CN104368387B - One kind is with 1,5 cyclo-octadiene/preparation method of the L phenylalanines as ligand Rh catalyst - Google Patents
One kind is with 1,5 cyclo-octadiene/preparation method of the L phenylalanines as ligand Rh catalyst Download PDFInfo
- Publication number
- CN104368387B CN104368387B CN201410385331.1A CN201410385331A CN104368387B CN 104368387 B CN104368387 B CN 104368387B CN 201410385331 A CN201410385331 A CN 201410385331A CN 104368387 B CN104368387 B CN 104368387B
- Authority
- CN
- China
- Prior art keywords
- octadiene
- cyclo
- catalyst
- take
- reagent
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses one kind is with 1,5 cyclo-octadiene/preparation method of the L phenylalanines as ligand Rh catalyst：Take RhCl3·3H2O（50 mg,0.239 mmol）It is placed in Xie Erkou flasks, under nitrogen protection, injects ethanol（3.0 mL）And water（1.0 mL）Mixed solvent, stir to being completely dissolved；1,5 cyclo-octadiene (0.2ml, 19.6mmol) are added, 60 DEG C of backflows after 30 min of stirring, are warmed up to, reaction has precipitation to generate, washed with ethanol three times to obtain [Rh (cod) Cl] after terminating2Catalyst；Take L phenylalanines（20mg,0.13mmol）It is placed in a reagent bottle with NaOH (5.50mg, 0.13mmol), adds deionized water（0.6 mL）, stirring and dissolving obtains reagent A；Take [Rh (cod) Cl]2(30mg, 0.06mmol) is placed in Xie Erkou bottles, nitrogen charging gas shielded, injects 3mL methyl alcohol stirring and dissolvings, then reagent A is injected in oblique two mouthfuls of bottles, stirs 90min；There are a large amount of precipitations to generate, reaction end is centrifuged, and vacuumizes drying, tests to product.The new rhodium complex catalyst of gained of the invention can further improve its polymerisation conversion and stereoselectivity when replaced acetylene polymerization is catalyzed.
Description
Technical field
The invention belongs to macromolecular material and engineering field, more particularly to one kind with 1,5- cyclo-octadiene/L-phenylalanine are
The preparation method of ligand Rh catalyst.
Background technology
The successful development of rhodium catalyst is China opens the new situation realizing Domestic Catalyst, and will be to China's carbonyl
The development of base compound probability plays a part of promotion.At present, along with the research of poly- replaced acetylene and the gradually popularization of application,
New problem is occurred in that, i.e., in replaced acetylene polymerization process, how further to be improved its polymerisation conversion and three-dimensional spiral is selected
Property, therefore, the higher rhodium catalyst selectively preferably with various l-amino acids as part of the new activity of exploration has important
Scientific meaning and researching value.
The content of the invention
It is an object of the invention to provide one kind is with 1,5- cyclo-octadiene/preparation of the L-phenylalanine as ligand Rh catalyst
Method, can be greatly improved conversion ratio when replaced acetylene is polymerized and stereoselectivity.
The purpose of the present invention is achieved through the following technical solutions：One kind is with 1,5- cyclo-octadiene/L-phenylalanine
For the preparation method of ligand Rh catalyst, methods described the step of it is as follows：
（1）Take L-phenylalanine (20mg, 0.13mmol) and NaOH (5.50mg, 0.13mmol) is placed in a reagent bottle
In, add deionized water（0.6 mL）, stirring and dissolving obtains reagent A；
（2）Take RhCl3·3H2O（50mg,0.239mmol）It is placed in Xie Erkou flasks, under the protection of nitrogen, injects second
The mixed solvent of alcohol (3.0 mL) and water (1.0 mL), stirs to being completely dissolved, add 1,5- cyclo-octadiene (0.2ml,
After 19.6mmol) stirring 30 min, temperature rising reflux obtains product [Rh (cod) Cl]2；
(3) take [Rh (cod) Cl]2(30mg, 0.06mmol) is placed in Xie Erkou bottles, nitrogen charging gas shielded, injects 3mL first
Alcohol stirring and dissolving
（4）By step（1）The reagent A implantation step of gained（3）In resulting solution, stir 2 hours；
（5）By step（4）Gained precipitation and centrifugal separation, vacuumizes drying.
Beneficial effects of the present invention：New rhodium complex catalyst with 1,5- cyclo-octadiene/L-phenylalanine as part
When catalysis replaced acetylene is polymerized, its polymerisation conversion and stereoselectivity can be further improved.
Description of the drawings
Fig. 1 is Rh (cod) nucleus magnetic hydrogen spectrums (L-phenylalanine).
1H-NMR(600MHz, CDCl3, δ): 7.37-7.40(d, 1H, PhH), 7.30-7.33(d, 2H,
PhH), 7.26-7.28(d, 2H, PhH), 4.47(s, 4H, -CH=CH), 3.70-3.73(m, 1H, CH2CHNH),
3.45-3.51(d, 2H, PhCH 2), 3.10-3.14(m, 1H, NH), 2.23-2.40(d, 2H, CH 2CH2), 1.17-
1.86(d, 2H, CH2CH 2)
Fig. 2 is Rh (cod) scanning electron microscope (SEM) photographs (L-phenylalanine).
It is observed that columnar shape is presented for catalyst and form is preferable from SEM figures, from whole figure it can be seen that dividing
Cloth also than more uniform, arranges tight, and uniform in size, particle diameter distribution is narrower and surface is smooth, and this is mainly due to phenylalanine pole
The crystalline texture of formation rule is easily coordinated with rhodium, special cylindrical structural is resulted in.
Specific embodiment
In order that objects and advantages of the present invention become more apparent, the present invention is carried out further in detail below in conjunction with example
Describe in detail bright.It should be appreciated that instantiation described herein is not intended to limit the present invention only to explain the present invention.
Being embodied as the present invention is as follows：One kind is with 1,5- cyclo-octadiene/system of the L-phenylalanine as ligand Rh catalyst
The step of Preparation Method, methods described, is as follows：
(1) take L-phenylalanine (20mg, 0.13mmol) and NaOH (5.50mg, 0.13mmol) is placed in a reagent bottle
In, add deionized water（0.6 mL）, stirring and dissolving obtains reagent A；
(2) take RhCl3·3H2O（50mg,0.239mmol）It is placed in Xie Erkou flasks, under the protection of nitrogen, injects second
The mixed solvent of alcohol (3.0 mL) and water (1.0 mL), stirs to being completely dissolved, add 1,5- cyclo-octadiene (0.2ml,
After 19.6mmol) stirring 30 min, temperature rising reflux obtains product [Rh (cod) Cl]2；
(3) take [Rh (cod) Cl]2(30mg, 0.06mmol) is placed in Xie Erkou bottles, nitrogen charging gas shielded, injects 3mL first
Alcohol stirring and dissolving
(4) by step（1）The reagent A implantation step of gained（3）In resulting solution, stir 2 hours；
（5）By step（4）Gained precipitation and centrifugal separation, vacuumizes drying.
Originally the new rhodium complex catalyst of gained is embodied as when replaced acetylene polymerization is catalyzed, can further improve which
Polymerisation conversion and stereoselectivity.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (1)
1. one kind with 1,5- cyclo-octadiene/L-phenylalanine for ligand Rh catalyst preparation method, it is characterised in that the side
The step of method, is as follows：
（1）20mg ALANINEs and 5.50mg NaOH are taken, is placed in a reagent bottle, add 0.6 mL deionized waters, stirring
Dissolving, obtains reagent A；
（2）Take 50mg RhCl3·3H2O is placed in Xie Erkou flasks, under the protection of nitrogen, injects 3.0 mL ethanol and 1.0
The mixed solvent of mL water, stirs to being completely dissolved, and after adding 0.2mL 1,5- cyclo-octadiene to stir 30 min, temperature rising reflux must be produced
Product [Rh (cod) Cl]2；
(3) take 30mg [Rh (cod) Cl]2It is placed in Xie Erkou bottles, nitrogen charging gas shielded, injects 3mL methyl alcohol stirring and dissolvings；
（4）By step（1）The reagent A implantation step of gained（3）In resulting solution, stir 2 hours；
（5）By step（4）Gained precipitation and centrifugal separation, vacuumizes drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410385331.1A CN104368387B (en) | 2014-08-07 | 2014-08-07 | One kind is with 1,5 cyclo-octadiene/preparation method of the L phenylalanines as ligand Rh catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410385331.1A CN104368387B (en) | 2014-08-07 | 2014-08-07 | One kind is with 1,5 cyclo-octadiene/preparation method of the L phenylalanines as ligand Rh catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104368387A CN104368387A (en) | 2015-02-25 |
| CN104368387B true CN104368387B (en) | 2017-04-05 |
Family
ID=52547733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410385331.1A Expired - Fee Related CN104368387B (en) | 2014-08-07 | 2014-08-07 | One kind is with 1,5 cyclo-octadiene/preparation method of the L phenylalanines as ligand Rh catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104368387B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107556460A (en) * | 2017-09-05 | 2018-01-09 | 齐齐哈尔大学 | A kind of preparation method of ethyl diazoacetate polymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3755194A (en) * | 1969-02-12 | 1973-08-28 | O Eremenko | Hydrogenation catalyst |
| CN102276768A (en) * | 2011-06-07 | 2011-12-14 | 哈尔滨工程大学 | Preparation method and application method of polyphenylacetylene derivative |
| CN103588816A (en) * | 2013-08-31 | 2014-02-19 | 齐齐哈尔大学 | Preparation method of rhodium catalyst by using 2,5-norbornadiene (nbd) and 2-aminonicotinic acid as ligands |
-
2014
- 2014-08-07 CN CN201410385331.1A patent/CN104368387B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3755194A (en) * | 1969-02-12 | 1973-08-28 | O Eremenko | Hydrogenation catalyst |
| CN102276768A (en) * | 2011-06-07 | 2011-12-14 | 哈尔滨工程大学 | Preparation method and application method of polyphenylacetylene derivative |
| CN103588816A (en) * | 2013-08-31 | 2014-02-19 | 齐齐哈尔大学 | Preparation method of rhodium catalyst by using 2,5-norbornadiene (nbd) and 2-aminonicotinic acid as ligands |
Non-Patent Citations (1)
| Title |
|---|
| Rh-Mediated Polymerization of Carbenes: Mechanism and Stereoregulation;Erica Jellema, et al;《J. AM. CHEM. SOC.》;20070823;第129卷;第11639页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104368387A (en) | 2015-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Efficient and reusable amine-functionalized polyacrylonitrile fiber catalysts for Knoevenagel condensation in water | |
| Xie et al. | Progress in asymmetric biomimetic transamination of carbonyl compounds | |
| Wu et al. | A Highly Active and Recyclable Catalyst: Phosphine Dendrimer‐Stabilized Nickel Nanoparticles for the Suzuki Coupling Reaction | |
| CN103601856B (en) | Polymer microballoon of a kind of loaded chiral catalyzer and its preparation method and application | |
| CN102643513A (en) | Preparation method of meta-aminophenol-formaldehyde resin spheres and preparation method of carbon spheres | |
| CN107442177A (en) | The method that 5 hydroxymethylfurfural selective hydrogenations synthesize 2,5 furyl dimethyl carbinols | |
| CN104368387B (en) | One kind is with 1,5 cyclo-octadiene/preparation method of the L phenylalanines as ligand Rh catalyst | |
| CN103613756A (en) | Method for preparing chiral polyaniline by protein induction | |
| CN102580353B (en) | Preparation method of solid phase extraction column of molecular imprinted of phenolic environmental estrogens | |
| Zhao et al. | Ecofriendly construction of enzyme reactor based on three-dimensional porous cryogel composites | |
| Wu et al. | Template size matched film thickness for effectively in situ surface imprinting: A model study of glycoprotein imprints | |
| CN104387712A (en) | Nano composite carrier with superparamagnetism and preparation method thereof | |
| CN104324750B (en) | Preparation method of rhodium catalyst with 1,5-cyclooctadiene/L-alanine as ligand | |
| Mo et al. | Novel optoelectronic metal organic framework material perylene tetracarboxylate magnesium: preparation and biosensing | |
| CN103588816B (en) | The preparation method that one is ligand Rh catalyst with 2,5-norbornadiene (nbd) and 2-amino-nicotinic acid | |
| CN102153500B (en) | Method for synthesizing diindolylmethane derivative | |
| CN104759292B (en) | Organic molecule cage supported catalyst and its preparation method and use | |
| CN105964306A (en) | Poly(ionic liquid)-based magnetic nanoparticle and its preparation method and use in three-ingredient reaction | |
| CN106008795A (en) | Method for synthesizing cyclic polymer self-healing gel | |
| CN109261136B (en) | Preparation method of magnetic melamine urea formaldehyde resin integral material | |
| Chen et al. | Magnetically-separable quasi-homogeneous catalyst: Brush-type ionic liquid polymer coated magnetic polymer microspheres for tandem reactions to produce 4H-pyrans/biodiesel | |
| CN116429954B (en) | Transdermal detection method for azelaic acid | |
| CN107417853A (en) | A kind of preparation method of porous polypropylene nitrile | |
| CN103483479B (en) | A kind of single electron transfer active free radical polymerization prepares the method for PDMAEMA | |
| CN107999102B (en) | Preparation and performance test of plasma enhanced HER catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170405 Termination date: 20180807 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |