CN110386854A - A kind of preparation method of the aryl alkynes of visible light catalytic - Google Patents

A kind of preparation method of the aryl alkynes of visible light catalytic Download PDF

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CN110386854A
CN110386854A CN201910725526.9A CN201910725526A CN110386854A CN 110386854 A CN110386854 A CN 110386854A CN 201910725526 A CN201910725526 A CN 201910725526A CN 110386854 A CN110386854 A CN 110386854A
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aryl
visible light
alkynes
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light catalytic
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程凯
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University of Shaoxing
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Abstract

This patent discloses a kind of short-cut methods that direct synthesizing aryl acetylene hydrocarbon compound is catalyzed by photoredox.Using aryl NITRODIAZONIUM FLUOROBORATE as aryl radical source, pass through the different types of aryl alkynes of decarboxylation procedure fabricated in situ.The reaction have good functional group tolerance, simple household visible light source can be used, it is mild, neutral and without transition metal reaction condition under synthesize different functional groups aryl alkynes.

Description

A kind of preparation method of the aryl alkynes of visible light catalytic
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of preparation method of the aryl alkynes of visible light catalytic.
Background technique
The aryl and heteroaryl alkynes of functionalization are most basic and most important p- conjugated systems in organic chemistry filed, They are widely used high value added products in contemporary organic synthesis and material science.Therefore, new aryl alkynes is efficient The development of synthetic method is persistently by the concern of chemist.Although originating from aryl/alkenyl halide and terminal alkyne Sonogashira cross-coupling reaction is the effective ways that alkyne moiety is introduced to organic molecule.It should be noted that can be with Use aryl propiolic acid as the substitute of terminal aryl group acetylene.Based on this viewpoint, the structure of aryl alkynes is that synthesis p- is total One of important foundation stone of compound conjugate, therefore it is a kind of attractive grind that the decarboxylation of aryl propiolic acid, which is coupled at organic chemistry, Study carefully.
The alkynyl carboxylic acids such as aryl propiolic acid derivative has been received significant attention as the alkynyl source of synthesizing aryl alkynes.Make Aryl propiolic acid is used there are several advantages as alkynes source.For example, aryl propiolic acid is being handled and is being stored as alkynes source compared with acetylene It is upper to be easier, and it is more cheaper than the substitute in the alkynyls source such as trimethyl silicane ethyl-acetylene and bis- (tributyl) acetylene.In addition, Aryl propiolic acid derivative is easily prepared and does not need chromatogram purification.Finally, aryl propiolic acid is usually safety without difficulty The solid of smelling and facilitate storage and transport.
It can be seen that light energy source is since it is abundant, renewable, at a low price, be easy to get the property friendly with ecology, had had become in recent years A kind of strong Green tactics in chemical machine.In recent years, many new visible light mediated responses can be used for efficient, quick Prepare fine chemical product.
Although transition metal-catalyzed decarboxylic reaction has been achieved for success, it develops more square under mild conditions Just more effective way also has high expectation.Using visible light photoredox coupling strategies decarboxylation alkynyl in recent years Through obtaining extensive concern, and have been achieved for some important achievements (such as Scheme1) (.Jin, H.Fu, Asian J.Org.Chem.2017,6,368–385.).Chen and his colleague report the visible light photooxidation of NOP and alkynyl sulfone also Former decarboxylation coupling (Scheme1, A) (J.Yang, J.Zhang, L.Qi, C.Hu, Y.Chen, Chem.Commun.2015,51, 5275–5278.).Seminar's independent studies of the same year, Xiao and Waser visible light photoredox decarboxylation alkynyl of carboxylic acid Change reacts (Scheme1, B) (a) Q.-Q.Zhou, W.Guo, W. Ding, X.Wu, X.Chen, L.-Q.Lu, W.- with BI- alkynes J.Xiao,Angew.Chem.Int.Ed.2015,54, 11196–11199；b)F.Le Vaillant,T.Courant, J.Waser,Angew.Chem.Int. Ed.2015,54,11200–11204.).Then Li and Cheng et al. are reported with DCA (9,10- dicyano anthracene) is the double alkynes of similar visible light-inducing and alkyl carboxylic of organic photoredox catalyst (Scheme1, C) The coupling of acid decarboxylation base (C.Yang, J.-D.Yang, Y.-H.Li, X.Li, J.-P. Cheng, J.Org.Chem.2016,81, 12357-12363.).The seminar of Wang and Li reports the visible light photoredox decarboxylation alkylation an of 2-ketoacid, it Be using alkynyl bromine be alkynyl precursor, with NHPI (n-Hydroxyphthalimide) be catalyst, in sunlight or the photograph of blue light Penetrate lower synthesis acetylenic ketone (H.Tan, H.Li, W.Ji, L.Wang, Angew.Chem.Int.Ed.2015,54,8374-8377.).It is several At the same time, it is reagent/photoredox dual catalyst system that Chen and his colleague, which have studied one by high price iodine, with Alkynes as free radical aceeptor, BI-OAc be donor decarboxylation alkynylation reaction (Scheme1, E) (H.Huang, G.Zhang, Y.Chen,Angew.Chem. Int.Ed.2015,54,7872–7876.).Then Fu et al. has studied a kind of utilization N- neighbour's benzene Dicarboximide oxalates carries out the effective ways that visible light light photoredox chemo-selective synthesizes interior alkynes with alkynes sulfone (Scheme1, F) (C.Gao, J.Li, J.Yu, H.Yang, H.Fu, Chem.Commun. 2016,52,7292-7294.), immediately They report one using catalyst system of the photoredox with copper in conjunction with, the NOP derivative and end alkynes of a-amino acid Hydrocarbon reaction new and effective decarboxylation alkylated reaction (H.Zhang, P.Zhang, M.Jiang, H.Yang, H.Fu, Org.Lett.2017,19, 1016-1019.).Despite the substantial progress that has been made, this field remains challenge, Such as low Atom economy, substrate synthesis difficulty, oxidant applying/alkali of hyperstoichiometry and higher cost, these are all Their attractions in terms of functional group tolerance are inevitably reduced, the visible light photooxidation based on alkynyl carboxylic acid's decarboxylation There is still a need for further researchs for the alkynyl of reduction.
The decarboxylation alkynyl that Scheme 1 is coupled by visible light photoredox
Powerful, the party will be become in synthetic method by being introduced into aryl by the catalysis of visible light photoredox at present The key concept of method is to generate phenyl radical by single electron transfer (SET) process using photochemical catalyst under visible light.To the greatest extent The pyridine complex of pipe ruthenium and iridium is the catalyst of many photoredox reactions due to its unique spectrochemical property, but it The disadvantages of there are genotoxic potential, low sustainability and high costs, limit these non-sustainability catalyst in commercial scale Application in production.From the point of view of industrial point of view, the visible light catalytic that organic dyestuff promotes is that a kind of cost efficiency is high, sustainable Photoredox catalysis, it is organic compared with the photoredox that the pyridine complex catalyst of widely used Ru and Ir promotes Relatively late, example is less for the application of photoredox catalyst." no gold of the organic chromophore as transition metal photocatalysts Belong to " substitute, many radical reactions can be carried out.In addition, the diversity of these organic dyestuff may be by expanding most Number synthetic methods in sluggish substrate spectrum come promote abnormal response, especially eosin Y synthesis conversion in be widely used as Organic photochemical catalyst.No metal photoredox catalysis is related to the one-photon excitation of dye molecule, by forming its free radical yin Ion can activate substrate, to form new carbon-carbon bond.
Summary of the invention
The present invention provides a kind of preparation method of the aryl alkynes of visible light catalytic, the preparation method dark reaction condition temperature With, it is easy to operate, it is participated in without transition metal, and there is preferable yield.
A kind of preparation method of the aryl alkynes of visible light catalytic, comprising:
Under the action of visible light, additive and photochemical catalyst, aryl propiolic acid and aryl NITRODIAZONIUM FLUOROBORATE are organic It is reacted in solvent, obtains the aryl alkynes after post treatment after reaction；
Shown in the structure such as formula (II) of the aryl propiolic acid:
Shown in the structure such as formula (III) of the aryl NITRODIAZONIUM FLUOROBORATE:
Ar2N2BF4 (III)
Shown in the structure such as formula (I) of the aryl alkynes:
In formula (I)~(III), Ar1And Ar2Independently selected from substitution or unsubstituted aryl, taking on the aryl Dai Ji is selected from C1~C4Alkoxy, C1~C4Alkyl, phenyl, halogen, cyano, nitro, C1~C4Alkanoyl, aldehyde radical or fluoroform Base.
Preferably, the Ar1Selected from substitution or unsubstituted phenyl, thienyl or indyl；
Substituent group on the phenyl is selected from methoxyl group, methyl, phenyl, F, cyano, nitro, chlorine, acetyl group or aldehyde radical.
Preferably, the Ar2Selected from substitution or unsubstituted phenyl, thienyl or indyl；
Substituent group on the phenyl be selected from methoxyl group, methyl, F, Cl, Br, cyano, nitro, acetyl group, trifluoromethyl or Aldehyde radical.
Reaction additive, photochemical catalyst and solvent used can generate large effect to reaction, preferably, described Additive be BI-OAc, BI-OMe or BI-OH.
Wherein, the structure of BI-OAc, BI-OMe or BI-OH are as follows:
BI-OAc:R is OAc
BI-OH:R is OH
BI-OMe:R is OMe
Preferably, the photochemical catalyst is Eosin Y (eosin Y).
Preferably, the solvent be 1,2- dichloroethanes (DCE), Isosorbide-5-Nitrae-dioxane, methylene chloride, acetonitrile, DMSO or DMF.
Preferably, reaction carries out under the protection of nitrogen or argon gas.
Preferably, reaction temperature is 20~30 DEG C, the reaction time is 12~24 hours.
Preferably, with molar amount, aryl propiolic acid: aryl NITRODIAZONIUM FLUOROBORATE: additive: photochemical catalyst=1:1 ~1.2:1~1.2:0.01~0.05.
Reaction equation of the invention is as follows:
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) reaction condition of the invention is mild, and reaction can occur under the irradiation of room temperature and visible light source, also, Reaction catalyst used is simple, is not necessarily to transition metal；
(2) functional group tolerance of reaction substrate of the invention is good, meanwhile, reaction yield is higher.
Specific embodiment
Embodiment 1
Under nitrogen protection, phenylpropiolic acid (0.5mmol), phenyl NITRODIAZONIUM FLUOROBORATE are added into reaction tube (0.5mmol), additive (0.6mmol), photochemical catalyst (1mol%), reaction dissolvent (1mL), at 25 DEG C, it is seen that light source It is reacted under (3.0W) effect, TLC monitoring reaction, after reaction, filtering, rotation removes solvent to 12h, and column chromatography for separation obtains Target product, reaction condition and reaction result are shown in Table 1.
Reaction equation is as follows:
The reaction condition and reaction result of 1 embodiment 1 of table
Embodiment 2
Under nitrogen protection, phenylpropiolic acid (0.5mmol), aryl NITRODIAZONIUM FLUOROBORATE are added into reaction tube (0.5mmol), additive B I-OAc (0.6mmol), photochemical catalyst Eosin Y (1mol%), reaction dissolvent DCE (1mL), 25 DEG C, it is seen that it is reacted under light source green light LED lamp (3.0W) effect, TLC monitoring reaction, after reaction, filtering, rotation removes 12h Solvent, column chromatography for separation obtain target product.
Reaction equation and reaction result are as follows:
Embodiment 3
Under nitrogen protection, aryl propiolic acid (0.5mmol), phenyl NITRODIAZONIUM FLUOROBORATE are added into reaction tube (0.5mmol), additive B I-OAc (0.6mmol), photochemical catalyst Eosin Y (1mol%), reaction dissolvent DCE (1mL), 25 DEG C, it is seen that it is reacted under light source green light LED lamp (3.0W) effect, TLC monitoring reaction, after reaction, filtering, rotation removes 12h Solvent, column chromatography for separation obtain target product.
Reaction equation and reaction result are as follows:
The characterize data of portion of product is as follows:
1-Methoxy-4-(phenylethynyl)benzene(2a,3a)
White solid (88mg, 85%)1H NMR(CDCl3, 400MHz): δ 7.52 (dt, J=4.0,2.0Hz, 2H), 7.49-7.45 (m, 2H), 7.36-7.28 (m, 3H), 6.88 (d, J=8.8Hz, 2H), 3.84 (s, 3H)13C NMR (CDCl3,100MHz):δ159.5,133.1,131.6,128.3, 127.8,123.6,115.3,114.0,89.5,88.1, 55.2.HRMS(EI)Calcd for C15H13O [M+H]+,209.0961；found,209.0970.
1-Methyl-4-(phenylethynyl)benzene(2b,3b)
Yellow solid (78mg, 81%)1H NMR(400MHz,CDCl3)δ7.58–7.52(m, 2H),7.47(dd, J=8.0,1.6Hz, 2H), 7.39-7.33 (m, 3H), 7.19 (d, J=7.6Hz, 2 H), 2.39 (s, 3H)13C NMR (100MHz,CDCl3)δ138.4,131.5,131.5,129.2, 128.3,128.0,123.5,120.3,89.6,88.8, 21.5.HRMS(EI)Calcd for C15H13 [M+H]+,193.1012；found,193.1007.
1,2-Diphenylethyne(2c)
White solid (74mg, 83%)1H NMR(400MHz,CDCl3): δ 7.61 (dd, J=6.4,1.6Hz, 4H),7.51–7.33(m,6H)；13C NMR(100MHz,CDCl3):δ131.7, 128.4,128.3,123.4,89.5.HRMS (EI)Calcd for C14H11[M+H]+,179.0855； found,179.0862.
1-Fluoro-4-(phenylethynyl)benzene(2d,3d)
White solid (75mg, 77%)1H NMR(CDCl3,400MHz):δ7.55–7.50(m, 4H),7.38– 7.32 (m, 3H), 7.05 (t, J=8.8Hz, 2H)13C NMR(CDCl3,100MHz): δ162.5(d,1JCF=249.2Hz), 133.4(d,3JCF=8.2Hz), 131.6,128.5,128.4,123.3,119.3 (d,4JCF=3.6Hz), 115.7 (d,2JCF =22.4Hz), 89.2,88.3.HRMS (EI) Calcd for C14H10F[M+H]+,197.0761；found,197.0755.
1-Nitro-4-(phenylethynyl)benzene(2e,3f)
White solid (77mg, 69%)1H NMR(CDCl3, 400MHz): δ 8.22 (d, J=8.8 Hz, 2H), 7.68 (d, J=8.8Hz, 2H), 7.58-7.54 (m, 2H), 7.38 (dd, J=5.4,1.6Hz, 3H)13C NMR(CDCl3, 100MHz):δ147.0,132.3,131.8,130.4,129.2,128.6, 123.8,122.1,94.6,87.6.HRMS(EI) Calcd for C14H10NO2[M+H]+,224.0706； found,22.0713.
1-(Phenylethynyl)-4-(trifluoromethyl)benzene(2f)
White solid (89mg, 72%)1H NMR(400MHz,CDCl3):δ7.70–7.62(m, 4H),7.59(dd, J=6.4,2.8Hz, 2H), 7.45-7.35 (m, 3H)13C NMR(100MHz, CDCl3):δ132.0,131.9,129.0, 128.6,125.5,125.44,125.41,125.36,122.8, 91.9,88.1.HRMS(EI)Calcd for C15H10F3[M+ H]+,247.0724；found,247.0718.
1-(4-(phenylethynyl)phenyl)ethan-1-one(2g,3m).
Yellow solid (88mg, 75%)1H NMR(400MHz,CDCl3):δ7.98–7.92(m, 2H),7.62(d, J=8.4Hz, 2H), 7.56 (dd, J=6.8,3.2Hz, 2H), 7.40-7.35 (m, 3 H), 2.63 (s, 3H)13C NMR (100MHz,CDCl3):δ197.3,136.3,131.8,131.7, 128.9,128.5,128.4,128.2,122.6,92.7, 88.5,26.6.HRMS(EI)Calcd for C16H13O[M+H]+,221.0961；found,221.0964.
4-(phenylethynyl)benzonitrile(2h,3e).
Yellow solid (71mg, 70%)1H NMR(400MHz,CDCl3): δ 7.66 (d, J=8.4 Hz, 2H), 7.62 (d, J=8.4Hz, 2H), 7.58-7.53 (m, 2H), 7.40 (dd, J=5.2,2.0 Hz, 3H)13C NMR(100MHz, CDCl3):δ132.08,132.04,131.7,129.1,128.6, 128.3,122.3,118.6,111.6,93.8, 87.7.HRMS(EI)Calcd for C15H10N[M+H]+, 204.0808；found,204.0812.
4-(phenylethynyl)benzaldehyde(2i,3n).
Yellow solid (68mg, 66%)1H NMR(400MHz,CDCl3): δ 10.05 (s, 1H), 7.88 (d, J= 8.4Hz, 2H), 7.70 (d, J=8.0Hz, 2H), 7.60-7.50 (m, 2H), 7.44-7.36 (m, 3H)13C NMR(100MHz, CDCl3):δ192.19,192.17,136.3, 132.9,132.5,130.5,130.3,129.6,129.2,123.3,94.2, 89.2.HRMS(EI)Calcd for C15H11O[M+H]+,207.0804；found,207.0813.
1-methyl-3-(phenylethynyl)benzene(2j,3i).
Yellow oil (79mg, 82%)1H NMR(400MHz,CDCl3):δ7.62–7.57(m, 2H),7.45–7.36 (m, 5H), 7.30 (td, J=7.6,1.6Hz, 1H), 7.21 (d, J=7.6Hz, 1 H), 2.42 (s, 3H)13C NMR (100MHz,CDCl3):δ138.2,132.2,131.5,129.2, 128.7,128.6,128.4,128.3,128.2,123.5, 123.1,89.6,89.1,21.2.HRMS(EI) Calcd for C15H13[M+H]+,193.1012；found,193.1019.
1-methyl-2-(phenylethynyl)benzene(2k,3j).
Colorless oil (69mg, 72%)1HNMR(400 MHz,CDCl3):δ7.64–7.59(m, 2H),7.57 (s, 1H), 7.39 (dd, J=9.2,7.2Hz, 3H), 7.31-7.26 (m, 2H), 7.24 (dd, J=8.0,4.4Hz, 1H), 2.58(s,3H).13C NMR(100MHz,CDCl3):δ140.2, 131.8,131.6,129.6,128.4,128.3,128.2, 125.5,123.6,123.2,93.4,88.5,20.8. HRMS(EI)Calcd for C15H13[M+H]+,193.1012； found,193.1007.
1,3-dimethyl-2-(phenylethynyl)benzene(2l,3l).
Colorless oil (65mg, 63%)1H NMR(400MHz,CDCl3): δ 7.58 (dd, J=6.4,2.0Hz, 2H), 7.43-7.32 (m, 3H), 7.19-7.15 (m, 1H), 7.12 (dd, J=7.6,2.4Hz, 2H), 2.58 (s, 6H)13C NMR(100MHz,CDCl3):δ140.3,131.5,128.4, 128.2,127.8,126.6,123.9,123.1,97.9, 87.2,21.2.HRMS(EI)Calcd for C15H13[M+H]+,207.1168；found,207.1161.
1-chloro-4-(phenylethynyl)benzene(2m).
White solid (84mg, 79%)1H NMR(400MHz,CDCl3):δ7.62–7.55(m, 2H),7.50(d,J =8.4Hz, 2H), 7.43-7.33 (m, 5H)13C NMR(100MHz, CDCl3):δ134.4,132.9,131.7,128.8, 128.6,128.5,123.1,121.9,90.5, 88.4.HRMS(EI)Calcd for C14H10Cl[M+H]+,213.0466； found,213.0473.
1-bromo-4-(phenylethynyl)benzene(2n).
White solid (105mg, 82%)1H NMR(400MHz,CDCl3):δ7.57–7.46(m, 4H),7.42– 7.31(m,5H).13C NMR(100MHz,CDCl3):δ133.2,131.8,131.7, 128.7,128.5,123.1,122.6, 122.4,90.7,88.5.HRMS(EI)Calcd for C14H10Br [M+H]+,256.9960；found,256.9966.
1-(phenylethynyl)naphthalene(2o).
White solid (87mg, 76%)1H NMR(400MHz,CDCl3): δ 8.55 (d, J=8.4 Hz, 1H), 7.89 (dt, J=21.2,11.4Hz, 3H), 7.80-7.66 (m, 3H), 7.60 (dd, J=14.4,7.2Hz, 1H), 7.56-7.37 (m,4H).13C NMR(100MHz,CDCl3):δ133.8,133.7, 132.1,130.8,129.2,128.9,128.8, 128.7,127.2,126.9,126.7,125.7,123.9, 121.4,94.8,88.0.HRMS(EI)Calcd for C18H13 [M+H]+,229.1012；found, 229.1002.
3-(phenylethynyl)pyridine(2p).
White solid (59mg, 66%)1H NMR(400MHz,CDCl3): δ 8.78 (s, 1H), 8.56 (d, J= 4.0Hz, 1H), 7.83 (d, J=8.0Hz, 1H), 7.61-7.53 (m, 2H), 7.42-7.36 (m, 3H), 7.30 (ddd, J= 8.0,4.8,1.0Hz,1H).13C NMR(100MHz, CDCl3):δ152.3,148.5,138.4,128.8,128.6,123.1, 122.6,92.7,85.8.HRMS (EI)Calcd for C13H10N[M+H]+,180.0808；found,180.0800.
4,6-dimethoxy-2-(phenylethynyl)pyrimidine(2q).
Yellow solid (76mg, 63%)1H NMR(400MHz,CDCl3):δ7.72–7.66(m, 2H),7.44– 7.36(m,3H),6.04(s,1H),4.02(s,6H).13C NMR(100MHz, CDCl3):δ171.2,151.2,132.7, 129.5,128.5,121.5,90.1,88.1,86.6,54.4. HRMS(EI)Calcd for C14H13N2O2[M+H]+, 241.0972；found,241.0965.
3-methoxy-6-(phenylethynyl)pyridazine(2r).
Yellow solid (61mg, 58%)1H NMR(400MHz,CDCl3):δ7.63–7.56(m, 2H),7.50(d, J=9.2Hz, 1H), 7.36 (dd, J=5.4,2.0Hz, 3H), 6.93 (d, J=9.2 Hz, 1H), 4.16 (s, 3H)13C NMR (100MHz,CDCl3):δ163.4,143.6,132.3, 132.1,129.2,128.3,121.9,116.7,92.1,85.6, 55.1.HRMS(EI)Calcd for C13H11N2O[M+H]+,211.0866；found,211.0858.
4-(phenylethynyl)-1,1'-biphenyl(3c).
White solid (107mg, 84%)1H NMR(400MHz,CDCl3): δ 7.64 (dt, J=8.0,6.0Hz, 8H), 7.51 (t, J=7.6Hz, 2H), 7.46-7.35 (m, 4H)13C NMR(100 MHz,CDCl3):δ141.4,140.8, 132.5,132.1,129.3,128.8,128.7,128.1,127.5, 123.8,122.7,90.6,89.8.HRMS(EI) Calcd for C20H15[M+H]+,255.1168； found,255.1159.
1-methoxy-3-(phenylethynyl)benzene(3g).
Yellow solid (75mg, 72%)1H NMR(400MHz,CDCl3):δ7.63–7.55(m, 2H),7.40– 7.36 (m, 3H), 7.30 (dd, J=8.4,7.6Hz, 1H), 7.18 (d, J=7.6Hz, 1 H), 7.12 (dd, J=2.8, 1.4Hz, 1H), 6.94 (ddd, J=8.2,2.8,1.0Hz, 1H), 3.85 (s, 3H)13C NMR(100MHz,CDCl3):δ 159.3,131.6,129.5,128.41,128.36, 124.3,124.2,123.1,116.3,115.1,89.3,89.1, 55.3.HRMS(EI)Calcd for C15H13O[M+H]+,209.0961；found,209.0954.
1-methoxy-2-(phenylethynyl)benzene(3h).
Yellow solid (74mg, 71%)1H NMR(400MHz,CDCl3): δ 7.59 (dd, J=8.0,1.6Hz, 2H), 7.54 (dd, J=7.6,1.6Hz, 1H), 7.40-7.33 (m, 4H), 7.01-6.90 (m, 2H), 3.96 (s, 3H)13C NMR(100MHz,CDCl3):δ159.8,133.6, 131.6,129.8,128.7,128.4,128.3,128.2,126.2, 123.5,120.4,112.4,110.6, 93.5,85.8,55.9.HRMS(EI)Calcd for C15H13O[M+H]+, 209.0961；found, 209.0966.
1-Chloro-2-(phenylethynyl)benzene(3k).
Yellow oil (78mg, 74%)1H NMR(400MHz,CDCl3): δ 7.59 (td, J=7.6,3.3Hz, 3H), 7.45 (dd, J=6.9,2.3Hz, 1H), 7.40-7.37 (m, 3H), 7.30-7.24 (m, 2H)13C NMR(100MHz, CDCl3):δ136.1,133.4,131.9,129.5,129.4, 128.8,128.5,126.6,123.4,123.1,94.7, 86.3.HRMS(EI)Calcd for C14H10Cl [M+H]+,213.0466；found,213.0458.
2-(phenylethynyl)thiophene(3o).
Colorless oil (63mg, 69%)1H NMR(400MHz,CDCl3):δ7.58–7.50(m, 2H),7.36 (dd, J=4.8,3.0Hz, 3H), 7.33-7.29 (m, 2H), 7.04 (ddd, J=5.0,3.2,2.0Hz, 1H)13C NMR (100MHz,CDCl3):δ131.9,131.5,128.4,128.3, 127.3,127.1,123.2,122.9,93.1, 82.6.HRMS(EI)Calcd for C12H9S[M+H]+, 185.0415；found,185.0422.
6-(phenylethynyl)imidazo[1,2-b]pyridazine(3p).
Yellow solid (64mg, 58%)1H NMR(400MHz,CDCl3): δ 7.99 (d, J=9.6Hz, 2H), 7.82 (s, 1H), 7.63 (d, J=8.0Hz, 2H), 7.43 (m, 3H), 7.25 (d, J=9.2Hz, 1H)13C NMR(100MHz, CDCl3):δ138.7,137.9,134.6,132.0, 129.7,128.6,125.2,121.3,120.6,117.1,92.4, 84.9.HRMS(EI)Calcd for C14H10N3[M+H]+,220.0869；found,220.0852.
1-methyl-3-(phenylethynyl)-1H-pyrrolo[2,3-b]pyridine(3q).
Dark yellow solid (60mg, 52%)1H NMR(400MHz,CDCl3): δ 8.39 (dd, J=4.8, 1.6Hz, 1H), 8.08 (dd, J=7.6,1.6Hz, 1H), 7.58-7.51 (m, 2H), 7.42 (s, 1H), 7.38-7.28 (m, 3H), 7.14 (dd, J=7.6,4.8Hz, 1H), 3.89 (s, 3H)13C NMR(100MHz,CDCl3):δ147.2,144.0, 132.2,131.3,128.4,128.3,127.9, 123.9,121.4,116.6,95.7,91.2,82.3,31.3.HRMS(EI) Calcd for C16H13N2 [M+H]+,220.0869；found,220.0852.
prop-1-yne-1,3-diyldibenzene(3r).
Colorless oil (41mg, 43%)1H NMR(400MHz,CDCl3):δ7.55–7.52(m, 1H),7.50– 7.46 (m, 3H), 7.41 (t, J=7.6Hz, 2H), 7.38-7.28 (m, 5H), 3.90 (s, 2H)13C NMR(100MHz, CDCl3):δ136.8,131.6,128.6,128.2,128.0,127.9, 126.6,123.8,87.5,82.8,25.9.HRMS (EI)Calcd for C15H13[M+H]+,193.1012； found,193.1022.

Claims (9)

1. a kind of preparation method of the aryl alkynes of visible light catalytic characterized by comprising
Under the action of visible light, additive and photochemical catalyst, aryl propiolic acid and aryl NITRODIAZONIUM FLUOROBORATE are in organic solvent In reacted, obtain the aryl alkynes after post treatment after reaction；
Shown in the structure such as formula (II) of the aryl propiolic acid:
Shown in the structure such as formula (III) of the aryl NITRODIAZONIUM FLUOROBORATE:
Ar2-N2BF4 (III)
Shown in the structure such as formula (I) of the aryl alkynes:
In formula (I)~(III), Ar1And Ar2Independently selected from replacing or unsubstituted aryl, the substituent group on the aryl Selected from C1~C4Alkoxy, C1~C4Alkyl, phenyl, halogen, cyano, nitro, C1~C4Alkanoyl, aldehyde radical or trifluoromethyl.
2. the preparation method of the aryl alkynes of visible light catalytic according to claim 1, which is characterized in that the Ar1Choosing From substitution or unsubstituted phenyl, thienyl or indyl；
Substituent group on the phenyl is selected from methoxyl group, methyl, phenyl, fluorine-based, cyano, nitro, chlorine, acetyl group or aldehyde radical.
3. the preparation method of the aryl alkynes of visible light catalytic according to claim 1, which is characterized in that the Ar2Choosing From substitution or unsubstituted phenyl, thienyl or indyl；
Substituent group on the phenyl is selected from methoxyl group, methyl, F, Cl, Br, cyano, nitro, acetyl group, trifluoromethyl or aldehyde Base.
4. the preparation method of the aryl alkynes of visible light catalytic according to claim 1, which is characterized in that the addition Agent is BI-OAc, BI-OMe or BI-OH.
5. the preparation method of the aryl alkynes of visible light catalytic according to claim 1, which is characterized in that the light is urged Agent is Eosin Y (eosin Y).
6. the preparation method of the aryl alkynes of visible light catalytic according to claim 1, which is characterized in that the solvent For 1,2- dichloroethanes, 1,4- dioxane, methylene chloride, acetonitrile, DMSO or DMF.
7. the preparation method of the aryl alkynes of visible light catalytic according to claim 1, which is characterized in that reaction is in nitrogen Or it is carried out under the protection of argon gas.
8. the preparation method of the aryl alkynes of visible light catalytic according to claim 1, which is characterized in that reaction temperature is 20~30 DEG C, the reaction time is 12~24 hours.
9. the preparation method of the aryl alkynes of visible light catalytic according to claim 1, which is characterized in that with mole Meter, aryl propiolic acid: aryl NITRODIAZONIUM FLUOROBORATE: additive: photochemical catalyst=1:1~1.2:1~1.2:0.01~0.05.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072531A (en) * 2019-12-16 2020-04-28 江南大学 Synthesis method of β -ketosulfone compound
CN114716288A (en) * 2022-04-20 2022-07-08 南京工业大学 Method for realizing decarboxylation and alkynylation of amino acid by utilizing micro-flow field visible light catalysis technology
CN115677442A (en) * 2022-10-27 2023-02-03 化学与精细化工广东省实验室 Method for synthesizing alkylaryl alkyne compound by photocatalysis

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072531A (en) * 2019-12-16 2020-04-28 江南大学 Synthesis method of β -ketosulfone compound
CN111072531B (en) * 2019-12-16 2021-09-24 江南大学 Synthesis method of beta-ketosulfone compound
CN114716288A (en) * 2022-04-20 2022-07-08 南京工业大学 Method for realizing decarboxylation and alkynylation of amino acid by utilizing micro-flow field visible light catalysis technology
CN114716288B (en) * 2022-04-20 2023-01-24 南京工业大学 Method for realizing decarboxylation and alkynylation of amino acid by utilizing micro-flow field visible light catalysis technology
CN115677442A (en) * 2022-10-27 2023-02-03 化学与精细化工广东省实验室 Method for synthesizing alkylaryl alkyne compound by photocatalysis
CN115677442B (en) * 2022-10-27 2024-05-10 化学与精细化工广东省实验室 Method for synthesizing alkylaryl alkyne compound by photocatalysis

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