CN103242357A - Synthesis method of polysubstituted silole derivative - Google Patents
Synthesis method of polysubstituted silole derivative Download PDFInfo
- Publication number
- CN103242357A CN103242357A CN2013101695094A CN201310169509A CN103242357A CN 103242357 A CN103242357 A CN 103242357A CN 2013101695094 A CN2013101695094 A CN 2013101695094A CN 201310169509 A CN201310169509 A CN 201310169509A CN 103242357 A CN103242357 A CN 103242357A
- Authority
- CN
- China
- Prior art keywords
- synthetic method
- reaction
- aryl
- polysubstituted
- polar solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Catalysts (AREA)
Abstract
The invention provides a synthesis method of a polysubstituted silole derivative. The polysubstituted silole derivative is prepared by reacting a 2-(trimethylsilyl)aryl trifluoromethane sulfonate derivative with alkyne in the presence of a catalyst. The synthesis method is pretty high in yield rate, scientific, reasonable, accessible in raw materials, wide in application range, high in separation yield rate, simple in experiment equipment, simple and easy in operation implementation, and conductive to further development and application.
Description
Technical field
The invention belongs to the organic synthesis field, relate to the universal synthesis method with multiple substituting group sila cyclopentadiene derivant.
Background technology
Have polysubstituted sila cyclopentadiene (thiophene is coughed up) derivative and have lower reduction potential and lowest unoccupied molecular orbital (LUMO), stronger electronics flowability and electron affinity are arranged, it is very strong to accept electronic capability.The electronic structure of this uniqueness makes it have great application prospect in the photoelectron material field, as is used as electroluminescence (EL) material, photodiode (LED) organic semiconductor material, electron transport material, nonlinear optical material etc.The synthetic method of reporting is at present used the metal reagent of equivalent more, and reaction is relatively harsher, and functional group's tolerance is low, thereby can't effectively realize polysubstituted group, has also limited the diversity of substituted radical.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic universal method of multiple substituent sila cyclopentadiene derivant that has.Technical scheme of the present invention is as follows:
A kind of synthetic method of polysubstituted sila cyclopentadiene derivant, be that the catalyzer shown in the common and formula (III) reacts in non-polar solvent with the alkynes shown in 2-(trimethyl silicane) the aryl trifluoro-methanyl sulfonate derivative shown in the formula (I) and the formula (II), temperature of reaction is between the boiling point of 90 ℃ and described non-polar solvent;
Wherein:
R
1Be the substituting group of optional position on the phenyl ring, can for single replacement, polysubstituted or and ring structure, its expression:
Carbonatoms is 1-12 or more alkyl, such as: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-..., undecyl, dodecyl, tridecyl ..., octadecyl etc., more preferably C1-6 alkyl, more preferably C1-4 alkyl;
Carbonatoms is the aryl of 6-12, such as phenyl, xenyl, naphthyl etc.;
Or carbonatoms is the heterocyclic aryl of 2-5, such as thienyl, thiazolyl, pyridyl etc.
Above-mentioned group can be substituted base and replace, and described substituting group can be common C1-4 alkyl or alkoxyl group, hydrogen atom, halogen atom (F, Cl, Br), cyano group, nitro etc.
R
2And R
3Can be the same or different, independently of one another expression:
Carbonatoms is the silylation of 3-12, such as trimethyl silicon based, triethyl is silica-based, three third classes are silica-based etc.;
Carbonatoms is the aryl of 6-12, such as phenyl, xenyl, naphthyl etc.;
Or carbonatoms is the heterocyclic aryl of 2-5, such as thienyl, thiazolyl, pyridyl etc.
Above-mentioned group can be substituted base and replace, and described substituting group can be common C1-4 alkyl or alkoxyl group, hydrogen atom, halogen atom (F, Cl, Br), cyano group, nitro etc.
Catalyzer used in the present invention is the mixture of chlorination Allylpalladium or its dipolymer, tri-tert phosphorus, lithium ethoxide and Potassium Bromide or 4 bromide.The equal useful commercial reagent of all reagent need not special processing.
Non-polar solvent used in the present invention can be toluene, dimethylbenzene or 1,4-dioxane etc. or their mixture.This non-polar solvent useful commercial reagent gets final product through molecular sieve drying before using.The moiety of described non-polar solvent can be identical, also can be different, and have no special requirements.
The mol ratio preferable range of various reaction raw materials of the present invention or reagent is as shown in table 1:
The preferred molar ratio of the various reaction raw materials of table 1. or reagent
In the last table, when the chlorination Allylpalladium in the catalyst system therefor substituted with its dipolymer, then consumption was 0.025 molar equivalent.
The inventive method does not have strict restriction to the ratio of non-polar solvent, as long as reaction solution is evenly stirred, the compound (I) of preferred 1mmol is dissolved in the non-polar solvent that volume is no less than 5mL.
It is how much slightly different according to different raw materials that the inventive method respectively goes on foot the reaction times, detects to disappear with raw material to be as the criterion general 6-24 hour.
The present invention adopts oil bath (for example silicone oil, paraffin wet goods) or other modes to heat, as long as maintain temperature of reaction.
The present invention can carry out aftertreatment to the reaction solution that obtains after the reaction, aftertreatment is normally filtered, and washs filter residue with ethyl acetate then, and washings and filtrate are merged, simple filtrate concentrates then, and the filtrate concentration process adopts air distillation, underpressure distillation or evaporates with Rotary Evaporators.
In order to obtain more highly purified product, preferably the product after the aftertreatment is carried out purifying, described purge process can be made eluent with the solvent of certain polarity, and the chromatographic column separation gets final product.Selected eluent has certain difference according to the opposed polarity of product.Generally speaking, eluent is selected the mixed solvent of sherwood oil and ethyl acetate for use, and volume ratio is 1:(0.001-0.02).The chromatographic column of using such as laboratory silicagel column commonly used or performance liquid chromatographic column etc., used silica gel is the 200-300 order.
The present invention utilizes 2-(trimethyl silicane) aryl trifluoro-methanyl sulfonate derivative and alkynes reaction, under catalyst action, prepare polysubstituted sila cyclopentadiene (thiophene is coughed up) derivative, productive rate is higher, synthetic method is scientific and reasonable, thereby a kind of synthetic universal method of multiple substituent sila cyclopentadiene derivant that has is provided.This method raw material is easy to get, and is applied widely, high isolated yield, and experimental installation and operation is simple is convenient to further Application and Development.
Embodiment
Further describe the present invention below in conjunction with embodiment, but the scope that does not limit the present invention in any way.
Embodiment 1---preparation formula IVa(R
1=H, R
2=R
3=Ph) compound:
Under nitrogen protection, in the 50mL reaction tubes, add 2-(trimethyl silicane) the phenyl trifluoromethanesulfonate methane sulfonates of 1mmol, the tolane of 1.2mmol; 0.05mmol the chlorination Allylpalladium; 0.1mmol tri-tert phosphorus, the lithium ethoxide of 3mmol, the Potassium Bromide of 2mmol and the toluene solvant of 5mL.Adopt oil bath that temperature of reaction is constant in 120 ℃ of following reactions 24 hours.Cooled and filtered, concentrated filtrate obtains crude product.Decolouring separates crude product through silicagel column, makees eluent with sherwood oil, obtains 1,1-dimethyl-2, and 3-phenylbenzene benzo thiophene is coughed up 250mg(purity＞98%, colorless solid), isolated yield 80%.The nuclear magnetic data of this compound is as follows:
1H NMR (400MHz, CDCl
3) δ: 0.47 (s, 6H, CH
3), 6.96-6.99 (m, 2H, CH), 7.04-7.07 (m, 2H, CH), 7.11-7.14 (m, 2H, CH), 7.18-7.21 (m, 2H, CH), 7.26-7.34 (m, 5H, CH), 7.60-7.62 (m, 1H, CH);
13C NMR (100MHz, CDCl
3) δ :-3.51 (2CH
3), 123.98,125.66,126.65,127.05,127.93 (2CH), 128.34 (2CH), 128.59 (2CH), 129.66 (2CH), 129.76,131.62,138.13,138.16,139.96,142.99,150.71,153.12.
Embodiment 2---preparation formula IVb(R
1=OMe, R
2=Ph, R
3=TMS) compound:
Under nitrogen protection; 2-(the trimethyl silicane)-3-p-methoxy-phenyl trifluoro-methanyl sulfonate that in the 50mL reaction tubes, adds 1mmol; 1.2mmol phenylacetylene base trimethyl silane; 0.05mmol the chlorination Allylpalladium; 0.1mmol tri-tert phosphorus; the lithium ethoxide of 3mmol, the Potassium Bromide of 2mmol and the xylene solvent of 5mL.Adopt oil bath that temperature of reaction is constant in 120 ℃ of following reactions 24 hours.Cooled and filtered, concentrated filtrate obtains crude product.Decolouring separates crude product through silicagel column, makees eluent with sherwood oil, obtains 1,1-dimethyl-2-(trimethyl silicane)-3-phenyl-7-methoxyl group benzo thiophene and coughs up 220mg(purity＞98%, colourless oil liquid), isolated yield 65%.The nuclear magnetic data of this compound is as follows:
1H NMR (400MHz, CDCl
3) δ: 0.49 (s, 6H, CH
3), 3.85 (s, 3H, CH
3), 6.69 (d, J=7.5Hz, 1H, CH), 6.76 (d, J=8.2Hz, 1H, CH), 6.96-6.98 (m, 2H, CH), 7.04-7.32 (m, 9H, CH);
13C NMR (100MHz, CDCl
3) δ :-4.03 (2CH
3), 55.41,109.03,117.41,123.60,125.57,126.93,127.87 (2CH), 128.22 (2CH), 128.57 (2CH), 129.68 (2CH), 131.87,138.32,140.07,143.85,152.32,152.35,162.96.
Embodiment 3---preparation formula IVc(R
1=2F, R
2=R
3=Ph) compound:
Under nitrogen protection; the 2-(trimethyl silicane)-4 that in the 50mL reaction tubes, adds 1mmol; 5-phenyl-difluoride base trifluoro-methanyl sulfonate; the tolane of 2mmol; 0.025mmol chlorination Allylpalladium dipolymer, the tri-tert phosphorus of 0.1mmol, the lithium ethoxide of 2mmol; 1 of the 4 bromide of 1mmol and 6mL, 4-dioxane solvent.Adopt oil bath that temperature of reaction is constant in 120 ℃ of following reactions 12 hours.Cooled and filtered, concentrated filtrate obtains crude product.Decolouring separates crude product through silicagel column, makees eluent with sherwood oil, obtains 1,1-dimethyl-3,4-phenylbenzene-5,6-phenyl-difluoride and thiophene are coughed up 174mg(purity〉98%, white solid), isolated yield 50%.The nuclear magnetic data of this compound is as follows:
1H NMR (CDCl3,399.78MHz) δ: 0.47 (s, 9H), 6.85 (dd, JH-F=11.8Hz, JH-F=7.6Hz), 6.93-6.96 (m, 2H), 7.06-7.17 (m, 5H), 7.28-7.38 (m, 4H);
13C NMR (CDCl3,100.53MHz) δ :-3.62,113.4 (d, JC-F=18.2Hz), 120.2 (d, JC-F=16.3Hz), 126.0,127.5,128.0,128.5,128.6,129.4,134.5 (t, JC-F=3.9Hz), 137.4,139.3,143.8 (d, JC-F=3.8Hz), 147.6 (dd, JC-F=5.3Hz, JC-F=3.8Hz), 149.7 (dd, JC-F=258Hz, JC-F=13.0Hz), 151.3,151.5 (dd, JC-F=248Hz, JC-F=13.0Hz).
Embodiment 4---preparation formula IVd(R
1=OMe, R
2=R
3=2-Thenyl) compound:
Under nitrogen protection; 2-(the trimethyl silicane)-3-p-methoxy-phenyl trifluoro-methanyl sulfonate that in the 50mL reaction tubes, adds 1mmol; 1.2mmol two (2-thiophene) acetylene; 0.025mmol chlorination Allylpalladium dipolymer; 0.1mmol tri-tert phosphorus; the lithium ethoxide of 1mmol, the 4 bromide of 1mmol and the toluene solvant of 8mL.Adopt oil bath that temperature of reaction is constant in 120 ℃ of following reactions 24 hours.Cooled and filtered, concentrated filtrate obtains crude product.Decolouring separates crude product through silicagel column, makees eluent with sherwood oil, obtains 1,1-dimethyl-3, and 4-two (2-thiophene)-7-methoxyl group benzo thiophene is coughed up 258mg(purity〉98%, white solid), isolated yield 73%.The nuclear magnetic data of this compound is as follows:
1H NMR (400MHz, CDCl
3) δ: 0.57 (s, 6H, CH
3), 3.85 (s, 3H, CH
3), 6.63 (d, J=7.5Hz, 1H, CH), 6.75 (d, J=8.2Hz, 1H, CH), 6.93-7.02 (m, 3H, CH), 7.16-7.22 (m, 2H, CH), 7.28 (t, J=7.9Hz, 1H, CH), 7.54 (dd, J=5.1,0.9Hz, 1H, CH);
13C NMR (100MHz, CDCl
3) δ :-3.30 (2CH
3), 55.43,109.01,117.07,121.78,126.14,127.07 (2CH), 127.87,127.93,128.06,132.36,138.10,139.90,141.57,142.54,153.06,162.85.
Embodiment 5---preparation formula IVe(R
1=Naph, R
2=R
3=Ph) compound:
Under nitrogen protection; 2-(the trimethyl silicane)-naphthyl trifluoro-methanyl sulfonate that in the 50mL reaction tubes, adds 1mmol; the tolane of 1mmol; 0.025mmol chlorination Allylpalladium dipolymer; 0.1mmol tri-tert phosphorus; the lithium ethoxide of 3mmol, the Potassium Bromide of 1mmol and the toluene solvant of 7mL.Adopt oil bath that temperature of reaction is constant in 120 ℃ of following reactions 24 hours.Cooled and filtered, concentrated filtrate obtains crude product.Decolouring separates crude product through silicagel column, makees eluent with sherwood oil, obtains 1,1-dimethyl-3, and 4-phenylbenzene naphtho-thiophene is coughed up 210mg(purity〉98%, white solid), isolated yield 58%.The nuclear magnetic data of this compound is as follows:
1H NMR (400MHz, CDCl
3) δ: 0.52 (s, 6H, CH
3), 7.00-7.16 (m, 6H, CH), 7.23-7.27 (m, 1H, CH), 7.33-7.42 (m, 6H, CH), 7.64-7.67 (m, 1H, CH), 7.81-7.83 (m, 1H, CH), 8.06 (m, 1H, CH);
13C NMR (100MHz, CDCl
3) δ :-2.87 (2CH
3), 122.43,125.75,125.79,126.47,127.15,127.82,127.95 (2CH), 128.39 (2CH), 128.45,128.58 (2CH), 129.77 (2CH), 132.37,132.69,134.59,136.45,138.20,140.07,144.72,147.55,153.65.
Embodiment 6---preparation formula IVf(R
1=OMe, R
2=R
3=1-Naph) compound:
Under nitrogen protection; 2-(the trimethyl silicane)-3-p-methoxy-phenyl trifluoro-methanyl sulfonate that in the 50mL reaction tubes, adds 1mmol; 1.2mmol dinaphthyl acetylene; 0.025mmol chlorination Allylpalladium dipolymer; 0.1mmol tri-tert phosphorus; the lithium ethoxide of 3mmol, the Potassium Bromide of 2mmol and the toluene solvant of 10mL.Adopt oil bath that temperature of reaction is constant in 120 ℃ of following reactions 24 hours.Cooled and filtered, concentrated filtrate obtains crude product.Decolouring separates crude product through silicagel column, makees eluent with sherwood oil, obtains 1,1-dimethyl-3, and 4-dinaphthyl-7-methoxyl group benzo thiophene is coughed up 296mg(purity〉98%, white solid), isolated yield 67%.The nuclear magnetic data of this compound is as follows:
1H NMR (400MHz, CDCl
3) δ: 0.46 (s, 3H, CH
3), 0.49 (s, 3H, CH
3), 3.88 (s, 3H, CH
3), 6.27 (d, J=7.5Hz, 1H, CH), 6.77 (d, J=8.2Hz, 1H, CH), 6.92 (br, 1H, CH), 7.11-7.17 (m, 4H, CH), and 7.31-7.36 (m, 4H, CH), 7.45 (d, J=8.2Hz, 1H, CH), 7.54 (dd, J=7.6,1.3Hz, 1H, CH), and 7.65-7.70 (m, 2H, CH), 7.88 (d, J=7.6Hz, 1H, CH), 8.01 (d, J=7.3Hz, 1H, CH);
13C NMR (100MHz, CDCl
3) δ :-4.13 ,-3.69,55.43,109.11,117.97,123.72,124.86,125.23,125.27,125.35 (2CH), 125.42 (3CH), 125.63,126.58,126.67,127.26,127.94,128.05,131.58,131.84,132.09,133.20,133.35,135.93,138.56,146.97,152.40,153.34,162.99.
Embodiment 7---preparation formula IVg(R
1=OMe, R
2=R
3=4-F Ph) compound:
Under nitrogen protection; 2-(the trimethyl silicane)-3-p-methoxy-phenyl trifluoro-methanyl sulfonate that in the 50mL reaction tubes, adds 1mmol; two (4-fluorophenyl) acetylene of 2mmol; 0.025mmol chlorination Allylpalladium dipolymer; 0.1mmol tri-tert phosphorus; the lithium ethoxide of 2mmol, the 4 bromide of 1.5mmol and the toluene solvant of 5mL.Adopt oil bath that temperature of reaction is constant in 120 ℃ of following reactions 24 hours.Cooled and filtered, concentrated filtrate obtains crude product.Decolouring separates crude product through silicagel column, makees eluent with sherwood oil, obtains 1,1-dimethyl-3, and 4-two (4-fluorophenyl)-7-methoxyl group benzo thiophene is coughed up 223mg(purity〉98%, white solid), isolated yield 59%.The nuclear magnetic data of this compound is as follows:
1H NMR (400MHz, CDCl
3) δ: 0.47 (s, 6H, CH
3), 3.86 (s, 3H, CH
3), 6.66 (d, J=7.5Hz, 1H, CH), 6.77-6.91 (m, 5H, CH), 7.01 (t, J=8.8Hz, 2H, CH), 7.11-7.15 (m, 2H, CH), 7.28 (t, J=7.9Hz, H, CH);
13CNMR (100MHz, CDCl
3) δ :-4.18 (2CH
3), 55.43,109.22,114.96 (d, J=21.0Hz, 2CH), 115.37 (d, J=21.1Hz, 2CH), 117.19,123.38,129.93 (d, J
C-F=7.8Hz, 2CH), 131.35 (d, J
C-F=7.8Hz, 2CH), 132.02,133.85 (d, J
C-F=3.4Hz), 135.88 (d, J
C-F=3.5Hz), 143.41,151.39,151.95,160.24 (d, J
C-F=88.1Hz), 162.69 (d, J
C-F=88.9Hz), 163.05.
Embodiment 8---preparation formula IVh(R
1=Me, R
2=R
3=Ph) compound:
Under nitrogen protection; 2-(the trimethyl silicane)-4-aminomethyl phenyl trifluoro-methanyl sulfonate that in the 50mL reaction tubes, adds 1mmol; 1.5mmol tolane; 0.025mmol chlorination Allylpalladium dipolymer; 0.1mmol tri-tert phosphorus; the lithium ethoxide of 1mmol, the 4 bromide of 1mmol and the toluene solvant of 5mL.Adopt oil bath that temperature of reaction is constant in 120 ℃ of following reactions 24 hours.Cooled and filtered, concentrated filtrate obtains crude product.Decolouring separates crude product through silicagel column, makees eluent with sherwood oil, obtains 1,1-dimethyl-3, and 4-phenylbenzene-6-methyl benzo thiophene is coughed up 183mg(purity〉98%, faint yellow solid), isolated yield 56%.The nuclear magnetic data of this compound is as follows:
1H NMR (400MHz, CDCl
3) δ: 0.46 (s, 6H, CH
3), 2.37 (s, 3H, CH
3), 6.93-6.98 (m, 3H, CH), 7.03-7.13 (m, 4H, CH), 7.18-7.20 (m, 2H, CH), 7.26-7.33 (m, 3H, CH), 7.44 (s, 1H, CH);
13C NMR (100MHz, CDCl
3) δ :-3.42 (2CH
3), 21.21,123.80,125.51,126.96,127.89 (2CH), 128.29 (2CH), 128.59 (2CH), 129.59 (2CH), 130.26,132.60,136.30,138.21,138.32,140.04,141.71,148.14,153.02.
Claims (10)
1. the synthetic method of a polysubstituted sila cyclopentadiene derivant, it is characterized in that, be that the catalyzer shown in the common and formula (III) reacts in non-polar solvent with the alkynes shown in 2-(trimethyl silicane) the aryl trifluoro-methanyl sulfonate derivative shown in the formula (I) and the formula (II), temperature of reaction is between the boiling point of 90 ℃ and described non-polar solvent;
Wherein, R
1, R
2And R
3The C of expression replacement independently of one another or non-replacement
1-12Alkyl, C
3-12Silylation, C
6-12Aryl or C
2-5Heterocyclic aryl.
2. synthetic method as claimed in claim 1 is characterized in that, described catalyzer is the mixture of chlorination Allylpalladium or its dipolymer, tri-tert phosphorus, lithium ethoxide and Potassium Bromide or 4 bromide.
3. synthetic method as claimed in claim 1 is characterized in that, described non-polar solvent is selected from one or more in toluene, dimethylbenzene or 1, the 4-dioxane.
4. synthetic method as claimed in claim 1 is characterized in that, the molar equivalent of described 2-(trimethyl silicane) aryl trifluoro-methanyl sulfonate derivative (I) and alkynes (II) is than being 1:1-2.
5. synthetic method as claimed in claim 1 is characterized in that, chlorination Allylpalladium in the described catalyzer (III), and tri-tert phosphorus, lithium ethoxide, the molar equivalent of Potassium Bromide is than being 0.05:0.1:1-3:1-2.
6. synthetic method as claimed in claim 1 is characterized in that, comprises that also the reaction solution to obtaining after the reaction carries out aftertreatment, and described aftertreatment after comprising filtration and using ethyl acetate washing filter residue merges filtrate and washings.
7. synthetic method as claimed in claim 6 is characterized in that, described aftertreatment also comprises the filtrate after merging is concentrated, and concentration process adopts air distillation, underpressure distillation or evaporates with Rotary Evaporators.
8. synthetic method as claimed in claim 6 is characterized in that, by chromatographic column separation and purification after-treatment products, the purifying eluent is the mixed solvent of sherwood oil and ethyl acetate, and described chromatographic column comprises silicagel column or performance liquid chromatographic column.
9. synthetic method as claimed in claim 8 is characterized in that, the volume ratio of described eluent PetroChina Company Limited.'s ether and ethyl acetate is 1:0.001-0.02.
10. synthetic method as claimed in claim 8 is characterized in that, the silica gel in the described silicagel column is the 200-300 order.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310169509.4A CN103242357B (en) | 2013-05-09 | 2013-05-09 | A kind of synthetic method of polysubstituted Silole derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310169509.4A CN103242357B (en) | 2013-05-09 | 2013-05-09 | A kind of synthetic method of polysubstituted Silole derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103242357A true CN103242357A (en) | 2013-08-14 |
| CN103242357B CN103242357B (en) | 2016-04-27 |
Family
ID=48922261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310169509.4A Expired - Fee Related CN103242357B (en) | 2013-05-09 | 2013-05-09 | A kind of synthetic method of polysubstituted Silole derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103242357B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015188790A1 (en) * | 2014-06-13 | 2015-12-17 | The University Of Hong Kong | Robust photochromic compounds with silicon- or phosphorus-containing heterocyclic ring and production thereof |
| CN105461743A (en) * | 2016-01-06 | 2016-04-06 | 山西大学 | Five-membered bi-heterocyclic symmetrical aryl derivative and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005036666A2 (en) * | 2003-09-16 | 2005-04-21 | Dow Global Technologies Inc. | Method of preparing an insoluble polymer film on a substrate from a soluble polymer containing labile solubilizing groups |
| US20110023964A1 (en) * | 2008-04-11 | 2011-02-03 | Toray Industries, Inc. | Electron donating material, material for photovoltaic devices and photovoltaic device |
-
2013
- 2013-05-09 CN CN201310169509.4A patent/CN103242357B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005036666A2 (en) * | 2003-09-16 | 2005-04-21 | Dow Global Technologies Inc. | Method of preparing an insoluble polymer film on a substrate from a soluble polymer containing labile solubilizing groups |
| US20110023964A1 (en) * | 2008-04-11 | 2011-02-03 | Toray Industries, Inc. | Electron donating material, material for photovoltaic devices and photovoltaic device |
Non-Patent Citations (4)
| Title |
|---|
| KENJI MOCHIDA等，: "Palladium-Catalyzed Intramolecular Coupling of 2-[(2-Pyrrolyl)silyl]aryl", 《J. AM. CHEM. SOC.》, vol. 131, 2 June 2009 (2009-06-02) * |
| MAMORU TOBISU等，: "Rhodium-Catalyzed Coupling of 2-Silylphenylboronic Acids with Alkynes Leading to Benzosiloles: Catalytic Cleavage of the Carbon-Silicon Bond in Trialkylsilyl Groups", 《J. AM. CHEM. SOC.》, 13 May 2009 (2009-05-13), pages 7506 - 7507 * |
| MASAHIRO ONOE等，: "Rhodium-Catalyzed Carbon−Silicon Bond Activation for Synthesis of Benzosilole Derivatives", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 134, 5 November 2012 (2012-11-05) * |
| TIANHAO MENG等，: "Synthesis of gem-dihaloenynes and butatrienes from gem-dihalovinyl derivatives", 《TETRAHEDRON LETTERS》, 18 June 2012 (2012-06-18), pages 4555 - 4557 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015188790A1 (en) * | 2014-06-13 | 2015-12-17 | The University Of Hong Kong | Robust photochromic compounds with silicon- or phosphorus-containing heterocyclic ring and production thereof |
| KR20170005846A (en) * | 2014-06-13 | 2017-01-16 | 더 유니버시티 오브 홍콩 | Robust photochromic compounds with silicon- or phosphorus-containing heterocyclic ring and production thereof |
| EP3154990A4 (en) * | 2014-06-13 | 2018-01-03 | The University of Hong Kong | Robust photochromic compounds with silicon- or phosphorus-containing heterocyclic ring and production thereof |
| KR101938649B1 (en) * | 2014-06-13 | 2019-04-10 | 더 유니버시티 오브 홍콩 | Robust photochromic compounds with silicon- or phosphorus-containing heterocyclic ring and production thereof |
| CN105461743A (en) * | 2016-01-06 | 2016-04-06 | 山西大学 | Five-membered bi-heterocyclic symmetrical aryl derivative and preparation method thereof |
| CN105461743B (en) * | 2016-01-06 | 2017-12-05 | 山西大学 | Double symmetrical aryl derivatives of miscellaneous five-membered ring and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103242357B (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10730838B2 (en) | Green preparation method for quinoline compounds | |
| CN107235995B (en) | Chiral dihydrosilane compound and synthesis method and application thereof | |
| CN109423297B (en) | Dibenzothiophene liquid crystal compound and preparation method and application thereof | |
| JP5969759B2 (en) | Organoboron compound and method for producing the same | |
| CN103242357B (en) | A kind of synthetic method of polysubstituted Silole derivative | |
| CN111253208A (en) | Preparation method of 1-iodoalkyne | |
| CN114105921A (en) | Cyclopentyl benzofuran liquid crystal compound and application thereof | |
| CN108911937B (en) | Synthesis method of tetraarylethylene compound | |
| CN103113174B (en) | Preparation method of phenolic compounds | |
| CN113930246B (en) | Liquid crystal compound and application thereof | |
| CN109082281B (en) | Liquid crystal compound with negative dielectric anisotropy as well as preparation method and application thereof | |
| CN114196417A (en) | Liquid crystal compound containing cyclopentyl and application | |
| KR102082532B1 (en) | Method for producing borinic acid derivative, and novel borinic acid derivative | |
| CN107709303B (en) | Substituted imidazolium sulfanes and their use | |
| Braga et al. | Mild and efficient one-pot synthesis of chiral β-chalcogen amides via 2-oxazoline ring-opening reaction mediated by indium metal | |
| CN107382782B (en) | Method for synthesizing polyaryl substituted naphthol derivative | |
| CN109423298B (en) | Novel dibenzothiophene liquid crystal compound and preparation method and application thereof | |
| CN106905133B (en) | Spiro-fluorene-indene diketone compound and preparation method and application thereof | |
| Cheval et al. | Vinyl nosylates as partner in copper and silver co-catalyzed Sonogashira cross-coupling reactions | |
| CN106366069B (en) | A kind of preparation method of N- heteroaryl carbazole compound | |
| CN109608456A (en) | A kind of synthetic method of quinoline diindyl quinoline derivant | |
| JP4362683B2 (en) | Asymmetric dihydrophenazine derivative and method for producing the same | |
| CN111484853B (en) | Liquid crystal compound and preparation method and application thereof | |
| CN109265311B (en) | Phenyl fluorene derivative and preparation method and application thereof | |
| CN103113181B (en) | A kind of synthetic method of polysubstituted cyclopentadiene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160427 Termination date: 20170509 |