CN102964370B - 2,3,5-trisubstituted thiophenes and its production and use - Google Patents
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Abstract
The invention belongs to organic chemistry and material chemistry technical field, relate to a kind of such as formula (1)
(1) 2,3,5-trisubstituted thiophenes shown in and its production and use, wherein R is the aryl containing substituted radical, and described aryl is phenyl, naphthyl or thiophene, pyridine equiconjugate heterocyclic aryl; Described substituted radical is selected to methyl, to methoxyl group, to amyl group, to bromine, to fluorine, an aminomethyl phenyl, or thiophene, the heterocyclic aryl etc. such as pyridine.The method provided by the invention is applicable to dissimilar 1,3-di-alkine compounds, and reaction conditions is gentle, easy and simple to handle.The present invention is organic synthesis intermediate, and the synthesis of macromolecular material intermediate provides effective short-cut method.
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, in modern chemistry, has important application.Comprising synthetic chemistry, materials chemistry, optical chemical.The character of introducing to thiophenes of triisopropylsilyl group has had significant change, and triisopropylsilyl group as the blocking group in chemosynthesis and can replace group (e.g., triisopropylsilyl group can be converted to hydroxyl) in addition.[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 is mainly by the pass ring rearrangement reaction of 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 more difficult preparation of precursor simultaneously required for this method, and its scope of application is only limitted to the replacement synthesis of thionaphthene material.The method that an other class prepares siliceous substituent thiophenes introduces 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 also had by the research that chemical reaction is incorporated on thiophenes 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 the siliceous substituent thiophenes of above-mentioned synthesis all needs the katalysis of transition metal, and reaction conditions often needs low temperature, and feed precursor preparation is also more difficult.Therefore, new more easy-operating this compounds of synthetic method synthesis needed badly.
Summary of the invention
The defect that the object of the invention is to for overcoming 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 2,3,5-trisubstituted thiophenes, its structure as the formula (1):
Wherein R is the aryl containing 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 synthesizes 2,3,5-trisubstituted thiophenes by 1,3-di-alkine compounds and triisopropyl silicon sulphur sodium.
A kind of preparation method of above-mentioned 2,3,5-trisubstituted thiophenes as the formula (1), comprises following steps:
(1) in the drying receptacle under argon shield, 1,3-di-alkine compounds is added successively, triisopropyl silicon sulphur sodium and organic solvent;
(2) at a certain temperature, stirring reaction;
(3) after question response terminates, add saturated aqueous common salt, then with ether or extraction into ethyl acetate, collect organic item, be separated the target product obtained as the formula (1).
The structural formula of 1,3-described di-alkine compounds is
wherein R is selected from the aryl containing substituted radical; Wherein said aryl is phenyl, naphthyl or conjugation heterocyclic aryl, the wherein said preferred thiophene of 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., and the wherein said preferred thiophene of heterocyclic aryl, pyridine.
The mol ratio of 1,3-described 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 DEG C-160 DEG C, preferably 120 DEG C-160 DEG C.
The reaction times of described step (2) is 1 hour-3 hours, preferably 1 hour-2 hours.
Separation in 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-light petrol mixed solvent.
Described thin-layer chromatography or the developping agent of column chromatography are the mixed solvent of non-polar solvent or non-polar solvent and polar solvent, 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 2,3,5-trisubstituted thiophenes are used as the purposes of organic synthesis intermediate or macromolecular material intermediate.
2,3,5-trisubstituted thiophenes of the present invention are 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 is obtained, can be represented by the formula:
The present invention has following beneficial effect:
Method of the present invention is a kind of effective with acetonitrile, DMF, or methyl-sulphoxide etc. be solvent, by the method for triisopropyl silicon sulphur sodium and 1,3-di-alkine compounds synthesis, 2,3,5-trisubstituted thiophenes.The method is applicable to dissimilar 1,3-di-alkine compounds, and reaction conditions is gentle, easy and simple to handle.The present invention is organic synthesis intermediate, and the synthesis of macromolecular material intermediate provides effective short-cut method.Present method is simple to operate, and productive rate is considerable, and is the novel method preparing this compounds first, and prepared product can be organic synthesis intermediate, and aromatic polymer intermediates provides starting material.
Accompanying drawing explanation
Fig. 1 is the uv-absorbing spectrogram of obtained product in the embodiment of the present invention, and wherein curve 3a is 2,5-phenylbenzene-3-sec.-propyl silicon thiophene (P1), 4a is 2,5-diphenyl thiophene; 3d be 2,5-bis-to penta phenyl-3-sec.-propyl silicon thiophene, 4d is that 2,5-bis-is to penta tolylthiophene; 3h is 2,5-bis--(2-thiophene)-3-sec.-propyl silicon thiophene, and 4h is 2,5-bis--(2-thiophene) thiophene.
Embodiment
The present invention is further illustrated below by 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 the differential responses of 1,3-di-alkynes and triisopropyl silicon sulphur sodium in embodiment 1.Product 3a prepared by the present embodiment can be used as organic synthesis intermediate or macromolecular material intermediate (3a obtained in the present embodiment is P1).
Table 1
Wherein, DMF is N; dinethylformamide; a; experiment numbers 21 is the experiments carried out under argon shield, b, and experiment numbers 22 is the experiments adopting triisopropyl silicon mercaptan (substituting triisopropyl silicon sulphur sodium) to carry out; c, the result (productive rate) that experiment numbers 3 obtains is that product has other by products.
(1) at the egg type bottle of a drying, DMF(2mL is added successively) and 1,3-di-alkynes (0.2mmoL), triisopropyl silicon sulphur sodium;
(2) stirring reaction (see temperature term in list) at a certain temperature.
(3) question response terminates rear (thin-layer chromatography board monitoring), adds 20ml saturated aqueous common salt, with 5ml extracted with diethyl ether (totally three times), collects organic item, and after underpressure distillation removes desolventizing, residue thin-layer chromatography (sherwood oil) obtains target product.
Embodiment 2
1,3-di-alkynes and the repercussion study of triisopropyl silicon sulphur sodium
(1) by 1,3-di-alkynes (0.2mmoL), triisopropyl silicon sulphur sodium (0.4mmol) adds in glass reaction tube, after the air argon replaces in reaction tubes, adds the dry DMF(2ml heavily steamed);
Stirring reaction 1 or 2 hours at (2) 150 DEG C;
(3) after reaction terminates, add 20ml saturated aqueous common salt, with 5ml extracted with diethyl ether (totally three times), collect organic item, after underpressure distillation removes desolventizing, residue thin-layer chromatography obtains the mixed solution that target product 3(developping agent is sherwood oil or petroleum ether-ethyl acetate, wherein polar solvent: 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 benzene phenyl | 1 | P4 | 69 |
| 5 | To bromophenyl | 1 | P5 | 53 |
| 6 | To fluorophenyl | 1 | P6 | 53 |
| 7 | 2-thienyl | 1 | P7 | 72 |
| 8 | 3-thienyl | 1 | P8 | 40 |
| 9 | To penta phenyl | 2 | P9 | 49 |
Table 2 is raw material and the productive rate thereof of product P 1-P9 prepared by embodiment 2.Target product 3 is wherein corresponding with corresponding product P 1-P9, and its Raw 1 is consistent with the R group in 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 synthesis of medicine, agricultural chemicals, dyestuff, chemical reagent.[Lu Yong, Yuan Shaobo. thiophene and derivatives, meticulous and specialty chemicals, 2002,22, the compound 3 as follows 5.] related in the present invention, wherein R substituent group is selected to methyl, to methoxyl group, to bromine, to fluorine, a methyl or heterocyclic aryl etc., the wherein said preferred thiophene of heterocyclic aryl, pyridine.This compounds can as the important intermediate of chemical reaction, for the synthesis of target compound provides reaction raw materials.They can pass through corresponding chemical reaction, can obtain product 4 and 5 as follows.Product 4 is 2,5-bis-substituted thiophene, and this kind of material (product as being converted to by product P 5) with correlation function functional group often can as the application of liquid crystal material and complex functionality material precursor.[a) Tang, J.L., Zhao, X.M.RSCAdv., 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 2 containing hydroxyl, 3,5-tri-substituted thiophene, this kind of material much can have compound (product as being converted to by the product P 7) [Qu Qichao of pharmaceutical activity by the derivative synthesis of hydroxyl, Han Xiangen. the synthesis of three thiophene and application thereof, Gansu petroleum and chemical industry, 2008,4,11.].
In addition containing the thiophene product P1-P9 of triisopropyl, irradiate obtained fluorescence color by fluorescence completely different with the fluorescence color not containing triisopropyl thiophenic materials 2,5-bis-substituted thiophene.Therefore in thiophene, introduce the character of triisopropyl to thiophene have a certain impact.According to the character of current report associated materials, a lot of compound has new character to occur after introducing 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 the embodiment of the present invention obtains.Wherein 3a is 2,5-phenylbenzene-3-sec.-propyl silicon thiophene (P1), 4a is 2,5-diphenyl thiophene; 3d be 2,5-bis-to penta phenyl-3-sec.-propyl silicon thiophene, 4d is that 2,5-bis-is to penta tolylthiophene; 3h is 2,5-bis--(2-thiophene)-3-sec.-propyl silicon thiophene, and 4h is 2,5-bis--(2-thiophene) thiophene.Shown by the ultraviolet absorpting spectrum tested, reaction substrate its optical property after connecting triisopropylsilyl group there occurs significant change (benzene radicals red shift, heterocyclic group blue shift.), therefore it has modifying function in photoelectric material.
P1:2,5-phenylbenzene-3-sec.-propyl silicon thiophene
Colourless oil liquid, 52%, yield.
1HNMR(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);
13CNMR(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-MSm/z392[M]
+;HRMS(ESI)calcd.forC
25H
32SSi[M]
+392.1994,found392.1990.
P2:2,5-bis-tolyl-3-sec.-propyl silicon thiophene
Colourless oil liquid, 55%, yield.
1HNMR(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);
13CNMR(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-MSm/z420[M]
+;HRMS(ESI)calcd.forC
27H
36SSi[M]
+420.2307,found420.2306.
P3:2,5-di-p-tolyl-3-sec.-propyl silicon thiophene
Colorless solid, 43%, yield, 101-103 DEG C, fusing point.
1HNMR(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);
13CNMR(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-MSm/z420[M]
+;HRMS(ESI)calcd.forC
27H
36SSi[M]
+420.2307,found420.2303.
P4:2,5-bis-pairs of benzene phenyl-3-sec.-propyl silicon thiophene
Colorless solid, 69%, yield, 170-172 DEG C, fusing point.
1HNMR(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);
13CNMR(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-MSm/z544[M]
+;HRMS(ESI)calcd.forC
37H
40SSi[M]
+544.2620,found544.2618.
P5:2,5-bis-pairs of bromophenyl-3-sec.-propyl silicon thiophene
Colorless solid, 53%, yield, 136-137 DEG C, fusing point.
1HNMR(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);
13CNMR(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-MSm/z550[M+2]
+;HRMS(ESI)calcd..forC
25H
30Br
2SSi[M]
+548.0204,found548.0209.
P6:2,5-bis-pairs of fluorophenyl-3-sec.-propyl silicon thiophene
Colorless solid, 53%, yield, 107-108 DEG C, fusing point.
1HNMR(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);
13CNMR(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;
19FNMR(376MHz,CDCl
3):δ-113.55,-114.84;IR(KBr):516,624,678,1234,1385,1457,1496,1507,1559,1636,2050cm
-1;ESI-MSm/z428[M]
+;HRMS(ESI)calcd.forC
25H
30F
2SSi[M]
+428.1806,found428.1807.
P7:2,5-bis--(2-thiophene)-3-sec.-propyl silicon thiophene
Colourless oil liquid, 72%, yield.
1HNMR(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);
13CNMR(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-MSm/z404[M]
+;HRMS(ESI)calcd.forC
21H
28S
3Si[M]
+404.1122,found404.1127.
P8:2,5-bis--(3-thiophene)-3-sec.-propyl silicon thiophene
Colorless solid, 40%, yield, 84-86 DEG C, fusing point.
1HNMR(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);
13CNMR(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-MSm/z404[M]
+;HRMS(ESI)calcd.forC
21H
28S
3Si[M]
+404.1122,found404.1125.
P9:2,5-bis-is to penta phenyl-3-sec.-propyl silicon thiophene
Colourless oil liquid, 49%, yield.
1HNMR(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);
13CNMR(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/z532[M]
+;HRMS(ESI)calcd.forC
35H
52SSi[M]
+532.3559,found532.3553.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (9)
1. the preparation method of a trisubstituted thiophenes, is characterized in that: comprise following steps:
(1) in the drying receptacle under argon shield, 1,3-di-alkine compounds is added successively, triisopropyl silicon sulphur sodium and organic solvent; Described organic solvent is DMF,
(2) at a certain temperature, stirring reaction;
The temperature of reaction of described step (2) is 120 DEG C-160 DEG C,
(3) after question response terminates, add saturated aqueous common salt, then with ether or extraction into ethyl acetate, collect organic phase, be separated and obtain such as formula the target product shown in (1).
2. preparation method according to claim 1, is characterized in that: the structural formula of 1,3-described di-alkine compounds is
wherein R is selected from the aryl containing substituted radical; Wherein said aryl is phenyl, naphthyl or conjugation heterocyclic aryl.
3. preparation method according to claim 2, is characterized in that: described conjugation heterocyclic aryl is thiophene or pyridine.
4. preparation method according to claim 2, is characterized in that: described substituted radical is selected to methyl, to methoxyl group, to amyl group, to bromine, to fluorine, an aminomethyl phenyl or heterocyclic aryl.
5. preparation method according to claim 4, is characterized in that: described heterocyclic aryl is thiophene or pyridine.
6. preparation method according to claim 1, is characterized in that: the mol ratio of 1,3-described di-alkine compounds and triisopropyl silicon sulphur sodium is 1:(1-3).
7. preparation method according to claim 1, is characterized in that: the reaction times of described step (2) is 1 hour-2 hours.
8. preparation method according to claim 1, is characterized in that: the separation in 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-light petrol mixed solvent;
Described thin-layer chromatography or the developping agent of column chromatography are the mixed solvent of non-polar solvent or non-polar solvent and polar solvent, wherein polar solvent: the volume ratio of non-polar solvent is=1/5-1000.
9. preparation method according to claim 8, is characterized in that: described thin-layer chromatography or the developping agent of column chromatography are the mixed solution of sherwood oil or petroleum ether-ethyl acetate.
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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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| Direct and Selective Arylation of Tertiary Silanes with Rhodium Catalyst;Yoshinori Yamanoi等，;《J. Org. Chem.》;20080806;第73卷(第17期);第6671-6678页，尤其是第6675页表4化合物40 * |
| Victor Navarro-Fuster等，.Effect of ring fusion on the amplified spontaneous emission properties of oligothiophenes.《Journal of Materials Chemistry》.2009,第19卷第6556–6567页. * |
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