CN106478627A - A kind of 6,12,18 triaryl, 5,11,17 benzo three quinoline and its synthetic method - Google Patents
A kind of 6,12,18 triaryl, 5,11,17 benzo three quinoline and its synthetic method Download PDFInfo
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- CN106478627A CN106478627A CN201610784693.7A CN201610784693A CN106478627A CN 106478627 A CN106478627 A CN 106478627A CN 201610784693 A CN201610784693 A CN 201610784693A CN 106478627 A CN106478627 A CN 106478627A
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- 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
- C07D471/14—Ortho-condensed systems
Abstract
The invention discloses a kind of 6,12,18 triaryls 5,11,17 benzo three quinoline and its synthetic method, such compound has formula, it has big planar rigidity aromatic proton, there is potential G tetrad DNA recognition reaction and the performance applying to discotic mesogenic material, the research and development for organic electronic device and bioorganic chemistry association area provide strong technical support, have very high practical value；The synthetic method of such compound is to be raw material from equal tribromo-benzene and o-bromoaniline, synthesize this invention needed raw material 6 through Buchwald Hartwig reaction, hydrolysis of ester group and phosphorus oxychloride cyclization three step, 12,18 trichlorines 5,11,17 benzo three quinoline, is then passed through Suzuki coupling one step and efficiently synthesizes.The inventive method has：The equal commercially available of agents useful for same, extensively, cheap, catalyst amount is few, need not additionally add any Phosphine ligands for raw material sources, and simplifies postprocessing working procedures while keeping good catalytic effect, additionally, having substrate universality preferably, is easy to the features such as modify.
Description
Technical field
The present invention relates to organic photoelectrical material and bioorganic chemistry crossing domain, specifically a kind of 6,12,18- tri-
Aryl -5,11,17- benzo three quinoline and its synthetic method.
Background technology
Comprise the larger Pi-conjugated systems molecule of an aromatic proton rigid plane center and peripheral soft chain, because it is in molecule
The importance showing in the energy of level and charge-conduction research, is considered template body in organic electronic device association area
System, is widely used in Organic Light Emitting Diode (OLEDs), photovoltaic diode (PVD), organic field effect tube (OFETs), has
Machine solaode (OPVs), in the middle of the research and development in the new field such as sensor and liquid crystal material, is subject to increasing in recent years
Concern.
However, in these planar conjugate systems, C3Symmetrical plane aroma system is particularly important.Uwe in 2016
H.F.Bunz et al. six favorable solubilities have been synthesized with very short route it is easy to modify benzo three naphthalene compound.This kind of
Compound can be also splendid photovoltaic diode as outstanding emission source in Organic Light Emitting Diode (OLEDs) simultaneously
(PVD) donor material (Elias C.R ü diger, Frank Rominger, Lena Steuer, and Uwe
H.F.Bunz.J.Org.Chem.2016,81,193-196)；Calendar year 2001 Matthias Lehmann et al. and Chi Wi in 2003
Ong et al. successively reports the synthesis of the benzo three quinoxaline derivant (HATNA) of alkylthio group and alkoxyl replacement
(Kestemont,G.；de Halleux,V.；Lehmann,M.；Ivanov,D.A.；Watson,M.；Geerts,
Y.H.Chem.Commun.2001,2074-2075；Ong,C.W.；Liao,S.-C.；Chang,T.H.；Hsu,H.-
F.Tetrahedron Lett.2003,44,1477-1480), subsequently, Matthias Lehmann in 2004 et al. reports benzene
And three quinoxaline derivant (HATNA) property research and analysis on application in discotic mesogenic material (V.Lemaur,
D.A.da Silva Filho,V.Coropceanu,M.Lehmann,Y.Geerts,J.Piris,M.G.Debije,A.M.van
de Craats,K.Senthilkumar,L.D.A.Siebbeles,J.M.Warman,J.-L.Brdas,J.Cornil,
J.Am.Chem.Soc.2004,126,3271-3279)；Zhang Fan in 2016 et al. has synthesized two kinds and has carried triple boron atoms
Benzo three quinolines at center, around boron atom, crowded space frame is mixed big planar rigidity conjugated system and is made
Such compound shows big Stokes shift and adjustable electrochemical behavior, and its LUMO orbital energy as little as-
3.18eV, shown in the above structural formula of compound such as following formula (1)：
Additionally, C3Application in bioorganic chemistry for the symmetrical plane aroma system also gradually causes the weight of people
Depending on.Due to its big Pi-conjugated systems allow such compound by with the effect of the pi-pi accumulation of G- tetrad DNA realize right
The specific recognition of DNA, is therefore expected to target cancer cell, contributes to the treatment to some difficult diseases.Mark in 2003
S.Searle et al. finds that PHPS4 can reduce the propagation of breast cancer cell as telomerase inhibitor, thus to related drugs
Research and development provide reference；Marie-Paule Teulade-Fichou in 2011 et al. has synthesized TrisQ and TrisK two class chemical combination
Thing, to tetrad for stablizing thus binding to this two classes compound to self structure, and then makes functional
DNA is changed into non-functional DNA, shown in the above structural formula of compound such as following formula (2)：
However, for molecular recognition, tetrad structure is combined with which kind of certain types of molecular specificity is not yet come to a conclusion.
Therefore, it is reported despite hundreds of tetrad part, but only sub-fraction is carried out with X-ray or nuclear-magnetism (NMR)
Characterize, but in general, structural analyses have shown that：Big conjugation fragrance plane can be mixed in two using pi-pi accumulation
In individual tetrad connection interlayer.
In view of above-mentioned structure activity relationship, such comprises a fragrance to develop a kind of synthesis efficient, cheap, applied widely
The method of the larger Pi-conjugated systems molecule of core rigid plane center and peripheral soft chain seems extremely important.
Content of the invention
It is an object of the invention to provide a class 6,12,18 triaryl -5,11,17- benzo three quinoline and such
The synthetic method of derivant, its equal commercially available of synthetic method agents useful for same, raw material sources are extensively, cheap, and catalyst is used
Amount is few, simplifies postprocessing working procedures while keeping good catalytic effect.
The concrete technical scheme realizing the object of the invention is：
A kind of 6,12,18- triaryl -5,11,17- benzo three quinoline, feature is that such compound has following formula
Structure：
Wherein：
R1It is hydrogen or methyl；R2It is hydrogen or methyl；
R3It is hydrogen, C6 and following straight chain or the alkyl containing side chain or alkoxyl, phenoxy group or benzyloxy.
A kind of 6,12,18- triaryl -5, the synthetic method of 11,17- benzo three quinoline, the method includes following
Concrete steps:Step 1：Buchwald-Hartwig reaction
Under room temperature, reaction vessel sequentially adds equal tribromo-benzene, artificial neroli oil, cesium carbonate and toluene, nitrogen environment
Lower addition tri-butyl phosphine tetrafluoroborate and palladium, are stirred at reflux 24-72h under nitrogen atmosphere, are cooled to room temperature, filter,
Rotary Evaporators rotation removes solvent, adds the mixed solution of dichloromethane and ammonium chloride (1M), point liquid, organic faciess anhydrous sodium sulfate
It is dried, Rotary Evaporators rotation obtains crude product, ethyl acetate and petroleum ether recrystallization except solvent, and column chromatography obtains purpose compound 1,3,
5- tri- (2- methoxycarbonyl group aniline) benzene；Wherein, equal tribromo-benzene, artificial neroli oil, cesium carbonate, tri-butyl phosphine tetrafluoroborate and
The ratio of the amount of the material of palladium is 1:3.0-6.0:6.0-10.0:0.03-0.3:0.01-0.10；Dichloromethane and ammonium chloride
The volume ratio of solution is 1-3:1；
Step 2：Hydrolysis of ester group
Under room temperature, reaction vessel adds compound 1,3,5- tri- (the 2- methoxycarbonyl group aniline) benzene that step 1 obtains, will
It is dissolved in acetone, is subsequently added under 5% sodium hydrate aqueous solution, nitrogen atmosphere that to be stirred at reflux to system be clear
Liquid, is cooled to room temperature, adds dichloromethane and water, and point liquid is left and taken aqueous phase, is acidified to pH=1, mistake with dilute hydrochloric acid (1M or 2M)
Filter, gained solid is vacuum dried 2h at 100 DEG C and obtains crude product, and ethyl alcohol recrystallization obtains purpose compound 1,3,5- tri- (2- carboxylic
Base aniline) benzene；The ratio of the wherein amount of material of 1,3,5- tri- (2- methoxycarbonyl group aniline) benzene and sodium hydroxide is 1:10.0-
24.0；
Step 3：Phosphorus oxychloride cyclization
Under room temperature, compound 1,3,5- tri- (2- carboxyanilino) benzene that addition step 2 obtains in reaction vessel, 110 DEG C
Lower vacuum drying 4h, is subsequently adding under excessive phosphorus oxychloride, nitrogen atmosphere and is stirred at reflux 16h, and Rotary Evaporators rotation is not except anti-
The phosphorus oxychloride answered, is cooled to room temperature, adds excessive dichloromethane, is slowly added in 15% ammonia of frozen water cooling,
Filter, dichloromethane repeatedly washs, and then be washed once with ether, is vacuum dried to obtain purpose compound 6,12,18- tri- at 50 DEG C
Chloro- 5,11,17- benzo three quinoline；
Step 4：Suzuki is coupled
6,12,18- tri- chloro- 5 are sequentially added in reaction vessel, 11,17- benzo three quinoline, phenylboric acid, alkali and solvent,
Add catalyst or catalyst and part under nitrogen environment, be stirred at reflux under designated solvent and complete to TLC display reaction, cooling
To room temperature, dichloromethane extracts, anhydrous sodium sulfate drying, obtains described 6 by column chromatography for separation, 12,18- triaryl -5, and 11,
17- benzo three quinoline；
Wherein：Described catalyst is selected from：Palladium Pd (OAc)2, tetrakis triphenylphosphine palladium Pd (PPh3)4Or Pd-132；Its
Consumption is：X% mole, x is 0.05-22.5；
Described part is selected from：Tricyclohexyl phosphine (PCy3) or triphenylphosphine (PPh3)；Its consumption is：Y% mole, y is
22.5-67.5；
Described solvent is selected from：Toluene and the mixed solvent of water or glycol dimethyl ether (DME) and water；Its consumption is every mmoles
Your chloro- 5,11,17- benzo three quinoline of (mmol) 6,12,18- tri- is corresponding to use mixed solvent 10～30mL；Toluene and water volume
Than for 4:1 or 9:1；Glycol dimethyl ether and water volume ratio are 20:1 or 10:1；
Described alkali is selected from：Three hypophosphite monohydrate potassium, anhydrous phosphoric acid potassium or cesium carbonate；Its consumption is：Every mM of (mmol) 6,
Chloro- 5,11,17- benzo three quinoline of 12,18- tri- is corresponding to use 3.6～9 mMs of (mmol) alkali；
Response time：8～36 hours.
Described Pd-132 is double [di-t-butyl-(4- dimethylaminophenyl) phosphine] palladium (II) of dichloro, has formula：
Beneficial effects of the present invention：This equal commercially available of synthetic method agents useful for same, solvent all need not process and can directly make
With extensively, cheap, catalyst amount is few for raw material sources, simplifies post processing work while keeping good catalytic effect
Sequence.Additionally, substrate universality preferably, is easy to modify, can be organic electronic device and bioorganic chemistry to the present invention
Research is done one's bit.
Brief description
Fig. 1 is the synthesis road of the object of the invention compound 6,12,18 triaryl -5,11,17- benzo three quinoline
Line；
Fig. 2～Figure 30 is the nuclear magnetic spectrogram that raw material of the present invention and embodiment 1-16 prepare gained compound.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.It will be understood that the present invention's is embodied as
Example is only used for illustrating the present invention, is not used in restriction the scope of the present invention.
Embodiment 1
Under room temperature, sequentially add in reaction vessel equal tribromo-benzene (1.0equiv.), artificial neroli oil (3.5equiv.),
Cesium carbonate (6.0equiv.) and toluene, add tri-butyl phosphine tetrafluoroborate (0.18equiv.) and acetic acid under nitrogen environment
Palladium (0.06equiv.), is stirred at reflux 72h under nitrogen atmosphere, is cooled to room temperature, filters, and Rotary Evaporators rotation removes solvent, adds
(volume ratio is 2 to the mixed solution of dichloromethane and ammonium chloride (1M):1) liquid, organic faciess anhydrous sodium sulfate drying, rotation, are divided
Evaporimeter rotation obtains crude product, ethyl acetate and petroleum ether recrystallization except solvent, and column chromatography obtains purpose compound 1,3,5- tri- (2- first
Oxygen carbonyl aniline) benzene be white solid, yield be 87%.1H NMR(500MHz,CDCl3) δ 9.45 (s, 3H), 7.96 (d, J=
8.0Hz, 3H), 7.36 (d, J=3.6Hz, 6H), 6.84 (s, 3H), 6.78 6.73 (m, 3H), 3.90 (s, 9H).Data above
Proof obtains purpose compound, and accompanying drawing 2 is its nucleus magnetic hydrogen spectrum.
Embodiment 2
Under room temperature, reaction vessel adds compound 1,3,5- tri- (the 2- methoxycarbonyl group aniline) benzene that embodiment 1 obtains
(1.0equiv.), it is dissolved in acetone, be subsequently added into 5% sodium hydroxide (12.0equiv.) aqueous solution, nitrogen atmosphere
Under be stirred at reflux 16h, system is clear liquid, is cooled to room temperature, and (volume ratio is 1 to add dichloromethane and water:1), stay
Water intaking phase, is acidified to pH=1 with dilute hydrochloric acid (1M), filters, and gained solid is vacuum dried 2h at 100 DEG C and obtains crude product, second
It is white solid that alcohol is recrystallized to give purpose compound 1,3,5- tri- (2- carboxyanilino) benzene, and yield is 92%.1H NMR
(500MHz, DMSO) δ 13.09 (s, 3H), 9.57 (s, 3H), 7.89 (d, J=7.7Hz, 3H), 7.45 (t, J=7.7Hz, 3H),
7.38 (d, J=8.4Hz, 3H), 6.81 (t, J=7.5Hz, 3H), 6.76 (s, 3H).Data above proves to obtain purpose chemical combination
Thing, accompanying drawing 3 is its nucleus magnetic hydrogen spectrum.
Embodiment 3
Under room temperature, reaction vessel adds compound 1,3,5- tri- (2- carboxyanilino) benzene that embodiment 2 obtains
(1.0equiv.), it is vacuum dried 4h at 110 DEG C, be subsequently adding and be stirred at reflux 16h under excessive phosphorus oxychloride, nitrogen atmosphere, rotation
Turn evaporimeter rotation and remove unreacted phosphorus oxychloride, be cooled to room temperature, add dichloromethane, be slowly added into the 15% of frozen water cooling
Ammonia in, filter, dichloromethane repeatedly washs, and then be washed once with ether, is vacuum dried to obtain purpose compound at 50 DEG C
6,12,18- tri- chloro- 5,11,17- benzo three quinoline is yellow-brown solid, and yield is 70%.1H NMR(500MHz,CDCl3)δ
8.69 (d, J=8.5Hz, 3H), 8.34 (d, J=8.3Hz, 3H), 7.92 7.87 (m, 3H), 7.80 7.75 (m, 3H).More than
Data proves to obtain purpose compound, and accompanying drawing 4 is its nucleus magnetic hydrogen spectrum.
Embodiment 4
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to methylphenylboronic acid II-1 (163mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixed solvent
(5mL, volume ratio is 4 for toluene and water:1), add catalyst Pd-132 (0.14mg, 0.1mol%) under nitrogen atmosphere, stir back
Stream 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous sodium sulfate
It is dried, it is white solid that column chromatography (petrol ether/ethyl acetate=200/1) obtains product 1, yield is 75%.Rf=0.60 (PE/
), EA=20/1 277-279 DEG C of M.p,1H NMR(500MHz,CDCl3) δ 7.65 (d, J=8.5Hz, 3H), 7.56 (t, J=
7.4Hz, 3H), 7.39 (d, J=8.0Hz, 6H), 7.35 (d, J=7.6Hz, 3H), 7.24 (d, J=7.8Hz, 6H), 7.17 (d,
J=8.4Hz, 3H), 2.61 (s, 9H)；13C NMR(125MHz,CDCl3)δ149.68,148.41,146.26,138.96,
135.66,129.61,129.32,129.05,128.62,127.78,127.29,126.30,123.09,21.49；HRMS
(ESI):Exact mass calcd for C48H34N3[M+H]+:652.2747,Found:652.2749.Data above proves
Obtain purpose compound, accompanying drawing 5,6 is respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 5
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to ethyl phenylboric acid II-2 (180mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixed solvent
(5mL, volume ratio is 4 for toluene and water:1), add catalyst Pd-132 (0.14mg, 0.1mol%) under nitrogen atmosphere, stir back
Stream 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous sodium sulfate
It is dried, it is light green solid that column chromatography (petrol ether/ethyl acetate=200/1) obtains product 2, yield is 72%.Rf=0.66
(PE/EA=20/1), 222-224 DEG C of M.p,1H NMR(500MHz,CDCl3) δ 7.66 (d, J=8.5Hz, 3H), 7.53 (t, J
=6.9Hz, 3H), 7.40 (d, J=8.0Hz, 6H), 7.35 (t, J=7.0Hz, 3H), 7.25 (d, J=3.6Hz, 6H), 7.17
(d, J=7.8Hz, 3H), 2.90 (q, J=7.5Hz, 6H), 1.48 (t, J=7.6Hz, 9H)；13C NMR(125MHz,CDCl3)δ
149.65,148.45,146.20,142.29,139.25,129.50,129.46,129.08,127.73,127.53,127.32,
126.30,123.12,29.05,16.37；HRMS(ESI):Exact mass calcd for C51H40N3[M+H]+:
694.3217,Found:694.3218.Data above prove obtain purpose compound, accompanying drawing 7,8 be respectively its nucleus magnetic hydrogen spectrum and
Carbon is composed.
Embodiment 6
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to propyl group phenylboric acid II-3 (197mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixed solvent
(5mL, volume ratio is 4 for toluene and water:1), add catalyst Pd-132 (0.14mg, 0.1mol%) under nitrogen atmosphere, stir back
Stream 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous sodium sulfate
It is dried, it is light green solid that column chromatography (petrol ether/ethyl acetate=200/1) obtains product 3, yield is 70%.Rf=0.58
(PE/EA=20/1)；M.p 226-227℃；1H NMR(500MHz,CDCl3) δ 7.65 (d, J=8.6Hz, 3H), 7.52 (t, J
=7.5Hz, 3H), 7.39 (d, J=6.8Hz, 6H), 7.37 7.34 (m, 3H), 7.26 (dd, J=7.8,1.7Hz, 6H), 7.19
(d, J=9.2Hz, 3H), 2.84 (t, J=7.5Hz, 6H), 1.95 1.86 (m, 6H), 1.16 (t, J=7.3Hz, 9H)；13C
NMR(125MHz,CDCl3)δ149.67,148.45,146.21,140.62,139.27,129.49,129.44,128.99,
128.13,127.77,127.30,126.30,123.10,38.18,25.13,14.07；HRMS(ESI):Exact mass
calcd for C54H46N3[M+H]+:736.3686,Found:736.3681.Data above proves to obtain purpose compound, attached
Fig. 9,10 be respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 7
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to n-butylbenzene boric acid II-4 (214mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixing is molten
(5mL, volume ratio is 4 for agent toluene and water:1), catalyst Pd-132 (0.14mg, 0.1mol%), stirring are added under nitrogen atmosphere
Backflow 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous slufuric acid
Sodium is dried, and it is light green solid that column chromatography (petrol ether/ethyl acetate=200/1) obtains product 4, and yield is 46%.Rf=0.66
(PE/EA=20/1)；M.p 207-208℃；1H NMR(500MHz,CDCl3) δ 7.64 (d, J=8.4Hz, 3H), 7.52 (t, J
=8.1Hz, 3H), 7.38 (d, J=7.9Hz, 6H), 7.35 (t, J=8.1Hz, 3H), 7.26 7.23 (m, 6H), 7.20 (d, J
=8.3Hz, 3H), 2.86 (t, J=7.6Hz, 6H), 1.89 1.83 (m, 6H), 1.59 (dt, J=14.9,7.4Hz, 6H),
1.08 (t, J=7.4Hz, 9H)；13C NMR(125MHz,CDCl3)δ149.68,148.45,146.25,140.82,139.22,
129.51,129.36,129.04,128.04,127.80,127.30,126.26,123.10,35.75,34.29,22.54,
14.16；HRMS(ESI):Exact mass calcd for C57H52N3[M+H]+:778.4156,Found:778.4150.With
Upper data proves to obtain purpose compound, and accompanying drawing 11,12 is respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 8
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to amyl group phenylboric acid II-5 (230mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixed solvent
(5mL, volume ratio is 4 for toluene and water:1), add catalyst Pd-132 (0.14mg, 0.1mol%) under nitrogen atmosphere, stir back
Stream 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous sodium sulfate
It is dried, it is light green solid that column chromatography (petrol ether/ethyl acetate=200/1) obtains product 5, yield is 60%.Rf=0.65
(PE/EA=20/1)；M.p 142-144℃；1H NMR(500MHz,CDCl3) δ 7.64 (d, J=8.5Hz, 3H), 7.52 (t, J
=7.5Hz, 3H), 7.39 (d, J=7.9Hz, 6H), 7.37 7.33 (m, 3H), 7.24 (s, 6H), 7.19 (d, J=8.3Hz,
3H), 2.89 2.81 (m, 6H), 1.92 1.83 (m, 6H), 1.49 (dt, J=14.0,4.8Hz, 12H), 1.01 (t, J=
7.0Hz,9H)；13C NMR(125MHz,CDCl3)δ149.67,148.46,146.21,140.89,139.21,129.48,
129.42,129.00,128.05,127.78,127.32,126.30,123.09,36.08,31.89,31.76,22.80,
14.19；HRMS(ESI):Exact mass calcd for C60H58N3[M+H]+:820.4625,Found:820.4627.With
Upper data proves to obtain purpose compound, and accompanying drawing 13,14 is respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 9
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), p-isopropyl phenylboric acid II-6 (197mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixing is molten
(5mL, volume ratio is 4 for agent toluene and water:1), catalyst Pd-132 (0.14mg, 0.1mol%), stirring are added under nitrogen atmosphere
Backflow 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous slufuric acid
Sodium is dried, and it is light green solid that column chromatography (petrol ether/ethyl acetate=200/1) obtains product 6, and yield is 44%.Rf=0.64
(PE/EA=20/1)；M.p 298-300℃；1H NMR(500MHz,CDCl3) δ 7.67 (d, J=8.5Hz, 3H), 7.50 (t, J
=7.5Hz, 3H), 7.42 (d, J=8.0Hz, 6H), 7.34 (t, J=7.6Hz, 3H), 7.25 (t, J=4.2Hz, 6H), 7.16
(d, J=8.3Hz, 3H), 3.15 (dt, J=13.8,6.9Hz, 3H), 1.48 (d, J=6.9Hz, 18H)；13C NMR(125MHz,
CDCl3)δ149.65,148.47,146.87,146.22,139.38,129.58,129.30,129.07,127.72,127.34,
126.25,126.01,123.15,34.25,24.40；HRMS(ESI):Exact mass calcd for C54H46N3[M+H]+:
736.3686,Found:736.3680.Data above proves to obtain purpose compound, and accompanying drawing 15,16 is respectively its nucleus magnetic hydrogen spectrum
With carbon spectrum.
Embodiment 10
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to tert-butylbenzeneboronic acid II-7 (214mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixing is molten
(5mL, volume ratio is 4 for agent toluene and water:1), catalyst Pd-132 (0.14mg, 0.1mol%), stirring are added under nitrogen atmosphere
Backflow 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous slufuric acid
Sodium is dried, and it is white solid that column chromatography (petrol ether/ethyl acetate=200/1) obtains product 7, and yield is 34%.Rf=0.64
(PE/EA=20/1)；M.p 238-240℃；1H NMR(500MHz,CDCl3) δ 7.69 (d, J=8.0Hz, 3H), 7.59 (d, J
=8.3Hz, 6H), 7.50 (t, J=6.9Hz, 3H), 7.37 7.34 (m, 3H), 7.28 (d, J=8.3Hz, 6H), 7.15 (d, J
=8.2Hz, 3H), 1.55 (s, 27H)；13C NMR(125MHz,CDCl3)δ149.75,149.20,148.57,146.31,
139.09,129.70,129.37,128.91,127.82,127.48,126.35,124.96,123.28,34.89,
31.82.HRMS(ESI):Exact mass calcd for C57H52N3[M+H]+:778.4156,Found:778.4147.With
Upper data proves to obtain purpose compound, and accompanying drawing 17,18 is respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 11
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to methoxyphenylboronic acid II-8 (182mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixing is molten
(5mL, volume ratio is 4 for agent toluene and water:1), catalyst Pd-132 (0.14mg, 0.1mol%), stirring are added under nitrogen atmosphere
Backflow 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous slufuric acid
Sodium is dried, and it is light green color that column chromatography (petrol ether/ethyl acetate=100/1 is arrived in petrol ether/ethyl acetate=200/1) obtains product 8
Solid, yield is 82%.Rf=0.13 (PE/EA=20/1)；M.p 284-286℃；1H NMR(500MHz,DMSO)δ7.72–
7.64 (m, 3H), 7.55 (d, J=8.1Hz, 3H), 7.51 7.44 (m, 3H), 7.22 (d, J=7.8Hz, 6H), 7.14 (dd, J
=15.0,8.3Hz, 9H), 3.92 (s, 9H)；13C NMR(125MHz,DMSO)δ158.66,149.54,148.28,146.06,
133.62,130.62,130.48,129.32,127.74,127.38,127.20,123.12,113.98,55.80；HRMS
(ESI):Exact mass calcd for C48H34N3O3[M+H]+:700.2595,Found:700.2614.Data above is demonstrate,proved
Bright obtain purpose compound, accompanying drawing 19,20 be respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 12
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to hexyloxy phenylboric acid II-9 (267mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixing is molten
(5mL, volume ratio is 4 for agent toluene and water:1), catalyst Pd-132 (0.14mg, 0.1mol%), stirring are added under nitrogen atmosphere
Backflow 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous slufuric acid
Sodium is dried, and it is light green color that column chromatography (petrol ether/ethyl acetate=100/1 is arrived in petrol ether/ethyl acetate=200/1) obtains product 9
Solid, yield is 41%.Rf=0.44 (PE/EA=20/1)；M.p 104-106℃；1H NMR(500MHz,CDCl3)δ7.67
(d, J=8.4Hz, 3H), 7.55 (t, J=7.5Hz, 3H), 7.36 (t, J=7.6Hz, 3H), 7.29 (d, J=8.3Hz, 3H),
7.24 (d, J=8.6Hz, 6H), 7.11 (d, J=8.6Hz, 6H), 4.16 (t, J=6.6Hz, 6H), 1.96 1.88 (m, 6H),
1.59 (dd, J=14.7,7.6Hz, 6H), 1.47 1.38 (m, 12H), 0.96 (t, J=7.0Hz, 9H)；13C NMR(126MHz,
CDCl3)δ158.01,149.82,148.15,146.31,134.01,130.28,129.59,129.51,128.01,127.27,
126.31,123.30,114.24,68.34,31.70,29.42,25.86,22.71,14.12；HRMS(ESI):Exact mass
calcd for C63H64N3O3[M+H]+:910.4942,Found:910.4941.Data above proves to obtain purpose compound,
Accompanying drawing 21,22 is respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 13
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to benzyloxy phenylboric acid II-10 (274mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixing
(5mL, volume ratio is 4 for solvent toluene and water:1), add catalyst Pd-132 (0.14mg, 0.1mol%) under nitrogen atmosphere, stir
Mix backflow 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous sulfur
Sour sodium is dried, and it is yellow that column chromatography (petrol ether/ethyl acetate=100/1 is arrived in petrol ether/ethyl acetate=200/1) obtains product 10
Solid, yield is 52%.Rf=0.42 (PE/EA=20/1)；M.p 224-225℃；1H NMR(500MHz,CDCl3)δ7.65
(d, J=8.4Hz, 3H), 7.58 (t, J=7.2Hz, 6H), 7.54 (d, J=7.4Hz, 3H), 7.46 (t, J=7.3Hz, 6H),
7.38 (dd, J=13.0,6.7Hz, 6H), 7.25 (s, 9H), 7.19 (d, J=8.1Hz, 6H), 5.27 (s, 6H)；13C NMR
(125MHz,CDCl3)δ157.66,149.74,148.01,146.29,137.42,134.51,130.33,129.70,
129.48,128.69,127.99,127.48,127.24,126.37,123.25,114.56,70.25.；HRMS(ESI):
Exact mass calcd for C66H46N3O3[M+H]+:928.3534,Found:928.3555.Data above proves to obtain
Purpose compound, accompanying drawing 23,24 is respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 14
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to phenoxy group phenylboric acid II-11 (257mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixing
(5mL, volume ratio is 4 for solvent toluene and water:1), add catalyst Pd-132 (0.14mg, 0.1mol%) under nitrogen atmosphere, stir
Mix backflow 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous sulfur
Sour sodium is dried, and it is pale yellow that column chromatography (petrol ether/ethyl acetate=100/1 is arrived in petrol ether/ethyl acetate=200/1) obtains product 11
Color solid, yield is 61%.Rf=0.42 (PE/EA=20/1)；M.p 250-251℃；1H NMR(500MHz,CDCl3)δ
7.70 (d, J=8.5Hz, 3H), 7.66 (t, J=7.5Hz, 3H), 7.46 (dd, J=7.8,5.2Hz, 6H), 7.43 (d, J=
8.3Hz, 6H), 7.34 (d, J=8.4Hz, 6H), 7.25 (d, J=2.1Hz, 12H), 7.16 (t, J=7.3Hz, 3H)；13C NMR
(125MHz,CDCl3)δ157.73,155.91,149.64,147.74,146.35,136.87,130.62,129.84,
129.80,129.49,127.83,127.21,126.67,123.19,118.85,118.80.；HRMS(ESI):Exact mass
calcd for C63H40N3O3[M+H]+:886.3064,Found:886.3070.Data above proves to obtain purpose compound,
Accompanying drawing 25,26 is respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 15
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), a methylphenylboronic acid II-12 (163mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixing is molten
(5mL, volume ratio is 4 for agent toluene and water:1), catalyst Pd-132 (0.14mg, 0.1mol%), stirring are added under nitrogen atmosphere
Backflow 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous slufuric acid
Sodium is dried, and it is white solid that column chromatography (petrol ether/ethyl acetate=200/1) obtains product 12, and yield is 39%.Rf=0.65
(PE/EA=20/1)；M.p>300℃；1H NMR(500MHz,CDCl3) δ 7.64 (d, J=8.5Hz, 3H), 7.58 (t, J=
7.5Hz, 3H), 7.47 (t, J=7.5Hz, 3H), 7.39 (dd, J=16.5,8.3Hz, 6H), 7.19 (d, J=8.8Hz, 6H),
7.15 (d, J=7.4Hz, 3H), 2.48 (s, 9H)；13C NMR(125MHz,CDCl3)δ149.55,148.46,146.16,
142.01,137.50,129.70,129.48,127.70,127.35,126.84,126.35,126.12,122.88,21.73；
HRMS(ESI):Exact mass calcd for C48H34N3[M+H]+:652.2747,Found:652.2747.Data above
Proof obtains purpose compound, and accompanying drawing 27,28 is respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 16
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), a methylphenylboronic acid II-13 (180mg, 1.2mmol), cesium carbonate (391mg, 1.2mmol), mixing is molten
(5mL, volume ratio is 4 for agent toluene and water:1), catalyst Pd-132 (0.14mg, 0.1mol%), stirring are added under nitrogen atmosphere
Backflow 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous slufuric acid
Sodium is dried, and it is light green solid that column chromatography (petrol ether/ethyl acetate=200/1) obtains product 13, and yield is 41%.Rf=0.70
(PE/EA=20/1)；M.p>300℃；1H NMR(500MHz,CDCl3) δ 7.57 (t, J=6.7Hz, 3H), 7.48 (t, J=
7.1Hz,3H),7.43–7.31(m,6H),7.26–7.11(m,6H),6.99–6.77(m,3H),2.65–2.41(m,9H),
2.05–1.77(m,9H)；13C NMR(125MHz,CDCl3)δ149.68,148.55,146.69,141.91,135.92,
135.31,134.61,129.77,129.36,128.01,127.35,127.11,126.45,125.85,125.35,125.19,
122.95,20.65,16.97.HRMS(ESI):Exact mass calcd for C51H40N3[M+H]+:694.3217Found:
694.3240.Data above proves to obtain purpose compound, and accompanying drawing 29,30 is respectively its nucleus magnetic hydrogen spectrum and carbon spectrum.
Embodiment 17
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to methylphenylboronic acid II-1 (163mg, 1.2mmol), anhydrous phosphoric acid potassium (382mg, 1.8mmol), mixing
(5mL, volume ratio is 4 for solvent toluene and water:1), sequentially add catalyst Pd (PPh under nitrogen atmosphere3)4(52mg,
0.045mmol), part PPh3(24mg, 0.09mmol) is stirred at reflux 24h, and TLC detection raw material substantially reacts complete, cooling
To room temperature, extract (15mL × 3) with dichloromethane, anhydrous sodium sulfate drying, column chromatography (pure petroleum ether to petroleum ether/acetic acid second
Ester=200/1) obtain product 1 for white solid, yield is 20%.Compound data is with embodiment 1.
Embodiment 18
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to methylphenylboronic acid II-1 (163mg, 1.2mmol), anhydrous phosphoric acid potassium (382mg, 1.8mmol), mixing
(5mL, volume ratio is 4 for solvent toluene and water:1), sequentially add catalyst Pd (PPh under nitrogen atmosphere3)4(52mg,
0.045mmol), part PCy3(25mg, 0.09mmol) is stirred at reflux 24h, and TLC detection raw material substantially reacts complete, cooling
To room temperature, extract (15mL × 3) with dichloromethane, anhydrous sodium sulfate drying, column chromatography (pure petroleum ether to petroleum ether/acetic acid second
Ester=200/1) obtain product 1 for white solid, yield is 25%.Compound data is with embodiment 1.
Embodiment 19
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to methylphenylboronic acid II-1 (163mg, 1.2mmol), three hypophosphite monohydrate potassium (479mg, 1.8mmol), mixes
(5mL, volume ratio is 4 for bonding solvent toluene and water:1), sequentially add catalyst Pd (OAc) under nitrogen atmosphere2(10mg,
0.045mmol), part PCy3(25mg, 0.09mmol) is stirred at reflux 24h, and TLC detection raw material substantially reacts complete, cooling
To room temperature, extract (15mL × 3) with dichloromethane, anhydrous sodium sulfate drying, column chromatography (pure petroleum ether to petroleum ether/acetic acid second
Ester=200/1) obtain product 1 for white solid, yield is 60%.Compound data is with embodiment 1.
Embodiment 20
The chloro- 5,11,17- benzo three quinoline I of 6,12,18- tri- that embodiment 3 is obtained is sequentially added in 25mL reaction bulb
(97mg, 0.2mmol), to methylphenylboronic acid II-1 (163mg, 1.2mmol), anhydrous phosphoric acid potassium (253mg, 1.2mmol), second two
(5mL, volume ratio is 20 for diethylene glycol dimethyl ether (DME) and water:1), add catalyst Pd-132 (7mg, 5mol%) under nitrogen atmosphere, stir
Mix backflow 24h, TLC detection raw material substantially reacts complete, is cooled to room temperature, extracts (15mL × 3) with dichloromethane, anhydrous sulfur
Sour sodium is dried, and it is white solid that column chromatography (pure petroleum ether is to petrol ether/ethyl acetate=200/1) obtains product 1, and yield is
40%.Compound data is with embodiment 1.
Claims (3)
1. one kind 6,12,18- triaryl -5,11,17- benzo three quinoline is it is characterised in that under such compound has
Formula structure：
Wherein：
R1It is hydrogen or methyl；R2It is hydrogen or methyl；
R3It is hydrogen, C6 and following straight chain or the alkyl containing side chain or alkoxyl, phenoxy group or benzyloxy.
2. 6,12,18- triaryl -5 described in a kind of claim 1, the synthetic method of 11,17- benzo three quinoline, it is special
Levy and be, the method includes step in detail below:
Step 1：Buchwald-Hartwig reaction
Under room temperature, reaction vessel sequentially adds equal tribromo-benzene, artificial neroli oil, cesium carbonate and toluene, add under nitrogen environment
Enter and be stirred at reflux 24-72h under tri-butyl phosphine tetrafluoroborate and palladium, nitrogen atmosphere, be cooled to room temperature, filter, rotation
Evaporimeter rotation removes solvent, adds the mixed solution of the ammonium chloride solution of dichloromethane and 1mol/L, point liquid, the anhydrous sulfur of organic faciess
Sour sodium is dried, and Rotary Evaporators rotation obtains crude product, ethyl acetate and petroleum ether recrystallization except solvent, and column chromatography obtains purpose compound
1,3,5- tri- (2- methoxycarbonyl group aniline) benzene；Wherein equal tribromo-benzene, artificial neroli oil, cesium carbonate, tri-butyl phosphine Tetrafluoroboric acid
The ratio of the amount of the material of salt and palladium is 1:3.0-6.0:6.0-10.0:0.03-0.3:0.01-0.10；Dichloromethane and
The volume ratio of the ammonium chloride solution of 1mol/L is 1-3:1；
Step 2：Hydrolysis of ester group
Under room temperature, reaction vessel adds compound 1,3,5- tri- (the 2- methoxycarbonyl group aniline) benzene that step 1 obtains, it is molten
Solution, in acetone, is subsequently added into the sodium hydrate aqueous solution that mass fraction is 5%, and it is clear for being stirred at reflux under nitrogen atmosphere to system
Clear prescribed liquid, is cooled to room temperature, adds dichloromethane and water, and point liquid leaves and takes aqueous phase, with dilute salt of 1mol/L or 2mol/L
Acid is acidified to pH=1, filters, and gained solid is vacuum dried 2h at 100 DEG C and obtains crude product, and ethyl alcohol recrystallization obtains purpose chemical combination
Thing 1,3,5- tri- (2- carboxyanilino) benzene；The wherein amount of material of 1,3,5- tri- (2- methoxycarbonyl group aniline) benzene and sodium hydroxide
Than for 1:10.0-1:24.0；
Step 3：Phosphorus oxychloride cyclization
Under room temperature, reaction vessel adds compound 1,3,5- tri- (2- carboxyanilino) benzene that step 2 obtains, true at 110 DEG C
Sky is dried 4h, is subsequently adding under excessive phosphorus oxychloride, nitrogen atmosphere and is stirred at reflux 16h, and Rotary Evaporators rotation is except unreacted
Phosphorus oxychloride, is cooled to room temperature, adds excessive dichloromethane, is slowly added in 15% ammonia of frozen water cooling, filters,
Dichloromethane repeatedly washs, and then be washed once with ether, is vacuum dried to obtain purpose compound 6,12,18- tri- chloro- 5 at 50 DEG C,
11,17- benzo three quinoline；
Step 4：Suzuki is coupled
6,12,18- tri- chloro- 5 are sequentially added in reaction vessel, 11,17- benzo three quinoline, phenylboric acid, alkali and solvent, nitrogen
Add catalyst or catalyst and part under environment, be stirred at reflux under designated solvent and complete to TLC display reaction, be cooled to room
Temperature, dichloromethane extracts, anhydrous sodium sulfate drying, obtains described 6 by column chromatography for separation, 12,18- triaryl -5, and 11,17-
Benzo three quinoline；
Wherein：Described catalyst is selected from：Palladium, tetrakis triphenylphosphine palladium or Pd-132；Its consumption is：X% mole, x is
0.05-22.5；
Described part is selected from：Tricyclohexyl phosphine or triphenylphosphine；Its consumption is：Y% mole, y is 22.5-67.5；
Described solvent is selected from：Toluene and the mixed solvent of water or glycol dimethyl ether and water；Its consumption is every mM 6,12,
Chloro- 5,11,17- benzo three quinoline of 18- tri- is corresponding to use mixed solvent 10～30mL；Toluene and water volume ratio are 4:1 or 9:1；
Glycol dimethyl ether and water volume ratio are 20:1 or 10:1；
Described alkali is selected from：Three hypophosphite monohydrate potassium, anhydrous phosphoric acid potassium or cesium carbonate；Its consumption is：Every mM of 6,12,18- tri- is chloro-
5,11,17- benzo three quinoline is corresponding to use 3.6～9 mMs of alkali；
Response time：8～36 hours.
3. method according to claim 2 is it is characterised in that described Pd-132 is dichloro pair [di-t-butyls-(4- diformazan
Base aminophenyl) phosphine] palladium (II), there is formula：
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| CN111499900A (en) * | 2020-04-20 | 2020-08-07 | 上海应用技术大学 | Two-dimensional polymer film based on disc-shaped tri-boron nuclear molecules and preparation and application thereof |
| CN112094638A (en) * | 2019-06-18 | 2020-12-18 | 上海和辉光电有限公司 | Organic light-emitting material and OLED device |
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| CN112094638A (en) * | 2019-06-18 | 2020-12-18 | 上海和辉光电有限公司 | Organic light-emitting material and OLED device |
| CN111499900A (en) * | 2020-04-20 | 2020-08-07 | 上海应用技术大学 | Two-dimensional polymer film based on disc-shaped tri-boron nuclear molecules and preparation and application thereof |
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