CN108069894A - A kind of new Salen ligands synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde and preparation method thereof - Google Patents
A kind of new Salen ligands synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde and preparation method thereof Download PDFInfo
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- CN108069894A CN108069894A CN201611005421.9A CN201611005421A CN108069894A CN 108069894 A CN108069894 A CN 108069894A CN 201611005421 A CN201611005421 A CN 201611005421A CN 108069894 A CN108069894 A CN 108069894A
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- cyclohexanediamine
- pyridine
- formaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
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Abstract
The new Salen ligands and its synthetic method synthesized with 2 formaldehyde of pyridine by 1,2 cyclohexanediamine the present invention relates to one kind.The ligand has the ability of quad-tree index.Synthetic schemes is that will be dissolved in dichloromethane by 2 formaldehyde of pyridine of metering ratio, be then transferred in three-necked flask, add in drier anhydrous magnesium sulfate, and 1,2 cyclohexanediamine is slowly dropped into three-necked flask, 40 DEG C of oil baths, when reflux 12 is small.It treats after reaction, solution is placed in beaker, and faint yellow solid is precipitated in solvent volatilization in beaker, then cleans with absolute ethyl alcohol the oily liquids on yellow solid surface and obtain target product.Described 1, the mass ratio of 2 cyclohexanediamine and 2 formaldehyde of pyridine are：1: 1.87, yield 82.1%.
Description
Technical field
The invention belongs to organic chemical synthesis technical fields, and in particular to one kind is by 1,2- cyclohexanediamine and pyridine -2- first
New Salen ligands of aldehyde synthesis and preparation method thereof.
Technical background
Aldehyde and the alkali compounds of ammonia condensation reaction generation are commonly referred to as schiff bases, by 2 identical aldehyde molecules and 1
The chelating schiff bases (Sali-cylaldehydoethylenediamine) of two amine molecules condensation generation is then referred to as Salen.
N, O of Salen complexs and the structure of metallic ion coordination, have with characteristic similar in biotic environment, thus in molecular recognition
Field attracts wide attention.In addition, Salen complexs are with its simple in structure, wide variety, synthetic route is simple, is catalyzed
The advantages that agent is easily recycled is widely used in all kinds of asymmetric catalysis [KLEIJ W A.Eur J by favor
Inorg Chem, 2009 (2)：193-205.].Variation of the Salen ligands of document report in structure at present is mostly focused on
The part of salicylide for diamine portion, generally uses ethylenediamine or cyclohexanediamine.The skeleton structure of diamines is to matching somebody with somebody
Close the molecular recognition of object, catalytic performance can have an impact that [Gao Yong waits Yanan University journal：Natural science edition, 2008,27
(1)：46-47.].
In recent years, domestic structure and innovation research on Salen also results in numerous concerns.Such as Ruan Wen is beautiful et al.
[the Shandong chemical industry such as child's dawn fine jade, 2016,45 (1)：46-50.] with 1,2- dimethoxy-4 's, bis- amido benzene of 5- and o-vanillin are
2 kinds of new Salen ligands H of Material synthesis2L1And H2L2And corresponding metal complex ML1And ML2(M=Ni, Cu, Zn), and
Using NMR spectrum, uv-visible absorption spectra, it is infrared the methods of characterized, explore ligand and its complex
Photoluminescent property.Then on this basis, and the Salen type ligands H containing terminal acetylene has been synthesized2Ln and its series metal cooperation
Object MLn (n=1~4；M=Ni, Cu, Mn) and with N2O2Ni, Cu complex of coordination mode；Prosperous et al. [the Liu Zhichang of Liu Zhi
Wait Leshan Teachers College journal, 2002,17 (4)：30-33.] by salicylide and ethylenediamine, propane diamine, o-phenylenediamine, to benzene
Diamine reactant has synthesized 4 kinds of Salen ligands, then them is allowed with Co (II), Ni (II), the reaction of Zn (II) metal ion, to close respectively
Into 12 kinds of Salen metal complexs.Feng Jianhua et al. [the application chemical industry such as Feng Jianhua, 2014,43 (6)：1006-1008.] with
3,5- bis- bromo- Benzaldehyde,2-hydroxies and Isosorbide-5-Nitrae-diamines oxygen butane, 1,3- diamines Ethylene Oxide, 1,2- diamines oxidative ethane are raw material,
The double oxime compounds of 3 kinds of new Salen have been synthesized in anhydrous ethanol solvent.Using the double oxime compounds of Salen and cobalt acetate as raw material,
A kind of transition metal Co complexs are synthesized.The result shows that the double oxime compounds of synthesized new Salen have with cobalt (II) ion
Stronger coordination ability.
In order to obtain the complex of low dimensional structures, it can be coordinated with multiple tooth Nitrogen-Containing Heterocyclic Ligand and rare earth element, obtain low-dimensional
The complex of structure, therefore 1 has been selected, 2- cyclohexanediamine and the new Salen ligands of pyridine-2-formaldehyde reaction synthesis.
The content of the invention
The object of the present invention is to provide the new Salen ligands that one kind is synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde
And preparation method thereof.The ligand has quad-tree index ability, is with a wide range of applications.
The infrared spectrum of new Salen ligands disclosed by the invention is as shown in Figure 1, it is characterised in that its infrared spectrum is special
Levy peak：3444cm-1(m), 3062cm-1(w), 2929cm-1(s), 2854cm-1(m), 1644cm-1(s), 1585cm-1(s),
1463cm-1(s), 1384cm-1(w), 1130cm-1(w), 1078cm-1(w), 989cm-1(m), 943cm-1(w), 838cm-1(w),
777cm-1(m), 667cm-1(w)。
The preparation method of the present invention is as follows：
It will be by 1：The pyridine-2-formaldehyde of 2.2 metering ratios is dissolved in dichloromethane, is then transferred in three-necked flask, adds in dry
Drying prescription anhydrous magnesium sulfate, and 1,2- cyclohexanediamine is slowly dropped into three-necked flask, 40 DEG C of oil baths, when reflux 12 is small.It waits to react
After, solution is placed in beaker, and faint yellow solid is precipitated in beaker, then cleans yellow solid with absolute ethyl alcohol for solvent volatilization
The oily liquids on surface obtains target product.1, the 2- cyclohexanediamine and the mass ratio of pyridine-2-formaldehyde are：1∶
1.87。
Description of the drawings
The infrared spectrum of Fig. 1 ligands
Specific embodiment
The synthesis of 1 ligand of embodiment：
The pyridine-2-formaldehyde of 0.22mmol (0.0236g) is dissolved in dichloromethane first, is then transferred to the three of 100ml
In mouth flask, anhydrous magnesium sulfate is added, and three-necked flask is positioned in oil bath pan, passes through the perseverance of connection above three-necked flask
Dropping funel is pressed, 1, the 2- cyclohexanediamine of 0.1mmol (0.0114g) is slowly dropped into three-necked flask, 40 DEG C of oil baths, reflux 12 is small
When.It treats after reaction, solution is placed in beaker, and faint yellow solid is precipitated in beaker, then is cleaned with absolute ethyl alcohol for solvent volatilization
The oily liquids on yellow solid surface obtains product.1, the 2- cyclohexanediamine and the mass ratio of pyridine-2-formaldehyde are：
1: 1.87, yield 82.1%.
With pellet technique, Nicolet330FT-IR infrared spectrometers are in 4000-400cm-1It is interior to measure the red of complex
External spectrum.See Fig. 1：The infrared spectrum of ligand.
Claims (5)
1. a kind of new Salen ligands synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde and preparation method thereof.The ligand has
There is the ability of quad-tree index.
2. the new Salen ligands according to claim 1 synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde, special
Sign is its infrared spectrum characteristic peak：3444cm-1(m), 3062cm-1(w), 2929cm-1(s), 2854cm-1(m), 1644cm-1(s), 1585cm-1(s), 1463cm-1(s), 1384cm-1(w), 1130cm-1(w), 1078cm-1(w), 989cm-1(m),
943cm-1(w), 838cm-1(w), 777cm-1(m), 667cm-1(w)。
3. the synthesis of the new Salen ligands according to claim 1 synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde
Method, it is characterised in that it comprises the following steps：
1) dichloromethane will be dissolved in by the pyridine-2-formaldehyde of 1: 2.2 metering ratio；
2) it is transferred in three-necked flask, adds in 1g anhydrous magnesium sulfates, and 1,2- cyclohexanediamine is slowly dropped into three-necked flask；
3) 40 DEG C of oil baths, when reflux 12 is small；
4) treat after reaction, solution is placed in beaker, and faint yellow solid is precipitated in beaker, then uses absolute ethyl alcohol for solvent volatilization
The oily liquids for cleaning yellow solid surface obtains target product.
4. the synthesis of the new Salen ligands according to claim 3 synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde
Method, it is characterised in that 1, the 2- cyclohexanediamine and the mass ratio of pyridine-2-formaldehyde are：1: 1.87, yield is
82.1%.
5. the synthesis of the new Salen ligands according to claim 3 synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde
Method, it is characterised in that anhydrous magnesium sulfate is added in reaction and makees drier.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292581A (en) * | 2021-05-12 | 2021-08-24 | 东南大学 | Novel coordination circular polarization luminescent crystalline compound and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103447091A (en) * | 2013-09-05 | 2013-12-18 | 中国科学院长春应用化学研究所 | Quadridentate pyridyl schiff base metal complex and preparation method thereof as well as preparation method of cyclic carbonate |
| CN104558053A (en) * | 2015-01-29 | 2015-04-29 | 河北工业大学 | Salen-Fe-like complex, and preparation method and application thereof |
-
2016
- 2016-11-11 CN CN201611005421.9A patent/CN108069894A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103447091A (en) * | 2013-09-05 | 2013-12-18 | 中国科学院长春应用化学研究所 | Quadridentate pyridyl schiff base metal complex and preparation method thereof as well as preparation method of cyclic carbonate |
| CN104558053A (en) * | 2015-01-29 | 2015-04-29 | 河北工业大学 | Salen-Fe-like complex, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| CLIFF R. BAAR,ET AL.: ""Activation of Imines by Platinum(II) To Give Aminoalkyl Complexes: Scope and Limitations of the Reaction"", 《ORGANOMETALLICS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292581A (en) * | 2021-05-12 | 2021-08-24 | 东南大学 | Novel coordination circular polarization luminescent crystalline compound and preparation method and application thereof |
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