CN109206411A - One kind complex of cube containing sodium and preparation method thereof - Google Patents
One kind complex of cube containing sodium and preparation method thereof Download PDFInfo
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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Abstract
The present invention provides one kind complex of cube containing sodium and preparation method thereof, and the coordination chemistry formula of cube containing sodium is C27H24Br0.5Na0.5N10, the structural formula of the organic ligand in complex are as follows:The organic ligand is coordinated using four tooth chelating modes and a Na (I).The complex of cube containing sodium proposed by the present invention, three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine selected are as organic ligand, three pyridines amine therein is tetradentate ligands, it can be coordinated with Na, simultaneously as NH group and halide ion and easily forming hydrogen bond on pyrazoles, stable chelating cyclic structure can be formed, and the complex obtained is the complex with multiple cube, has extraordinary potential application prospect in the fields such as ion identification and detection.
Description
Technical field
The invention belongs to metal organic complex fields, and in particular to a kind of complex and its preparation containing sodium.
Background technique
In recent years, metal organic complex is due to its topological structure abundant, the accumulation mode of multiplicity, make its light, electricity,
Magnetic, photocatalytic degradation and gas storage etc. show huge application potential.Cubic type complex is three Vygens
Belong to the important branch of organic coordination compound, Cube for designing algorithm type complex is the previous research topic being concerned by people of mesh, system
The effort of standby cubic type complex focuses mostly in organic bridge ligand of appropriate design, then passes through coordinate bond or hydrogen again
Weak interactions such as key etc. are assembled with metallic atom and are formed.So far, scientists be prepared for a large amount of single, double, triples,
The cubic type structure of coordination compound at four centers.
At present, it has been reported that the metal organic complex overwhelming majority be using d p-block element p as the complex of center ion, with
S p-block element p is the less of center ion.In addition, hydrogen bond is a kind of directive intermolecular force.It exists to certainization
The property for closing object has considerable influence, thus, one for constructing hydrogen bond always using halide ion and being in chemical research is important
Content achieves many progress in ionic liquid, molecular crystal building.In this research direction, organic compound three
((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine has the characteristics that coordination mode is versatile and flexible, coordination site is abundant, extensive
For the synthesis of metal complex materials, and assign metal organic complex a variety of unexpected technical characteristics.
Summary of the invention
For short slab present in existing technology of preparing and deficiency, the primary purpose of the present invention is that providing a kind of vertical containing sodium
Cube complex.
The crystal formed another object of the present invention is to provide the complex of cube containing sodium.
Another object of the present invention is to provide a kind of preparation methods of complex of cube containing sodium.
Realize above-mentioned purpose technical solution of the present invention are as follows:
A kind of complex of cube containing sodium, the coordination chemistry formula of cube containing sodium are C27H24Br0.5Na0.5N10, cooperation
The structural formula of organic ligand in object are as follows:
The organic ligand is coordinated using four tooth chelating modes and a Na (I).
Wherein, the complex of cube containing sodium be eight-coordinate hexahedron structure, hexahedral center be Na (I) from
Son, eight vertex are occupied by 8 nitrogen-atoms of two organic ligands.
The crystal that the complex of cube containing sodium is formed, the crystal are trigonal system, R-3 space group, structure cell ginseng
Number is a=17.7212 (5), b=17.7212 (5), c=13.8699 (4), α=β=90 °, γ=120 °, V=3772.2
(2)。
The preparation method of the complex of cube containing sodium is the anion balanced using Br (I) as cationic charge,
It reacts and obtains with organic ligand three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine.
Further, the preparation method, comprising steps of
(1) water is added in NaBr, is formulated as mixed liquor a；
(2) organic ligand three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine is added to organic solvent,
Stirring forms mixed liquor b at room temperature；
(3) mixed liquor b is added into mixed liquor a, is reacted at room temperature.
In step (3), mixed liquor b is added into mixed liquor a, the cube containing sodium is obtained after standing volatilization 1-2 weeks
The crystal of complex.
If after mixed liquor b is added into mixed liquor a, liquid is directly concentrated and is spin-dried for just not instead of crystal form, Gu
Body powder.
Wherein, organic ligand three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine be prepared by the following method and
:
S1 is added three into reaction dissolvent [(5- bromopyridine) -2- methyl)] amine, potassium carbonate and four (triphenyl phosphorus) palladiums,
1- (oxinane -2- base) -1H- pyrazoles -4- pinacol borate, heating reaction are added under gas shield；
S2 isolates three ((5- (1- (oxinane -2- the base) -1H- pyrazoles -4- base) pyridine -2- bases) that step S1 is obtained
Methyl) amine, it is dissolved in solvent and hydrochloric acid is added, acidification hydrolization reaction occurs at room temperature；The solvent be methylene chloride, chloroform,
One of methanol, ethyl acetate, difluorodibromomethane are a variety of；
Sodium hydrate aqueous solution is added dropwise into reaction system by S3, and adjusting pH value is 7-8.
Wherein, in step S1, the reaction dissolvent is n-butanol, ethylene glycol, tetrahydrofuran, toluene, water, propylene glycol, third
One of triol is a variety of；
Preferably, the reaction dissolvent is water and n-butanol volume ratio 1:(1~6) mixed solvent.
Described three [(5- bromopyridine) -2- methyl)] amine, potassium carbonate, four (triphenyl phosphorus) palladiums and 1- (oxinane -2-
Base) -1H- pyrazoles -4- pinacol borate ratio be (1~2): (20~30): (0.1~0.3): (5~8).
It is highly preferred that in step (1), mole of described three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine and NaBr
Than for (1.5~2.5): 1.
Wherein, the organic solvent is at least one of dimethylformamide, dimethyl acetamide.
It is further preferred that the volume ratio of the mixed liquor b and mixed liquor a is 1:(4~7).
The concentration of mixed liquor b and mixed liquor a can be formulated as 0.001~1mol/L independently of each other.
The beneficial effects of the present invention are:
The complex of cube containing sodium proposed by the present invention, three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine of selection
As organic ligand, three pyridines amine therein is tetradentate ligands, can be coordinated with Na, simultaneously as NH group and halogen on pyrazoles
Plain ion and easily formation hydrogen bond, can form stable chelating cyclic structure, and the complex obtained is that have multiple cube
Complex, ion identification and detection etc. fields have extraordinary potential application prospect.
Detailed description of the invention
Fig. 1 is the coordination context diagram of the sodium ion in the complex of cube containing sodium of the invention.
Fig. 2 is the multiple cube structure schematic diagram of the complex of cube containing sodium of the invention.
Specific embodiment
Illustrate the present invention below by most preferred embodiment.Those skilled in the art institute it should be understood that, embodiment is only used to
It illustrates rather than for limiting the scope of the invention.
In embodiment, three [(5- bromopyridine) -2- methyl)] amine and 1- (oxinane -2- base) -1H- pyrazoles -4- boric acid frequency
Which alcohol ester is purchased from Chemical Co., Ltd. of Beijing Hua Weirui section.
In embodiment, unless otherwise instructed, means used are the means of this field routine.
Embodiment 1:
((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine organic ligand three used in the present invention, the entitled tris of English
((5- (1H-pyrazol-4-yl) pyridin-2-yl) methyl) amine, shown in chemical structural formula such as formula (I).According to
The preparation of lower section method:
Step 1: the synthesis of three ((5- (1- oxinane-pyrazoles -4- base) pyridine -2- base) methyl) amine: in gas shield
Under, to [(5- bromopyridine) -2- the methyl)] amine that is added three in the mixed solvent (volume ratio 5:1) of the 150mL tert-butyl alcohol and water
(1.05g, 1.99mmol), potassium carbonate (3.25g, 0.024mol), four (triphenyl phosphorus) palladiums (0.23g, 0.20mmol), 1- (four
Hydrogen pyrans -2- base) -1H- pyrazoles -4- pinacol borate (6.47mmol), it is heated to 90 degree of progress back flow reaction 72 hours.Subtract
Reaction dissolvent is distilled off in pressure, obtained crude product is dissolved in organic solvent dichloromethane, water extraction takes organic layer, after concentration
Low temperature crystallization obtains three ((5- (1- (oxinane -2- base) -1H- pyrazoles -4- base) pyridine -2- base) methyl) amine.
Step 2: the synthesis of three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine: with the round-bottomed flask of 250mL by three
((5- (1- (oxinane -2- base) -1H- pyrazoles -4- base) pyridine -2- base) methyl) amine 0.244g is dissolved in 30mL methanol, electromagnetism
Stirring, 2ml 1M concentrated hydrochloric acid is added dropwise in round-bottomed flask, and a whole night is stirred at room temperature after dripping off, and sodium hydroxide saturation is added
Solution adjusts pH value 7-8.Not molten solid is collected with Buchner funnel, and washing several times, is dried to obtain three ((5- (pyrazoles -4- base) pyrroles
Pyridine -2- base) methyl) amine.
Embodiment 2: the preparation of the complex of cube containing sodium
NaBr is added into distilled water, is stirred at room temperature to form mixed liquor a (0.01M)；
Organic ligand three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine processed of embodiment 1 is added to organic solvent two
In methylformamide (0.01M), it is stirred at room temperature to form mixed liquor b；
Then mixed liquor b is added into mixed liquor a, wherein three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine
Molar ratio with NaBr is that the volume ratio of 2:1, mixed liquor a and mixed liquor b are 1:5；Volatilization 2 weeks are stood at room temperature, obtain institute
State the complex of cube containing sodium C27H24Br0.5Na0.5N10, yield is 56% (being based on Na).
Embodiment 3: the preparation of the complex of cube containing sodium
The present embodiment operate substantially with embodiment 2, mixed liquor b is added into mixed liquor a, embodiment 2 be by stand,
Crystal can be obtained, for following structural characterization.And the present embodiment liquid is directly concentrated and is spin-dried for just not instead of crystal form,
To the complex of cube containing sodium C27H24Br0.5Na0.5N10Solid powder.
Structural characterization
Complex prepared by embodiment 2 carries out structural characterization.
Crystal X-ray diffraction data uses SuperNova, Dual, Cu at home/near, AtlasS2 single crystal diffraction
Instrument measurement.CuKa radiates (λ=1.54178), graphite monochromator, collects data with ω scanning mode, and carry out Lp factor correction
And empirical absorption correction.The position that other non-hydrogen atoms of metallic atom and part are first determined with direct method, then uses difference functions
Method and least square method find out remaining whole non-hydrogen atom coordinate, and with theoretical hydrogenation method obtain hydrogen atom position or from difference Fu
It finds on Li Yetu, structure is modified with complete matrix least square method.Crystallographic parameter is shown in Table 1, and structure is shown in the (upper left Fig. 1
Corner-kick indicates Br atom), Fig. 2.
The crystallographic parameter and structure elucidation of 1. polymer of table
Goodness-of-fit on F2: the degree of agreement based on F2 refine, R1a,wR2b[2 σ of I > (I)] observable spreads out
The identical factor penetrated, R1 a,wR2 b(all data): the identical factor of all data, Largest diff.peak and hole:
Maximum summit and peak valley on difference Fourier figure.
This contains sodium cube complex (Crystal system) and belongs to trigonal system (trigonal), R-3 space group
(Space group), cell parameter be a=17.7212 (5), b=17.7212 (5), c=13.8699 (4), α=β=90 °,
γ=120 °, V=3772.2 (2).Molecular weight (Formula weight) 540.01.
This contains sodium cube complex and contains independent Na in a crystallography+Atom (as shown in Figure 1), it is eight-coordinate
Monovalence sodium atom, in eight coordination atoms, wherein 6 nitrogen-atoms on pyridine ring, remaining 2 from participating in matching
The nitrogen-atoms of the amino of position.It is 2.595-2.655 angstroms that central atom and coordination atom, which are formed by Na-N coordinate bond bond distance, normal
(data that the crystal structure that X-RAY diffraction is surveyed obtains) are seen within the scope of the coordination bond lengths of Na-N.It is former according to coordination atom and metal
Son is formed by angle (data that the crystal structure that X-RAY diffraction is surveyed obtains) within the scope of 63.42-101.61 ° it is found that this is matched
Position central atom uses the coordination configuration of cube.In the complex, Na-N (2) bond distance of the same ligand is 2.595 angstroms
With 2.655 angstroms of bond distance of Na-N (1), N (1)-Na-N (2) bond angle is 63.47 ° and N (2)-Na-N (2 ') bond angle is 101.61 °, N
(1) distance and unequal, nitrogen-atoms N (2) composition plane that Na-N (1) key with Na atom be connected of the atom to three N (2) atoms
There is certain torsional angles.Therefore, which has embodied good flexibility ironically, and anion Br is not only acted as
The charge of entire molecule is balanced, while multiple N-H...Br key interaction can be constituted with the pyrazoles NH in body under unified central planning, is formd
Multiple cube structure as shown in Figure 2.
In this complex of cube containing sodium, three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine as organic ligand,
Three pyridines amine therein is tetradentate ligands, can be coordinated with Na, simultaneously as NH group and halide ion and easy shape on pyrazoles
At hydrogen bond, stable chelating cyclic structure can be formed, and the complex obtained is the complex with multiple cube, from
Son identification has extraordinary potential application prospect with fields such as detections.
Above embodiment be only preferred embodiments of the present invention will be described, not to the scope of the present invention into
Row limits, and without departing from the spirit of the design of the present invention, this field ordinary engineering and technical personnel is to technical side of the invention
The all variations and modifications that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (10)
1. a kind of complex of cube containing sodium, which is characterized in that the coordination chemistry of cube containing the sodium formula is
C27H24Br0.5Na0.5N10, the structural formula of the organic ligand in complex are as follows:
The organic ligand is coordinated using four tooth chelating modes and a Na (I).
2. the complex of cube containing sodium according to claim 1, which is characterized in that the complex of cube containing sodium is eight
The hexahedron structure of coordination, hexahedral center are Na (I) ion, and eight vertex are accounted for by 8 nitrogen-atoms of two organic ligands
According to.
3. the crystal that the complex of cube containing sodium described in claim 1 is formed, which is characterized in that the crystal is three prismatic crystals
System, R-3 space group, cell parameter are a=17.7212 (5), b=17.7212 (5), c=13.8699 (4), α=β=90 °, γ
=120 °, V=3772.2 (2).
4. the preparation method of the complex of cube containing sodium of any of claims 1 or 2, which is characterized in that using Br (I) as sun from
The anion of charge of the electron balance, reacts with organic ligand three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine and is obtained.
5. the preparation method according to claim 4, which is characterized in that comprising steps of
(1) water is added in NaBr, is formulated as mixed liquor a；
(2) organic ligand three ((5- (pyrazoles -4- base) pyridine -2- base) methyl) amine is added to organic solvent, in room temperature
Lower stirring forms mixed liquor b；
(3) mixed liquor b is added into mixed liquor a, is reacted at room temperature.
6. preparation method according to claim 4 or 5, which is characterized in that the three ((5- (pyrazoles -4- base) of organic ligand
Pyridine -2- base) methyl) amine is prepared by the following method and obtains:
S1 is added three into reaction dissolvent [(5- bromopyridine) -2- methyl)] amine, potassium carbonate and four (triphenyl phosphorus) palladiums, in gas
Protection is lower to be added 1- (oxinane -2- base) -1H- pyrazoles -4- pinacol borate, heating reaction；
S2 isolates three ((5- (1 (oxinane -2- base) -1H- pyrazoles -4- base) pyridine -2- base) first that step S1 reacts
Base) amine, it is dissolved in solvent and hydrochloric acid is added, acidification hydrolization reaction occurs at room temperature；The solvent be methylene chloride, chloroform, methanol,
One of ethyl acetate, difluorodibromomethane are a variety of；
Sodium hydrate aqueous solution is added dropwise into reaction system by S3, and adjusting pH value is 7~8.
7. preparation method according to claim 6, which is characterized in that in step S1, described three [(5- bromopyridine) -2- first
Base)] amine, potassium carbonate, four (triphenyl phosphorus) palladiums and 1- (oxinane -2- base) -1H- pyrazoles -4- pinacol borate mole
Ratio is (1~2): (20~30): (0.1~0.3): (5~8).
8. preparation method according to claim 5, which is characterized in that in step (1), the three ((5- (pyrazoles -4- base)
Pyridine -2- base) methyl) molar ratio of amine and NaBr is (1.5~2.5): 1.
9. the preparation method according to claim 5 or 8, which is characterized in that the organic solvent is dimethylformamide, two
At least one of methylacetamide.
10. the preparation method according to claim 5 or 8, it is characterised in that: the volume ratio of the mixed liquor b and mixed liquor a
For 1:(4~7).
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162508A (en) * | 1987-12-18 | 1992-11-10 | Compagnie Oris Industrie | Rare earth cryptates, processes for their preparation, synthesis intermediates and application as fluorescent tracers |
-
2018
- 2018-11-22 CN CN201811395036.9A patent/CN109206411A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162508A (en) * | 1987-12-18 | 1992-11-10 | Compagnie Oris Industrie | Rare earth cryptates, processes for their preparation, synthesis intermediates and application as fluorescent tracers |
Non-Patent Citations (2)
| Title |
|---|
| BÉATRICE ALPHA ET AL.: "116. Synthesis and characterization of the sodium and lithium cryptates of macrobicyclic ligands incorporating pyridine, bipyridine, and biisoquinoline units", 《HELVETICA CHIMICA ACTA》 * |
| HANS TOFTLUND ET AL.: "Surprisingly high stability of alkali-metal complexes of the ligand tris(2-pyridylmethyl)amine (TPA)", 《INORGANIC CHEMISTRY》 * |
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