CN102531814A - Preparation method for trans-cinnamic acid compound in water insoluble ionic liquid [bmim] PF6 - Google Patents
Preparation method for trans-cinnamic acid compound in water insoluble ionic liquid [bmim] PF6 Download PDFInfo
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- CN102531814A CN102531814A CN2011104353795A CN201110435379A CN102531814A CN 102531814 A CN102531814 A CN 102531814A CN 2011104353795 A CN2011104353795 A CN 2011104353795A CN 201110435379 A CN201110435379 A CN 201110435379A CN 102531814 A CN102531814 A CN 102531814A
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- cinnamic acid
- ionic liquid
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- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 30
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 title claims abstract description 20
- -1 trans-cinnamic acid compound Chemical class 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 9
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical class OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical class C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 34
- 150000003053 piperidines Chemical class 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 9
- 150000001851 cinnamic acid derivatives Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 235000013599 spices Nutrition 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000001246 bromo group Chemical group Br* 0.000 abstract description 2
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 abstract 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 229930016911 cinnamic acid Natural products 0.000 abstract 1
- 235000013985 cinnamic acid Nutrition 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 230000007935 neutral effect Effects 0.000 description 10
- 239000007790 solid phase Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- WMPDAIZRQDCGFH-UHFFFAOYSA-N 3-methoxybenzaldehyde Chemical compound COC1=CC=CC(C=O)=C1 WMPDAIZRQDCGFH-UHFFFAOYSA-N 0.000 description 8
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 8
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 description 4
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 4
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 4
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 4
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 4
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 4
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 description 4
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 description 3
- 238000010765 Doebner reaction Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- NQBWNECTZUOWID-QSYVVUFSSA-N cinnamyl cinnamate Chemical compound C=1C=CC=CC=1\C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-QSYVVUFSSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 238000003512 Claisen condensation reaction Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 238000003684 Perkin reaction Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 230000000118 anti-neoplastic effect Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000590 parasiticidal effect Effects 0.000 description 1
- 239000002297 parasiticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UZVNCLCLJHPHIF-NOJKMYKQSA-J zinc;(1e)-2-(ethylcarbamoylamino)-n-methoxy-2-oxoethanimidoyl cyanide;manganese(2+);n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[Zn+2].[S-]C(=S)NCCNC([S-])=S.[S-]C(=S)NCCNC([S-])=S.CCNC(=O)NC(=O)C(\C#N)=N\OC UZVNCLCLJHPHIF-NOJKMYKQSA-J 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic chemical industrial raw material preparation and particularly relates to a preparation method for trans-cinnamic acid compound (trans-3-arylpropaoicacid) in water insoluble ionic liquid [bmim] PF6. A series of trans-cinnamic acid compounds (trans-3-arylpropaoicacid) are prepared by using aromatic aldehyde and malonic acid as raw materials, adding a catalytic amount of piperidine and heating to react for 4 to 8 hours at the temperature of 80 to 90 DEG C in high yield mode. Products can be separated from an ionic liquid reacting system by extraction through alkaline solution. The ionic liquid can be recycled after recovery and dehydration processing, and yield is not remarkably reduced. The cinnamic acid compound prepared through the method has important application value in widely used fields of fine chemical engineering production fields of organic synthesis, biomedicine, medicine and pesticide, spice, photosensitive resin and the like. The compound can synthesize beta-arylvinyl bromide through decarboxylation bromo, is a valuable synthesis building block in organic chemistry, and has important application prospects in metal catalysis coupling reactions.
Description
Technical field
The invention belongs to the Organic Chemicals preparing technical field, be specifically related to a kind of water-insoluble ionic liquid [bmim] PF
6The preparation method of middle trans-cinnamic acid compound (anti--the 3-aromatic substituted acrylic acid).
Background technology
The trans-cinnamic acid compound of the inventive method preparation is a kind of important organic unsaturated acid compounds.At nature, styracin is metabolism building block important in plant lignin's building-up process.Cinnamic acid derivative has broad-spectrum antimicrobial, antimycotic and parasiticide is active.Many kinds of cinnamic acid derivatives have become treatment hypertension and antineoplastic important drugs.
1,2The research of cinnamic acid derivative receives much concern, not only because of its potential physiologically active that has, also because its important application in the Polymer Synthesizing field.With the trans-cinnamic acid is the many macromolecular compounds of building block synthetic, has special spectrochemical property.
3In the organic synthesis field, the trans-cinnamic acid verivate be used for synthetic various have stereospecificity (
Z)-configuration
4-15Or (
E)-configuration
16-23B-halo aromatic ethylene compound, become the important important intermediate of metal catalyzed coupling reaction.Owing to have wide practical use at fine chemical product production fields such as organic synthesis, biomedicine, medicine and agricultural chemicals, spices and photosensitive resins, synthesizing of trans-cinnamic acid realized mass-producing.
At present, the synthesis of trans styracin of classics and the main method of verivate thereof have the Perkin reaction method
24-26, Claisen condensation reaction method
27, the Knoevenagel-Doebner reaction method
28With the Heck reaction method
29-31Deng.Wherein the Knoevenagel-Doebner reaction method is one of effective means.Traditional Knoevenagel-Doebner reaction method need a large amount of use toxic and the pyridine that the smell is awful as solvent, and can consume a large amount of hydrochloric acid again in acidifying with when separating out product, the pyridinium salt that gives off also can pollute environment.
Ionic liquid is low, the recyclable green solvent that recycles of a kind of stable in properties, volatility.
32The inventive method is with water-insoluble ionic liquid [bmim] PF
6Be solvent, piperidines is a catalyzer, preparation trans-cinnamic acid and verivate thereof, and product is with the alkaline aqueous solution extracting and separating, and is easy and simple to handle, ionic liquid [bmim] PF
6, drying under reduced pressure recycles after handling.
Reference
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Summary of the invention
The object of the invention is to provide a kind of water-insoluble ionic liquid [bmim] PF
6The preparation method of middle trans-cinnamic acid compound (anti--the 3-aromatic substituted acrylic acid).
The final product that the present invention obtains is trans-cinnamic acid compound (anti--the 3-aromatic substituted acrylic acid).Its preparation route is following:
Water-insoluble ionic liquid [bmim] PF that the present invention proposes
6The preparation method of middle trans-cinnamic acid compound (anti--the 3-aromatic substituted acrylic acid), preparation process is following:
With aromatic aldehyde
1, propanedioic acid and [bmim] PF
6Join in the 50 mL round-bottomed flasks, stir adding piperidines down.Oil bath is heated to 80 ~ 90 ℃ of reaction 4 ~ 8 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times.Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid product and filter, be washed to neutrality, filter, drying under reduced pressure obtains white solid.Wherein, and the adjustable molar ratio of propanedioic acid and aromatic aldehyde (mmol: mmol) scope is 1.5-3: 1, and (mmol: mmol) scope is 0.1 ~ 0.3: 1 to the adjustable proportion of piperidines and aromatic aldehyde, ionic liquid [bmim] PF
6(mL: mmol) scope is 3 ~ 10: 1, and the TR of reaction is 80 ~ 90 ℃, reaction time range 4 ~ 8 h with the adjustable proportion of aromatic aldehyde.Among the present invention, said aromatic aldehyde comprises three kinds of situation such as ortho position, a position and para-orientation of phenyl ring; Substituent kind had both comprised electron-donating groups such as methyl, methoxyl group and hydroxyl, also comprised electron-withdrawing groups such as chlorine and bromine etc.
Present method prepares the trans-cinnamic acid compounds, in fine chemical product production fields such as macromolecular material, organic synthesis, biomedicine, medicine and agricultural chemicals, spices and photosensitive resin field such as be widely used crucial application prospect is arranged; This compounds can synthesize Beta-bromo aromatic ethylene compound through the decarboxylation bromo, is valuable synthetic " building block " in the organic chemistry, in metal catalyzed coupling reaction, has significant application value.
The inventive method is with water-insoluble ionic liquid [bmim] PF
6Be solvent, piperidines is a catalyzer, preparation styracin and verivate thereof, and product is with the alkaline aqueous solution extracting and separating, and is easy and simple to handle, ionic liquid [bmim] PF
6, drying under reduced pressure recycles after handling.This method has advantages such as raw material is easy to get, easy and simple to handle, reaction conditions gentleness; Product separation and purification step are easy, have avoided the use of organic solvent, have the effect of environmental emission reduction.
Embodiment
Followingly further specify the present invention, but can not limit content of the present invention through embodiment.
Embodiment 1: the preparation of anti--4-tolyl acrylic acid
The preparation method:
With the 4-tolyl aldehyde
1a(1 mmol), propanedioic acid (3 mmol) and [bmim] PF
6(10 mL) joins in the 50 mL round-bottomed flasks, stirs to add piperidines (0.3 mmol) down.Oil bath is heated to 85 ℃ of reaction 6 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times (10 * 3 mL).Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid phase prod and filter, washing is filtered to neutral, drying under reduced pressure obtains white solid anti--4-tolyl acrylic acid
2aWherein, the molar ratio of propanedioic acid and 4-tolyl aldehyde (mmol: mmol) be 3: 1, the molar ratio of piperidines and 4-tolyl aldehyde (mmol: mmol) be 0.3: 1, ionic liquid [bmim] PF
6Ratio (mL: mmol) be 10: 1 with the 4-tolyl aldehyde.
(E)-3-p-tolylacrylic?acid
2a. Mp:?198.1-200.1?
oC?(lit.?196-198
?oC).?IR?(KBr):?2920,?2594?(br),?1686,?1632,?1568,?1515,?1421,?1311,?1286,?937,?813?cm
-1.?
1H?NMR?(400?MHz,?DMSO-d
6):?δ?2.33?(3H,?s),?6.46?(1H,?d,?J?=?16.0?Hz),?7.23?(2H,?d,?J?=?7.6?Hz),?7.55?(1H,?d,?J?=?16.0?Hz),?7.57?(2H,?d,?J?=?7.6?Hz),?12.29?(1H,?s).
Embodiment 2: the preparation of anti--3-tolyl acrylic acid
The preparation method:
With the 3-tolyl aldehyde
1b(1 mmol), propanedioic acid (2 mmol) and [bmim] PF
6(5 mL) joins in the 50 mL round-bottomed flasks, stirs to add piperidines (0.2 mmol) down.Oil bath is heated to 80 ℃ of reaction 8 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times (10 * 3 mL).Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid phase prod and filter, washing is filtered to neutral, drying under reduced pressure obtains white solid anti--3-tolyl acrylic acid
2bWherein, the molar ratio of propanedioic acid and 3-tolyl aldehyde (mmol: mmol) be 2: 1, the molar ratio of piperidines and 3-tolyl aldehyde (mmol: mmol) be 0.2: 1, ionic liquid [bmim] PF
6Ratio (mL: mmol) be 5: 1 with the 3-tolyl aldehyde.
(E)-3-m-tolylacrylic?acid
2b.? Mp:?116.1-117.5?
oC?(lit.?116
?oC).?IR?(KBr):?2917,?2560?(br),?1682,?1633,?1430,?1324,?1247,?944,?787?cm
-1.?
1H?NMR?(400?MHz,?DMSO-d
6):?δ?2.33?(3H,?s),?6.50?(1H,?d,?J?=?16.0?Hz),?7.23?(1H,?d,?J?=?7.6?Hz),?7.30?(1H,?t,?J?=?7.0?Hz),?7.46?(1H,?d,?J?=?7.6?Hz),?7.50?(1H,?s),?7.55?(1H,?d,?J?=?16.0?Hz),?12.?35?(1H,?s).
Embodiment 3: the preparation of anti--4-methoxy cinnamic acid
The preparation method:
With the 4-methoxybenzaldehyde
1c(1 mmol), propanedioic acid (1.5 mmol) and [bmim] PF
6(3 mL) joins in the 50 mL round-bottomed flasks, stirs to add piperidines (0.1 mmol) down.Oil bath is heated to 90 ℃ of reaction 4 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times (10 * 3 mL).Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid phase prod and filter, washing is filtered to neutral, drying under reduced pressure obtains white solid anti--4-methoxy cinnamic acid
2cWherein, the molar ratio of propanedioic acid and 4-methoxybenzaldehyde (mmol: mmol) be 1.5: 1, the molar ratio of piperidines and 4-methoxybenzaldehyde (mmol: mmol) be 0.1: 1, ionic liquid [bmim] PF
6Ratio (mL: mmol) be 3: 1 with the 4-methoxybenzaldehyde.
(E)-3-(4-methoxyphenyl)acrylic?acid
2c.? Mp:?172.2-172.9?
oC?(lit.?173.5
?oC).?IR?(KBr):?2939,?2844?(br),?1686,?1624,?1598,?1514,?1257,?1217,?1174,?1027,?826?cm
-1.?
1H?NMR?(400?MHz,?DMSO-d
6):?δ?3.80?(3H,?s),?6.37?(1H,?d,?J?=?16.0?Hz),?6.97?(2H,?d,?J?=?8.8?Hz),?7.54?(1H,?d,?J?=?16.0?Hz),?7.64?(2H,?d,?J?=?8.8?Hz),?12.19?(1H,?s).
Embodiment 4: the preparation of anti--3-methoxy cinnamic acid
The preparation method:
With the 3-methoxybenzaldehyde
1d(1 mmol), propanedioic acid (312 mg, 2 mmol) and [bmim] PF
6(5 mL) joins in the 50 mL round-bottomed flasks, stirs to add piperidines (0.2 mmol) down.Oil bath is heated to 85 ℃ of reaction 4 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times (10 * 3 mL).Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid phase prod and filter, washing is filtered to neutral, drying under reduced pressure obtains white solid anti--3-methoxy cinnamic acid
2dWherein, the molar ratio of propanedioic acid and 3-methoxybenzaldehyde (mmol: mmol) be 2: 1, the molar ratio of piperidines and 3-methoxybenzaldehyde (mmol: mmol) be 0.2: 1, ionic liquid [bmim] PF
6Ratio (mL: mmol) be 5: 1 with the 3-methoxybenzaldehyde.
(E)-3-(3-methoxyphenyl)acrylic?acid
2d.? Mp:?117.0-119.2?
oC?(lit.?116-119
?oC).?IR?(KBr):?2965,?2840?(br),?1682,?1632,?1607,?1578,?1489,?1456,?1280,?1050,?945,?781?cm
-1.?
1H?NMR?(400?MHz,?DMSO-d
6):?δ?3.79?(3H,?s),?6.55?(1H,?d,?J?=?16.0?Hz),?6.98?(1H,?dd,?J?=?8.4,?6.0?Hz),?7.23-7.35?(3H,?m),?7.56?(1H,?d,?J?=?16.0?Hz),?12.37?(1H,?s).
Embodiment 5: the preparation of anti--4-hydroxycinnamic acid
The preparation method:
With the 4-hydroxy benzaldehyde
1e(1 mmol), propanedioic acid (2.5 mmol) and [bmim] PF
6(8 mL) joins in the 50 mL round-bottomed flasks, stirs to add piperidines (0.3 mmol) down.Oil bath is heated to 85 ℃ of reaction 6 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times (10 * 3 mL).Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid phase prod and filter, washing is filtered to neutral, drying under reduced pressure obtains white solid anti--4-hydroxycinnamic acid.Wherein, the molar ratio of propanedioic acid and 4-hydroxy benzaldehyde (mmol: mmol) be 2.5: 1, the molar ratio of piperidines and 4-hydroxy benzaldehyde (mmol: mmol) be 0.3: 1, ionic liquid [bmim] PF
6Ratio (mL: mmol) be 8: 1 with the 4-hydroxy benzaldehyde.
(E)-3-(4-hydroxyphenyl)acrylic?acid
2e.? Mp:?209.2-209.8?
oC?(lit.?210-213
?oC).?IR?(KBr):?3384,?2961,?2837?(br),?1672,?1628,?1602,?1590,?1512,?1450,?1245,?1214,?1173,?979,?834?cm
-1.?
1H?NMR?(400?MHz,?DMSO-d
6):?δ?6.29?(1H,?d,?J?=?16.0?Hz),?6.79?(2H,?d,?J?=?8.8?Hz),?7.50?(1H,?d,?J?=?16.0?Hz),?7.51?(2H,?d,?J?=?8.4?Hz)?,?9.95?(1H,?s),?12.11?(1H,?s).
Embodiment 6: the preparation of anti--4-chloro-cinnamic acid
The preparation method:
With the 4-chlorobenzaldehyde
1f(1 mmol), propanedioic acid (2 mmol) and [bmim] PF
6(5 mL) joins in the 50 mL round-bottomed flasks, stirs to add piperidines (0.2 mmol) down.Oil bath is heated to 90 ℃ of reaction 4 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times (10 * 3 mL).Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid phase prod and filter, washing is filtered to neutral, drying under reduced pressure obtains white solid anti--4-chloro-cinnamic acid
2fWherein, the molar ratio of propanedioic acid and 4-chlorobenzaldehyde (mmol: mmol) be 2: 1, the molar ratio of piperidines and 4-chlorobenzaldehyde (mmol: mmol) be 0.2: 1, ionic liquid [bmim] PF
6Ratio (mL: mmol) be 5: 1 with the 4-chlorobenzaldehyde.
(E)-3-(4-chlorophenyl)acrylic?acid
2f.? Mp:?248.5-249.1?
oC?(lit.?248-250
?oC).?IR?(KBr):?2968?(br),?1684,?1626,?1591,?1569,?1490,?1427,?1305,?1284,?1085,?821,?715?cm
-1.?
1H?NMR?(400?MHz,?DMSO-d
6):?δ?6.55?(1H,?d,?J?=?15.6?Hz),?7.48?(2H,?d,?J?=?8.4?Hz),?7.58?(1H,?d,?J?=?16.0?Hz),?7.73?(2H,?d,?J?=?8.4?Hz),?12.41?(1H,?s).
Embodiment 7: the preparation of anti--4-bromo-cinnamic acid
The preparation method:
With the 4-bromobenzaldehyde
1g(1 mmol), propanedioic acid (2 mmol) and [bmim] PF
6(5 mL) joins in the 50 mL round-bottomed flasks, stirs to add piperidines (0.2 mmol) down.Oil bath is heated to 85 ℃ of reaction 8 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times (10 * 3 mL).Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid phase prod and filter, washing is filtered to neutral, drying under reduced pressure obtains white solid anti--4-bromo-cinnamic acid
2gWherein, the molar ratio of propanedioic acid and 4-bromobenzaldehyde (mmol: mmol) be 2: 1, the molar ratio of piperidines and 4-bromobenzaldehyde (mmol: mmol) be 0.2: 1, ionic liquid [bmim] PF
6Ratio (mL: mmol) be 5: 1 with the 4-bromobenzaldehyde.
(E)-3-(4-bromophenyl)acrylic?acid?
2g.? Mp:?260.2-261.9?
oC?(lit.?260-265
?oC).?IR?(KBr):?2927,?2830?(br),?1683,?1626,?1586,?1488,?1425,?1305,?1284,?1070,?817?cm
-1.?
1H?NMR?(400?MHz,?DMSO-d
6):?δ?6.57?(1H,?d,?J?=?16.0?Hz),?7.57?(1H,?d,?J?=?16.0?Hz),?7.61?(2H,?d,?J?=?8.4?Hz),?7.66?(2H,?d,?J?=?8.4?Hz),?12.43?(1H,?s).
Embodiment 8: the preparation of anti--2-chloro-cinnamic acid
The preparation method:
With the 2-chlorobenzaldehyde
1a(1 mmol), propanedioic acid (2 mmol) and [bmim] PF
6(5 mL) joins in the 50 mL round-bottomed flasks, stirs to add piperidines (0.2 mmol) down.Oil bath is heated to 85 ℃ of reaction 8 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times (10 * 3 mL).Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid phase prod and filter, washing is filtered to neutral, drying under reduced pressure obtains white solid anti--2-chloro-cinnamic acid.Wherein, the molar ratio of propanedioic acid and 2-chlorobenzaldehyde (mmol: mmol) be 2: 1, the molar ratio of piperidines and 2-chlorobenzaldehyde (mmol: mmol) be 0.2: 1, ionic liquid [bmim] PF
6Ratio (mL: mmol) be 5: 1 with the 2-chlorobenzaldehyde.
(E)-3-(2-chlorophenyl)acrylic?acid?
2h.? Mp:?208.5-209.8?
oC?(lit.?208-210
?oC).?IR?(KBr):?2836?(br),?1686,?1622,?1590,?1566,?1470,?1441,?1278,?984,?755?cm
-1.?
1H?NMR?(400?MHz,?DMSO-d
6):?δ?6.61?(1H,?d,?J?=?16.0?Hz),?7.38-7.46?(2H,?m),?7.54?(1H,?d,?J?=?8.0?Hz),?7.88?(1H,?d,?J?=?16.0?Hz),?7.92?(1H,?d,?J?=?6.8?Hz),?12.61?(1H,?s).
Embodiment 9: the preparation of anti--2-bromo-cinnamic acid
The preparation method:
With the 2-bromobenzaldehyde
1a(1 mmol), propanedioic acid (2 mmol) and [bmim] PF
6(5 mL) joins in the 50 mL round-bottomed flasks, stirs to add piperidines (0.2 mmol) down.Oil bath is heated to 87 ℃ of reaction 8 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times (10 * 3 mL).Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid phase prod and filter, washing is filtered to neutral, drying under reduced pressure obtains white solid anti--2-bromo-cinnamic acid.Wherein, the molar ratio of propanedioic acid and 2-bromobenzaldehyde (mmol: mmol) be 2: 1, the molar ratio of piperidines and 2-bromobenzaldehyde (mmol: mmol) be 0.2: 1, ionic liquid [bmim] PF
6Ratio (mL: mmol) be 5: 1 with the 2-bromobenzaldehyde.
(E)-3-(2-bromophenyl)acrylic?acid?
2i.? Mp:?217.1-218.3?
oC?(lit.?217-219
?oC).?IR?(KBr):?2831?(br),?1686,?1622,?1562,?1466,?1275,?1223,?983,?755?cm
-1.?
1H?NMR?(400?MHz,?DMSO-d
6):?δ?6.57?(1H,?d,?J?=?16.0?Hz),?7.34-7.46?(2H,?m),?7.71?(1H,?d,?J?=?8.0?Hz),?7.85?(1H,?d,?J?=?16.0?Hz),?7.90?(1H,?d,?J?=?8.0?Hz),?12.64?(1H,?s).
Embodiment 10: anti--the acrylic acid preparation of 3-(3-pyridyl)
The preparation method:
With the 3-pyridylaldehyde
1a(1 mmol), propanedioic acid (2 mmol) and [bmim] PF
6(5 mL) joins in the 50 mL round-bottomed flasks, stirs to add piperidines (0.2 mmol) down.Oil bath is heated to 85 ℃ of reaction 8 h.The thin-layer chromatographic analysis detection reaction is cooled to room temperature with reaction solution after accomplishing.Reaction solution is with 10 % NaOH aqueous solution extractions three times (10 * 3 mL).Reclaim reactive ion liquid,, can reuse at 85 ℃ of following drying under reduced pressure 6 h.The NaOH aqueous solution that merges three extractions, stirring down, adding 10 % HCl are adjusted to pH=5.Separate out solid phase prod and filter, washing is filtered to neutral, drying under reduced pressure obtains white solid anti--3-(3-pyridyl) vinylformic acid.Wherein, the molar ratio of propanedioic acid and 3-pyridylaldehyde (mmol: mmol) be 2: 1, the molar ratio of piperidines and 3-pyridylaldehyde (mmol: mmol) be 0.2: 1, ionic liquid [bmim] PF
6Ratio (mL: mmol) be 5: 1 with the 3-pyridylaldehyde.
(E)-3-(pyridin-3-yl)acrylic?acid?
2j.? Mp:?231.1-231.9?
oC?(lit.?232-235
?oC).?IR?(KBr):?2926,?2449?(br),?1703,?1636,?1580,?1418,?1311,?1284,?975,?811?cm
-1.?
1H?NMR?(400?MHz,?DMSO-d
6):?δ?6.69?(1H,?d,?J?=?16.0?Hz),?7.45?(1H,?dd,?J?=?8.0,?4.8?Hz),?7.63?(1H,?d,?J?=?16.0?Hz),?8.16?(1H,?d,?J?=?8.0?Hz),?8.58?(1H,?d,?J?=?4.0?Hz),?8.85?(1H,?s),?12.53?(1H,?s).
Claims (7)
1. a water-insoluble ionic liquid [bmim] PF
6The preparation method of middle trans-cinnamic acid compound (anti--the 3-aromatic substituted acrylic acid) is characterized in that with water-insoluble ionic liquid [bmim] PF
6Be solvent, piperidines is a catalyzer, and product prepares the trans-cinnamic acid verivate with the alkaline aqueous solution extracting and separating.
2. in the prepared cinnamic acid derivative, substituent position comprises three kinds of situation such as ortho position, a position and contraposition on the phenyl ring; Substituent kind had both comprised electron-donating groups such as methyl, methoxyl group and hydroxyl, also comprised electron-withdrawing groups such as chlorine and bromine.
3. the preparation method of trans-cinnamic acid compound according to claim 1 (anti--the 3-aromatic substituted acrylic acid) is characterized in that with water-insoluble ionic liquid [bmim] PF
6Be solvent, piperidines is a catalyzer.
4. the preparation method of trans-cinnamic acid compound according to claim 1 (anti--the 3-aromatic substituted acrylic acid) is characterized in that with water-insoluble ionic liquid [bmim] PF
6Be solvent, after reaction is accomplished, with 10 % NaOH or the direct extracting and separating product of other alkaline aqueous solutions, ionic liquid [bmim] PF
6Through 80
oThe C drying under reduced pressure recycles after handling.
5. the preparation method of trans-cinnamic acid compound according to claim 1 (anti--the 3-aromatic substituted acrylic acid) is characterized in that ionic liquid [bmim] PF
6(mL: mmol) scope is 3 ~ 10: 1 with the adjustable proportion of aromatic aldehyde.
6. the preparation method of trans-cinnamic acid compound according to claim 1 (anti--the 3-aromatic substituted acrylic acid) is characterized in that the PF with [bmim]
6During for solvent, the TR of reaction is 80 ~ 90 ℃, reaction time range 4 ~ 8 h.
7. the preparation method of trans-cinnamic acid compound according to claim 1 (anti--the 3-aromatic substituted acrylic acid) is characterized in that the PF with [bmim]
6During for solvent, (mmol: mmol) scope is 1.5 ~ 3: 1 to the adjustable molar ratio of propanedioic acid and aromatic aldehyde, and (mmol: mmol) scope is 0.1 ~ 0.3: 1 to the adjustable proportion of piperidines and aromatic aldehyde.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565365A (en) * | 2008-04-22 | 2009-10-28 | 成都摩尔生物医药有限公司 | Preparation method of alpha, beta-unsaturated acid |
| CN101648865A (en) * | 2008-08-16 | 2010-02-17 | 彭金莲 | Polyphenol acrylic acid derivative and application thereof in medicaments |
| WO2010113005A2 (en) * | 2009-03-27 | 2010-10-07 | Council Of Scientific & Industrial Research | One pot multicomponent synthesis of some novel hydroxy stilbene derivatives with alpha, beta-carbonyl conjugation under microwave irradiation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565365A (en) * | 2008-04-22 | 2009-10-28 | 成都摩尔生物医药有限公司 | Preparation method of alpha, beta-unsaturated acid |
| CN101648865A (en) * | 2008-08-16 | 2010-02-17 | 彭金莲 | Polyphenol acrylic acid derivative and application thereof in medicaments |
| WO2010113005A2 (en) * | 2009-03-27 | 2010-10-07 | Council Of Scientific & Industrial Research | One pot multicomponent synthesis of some novel hydroxy stilbene derivatives with alpha, beta-carbonyl conjugation under microwave irradiation |
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| Title |
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| 《Chinese Chemical Letters》 20091231 Dong Jiang等 Doebner condensation in ionic liquids [Bmim]BF4 and [Bpy]BF4 to synthesize alpha, beta-unsaturated carboxylic acid 第279-282页 第20卷, * |
| DONG JIANG等: "Doebner condensation in ionic liquids [Bmim]BF4 and [Bpy]BF4 to synthesize α, β-unsaturated carboxylic acid", 《CHINESE CHEMICAL LETTERS》 * |
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