CN101429150B - Method for synthesis of 3,4-diaryl pyrrole derivant with photocatalysis - Google Patents

Method for synthesis of 3,4-diaryl pyrrole derivant with photocatalysis Download PDF

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CN101429150B
CN101429150B CN200710176862XA CN200710176862A CN101429150B CN 101429150 B CN101429150 B CN 101429150B CN 200710176862X A CN200710176862X A CN 200710176862XA CN 200710176862 A CN200710176862 A CN 200710176862A CN 101429150 B CN101429150 B CN 101429150B
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CN101429150A (en
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吴骊珠
王登慧
彭明丽
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention belongs to the field of catalysts, and in particular relates to a method of utilizing photochemistry to synthesize a 3, 4-diaryl pyrrole derivative. In the presence of a catalytic amount of divalent platinum complex catalysts and in an inert gas atmosphere, an acetonitrile or deuterated acetonitrile solution of a 3, 4- diaryl 2, 5-pyrroline derivative is irradiated with visible light (lambada is more than 400 nanometers and less than 570 nanometers), so as to obtain the 3, 4-diaryl pyrrole derivative. The method has the advantages of efficient reaction, simple separation and recyclable catalysts.

Description

Photochemical catalysis synthesizes 3, the method for 4-diaryl pyrrole derivant
Technical field
The invention belongs to catalyst field, particularly utilize photochemical method to synthesize 3, the 4-diaryl pyrrole derivant.
Background technology
Azoles has important pharmacologically active-antibiotic, anti-virus, anti-inflammatory, anticancer, and anti-oxidant etc., has a wide range of applications in, the Materials science synthetic at natural product and heterocycle.Therefore, structure flexibly, pyrrole ring has caused showing great attention to of chemists efficiently.Yet, occur in electronegativity better α position rather than β position on the heterocycle owing to the aromatic ring substitution reaction is easier, 3, the synthetic difficulty of the azoles that 4-replaces is bigger.The employing thermochemical method that mostly is of bibliographical information synthesizes 3, the pyrroles that 4-replaces, and typical example has: the Shiraishi of Japan, H. and Ishii, Y. adopts Sm (Oi-Pr) 3The alkene that the catalysis nitro replaces obtains polytype substituted azole with the imines cyclisation, and this reaction has regioselectivity (Tetrahedron, 1999,55,13957～13964); The Zelikin of the U.S., A. and Langer, R. etc. have reported and adopted the synthetic 3-alkyl pyrroles (J.Org.Chem., 1999,64,3379～3380) of Friedel-Crafts acidylate method when on pyrroles's nitrogen-atoms drawing electron group being arranged; The Liu in Hong Kong, J.-H., Chan, H.-W. and Wong, H.N.C. etc. have reported and have adopted 3 that the 4-silyl compound synthesizes 3 as lead compound, the pyrroles's that 4-replaces method (J.Org.Chem., 2000,65,3274～3283); The Airaksinen of Finland, A.J.M., Vepsalainen, J. reported that employing tosylmethyl isocyanide (TOSMIC) obtains 3 as Michael acceptors and 6/7-carboxyethyl-3-phenyl-3-tropen-2-ones one pot reaction high productivity, pyrroles (the J.Org.Chem. that 4-replaces, 2002,67,5019～5021), and the Smith of the U.S., N.D., Cosford, people such as N.D.P. then adopt TOSMIC and alkyl alkene one pot reaction to obtain 3-aryl and 3, pyrroles (the Org.Lett. that the 4-diaryl replaces, 2002,4,3537～3539); The Dieter of the U.S., R.K. and Yu, when H. has reported elevated temperature at PhI and K 2CO 3Existence under, Pd (PPh) 4The propadiene compounds cyclisation that catalytic amino replaces obtains 3, the azole compounds (Org.Lett., 2001,3,3855～3858) that 4-replaces; Belgian Verniest, G. and Kimpe, N.D. has reported 9-borabicyclo[3.3.1] nonane (9-BBN) reduction 3-and 4-pyrroline-2-one obtain corresponding azole compounds (Synlett., 2003,13,2013); Canadian Dhawan, R. and Arndtsen, B.A. have reported that palladium catalysis alkynes, imines and acyl chlorides coupled reaction obtain pyrroles (J.Am.Chem.Soc., 2004,126,468～469) or the like.
And have only only a few to disclose about 3, and 4-substituted pyrrole compound synthetic patent of invention, typical example is that publication number is the patent of CN 1097453A, wherein relates to the linked reaction that adopts low valent titanium reagent and synthesizes 3, the 4-substituted pyrrole compound.Also do not adopt photocatalysis method preparation 3 so far, the patent of 4-substituted pyrrole compound and bibliographical information.
Summary of the invention
The purpose of this invention is to provide a kind of photochemical catalysis efficiently synthetic 3, the method of 4-substituted pyrrole compound is characterized in using the catalyzer of catalytic amount, utilizes visible light can realize conversion process more fast, product is easy to separate, and catalyzer can be recycled.
Photochemical catalysis of the present invention synthetic 3, the reaction of 4-diaryl pyrrole derivant is in the presence of the divalence platinum complex catalyst of catalytic amount, and in rare gas element (argon gas or nitrogen etc.) atmosphere, utilize radiation of visible light 3,4-diaryl 2, the acetonitrile of 5-dihydro pyrrole derivates or deuterium obtain 3 for acetonitrile solution, the 4-diaryl pyrrole derivant.
Photochemical catalysis of the present invention synthesizes 3, and the reaction scheme of 4-diaryl pyrrole derivant is:
Figure GSB00000457458600021
Wherein: R 1, R 2, R 3Independently be substituted aryl, described substituted aryl is: R 1Be 4-phenyl, 4-aminomethyl phenyl, 4-chloro-phenyl-or 4-p-methoxy-phenyl, R 2Be 2,5-thioxene-3-base or substituted-phenyl, R 3Be 2,5-thioxene-3-base or substituted-phenyl.Substituting group in the described substituted-phenyl is H, CH 3, Cl, Br, I or OCH 3
Photochemical catalysis of the present invention synthesizes 3, and the concrete grammar of 4-diaryl pyrrole derivant may further comprise the steps:
1) in transparent reaction vessel (as quartz or glass test tube), with 3,4-replace 2,5-pyrrolin compound dissolution in acetonitrile or deuterium for acetonitrile solution in, its concentration is approximately 10 -2～10 -4Mol/l;
2) to step 1) obtain 3,4-replace 2, add micro-divalence platinum complex in the solution of 5-pyrrolin compound as catalyzer, its preferred concentration in solution is approximately 10 -5～10 -6Mol/l;
3) in rare gas element (argon gas or nitrogen etc.) atmosphere, radiation of visible light step 2 with wavelength 400nm＜λ＜570nm) is dissolved with 3,2 of 4-replacement, the transparent reaction vessel of 5-pyrrolin compound and catalyzer, light application time is different and different with reactant concn, the TLC detection reaction is carried out, and obtains 3, the 4-diaryl pyrrole derivant.
The present invention relates to 3,4-replace 2,5-pyrrolin compound has following structure:
Figure GSB00000457458600031
Wherein: R 1, R 2, R 3Independently be substituted aryl, described substituted aryl is: R 1Be 4-phenyl, 4-aminomethyl phenyl, 4-chloro-phenyl-or 4-p-methoxy-phenyl, R 2Be 2,5-thioxene-3-base or substituted-phenyl, R 3Be 2,5-thioxene-3-base or substituted-phenyl.Substituting group in the described substituted-phenyl is H, CH 3, Cl, Br, I or OCH 3
The divalence platinum complex catalyst that the present invention relates to is 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex or 6-phenyl 2,2 '-second bipyridine divalence platinum complex.
Described 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex has following structure:
R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4CH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be CH 2OH, R 3, R 4Independently be H; Or R 1Be H, R 2Be CH 2CH 2CH 3, R 3, R 4Independently be H; Or R 1Be (CH 3) 3C, R 2Be C 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4OCH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4Cl-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4OCOCH 3, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be Si (CH 3) 3, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be (CH 2) 2CH 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be CH 2OCOCH 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be Si (CH 3) 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be (CH 2) 5CH 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be C 6H 5, R 3, R 4Independently be H.
Described 6-phenyl 2,2 '-second bipyridine divalence platinum complex has following structure:
Figure GSB00000457458600041
R wherein 1Be C 6H 4CH 3-4, R 2Be C 6H 4CH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be C 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4Cl-4, R 3, R 4Independently be H.
The present invention adopts the divalence platinum complex as catalyzer, and adopts visible light, has realized by 3 4-diaryl 2,5-dihydro pyrrole derivates to 3, the conversion fully of 4-diaryl pyrrole derivant fast.Since the special property of divalence platinum complex, reaction obtain 3, azole compounds and solvent and catalyzer separate easily that 4-replaces, catalyzer can reuse.
Description of drawings
Fig. 1. the rayed argon gas of the embodiment of the invention 1 usefulness wavelength 400nm＜λ＜570nm or the N-rubigan-3 under the nitrogen atmosphere, 4-two (2,5-thioxene-3-yl)-2,5-pyrrolin and catalyzer 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H) the transparent pond of acetonitrile solution, the uv-absorbing of solution is with the variation of illumination, total light application time be 10 minutes, its medium and small figure is the difference spectrum; Arrow is represented absorption spectrum direction over time; 1～11 light application time is respectively 0,1, and 2,3,4,5,6,7,8,9,10 minutes.
Fig. 2. the embodiment of the invention 2 under argon gas or nitrogen atmosphere, N-rubigan-3,4-two (2,5-thioxene-3-yl)-2,5-pyrrolin and catalyzer 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC6H 5-4, R 3, R 4Independently for H) deuterium for carry out of acetonitrile solution along with illumination, its 1The variation of H NMR spectrogram, wherein the light application time of a～g is respectively 0,5, and 10,20,30,50,90 minutes.
Embodiment
The present invention is described in detail with specific embodiment below, but be not to concrete restriction of the present invention.
Embodiment 1.
With 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H) be catalyzer, N-rubigan-3,4-two (2,5-thioxene-3-yl)-2,5-pyrrolin are substrate, and its acetonitrile solution is carried out illumination with visible light.
3ml concentration in transparent glass vessels is 10 -5Mol/l 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H) acetonitrile solution in add 4.0mg N-rubigan-3,4-two (2,5-thioxene-3-yl)-2, the 5-pyrrolin makes 4.0mg N-rubigan-3, and 4-two (2,5-thioxene-3-yl)-2, the concentration of 5-pyrrolin in solution is 10 -2Mol/l.Light with wavelength 400nm＜λ＜570nm in argon gas or nitrogen atmosphere shines, and total light application time is 10 minutes.Detect the illumination process with UV-Vis, the absorption spectrum variation of solution is illustrated in fig. 1 shown below.Absorption spectrum shows that illumination finishes back N-rubigan-3, and it is corresponding 3 that 4-two (2,5-thioxene-3-yl)-2,5-pyrrolin are converted into fully, the azole compounds that 4-replaces.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer.
Embodiment 2.
With 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H) be catalyzer, N-rubigan-3,4-two (2,5-thioxene-3-yl)-2,5-pyrrolin are substrate, with its acetonitrile solution of 500W high voltage mercury lamp radiation, use the glass filter of 450nm.
To 0.6ml concentration is 10 -5Mol/l 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H) deuterium for adding 1.5mg 3 in the acetonitrile solution, 4-replace 2,5-pyrrolin compound, making it is 10 in the concentration in solution -2Mol/l.In argon gas or nitrogen atmosphere,, use the glass filter of 450nm with the above-mentioned mixing solutions of 500W high voltage mercury lamp radiation.Irradiation time is respectively 0,5, and 10,20,30,50,90 minutes (in Fig. 2, representing with a～g respectively).With 1The nuclear-magnetism that H NMR detects substrate in the illumination process changes, as shown in Figure 2.The nuclear-magnetism variation shows that substrate is converted into corresponding product fully.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer.
Embodiment 3.
Under argon gas or nitrogen protection, usefulness 500W high voltage mercury lamp radiation compound N-to phenyl-3,4-two (2,5-thioxene-3-yl)-2, (concentration is 10 to the 5-pyrrolin -2Mol/l is at 10ml CH 3In the CN solution) with catalytic amount 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4CH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H, at 10ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution uses the glass filter of 450nm, with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify product be N-to phenyl-3,4-two (2,5-thioxene-3-yl)-pyrroles.
Embodiment 4.
Under argon gas or nitrogen protection, usefulness 500W high voltage mercury lamp radiation compound N-to phenyl-3,4-two (2,5-thioxene-3-yl)-2, (concentration is 10 to the 5-pyrrolin -3Mol/l is at 10ml CH 3In the CN solution) with catalytic amount 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4CH 3-4, R 2Be C 6H 4CH 3-4, R 3, R 4Independently be H, at 10ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution uses the glass filter of 450nm, with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify product be N-to phenyl-3,4-two (2,5-thioxene-3-yl)-pyrroles.
Embodiment 5.
Under argon gas or nitrogen protection, usefulness 500W high voltage mercury lamp radiation compound N-to phenyl-3,4-two (2,5-thioxene-3-yl)-2, (concentration is 10 to the 5-pyrrolin -3Mol/l is at 10ml CH 3In the CN solution) with catalytic amount 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4CH 3-4, R 2Be CH 2OH, R 3, R 4Independently be H, at 10ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution, the glass filter that uses 450nm with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify product be N-to phenyl-3,4-two (2,5-thioxene-3-yl)-pyrroles.
Embodiment 6.
Under argon gas or nitrogen protection, usefulness 500W high voltage mercury lamp radiation compound N-to phenyl-3,4-two (2,5-thioxene-3-yl)-2, (concentration is 10 to the 5-pyrrolin -3Mol/l is at 10ml CH 3In the CN solution) with the 6-phenyl 2,2 of catalytic amount '-second bipyridine divalence platinum complex (R wherein 1Be C 6H 4CH 3-4, R 2Be C 6H 4CH 3-4, R 3, R 4Independently be H, at 10ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution uses the glass filter of 450nm, with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify product be N-to phenyl-3,4-two (2,5-thioxene-3-yl)-pyrroles.
Embodiment 7.
Under argon gas or nitrogen protection, usefulness 500W high voltage mercury lamp radiation compound N-to phenyl-3,4-two (2,5-thioxene-3-yl)-2, (concentration is 10 to the 5-pyrrolin -3Mol/l is at 10ml CH 3In the CN solution) with the 6-phenyl 2,2 of catalytic amount '-second bipyridine divalence platinum complex (R wherein 1Be C 6H 4CH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H, at 10ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution uses the glass filter of 450nm, with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify product be N-to phenyl-3,4-two (2,5-thioxene-3-yl)-pyrroles.
Embodiment 8.
Under argon gas or nitrogen protection, usefulness 500W high voltage mercury lamp radiation compound N-to phenyl-3,4-two (2,5-thioxene-3-yl)-2, (concentration is 10 to the 5-pyrrolin -3Mol/l is at 10ml CH 3In the CN solution) with the 6-phenyl 2,2 of catalytic amount '-second bipyridine divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 5, R 3, R 4Independently be H, at 10ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution uses the glass filter of 450nm, with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify product be N-to phenyl-3,4-two (2,5-thioxene-3-yl)-pyrroles.
Embodiment 9.
Under argon gas or nitrogen protection, usefulness 500W high voltage mercury lamp radiation compound N-to phenyl-3,4-two (2,5-thioxene-3-yl)-2, (concentration is 10 to the 5-pyrrolin -3Mol/l is at 10ml CH 3In the CN solution) with the 6-phenyl 2,2 of catalytic amount '-second bipyridine divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H, at 10ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution uses the glass filter of 450nm, with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify product be N-to phenyl-3,4-two (2,5-thioxene-3-yl)-pyrroles.
Embodiment 10.
Under argon gas or nitrogen protection, with 500W high voltage mercury lamp radiation compound N-p-methoxyphenyl-3,4-phenylbenzene-2, (concentration is 3 * 10 to the 5-pyrrolin -3Mol/l is at 10ml CH 3In the CN solution) with the terpyridyl divalence platinum complex of catalytic amount (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H, at 10ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution uses the glass filter of 450nm, with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify that product is a N-p-methoxyphenyl-3,4-phenylbenzene-pyrroles.
Embodiment 11.
Under argon gas or nitrogen protection, with 500W high voltage mercury lamp radiation compound N-phenyl-3,4-two (2,5-thioxene-3-yl)-2, (concentration is 10 to the 5-pyrrolin -2Mol/l is at 40ml CH 3In the CN solution) with catalytic amount 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H, at 40ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution uses the glass filter of 450nm, with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify that product is a N-phenyl-3,4-two (2,5-thioxene-3-yl)-pyrroles.
Embodiment 12.
Under argon gas or nitrogen protection, with 500W high voltage mercury lamp radiation compound N-p-methylphenyl-3,4-two (2,5-thioxene-3-yl)-2, (concentration is 10 to the 5-pyrrolin -2Mol/l is at 40mlCH 3In the CN solution) with catalytic amount 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H, at 40ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution uses the glass filter of 450nm, with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify that product is a N-p-methylphenyl-3,4-two (2,5-thioxene-3-yl)-pyrroles.
Embodiment 13.
Under the argon shield, with 500W high voltage mercury lamp radiation compound N-p-methoxyphenyl-3,4-two (2,5-thioxene-3-yl)-2, (concentration is 10 to the 5-pyrrolin -2Mol/l is at 40ml CH 3In the CN solution) with catalytic amount 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex (R wherein 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H, at 40ml CH 3Concentration in the CN solution is 10 -5Mol/l) acetonitrile solution uses the glass filter of 450nm, with TLC and 1H NMR monitoring reaction carries out.After reaction finished, steaming desolventized, and added ethyl acetate extraction, filtered, and filtrate is spin-dried for and promptly gets product, reclaims insoluble catalyzer. 1H NMR and MS identify that product is a N-p-methoxyphenyl-3,4-two (2,5-thioxene-3-yl)-pyrroles.

Claims (4)

1. photochemical catalysis synthetic 3, the method of 4-diaryl pyrrole derivant, it is characterized in that: in the presence of the divalence platinum complex catalyst of catalytic amount, and in atmosphere of inert gases, utilize radiation of visible light 3,4-diaryl 2, the acetonitrile of 5-dihydro pyrrole derivates or deuterium are for acetonitrile solution, obtain 3, the 4-diaryl pyrrole derivant;
Described 3,4-diaryl 2, the 5-dihydro pyrrole derivates has following structure:
Figure FSB00000435060200011
Wherein: R 1Be phenyl, 4-aminomethyl phenyl, 4-chloro-phenyl-or 4-p-methoxy-phenyl, R 2Be 2,5-thioxene-3-base or substituted-phenyl, R 3Be 2,5-thioxene-3-base or substituted-phenyl;
Substituting group in the described substituted-phenyl is H, CH 3, Cl, Br, I or OCH 3
Described divalence platinum complex is 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex or 6-phenyl-2,2 '-second bipyridine divalence platinum complex;
Wherein, described 2,2 ': 6 ', 2 "-terpyridyl divalence platinum complex has following structure:
Figure FSB00000435060200012
R in the formula 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4CH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be CH 2OH, R 3, R 4Independently be H; Or R 1Be H, R 2Be CH 2CH 2CH 3, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4OCH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4Cl-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be Si (CH 3) 3, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be (CH 2) 2CH 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be CH 2OCOCH 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be Si (CH 3) 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be (CH 2) 5CH 3, R 3, R 4Independently be H; Or R 1Be H, R 2Be C 6H 5, R 3, R 4Independently be H;
Described 6-phenyl-2,2 '-second bipyridine divalence platinum complex has following structure:
Figure FSB00000435060200021
R in the formula 1Be C 6H 4CH 3-4, R 2Be C 6H 4CH 3-4, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be C 6H 4C ≡ CC 6H 5-4, R 3, R 4Independently be H; Or R 1Be C 6H 4OCH 3-4, R 2Be C 6H 5, R 3, R 4Independently be H; Or R 1Be C 6H 4CH 3-4, R 2Be C 6H 5, R 3, R 4Independently be H.
2. method according to claim 1 is characterized in that: described 3, and 4-diaryl 2, the 5-dihydro pyrrole derivates is 10 at acetonitrile or deuterium for the concentration in the acetonitrile solution -2～10 -4Mol/l.
3. method according to claim 1 and 2 is characterized in that: described divalence platinum complex catalyst is 10 at acetonitrile or deuterium for the concentration in the acetonitrile solution -5～10 -6Mol/l.
4. method according to claim 1 is characterized in that: described wavelength of visible light 400nm＜λ＜570nm.
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