CN102010279A - Method for preparing vinylaromatic derivatives - Google Patents
Method for preparing vinylaromatic derivatives Download PDFInfo
- Publication number
- CN102010279A CN102010279A CN2010105677443A CN201010567744A CN102010279A CN 102010279 A CN102010279 A CN 102010279A CN 2010105677443 A CN2010105677443 A CN 2010105677443A CN 201010567744 A CN201010567744 A CN 201010567744A CN 102010279 A CN102010279 A CN 102010279A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reaction
- ethylene derivative
- aryl ethylene
- derivative according
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing vinylaromatic derivatives, belonging to the technical field of chemical synthesis. In the invention, polyethylene glycol-400 (PEG-400) is utilized as a solvent, palladium chloride is utilized as a catalyst, and iodo-substitued aromatic compounds and olefin compounds with the molar ratio of 1:1-1:3 react for 10-15min under radiation of focus microwaves in alkailine environment; and hydrochloric acid is added in the reaction liquid after complete reaction for acidizing to adjust the pH value of the reaction liquid to be 1-3, diethyl ether is utilized for extraction, drying is carried out by utilizing anhydrous magnesium sulfate, and then filtering, concentrating and separating are carried out to obtain the vinylaromatic derivatives. The preparation method has the advantages of easily obtained and cheap raw materials, mild reaction conditions, simple reaction process, low synthesis cost, high reaction speed, high efficiency and high product yield (up to 95%); the non-toxic PEG-400 is utilizes as the solvent, thus the postprocessing is simple; the solvent system is non-toxic, degradable and environment-friendly; and the palladium chloride serving as the catalyst has low price and small dosage, can be recycled, meets the green chemistry requirements, and has excellent industrial application prospect.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate to a kind of preparation method of aryl ethylene derivative.
Background technology
The aryl ethylene derivative as the important organic synthesis intermediate of a class, has important purposes in synthesizing of medicine, weedicide, natural product and advanced material.By the catalytic Heck cross-coupling reaction that occurs between halogenated aryl hydrocarbon and the olefin(e) compound of palladium, be the method that generates a kind of important of aryl ethylene derivative and use more.At present, the synthetic method of relevant polyaryl ethene derivatives report is a lot.Yet, in these methods great majority reactions be with the part of the phosphorus of palladium or nitrogen as catalyzer (
J. Org. Chem. 1999,64, and 10; Org. Lett.2003,5,983;
Adv. Synth. Catal.2007,349,2595;
J. Organomet. Chem.2001,622,89), these parts have toxicity and price comparison costliness usually.2003, Qingwei Yao etc. reported the catalytic Heck of a kind of palladium reaction (
J. Org. Chem.2003,68,7528), this reaction adopts ligand-free palladium to make catalyzer, and the reaction yield height but be reflected at environment is not very carried out among close friend's the DMA, and the reaction times is longer.2007, Michael A. K. Vogel etc. reported equally the catalytic Heck of a kind of palladium at room temperature reaction (
Adv. Synth. Catal.2007,349,1019), the reaction conditions gentleness, however this reaction selects for use DMF to make solvent, and environment is unfriendly, and the reaction times is also grown (11-37 h).
As can be seen, though these method reaction conditions gentlenesses, yield is higher, but still has many problems: (1) reaction adopts the part palladium to make catalyzer, the reaction cost height; (2) long reaction time; (3) reaction solvent toxicity is bigger, and environment is unfriendly; (4) reaction system complexity.Therefore develop a kind of efficient, fast, the method for economy, eco-friendly synthesizing aryl ethene derivatives receives people's very big concern all the time.
Summary of the invention
The objective of the invention is at problems of the prior art, a kind of preparation method of aryl ethylene derivative with low cost, efficient, quick, eco-friendly is provided.
The preparation method of aryl ethylene derivative of the present invention, be to make solvent with PEG-400, as catalyzer, in the mol ratio complete reaction in the potassium alkaline environment with 1:1 ~ 1:3 of iodo aromatic hydrocarbons and olefin(e) compound under the focused microwave radiation, the hydrochloric acid that adds concentration again and be 1 ~ 2mol/L in reaction solution is acidified to pH=1 ~ 3 with Palladous chloride, use extracted with diethyl ether then, anhydrous magnesium sulfate drying filters, and concentrates, the employing silica gel column chromatography separates, and gets the aryl ethylene derivative.
Described iodo aromatic hydrocarbons is iodobenzene, iodo-benzoic acid, paraiodoanisole or paraiodoaniline.
Described olefin(e) compound is vinylformic acid, vinyl cyanide, vinylbenzene or butyl acrylate.
Described focused microwave radiating power is 8 ~ 10W, and focused microwave radiating temperature is 100 ~ 130 ℃, and the reaction times is 10 ~ 15 minutes.
The consumption of described catalyzer Palladous chloride is 1 ~ 5% of an iodo aromatic hydrocarbons molar weight.
The consumption of described salt of wormwood is 0.5 ~ 3 times of iodo aromatic hydrocarbons molar weight.
The present invention compared with prior art has the following advantages:
1, the present invention is a raw material with iodo aromatic hydrocarbons and olefin(e) compound, and it is cheap and easy to get; The reaction conditions gentleness, reaction process is simple, and synthetic cost is low.
2, the present invention adopts the focused microwave radiation to assist reaction, and complete with internal reaction at 10 ~ 15 minutes, speed of response is fast, the efficient height; Product yield height (up to 95%).
3, the present invention adopts avirulent PEG-400 to make solvent, and aftertreatment is simple; The solvent system non-toxic degradable, environmentally friendly.
4, catalyzer Palladous chloride price, consumption is few, and can be recycled, and satisfies the requirement of Green Chemistry, has better industrial application prospects.
Embodiment
Below by specific embodiment the preparation method of aryl ethylene derivative of the present invention is done detailed explanation.
Embodiment 1,The preparation of styracin
Successively Palladous chloride, iodobenzene, vinylformic acid and salt of wormwood being joined among the PEG-400, is that 10W, temperature are reaction 10 minutes under 120 ℃ the focused microwave radiation at power; Reaction process is followed the tracks of with thin layer chromatography.After reacting completely, the hcl acidifying that drips volumetric molar concentration and be 2mol/L in reaction solution is to pH=1; With extracted with diethyl ether four times, extraction liquid; Use anhydrous magnesium sulfate drying, filter; Filtrate with RE-52AA type Rotary Evaporators 45 ℃ after concentrating concentrated solution; The silica gel that adds 2 ~ 3 times of concentrated solution quality in concentrated solution is mixed sample again, to mix sample and put into chromatography column, the adding sherwood oil carries out wash-out with ethyl acetate (volume ratio of sherwood oil and ethyl acetate is 1:2) to be separated, collect elutriant, elutriant is put into Rotary Evaporators, concentrate at 45 ℃, promptly get styracin.
Iodobenzene and acrylic acid mol ratio are 1:1.2; The consumption of Palladous chloride is 1% of an iodobenzene molar weight; The consumption of salt of wormwood is 0.5 times of iodobenzene molar weight.Product yield is 95%.
Warp
1HNMR,
13CNMR, MS, IR detects, and its product is pure product.Its each performance index or characterization data are as follows:
1H NMR (400 MHz, CDCl
3): δ=12.13 (s, 1H), 7.82 (d,
J=16Hz, 1H), 7.56-7.54 (m, 2H), 7.43-7.39 (m, 3H), 6.47 (d,
J=16Hz, 1H);
13C NMR (100 MHz, CDCl
3): δ=172.75,147.12,133.99,130.75,128.95,128.36,117.30; EI-MS (m/z): 148 [M
+], 105,77; IR (υ/cm
-1): 1682,1628,1419,767,705.
Its structural formula is:
Embodiment 2,The preparation of 4-o-carboxy cinnamic acid
Successively Palladous chloride, 4-Iodobenzoic acid, vinylformic acid and salt of wormwood being joined among the PEG-400, is that 8W, temperature are reaction 12 minutes under 120 ℃ the focused microwave radiation at power; Reaction process is followed the tracks of with thin layer chromatography.After reacting completely, the hcl acidifying that drips volumetric molar concentration and be 2mol/L in reaction solution is to pH=1; With extracted with diethyl ether four times, extraction liquid; Use anhydrous magnesium sulfate drying, filter; Filtrate with RE-52AA type Rotary Evaporators 45 ℃ after concentrating concentrated solution; The silica gel that adds 2 ~ 3 times of concentrated solution quality in concentrated solution is mixed sample again, to mix sample and put into chromatography column, the adding sherwood oil carries out wash-out with ethyl acetate (volume ratio of sherwood oil and ethyl acetate is 1:1) to be separated, collect elutriant, elutriant is put into Rotary Evaporators, concentrate at 45 ℃, promptly get the 4-o-carboxy cinnamic acid.
4-Iodobenzoic acid and acrylic acid mol ratio are 1:1.2; The consumption of Palladous chloride is 1% of a 4-Iodobenzoic acid molar weight; The consumption of salt of wormwood is 2 times of 4-Iodobenzoic acid molar weight.Product yield is 92%.
Warp
1HNMR,
13CNMR, MS, IR detects, and its product is pure product.Its each performance index or characterization data are as follows:
1H NMR (400 MHz, DMSO-d
6): δ=12.82 (s, 2H), 7.95 (d,
J=8.4Hz, 2H), 7.84-7.79 (m, 2H), 7.69-7.65 (m, 1H), 6.66 (d,
J=16.4Hz);
13C NMR (100 MHz, DMSO-d
6): δ=167.30,166.83,142.65,138.36,131.83,129.74,128.30,121.59; EI-MS (m/z): 192 [M
+], 147,105,76; IR (υ/cm
-1): 1689,1631,1566,1510,1469,847.
Its structure is as follows:
Embodiment 3,The preparation of 4-methoxyl group cinnamyl nitrile
Successively Palladous chloride, paraiodoanisole, vinyl cyanide and salt of wormwood being joined among the PEG-400, is that 10W, temperature are reaction 12 minutes under 120 ℃ the focused microwave radiation at power; Reaction process is followed the tracks of with thin layer chromatography.After reacting completely, the hcl acidifying that drips volumetric molar concentration and be 1mol/L in reaction solution is to pH=3; With extracted with diethyl ether four times, extraction liquid; Use anhydrous magnesium sulfate drying, filter; Filtrate with RE-52AA type Rotary Evaporators 45 ℃ after concentrating concentrated solution; The silica gel that adds 2 ~ 3 times of concentrated solution quality in concentrated solution is mixed sample again, to mix sample and put into chromatography column, the adding sherwood oil carries out wash-out with ethyl acetate (volume ratio of sherwood oil and ethyl acetate is 30:1) to be separated, collect elutriant, elutriant is put into Rotary Evaporators, concentrate at 45 ℃, promptly get 4-methoxyl group cinnamyl nitrile.
The mol ratio of paraiodoanisole and vinyl cyanide is 1:3; The consumption of Palladous chloride is 1% of a paraiodoanisole molar weight; The consumption of salt of wormwood is 2 times of paraiodoanisole molar weight.Product yield is 81%.
Warp
1HNMR,
13CNMR, MS, IR detects, and its product is pure product.Its each performance index or characterization data are as follows:
1H NMR (400 MHz, CDCl
3): δ=7.40-7.35 (m, 3H), 6.92-6.90 (m, 2H), 5.73 (d,
J=16.4Hz, 1H), 3.84 (s, 3H);
13C NMR (100 MHz, CDCl
3): δ=161.97,149.98,129.03,126.26,118.68,114.44,93.26,55.39; EI-MS (m/z): 159 [M
+], 133,128,77; IR (υ/cm
-1): 2213,1602,1510,844.
Its structure is as follows:
Embodiment 4,The preparation of 4-amino-stilbene
Successively Palladous chloride, paraiodoaniline, vinylbenzene and salt of wormwood being joined among the PEG-400, is that 10W, temperature are reaction 12 minutes under 120 ℃ the focused microwave radiation at power; Reaction process is followed the tracks of with thin layer chromatography.After reacting completely, the hcl acidifying that drips volumetric molar concentration and be 1mol/L in reaction solution is to pH=3; With extracted with diethyl ether four times, extraction liquid; Use anhydrous magnesium sulfate drying, filter; Filtrate with RE-52AA type Rotary Evaporators 45 ℃ after concentrating concentrated solution; The silica gel that adds 2 ~ 3 times of concentrated solution quality in concentrated solution is mixed sample again, to mix sample and put into chromatography column, the adding sherwood oil carries out wash-out with ethyl acetate (volume ratio of sherwood oil and ethyl acetate is 15:1) to be separated, collect elutriant, elutriant is put into Rotary Evaporators, concentrate at 45 ℃, promptly get the 4-amino-stilbene.
Paraiodoaniline and cinnamic mol ratio are 1:1.5; The consumption of Palladous chloride is 5% of a paraiodoaniline molar weight; The consumption of salt of wormwood is 2 times of paraiodoaniline molar weight.Product yield is 85%.
Warp
1HNMR,
13CNMR, MS, IR detects, and its product is pure product.Its each performance index or characterization data are as follows:
1H NMR (400 MHz, CDCl
3): δ=7.47 (m, 2H), 7.34-7.30 (m, 4H), 7.24-7.18 (m, 1H), 7.04-6.89 (m, 2H), 6.68-6.65 (m, 2H), 3.72 (s, 2H);
13C NMR (100 MHz, CDCl
3): δ=146.10,137.89,128.62,128.56,127.95,127.71,126.85,126.05,125.04,115.15; EI-MS (m/z): 196, [M
++ 1], 195 [M
+], 180,165,152,96,77; IR (υ/cm
-1): 3444,3361,1614,1590,1514,1446,817,752,688.
Its structural formula is as follows:
Embodiment 5,The preparation of toluylene
Successively Palladous chloride, iodobenzene, vinylbenzene and salt of wormwood being joined among the PEG-400, is that 10W, temperature are reaction 12 minutes under 120 ℃ the focused microwave radiation at power; Reaction process is followed the tracks of with thin layer chromatography.After reacting completely, the hcl acidifying that drips volumetric molar concentration and be 1mol/L in reaction solution is to pH=2; With extracted with diethyl ether four times, extraction liquid; Use anhydrous magnesium sulfate drying, filter; Filtrate with RE-52AA type Rotary Evaporators 45 ℃ after concentrating concentrated solution; The silica gel that adds 2 ~ 3 times of concentrated solution quality in concentrated solution is mixed sample again, to mix sample and put into chromatography column, the adding sherwood oil carries out wash-out with ethyl acetate (volume ratio of sherwood oil and ethyl acetate is 30:1) to be separated, collect elutriant, elutriant is put into Rotary Evaporators, concentrate at 45 ℃, promptly get toluylene.
Iodobenzene and cinnamic mol ratio are 1:1.5; The consumption of Palladous chloride is 2% of an iodobenzene molar weight; The consumption of salt of wormwood is 3 times of iodobenzene molar weight.Product yield is 78%.
Warp
1HNMR,
13CNMR, MS, IR detects, and its product is pure product.Its each performance index or characterization data are as follows:
1H NMR (400 MHz, CDCl
3): δ=7.53-7.50 (m, 4H), 7.38-7.34 (m, 4H), 7.28-7.24 (m, 2H), 7.11 (s, 2H);
13C NMR (100 MHz, CDCl
3): δ=137.29,128.67,127.61,126.49; EI-MS (m/z): 180 [M
+], 165,152,102,89,76,63,51,39; IR (υ/cm
-1): 1492,1449,763,690.
Its structure is as follows:
Embodiment 6,The preparation of the positive butyl ester of styracin
Successively Palladous chloride, iodobenzene, butyl acrylate and salt of wormwood being joined among the PEG-400, is that 10W, temperature are reaction 15 minutes under 100 ℃ the focused microwave radiation at power; Reaction process is followed the tracks of with thin layer chromatography.After reacting completely, the hcl acidifying that drips volumetric molar concentration and be 2mol/L in reaction solution is to pH=3; With extracted with diethyl ether four times, extraction liquid; Use anhydrous magnesium sulfate drying, filter; Filtrate with RE-52AA type Rotary Evaporators 45 ℃ after concentrating concentrated solution; The silica gel that adds 2 ~ 3 times of concentrated solution quality in concentrated solution is mixed sample again, to mix sample and put into chromatography column, the adding sherwood oil carries out wash-out with ethyl acetate (volume ratio of sherwood oil and ethyl acetate is 20:1) to be separated, collect elutriant, elutriant is put into Rotary Evaporators, concentrate at 45 ℃, promptly get the positive butyl ester of styracin.
The mol ratio of iodobenzene and butyl acrylate is 1:1.5; The consumption of Palladous chloride is 1% of an iodobenzene molar weight; The consumption of salt of wormwood is 2 times of iodobenzene molar weight.Product yield is 71%.
Warp
1HNMR,
13CNMR, MS, IR detects, and its product is pure product.Its each performance index or characterization data are as follows:
1H NMR (400 MHz, CDCl3): δ=7.70 (d,
J=15.6Hz, 1H), 7.53-7.50 (m, 2H), 7.38-7.35 (m, 3H), 6.46 (d,
J=16Hz, 1H), 4.22 (t,
J=6.4Hz, 2H), 1.72-1.65 (m, 2H), 1.48-1.39 (m, 2H), 0.98 (t,
J=7.2Hz, 3H);
13C NMR (100 MHz, CDCl
3): δ=167.14,144.49,134.40,130.14,128.80,127.99,118.22,64.37,30.71,19.15,13.70; EI-MS (m/z): 204 [M
+], 131,103,77; IR (υ/cm
-1): 1713,1637,1578,1495,1451,767,709.
Its structural formula is as follows:
Embodiment 7,The preparation of 4-methoxy cinnamic acid
Successively Palladous chloride, paraiodoanisole, vinylformic acid and salt of wormwood being joined among the PEG-400, is that 12W, temperature are reaction 10 minutes under 130 ℃ the focused microwave radiation at power; Reaction process is followed the tracks of with thin layer chromatography.After reacting completely, the hcl acidifying that drips volumetric molar concentration and be 2mol/L in reaction solution is to pH=1; With extracted with diethyl ether four times, extraction liquid; Use anhydrous magnesium sulfate drying, filter; Filtrate with RE-52AA type Rotary Evaporators 45 ℃ after concentrating concentrated solution; The silica gel that adds 2 ~ 3 times of concentrated solution quality in concentrated solution is mixed sample again, to mix sample and put into chromatography column, the adding sherwood oil carries out wash-out with ethyl acetate (volume ratio of sherwood oil and ethyl acetate is 1:2) to be separated, collect elutriant, elutriant is put into Rotary Evaporators, concentrate at 45 ℃, promptly get the 4-methoxy cinnamic acid.
Paraiodoanisole and acrylic acid mol ratio are 1:1.5; The consumption of Palladous chloride is 1% of a paraiodoanisole molar weight; The consumption of salt of wormwood is 2 times of paraiodoanisole molar weight.Product yield is 87%.
Warp
1HNMR,
13CNMR, MS, IR detects, and its product is pure product.Its each performance index or characterization data are as follows:
1H NMR (400 MHz, DMSO-d
6): δ=11.58 (s, 1H), 7.73 (d,
J=14Hz, 1H), 7.51 (s, 2H), 6.93 (s, 2H), 6.30 (d,
J=15.2,1H), 3.85 (s, 3H);
13C NMR (100 MHz, DMSO-d
6): δ=167.82,160.93,143.74,129.94,126.81,116.47,114.33,55.29; EI-MS (m/z): 178 [M
+], 147,133,105,76; IR (υ/cm
-1): 1683,1623,1597,1510,1429,826.
Its structure is as follows:
Claims (8)
1. the preparation method of an aryl ethylene derivative, be to make solvent with PEG-400, with Palladous chloride as catalyzer, under the focused microwave radiation, iodo aromatic hydrocarbons and olefin(e) compound are with mol ratio complete reaction in the potassium alkaline environment of 1:1 ~ 1:3, in reaction solution, add hydrochloric acid again and be acidified to pH=1 ~ 3, use extracted with diethyl ether, anhydrous magnesium sulfate drying then, filter, concentrate, separate, get the aryl ethylene derivative.
2. the preparation method of aryl ethylene derivative according to claim 1, it is characterized in that: described iodo aromatic hydrocarbons is iodobenzene, iodo-benzoic acid, paraiodoanisole or paraiodoaniline.
3. the preparation method of aryl ethylene derivative according to claim 1, it is characterized in that: described olefin(e) compound is vinylformic acid, vinyl cyanide, vinylbenzene or butyl acrylate.
4. the preparation method of aryl ethylene derivative according to claim 1, it is characterized in that: described focused microwave radiating power is 8 ~ 12W, and focused microwave radiating temperature is 100 ~ 130 ℃, and the reaction times is 10 ~ 15 minutes.
5. the preparation method of aryl ethylene derivative according to claim 1, it is characterized in that: the consumption of described catalyzer Palladous chloride is 1 ~ 5% of an iodo aromatic hydrocarbons molar weight.
6. the preparation method of aryl ethylene derivative according to claim 1, it is characterized in that: the consumption of described salt of wormwood is 0.5 ~ 3 times of iodo aromatic hydrocarbons molar weight.
7. the preparation method of aryl ethylene derivative according to claim 1, it is characterized in that: the concentration of described hydrochloric acid is 1 ~ 2mol/L.
8. the preparation method of aryl ethylene derivative according to claim 1, it is characterized in that: described separation adopts silica gel column chromatography to separate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105677443A CN102010279A (en) | 2010-12-01 | 2010-12-01 | Method for preparing vinylaromatic derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105677443A CN102010279A (en) | 2010-12-01 | 2010-12-01 | Method for preparing vinylaromatic derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102010279A true CN102010279A (en) | 2011-04-13 |
Family
ID=43840637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105677443A Pending CN102010279A (en) | 2010-12-01 | 2010-12-01 | Method for preparing vinylaromatic derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102010279A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746124A (en) * | 2012-07-24 | 2012-10-24 | 苏州大学 | Method for preparing substituted alkene |
| CN102746076A (en) * | 2012-07-24 | 2012-10-24 | 苏州大学 | Preparation method of substituted alkene |
| CN104058952A (en) * | 2014-06-09 | 2014-09-24 | 青岛东方循环能源有限公司 | Preparation method of cinnamic acid |
-
2010
- 2010-12-01 CN CN2010105677443A patent/CN102010279A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| VALERIE DECLERK ET AL.: "Microwave-assisted copper-catalyzed heck reaction in PEG solvent", 《SYNLETT.》 * |
| WEI HAN ET AL.: "A ligand-free Heck reaction catalyzed by the in situ-generated palladium nanoparticles in PEG-400", 《CHINESE CHEMICAL LETTERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746124A (en) * | 2012-07-24 | 2012-10-24 | 苏州大学 | Method for preparing substituted alkene |
| CN102746076A (en) * | 2012-07-24 | 2012-10-24 | 苏州大学 | Preparation method of substituted alkene |
| CN102746076B (en) * | 2012-07-24 | 2015-02-11 | 苏州大学 | Preparation method of substituted alkene |
| CN104058952A (en) * | 2014-06-09 | 2014-09-24 | 青岛东方循环能源有限公司 | Preparation method of cinnamic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10011557B2 (en) | Method for producing biphenylamines from azobenzenes by ruthenium catalysis | |
| CN103664769B (en) | Synthesis method of dipyridyl derivative or analogue | |
| CN114805068B (en) | Preparation method of chiral alpha-hydroxy-beta-keto ester compound | |
| CN102010280B (en) | Preparation method of biaryl compound | |
| CN102351691B (en) | Method for synthesizing adipic acid monoethyl ester | |
| CN102010279A (en) | Method for preparing vinylaromatic derivatives | |
| CN102060701B (en) | Method for synthesizing beta-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate | |
| CN102050705B (en) | Novel method for preparing resveratrol through decarbonylation heck reaction | |
| CN103193608A (en) | Method for preparing dimethoxy benzaldehyde from veratrole | |
| CN108218699B (en) | Method for synthesizing 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester by catalysis of acidic ionic liquid | |
| CN108997299A (en) | A kind of organic room temperature phosphorimetry material of efficient and long life and preparation method thereof | |
| CN103172639B (en) | A kind of preparation method of the hexa-atomic two ring guanidines based on Guanidinium hydrochloride | |
| CN102702143A (en) | Method for preparing 2-acetylfuran | |
| CN101781222A (en) | Method for preparing enamine ketone compound | |
| CN104592104A (en) | Method for preparing 2-chloronicotinic acid | |
| Oh et al. | Double suzuki reactions of organoboronic acids with 1, n-dibromides | |
| CN102702175B (en) | Preparation method of indole-3-succinimide | |
| CN105541786B (en) | A kind of Montelukast side-chain intermediate and preparation method thereof | |
| CN105237340B (en) | Novel synthesis method for 4,4,4-trifluorobutanol | |
| CN109438402B (en) | Benzofuranone derivatives and synthesis method thereof | |
| CN107353245A (en) | A kind of synthetic method of quinolines | |
| CN109651344B (en) | Benzofuran triarylmethane compounds and green catalytic synthesis method thereof | |
| CN113336667A (en) | Method suitable for industrial production of intermediate of roxasistat | |
| CN108409672B (en) | Method for synthesizing polysubstituted pyrimidine under catalysis of copper salt | |
| CN115028641B (en) | Method for synthesizing 5, 8-difunctional substituted imidazo [1,2-a ] pyrazine compound by cobalt catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110413 |