CN105481884A - Copper-bearing chirality helical coordination polymer and preparation method and application thereof - Google Patents
Copper-bearing chirality helical coordination polymer and preparation method and application thereof Download PDFInfo
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- CN105481884A CN105481884A CN201510927430.2A CN201510927430A CN105481884A CN 105481884 A CN105481884 A CN 105481884A CN 201510927430 A CN201510927430 A CN 201510927430A CN 105481884 A CN105481884 A CN 105481884A
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- ligand polymer
- cupric
- cdpa
- helical
- chirality
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920001795 coordination polymer Polymers 0.000 title abstract 7
- 239000013256 coordination polymer Substances 0.000 title abstract 7
- 239000010949 copper Substances 0.000 title abstract 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract 5
- 229910052802 copper Inorganic materials 0.000 title abstract 5
- 239000003446 ligand Substances 0.000 claims abstract description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 8
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims abstract description 7
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- -1 2-pyridine anilide Chemical class 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006842 Henry reaction Methods 0.000 abstract 1
- 239000013522 chelant Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a copper-bearing chirality helical coordination polymer and a preparation method and application thereof. The chemical formula is {[Cu (R,R-cdpa) (H2O)2].2NO3. 2H2O}. The preparation method comprises the steps of adding 5 mL of methanol solution into copper dinitrate-water(1/3) and R,R-cdpa to be mixed to obtain suspension liquid and enabling the suspension liquid to stand at room temperature to obtain the copper-bearing chirality helical coordination polymer. The copper-bearing chirality helical coordination polymer has the advantages that a double chelate ligand R,R-cdpa based on chiraity cyclohexanediamine and Cu (II) are utilized to prepare a one-dimensional helical coordination polymer, and the coordination polymer has a right hand 31 helical structure and has second-order non-linear optical activity. The preparing technology is simple, a complex synthesis device is not needed, the production cost is reduced, and the prepared coordination polymer can be applied to asymmetric Henry reaction of aromatic aldehyde and nitromethane.
Description
Technical field
The invention belongs to chemical field, particularly relate to a kind of cupric chiral helical ligand polymer and preparation method thereof and application.
Background technology
Chirality ligand polymer/chiral metal-organic backbone, as the desirable solid chiral catalyst of a class, has structure diversification, does not need external load, avtive spot is homogeneous, reusable edible and provide the advantages such as crystalline structure.Lot of domestic and international seminar has made a large amount of fruitful work in the asymmetry catalysis of chirality ligand polymer/chiral metal-organic backbone, but mainly concentrate on the ligand polymer of higher dimensionality (two and three dimensions), particularly there is the metal-organic framework materials of pore passage structure.In addition, chiral helical ligand polymer is as a kind of stand-in of DNA coiled strand, and it should have potential using value in asymmetry catalysis, but in document also there is not the report of this respect.
Meanwhile, constructing of one dimension chiral helical coordination thing is focus and the difficult point of coordination chemistry always, uses two chelating ligand to be beneficial to constructing of one dimensional helical chain.And the adducts of existing chirality cyclohexanediamine and Cu (II) salt is applied in the report of asymmetric Henle reaction aspect in document.
Summary of the invention
Goal of the invention: that the first object of the present invention is to provide a kind of one dimension and there is the right hand 3
1the cupric chiral helical ligand polymer of spirane structure; The second object of the present invention is to provide the preparation method of this ligand polymer; The third object of the present invention is to provide the application of this ligand polymer.
Technical scheme: a kind of cupric chiral helical ligand polymer of the present invention, its chemical formula is { [Cu (R, R-cdpa) (H
2o)
2] .2NO
3.2H
2o}
n, wherein, R, R-cdpa are (-)-N, N'-(1R, 2R)-1,2-diamino hexahydroaniline two base two (2-pyridine anilide), the chirality pair chelated organic ligands that it be is parent with chirality cyclohexanediamine.Furtherly, this ligand polymer belongs to trigonal system, and its spacer is P3
121, crystallization parameters is
wherein, to be respectively the rib of three ribs of structure cell long for a, b, c.
Furtherly, R, R-cdma part of the present invention adopts the nitrogen-atoms on pyridine and the Sauerstoffatom on amide group and the coordination of two Cu (II) respectively, and its structural formula is:
Of the present inventionly prepare cupric chiral helical ligand polymer method, comprise the steps: 0.1mmolCu (NO
3)
23H
2the R of O and 0.1mmol, R-cdpa add 5mL methanol solution and mix, and obtained suspension liquid, filters after this suspension liquid is at room temperature stirred 0.5 ~ 1h, and filtrate at room temperature leaves standstill, volatilization naturally, after 1 ~ 2 week, i.e. and obtained cupric chiral helical ligand polymer.
Cupric chiral helical ligand polymer of the present invention is applied to the asymmetric Henle reaction of aromatic aldehyde and Nitromethane 99Min..
Beneficial effect: compared with prior art, its remarkable advantage is that the present invention adopts two chelating ligand R, R-cdpa and Cu (II) based on chirality cyclohexanediamine to prepare a kind of one dimension spiral ligand polymer, and the ligand polymer of preparation has the right hand 3
1spirane structure, has second order non-linear optical active; Meanwhile, preparation technology of the present invention is simple, without the need to the synthesis device of complexity, reduces production cost; In addition, the ligand polymer of preparation can be applied to the asymmetric Henle reaction of aromatic aldehyde and Nitromethane 99Min., thus explores and feasibility study for chiral helical title complex provides originality as the application of heterogeneous catalyst in asymmetry catalysis.
Accompanying drawing explanation
In Fig. 1, a is the molecular structure of the ligand polymer that the present invention obtains;
In Fig. 1, b is the one-dimensional linear topological diagram of the ligand polymer that the present invention obtains.
Embodiment
A kind of cupric chiral helical ligand polymer of the present invention, its chemical formula is { [Cu (R, R-cdpa) (H
2o)
2] .2NO
3.2H
2o}
n, wherein, R, R-cdpa are (-)-N, N'-(1R, 2R)-1,2-diamino hexahydroaniline two base two (2-pyridine anilide), the chirality pair chelated organic ligands that it be is parent with chirality cyclohexanediamine.Furtherly, this ligand polymer belongs to trigonal system, and its spacer is P3
121, crystallization parameters is
wherein, to be respectively the rib of three ribs of structure cell long for a, b, c.
Furtherly, R, R-cdma part of the present invention adopts the nitrogen-atoms on pyridine and the Sauerstoffatom on amide group and the coordination of two Cu (II) respectively, and its structural formula is:
Of the present inventionly prepare cupric chiral helical ligand polymer method, comprise the steps: 0.1mmolCu (NO
3)
23H
2the R of O and 0.1mmol, R-cdpa add 5mL methanol solution and mix, and obtained suspension liquid, filters after this suspension liquid is at room temperature stirred 0.5 ~ 1h, and filtrate at room temperature leaves standstill, volatilization naturally, after 1 ~ 2 week, i.e. and obtained cupric chiral helical ligand polymer.
Cupric chiral helical ligand polymer of the present invention is applied to the asymmetric Henle reaction of aromatic aldehyde and Nitromethane 99Min..Furtherly, aromatic aldehyde is that (substituting group is H, 2-/3-/4-NO for 1-naphthaldehyde and single-substituted formaldehyde
2, 2-/3-/4-F, 2-/4-Cl, 2-/3-/4-Br, 4-OCH
3or 4-Ph).
Embodiment 1
By the Cu (NO of 0.1mmol (0.024g)
3)
23H
2the R of O and 0.1mmol (0.032g), R-cdpa adds the mixing of 5mL methanol solution, obtained suspension liquid, filter after this suspension liquid is at room temperature stirred 0.5h, filtrate at room temperature leaves standstill, volatilization naturally, after 1 week, i.e. obtained cupric chiral helical ligand polymer, by obtained ligand polymer through Advances in crystal X-ray diffraction analysis, the molecular structure obtained is as shown in a in Fig. 1, and its one-dimensional linear is topological as shown in b in Fig. 1, as shown in Figure 1, this ligand polymer, compared with urea, has second order non-linear optical activity and asymmetry catalysis activity.
Embodiment 2
By the Cu (NO of 0.1mmol (0.024g)
3)
23H
2the R of O and 0.1mmol (0.032g), R-cdpa add the mixing of 5mL methanol solution, obtained suspension liquid, filter after this suspension liquid is at room temperature stirred 1h, filtrate at room temperature leaves standstill, volatilization naturally, after 2 weeks, i.e. and obtained cupric chiral helical ligand polymer.
Embodiment 3
0.5mmol ligand polymer is added in the small test tube of 4mL, 1mL Virahol (i-PrOH) and 5mmolN, N-diisopropylethylamine (DIPEA) obtains a blue suspension, then in suspension, the aromatic aldehyde of 0.5mmol and the Nitromethane 99Min. of 5mmol is added, test tube is put into low-temp reaction device, filter react 168h under-20 DEG C of conditions after, filtrate is crossed column purification, wherein, weighting agent is silica gel, moving phase is sherwood oil and the ethyl acetate mixed solvent of volume ratio 4:1, gained solution is concentrated, after vacuum-drying, namely catalysate is obtained, its catalyzed reaction equation is shown below.
By the high-performance liquid chromatogram determination e.e. value of the catalysate of gained with chiral column.Wherein, chiral column used and liquid-phase condition, and the e.e. value of products therefrom is as shown in table 1.
The e.e. value of table 1 catalysate
As shown in Table 1, when this chiral helical title complex is as Primary Catalysts, the asymmetric Henle reaction of aromatic aldehyde and Nitromethane 99Min. can obtain good asymmetry catalysis effect; It is likely applied in industrial reaction.
Claims (7)
1. a cupric chiral helical ligand polymer, is characterized in that: the chemical formula of this ligand polymer is { [Cu (R, R-cdpa) (H
2o)
2] .2NO
3.2H
2o}
n, wherein, R, R-cdpa are (-)-N, N'-(1R, 2R)-1,2-diamino hexahydroaniline two base two (2-pyridine anilide), the chirality pair chelated organic ligands that it be is parent with chirality cyclohexanediamine.
2. cupric chiral helical ligand polymer according to claim 1, is characterized in that: described ligand polymer belongs to trigonal system, and its spacer is P3
121.
3. cupric chiral helical ligand polymer according to claim 1, is characterized in that: the crystallization parameters of described ligand polymer is
wherein, to be respectively the rib of three ribs of structure cell long for a, b, c.
4. cupric chiral helical ligand polymer according to claim 1, is characterized in that: the structural formula of described R, R-cdpa part is:
5. cupric chiral helical ligand polymer according to claim 4, is characterized in that: described R, R-cdpa part is respectively with the nitrogen-atoms on pyridine and the Sauerstoffatom on amide group and the coordination of two Cu (II).
6. prepare a method for cupric chiral helical ligand polymer according to claim 1, it is characterized in that comprising as step: by 0.1mmolCu (NO
3)
23H
2the R of O and 0.1mmol, R-cdpa add 5mL methanol solution and mix, and obtained suspension liquid, filters after this suspension liquid is at room temperature stirred 0.5 ~ 1h, and filtrate at room temperature leaves standstill, volatilization naturally, after 1 ~ 2 week, i.e. and obtained cupric chiral helical ligand polymer.
7. a cupric chiral helical ligand polymer according to claim 1 is applied to the asymmetric Henle reaction of aromatic aldehyde and Nitromethane 99Min..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510927430.2A CN105481884A (en) | 2015-12-14 | 2015-12-14 | Copper-bearing chirality helical coordination polymer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510927430.2A CN105481884A (en) | 2015-12-14 | 2015-12-14 | Copper-bearing chirality helical coordination polymer and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105481884A true CN105481884A (en) | 2016-04-13 |
Family
ID=55669198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510927430.2A Pending CN105481884A (en) | 2015-12-14 | 2015-12-14 | Copper-bearing chirality helical coordination polymer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105481884A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265703A (en) * | 2018-11-20 | 2019-01-25 | 东南大学 | It is a kind of three-dimensional containing zinc/copper chiral metal organic framework material and preparation method thereof |
-
2015
- 2015-12-14 CN CN201510927430.2A patent/CN105481884A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 曹青娜: "具有多重手性元素的手性配位聚合物的合成、结构与性质研究", 《万方学位论文数据库》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265703A (en) * | 2018-11-20 | 2019-01-25 | 东南大学 | It is a kind of three-dimensional containing zinc/copper chiral metal organic framework material and preparation method thereof |
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Application publication date: 20160413 |