1H, Ar-H), 7.78 (t, J = 8.0 Hz, 1H,
Ar-H), 8.10 (d, J = 8.0 Hz, 1H, Ar-H), 8.19 (d, J = 7.5 Hz, 1H, Ar-H), 8.22
(d, J = 9.0 Hz, 2H, Ar-H), 8.45 (d, J = 8.5 Hz, 2H, Ar-H), 8.61 (s, 1H, Ar-H), 8.67 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ0.8, 2.2, 2.3, 104.9, 109.2,
116.2, 119.6, 121.0, 124.4, 125.2, 128.5, 128.56, 128.61, 128.7, 128.8,
129.9, 132.2, 139.9, 143.0, 146.1, 146.9 ppm。
Embodiment six: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), two silicon substrate naphthalene of oxygen
(7,1.0 ~ 1.2 eq), 2- p-methoxyphenyl indolizine (4a, 0.5 eq), cesium fluoride (9.5~10.0 eq), gained benzene
Diindyl piperazine and isoindole derivatives are as follows: 1- p-methoxyphenyl benzindole piperazine simultaneously [3,4,5-ab] iso-indoles (10a), yield
68%.The structure of the compound are as follows:
10a: molecular formula: C25H17NO
Chinese name: 1- p-methoxyphenyl benzindole piperazine simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Methoxyphenyl benzo[f]indolizino[3,4,5-ab]isoindole
Molecular weight: 347.13
Fusing point: 215-217 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3): δ 3.97 (s, 3H, OCH3), 7.15 (s,
1H, Ar-H), 7.20 (d, J = 8.5 Hz, 2H, Ar-H), 7.53-7.56 (m, 1H, Ar-H), 7.59-7.64
(m, 2H, Ar-H), 7.95 (d, J = 8.5 Hz, 1H, Ar-H), 8.01 (d, J = 7.0 Hz, 1H, Ar-
H), 8.05-8.06 (m, 2H, Ar-H), 8.13 (d, J = 8.5 Hz, 1H, Ar-H), 8.16 (d, J = 8.5
Hz, 1H, Ar-H), 8.76 (s, 1H, Ar-H), 8.95 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 55.5,102.5,106.1,114.6,
115.4, 116.5, 118.8, 119.9, 121.9, 124.5, 126.2, 128.37, 128.41, 128.5,
128.8, 129.2, 129.6, 129.7, 129.91, 129.94, 130.1, 133.4, 159.1 ppm。
Embodiment seven: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), two silicon substrate naphthalene of oxygen
(7,1.0 ~ 1.2 eq), 2- p-methylphenyl indolizine (4b, 0.5 eq), cesium fluoride (9.5~10.0 eq), gained benzo
Indolizine and isoindole derivatives are as follows: 1- p-methylphenyl benzindole piperazine simultaneously [3,4,5-ab] iso-indoles (10b), yield 54%.
The structure of the compound are as follows:
10b: molecular formula: C25H17N
Chinese name: 1- p-methylphenyl benzindole piperazine simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Methylphenyl benzo[f]indolizino[3,4,5-ab]isoindole
Molecular weight: 331.14
Fusing point: 195-196 DEG C
Appearance: yellow powder
Outer nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3): δ 2.52 (s, 3H, CH3), 7.19 (s,
1H, Ar-H), 7.47 (d, J = 8.0 Hz, 2H, Ar-H), 7.53-7.56 (m, 1H, Ar-H), 7.59-7.64
(m, 2H, Ar-H), 7.96 (d, J = 8.5 Hz, 1H, Ar-H), 8.01-8.03 (m, 3H, Ar-H), 8.12
(d, J = 8.5 Hz, 1H, Ar-H), 8.16 (d, J = 8.0 Hz, 1H, Ar-H), 8.78 (s, 1H, Ar-
H), 8.95 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 21.4,102.8,106.2,114.1,
115.6, 116.7, 119.0, 120.0, 121.9, 124.5, 126.2, 128.36, 128.40, 128.45,
128.48, 128.8, 129.3, 129.7, 129.8, 130.10, 130.14, 133.4, 137.1 ppm。
Embodiment eight:
Iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), two silicon substrate naphthalene of oxygen (7,1.0 ~
1.2 eq), 2-phenylindone piperazine (4c, 0.5 eq), cesium fluoride (9.5~10.0 eq), gained benzindole piperazine and iso-indoles
Derivative are as follows: 1- phenyl benzindole piperazine simultaneously [3,4,5-ab] iso-indoles (10c), yield 72%.The structure of the compound are as follows:
10c: molecular formula: C24H15N
Chinese name: 1- phenyl benzindole piperazine simultaneously [3,4,5-ab] iso-indoles
English name: 1-Phenyl benzo [f]indolizino[3,4,5-ab]isoindole
Molecular weight: 317.12
Fusing point: 198-200 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3): δ 7.22 (s, 1H, Ar-H), 7.46-7.49
(m, 1H, Ar-H), 7.54-7.57 (m, 1H, Ar-H), 7.59-7.62 (m, 1H, Ar-H), 7.63-7.67
(m, 3H, Ar-H), 7.98 (d, J = 8.5 Hz, 1H, Ar-H), 8.02 (d, J = 7.0 Hz, 1H, Ar-
H), 8.12-8.14 (m, 3H, Ar-H), 8.16 (d, J = 8.0 Hz, 1H, Ar-H), 8.78 (s, 1H, Ar-
H), 8.95 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 103.0,106.3,115.7,116.7,
119.1, 120.0, 121.9, 124.6, 126.2, 127.3, 128.40, 128.41, 128.5, 128.8,
129.1, 129.4, 129.7, 129.9, 130.0, 130.1, 133.4, 136.3 ppm。
Embodiment nine: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), two silicon substrate naphthalene of oxygen
(7,1.0 ~ 1.2 eq), 2- rubigan indolizine (4d, 0.5 eq), cesium fluoride (9.5~10.0 eq), gained benzo Yin
Diindyl piperazine and isoindole derivatives are as follows: 1- rubigan benzindole piperazine simultaneously [3,4,5-ab] iso-indoles (10d), yield 56%.The change
Close the structure of object are as follows:
10d: molecular formula: C24H14ClN
Chinese name: 1- rubigan benzindole piperazine simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Chlorophenyl benzo[f]indolizino[3,4,5-ab]isoindole
Molecular weight: 351.08
Fusing point: 212-213 DEG C
Appearance: yellow powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3): δ 7.16 (s, 1H, Ar-H), 7.54-7.57
(m, 1H, Ar-H), 7.60-7.62 (m, 3H, Ar-H), 7.63 (d, J = 7.0 Hz, 1H, Ar-H), 7.96
(d, J = 8.5 Hz, 1H, Ar-H), 8.01 (d, J = 7.0 Hz, 1H, Ar-H), 8.02-8.04 (m, 2H,
Ar-H), 8.11 (d, J = 8.5 Hz, 1H, Ar-H), 8.15 (d, J = 8.0 Hz, 1H, Ar-H), 8.69
(s, 1H, Ar-H), 8.93 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 102.9,106.5,115.8,116.5,
119.1, 120.3, 122.0, 124.7, 126.4, 128.2, 128.38, 128.43, 128.6, 128.8,
129.3, 129.4, 129.6, 129.8, 130.1, 133.1, 133.4, 134.8 ppm。
Embodiment ten: iodobenzene diacetate salt (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), two silicon substrate naphthalene of oxygen
(7,1.0 ~ 1.2 eq), 2- p-nitrophenyl indolizine (4e, 0.5 eq), cesium fluoride (9.5~10.0 eq), gained benzo
Indolizine and isoindole derivatives are as follows: 1- p-nitrophenyl-benzindole piperazine simultaneously [3,4,5-ab] iso-indoles (10e), yield
42%.The structure of the compound are as follows:
10e: molecular formula: C24H14N2O2
Chinese name: 1- p-nitrophenyl benzindole piperazine simultaneously [3,4,5-ab] iso-indoles
English name: 1-p-Nitrophenylbenzo[f]indolizino[3,4,5-ab]isoindole
Molecular weight: 362.11
Fusing point: 197-199 DEG C
Appearance: red powder
Nuclear magnetic resonance spectroscopy:1H NMR (500 MHz, CDCl3): δ 7.25 (s, 1H, Ar-H), 7.58-7.61
(m, 1H, Ar-H), 7.65-7.68 (m, 2H, Ar-H), 8.00 (d, J = 8.5 Hz, 1H, Ar-H), 8.05
(d, J = 7.0 Hz, 1H, Ar-H), 8.15 (d, J = 8.5 Hz, 1H, Ar-H), 8.17 (d, J = 8.0
Hz, 1H, Ar-H), 8.24-8.26 (m, 2H, Ar-H), 8.49-8.51 (m, 2H, Ar-H), 8.72 (s, 1H,
Ar-H), 8.96 (s, 1H, Ar-H) ppm。
Carbon-13 nmr spectra:13C NMR (125 MHz, CDCl3): δ 103.5,107.1,114.1,116.3,
116.8, 119.7, 120.9, 122.3, 124.5, 125.1, 126.7, 128.5, 128.7, 128.8, 128.9,
129.7, 129.88, 129.91, 130.9, 133.45, 133.53, 139.3 ppm。
[a]It is measured in dichloromethane solvent.[b]Maximum absorption wavelength.[c]Maximum emission wavelength.[d]0.1N H2SO4Kui
Peaceful solution is standard (Φ365 =0.54) it tests.[e]Decomposition temperature is measured with thermogravimetric analysis, under nitrogen protection, heating speed
10 oC/ minutes.
[a]Measured in acetonitrile solvent using cyclic voltammetry oxidizing potential (E ox), platinum electrode makees working electrode, and platinum filament is made
Auxiliary electrode, saturated calomel electrode (SCE) make reference electrode, agar bridge, and 0.1 M tetrabutyl ammonium hexafluorophosphate makees electrolyte,
Make external standard calculating, sweep speed 100 mV/s, E with ferrocene (- 4.8 eV of vacuum dissociation energy)1/2(Fc/Fc+)=0.43V。[b]
HOMO = -[E ox – [E 1/2 (Fc/Fc+)] + 4.8]。[c]Energy level difference Eg is estimated by UV absorption in methylene chloride.[d]
LUMO = HOMO + Optical band gap。
Claims (2)
1. a kind of benzindole piperazine and isoindole derivatives, it is characterised in that the compound has the following structure:
Wherein, R is methyl or chlorine.
2. a kind of method for preparing benzindole piperazine according to claim 1 and isoindole derivatives, it is characterised in that the party
Method has following steps:
A. under the protection of inert gas, trifluoromethanesulfonic acid is added to the methylene chloride of iodobenzene diacetate salt by ice-water bath condition
In solution, ice-water bath reacts 0.5~1 hour, reacts at room temperature 1~2 hour；The reaction solution is added to oxygen under the conditions of ice-water bath
In the dichloromethane solution of two silicon substrate naphthalenes, continues ice-water bath and react 0.5~1 hour, react at room temperature 3~4 hours, use methylene chloride
Phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthalene] three fluosulfonic acid iodide are extracted, washing, drying simultaneously revolve solvent；
B. under inert gas protection, by phenyl obtained by step a [adjacent (hydroxyl dimethyl silicon substrate) naphthalene] three fluosulfonic acid iodide
Acetonitrile solution be added portionwise in the dichloromethane solution or acetonitrile solution of 2- (hetero) aryl indole oxazine derivatives and cesium fluoride, flow back
1~1.5 hour, through separating-purifying, obtain final product benzindole piperazine and isoindole derivatives；
The structural formula of the iodobenzene diacetate salt are as follows: PhI (OAc)2；
The structural formula of the two silicon substrate naphthalene of oxygen are as follows:
Three fluosulfonic acid iodide its structural formula of the phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthalene] are as follows:
The structural formula of the 2- (hetero) aryl indole oxazine derivatives are as follows:Wherein R is methyl or chlorine；
The iodobenzene diacetate salt, trifluoromethanesulfonic acid, two silicon substrate naphthalene of oxygen, 2- (hetero) aryl indole oxazine derivatives, cesium fluoride (CsF)
Molar ratio are as follows: 1.0~1.5:2.5~3.0:1.0~1.2:0.5:9.5~10.0.
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