CN102584784A - Preparing method of 2,5-disubstituted thiophene compound - Google Patents
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Abstract
The invention belongs to the technical field of organic chemistry, and relates to a preparing method of a 2,5-disubstituted thiophene compound which is showed in a formula (1). The method comprises the following steps of: adding an organic solvent, a 1,3-diyne compound and a sodium salt in a dried container in turn; stirring for reaction at certain temperature; adding saturated saline solution after the reaction is finished, extracting by the organic solvent, collecting organic phases and separating to obtain the target product showed in the formula (1). The method provided by the invention can be applicable to various types of 1,3-diyne compounds, the reaction condition is mild and the operation is simple and convenient. In addition, the reaction yield is high. The preparing method can be applicable to synthesizing the asymmetric 2,5-disubstituted thiophene compound, and an effective, simple and convenient method is provided for synthesis of a medical intermediate, a material intermediate and a liquid crystal material.
Description
Technical field
The invention belongs to technical field of organic chemistry, relate to a kind of 2, the preparation method of 5-two substituted thiophene compounds.
Background technology
Sulfur-bearing conjugation aromatic compound is very important organic synthesis intermediate; And this type conjugated thiophene-based material is at medicine; Agricultural chemicals; There are important application [a) Press, J.B.In The Chemistry of Heterocyclic Derivatives.Thiophene and its Derivatives in aspects such as materials chemistry; Gronowitz, S., Ed.; Wiley:New York, 1984; Vol.44 (Part 1), pp353-456; B) Press, J.B.In Heterocyclic Chemistry.Thiophene and its Derivatives; Gronowitz, S., Ed.; Wiley:New York, 1990; Vol.44 (Part 4), pp 397-502; C) N.L.Campbell, W.L.Duffy, G.I.Thomas, J.H.Wild, S.M.Kelly, K.Bartle, M.Neill, V.Minter, R.P.Tuffin, J.Mater.Chem., 2002,12,2706; D) L.Y.Lin, C.W.Lu, W.C.Huang, Y.H.Chen, H.W.Lin, K.T.Wong, Org.Lett., 2011,13,4962.].The compound method of the simple thiophene of known preparation mainly is through to 1, the vulcanization reaction of 4-dione compounds obtains, and this wherein comprises very famous organic synthesis name reaction like Knorr Reaction and Paal-Knorr reaction.The normal sulphur source of adopting of this type compound method comprises thiophosphoric anhydride (P
2S
5), Steliou reaction reagent, and Lawesson ' s reaction reagent.In addition under the katalysis of transition metal copper, 1,4-two iodo-1,3-connect that diolefin and potassium sulphide reaction are synthetic to have substituent thiophene-based material [a) C.Paal, Ber., 1885,18,367; B) F.Freeman, D.S.H.L.Kim, J.Org.Chem., 1992,57,1723; C) A.A.Kiryanov, P.Sampson, A.J.Seed, J.Org.Chem., 2001,66,7925.d) K.T.Potts; S.A.Nye, K.A.Smith, J.Org.Chem., 1992,57,3895.e) W.You, X.Y.Yan; Q.Liao, C.J.Xi, Org.Lett., 2010,12,3930.].And we learn in bibliographical information, 1, and 3-di-alkine compounds has important use [a) Q.W.Zheng, R.M.Hua, Tetrahedron Lett., 2010,51,4512 aspect pyrroles and furans synthetic; B) S.Kramer, J.L.H.Madsen, M.Rottlander, T.Skrydstrup, Org.Lett., 2010,12,2758; C) V.Lavallo, G.D.Frey, B.Donnadieu, M.Soleihavoup, G.Bertrand; Angew.Chem.Int.Ed.2008,47,5224.] and utilizing 1, the report of 3-di-alkine compounds synthesizing thiofuran is very few; It is big that they often have operation easier, undesirable restriction [K.T.Potts, S.A.Nye, the K.A.Smith of waiting of product yield; J.Org.Chem., 1992,57,3895.].Traditional thiophene compound method, sulfide sulfur-bearing rate is low, and reflection substrate preparation process is numerous and diverse, and productive rate is not satisfactory, and wherein partial reaction also needs could accomplish by the katalysis of transition metal.And utilize cheap inorganic sulphide, and in reaction, have more Atom economy, also have more challenge.Simultaneously, the short-cut method of the catalyst-free of reflection system also has more researching value.Through research, we have invented by 1,3-di-alkine compounds and Sodium sulfhydrate, sodium sulphite, or the Synthetic 2 of sodium sulphite hydrate two-forty high yield, 5-two substituted thiophene compounds.Synthesized simultaneously asymmetrical 2,5-two substituted thiophene compounds (reported and had potential liquid crystal property).
Summary of the invention
The objective of the invention is to for the defective that overcomes prior art provides a kind of 2 the preparation method of 5-two substituted thiophene compounds.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
A kind of suc as formula 2 shown in (1), the preparation method of 5-two substituted thiophene compounds comprises following steps:
R wherein
1Or R
2Be selected from C
1-C
16Alkyl, C
4-C
10Heterocyclic radical that contains N, O or S or C
4-C
10Heteroaryl that contains N, O or sulphur or aryl;
The heterocyclic radical of the described N of containing, O or S is that furans, thiophene, pyrroles, imidazoles, pyrazoles, pyridine, α-pyrans, r-pyrans, pyrimidine or quinoline are given repeated exhortations etc.;
Described C
4-C
10The heteroaryl that contains N, O or S or aryl be selected from that furans, thiophene, pyrroles, imidazoles, pyrazoles, pyridine, α-pyrans, r-pyrans, pyrimidine, quinoline are given repeated exhortations, biphenol compound or anthracene etc.;
Described R
1With R
2Identical or different;
Described aryl is a phenyl or naphthyl;
(1) in the exsiccant container, adds organic solvent, 1,3-di-alkine compounds and sodium salt successively;
(2) at a certain temperature, stirring reaction; After question response finishes, add saturated aqueous common salt, with the organic extractant extraction, collect organic phase again, separate obtaining suc as formula the title product shown in (1).
Described 1, the structural formula of 3-di-alkine compounds does
R wherein
1Or R
2Be selected from C
1-C
16Alkyl, C
4-C
10Heterocyclic radical that contains N, O or sulphur or C
4-C
10Heteroaryl that contains N, O or sulphur or aryl;
The heterocyclic radical of the wherein said N of containing, O or S is that furans, thiophene, pyrroles, imidazoles, pyrazoles, pyridine, α-pyrans, r-pyrans, pyrimidine or quinoline are given repeated exhortations etc.;
Described C
4-C
10The heteroaryl that contains N, O or S or aryl be selected from that furans, thiophene, pyrroles, imidazoles, pyrazoles, pyridine, α-pyrans, r-pyrans, pyrimidine, quinoline are given repeated exhortations, biphenol compound or anthracene etc.
Described R
1Or R
2Identical or different.
Described sodium salt is selected from Sodium sulfhydrate, sodium sulphite or sodium sulphite hydrate (Na
2S9H
2O).
Described 1, the mol ratio of 3-di-alkine compounds and sodium salt is 1: 0.5-9, preferred 1: 0.5～3.
Organic solvent in the described step (1) is selected from non-protonic solvent, preferred acetonitrile, N, dinethylformamide or methyl-sulphoxide, further preferred N, dinethylformamide.The temperature of reaction of described step (2) is-30 ℃-150 ℃, preferred 0 ℃-80 ℃.
The reaction times of described step (2) is 10 minutes-48 hours.
The organic extractant of described step (2) is selected from ether or ETHYLE ACETATE.
Separate mode in the described step (2) is selected from recrystallization, thin-layer chromatography, column chromatography or underpressure distillation.
The solvent of described recrystallization is ETHYLE ACETATE or ETHYLE ACETATE-normal hexane mixed solvent.
The developping agent of described thin-layer chromatography or column chromatography is the mixed solvent of non-polar solvent and polar solvent; Be preferably sherwood oil-methylene dichloride, petroleum ether-ethyl acetate or sherwood oil-ether, its volume ratio is respectively: non-polar solvent: polar solvent=100-20/1.For example: petrol ether/ethyl acetate=100-20/1, sherwood oil/methylene dichloride=100-20/1.
Of the present invention 2,5-two substituted thiophene compounds are with Sodium sulfhydrate, sodium sulphite, or sodium sulphite hydrate and 1; 3-di-alkine compounds is a raw material, at acetonitrile, and N; Dinethylformamide, or non-protonic solvent such as methyl-sulphoxide exists and effect down reaction make, available following formula is represented:
Above-mentioned 2, the purposes of 5-two substituted thiophene compounds is as photovaltaic material, liquid crystal material, medical midbody or organic synthesis intermediate.
The present invention has following beneficial effect:
Method of the present invention is a kind of effectively with N, and dinethylformamide is a solvent, by Sodium sulfhydrate, and sodium sulphite, or sodium sulphite hydrate and 1,3-di-alkine compounds Synthetic 2, the method for 5-two substituted thiophene compounds.This method is applicable to dissimilar 1,3-di-alkine compounds, and reaction conditions is gentle, and is easy and simple to handle.The productive rate integral body of reacting in addition is better (being generally 72%-99%) also, and wherein low individually is 12%.The present invention can be applied to not becoming 2, and 5-two substituted thiophene compounds synthetic is medicine intermediate, and material intermediate and liquid crystal material synthetic provides effective short-cut method.
Embodiment
Further specify the present invention with embodiment below.
Embodiment 1:1,3-di-alkynes and Sodium sulfhydrate dissolvant of reaction system, the research of temperature and time
Wherein T refers to temperature, and t refers to the time.
Wherein, THF is a THF, H
2O is a water, and DMF is N, dinethylformamide.Solvent ratios is a volume ratio in the experiment numbers 4.
At an exsiccant egg type bottle, add N successively, dinethylformamide (2mL) and 1,3-diine (0.2mmoL), Sodium sulfhydrate (0.6mmol), stirring reaction under suitable temp (seeing temperature term in the tabulation).
Question response finishes back (thin-layer chromatography board monitoring), adds the 20ml saturated aqueous common salt, with 5ml extracted with diethyl ether (totally three times); Collect organic; The residue thin-layer chromatography obtains title product (sherwood oil, or petrol ether/ethyl acetate=10: 1, volume ratio) after the removal of solvent under reduced pressure.
Embodiment 2:1,3-di-alkynes and sulfide repercussion study
Embodiment 3:1,3-di-alkynes and Sodium sulfhydrate repercussion study
At an exsiccant egg type bottle, add N successively, dinethylformamide (2mL) and 1,3-di-alkynes (0.2mmoL), Sodium sulfhydrate (0.6mmol), 25 ℃ or 80 ℃ of following stirring reactions.
After reaction finishes, add the 20ml saturated aqueous common salt, with 5ml extracted with diethyl ether (totally three times), collect organic item, the residue thin-layer chromatography obtains title product (sherwood oil, or petrol ether/ethyl acetate=10: 1, volume ratio) after the removal of solvent under reduced pressure.
Embodiment 4:1,3-di-alkynes and the research of sodium sulphite hydrate reaction
At an exsiccant egg type bottle, add N successively, dinethylformamide (2mL) and 1,3-diine (0.2mmoL), sodium sulphite hydrate (0.6mmol), 25 ℃ or 80 ℃ of following stirring reactions.
After reaction finishes, add the 20ml saturated aqueous common salt, with 5ml extracted with diethyl ether (totally three times), collect organic item, the residue thin-layer chromatography obtains title product (sherwood oil, or petrol ether/ethyl acetate=10: 1, volume ratio) after the removal of solvent under reduced pressure.
P1-P9 is the product that the embodiment of the invention 3 or embodiment 4 make.
P1:2, the 5-dibenzo thiophene
White solid, 99% (embodiment 3,25 ℃ of temperature of reaction), 99% (embodiment 4,25 ℃ of temperature of reaction) yield, 148-150 ℃, fusing point.
1H?NMR(400MHz，CDCl
3)：δ7.29(dd，J＝7.6Hz，4H)，7.30(s，2H)，7.39(dd，J＝8.0，7.6Hz，4H)，7.64(dd，J＝8.0，0.8Hz，4H).
P2:2, two toluene thiophene of 5-
White solid, 99% (embodiment 3,25 ℃ of temperature of reaction), 99% (embodiment 4,25 ℃ of temperature of reaction)
1H?NMR(400MHz，CDCl
3)：δ2.40(s，6H)，7.10(d，J＝7.2Hz，2H)，7.28(dd，J＝9.2，6.8Hz，2H)，7.27(s，2H)，7.44(d，J＝7.6Hz，2H)，7.45(s，2H).
P3:2, two pairs of toluene thiophene of 5-
White solid, 96% (embodiment 3,80 ℃ of temperature of reaction), 91% (embodiment 4,25 ℃ of temperature of reaction) yield, 170-172 ℃, fusing point.
1H?NMR(400MHz，CDCl
3)：δ2.36(s，6H)，7.18(d，J＝8.0Hz，4H)，7.22(s，2H)，7.51(d，J＝8.0Hz，4H).
P4:2, two pairs of methyl-phenoxide thiophene of 5-
Light yellow solid, 76% (embodiment 3,80 ℃ of temperature of reaction), 99% (embodiment 4,80 ℃ of temperature of reaction) yield, 219-220 ℃, fusing point.
1H?NMR(400MHz，CDCl
3)：δ3.84(s，6H)，6.92(d，4H，J＝8.4Hz)，7.15(s，2H)，7.55(d，4H，J＝8.4Hz).
P5:2, two pairs of bromobenzene thiophene of 5-
White solid, 98% (embodiment 3,25 ℃ of temperature of reaction), 98% (embodiment 4,25 ℃ of temperature of reaction) yield, 202-203 ℃, fusing point.
1H?NMR(400MHz，CDCl
3)：δ7.27(s，2H)，7.47(d，J＝8.8Hz，4H)，7.51(d，J＝8.4Hz，4H).
P6:2, two pairs of fluorobenzene thiophene of 5-
White solid, 99% (embodiment 3,25 ℃ of temperature of reaction), 99% (embodiment 4,25 ℃ of temperature of reaction) yield, 159-160 ℃, fusing point.
1H?NMR(400MHz，CDCl
3)：δ7.08(dd，J＝8.8，8.4Hz，4H)，7.19(s，2H)，7.57(ddd，J＝8.8，8.8，2.0Hz，4H).
19F?NMR(400MHz，CDCl
3)：δ-114.30.
P7:2,5-two-2-pyridine thiophene
White solid, 86% (embodiment 3,25 ℃ of temperature of reaction), 72% (embodiment 4,25 ℃ of temperature of reaction) yield, 155-156 ℃, fusing point.
1H?NMR(400MHz，CDCl
3)：δ7.17(ddd，J＝6.8，6.4，2.0Hz，2H)，7.63(s，2H)，7.65-7.76(m，4H)，8.60(d，J＝4.8Hz，2H).
P8:2, two pairs of amylbenzene thiophene of 5-
White solid, 94% (embodiment 3,25 ℃ of temperature of reaction), 99% (embodiment 4,80 ℃ of temperature of reaction) yield, 132-134 ℃, fusing point.
1H?NMR(400MHz，CDCl
3)：δ0.90(t，J＝6.4Hz，6H)，1.29-1.41(m，8H)，1.57-1.70(m，4H)，2.61(t，J＝7.6Hz，4H)，7.19(d，J＝8.0Hz，4H)，7.23(s，2H)，7.53(d，J＝8.0Hz，4H).
P9:2,5-diamyl thiophene
Colourless liquid, 0.5% (embodiment 3,80 ℃ of temperature of reaction), 12% (embodiment 4,80 ℃ of temperature of reaction) yield.
1H?NMR(400MHz，CDCl
3)：δ0.90(t，J＝7.2Hz，6H)，1.30-1.36(m，8H)，1.61-1.67(m，4H)，2.73(t，J＝7.6Hz，4H)，6.55(s，2H).
Embodiment 5: asymmetric 1,3-di-alkynes synthetic and with the research of sodium sulphite hydrate reaction
At an exsiccant egg type bottle, add N successively, dinethylformamide (2mL) and 1,3-di-alkynes (0.2mmoL), sodium sulphite hydrate (0.6mmol), 80 ℃ of following stirring reactions.After reaction finishes, add the 20ml saturated aqueous common salt, with 5ml extracted with diethyl ether (totally three times), collect organic item, the residue thin-layer chromatography obtains title product (sherwood oil, or petrol ether/ethyl acetate=10: 1, volume ratio) after the removal of solvent under reduced pressure.
P1:2-(4-anisole)-5-(4-amylbenzene) thiophene
Faint yellow solid, 97% yield, 132-134 ℃, fusing point.
1H?NMR(400MHz，CDCl
3)：δ0.90(t，J＝6.8Hz，3H)，1.32-1.35(m，4H)，1.59-1.66(m，2H)，2.61(t，J＝7.6Hz，2H)，3.83(s，3H)，6.91(d，J＝8.8Hz，2H)，7.14-7.22(m，4H)，7.53(dd，J＝9.2，8.4Hz，4H)，
13C?NMR(400MHz，CDCl
3)：δ14.0，22.5，31.1，31.5，35.6，55.3，114.3，122.9，123.4，125.4，126.8，127.3，128.9，131.2，142.3，142.8，143.0，159.2；ESI-MS?m/z?336[M+H]
+；HRMS(ESI)calcd.for?C
22H
24OS[M+H]
+336.1548，found?336.1552.
P2:2-(4-anisole)-5-(4-amyl group) thiophene
White solid, 99% yield, 60-61 ℃, fusing point.
1H?NMR(400MHz，CDCl
3)：δ0.91(t，J＝6.8Hz，3H)，1.33-1.39(m，4H)，1.65-1.73(m，2H)，2.80(t，J＝8.0Hz，2H)，3.82(s，3H)，6.70(d，J＝3.6Hz，1H)，6.89(d，J＝8.8Hz，2H)，7.00(d，J＝3.6Hz，1H)，7.48(d，J＝9.2Hz，2H).
Wherein, the synthetic precursor of above-mentioned product is following:
S1:1-(4-benzyloxy)-4-benzene amyl group-1,3-fourth di-alkynes
Faint yellow solid, 76-78 ℃, fusing point.
1H?NMR(400MHz，CDCl
3)：δ0.89(t，J＝6.8Hz，3H)，1.25-1.34(m，4H)，1.55-1.64(m，2H)，2.60(t，J＝7.6Hz，2H)，3.82(s，3H)，6.85(d，J＝8.8Hz，2H)，7.14(d，J＝8.0Hz，2H)，7.44(dd，J＝8.8，8.4Hz，4H)；
13C?NMR(400MHz，CDCl3)：δ14.0，22.5，30.8，31.4，35.9，55.3，72.9，73.5，81.4，81.4，113.9，114.1，119.1，128.5，132.4，134.1，144.4，160.3；ESI-MS?m/z?302[M+H]
+；HRMS(ESI)calcd.for?C
22H
22O[M+H]
+302.1671，found?302.1670.
S2:1-(4-benzyloxy)-4-amyl group-1,3-fourth di-alkynes
Thick weak yellow liquid.
1H?NMR(400MHz，CDCl
3)：δ0.91(t，J＝7.2Hz，3H)，1.28-1.43(m，4H)，1.53-1.61(m，2H)，2.35(t，J＝7.2Hz，3H)，3.81(s，3H)，6.82(d，J＝8.8Hz，2H)，7.41(d，J＝8.8Hz，2H)，
13C?NMR(400MHz，CDCl3)：δ13.9，19.5，22.1，28.0，31.0，49.4，55.3，65.2，73.1，74.8，84.2，114.0，134.0，160.0；ESI-MS?m/z?226[M+H]
+；HRMS(ESI)calcd.for?C
16H
18O[M+H]
+226.1358，found?226.1359.
The above-mentioned description to embodiment is can understand and use the present invention for ease of the those of ordinary skill of this technical field.The personnel of skilled 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 suc as formula 2 shown in (1), and the preparation method of 5-two substituted thiophene compounds is characterized in that: comprise following steps:
R wherein
1Or R
2Be selected from C
1-C
16Alkyl, C
4-C
10Heterocyclic radical that contains N, O or S or C
4-C
10Heteroaryl that contains N, O or sulphur or aryl;
The heterocyclic radical of the described N of containing, O or S is that furans, thiophene, pyrroles, imidazoles, pyrazoles, pyridine, α-pyrans, r-pyrans, pyrimidine or quinoline are given repeated exhortations;
Described C
4-C
10The heteroaryl that contains N, O or S or aryl be selected from that furans, thiophene, pyrroles, imidazoles, pyrazoles, pyridine, α-pyrans, r-pyrans, pyrimidine, quinoline are given repeated exhortations, biphenol compound or anthracene;
Described R
1With R
2Identical or different;
Described aryl is a phenyl or naphthyl;
(1) in the exsiccant container, adds organic solvent, 1,3-di-alkine compounds and sodium salt successively;
(2) at a certain temperature, stirring reaction; After question response finishes, add saturated aqueous common salt, use organic solvent extraction again, collect organic, separate obtaining suc as formula the title product shown in (1).
2. preparation method according to claim 1 is characterized in that: described 1, the structural formula of 3-di-alkine compounds does
R wherein
1Or R
2Be selected from C
1-C
16Alkyl, C
4-C
10Heterocyclic radical that contains N, O or sulphur or C
4-C
10Heteroaryl that contains N, O or sulphur or aryl;
Or described R
1Or R
2Identical or different.
3. preparation method according to claim 2 is characterized in that: the heterocyclic radical of the described N of containing, O or S is that furans, thiophene, pyrroles, imidazoles, pyrazoles, pyridine, α-pyrans, r-pyrans, pyrimidine or quinoline are given repeated exhortations.
4. preparation method according to claim 2 is characterized in that: described C
4-C
10The heteroaryl that contains N, O or S or aryl be selected from that furans, thiophene, pyrroles, imidazoles, pyrazoles, pyridine, α-pyrans, r-pyrans, pyrimidine, quinoline are given repeated exhortations, biphenol compound or anthracene.
5. preparation method according to claim 1 is characterized in that: described sodium salt is selected from Sodium sulfhydrate, sodium sulphite or Na
2S9H
2O;
Or described 1, the mol ratio of 3-di-alkine compounds and sodium salt is 1: 0.5-9, preferred 1: 0.5～3.
6. preparation method according to claim 1 is characterized in that: the organic solvent in the described step (1) is selected from non-protonic solvent, preferred acetonitrile, N, dinethylformamide or methyl-sulphoxide, further preferred N, dinethylformamide.
7. preparation method according to claim 1 is characterized in that: the organic extractant of described step (2) is selected from ether or ETHYLE ACETATE.
8. preparation method according to claim 1 is characterized in that: the separate mode in the described step (2) is selected from recrystallization, thin-layer chromatography, column chromatography or underpressure distillation.
9. preparation method according to claim 1 is characterized in that: the solvent of described recrystallization is ETHYLE ACETATE or ETHYLE ACETATE-normal hexane mixed solvent;
Or the developping agent of described thin-layer chromatography or column chromatography is the mixed solvent of non-polar solvent and polar solvent; Be preferably sherwood oil-methylene dichloride, petroleum ether-ethyl acetate or sherwood oil-ether, its volume ratio is respectively: non-polar solvent: polar solvent=100-20/1.
10. preparation method according to claim 1 is characterized in that: the temperature of reaction of described step (2) is-30 ℃-150 ℃, preferred 0 ℃-80 ℃;
Or the reaction times of described step (2) is 10 minutes-48 hours.
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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 |
| CN104370877A (en) * | 2014-10-20 | 2015-02-25 | 同济大学 | 2,5-disubstituted thiophene compound and preparation method thereof |
| CN104402839A (en) * | 2014-10-20 | 2015-03-11 | 同济大学 | (E)-2,4,5-trisubstituted-(1-propenyl)oxazole ring compound and preparation method thereof |
| CN106008452A (en) * | 2016-06-06 | 2016-10-12 | 宜春学院 | Method for preparing 2,5-disubstituted thiophene |
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|---|---|---|---|---|
| CN102964370A (en) * | 2012-12-10 | 2013-03-13 | 同济大学 | 2,3,5-trisubstituted thiophene compound, as well as preparation method and use thereof |
| CN102964370B (en) * | 2012-12-10 | 2016-01-20 | 同济大学 | 2,3,5-trisubstituted thiophenes and its production and use |
| 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 |
| CN104370877A (en) * | 2014-10-20 | 2015-02-25 | 同济大学 | 2,5-disubstituted thiophene compound and preparation method thereof |
| CN104402839A (en) * | 2014-10-20 | 2015-03-11 | 同济大学 | (E)-2,4,5-trisubstituted-(1-propenyl)oxazole ring compound and preparation method thereof |
| CN104402839B (en) * | 2014-10-20 | 2016-11-02 | 同济大学 | A kind of (E)-2,4,5-three replacement-(1-acrylic) azoles cyclics and preparation method thereof |
| CN104370877B (en) * | 2014-10-20 | 2018-04-17 | 同济大学 | A kind of 2,5 2 substituted thiophene class compounds and preparation method thereof |
| CN106008452A (en) * | 2016-06-06 | 2016-10-12 | 宜春学院 | Method for preparing 2,5-disubstituted thiophene |
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