CN102964370A - 2,3,5-trisubstituted thiophene compound, as well as preparation method and use thereof - Google Patents
2,3,5-trisubstituted thiophene compound, as well as preparation method and use thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic chemistry and material chemistry and relates to a 2,3,5-trisubstituted thiophene compound as shown in formula (1), as well as a preparation method and a use thereof, wherein R is an aryl group containing a substituent group, and the aryl group is a phenyl group, a naphthyl group or thiophene, pyridine and other conjugated heterocyclic aryl groups; and the substituent group is selected from a p-methyl group, a p-methoxyl group, a p-amyl group, a p-bromo- group, a p-fluoro- group, an m-methylphenyl group or thiophene, pyridine and other heterocyclic aryl groups. The method provided by the invention can be suitable for different types of 1, 3-diyne compounds, the reaction conditions are mild, and the operation is simple and convenient. The 2,3,5-trisubstituted thiophene compound disclosed by the invention is an organic synthesis intermediate, and an effective simple and convenient method is further provided for synthesis of intermediates of polymer materials.
Description
Technical field
The invention belongs to organic chemistry and material chemistry technical field, relate to a kind of 2,3,5-trisubstituted thiophenes and its production and use.
Background technology
Siliceous substituent thiophenes has important application in modern chemistry.Comprising synthetic chemistry, materials chemistry, optics chemistry.The introducing of triisopropylsilyl group has had significant change to the character of thiophenes, in addition triisopropylsilyl group can be used as the blocking group in the chemosynthesis and replace group (as, triisopropylsilyl group can be converted to hydroxyl).[a) Fuster, V.N., Calzado, E.M., Ramirez, M.G., Boj, P.G., Henssler, J.T., Matzger, A.J., Hernandez, V., Navarrete, T.L., Garcia, M.A.D., J.Mater.Chem., 2009,19,6556; B) Bols, M.Chem.Rev., 1995,95,1253; C) Fleming, L., Barbero, A., Walter, D.Chem.Rev., 1997,97,2063; D) Cunico, R.F., Bedell, L.J.Org.Chem., 1980,45,4797; E) Rucker, C.Chem.Rev., 1995,95,1009; F) Ohshita, J., Kangai, S., Tada, Y., Yoshida, H., Sakamaki, K., Kunai, A., Kunugi, Y.J.Organomet.Chem., 2007,692,1020; G) Barbarella, G., Zambianchi, M., Pudova, O., Paladini, V., Ventola, A., Cipriani, F., Gigli, G., Cingolani, R., Citro, G.J.Am.Chem.Soc., 2001,123,11600.] synthetic method of the siliceous substituent thiophenes of known preparation mainly is the pass ring rearrangement reaction by the adjacent alkynyl benzene sulphur silicide of golden catalysis.[Nakamura, I., Sato, T., Terada, M., Yamamoto, Y.Org.Lett., 2007,9,4081.] this synthetic method needs the katalysis of Precious Metals-Gold, the simultaneously difficult preparation of the needed precursor of this method, and its scope of application to only limit to the replacement of thionaphthene material synthetic.The method that an other class prepares siliceous substituent thiophenes is to introduce other groups by the chemical reaction of siliceous substituting group thiophene compound.[Chen, L., Roger, J., Bruneau, C., Dixneuf, P.H., Doucet, H.Chem.Commun., 2011,47,1872.] and siliceous substituting group is incorporated into research on the thiophenes by chemical reaction also has and relate to.[a) Yamanoi, Y., Nishihara, H.J.Org.Chem., 2008,73,6671; B) Muschelknautz, C., Dostert, C., Muller, T.J.J.Synlett., 2010,3,415; C) Chicart, P., Corriu, R.J.P., Moreau, J.J.E.Chem.Mater., 1991,3,8.] method of above-mentioned synthetic siliceous substituent thiophenes all needs the katalysis of transition metal, and reaction conditions often needs low temperature, and the preparation of raw material precursor is difficulty also.Therefore, new more easy-operating synthetic method is that synthetic this compounds is needed badly.
Summary of the invention
The object of the invention is to for the defective that overcomes prior art provides a kind of 2,3 5-trisubstituted thiophenes and its production and use.
For achieving the above object, the present invention is by the following technical solutions:
A kind of 2,3, the 5-trisubstituted thiophenes, its structure as the formula (1):
Wherein R is the aryl that contains substituted radical,
Described aryl is phenyl, naphthyl or conjugation heterocyclic aryl.
Described conjugation heterocyclic aryl is selected from thiophene or pyridine etc.
Described substituted radical is selected to methyl, to methoxyl group, to amyl group, to bromine, to fluorine, an aminomethyl phenyl or heterocyclic aryl etc.
Described heterocyclic aryl is selected from thiophene or pyridine etc.
The present invention is by 1,3-di-alkine compounds and synthetic 2,3, the 5-trisubstituted thiophenes of triisopropyl silicon sulphur sodium.
A kind of above-mentioned as the formula (1) 2,3, the preparation method of 5-trisubstituted thiophenes comprises following steps:
(1) in the drying receptacle under the argon shield, adds successively 1,3-di-alkine compounds, triisopropyl silicon sulphur sodium and organic solvent;
(2) at a certain temperature, stirring reaction;
(3) after question response finishes, add saturated aqueous common salt, again with ether or ethyl acetate extraction, collect organic, separate the target product that obtains as the formula (1).
Described 1, the structural formula of 3-di-alkine compounds is
Wherein R is selected from the aryl that contains substituted radical; Wherein said aryl is phenyl, naphthyl or conjugation heterocyclic aryl, the preferred thiophene of wherein said conjugation heterocyclic aryl, pyridine.
Described substituted radical is selected to methyl, to methoxyl group, to amyl group, to bromine, to fluorine, an aminomethyl phenyl or heterocyclic aryl etc., the preferred thiophene of wherein said heterocyclic aryl, pyridine.
Described 1, the mol ratio of 3-di-alkine compounds and triisopropyl silicon sulphur sodium is 1:(1-3).
Described organic solvent is selected from non-protonic solvent, preferred acetonitrile, DMF or methyl-sulphoxide, further preferred DMF.
The temperature of reaction of described step (2) is 100 ℃-160 ℃, preferred 120 ℃-160 ℃.
The reaction times of described step (2) is 1 hour-3 hours, preferred 1 hour-2 hours.
Separation in the described step (3) is selected from recrystallization, thin-layer chromatography, column chromatography or underpressure distillation.
The solvent of described recrystallization is ethyl acetate or ethyl acetate-sherwood oil mixed solvent.
The developping agent of described thin-layer chromatography or column chromatography is the mixed solvent of non-polar solvent or non-polar solvent and polar solvent, and the mixed solution of preferred sherwood oil or petroleum ether-ethyl acetate, wherein polar solvent: the volume ratio of non-polar solvent is=1/5-1000.
A kind of above-mentioned 2,3, the 5-trisubstituted thiophenes is as the purposes of organic synthesis intermediate or macromolecular material intermediate.
Of the present invention 2,3, the 5-trisubstituted thiophenes is under argon shield, with triisopropyl silicon sulphur sodium and 1; 3-di-alkine compounds is raw material, at acetonitrile, and N; dinethylformamide, or the non-protonic solvent such as methyl-sulphoxide exists and the lower reaction of effect makes, and can be represented by the formula:
The present invention has following beneficial effect:
Method of the present invention is a kind of effectively with acetonitrile, DMF, or methyl-sulphoxide etc. is solvent, by triisopropyl silicon sulphur sodium and 1, and the method for synthetic 2,3, the 5-trisubstituted thiophenes of 3-di-alkine compounds.The method is applicable to dissimilar 1,3-di-alkine compounds, and reaction conditions is gentle, and is easy and simple to handle.The present invention is organic synthesis intermediate, and macromolecular material intermediate synthetic provides effective short-cut method.Present method is simple to operate, and productive rate is considerable, and is the novel method for preparing first this compounds, and prepared product can be organic synthesis intermediate, and the polymer intermediate provides starting material.
Description of drawings
Fig. 1 is the uv-absorbing spectrogram that makes product in the embodiment of the invention, and wherein curve 3a is 2,5-phenylbenzene-3-sec.-propyl silicon thiophene (P1), and 4a is 2,5-diphenyl thiophene; 3d is two pairs of penta phenyl of 2,5--3-sec.-propyl silicon thiophene, and 4d is two pairs of penta phenyl thiophene of 2,5-; 3h is 2,5-two-(2-thiophene)-3-sec.-propyl silicon thiophene, and 4h is 2,5-two-(2-thiophene) thiophene.
Embodiment
The below further specifies the present invention with embodiment.
Embodiment 1
The solvent of 1,3-di-alkynes and triisopropyl silicon sulphur sodium reaction system, the research of temperature and time
Wherein T refers to temperature, and t refers to the time.
Table 1 is among the embodiment 11, the differential responses of 3-di-alkynes and triisopropyl silicon sulphur sodium.The product 3a of present embodiment preparation can be used as organic synthesis intermediate or macromolecular material intermediate (3a that makes in the present embodiment is P1).
Table 1
Wherein, DMF is N; dinethylformamide; a; experiment numbers 21 is experiments of carrying out under argon shield, b, and experiment numbers 22 is experiments of adopting triisopropyl silicon mercaptan (substituting triisopropyl silicon sulphur sodium) to carry out; c, the result that experiment numbers 3 obtains (productive rate) are that product has other by products.
(1) at the egg type bottle of a drying, add successively DMF(2mL) and 1,3-di-alkynes (0.2mmoL), triisopropyl silicon sulphur sodium;
(2) stirring reaction (seeing temperature term in the tabulation) at a certain temperature.
(3) after question response finishes (thin-layer chromatography board monitoring), add the 20ml saturated aqueous common salt, with 5ml extracted with diethyl ether (totally three times), collect organic, residue thin-layer chromatography (sherwood oil) obtains target product after the underpressure distillation desolventizing.
Embodiment 2
1,3-di-alkynes and the repercussion study of triisopropyl silicon sulphur sodium
(1) with 1,3-di-alkynes (0.2mmoL), triisopropyl silicon sulphur sodium (0.4mmol) adds in the glass reaction tube, with the air in the reaction tubes with argon replaces after, add the dry DMF(2ml that heavily steams);
(2) 150 ℃ of lower stirring reactions 1 or 2 hours;
(3) after reaction finishes, add the 20ml saturated aqueous common salt, with 5ml extracted with diethyl ether (totally three times), collect organic, to obtain target product 3(developping agent be the mixed solution of sherwood oil or petroleum ether-ethyl acetate, wherein polar solvent to the residue thin-layer chromatography after the underpressure distillation desolventizing: the volume ratio of non-polar solvent is=1/5-1000).
Partial correlation results following (as shown in table 2):
Table 2
| Experiment numbers | R | Time (h) | Product 3 | Productive rate (%) |
| 1 | Phenyl | 1 | P1 | 52 |
| 2 | Between tolyl | 1 | P2 | 55 |
| 3 | P-methylphenyl | 2 | P3 | 43 |
| 4 | To the benzene phenyl | 1 | P4 | 69 |
| 5 | To bromophenyl | 1 | P5 | 53 |
| 6 | To fluorophenyl | 1 | P6 | 53 |
| 7 | The 2-thienyl | 1 | P7 | 72 |
| 8 | The 3-thienyl | 1 | P8 | 40 |
| 9 | To penta phenyl | 2 | P9 | 49 |
Table 2 is raw material and the productive rate thereof of the product P 1-P9 of embodiment 2 preparations.Target product 3 wherein is corresponding with corresponding product P 1-P9, and its Raw 1 is consistent with the R group in the product 3.
Wherein P1-P9 can be used as organic synthesis intermediate or photoelectric material intermediate.
Thiophenes and derivative thereof are widely used in the synthetic of medicine, agricultural chemicals, dyestuff, chemical reagent.[Lu Yong, Yuan Shaobo. thiophene and derivatives, meticulous and specialty chemicals, 2002,22, the compound as follows 3 that 5.] relates among the present invention, wherein the R substituted radical is selected to methyl, to methoxyl group, to bromine, to fluorine, a methyl or heterocyclic aryl etc., the preferred thiophene of wherein said heterocyclic aryl, pyridine.This compounds can be used as the important intermediate of chemical reaction, and the synthetic reaction raw materials that provides of target compound is provided.They can pass through corresponding chemical reaction, can obtain product as follows 4 and 5.Product 4 is 2,5-, two substituted thiophenes, and this class material (such as the product that is converted to by product P 5) with correlation function functional group often can be used as the application of liquid crystal material and complex functionality material precursor.[a) Tang, J.L., Zhao, X.M.RSC Adv., 2012,2,5488; B) Campbell, N.L., Duffy, W.L., Thomas, G.I., Wild, J.H., Kelly, S.M., Bartle, K., Neill, M., Minter, V., Tuffin, R.P.J.Mater.Chem., 2002,12,2706.] product 5 is for containing 2 of hydroxyl, 3,5-, three substituted thiophenes, this class material can be by synthetic compound (such as the product that is converted to by the product P 7) [Qu Qichao that much has pharmaceutical activity of deriving of hydroxyl, Han Xiangen. the synthetic and application of three thiophene, Gansu petroleum and chemical industry, 2008,4,11.].
The thiophene product P 1-P9 that contains in addition triisopropyl shines resulting fluorescence color and does not contain triisopropyl thiophene material 2 by fluorescence, and the fluorescence color of 5-two substituted thiophenes is fully different.Therefore in thiophene, introduce triisopropyl the character of thiophene is had certain impact.According to the present character of report associated materials, a lot of compounds have new character to occur after introducing the triisopropyl group, as semi-conductor.[a)Miao,S.B.,Appleton,A.L.,Berger,N.,Barlow，S.,Marder,S.R.,Hardcastle,K.I.,Bunz,U.H.F.Chem.Eur.J.,2009,15,4990;b)Purushothaman,B.,Bruzek,M.,Parkin,S.R.,Miller,A.F.,Anthony，J.E.Angew.Chem.Int.Ed.,2011,50,7013;c)Liu,Y.Y.,Song,C.L.,Zeng,W.J.,Zhou,K.G.,Shi,Z.F.,Ma,C.B.,Yang,F.,Zhang,H.L.,Gong,X.J.Am.Chem.Soc.,2010,132,16349.]
Fig. 1 is the uv-absorbing spectrogram of the product that makes of the embodiment of the invention.Wherein 3a is 2,5-phenylbenzene-3-sec.-propyl silicon thiophene (P1), and 4a is 2,5-diphenyl thiophene; 3d is two pairs of penta phenyl of 2,5--3-sec.-propyl silicon thiophene, and 4d is two pairs of penta phenyl thiophene of 2,5-; 3h is 2,5-two-(2-thiophene)-3-sec.-propyl silicon thiophene, and 4h is 2,5-two-(2-thiophene) thiophene.Ultraviolet absorpting spectrum by test shows that significant variation (red shift of phenyl ring group, heterocyclic group blue shift have occured reaction substrate its optical property after connecting triisopropylsilyl group.), so it has modifying function in photoelectric material.
P1:2,5-phenylbenzene-3-sec.-propyl silicon thiophene
Colourless oil liquid, 52%, yield.
1H?NMR(400MHz,CDCl
3):δ1.00(d,J=7.2Hz,18H),1.11-1.17(m,3H),7.24-7.39(m,7H),7.48(d,J=7.6Hz,2H),7.60(d,J=7.6Hz,2H);
13C?NMR(100MHz,CDCl
3):δ12.3,18.9,125.9,127.2,127.5,128.1,128.8,130.4,130.7,133.9,134.4,136.6,143.2,151.2;IR(KBr):513,639,669,705,741,762,1143,1264,1457,2849,2877,2973cm
-1;ESI-MS?m/z?392[M]
+;HRMS(ESI)calcd.forC
25H
32SSi[M]
+392.1994,found?392.1990.
P2:2, two tolyls of 5--3-sec.-propyl silicon thiophene
Colourless oil liquid, 55%, yield.
1H?NMR(400MHz,CDCl
3):δ1.00(d,J=7.2Hz,18H),1.10-1.19(m,3H),236(s,3H),2.39(s,3H),7.07(d,J=7.6Hz,1H),7.16(d,J=7.6Hz,1H),7.20-7..31(m,5H),7.41(s,2H);
13C?NMR(100MHz,CDCl
3):δ12.3,18.9,21.3,21.4,123.1,126.7,127.4,127.4,128.0,128.7,128.8,130.6,131.1,133.6,134.4,136.5,137.0,138.4,143.1,151.3;IR(KBr):668,706,741,789,1264,1653,2878cm
-1;ESI-MS?m/z?420[M]
+;HRMS(ESI)calcd.for?C
27H
36SSi[M]
+420.2307,found?420.2306.
P3:2,5-di-p-tolyl-3-sec.-propyl silicon thiophene
Colorless solid, 43%, yield, 101-103 ℃, fusing point.
1H?NMR(400MHz,CDCl
3):δ1.00(d,J=7.2Hz,18H),1.10-1.19(m,3H),2.36(s,3H),2.39(s,3H),7.13(d,J=7.6Hz,2H),7.17(d,J=8.0Hz,2H),7.24(s,1H),7.36(d,J=8.0Hz,2H),7.48(d,J=8.0Hz,2H);
13C?NMR(100MHz,CDCl
3):δ12.3,18.9,21.2,21.3,125.8,128.2,129.5,130.2,131.7,133.4,133.7,136.9,137.8,143.1,150.9;IR(KBr):453,518,1507,1540,1559,1636,1653,1683cm
-1;ESI-MS?m/z?420[M]
+;HRMS(ESI)calcd.for?C
27H
36SSi[M]
+420.2307,found?420.2303.
P4:2, two pairs of benzene phenyl of 5--3-sec.-propyl silicon thiophene
Colorless solid, 69%, yield, 170-172 ℃, fusing point.
1H?NMR(400MHz,CDCl
3):δ1.03(d,J=7.2Hz,18H),1.16-1.23(m,3H),7.33-7.39(m,3H),7.45(d,J=7.6Hz,2H),7.48(d,J=7.2Hz,2H),7.56-7.63(m,8H),7.67(d,J=7.2Hz,2H),7.69(d,J=8.4Hz,2H);
13C?NMR(100MHz,CDCl
3):δ12.4,19.0,126.2,126.3,126.9,127.0,127.3,127.5,127.5,128.8,128.8,130.7,130.9,133.4,134.2,135.6,140.0,140.5,140.6,140.8,142.9,150.9;IR(KBr):442,516,738,1264,1507,1521,1541,1559,1636,2053cm
-1;ESI-MS?m/z?544[M]
+;HRMS(ESI)calcd.for?C
37H
40SSi[M]
+544.2620,found?544.2618.
P5:2, two pairs of bromophenyls of 5--3-sec.-propyl silicon thiophene
Colorless solid, 53%, yield, 136-137 ℃, fusing point.
1H?NMR(400MHz,CDCl
3):δ1.00(d,J=6.8Hz,18H),1.11-1.18(m,3H),7.26(s,1H),734(d,J=8.8Hz,2H),7.44(d,J=8.8Hz,2H);7.47-7.51(m,4h);
13C?NMR(100MHz,CDCl
3):δ12.3,18.9,121.2,122.6,127.4,130.8,131.2,131.8,132.0,133.1,134.7,135.4,142.4,149.9;IR(KBr):655,669,1345,1612,1631,1641,1659,2342,2360cm
-1;ESI-MS?m/z?550[M+2]
+;HRMS(ESI)calcd..forC
25H
30Br
2SSi[M]
+548.0204,found?548.0209.
P6:2, two pairs of fluorophenyls of 5--3-sec.-propyl silicon thiophene
Colorless solid, 53%, yield, 107-108 ℃, fusing point.
1H?NMR(400MHz,CDCl
3):δ1.00(d,J=7.6Hz,18H),1.08-1.16(m,3H),7.01-7.09(m,4H),7.20(s,1H),7.42-7.46(m,2H),7.53-7.56(m,2H);
13C?NMR(100MHz,CDCl
3):δ12.2,18.9,114.4,114.7,115.7,115.9,127.5,127.6,130.5,130.6,132.0,132.1,132.4,132.5,134.5,1423,149.7,161.0,161.6,163.5,164.1;
19F?NMR(376MHz,CDCl
3):δ-113.55,-114.84;IR(KBr):516,624,678,1234,1385,1457,1496,1507,1559,1636,2050cm
-1;ESI-MS?m/z?428[M]
+;HRMS(ESI)calcd.for?C
25H
30F
2SSi[M]
+428.1806,found?428.1807.
P7:2,5-two-(2-thiophene)-3-sec.-propyl silicon thiophene
Colourless oil liquid, 72%, yield.
1H?NMR(400MHz,CDCl
3):δ1.04(d,J=7.2Hz,18H),1.20-1.29(m,3H),6.99(d,J=4.0Hz,1H),7.01(d,J=4.0Hz,1H),7.13-7.14(m,2H),7.15(s,1H),7.20(d,J=6.0Hz,1H),7.32(d,J=6.0Hz,1H);
13C?NMR(100MHz,CDCl
3):δ12.4,19.0,123.9,124.3,126.6,127.8,128.8,131.4,136.8,136.8,136.9,137.5,141.4;IR(KBr):563,740,824,1019,1130,1263,1472,1541,1653,2877,2978cm
-1;ESI-MS?m/z?404[M]
+;HRMS(ESI)calcd.for?C
21H
28S
3Si[M]
+404.1122,found?404.1127.
P8:2,5-two-(3-thiophene)-3-sec.-propyl silicon thiophene
Colorless solid, 40%, yield, 84-86 ℃, fusing point.
1H?NMR(400MHz,CDCl
3):δ1.02(d,J=7.2Hz,18H),1.13-1.22(m,3H),7.16-7.17(m,2H),7.27-7.35(m,5H);
13C?NMR(100MHz,CDCl
3):δ12.3,18.9,119.4,124.6,124.8,126.2,126.2,130.1,130.7,134.4,135.4,136.4,138.0,144.0;IR(KBr):514,654,676,706,740,773,839,1141,1264,1636,2069,2864,2944cm
-1;ESI-MS?m/z?404[M]
+;HRMS(ESI)calcd.for?C
21H
28S
3Si[M]
+404.1122,found?404.1125.
P9:2, two pairs of penta phenyl of 5--3-sec.-propyl silicon thiophene
Colourless oil liquid, 49%, yield.
1H?NMR(400MHz,CDCl
3):δ0.90(t,J=6.8Hz,6H),0.99(d,J=7.2Hz,18H),1.13-1.16(m,3H),1.30-1.34(m,8H),1.61-1.66(m,4H),2.59-2.66(m,4H),7.13(d,J=7.6Hz,2H),7.17(d,J=8.0Hz,2H),7.24(s,1H),7.37(d,J=8.0Hz,2H),7.50(d,J=8.0Hz,2H);
13C?NMR(100MHz,CDCl3):δ12.3,13.4,13.5,14.0,14.0,18.1,18.3,18.9,31.0,31.1,31.3,31.5,125.8,127.5,128.8,130.2,130.2,131.9,133.6,133.9,142.0,142.9,143.0,150.9;IR(KBr):787,1559,1636,2863,2959cm-1;ESI-MSm/z?532[M]
+;HRMS(ESI)calcd.for?C
35H
52SSi[M]
+532.3559,found?532.3553.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. one kind 2,3, the 5-trisubstituted thiophenes is characterized in that: structure as the formula (1):
Wherein R is the aryl that contains substituted radical.
2. according to claim 12,3, the 5-trisubstituted thiophenes is characterized in that: described aryl is phenyl, naphthyl or conjugation heterocyclic aryl;
Or described substituted radical is selected to methyl, to methoxyl group, to amyl group, to bromine, to fluorine, an aminomethyl phenyl or heterocyclic aryl.
3. according to claim 22,3, the 5-trisubstituted thiophenes is characterized in that: described conjugation heterocyclic aryl is selected from thiophene or pyridine;
Or described heterocyclic aryl is selected from thiophene or pyridine.
Among the claims 1-3 arbitrary described as the formula (1) 2,3, the preparation method of 5-trisubstituted thiophenes is characterized in that: comprise following steps:
(1) in the drying receptacle under the argon shield, adds successively 1,3-di-alkine compounds, triisopropyl silicon sulphur sodium and organic solvent;
(2) at a certain temperature, stirring reaction;
(3) after question response finishes, add saturated aqueous common salt, again with ether or ethyl acetate extraction, collect organic, separate the target product that obtains as the formula (1).
5. preparation method according to claim 4 is characterized in that: described 1, the structural formula of 3-di-alkine compounds is
Wherein R is selected from the aryl that contains substituted radical; Wherein said aryl is phenyl, naphthyl or conjugation heterocyclic aryl; Wherein the conjugation heterocyclic aryl is preferably thiophene or pyridine.
6. preparation method according to claim 4 is characterized in that: described substituted radical be selected to methyl, to methoxyl group,, to amyl group, to bromine, to fluorine, an aminomethyl phenyl or heterocyclic aryl, wherein the heterocyclic aryl is preferably thiophene or pyridine;
Or described 1, the mol ratio of 3-di-alkine compounds and triisopropyl silicon sulphur sodium is 1:(1-3).
7. preparation method according to claim 4, it is characterized in that: described organic solvent is selected from non-protonic solvent, preferred acetonitrile, DMF or methyl-sulphoxide, further preferred DMF.
8. preparation method according to claim 4, it is characterized in that: the temperature of reaction of described step (2) is 100 ℃-160 ℃, preferred 120 ℃-160 ℃;
Or the reaction times of described step (2) be 1 hour-3 hours, preferred 1 hour-2 hours.
9. preparation method according to claim 4, it is characterized in that: the separation in the described step (3) is selected from recrystallization, thin-layer chromatography, column chromatography or underpressure distillation;
The solvent of wherein said recrystallization is ethyl acetate or ethyl acetate-sherwood oil mixed solvent;
The developping agent of described thin-layer chromatography or column chromatography is the mixed solvent of non-polar solvent or non-polar solvent and polar solvent, and the mixed solution of preferred sherwood oil or petroleum ether-ethyl acetate, wherein polar solvent: the volume ratio of non-polar solvent is=1/5-1000.
10. arbitrary described 2,3 among the claims 1-4, the 5-trisubstituted thiophenes is as the purposes of organic synthesis intermediate or macromolecular material intermediate.
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| WO2004048927A2 (en) * | 2002-11-22 | 2004-06-10 | Lumera Corporation | Second order nonlinear optical chromophores, polymers containing same, and electro-optic devices therefrom |
| CN102146015A (en) * | 2011-03-02 | 2011-08-10 | 同济大学 | 1,3 conjugated diyne compound and preparation method thereof |
| CN102584784A (en) * | 2012-01-13 | 2012-07-18 | 同济大学 | Preparing method of 2,5-disubstituted thiophene compound |
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| WO2004048927A2 (en) * | 2002-11-22 | 2004-06-10 | Lumera Corporation | Second order nonlinear optical chromophores, polymers containing same, and electro-optic devices therefrom |
| CN102146015A (en) * | 2011-03-02 | 2011-08-10 | 同济大学 | 1,3 conjugated diyne compound and preparation method thereof |
| CN102584784A (en) * | 2012-01-13 | 2012-07-18 | 同济大学 | Preparing method of 2,5-disubstituted thiophene compound |
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| CN103724289A (en) * | 2013-12-23 | 2014-04-16 | 同济大学 | (E)-2,4,5-tri-substituted-(1-allyl) oxazole cyclic compound as well as synthetic method and applications thereof |
| CN103724289B (en) * | 2013-12-23 | 2015-08-19 | 同济大学 | (E)-2,4,5-tri-replace-(1-propenyl) oxazole ring compounds and synthetic method and application |
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