CN105566652A - Right-hand 31 helix ligand polymer, and preparation method and application thereof - Google Patents

Right-hand 31 helix ligand polymer, and preparation method and application thereof Download PDF

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Publication number
CN105566652A
CN105566652A CN201510926715.4A CN201510926715A CN105566652A CN 105566652 A CN105566652 A CN 105566652A CN 201510926715 A CN201510926715 A CN 201510926715A CN 105566652 A CN105566652 A CN 105566652A
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ligand polymer
spiral
right hand
cdma
ligand
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程林
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Southeast University
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a right-hand 31 helix ligand polymer, and a preparation method and application thereof. The chemical formula of the ligand polymer is {[Cu(R,R-cdma)(H2O)].2NO3.2H2O}n. The preparation method comprises the steps that Cu(NO3)2 3H2O and R,R-cdma are added into 5mL of methanol solution to be mixed for preparing turbid liquid; after the turbid liquid is subjected to still standing at room temperature, the right-hand 31 helix ligand polymer is prepared. The ligand polymer, the preparation method and the application have the advantages that the helix ligand polymer is built by Cu(II) and double-chelate ligand based on chiral hexamethylene diamine; the helix ligand polymer has a right-hand 31 helix structure and second-order nonlinear optical activity; meanwhile, the preparation process is simple; complicated synthesis equipment is not needed; the production cost is reduced. In addition, the prepared ligand polymer can be applied to asymmetric Henry reaction of aromatic aldehyde and nitromethane.

Description

A kind of right hand 3 1spiral ligand polymer and preparation method thereof and application
Technical field
The invention belongs to chemical field, particularly relate to a kind of right hand 3 1spiral ligand polymer and preparation method thereof and application.
Background technology
Owing to having structure diversification, do not need external load, avtive spot is homogeneous, reusable edible and provide the advantages such as crystalline structure, chirality ligand polymer/chiral metal-organic backbone has very large development potentiality in asymmetry catalysis.In recent years, 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.Meanwhile, as a kind of stand-in of DNA coiled strand, one dimension chiral helical ligand polymer has potential using value in asymmetry catalysis, but does not also have the research of this respect to report in document.
In addition, it is focus and the difficult point of coordination chemistry that the orientation of one dimension chiral helical coordination thing is constructed always, and more successful example uses two chelating ligand.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 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: the right hand 3 of the present invention 1the chemical formula of spiral ligand polymer is { [Cu (R, R-cdma) (H 2o)] .2NO 3.2H 2o} n, wherein, R, R-cdma are (-)-N, N'-(1R, 2R)-1,2-diamino hexahydroaniline two base two (6-methyl-2-pyridine anilide).Furtherly, the crystallization parameters of this ligand polymer is wherein, to be respectively the rib of three ribs of structure cell long for a, b, c.
Furtherly, R in ligand polymer of the present invention, R-cdma part adopts trans pair of chelating pattern and the coordination of two Cu (II), and the tetragonal pyramid structure that Cu (II) is pentacoordinate, the base plane of tetragonal pyramid is occupied by two nitrogen-atoms of two chelating ligands and two Sauerstoffatoms, and the vertex position of tetragonal pyramid is occupied by a water molecules, bottom tetragonal pyramid, four atoms of coordination are not in same plane, wherein, the structural formula of R, R-cdma part is:
The right hand 3 of the present invention 1the preparation method of spiral ligand polymer comprises the steps: the Cu (NO of 0.1mmol 3) 23H 2the R of O and 0.1mmol, R-cdma add the mixing of 5mL methanol solution, 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 the obtained right hand 3 1spiral ligand polymer.
The right hand 3 of the present invention 1spiral ligand polymer 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-cdma and Cu (II) based on chirality cyclohexanediamine to construct a kind of one dimension spiral ligand polymer, and it has the right hand 3 1spirane structure, and there is 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 the application of chiral helical chain ligand polymer in asymmetry catalysis is achieved, for the application of this type title complex provides new approaches.
Accompanying drawing explanation
Fig. 1 a is the molecular structure of the ligand polymer that the present invention obtains;
Fig. 1 b is the one-dimensional linear topological diagram of the ligand polymer that the present invention obtains.
Embodiment
The right hand 3 of the present invention 1the chemical formula of spiral ligand polymer is { [Cu (R, R-cdma) (H 2o)] .2NO 3.2H 2o} n, wherein, R, R-cdma are (-)-N, N'-(1R, 2R)-1,2-diamino hexahydroaniline two base two (6-methyl-2-pyridine anilide).Furtherly, the crystallization parameters of this ligand polymer is wherein, to be respectively the rib of three ribs of structure cell long for a, b, c.
Furtherly, R in ligand polymer of the present invention, R-cdma part adopts trans pair of chelating pattern and the coordination of two Cu (II), and the tetragonal pyramid structure that Cu (II) is pentacoordinate, the base plane of tetragonal pyramid is occupied by two nitrogen-atoms of two chelating ligands and two Sauerstoffatoms, and the vertex position of tetragonal pyramid is occupied by a water molecules, bottom tetragonal pyramid, four atoms of coordination are not in same plane, wherein, the structural formula of R, R-cdma part is:
The right hand 3 of the present invention 1the preparation method of spiral ligand polymer comprises the steps: the Cu (NO of 0.1mmol 3) 23H 2the R of O and 0.1mmol, R-cdma add the mixing of 5mL methanol solution, 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 the obtained right hand 3 1spiral ligand polymer.
The right hand 3 of the present invention 1spiral ligand polymer 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 3) 23H 2the R of O and 0.1mmol, R-cdma add 5mL methanol solution and mix, and obtained suspension liquid, filters after this suspension liquid is at room temperature stirred 0.5h, and filtrate at room temperature leaves standstill, volatilization naturally, after 1 week, i.e. and the obtained right hand 3 1spiral ligand polymer, by obtained ligand polymer through Advances in crystal X-ray diffraction analysis, the molecular structure obtained is as shown in Figure 1a, its one-dimensional linear topology is as shown in 1b, from Fig. 1 a, 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 3) 23H 2the R of O and 0.1mmol, R-cdma add the mixing of 5mL methanol solution, and obtained suspension liquid, filters after this suspension liquid is at room temperature stirred 1h, and filtrate at room temperature leaves standstill, volatilization naturally, after 2 weeks, i.e. and the obtained right hand 3 1spiral 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, this right hand 3 1helical Complex, can the asymmetric Henle reaction of catalysis aromatic aldehyde and Nitromethane 99Min. as chiral catalyst, and obtains higher ee value and good asymmetry catalysis effect.

Claims (7)

1. a right hand 3 1spiral ligand polymer, is characterized in that: the chemical formula of this ligand polymer is { [Cu (R, R-cdma) (H 2o)] .2NO 3.2H 2o} n, wherein, R, R-cdma are (-)-N, N'-(1R, 2R)-1,2-diamino hexahydroaniline two base two (6-methyl-2-pyridine anilide).
2. the right hand 3 according to claim 1 1spiral ligand polymer, 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.
3. the right hand 3 according to claim 1 1spiral ligand polymer, is characterized in that: the structural formula of described R, R-cdma part is:
4. the right hand 3 according to claim 3 1spiral ligand polymer, is characterized in that: the R in described ligand polymer, R-cdma part adopts trans pair of chelating pattern and the coordination of two Cu (II).
5. the right hand 3 according to claim 4 1spiral ligand polymer, it is characterized in that: the tetragonal pyramid structure that described Cu (II) is pentacoordinate, the base plane of tetragonal pyramid is occupied by two nitrogen-atoms of two chelating ligands and two Sauerstoffatoms, the vertex position of tetragonal pyramid is occupied by a water molecules, and bottom tetragonal pyramid, four atoms of coordination are not in same plane.
6. prepare the right hand 3 according to claim 1 for one kind 1the method of spiral ligand polymer, is characterized in that comprising the steps: the Cu (NO by 0.1mmol 3) 23H 2the R of O and 0.1mmol, R-cdma 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 the obtained right hand 3 1spiral ligand polymer.
7. a right hand 3 according to claim 1 1spiral ligand polymer is applied to the asymmetric Henle reaction of aromatic aldehyde and Nitromethane 99Min..
CN201510926715.4A 2015-12-14 2015-12-14 Right-hand 31 helix ligand polymer, and preparation method and application thereof Pending CN105566652A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999032225A2 (en) * 1997-12-19 1999-07-01 The Board Of Trustees Of The Leland Stanford Junior University Catalytic composition based on chiral ligands with molybdenum, tungsten or chromium and method for asymmetric alkylation of allylic substrates
US20020198383A1 (en) * 1997-12-19 2002-12-26 Trost Barry M. Catalytic compositions and methods for asymmetric allylic alkylation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999032225A2 (en) * 1997-12-19 1999-07-01 The Board Of Trustees Of The Leland Stanford Junior University Catalytic composition based on chiral ligands with molybdenum, tungsten or chromium and method for asymmetric alkylation of allylic substrates
US20020198383A1 (en) * 1997-12-19 2002-12-26 Trost Barry M. Catalytic compositions and methods for asymmetric allylic alkylation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张秀英: "手性配位聚合物的合成、表征及其在不对称催化反应中的应用", 《万方学位论文数据库》 *

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Application publication date: 20160511