CN109705028A - Five tooth nitrogen ligands of one kind and its complex, preparation method and application - Google Patents
Five tooth nitrogen ligands of one kind and its complex, preparation method and application Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 239000003446 ligand Substances 0.000 title claims abstract description 95
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- ACYBVNYNIZTUIL-UHFFFAOYSA-N n'-benzylethane-1,2-diamine Chemical compound NCCNCC1=CC=CC=C1 ACYBVNYNIZTUIL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- JWWVWJOIKZNCSU-UHFFFAOYSA-N methanesulfonic acid;2,2,2-trifluoroacetic acid Chemical compound CS(O)(=O)=O.OC(=O)C(F)(F)F JWWVWJOIKZNCSU-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000013110 organic ligand Substances 0.000 abstract description 6
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- -1 rare earth ion Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical class O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- JPMRGPPMXHGKRO-UHFFFAOYSA-N 2-(chloromethyl)pyridine hydrochloride Chemical compound Cl.ClCC1=CC=CC=N1 JPMRGPPMXHGKRO-UHFFFAOYSA-N 0.000 description 1
- AHISYUZBWDSPQL-UHFFFAOYSA-N 6-methylpyridine-2-carbaldehyde Chemical compound CC1=CC=CC(C=O)=N1 AHISYUZBWDSPQL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- OBHWOLDGXCOBAK-UHFFFAOYSA-N [F].CS(O)(=O)=O Chemical compound [F].CS(O)(=O)=O OBHWOLDGXCOBAK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- DGZXMSLLXBWIFG-UHFFFAOYSA-N formaldehyde;pyridine Chemical class O=C.C1=CC=NC=C1 DGZXMSLLXBWIFG-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Abstract
The present embodiments relate to organic ligand fields, and in particular to five tooth nitrogen ligands of one kind and its complex, preparation method and application.Five teeth nitrogen ligand provided in an embodiment of the present invention, molecular formula C27H31N5X1X2 is made by N- benzyl ethylenediamine, pyridine carboxaldehyde class and pyridine hydrochloride for raw material.The embodiment of the invention also provides the complexs of the five tooth nitrogen ligands formed by five tooth nitrogen ligands and transition metal or rare earth ion.Five teeth nitrogen ligand provided by the invention is a kind of Novel Ligands, a kind of new structural model is provided for field of coordinative chemistry, it can form stable complex, the complex of formation can be used for being catalyzed reaction as a kind of multiple tooth, multiple spot coordination organic ligand with transition metal or rare earth ion.Because of N5X group in-X ligand can generate synergistic effect with central metal, and the catalytic efficiency of complex can be improved.
Description
Technical field
The present invention relates to organic ligand fields, and in particular to a kind of five tooth nitrogen ligands and its complex, preparation method and answers
With.
Background technique
In recent years, due to the important application potentiality in fields such as medicine, photochemistry, catalysis, research preparation has different skies
Between the organometallic complex of configuration be a hot spot direction.The structure and property for studying organic ligand, can be in Coordinative Chemistry
Field provides more more novel structural models for people, in spatial chemistry, ligand chemical, bioinorganic chemistry, magnetism, spectrum
It learns the scientific domains such as research and reaction mechanism and all has significance.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
Goal of the invention
The purpose of the present invention is to provide a kind of five tooth nitrogen ligands and its complexs, preparation method and application.The present invention mentions
Five tooth nitrogen ligand (the hereinafter referred to as N supplied5- X ligand) it is a kind of Novel Ligands, a kind of new knot is provided for field of coordinative chemistry
Structure model can be formed stable as a kind of multiple tooth, multiple spot coordination organic ligand with transition metal or rare earth ion
Complex, the complex of formation can be used for being catalyzed reaction.Because of N5X group in-X ligand can be generated with central metal cooperates with work
With the catalytic efficiency of complex can be improved.The preparation method of five teeth nitrogen ligand and its complex provided by the invention, with N- benzyl
The common agents such as ethylenediamine, pyridine carboxaldehyde class and pyridine hydrochloride are raw material, and step is simple, controllably.
Solution
Purpose to realize the present invention, the embodiment of the invention provides a kind of five tooth nitrogen ligands, molecular formula is
C27H31N5X1X2, structural formula are as follows:
；Wherein, X1=-CH3、-OCH3、-Br、-NH2、-OH、-CH2OH ,-COOH or-COOMe, X2=-H；
Or X1 and X2 are-(CH) jointly4-；
Or X1 and X2 are-N (CH) jointly3-。
The embodiment of the invention also provides a kind of preparation methods of five tooth nitrogen ligands, include the following steps:
；
Wherein, NaBH4The schiff bases generated for in-situ reducing aldehyde and amine reaction；
R=-CH3、-OCH3、-Br、-CH2OH or-COOMe, R0=-H；
Or R and R0 are-(CH) jointly4-；
Or R and R0 are-N (CH) jointly3-；
R1=-Cl or-Br.
The preparation method of above-mentioned five teeth nitrogen ligand in one possible implementation, works as R=-Br, when R0=-H, also wraps
It includes and-the Br in formula (3) compound is changed into-NH2The step of to prepare:
；Optionally, it still further comprises-NH2The step of being changed into-OH is to prepare:
。
The preparation method of above-mentioned five teeth nitrogen ligand in one possible implementation, works as R=-COOMe, when R0=-H,
Further include the steps that hydrolyzing to obtain-COOH to prepare by-the COOMe in formula (3) compound:
；
In one possible implementation, the preparation method includes following steps to the preparation method of above-mentioned five teeth nitrogen ligand
It is rapid:
N- benzyl ethylenediamine and formula (1) compound are taken, is dissolved in organic solvent 1, after stirring at room temperature, NaBH is added4,
Continue to stir；Organic solvent 1 is removed, water is added；It is extracted with organic solvent, collects organic phase；Formula (2) are added in organic phase
Compound prepares aqueous slkali, first plus half aqueous slkali, adds halogenated quaternary ammonium salt cationic class catalyst, stirs, and adds another
Half aqueous slkali, is stirred at room temperature；Organic phase is collected in extraction；The water in solvent is dried and removed, extractant is removed, obtains crude product；
Crude product is recrystallized to obtain five tooth nitrogen ligands in petroleum ether.
The preparation method of above-mentioned five teeth nitrogen ligand in one possible implementation, N- benzyl ethylenediamine: formula (1) chemical combination
Object: formula (2) compound: the molar ratio of alkali is 1:1:2:4.
In one possible implementation, halogenated quaternary ammonium salt cationic includes four to the preparation method of above-mentioned five teeth nitrogen ligand
Butylammonium bromide.Halogenated quaternary ammonium salt cationic is phase transfer catalyst.
In one possible implementation, organic solvent 1 includes methanol, second to the preparation method of above-mentioned five teeth nitrogen ligand
Alcohol, methylene chloride, tetrahydrofuran or 1, at least one of 2- dichloroethanes.
In one possible implementation, temperature when recrystallization is 60-90 to the preparation method of above-mentioned five teeth nitrogen ligand
℃。
The preparation method of above-mentioned five teeth nitrogen ligand in one possible implementation, after being dissolved in organic solvent 1, in room
Temperature stirring 0.5-3 days, is optionally 1 day.
In one possible implementation, NaBH is added in the preparation method of above-mentioned five teeth nitrogen ligand4, continue to stir 0.5-
It 3 days, is optionally 1 day.
In one possible implementation, halogenated quaternary ammonium salt cationic is added in the preparation method of above-mentioned five teeth nitrogen ligand
Afterwards, 2-100min is stirred；Optionally, 10-40min is stirred；Still optionally further, 30min is stirred.
The preparation method of above-mentioned five teeth nitrogen ligand in one possible implementation, after adding the other half aqueous slkali,
It stirs 0.5-3 days, is optionally 1 day at room temperature.
The embodiment of the invention also provides a kind of complex of five tooth nitrogen ligands, structural formula is as follows:
；X1=-CH3、-OCH3、-Br、-NH2、-OH、-CH2OH ,-COOH or-COOMe, X2=-H；Or X1 and X2 is common
For-(CH)4-；Or X1 and X2 are-N (CH) jointly3-；
M=Co, Ni, Cu, Fe, Ru, Ir, Mn；Z=OH-Or-NCCH3；N=1-5；Y=BF4 -Or F3CSO3 -。
The complex of above-mentioned five teeth nitrogen ligand is formed by above-mentioned five teeth nitrogen ligand and transition metal or rare earth ion.Five
5 N in tooth nitrogen ligand are connected with M with coordinate bond, and Z is also connected with M with coordinate bond.
The complex of above-mentioned five teeth nitrogen ligand in one possible implementation, the X1=-NH of the complex2, X2
=-H, M=Co, Z=OH-, n=2, Y=BF4 -；Its molecular formula are as follows: C29H31B2CoF8N7O2(Co (N is used below5-NH2(OH-))
(BF4)2It indicates).
The complex of above-mentioned five teeth nitrogen ligand in one possible implementation, the X1=-CH of the complex3, X2
=-H, M=Co, Z=OH-, n=2, Y=BF4 -；Its molecular formula are as follows: C30H31B2CoF8N6(Co (N is used below5-CH3(OH-))
(BF4)2It indicates).
The embodiment of the invention also provides the preparation methods of the complex of above-mentioned five teeth nitrogen ligand, include the following steps:
Above-mentioned five teeth nitrogen ligand and metal salt are stirred at room temperature in acetonitrile to obtain the final product.
The preparation method of the complex of above-mentioned five teeth nitrogen ligand in one possible implementation, includes the following steps:
Above-mentioned five teeth nitrogen ligand is dissolved in a solvent, acetonitrile is added, is added with stirring metal borofluoride or metal three
Fluorine mesylate, is stirred to obtain the final product.
The preparation method of the complex of above-mentioned five teeth nitrogen ligand in one possible implementation, five tooth nitrogen ligands and gold
The molar ratio for belonging to salt is 1:1.
In one possible implementation, solvent includes methanol to the preparation method of the complex of above-mentioned five teeth nitrogen ligand,
At least one of ethyl alcohol or methylene chloride.
The preparation method of the complex of above-mentioned five teeth nitrogen ligand in one possible implementation, solvent: the body of acetonitrile
Product ratio=1:5-1:1.
The embodiment of the invention also provides application of the complex of above-mentioned five teeth nitrogen ligand in catalysis reaction.The catalysis
Reaction includes electro-catalysis activation of small molecule, such as catalysis CO2Reduction, Catalytic Proton reduction, catalytic water oxidation or oxidation of hydrogen.
The effect of five teeth nitrogen ligand provided in an embodiment of the present invention is divided into: 1. directly with the first coordination sphere of metal bonding,
Its major function is to change the ligand field of central metal, to control the arrangement of d orbital electron, influences catalytic effect；2. not directly
With metal bonding, but the group by connecting with the first coordination sphere forms the second coordination environment, such as X group, major function
It is that driven terms of mechanics influences the functions such as substance transmitting.
Beneficial effect
(1) the five tooth nitrogen ligand N provided in the embodiment of the present invention5- X is a kind of Novel Ligands, is mentioned for field of coordinative chemistry
A kind of new structural model is supplied.It, can be with transition metal or rare earth metal as a kind of multiple tooth, multiple spot coordination organic ligand
Ion forms stable complex, and the complex of formation can be used for being catalyzed reaction.
(2) the five tooth nitrogen ligand N provided in the embodiment of the present invention5The complex of-X, because of N5X group in-X ligand can
Synergistic effect is generated with central metal, the catalytic efficiency of complex can be improved.
(3) preparation method of five teeth nitrogen ligand and its complex provided in an embodiment of the present invention, with N- benzyl ethylenediamine, pyrrole
The common agents such as pyridine formaldehydes and pyridine hydrochloride are raw material, and step is simple, controllably.
Detailed description of the invention
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Here as any embodiment illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Fig. 1 is the complex Co for the five tooth nitrogen ligands drawn in the embodiment of the present invention 4 using X- single crystal diffraction test data
(N5-NH2(OH–))2+(left side) and Co (N5-CH3(OH–))2+The ORTEP structure chart on (right side).
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise whole
In a specification and claims, it is to include that the term " include " or its transformations will be understood as
The element or component stated, and do not exclude other elements or other components.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In some embodiments, right
It is not described in detail in raw material well known to those skilled in the art, element, method, means etc., in order to highlight master of the invention
Purport.
Embodiment 1
Five tooth nitrogen ligand N of one kind5-CH3, structural formula is as follows:
。
Five teeth nitrogen ligand N5-CH3Preparation method include the following steps:
(1) 9.06g N- benzyl ethylenediamine (0.06mol) and 8.22g 6- methyl -2- pyridine carboxaldehyde (0.06mol) are taken, in
In 250mL round-bottomed flask, about 80mL anhydrous methanol is added as solvent, after being stirred at room temperature one day, 1 equivalent is added by amount
NaBH4, after continuing stirring 1 day, it is spin-dried for anhydrous methanol under decompression, 100mL water is added, then takes 150mL methylene chloride in three times
Organic phase is collected in extraction, is directly used in and is reacted in next step；
(2) 20.16g 2- chloromethyl pyridine hydrochloride (0.12mol) is added in this organic phase, then takes 9.6g NaOH
(0.24mol) is made into the solution of mass concentration 10%, and half is first added, and adds 0.50g tetrabutylammonium bromide, stirs 10 minutes
After add the other half NaOH solution；
(3) it stirs one day at room temperature, 150mL methylene chloride is taken to extract in three times, collect organic phase, add in organic phase
Enter appropriate anhydrous Na2SO4, after stirring one day at room temperature, filter, rotate out methylene chloride, obtain crude product；By crude product in stone
Pure products are recrystallized to give in oily ether (60-90 DEG C).
To five obtained tooth nitrogen ligand N5-CH3, at 25.0 DEG C, with 600MHz Bruker Nuclear Magnetic Resonance test this match
Body1H NMR spectra, as a result as follows:1H NMR(CDCl3,600MHz):δ8.48(d,2H),7.58(m,2H),7.48(m,
3H),7.26(m,7H),7.09(m,2H),6.97(d,1H),3.73(m,6H),3.58(s,2H),2.71(s,4H),2.50(s,
3H)。
Embodiment 2
Five tooth nitrogen ligand N of one kind5- X, structural formula difference are as shown in table 1 below:
Table 1
Wherein, the preparation method is the same as that of Example 1 for the five tooth nitrogen ligands of serial number 1-6, and difference is only that addition in step (1)
The type of formula (1) compound (pyridine carboxaldehyde) and quality difference, are specifically shown in Table 2.
Table 2
To five obtained tooth nitrogen ligand N5- X, at 25.0 DEG C, with the ligand of 600MHz Bruker Nuclear Magnetic Resonance test
's1H NMR spectra, as a result as follows:
N5-OCH3:1H NMR(CDCl3,600MHz):δ8.48(m,2H),7.56(m,2H),7.52(d,1H),7.48(m,
1H),7.45(m,1H),7.29(m,2H),7.25(m,2H),7.20(m,1H),7.10(m,2H),6.93(d,1H),3.86(s,
3H),3.82(s,2H),3.73(s,2H),3.68(s,2H),3.60(s,2H),2.76(s,2H),2.71(s,2H)；
N5- Br:1H NMR(CDCl3,600MHz):δ8.49(m,2H),7.58(m,2H),7.48(d,1H),7.41(m,
3H),7.27(m,5H),7.19(m,1H),7.12(m,2H),3.74(d,6H),3.60(s,2H),2.70(d,4H)。
Embodiment 3
1. five tooth nitrogen ligand N of one kind5-NH2, structural formula is as follows:
Above-mentioned five teeth nitrogen ligand N5-NH2Preparation method, referring to Efficient synthesis of
aminopyridine derivatives by copper catalyzed amination reactions；Chemical
Communications；2010,46,925–927.
It is specific as follows:
(1) 5.0005g (0.001mol) N is weighed5- Br (2 five tooth nitrogen ligand of serial number in 2 table 1 of embodiment) and 0.35g
(0.0025mol)K2CO3, be placed in a reaction flask, vacuumize, lead to nitrogen, repeat 3-4 time, guarantee react under nitrogen protection into
Row；
(2) 0.11g DMEDA (N, N'- dimethyl-ethylenediamine) is dissolved in 25ml ethylene glycol, and be added in reaction flask, then
Add 15.5ml NH3·H2O, whole process must carry out under conditions of logical nitrogen；
(3) 0.09g Cu is weighed2O (0.00063mol) is added in reaction flask under conditions of logical nitrogen；Stirring, temperature
Rise to 80 DEG C；It is reacted for 24 hours after temperature is stablized；
(4) it takes 150ml ethyl acetate to extract in three times, collects organic phase, appropriate anhydrous Na is added in organic phase2SO4,
After stirring 30min at room temperature, filters, rotate out methylene chloride, obtain crude product；Crude product crosses chromatographic column and obtains five tooth nitrogen of sterling
Ligand N5-NH2。
Five tooth nitrogen ligand N5-NH2Nuclear magnetic spectrogram result it is as follows:
N5-NH2:1H NMR(CDCl3,600MHz):δ8.49(2H,d),7.58(2H,m),7.49(1H,m),7.44(1H,
M), 7.36 (1H, m), 7.23~7.31 (5H, m), 7.12 (2H, m), 6.75 (1H, d), 6.44 (1H, d), 3.63~3.81
(8H, m), 2.73~2.79 (4H, m), 2.05 (2H, s)
2. five tooth nitrogen ligand N of one kind5- OH, structural formula are as follows:
Above-mentioned five teeth nitrogen ligand N5The preparation method of-OH includes the following steps:
Five tooth nitrogen ligand N of purification5-NH2It can further react to obtain N by conventional method5- OH, specific as follows:
(1) 40ml water is added in 100ml two mouth flask, is put into ice-water bath, the H of 8ml 98% is added while stirring2SO4,
Five tooth nitrogen ligand N are added when aqueous sulfuric acid is cooled to 0 DEG C5-NH2(3.4g 8mmol)；
(2) by NaNO2(1.03g 14.9mmol) is dissolved in 2ml water, (drop/5s) is slowly added dropwise into above-mentioned reaction solution,
Reaction temperature is kept to be always below 5 DEG C；After being added dropwise, reaction mixture stirs 45min at 3-5 DEG C, is warming up to again later
95 DEG C of reaction 15min；
(3) said mixture is cooled to room temperature, then adjusts solution to neutral or alkalescent with 50%NaOH, and be heated to 60
℃；
(4) above-mentioned reaction mixture is extracted after being cooled to room temperature with 300ml ethyl acetate in three times, collection organic phase, and
Appropriate anhydrous Na is added in organic phase2SO4, after stirring 30min at room temperature, filter, rotate out ethyl acetate, obtain crude product；Slightly
Product crosses chromatographic column, obtains five tooth nitrogen ligand N of sterling5-OH。
3. five tooth nitrogen ligand N of one kind5- COOH, structural formula are as follows:
Above-mentioned five teeth nitrogen ligand N5The preparation method of-COOH includes the following steps:
By five teeth nitrogen ligand N obtained5The hydrolysis of ester group of-COOMe (1 serial number 4 of table) is to get to five tooth nitrogen ligand N5-
COOH。
Embodiment 4
1. a kind of complex of five tooth nitrogen ligands, X1=-NH2, X2=-H, M=Co, Z=OH-；N=2；Y=BF4 -,
Molecular formula is C29H31B2CoF8N7O2(i.e. Co (N5-NH2(OH–))(BF4)2)。
Complex Co (the N of the five teeth nitrogen ligand5-NH2(OH–))(BF4)2Preparation method include the following steps:
The five tooth nitrogen ligand N that 0.5mmol embodiment 3 is prepared5-NH2It is dissolved in the methanol of 1mL, is then added
4mL acetonitrile is added with stirring 0.5mmol CoBF4·6H2O stirs 8h under air conditions, then by reaction solution lab scale
Pipe packing, is spread by ether, directly culture monocrystalline, is collected monocrystalline and is used for performance test.
Co (N obtained5-NH2(OH–))(BF4)2Nuclear magnetic spectrogram result it is as follows:
Co(N5-NH2(OH–))(BF4)2:1H NMR(DMSO,600MHz):δ8.95(1H,d),δ8.27(2H,m),7.65
~7.85 (6H, m), 7.47~7.54 (5H, m), 6.81 (1H, d), 6.52 (1H, d), 5.14 (1H, d), 4.98 (1H, d),
4.80 (1H, d), 3.99~4.03 (3H, m), 3.85 (1H, d), 3.21 (1H, m), 3.17 (1H, d), 3.07 (1H, m), 3.01
(1H,d),2.85(1H,m).
2. a kind of complex of five tooth nitrogen ligands, X1=-CH3, X2=-H, M=Co, Z=OH-；N=2；Y=BF4 -,
Molecular formula is C30H31B2CoF8N6(i.e. Co (N5-CH3(OH–))(BF4)2)。
Complex Co (the N of the five teeth nitrogen ligand5-CH3(NCCH3))(BF4)2Preparation method include the following steps:
The five tooth nitrogen ligand N that 0.5mmol embodiment 1 is prepared5-CH3It is dissolved in the methanol of 1mL, is then added
4mL acetonitrile is added with stirring 0.5mmol CoBF4·6H2O stirs 8h under air conditions, then by reaction solution lab scale
Pipe packing, is spread by ether, directly culture monocrystalline, is collected monocrystalline and is used for performance test.
Complex Co (N to five tooth nitrogen ligands being prepared5-NH2(OH–))(BF4)2With Co (N5-CH3(NCCH3))
(BF4)2, carry out structure determination with X-ray single crystal diffraction method is made using Bruker Kappa APEX-II x-ray diffractometer
With being incident radiation by graphite monochromatised Mo Ka ray, point diffraction is collected with -20 scanning modes.It is passed through using SHELXL-97
It crosses least square refinement and obtains cell parameter, solve crystal structure using SHELXL-97.All H atoms are by difference
Fourier is synthesized and is calculated through ideal position, and detailed crystallography determination data is as shown in table 3.
Wherein, the complex Co (N of five tooth nitrogen ligands5-NH2(OH–))(BF4)2To belong to anorthic system, space group is P -1,
Cell parameter are as follows:α=66.49 (2), β=74.61 (2) °,
γ=84.89 (2), z=2.
Utilize the complex Co (N for the five tooth nitrogen ligands that X- single crystal diffraction test data is drawn5-NH2(OH–))2+With Co (N5-
CH3(NCCH3)) cation ORTEP structure chart see Fig. 1 (counter ion and part hydrogen atom have omitted).As shown in Figure 1, Co (N5-
NH2(OH–))2+With Co (N5-CH3(NCCH3)) it is the octahedral structure with five toothings.
Table 3
Five teeth can be prepared in any five teeth nitrogen ligand that embodiment 1-3 is prepared with respective metal in a similar fashion
The metal complex of nitrogen ligand.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of five tooth nitrogen ligands, molecular formula C27H31N5X1X2, structural formula are as follows:
；Wherein, X1=-CH3、-OCH3、-Br、-NH2、-OH、-CH2OH ,-COOH or-COOMe, X2=-H；
Or X1 and X2 are-(CH) jointly4-；
Or X1 and X2 are-N (CH) jointly3-。
2. a kind of preparation method of five tooth nitrogen ligands, includes the following steps:
；R=-CH3、-OCH3、-Br、-CH2OH or-COOMe, R0=-H；Or R and R0 are-(CH) jointly4-；Or R and R0 is common
For-N (CH)3-；
R1=-Cl or-Br.
3. preparation method according to claim 2, it is characterised in that: work as R=-Br, further include by formula (3) when R0=-H
- Br in compound is changed into-NH2The step of to prepare:
；Optionally, it still further comprises-NH2The step of being changed into-OH is to prepare:
。
4. preparation method according to claim 2, it is characterised in that: work as R=-COOMe, further include by formula when R0=-H
(3)-the COOMe in compound hydrolyzes the step of obtaining-COOH to prepare:
。
5. preparation method according to claim 2, it is characterised in that: the preparation method includes the following steps:
N- benzyl ethylenediamine and formula (1) compound are taken, is dissolved in organic solvent 1, after stirring at room temperature, NaBH is added4, continue to stir
It mixes；Organic solvent 1 is removed, water is added；It is extracted with organic solvent, collects organic phase；Formula (2) chemical combination is added in organic phase
Object prepares aqueous slkali, first plus half aqueous slkali, adds halogenated quaternary ammonium salt cationic class catalyst, stirs, adds the other half
Aqueous slkali stirs at room temperature；Organic phase is collected in extraction；The water in solvent is dried and removed, extractant is removed, obtains crude product；It will be thick
Product recrystallizes to obtain five tooth nitrogen ligands in petroleum ether.
6. preparation method according to claim 5, it is characterised in that: N- benzyl ethylenediamine: formula (1) compound: formula (2) is changed
Close object: the molar ratio of alkali is 1:1:2:4；
And/or halogenated quaternary ammonium salt cationic includes tetrabutylammonium bromide；
And/or organic solvent 1 includes methanol, ethyl alcohol, methylene chloride, tetrahydrofuran or 1, at least one of 2- dichloroethanes；
And/or temperature when recrystallization is 60-90 DEG C；
And/or after being dissolved in organic solvent 1, it is stirred at room temperature 0.5-3 days；
And/or NaBH is added4, continue stirring 0.5-3 days；
And/or after halogenated quaternary ammonium salt cationic is added, 2-100min is stirred；
And/or after adding the other half aqueous slkali, stir 0.5-3 days at room temperature.
7. a kind of complex of five tooth nitrogen ligands, structural formula are as follows:
；X1=-CH3、-OCH3、-Br、-NH2、-OH、-CH2OH ,-COOH or-COOMe, X2=-H；Or X1 and X2 be jointly-
(CH)4-；Or X1 and X2 are-N (CH) jointly3-；
M=Co, Ni, Cu, Fe, Ru, Ir, Mn；Z=OH-Or-NCCH3；N=1-5；Y=BF4 -Or F3SO3 -。
8. complex according to claim 7, it is characterised in that: the X1=-NH of the complex2, X2=-H, M=Co, Z
=OH-, n=2, Y=BF4 -；Its molecular formula are as follows: C29H31B2CoF8N7O2；
And/or the X1=-CH of the complex3, X2=-H, M=Co, Z=OH-, n=2, Y=BF4 -；Its molecular formula are as follows:
C30H31B2CoF8N6。
9. a kind of preparation method of the complex of five tooth nitrogen ligands, includes the following steps: five tooth nitrogen described in claim 1-6
Ligand and metal salt stir at room temperature in acetonitrile to obtain the final product；
Optionally, the preparation method includes the following steps: in a solvent to dissolve five tooth nitrogen ligands, acetonitrile is added, under stirring
Metal borofluoride or metal trifluoroacetate mesylate is added, stirs to obtain the final product；
Still optionally further, the molar ratio of five tooth nitrogen ligands and metal salt is 1:1；
And/or still optionally further, solvent includes methanol, at least one of ethyl alcohol or methylene chloride；
And/or still optionally further, solvent: volume ratio=1:5-1:1 of acetonitrile.
10. application of the complex of five teeth nitrogen ligand as claimed in claim 7 in catalysis reaction.
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| WO2013183591A1 (en) * | 2012-06-06 | 2013-12-12 | 保土谷化学工業株式会社 | Method for producing adamantanetriol |
Non-Patent Citations (4)
| Title |
|---|
| MASAKAZU TAMURA ET AL.: "Synthesis and superoxide dismutase activity of novel iron complexes", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| MOHAMMED K. ELMKADDEM ET AL.: "Efficient synthesis of aminopyridine derivatives by copper catalyzed amination reactions", 《CHEMICAL COMMUNICATIONS》 * |
| PEILI ZHANG ET AL.: "Electrocatalytic hydrogen evolution from neutral water by molecular cobalt tripyridine–diamine complexes", 《CHEMICAL COMMUNICATIONS》 * |
| 杨绿 等: "4-羟基吡啶合成研究", 《化学世界》 * |
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