CN104817483B - A kind of pair of carbonyl Benzazole compounds and its synthetic method - Google Patents

A kind of pair of carbonyl Benzazole compounds and its synthetic method Download PDF

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CN104817483B
CN104817483B CN201510103250.2A CN201510103250A CN104817483B CN 104817483 B CN104817483 B CN 104817483B CN 201510103250 A CN201510103250 A CN 201510103250A CN 104817483 B CN104817483 B CN 104817483B
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姜雪峰
张泽光
代志洪
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East China Normal University
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Abstract

It is in benzene, at 80 DEG C the invention discloses a kind of method of indoles double carbonylation, using α hydroxy-ketones and indoles as reaction raw materials, using oxygen as oxidant, in the presence of copper catalyst, reaction obtains double carbonyl Benzazole compounds shown in formula (III).Advantage of the present invention includes：Reaction is efficient, and yield is higher；Oxygen is used as oxidant；Reaction condition is gentle, without strong acid and strong base；Cheap metal is catalyzed；Reaction substrate is easily prepared；It can also be realized after reaction amplification.

Description

A kind of pair of carbonyl Benzazole compounds and its synthetic method
Technical field
The invention belongs to organic compound technique applied technical field, and in particular to the double carbonyl Benzazole compounds of a class and Its synthetic method.
Background technology
Double carbonyl compound is not only widely existed among a series of natural products with unique activity, and can be made Converted for important synthon to a variety of fluorescent materials.The Kui quinoline structure of such as heteroaromatic substitution can be closed by double carbonylation Object space is just made, and this class formation has many applications as light trigger and fluoride ions detector.Although traditional acyl chlorides Reagent is once used to build some double carbonyl structures, and yet with its toxicity and sensitiveness, this kind of tactful application is present Hinder.Simultaneously as outstanding fluorescent characteristic and the features such as be easy to function dough, the fluorescent material of the skeleton containing indoles was in recent years Increasingly cause the concern of people.
Natural products and derivatization application containing double carbonyl structures
Then, a kind of simple, green, high efficiency low cost, good, the environment-friendly, mild condition of compatibility and economic and practical are found The new methods of the double carbonyl indoles of structure just seem and be even more important.The present inventor is it has been investigated that α hydroxy-ketones are that a class is unique Compound, easily forms the oxidative coupling reaction of free radical and then generation and indoles, based on this, the present invention is carried in the α positions of carbonyl The reaction for preparing double carbonyl indoles as raw material using α hydroxy-ketones and indoles of copper catalysis dioxygen oxidation is gone out.
The content of the invention
Instant invention overcomes the shortcomings of traditional acyl chlorides coupling reaction, a kind of double carbonyls of efficiently structure are innovatively realized The method of indoles.The present invention uses cheap DDTC catalyst, using α hydroxy-ketones, indoles as raw material, using oxygen as oxidant, In have effectively achieved corresponding conversion at 80 DEG C in reaction dissolvent, double carbonyl indoles as shown in formula (III) are prepared.
Wherein, the course of reaction is as shown in formulas below.
In above reaction equation,
Ar is phenyl ring, heterocycle or substituted benzene ring；R is electron rich base, electron-deficient base or halogen atom；R ' be alkyl, pi-allyl, Benzyl or substituted benzyl.
Preferably, Ar is phenyl, 4- fluorophenyls, 4- methoxyphenyls, 4- chlorphenyls, 4- bromophenyls, 2- naphthyls, 2- benzos Thienyl, 2- benzofuranyls, 2- thienyls, 3- thienyls；R is 4- methyl formates base, 5- ethyoxyls, 5- methoxyl groups, 6- first Epoxide, 7- benzyloxies, 4- chlorine, 5- chlorine, 6- chlorine, 5- bromines；R ' is methyl, pi-allyl, benzyl or to methoxy-benzyl.
In the present invention, Ar, R, R ' include but are not limited to above-mentioned group.
Such as above reaction equation, the present invention is used as starting original by the use of the indoles shown in the α hydroxy-ketones shown in formula (I) and formula (II) Material, using oxygen as oxidising agent, in the presence of DDTC catalyst, is reacted in reaction dissolvent, is synthesized such as formula (III) double carbonyl benzazolyl compounds shown in.
In the present invention, the mole dosage of α hydroxy-ketone of the initiation material as shown in formula (I) and the indoles shown in formula (II) Ratio is 1:1-1:15.Preferably, both usage ratios are 1:3.
In the present invention, using oxygen as oxidising agent.
In the present invention, the copper catalyst is CuSO4,CuSO4 。5H2O,Cu(OAc)2,Cu(NO3)2,Cu(TFA)2,Cu (OTf)2,CuCl2,CuBr2,Cu(acac)2, CuO, CuOAc, CuI, CuBr, CuCl, CuTc, Cu etc..Preferably, the copper is urged Agent is CuTc.Wherein, the consumption of the catalyst is the 1-10mol% of the raw material α hydroxyacetone compounds as shown in formula (I). Preferably, the catalyst amount is the 10mol% of the raw material α hydroxyacetone compounds as shown in formula (I).
In the present invention, the reaction dissolvent be methanol, ethanol, isopropanol, the tert-butyl alcohol, water, DMSO, DMF, DMA, acetonitrile, Any one or any combination of acetone, tetrahydrofuran, toluene, benzene, dichloromethane, 1,2- dichloroethanes, chloroform.Preferably, The solvent is benzene.
Synthetic reaction of the present invention comprises the following steps：α hydroxy-ketones are added in reaction vessel, it is indoles, copper catalyst, molten Agent, in oxygen atmosphere, reacts in room temperature to stirred at reflux condition, obtains double carbonyl indoles chemical combination shown in formula (III) Thing.Preferably, reactions steps are reacted at a temperature of 80 DEG C.
In an instantiation, synthetic reaction of the present invention is in reaction bulb A, to add α hydroxyacetone compounds (X Mmol), indoles (Y mmol) catalyst CuTC (Z mmol), solvent (V mL), reaction system is in oxygen atmosphere, at 80 DEG C Stirring 6 hours, is stirred 4-24 hours.Monitor reaction process.After completion of the reaction, directly target product formula is obtained through column chromatography for separation (III) double carbonyl benzazolyl compounds shown in.
The invention also provides the double carbonyl Yin as shown in formula (III) prepared according to above-mentioned synthetic method of the invention Indole compound,
Ar is phenyl ring, heterocycle or substituted benzene ring；R is electron rich base, electron-deficient base or halogen atom；R ' be alkyl, pi-allyl, Benzyl or substituted benzyl.
Preferably, Ar is phenyl, 4- fluorophenyls, 4- methoxyphenyls, 4- chlorphenyls, 4- bromophenyls, 2- naphthyls, 2- benzos Thienyl, 2- benzofuranyls, 2- thienyls, 3- thienyls；R is 4- methyl formates base, 5- ethyoxyls, 5- methoxyl groups, 6- first Epoxide, 7- benzyloxies, 4- chlorine, 5- chlorine, 6- chlorine, 5- bromines；R ' is methyl, pi-allyl, benzyl or to methoxy-benzyl.
The invention also provides new double carbonyl benzazolyl compounds, shown in its structural formula such as formula (III),
Wherein, Ar is phenyl, 4- fluorophenyls, 4- methoxyphenyls, 4- chlorphenyls, 4- bromophenyls, 2- naphthyls, 2- benzo thiophenes Fen base, 2- benzofuranyls, 2- thienyls, 3- thienyls；R is 4- methyl formates base, 5- ethyoxyls, 5- methoxyl groups, 6- methoxies Base, 7- benzyloxies, 4- chlorine, 5- chlorine, 6- chlorine, 5- bromines；R ' is methyl, pi-allyl, benzyl or to methoxy-benzyl.
The invention also provides double carbonyl Benzazole compounds shown in formula (III) are in synthesis Kui quinoline class fluorescent material Using.
The present invention has advantages below：Reaction substrate is easily prepared；Reaction is efficient, high income；Oxygen is honest and clean as oxidant Valency, green is environmentally friendly；Reaction condition is gentle, without strong acid and strong base：Catalyst is cheap metal, economical；After reaction amplification It can also realize；Reaction substrate is easily prepared.The present invention is using the α hydroxyacetone compounds that easily prepare as reaction raw materials, with oxygen As sulfiding reagent, under cheap DDTC catalyst action, carry out oxidative coupling reaction with indoles and obtain double carbonyl indoles Compound.Operation is simple, and reaction condition is gentle, is adapted to large-scale industrial production.
Brief description of the drawings
Fig. 1 shows the ultra-violet absorption spectrum of the compound 1ac-7ac in the embodiment of the present invention.
Fig. 2 shows the fluorescence emission spectrum of the compound 1ac-7ac in the embodiment of the present invention.
Fig. 3 shows ultra-violet absorption spectrums of the compound 1ac in opposed polarity solvent in the embodiment of the present invention.
Fig. 4 shows fluorescence emission spectrums of the compound 1ac in opposed polarity solvent in the embodiment of the present invention.
Embodiment
With reference to specific examples below, the present invention is described in further detail, and of the invention protects content not limit to In following examples.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change and excellent Point is all included in the present invention, and using appended claims as protection domain.Implement the present invention process, condition, Reagent, experimental method etc., are the universal knowledege and common knowledge of this area, this hair in addition to the following content specially referred to It is bright that content is not particularly limited.Data given by following examples include concrete operations and reaction condition and product.Product is pure Degree is identified by nuclear-magnetism.
The synthetic reaction of double carbonyl benzazolyl compounds of the invention, comprises the following steps：(1) α hydroxyls are added in reaction vessel Base ketone, indoles, copper catalyst, solvent, in oxygen atmosphere, react in room temperature to stirred at reflux condition, obtain formula (III) institute The double carbonyl Benzazole compounds shown.Again purpose product is obtained through column chromatography for separation.
Wherein, double carbonyl benzazolyl compounds as shown in table 1, are to synthesize obtained product by the inventive method, still It there are no open source literature and disclose these compounds.
Double carbonyl benzazolyl compounds in table 1 can change into quinoxaline compound, comprise the following steps：Hold in reaction Double carbonyl indoles, o-phenylenediamine, solvent are added in device, is reacted under room temperature to counterflow condition, obtains the quinoline shown in formula (IV) Quinoline class compound.Again purpose product is obtained through column chromatography for separation.A series of this Kui quinoline structure all has good photoluminescent property And solvatochromism effect.
New double carbonyl benzazolyl compounds of the present invention of table 1
Embodiment 1
Compound 1ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And 1- methyl indols 1b (0.6mmol, 78.7mg) is added in reaction tube, then add after reaction dissolvent benzene (4mL), in oxygen During atmosphere is enclosed, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, direct column chromatography Product 1ab (43.4mg) yield is obtained after separation:83%；1H NMR(400MHz,CDCl3)δ8.53–8.42(m,1H),8.10 (dd, J=5.1,3.4Hz, 2H), 7.80 (s, 1H), 7.67-7.58 (m, 1H), 7.49 (t, J=7.7Hz, 2H), 7.43-7.36 (m,3H),3.83(s,3H)；13C NMR(100MHz,CDCl3)δ193.7,187.5,139.5,137.7,134.2,133.5, 130.3,128.7,126.4,124.2,123.5,122.7,112.9,109.9,33.7.MS(EI)m/z 263(M+).
Embodiment 2
Compound 2ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And 1- pi-allyl indoles 2b (0.6mmol, 94.8mg) are added in reaction tube, then add after reaction dissolvent benzene (4mL), In oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, direct post layer Product 2ab (39.6mg) yield is obtained after analysis separation:69%；1H NMR(400MHz,CDCl3)δ8.55–8.45(m,1H), 8.16-8.07 (m, 2H), 7.85 (s, 1H), 7.67-7.59 (m, 1H), 7.49 (dd, J=10.6,4.8Hz, 2H), 7.42- 7.33 (m, 3H), 6.05-5.91 (m, 1H), 5.25 (ddd, J=17.8,13.7,0.8Hz, 2H), 4.75 (dt, J=5.6, 1.4Hz,2H)；13C NMR(100MHz,CDCl3)δ193.6,187.6,138.5,137.1,134.2,133.4,131.4, 130.3,128.7,126.5,124.2,123.5,122.7,119.3,113.1,110.4,49.7.HRMS(EI)Calcd for C19H15NO2289.1103,Found289.1102.
Embodiment 3
Compound 3ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And 1- benzylindoles 3b (0.6mmol, 124.2mg) is added in reaction tube, then add after reaction dissolvent benzene (4mL), In oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, direct post layer Product 3ab (47.8mg) yield is obtained after analysis separation:71%；1H NMR(400MHz,CDCl3) δ 8.51 (d, J=7.8Hz, 1H), 8.18-8.06 (m, 2H), 7.92 (s, 1H), 7.67-7.59 (m, 1H), 7.50 (t, J=7.7Hz, 2H), 7.38 (m, 1H), 7.36–7.27(m,5H),7.20–7.13(m,2H),5.33(s,2H)；13C NMR(100MHz,CDCl3)δ193.5,187.6, 138.8,137.2,135.1,134.2,133.4,130.3,129.1,128.7,128.3,127.0,126.6,124.3, 123.5,122.8,113.3,110.6,51.1.HRMS(EI)Calcd for C23H17NO2339.1259,Found 339.1262.
Embodiment 4
Compound 4ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And 1- is added in reaction tube to methyl-benzyl indoles 4b (0.6mmol, 142.2mg), reaction dissolvent benzene (4mL) is then added Afterwards, in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, directly Product 4ab (45.1mg) yield is obtained after column chromatography for separation:63%；1H NMR(400MHz,CDCl3) δ 8.49 (d, J=7.6Hz, 1H), 8.17-8.04 (m, 2H), 7.88 (s, 1H), 7.62 (t, J=7.4Hz, 1H), 7.49 (t, J=7.7Hz, 2H), 7.43- 7.28 (m, 3H), 7.11 (d, J=8.6Hz, 2H), 6.89-6.78 (m, 2H), 5.25 (s, 2H), 3.77 (s, 3H)；13C NMR (100MHz,CDCl3)δ193.5,187.6,159.6,138.6,137.2,134.2,133.4,130.3,128.7,128.6, 126.9,126.7,124.2,123.5,122.7,114.4,113.2,110.6,55.3,50.7.HRMS(EI)Calcd for C24H19NO3369.1365,Found369.1369.
Embodiment 5
Compound 5ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And 4- methyl formate base indoles 5b (0.6mmol, 105.1mg) are added in reaction tube, reaction dissolvent benzene (4mL) is then added Afterwards, in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, directly Product 5ab (47.3mg) yield is obtained after column chromatography for separation:77%；1H NMR(400MHz,CDCl3)δ10.20(s,1H), 8.03-7.95 (m, 2H), 7.69 (d, J=3.3Hz, 1H), 7.60-7.53 (m, 1H), 7.49 (dd, J=7.4,0.8Hz, 1H), 7.42 (ddd, J=7.5,4.0,3.2Hz, 3H), 7.25-7.19 (m, 1H), 3.92 (s, 3H)；13C NMR(100MHz,CDCl3) δ193.4,188.0,170.4,137.4,137.2,134.4,133.3,130.3,128.7,126.8,123.7,123.1, 121.2,115.1,114.3,52.5.HRMS(EI)Calcd for C18H13NO4307.0845,Found 307.0848.
Embodiment 6
Compound 6ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And 5- ethyoxyl -1- methyl indols 6b (0.6mmol, 105.2mg) are added in reaction tube, reaction dissolvent benzene is then added After (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Reaction is monitored by thin-layer chromatography to terminate Afterwards, product 6ab (55.8mg) yield is obtained after direct column chromatography for separation:91%；1H NMR(400MHz,CDCl3)δ8.15–8.06 (m, 2H), 7.96 (d, J=2.3Hz, 1H), 7.72 (s, 1H), 7.66-7.56 (m, 1H), 7.49 (t, J=7.7Hz, 2H), 7.25 (d, J=8.7Hz, 1H), 7.00 (dd, J=8.9,2.5Hz, 1H), 4.17 (q, J=7.0Hz, 2H), 3.78 (s, 3H), 1.47 (t, J=7.0Hz, 3H)；13C NMR(100MHz,CDCl3)δ193.8,187.4,156.4,139.3,134.2,133.5, 132.5,130.3,128.7,127.3,114.9,112.5,110.8,104.9,64.1,33.9,14.9.HRMS(EI)Calcd for C19H17NO3307.1208,Found 307.1205.
Embodiment 7
Compound 7ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And 5- methoxyl group -1- methyl indols 7b (0.6mmol, 96.7mg) are added in reaction tube, reaction dissolvent benzene is then added After (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Reaction is monitored by thin-layer chromatography to terminate Afterwards, product 7ab (41.3mg) yield is obtained after direct column chromatography for separation:71%；1H NMR(400MHz,CDCl3)δ8.09(dd,J =8.3,1.2Hz, 2H), 7.97 (d, J=2.4Hz, 1H), 7.72 (s, 1H), 7.61 (dd, J=10.6,4.2Hz, 1H), 7.49 (t, J=7.8Hz, 2H), 7.25 (d, J=8.9Hz, 1H), 6.99 (dd, J=8.9,2.5Hz, 1H), 3.93 (s, 3H), 3.78 (s,3H)；13C NMR(100MHz,CDCl3)δ193.7,187.4,157.1,139.3,134.2,133.5,132.5,130.2, 128.7,127.2,114.5,112.5,110.8,103.9,55.8,33.9.HRMS(EI)Calcd for C18H15NO3293.1052,Found 293.1053.
Embodiment 8
Compound 8ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And 6- methoxyl group -1- methyl indols 8b (0.6mmol, 96.7mg) are added in reaction tube, reaction dissolvent benzene is then added After (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Reaction is monitored by thin-layer chromatography to terminate Afterwards, product 8ab (37.7mg) yield is obtained after direct column chromatography for separation:65%；1H NMR(400MHz,CDCl3)δ8.33(d,J =8.7Hz, 1H), 8.14-8.06 (m, 2H), 7.70 (s, 1H), 7.64-7.59 (m, 1H), 7.49 (t, J=7.7Hz, 2H), 7.03 (dd, J=8.7,2.2Hz, 1H), 6.82 (d, J=2.2Hz, 1H), 3.90 (s, 3H), 3.78 (s, 3H)；13C NMR (100MHz,CDCl3)δ193.7,187.5,157.8,138.9,138.7,134.2,133.5,130.3,128.7,123.4, 120.2,113.0,112.5,93.9,55.7,33.7.HRMS(EI)Calcd for C18H15NO3293.1052,Found 293.1051.
Embodiment 9
Compound 9ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And 7- benzyloxy -1- methyl indols 9b (0.6mmol, 142.4mg) are added in reaction tube, reaction dissolvent benzene is then added After (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Reaction is monitored by thin-layer chromatography to terminate Afterwards, product 9ab (62.1mg) yield is obtained after direct column chromatography for separation:85%；1H NMR(400MHz,CDCl3)δ8.16–8.05 (m, 3H), 7.73 (s, 1H), 7.62 (dd, J=10.5,4.3Hz, 1H), 7.56-7.46 (m, 4H), 7.41 (dd, J=10.1, 4.6Hz, 2H), 7.37-7.32 (m, 1H), 7.29-7.24 (m, 1H), 7.09 (dd, J=8.9,2.5Hz, 1H), 5.20 (s, 2H),3.77(s,3H)；13C NMR(100MHz,CDCl3)δ193.7,187.4,156.2,139.4,137.1,134.2, 133.5,132.7,130.2,128.7,128.5,127.9,127.7,127.3,115.0,112.6,110.9,105.4,70.6, 33.8.HRMS(EI)Calcd for C24H19NO3369.1365,Found 369.1362.
Embodiment 10
Compound 10ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And 4- chlorine 1- methyl indols 10b (0.6mmol, 99.0mg) are added in reaction tube, reaction dissolvent benzene (4mL) is then added Afterwards, in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, directly Product 10ab (35.2mg) yield is obtained after column chromatography for separation:60%；1H NMR(400MHz,CDCl3)δ8.14–8.04(m, 2H), 7.85 (s, 1H), 7.62 (t, J=7.4Hz, 1H), 7.49 (t, J=7.7Hz, 2H), 7.33 (dd, J=4.9,3.8Hz, 1H),7.26(m,2H),3.82(s,3H).13C NMR(100MHz,CDCl3)δ193.9,187.4,140.7,139.5,134.2, 133.4,130.3,128.7,127.6,124.6,124.6,123.8,113.2,108.7,34.0.HRMS(EI)Calcd for C17H12ClNO2297.0557,Found 297.0560.
Embodiment 11
Compound 11ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And the chloro- 1- methyl indols 11b (0.6mmol, 99.0mg) of 5- are added in reaction tube, reaction dissolvent benzene (4mL) is then added Afterwards, in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, directly Product 11ab (36.7mg) yield is obtained after column chromatography for separation:62%；1H NMR(400MHz,CDCl3) δ 8.48 (d, J= 1.8Hz, 1H), 8.14-8.05 (m, 2H), 7.83 (s, 1H), 7.64 (t, J=7.4Hz, 1H), 7.50 (t, J=7.7Hz, 2H), 7.32 (dt, J=17.4,5.3Hz, 2H), 3.83 (s, 3H)；13C NMR(100MHz,CDCl3)δ193.3,187.1,140.1, 136.1,134.4,133.3,130.3,129.6,128.8,127.4,124.6,122.3,112.4,111.0,34.0.HRMS (EI)Calcd for C17H12ClNO2297.0557,Found 297.0559.
Embodiment 12
Compound 12ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And the chloro- 1- methyl indols 12b (0.6mmol, 99.0mg) of 6- are added in reaction tube, reaction dissolvent benzene (4mL) is then added Afterwards, in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, directly Product 12ab (52.8mg) yield is obtained after column chromatography for separation:88%；1H NMR(400MHz,CDCl3) δ 8.38 (d, J= 8.5Hz, 1H), 8.08 (dd, J=5.1,3.3Hz, 2H), 7.80 (s, 1H), 7.67-7.59 (m, 1H), 7.49 (dd, J= 10.7,4.7Hz,2H),7.40–7.31(m,2H),3.80(s,3H)；13C NMR(100MHz,CDCl3)δ193.4,187.3, 139.9,138.1,134.4,133.2,130.3,130.2,128.8,124.8,124.0,123.6,112.9,110.2, 33.8.HRMS(EI)Calcd for C17H12ClNO2297.0557,Found 297.0558.
Embodiment 13
Compound 13ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and α hydroxy acetophenones 1a (0.2mmol, 1equiv., 27.2mg) And the bromo- 1- methyl indols 13b (0.6mmol, 126.0mg) of 5- are added in reaction tube, reaction dissolvent benzene (4mL) is then added Afterwards, in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, directly Product 13ab (41.9mg) yield is obtained after column chromatography for separation:62%；1H NMR(400MHz,CDCl3)δ8.65(s,1H),8.10 (d, J=7.7Hz, 2H), 7.81 (s, 1H), 7.65 (t, J=7.3Hz, 1H), 7.50 (dd, J=17.4,9.0Hz, 3H), 7.30–7.20(m,1H),3.83(s,3H)；13C NMR(100MHz,CDCl3)δ193.3,187.1,140.0,136.3, 134.4,133.3,130.3,128.7,127.9,127.2,125.3,117.3,112.3,111.4,33.9.HRMS(EI) Calcd for C17H12BrNO2341.0051,Found 341.0054.
Embodiment 14
Compound 14ab synthesis：
By fluoro- (α hydroxy acetophenones) 2a of catalyst CuTC (0.02mmol, 10mol%) and 4- (0.2mmol, 1equiv., 30.8mg) and 1- methyl indols 7b (0.6mmol, 96.7mg) is added in reaction tube, reaction dissolvent benzene (4mL) is then added Afterwards, in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, directly Product 14ab (44.5mg) yield is obtained after column chromatography for separation:72%；1H NMR(400MHz,CDCl3)δ8.22–8.07(m, 2H), 7.95 (d, J=2.2Hz, 1H), 7.74 (s, 1H), 7.25 (d, J=7.9Hz, 1H), 7.15 (t, J=8.6Hz, 2H), 6.99 (dd, J=8.9,2.4Hz, 1H), 3.92 (s, 3H), 3.79 (s, 3H)；13C NMR(100MHz,CDCl3)δ192.0, (186.9,167.7,165.1,157.2,139.4,133.1 d, J=9.6Hz), 132.6,130.0 (d, J=2.8Hz), (127.3,116.0,115.8,114.5,112.4,110.9,104.0,55.8 d, J=1.9Hz), 33.9；19F NMR (376MHz,CDCl3)δ-102.64(s,1F).HRMS(EI)Calcd for C18H14FNO3311.0958,Found 311.0956.
Embodiment 15
Compound 15ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and 4- methoxyl groups-(α hydroxy acetophenones) 3a (0.2mmol, 1equiv., 33.3mg) and 1- methyl indols 1b (0.6mmol, 78.7mg) be added in reaction tube, then add reaction it is molten After agent benzene (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Pass through thin-layer chromatography monitoring reaction knot Product 15ab (35.6mg) yield is obtained after Shu Hou, direct column chromatography for separation:61%；1H NMR(400MHz,CDCl3)δ8.54– 8.40(m,1H),8.13–8.04(m,2H),7.80(s,1H),7.44–7.33(m,3H),7.00–6.90(m,2H),3.87(s, 3H),3.82(s,3H)；13C NMR(100MHz,CDCl3)δ192.5,188.1,164.5,139.5,137.6,132.7, 126.4,126.3,124.1,123.4,122.6,114.0,112.9,109.9,55.6,33.7.HRMS(EI)Calcd for C18H15NO3293.1052,Found 293.1050.
Embodiment 16
Compound 16ab synthesis：
By chloro- (α hydroxy acetophenones) 4a of catalyst CuTC (0.02mmol, 10mol%) and 4- (0.2mmol, 1equiv., 34.0mg) and 1- methyl indols 1b (0.6mmol, 78.7mg) is added in reaction tube, reaction dissolvent benzene (4mL) is then added Afterwards, in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, directly Product 16ab (40.1mg) yield is obtained after column chromatography for separation:68%；1H NMR(400MHz,CDCl3) δ 8.46 (d, J= 2.5Hz,1H),8.09–8.00(m,2H),7.83(s,1H),7.50–7.44(m,2H),7.42–7.37(m,3H),3.84(s, 3H)；13C NMR(100MHz,CDCl3)δ192.2,186.7,140.8,139.7,137.7,131.8,131.7,129.1, 126.3,124.3,123.6,122.6,112.7,110.0,33.8.HRMS(EI)Calcd for C17H12ClNO2297.0557, Found297.0556.
Embodiment 17
Compound 17ab synthesis：
By bromo- (α hydroxy acetophenones) 5a of catalyst CuTC (0.02mmol, 10mol%) and 4- (0.2mmol, 1equiv., 43.0mg) and 1- methyl indols 1b (0.6mmol, 78.7mg) is added in reaction tube, reaction dissolvent benzene (4mL) is then added Afterwards, in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, directly Product 17ab (49.0mg) yield is obtained after column chromatography for separation:72%；1H NMR(400MHz,CDCl3)δ8.50–8.41(m, 1H),8.02–7.94(m,2H),7.82(s,1H),7.67–7.60(m,2H),7.40(m,3H),3.84(s,3H)；13C NMR (100MHz,CDCl3)δ192.4,186.6,139.6,137.7,132.3,132.1,131.7,129.7,126.4,124.3, 123.6,122.7,112.7,110.0,33.8.HRMS(EI)Calcd for C17H12BrNO2341.0051,Found 341.0053.
Embodiment 18
Compound 18ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and 2- (2- hydroxyacetyls) naphthalene 6a (0.2mmol, 1equiv., 37.3mg) and 1- methyl indols 1b (0.6mmol, 78.7mg) is added in reaction tube, reaction dissolvent benzene (4mL) is then added Afterwards, in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.After being terminated by thin-layer chromatography monitoring reaction, directly Product 18ab (51.3mg) yield is obtained after column chromatography for separation:82%；1H NMR(400MHz,CDCl3)δ8.63(s,1H),8.54 (dd, J=5.0,2.7Hz, 1H), 8.16 (dd, J=8.6,1.7Hz, 1H), 7.94 (dd, J=8.5,3.0Hz, 2H), 7.88 (d, J=8.1Hz, 1H), 7.84 (s, 1H), 7.65-7.59 (m, 1H), 7.57-7.51 (m, 1H), 7.46-7.37 (m, 3H), 3.83(s,3H)；13C NMR(100MHz,CDCl3)δ193.8,187.7,139.6,137.7,136.2,133.7,132.4, 130.7,130.0,129.1,128.7,127.8,126.9,126.4,124.4,124.2,123.5,122.7,113.0, 110.0,33.7.HRMS(EI)Calcd for C21H15NO2313.1103,Found 313.1100.
Embodiment 19
Compound 19ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and 2- (2- hydroxyacetyls) benzofuran 7a (0.2mmol, 1equiv., 35.3mg) and 1- methyl indols 1b (0.6mmol, 78.7mg) be added in reaction tube, then add reaction it is molten After agent benzene (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Pass through thin-layer chromatography monitoring reaction knot Product 19ab (49.7mg) yield is obtained after Shu Hou, direct column chromatography for separation:82%；1H NMR(400MHz,CDCl3)δ8.55– 8.47 (m, 1H), 8.16 (s, 1H), 8.02 (d, J=0.9Hz, 1H), 7.74 (d, J=7.9Hz, 1H), 7.63 (dd, J=8.5, 0.7Hz, 1H), 7.52 (ddd, J=8.4,7.2,1.2Hz, 1H), 7.44-7.36 (m, 3H), 7.36-7.29 (m, 1H), 3.85 (s,3H)；13C NMR(100MHz,CDCl3)δ183.6,181.9,156.3,150.0,140.3,137.5,129.3,127.2, 126.9,124.2,124.1,124.0,123.6,122.7,120.0,112.5,112.1,110.0,33.8.HRMS(EI) Calcd for C19H13NO3303.0895,Found 303.0898.
Embodiment 20
Compound 20ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and 2- (2- hydroxyacetyls) benzothiophene 8a (0.2mmol, 1equiv., 38.4mg) and 1- methyl indols 1b (0.6mmol, 78.7mg) be added in reaction tube, then add reaction it is molten After agent benzene (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Pass through thin-layer chromatography monitoring reaction knot Product 20ab (50.0mg) yield is obtained after Shu Hou, direct column chromatography for separation:78%；1H NMR(400MHz,CDCl3)δ8.57– 8.48 (m, 1H), 8.39 (s, 1H), 8.11 (s, 1H), 7.90 (d, J=8.8Hz, 2H), 7.53-7.46 (m, 1H), 7.44- 7.36(m,4H),3.84(s,3H)；13C NMR(100MHz,CDCl3)δ186.5,184.2,143.6,140.3,139.5, 139.1,137.5,134.7,128.1,126.8,126.6,125.1,124.2,123.5,122.8,122.6,112.1, 110.0,33.7.HRMS(EI)Calcd for C19H13NO2S319.0667,Found 319.0666.
Embodiment 21
Compound 21ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and 2- (2- hydroxyacetyls) benzofuran 7a (0.2mmol, 1equiv., 35.2mg) and 5- methoxyl group -1- methyl indols 7b (0.6mmol, 96.7mg) be added in reaction tube, Ran Houjia Enter after reaction dissolvent benzene (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Supervised by thin-layer chromatography After survey reaction terminates, product 21ab (51.8mg) yield is obtained after direct column chromatography for separation:78%；1H NMR(400MHz, CDCl3) δ 8.08 (s, 1H), 8.01 (d, J=0.9Hz, 1H), 7.97 (d, J=2.5Hz, 1H), 7.72 (d, J=7.9Hz, 1H), 7.61 (dd, J=8.5,0.7Hz, 1H), 7.50 (ddd, J=8.4,7.2,1.2Hz, 1H), 7.34-7.27 (m, 1H), 7.24 (d, J=1.9Hz, 1H), 6.98 (dd, J=8.9,2.5Hz, 1H), 3.92 (s, 3H), 3.82 (s, 3H)；13C NMR (100MHz,CDCl3)δ183.6,182.0,157.3,156.3,150.0,140.1,132.4,129.3,127.9,127.2, 124.1,124.0,120.0,114.5,112.6,111.8,110.9,104.1,55.8,34.0.HRMS(EI)Calcd for C20H15NO4333.1001,Found 333.0999.
Embodiment 22
Compound 22ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and 2- (2- hydroxyacetyls) benzothiophene 8a (0.2mmol, 1equiv., 38.4mg) and 5- methoxyl group -1- methyl indols 7b (0.6mmol, 96.7mg) be added in reaction tube, Ran Houjia Enter after reaction dissolvent benzene (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Supervised by thin-layer chromatography After survey reaction terminates, product 22ab (55.3mg) yield is obtained after direct column chromatography for separation:80%；1H NMR(400MHz, CDCl3) δ 8.40 (s, 1H), 8.06 (s, 1H), 8.01 (d, J=2.4Hz, 1H), 7.90 (d, J=8.5Hz, 2H), 7.49 (t, J =7.7Hz, 1H), 7.40 (t, J=7.5Hz, 1H), 7.30-7.23 (m, 1H), 7.00 (dd, J=8.9,2.4Hz, 1H), 3.95 (s,3H),3.82(s,3H)；13C NMR(100MHz,CDCl3)δ186.6,184.1,157.2,143.6,140.1,139.5, 139.1,134.6,132.4,128.1,127.9,126.6,125.1,122.9,114.5,111.9,110.9,104.1,55.8, 34.0.HRMS(EI)Calcd for C20H15NO3S349.0773,Found 349.0775.
Embodiment 23
Compound 23ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and 2- (2- hydroxyacetyls) thiophene 9a (0.2mmol, 1equiv., 28.4mg) and 5- methoxyl group -1- methyl indols 7b (0.6mmol, 96.7mg) be added in reaction tube, Ran Houjia Enter after reaction dissolvent benzene (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Supervised by thin-layer chromatography After survey reaction terminates, product 23ab (51.5mg) yield is obtained after direct column chromatography for separation:86%；1H NMR(400MHz, CDCl3) δ 8.11 (d, J=3.8Hz, 1H), 8.09 (s, 1H), 7.98 (d, J=2.4Hz, 1H), 7.79 (d, J=4.9Hz, 1H), 7.25 (d, J=8.9Hz, 1H), 7.21-7.14 (m, 1H), 6.98 (dd, J=8.9,2.5Hz, 1H), 3.93 (s, 3H), 3.81(s,3H)；13C NMR(100MHz,CDCl3)δ184.5,184.3,157.1,140.1,139.3,136.6,132.3, 128.3,127.9,114.3,111.7,110.8,104.1,55.8,33.9.HRMS(EI)Calcd for C16H13NO3S299.0616,Found 299.0617.
Embodiment 24
Compound 24ab synthesis：
By catalyst CuTC (0.02mmol, 10mol%) and 3- (2- hydroxyacetyls) thiophene 10a (0.2mmol, 1equiv., 28.4mg) and 5- methoxyl group -1- methyl indols 7b (0.6mmol, 96.7mg) be added in reaction tube, Ran Houjia Enter after reaction dissolvent benzene (4mL), in oxygen atmosphere, stirring reaction 6 hours under 80 DEG C of reaction temperatures.Supervised by thin-layer chromatography After survey reaction terminates, product 24ab (49.6mg) yield is obtained after direct column chromatography for separation:83%；1H NMR(400MHz, CDCl3) δ 8.49 (dd, J=2.9,1.1Hz, 1H), 7.97 (d, J=2.5Hz, 1H), 7.92 (s, 1H), 7.73 (dd, J= 5.1,1.1Hz, 1H), 7.35 (dd, J=5.1,2.9Hz, 1H), 7.25 (d, J=8.9Hz, 1H), 6.99 (dd, J=8.9, 2.5Hz,1H),3.93(s,3H),3.80(s,3H)；13C NMR(100MHz,CDCl3)δ186.7,186.2,157.1,139.8, 138.3,137.1,132.5,127.9,127.7,126.3,114.4,112.1,110.9,104.1,55.9,33.9.HRMS (EI)Calcd for C16H13NO3S299.0616,Found299.0617.
Embodiment 25
Compound 1ac synthesis：
By compound 1ab (0.2mmol, 52.7mg), o-phenylenediamine (0.3mmol, 32.5mg) is added in reaction tube, so Reaction dissolvent MeOH (2.5mL) and AcOH (2.5mL) is added afterwards, is stirred 2 hours at 60 DEG C.Monitored and reacted by thin-layer chromatography After end, product 1ac (65.5mg) is obtained after direct column chromatography for separation.Yield:98%；1H NMR(400MHz,CDCl3)δ 8.59-8.45 (m, 1H), 8.16 (dd, J=8.2,1.0Hz, 1H), 8.09 (dd, J=8.2,1.1Hz, 1H), 7.77-7.58 (m, 4H), 7.43 (t, J=6.3Hz, 3H), 7.31-7.22 (m, 3H), 6.58 (s, 1H), 3.60 (s, 3H)；13C NMR (100MHz,CDCl3)δ153.6,149.4,141.6,140.3,139.5,137.0,132.2,129.6,129.2,128.9, 128.8,128.6,128.5,127.2,122.6,122.4,121.0,113.3,109.2,33.0.HRMS(EI)Calcd for C23H17N3335.1422,Found 335.1419.
Embodiment 26
Compound 2ac synthesis：
By compound 16ab (0.2mmol, 59.6mg), o-phenylenediamine (0.3mmol, 32.5mg) is added in reaction tube, Then reaction dissolvent MeOH (2.5mL) and AcOH (2.5mL) is added, is stirred 2 hours at 60 DEG C.It is anti-by thin-layer chromatography monitoring After should terminating, product 2ac (76.7mg) is obtained after direct column chromatography for separation.Yield:99%；1H NMR(400MHz,CDCl3)δ 8.35 (d, J=7.7Hz, 1H), 8.13 (d, J=8.3Hz, 1H), 8.06 (d, J=8.1Hz, 1H), 7.72 (t, J=7.5Hz, 1H), 7.65 (t, J=7.5Hz, 1H), 7.60 (d, J=8.3Hz, 2H), 7.36 (d, J=8.3Hz, 2H), 7.30-7.20 (m, 3H),6.72(s,1H),3.66(s,3H)；13C NMR(100MHz,CDCl3)δ152.3,149.1,141.6,139.6,138.6, 137.1,135.0,131.8,130.8,129.8,128.9,128.8,128.7,128.7,127.0,122.7,122.1, 121.1,113.2,109.4,33.1.HRMS(EI)Calcd for C23H17N3335.1422,Found 335.1419.HRMS (EI)Calcd for C23H16ClN3369.1033,Found 369.1031.
Embodiment 27
Compound 3ac synthesis：
By compound 17ab (0.2mmol, 68.5mg), o-phenylenediamine (0.3mmol, 32.5mg) is added in reaction tube, Then reaction dissolvent MeOH (2.5mL) and AcOH (2.5mL) is added, is stirred 2 hours at 60 DEG C.It is anti-by thin-layer chromatography monitoring After should terminating, product 3ac (82.9mg) is obtained after direct column chromatography for separation.Yield:99%；1H NMR(400MHz,CDCl3)δ 8.35 (d, J=7.8Hz, 1H), 8.13 (d, J=8.2Hz, 1H), 8.05 (d, J=8.1Hz, 1H), 7.72 (t, J=7.5Hz, 1H), 7.65 (t, J=7.5Hz, 1H), 7.58-7.47 (m, 4H), 7.33-7.18 (m, 3H), 6.72 (s, 1H), 3.66 (s, 3H)；13C NMR(101MHz,CDCl3)δ152.3,149.0,141.6,139.6,139.1,137.1,131.8,131.7, 131.0,129.9,128.9,128.8,128.7,127.0,123.3,122.8,122.1,121.1,113.2,109.4, 33.2.HRMS(EI)Calcd for C23H16BrN3413.0531,Found 413.0528.
Embodiment 28
Compound 4ac synthesis：
By compound 20ab (0.1mmol, 32.0mg), o-phenylenediamine (0.15mmol, 16.8mg) is added in reaction tube, Then reaction dissolvent MeOH (1.2mL) and AcOH (1.2mL) is added, is stirred 2 hours at 60 DEG C.It is anti-by thin-layer chromatography monitoring After should terminating, product 4ac (33.6mg) is obtained after direct column chromatography for separation.Yield:86%；1H NMR(400MHz,CDCl3)δ 8.17-8.05 (m, 2H), 7.94 (d, J=8.0Hz, 1H), 7.84 (d, J=7.9Hz, 1H), 7.75-7.64 (m, 2H), 7.54 (d, J=10.8Hz, 2H), 7.42-7.23 (m, 5H), 7.15 (t, J=7.5Hz, 1H), 3.79 (s, 3H)；13C NMR (100MHz,CDCl3)δ148.3,147.4,142.8,141.2,140.9,140.0,139.9,137.1,130.9,130.0, 129.2,128.9,128.7,126.8,126.0,125.3,124.4,124.3,122.5,122.2,121.4,120.9, 113.6,109.5,33.2.HRMS(EI)Calcd for C25H17N3S391.1143,Found 391.1141.
Embodiment 29
Compound 5ac synthesis：
By compound 19ab (0.07mmol, 21.3mg), o-phenylenediamine (0.1mmol, 10.9mg) is added in reaction tube, Then reaction dissolvent MeOH (1mL) and AcOH (1mL) is added, is stirred 2 hours at 60 DEG C.Pass through thin-layer chromatography monitoring reaction knot Product 5ac (22.6mg) is obtained after Shu Hou, direct column chromatography for separation.Yield:89%；1H NMR(400MHz,CDCl3)δ8.26– 8.18 (m, 1H), 8.17-8.10 (m, 1H), 8.01 (d, J=8.0Hz, 1H), 7.80-7.68 (m, 2H), 7.58 (dd, J= 8.3,0.6Hz, 1H), 7.51 (d, J=7.7Hz, 1H), 7.40 (d, J=8.2Hz, 1H), 7.38-7.32 (m, 1H), 7.32- 7.27 (m, 2H), 7.26-7.20 (m, 1H), 7.20-7.14 (m, 1H), 7.05 (d, J=0.8Hz, 1H), 3.81 (s, 3H)；13C NMR(100MHz,CDCl3)δ155.1,153.2,148.7,143.7,141.4,139.9,137.1,130.7,130.4, 129.3,129.2,128.8,128.2,126.8,125.7,123.2,122.6,121.8,121.4,121.0,113.5, 111.9,109.8,109.5,33.2.HRMS(EI)Calcd for C25H17N3O375.1372,Found 375.1374.
Embodiment 30
Compound 6ac synthesis：
By compound 22ab (0.2mmol, 69.8mg), o-phenylenediamine (0.3mmol, 32.5mg) is added in reaction tube, Then reaction dissolvent MeOH (2.5mL) and AcOH (2.5mL) is added, is stirred 2 hours at 60 DEG C.It is anti-by thin-layer chromatography monitoring After should terminating, product 6ac (74.8mg) is obtained after direct column chromatography for separation.Yield:89%；1H NMR(400MHz,CDCl3)δ 8.09-7.98 (m, 2H), 7.78 (d, J=8.1Hz, 1H), 7.69-7.59 (m, 2H), 7.57-7.43 (m, 2H), 7.35 (s, 1H), 7.30-7.24 (m, 2H), 7.24-7.15 (m, 3H), 6.83 (dd, J=8.9,2.4Hz, 1H), 3.72 (s, 3H), 3.59 (s,3H)；13C NMR(100MHz,CDCl3)δ155.1,148.6,147.4,142.7,141.3,140.9,140.0,132.4, 131.4,130.0,129.1,128.9,128.6,127.2,126.0,125.3,124.4,124.4,122.2,113.3, 113.2,110.4,102.8,55.6,33.4.HRMS(EI)Calcd for C26H19N3OS421.1249,Found 421.1253.
Embodiment 31
Compound 7ac synthesis：
By compound 21ab (0.2mmol, 66.6mg), o-phenylenediamine (0.3mmol, 32.5mg) is added in reaction tube, Then reaction dissolvent MeOH (2.5mL) and AcOH (2.5mL) is added, is stirred 2 hours at 60 DEG C.It is anti-by thin-layer chromatography monitoring After should terminating, product 7ac (75.9mg) is obtained after direct column chromatography for separation.Yield:94%；1H NMR(400MHz,CDCl3)δ 8.22 (dd, J=8.1,1.5Hz, 1H), 8.13 (dd, J=8.2,1.3Hz, 1H), 7.75 (pd, J=6.9,1.6Hz, 2H), 7.59 (d, J=8.3Hz, 1H), 7.53 (d, J=7.7Hz, 1H), 7.41 (d, J=2.4Hz, 1H), 7.38-7.30 (m, 2H), 7.30-7.21 (m, 2H), 7.09 (s, 1H), 6.93 (dd, J=8.9,2.4Hz, 1H), 3.78 (s, 3H), 3.67 (s, 3H)；13C NMR(100MHz,CDCl3)δ155.2,155.1,153.4,148.9,143.6,141.5,139.8,132.4,131.2, 130.4,129.2,129.2,128.7,128.2,127.2,125.7,123.2,121.8,113.1,111.8,110.3, 109.6,102.8,55.6,33.4.HRMS(EI)Calcd for C26H19N3O2405.1477,Found 405.1474.
The ultra-violet absorption spectrum of compound 1ac-7ac in the embodiment of the present invention is as shown in figure 1, compound 1ac-7ac Fluorescence emission spectrum is as shown in Fig. 2 ultra-violet absorption spectrums of the compound 1ac in opposed polarity solvent is as shown in figure 3, compound Fluorescence emission spectrums of the 1ac in opposed polarity solvent is as shown in Figure 4.

Claims (3)

1. the synthetic method of a kind of pair of carbonyl Benzazole compounds, it is characterised in that using alpha-alcohol ketone and indoles as reaction raw materials, Using oxygen as oxidant, in the presence of copper catalyst, reaction obtains double carbonyl Yin as shown in formula (III) in reaction dissolvent Diindyl class compound；The course of reaction is as shown in reaction equation：
Wherein, Ar is phenyl, 4- fluorophenyls, 4- methoxyphenyls, 4- chlorphenyls, 4- bromophenyls, 2- naphthyls, 2- benzothiophenes Base, 2- benzofuranyls, 2- thienyls, 3- thienyls；R be 4- methyl formates base, 5- ethyoxyls, 5- methoxyl groups, 6- methoxyl groups, 7- benzyloxies, 4- chlorine, 5- chlorine, 6- chlorine, 5- bromines；R ' is methyl, pi-allyl, benzyl or to methoxy-benzyl；
The copper catalyst is CuSO4, CuSO4·5H2O, Cu (OAc)2, Cu (NO3)2, Cu (TFA)2, Cu (OTf)2, CuCl2, CuBr2, Cu (acac)2, CuO, CuOAc, CuI, CuBr, CuCl, CuTc, or Cu；The consumption of the copper catalyst is α hydroxy-ketones 1-10mol%；
The reaction dissolvent is methanol, ethanol, isopropanol, the tert-butyl alcohol, DMSO, DMF, DMA, acetonitrile, acetone, tetrahydrofuran, first Any one or any combination of benzene, benzene, dichloromethane, 1,2- dichloroethanes, chloroform；
The reaction is carried out under the conditions of 80 DEG C.
2. the synthetic method of double carbonyl Benzazole compounds as claimed in claim 1, it is characterised in that in the reaction, institute The mole dosage ratio for stating α hydroxy-ketones and indoles is 1:1-1:15.
3. the synthetic method of carbonyl Benzazole compounds as claimed in claim 1 double, it is characterised in that methods described include with Lower step：
α hydroxy-ketones, indoles, copper catalyst, reaction dissolvent are added in reaction vessel, in oxygen atmosphere, in room temperature to backflow Under the conditions of stirring reaction, obtain double carbonyl Benzazole compounds shown in formula (III).
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* Cited by examiner, † Cited by third party
Title
AlCl3 induced (hetero)arylation of 2,3-dichloroquinoxaline: A one-pot synthesis of mono/disubstituted quinoxalines as potential antitubercular agents;K. Shiva Kumar，等;《Bioorganic & Medicinal Chemistry》;20120117;第20卷;全文 *
Copper-Catalyzed C-H Oxidation/Cross-Coupling of a-Amino Carbonyl Compounds;Ji Cheng Wu,等;《Angew. Chem. Int. Ed.》;20121231;全文 *
Diindolylquinoxalines: Effective Indole-Based Receptors for Phosphate Anion;Jonathan L. Sessler，等;《J. AM. CHEM. SOC.》;20061206;第128卷(第51期);scheme1 *
Direct Regioselective Oxidative Cross-Coupling of Indoles with Methyl Ketones: A Novel Route to C3-Dicarbonylation of Indoles;Qinghe Gao,等;《Org. Lett.》;20141215;第17卷;136页scheme4中化合物3ag *
Modulation of A2B adenosine receptor by 1-Benzyl-3-ketoindole derivatives;Sabrina Taliani，等;《European Journal of Medicinal Chemistry》;20130908;第69卷;全文 *

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