CN106349253B - A kind of synthetic method of 2- methyl-thiophenes simultaneously [3,4-b]-Isosorbide-5-Nitrae-oxygen thia hexane - Google Patents
A kind of synthetic method of 2- methyl-thiophenes simultaneously [3,4-b]-Isosorbide-5-Nitrae-oxygen thia hexane Download PDFInfo
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- CN106349253B CN106349253B CN201610773392.4A CN201610773392A CN106349253B CN 106349253 B CN106349253 B CN 106349253B CN 201610773392 A CN201610773392 A CN 201610773392A CN 106349253 B CN106349253 B CN 106349253B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
- C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D497/04—Ortho-condensed systems
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Abstract
The invention discloses a kind of 2 methylthiophenes simultaneously [3,4 b] 1, the synthetic method of 4 oxygen thia hexanes, with 3,4 ethene dioxythiophenes for raw material, it is reacted with 1 sulfydryl, 2 propyl alcohol and toluenesulfonic acid and generates product, it is not necessary that catalyst is added in reaction process, method is simple, and product yield is high, cost of material is low, is very suitable for industrialized production.
Description
Technical field
The present invention relates to organic chemistry fileds, and in particular to a kind of 2- methyl-thiophenes simultaneously [3,4-b]-Isosorbide-5-Nitrae-oxygen thia oneself
The synthetic method of alkane.
Background technology
The derivative Polyglycolic acid fibre that Bayer A.G synthesized polythiophene first in 1988, i.e.,
PEDOT, it is with 3,4-ethylene dioxythiophene（That is 3,4-rthylene dioxythiophene is abbreviated as EDOT）For monomer, have conductivity it is high,
The features such as environmental stability is good causes the broad interest of scientists.After PEDOT is successfully developed, adulterates and obtain with PSS
Many advantages, such as with high conductivity, high mechanical properties is many applications of antistatic figure layer, solid electrolyte capacitators etc..
Therefore, it is necessary to the synthetic method of suitable 2- methyl-thiophenes simultaneously [3,4-b]-Isosorbide-5-Nitrae-oxygen thia hexane is found, with
Expand the raw material sources of solid electrolyte.It is just described in Chinese patent CN200410055297.8, using 3,4- bis-
Ethoxythiophene is that starting material synthesizes 2- methyl-thiophenes simultaneously [3,4-b]-Isosorbide-5-Nitrae-oxygen thia hexane (EMOTT), yield 47.6%.
Raw material is somewhat expensive, and yield is relatively low, is not suitable for industrial production.
Invention content
To overcome the expensive starting materials of the prior art, product yield is relatively low, is not suitable for industrial production defect, the present invention is directed to carry
For a kind of new 2- methyl-thiophenes simultaneously [3,4-b]-Isosorbide-5-Nitrae-oxygen thia hexane synthetic method, to expand the raw material of solid electrolyte
Source.
The present invention provides a kind of preparation method of 2- methyl-thiophenes simultaneously [3,4-b]-Isosorbide-5-Nitrae-oxygen thia hexane, with 3,4- second
Alkene dioxy thiophene is raw material, is reacted with 1- sulfydryl -2- propyl alcohol and toluenesulfonic acid and generates product；
The reaction molar ratio of wherein 3,4- ethene dioxythiophenes, 1- sulfydryl -2- propyl alcohol and toluenesulfonic acid is：1：(1-
2)：(0.05-0.1).
Preferably, the reaction molar ratio of 3,4-rthylene dioxythiophene, 1- sulfydryl -2- propyl alcohol and toluenesulfonic acid is：1：
(1.3-1.6)：(0.07-0.09).
Preferably, the reaction dissolvent is toluene, is reacted in logical N2Under the conditions of synthesis under normal pressure.
Preferably, the reaction time is 5~15h, and the reaction temperature is 0~200 DEG C.
Preferably, the reaction time is 6~8h, and the reaction temperature is 50~150 DEG C.
Preferably, the reaction temperature is 120 DEG C.
Advantageous effect
Catalyst is needed without addition in this method reaction process, and reaction condition is mild, method is simple, and product yield is high, non-
Often suitable industrialized production.
Specific implementation mode
Comparative example 1：
3, the 4- diethoxy thiophene of 32.31g (187.6mmo1), the 2 mercapto ethanol of 29.31 g (375.2mmol) and
The p-methyl benzenesulfonic acid monohydrate of 3.56g (18.7mmo1) is heated to reflux 5 hours under nitrogen atmosphere in 400m1 toluene.
It continuously to be removed in this period and be formed by toluene and ethyl alcohol and supplement fresh toluene.Then according to thin-film chromatography monitor come
Determine whether reaction is completed.Reaction mixture cooled and filtered and is washed with water to neutrality under room temperature (23 C).Over sodium sulfate
It is distilled under mixture 0.07mbar (b.p.59-62 DEG C) after drying, distillation further purifies (eluant, eluent with silica gel chromatographic column:
Toluene).The yield for obtaining thieno [3,4-b]-Isosorbide-5-Nitrae-oxygen thia hexane (EMOTT) is 53%.
Comparative example 2：
3, the 4- diethoxy thiophene of 11.68g (67.8mmo1), the 1- sulfydryl -2- propyl alcohol of 12.5 g (135.6mmol)
It is heated to reflux under nitrogen atmosphere in 200m1 toluene 10 hours with the p-methyl benzenesulfonic acid monohydrate of 1.29g (6.8mmo1).
It continuously to remove during this period and be formed by toluene and ethyl alcohol and supplement fresh toluene.Then according to thin-film chromatography monitor
To determine whether reaction is completed.Reaction mixture cooled and filtered and is washed with water to neutrality under room temperature (23 C).In sodium sulphate
It is distilled under mixture 0.07mbar (b.p.59-62 DEG C) after upper drying, distillation is further with silica gel chromatographic column purification (elution
Agent:Toluene).Obtain 2- methyl-thiophenes simultaneously [3,4-b]-Isosorbide-5-Nitrae-oxygen thia hexane (EMOTT) yield be 47%.
Embodiment 1：
20g(140.67mmol) EDOT,19.44g（211.00mmol）1- sulfydryl -2- propyl alcohol and 2g（11.6mmol）It is right
Toluenesulfonic acid is in the reflux in toluene 15 hours of 120g, 120 DEG C of reaction temperature.It after having reacted, filters, washing is steamed after concentration
Evaporate to obtain product：14.54g (yield：60.00%).Compound identification：2- methyl-thiophenes simultaneously [3,4-b] -1,4- oxygen thia hexanes
In yellowish oily 1H-NMR (400MHz) δ (CDCl3, ppm):6.72(d,1H,J=3.54Hz),6.44(d,1H,I=
3.54Hz), 4.33 (X section of q and ABX, 1H, JXCH3=6.2Hz, JAX=1.9Hz, 9.0Hz), the 2.89 (portions B of ABX
Point, 1H, JAB=1.9Hz, 2.83 (part A of ABX, 1H, JAB=13.1Hz) 1.45 (d, 3H, JXCH3=6.2Hz).
Embodiment 2：
10g(70.36mmol) EDOT,9.2 g（100.00mmol）1- sulfydryl -2- propyl alcohol and 1.0g（6.0 mmol）It is right
Toluenesulfonic acid is in the reflux in toluene 12 hours of 65g, 120 DEG C of reaction temperature.It after having reacted, filters, washing is distilled after concentration
Obtain product：7.2g (yields：64.00%).Compound identification：Simultaneously [3,4-b] -1,4- oxygen thia hexanes are in micro- to 2- methyl-thiophenes
Oily 1H-NMR (400MHz) δ (CDCl3, ppm) of yellow:6.72(d,1H,J=3.54Hz),6.44(d,1H,I=
3.54Hz), 4.33 (X section of q and ABX, 1H, JXCH3=6.2Hz, JAX=1.9Hz, 9.0Hz), the 2.89 (portions B of ABX
Point, 1H, JAB=1.9Hz, 2.83 (part A of ABX, 1H, JAB=13.1Hz) 1.45 (d, 3H, JXCH3=6.2Hz).
It can be seen that the present invention, which obtains product yield, is substantially better than preparation method disclosed in the prior art.
Above-described embodiment simply to illustrate that the present invention technical concepts and features, it is in the art the purpose is to be to allow
Those of ordinary skill cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
It is the equivalent changes or modifications made by the essence according to the content of present invention, should all covers within the scope of the present invention.
Claims (6)
1. a kind of preparation method of 2- methyl-thiophenes simultaneously [3,4-b]-Isosorbide-5-Nitrae-oxygen thia hexane, which is characterized in that with 3,4- second
Alkene dioxy thiophene is raw material, is reacted with 1- sulfydryl -2- propyl alcohol and toluenesulfonic acid and generates product；
The reaction molar ratio of wherein 3,4- ethene dioxythiophenes, 1- sulfydryl -2- propyl alcohol and toluenesulfonic acid is：1：(1-2)：
(0.05-0.1)。
2. preparation method according to claim 1, which is characterized in that 3,4-rthylene dioxythiophene, 1- sulfydryl -2- propyl alcohol
Reaction molar ratio with toluenesulfonic acid is：1：(1.3-1.6)：(0.07-0.09).
3. preparation method according to claim 1 or 2, which is characterized in that the reaction dissolvent is toluene, and reaction is logical
N2Under the conditions of synthesis under normal pressure.
4. preparation method according to claim 3, which is characterized in that the reaction time is 5~15h, and described is anti-
It is 0~200 DEG C to answer temperature.
5. preparation method according to claim 4, which is characterized in that the reaction time is 6~8h, the reaction
Temperature is 50~150 DEG C.
6. preparation method according to claim 5, which is characterized in that the reaction temperature is 120 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1577657A (en) * | 2003-07-14 | 2005-02-09 | H.C.施塔克股份有限公司 | Polythiophenes having alkyleneoxythia thiophene units in electrolyte capacitors |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1577657A (en) * | 2003-07-14 | 2005-02-09 | H.C.施塔克股份有限公司 | Polythiophenes having alkyleneoxythia thiophene units in electrolyte capacitors |
Non-Patent Citations (1)
| Title |
|---|
| Enhanced longterm stability of aluminum solid electrolyte capacitor containing thiophene derivatives as a solid electrolyte;Myeongjin Kim，等;《Synthetic Metals》;20130102;第162卷(第24期);2361-2369 * |
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