CN111349121A - Cobalt carbonyl complex and preparation method thereof - Google Patents
Cobalt carbonyl complex and preparation method thereof Download PDFInfo
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- CN111349121A CN111349121A CN201811562724.XA CN201811562724A CN111349121A CN 111349121 A CN111349121 A CN 111349121A CN 201811562724 A CN201811562724 A CN 201811562724A CN 111349121 A CN111349121 A CN 111349121A
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- pyridylmethyl
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 83
- 239000010941 cobalt Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 41
- 238000010668 complexation reaction Methods 0.000 title description 2
- -1 bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) Chemical group 0.000 claims abstract description 89
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000012046 mixed solvent Substances 0.000 claims abstract description 32
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims abstract description 30
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 230000005587 bubbling Effects 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 29
- 239000007795 chemical reaction product Substances 0.000 claims description 28
- 239000012043 crude product Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
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- 239000000706 filtrate Substances 0.000 claims description 8
- UVGZZQFIUPSTIE-UHFFFAOYSA-N n-[6-(bromomethyl)pyridin-2-yl]-2,2-dimethylpropanamide Chemical compound CC(C)(C)C(=O)NC1=CC=CC(CBr)=N1 UVGZZQFIUPSTIE-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 claims description 6
- QUXLCYFNVNNRBE-UHFFFAOYSA-N 6-methylpyridin-2-amine Chemical compound CC1=CC=CC(N)=N1 QUXLCYFNVNNRBE-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 claims description 5
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- MAZMJMLUKYPLEI-UHFFFAOYSA-N 2,2-dimethyl-n-(6-methylpyridin-2-yl)propanamide Chemical compound CC1=CC=CC(NC(=O)C(C)(C)C)=N1 MAZMJMLUKYPLEI-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000004896 high resolution mass spectrometry Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000005588 protonation Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000004700 cobalt complex Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical group NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- VCWNAJUHTLWQQT-XCHBPHIQSA-N 4-o-methyl-tpa Chemical compound C([C@@]1(C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)OC)C(CO)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C VCWNAJUHTLWQQT-XCHBPHIQSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920005654 Sephadex Polymers 0.000 description 1
- 239000012507 Sephadex™ Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical group [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- DTSFAVOKEUXEMO-UHFFFAOYSA-N oxidanium;perchlorate;hydrate Chemical compound O.O.OCl(=O)(=O)=O DTSFAVOKEUXEMO-UHFFFAOYSA-N 0.000 description 1
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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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention discloses a cobalt carbonyl complex and a preparation method thereof, wherein the molecular formula of the cobalt carbonyl complex is [ Co (bapa)) (O2CO)]ClO4·2H2O, wherein bapa represents bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine. The preparation method comprises the following steps: will [ Co (H) ]2O)6](ClO4)2、bapa、NaHCO3And H2Mixing the O/methanol mixed solvent, introducing air for bubbling, stirring, reacting and post-treating to obtain the cobalt carbonyl complex. The cobalt carbonyl complex is a brand-new cobalt carbonyl (III) complex with a tripodal ligand, serves as a novel structural model, provides an important research object for the research of coordination chemistry, has extremely high academic value, has the advantages of mild reaction conditions, low energy consumption, high purification efficiency and the like, and has very important significance for preparing the cobalt carbonyl complex.
Description
Technical Field
The invention belongs to the field of organic metal complexes, relates to a cobalt carbonyl complex and a preparation method thereof, and particularly relates to a bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine cobalt carbonyl (III) dihydrate perchlorate complex and a preparation method thereof.
Background
The tripodal ligand has semi-rigid structural characteristics, three side chains of the tripodal ligand can be freely overturned to form a cavity, and the tripodal ligand is rich in variable side chain substituent types, so that the tripodal ligand shows specific selective coordination capacity and variable coordination modes when being coordinated with metal ions. The tripodal ligand compound and the complex thereof show good application prospects in the aspects of optics, electrics, magnetics and the like. In recent years, the structural design and preparation of novel tripodal ligands and their complexes have been studied as one of the subjects of intense research in the fields of organic chemistry, coordination chemistry, supramolecular chemistry, and the like.
Taking the preparation and acidolysis characteristics of a tripodal cobalt carbonyl complex as an example, even a chelated metal complex cannot protect a carbonate from acid hydrolysis because a quaternary carbonate chelating ring becomes strained during protonation, resulting in hydrolysis of most of the coordinated carbonate through a ring-opening reaction in an acidic aqueous solution. The Allan Blackman group and its leading physicians have been studying tripodal cobalt (III) carbonyl complexes and tripodal copper (II) carbonyl complexes and have published in Inorganic Chemistry a "stability of coordinated carbonyl compounds in acidic aqueous solutions: the influence of steric resistance on protonation in the chelate cobalt carbonyl (III) -containing complex, designs the structure and synthesizes [ Co (tpa) (O)2CO)]ClO4·H2O、[Co(Me-tpa)(O2CO)]ClO4·0.5H2O、[Co(Me3-tpa)(O2CO)]ClO43 tripodal cobalt carbonyl complexes in total and matchedThe acidolysis rate of the compound is researched, and the results show that: under the same conditions, the acidolysis rate ratio of the complex containing the methylated ligand [ Co (tpa) (O)2CO)]+25 to 90 times slower and for a large reason due to space considerations; and proposes its possibility of acidolysis: that is, under acidic conditions, the introduced 6-methylpyridinyl ring causes distortion of the tripodal ligand, and C ═ O is cleaved to generate a hydroxyl group.
The chemical structure and the spatial arrangement of the tripodal ligand are different, and the tripodal ligand and the oxygen atom on the carbonyl form the strength of an intramolecular hydrogen bond, which can cause the change of the transfer mechanism and the protonation rate of protons in the acidolysis process, thereby changing the acidolysis mechanism. Therefore, the construction and preparation of the novel model tripodia cobalt carbonyl coordination compound have important academic positions in basic researches such as preparation of organometallic complex subject and reactivity thereof. Therefore, different substitution numbers, different space substitution positions and different types of substituent groups are designed in the tripodal ligand, so that a plurality of tripodal ligands can be constructed respectively, and the substituent groups on the different tripodal ligands can form intramolecular hydrogen bonds with different strengths and numbers with carbonyl oxygen in the space positions, so that the method has very important significance for the acidolysis research of the tripodal cobalt complex.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a cobalt carbonyl complex and a preparation method thereof, and provides a new structural model for the basic subject fields of coordination chemistry and the like.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a cobalt carbonyl complex, the molecular formula of the cobalt carbonyl complex is [ Co (bapa)) (O2CO)]ClO4·2H2O, wherein bapa represents bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine.
In a further improvement of the above cobalt carbonyl complex, the cobalt carbonyl complex has a structural formula shown in formula (I) or formula (II):
in the cobalt carbonyl complex, the cobalt carbonyl complex is further improved, the cobalt carbonyl complex belongs to a triclinic crystal system, the space point group is P-1, and the unit cell parameters are as follows:
α＝79.9350(10)°，β＝77.5380(10)°，γ＝86.4720(10)°，z＝2。
as a general technical concept, the present invention also provides a preparation method of the cobalt carbonyl complex, comprising the steps of:
(1) will [ Co (H) ]2O)6](ClO4)2Bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine, NaHCO3And H2Mixing the O/methanol mixed solvent to obtain a mixed solution;
(2) and (2) introducing air into the mixed solution obtained in the step (1) for bubbling, stirring to enable the mixed solution to react, and carrying out aftertreatment on the obtained reaction product to obtain the cobalt carbonyl complex.
In a further improvement of the above-mentioned process for producing a bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine, the process comprises the steps of:
(a) dissolving 2-amino-6-methylpyridine in CH2Cl2Adding pivaloyl chloride dropwise into a triethylamine mixed solvent for reaction, and carrying out aftertreatment on an obtained reaction product to obtain 2-pivaloyl amido-6-methylpyridine;
(b) dissolving the 2-pivaloyl-6-methylpyridine obtained in the step (a) in carbon tetrachloride without air, adding N-bromosuccinimide and azobisisobutyronitrile, reacting under the protection of nitrogen, and carrying out aftertreatment on the obtained reaction product to obtain 2-pivaloyl-6-bromomethylpyridine;
(c) 2-pivaloylamino-6-Bromomethylpyridine and 2-picolylamine soluble in 1, 4-dioxane/H2Adding KOH into a mixed solvent of O for reaction, and carrying out aftertreatment on an obtained reaction product to obtain bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine;
(d) dissolving the bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine obtained in the step (c) in ethanol, adding KOH for reaction, and carrying out aftertreatment on the obtained reaction product to obtain the bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine.
In the above preparation method, further improvement is that in the step (a): the 2-amino-6-methylpyridine and CH2Cl2The ratio of the triethylamine mixed solvent is 0.07 mmol-0.08 mmol: 100 mL; the pivaloyl chloride and CH2Cl2The ratio of the triethylamine mixed solvent is 0.10 mmol-0.12 mmol: 100 mL; the CH2Cl2CH in triethylamine mixed solvent2Cl2The ratio of triethylamine to triethylamine is 6 mL-8 mL: 1 g.
In the above preparation method, further improvement is that in the step (b): the mol ratio of the 2-pivaloyl amido-6-methylpyridine, the N-bromosuccinimide and the azobisisobutyronitrile is 1: 0.05.
In the above preparation method, further improvement is that in the step (c): the mol ratio of the 2-picolylamine, the 2-pivaloylamino-6-bromomethylpyridine and the KOH is 3.25: 7.50: 13.00; the 1, 4-dioxane/H21, 4-dioxane and H in O mixed solvent2The volume ratio of O is 4: 1.
In the above preparation method, further improvement is that in the step (d): the proportion of the bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine, ethanol and KOH is 3.25mmol, 163mL, 160 mmol.
In the above preparation method, further improvement is that in the step (a): the reaction is carried out under stirring conditions; the reaction time is 12-24 h; the post-treatment comprises the following steps: filtering the reaction product, removing the precipitate, and removing the solvent in the obtained filtrate to obtain a crude product of 2-pivaloyl-6-methylpyridine; recrystallizing the crude product of the 2-pivaloyl-6-methylpyridine by using diethyl ether, washing and drying to obtain the 2-pivaloyl-6-methylpyridine.
In the above preparation method, further improvement is that in the step (b): the reaction time is 6-12 h; the post-treatment comprises the following steps: removing the solvent in the reaction product to obtain a crude product of 2-pivaloylamino-6-bromomethylpyridine; taking petroleum ether/ethyl acetate as eluent, and carrying out chromatographic separation on the crude product of the 2-pivaloyl-6-bromomethylpyridine by adopting a silicon dioxide column to obtain the 2-pivaloyl-6-bromomethylpyridine; the volume ratio of the petroleum ether to the ethyl acetate in the eluent is 8: 1.
In the above preparation method, further improvement is that in the step (c): the reaction is carried out under stirring conditions; the reaction time is 2 to 4 days; the post-treatment comprises the following steps: neutralizing the reaction product by adopting 1mol/L HCl solution, and evaporating the reaction product under the vacuum condition to obtain a crude product of bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine; recrystallizing the crude product of bis (6-pivaloyl-2-pyridylmethyl) (2-pyridylmethyl) amine with diethyl ether to obtain bis (6-pivaloyl-2-pyridylmethyl) (2-pyridylmethyl) amine.
In the above preparation method, further improvement is that in the step (d): the reaction is carried out under stirring conditions; the temperature of the reaction is 60 ℃; the reaction time is 4 to 7 days; the post-treatment comprises the following steps: removing solvent from the reaction product, dissolving the obtained solid substance in water, and using CH2Cl2Extracting for at least 5 times; after the extraction is completed, removing CH in the solid substance obtained by extraction2Cl2Obtaining crude product of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine; dissolving bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine in methanol, adding activated carbon to remove impurities, filtering, and evaporating to obtain bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine.
In a further improvement of the above preparation method, the step (1) includes the following steps:
(1.1) mixing [ Co (H)2O)6](ClO4)2Dissolved in H2In a mixed solvent of O/methanol to obtain [ Co (H)2O)6](ClO4)2A solution; dissolving bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine in H2Obtaining a solution of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine in an O/methanol mixed solvent;
(1.2) mixing [ Co (H)2O)6](ClO4)2Adding the solution into bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine solution, and adding NaHCO3And stirring to obtain a mixed solution.
In the above preparation method, further improvement is provided, wherein the [ Co (H)2O)6](ClO4)2Bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine and NaHCO3The molar ratio of (A) to (B) is 1-1.03: 1; said [ Co (H) ]2O)6](ClO4)2And H2The proportion of the O/methanol mixed solvent is 4.06 mmol: 24 mL; said bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine and H2The proportion of the O/methanol mixed solvent is 3.96 mmol: 72 mL; said H2H in O/methanol mixed solvent2The volume ratio of O to methanol is 1: 1.
In a further improvement of the above production method, in the step (2), the bubbling rate of the air in the bubbling process is controlled to emit 1 to 2 bubbles per second; the stirring time is 36-144 h; the post-treatment comprises the following steps: filtering the reaction product, and removing the solvent in the filtrate obtained by filtering by adopting a vacuum rotary drying method to obtain a carbonyl cobalt complex crude product; and dissolving the crude cobalt carbonyl complex in deionized water, purifying the cobalt carbonyl complex by using SP-C25 type cation exchange resin, removing the solvent, crystallizing, and drying to obtain the cobalt carbonyl complex.
In the present invention, bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa) has a structural formula represented by formula (III):
in the invention, the space structure of the cobalt carbonyl complex takes Co as the center, the coordination number of Co ions is 6, 4N on bapa and two O on carbonyl form an octahedral space configuration, and two substituted amino groups are positioned on a pyridine ring in the axial direction or the radial direction.
In the preparation method, when the bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa) and cobalt ions form a complex, two isomers in axial direction and in face direction can be formed in spatial configuration, namely, after the reaction is finished, the obtained reaction product consists of cobalt carbonyl complex containing two different spatial configurations.
In the preparation method of the invention, the cobalt carbonyl complex [ Co (bapa) (O)2CO)]ClO4·2H2The preparation principle of O is as follows:
in the preparation method of the present invention, the principle of preparing bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa) is as follows:
compared with the prior art, the invention has the advantages that:
(1) the invention provides a cobalt carbonyl complex with a molecular formula of [ Co (bapa) (O)2CO)]ClO4·2H2O, wherein bapa represents bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine. In the invention, bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine is a multidentate, multi-point coordinated tripodal organic ligand which can form a stable complex with transition metal cobalt, the cobalt hydroxycomplex with bapa has 2 substituted amino groups, the substituted amino groups can form intramolecular hydrogen bonds with oxygen on carbonyl at proper spatial positions, and the formation of the intramolecular hydrogen bonds can influence the transfer process of protons, thereby influencing the acidolysis rate and acidolysis mechanism, and the substituted amino groups on the complex can form intramolecular hydrogen bonds with oxygen on the carbonylThe spatial position and the number of amino groups play an important role in researching the tripodal cobalt carbonyl complex in the acidolysis ring-opening process. The cobalt carbonyl complex is a brand-new cobalt carbonyl (III) complex with a tripodal ligand, serves as a novel structural model, provides an important research object for the research of coordination chemistry, and has extremely high academic value.
(2) The invention provides a preparation method of a cobalt carbonyl complex, which is prepared by reacting [ Co (H)2O)6](ClO4)2Bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine, NaHCO3And H2Mixing the O/methanol mixed solvent, stirring and reacting under the action of air foaming at room temperature to obtain the cobalt carbonyl complex, wherein the reaction condition is mild, and the energy consumption is low. In the invention, the SP-C25 type cation exchange resin is also adopted to purify the cobalt carbonyl complex, and the purification efficiency is high. The preparation method of the cobalt carbonyl complex has the advantages of mild reaction conditions, low energy consumption, high purification efficiency and the like, and has very important significance for preparing the cobalt carbonyl complex.
(3) In the preparation method, the bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine is prepared by four-step reaction, separation and purification by using 2-amino-6-methylpyridine and 2-pyridylmethyl amine as raw materials. In the preparation process of the bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine, a preparation step with short process flow is adopted, and a reagent which is low in price and easy to separate from a product is preferably used as a reagent for preparation, so that the preparation cost is reduced, and the yield is improved. For example, in the step of preparing the intermediate product 2-pivaloyl-6-bromomethylpyridine, the crude 2-pivaloyl-6-bromomethylpyridine is chromatographically separated by using a silica column, preferably petroleum ether/ethyl acetate (8: 1) is used as an eluent to replace the higher-price hexane/ethyl acetate (6: 1), thereby further reducing the preparation cost.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a high-resolution mass spectrum of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine obtained in example 1 of the present invention.
FIG. 2 shows NMR of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine obtained in example 1 of the present invention1H NMR spectrum.
FIG. 3 is a high resolution mass spectrum of a cobalt carbonyl complex prepared in example 1 of the present invention.
FIG. 4 is an asymmetric structural diagram of a cobalt carbonyl complex plotted using X-ray single crystal diffraction test data in example 1 of the present invention.
FIG. 5 is a graph of [ Co (bapa) (O) in cobalt carbonyl complexes plotted using X-ray single crystal diffraction test data in example 1 of the present invention2CO)]+Crystal packing diagram of cation.
FIG. 6 shows NMR of cobalt carbonyl complex prepared in example 1 of the present invention1H NMR spectrum.
FIG. 7 is a UV-Vis spectrum of a cobalt carbonyl complex prepared in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
Example 1:
a cobalt carbonyl complex with a molecular formula of [ Co (bapa)) (O2CO)]ClO4·2H2O, wherein bapa represents bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine.
In the present embodiment, the structural formula of the cobalt carbonyl complex is shown as formula (i) or formula (ii), which indicates that the cobalt carbonyl complex of the present invention contains two structural isomers, that is, an axial isomer or a face isomer.
In this example, cobalt carbonyl was preparedThe compound belongs to a triclinic system, the space point group is P-1, and the unit cell parameters are as follows:
α＝79.9350(10)°，β＝77.5380(10)°，γ＝86.4720(10)°，z＝2。
a preparation method of the cobalt carbonyl complex of the embodiment comprises the following steps:
(1) preparation of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa):
(1.1) 250mL of CH2Cl2Was mixed with 32.8868g triethylamine (0.17mmol) to give CH2Cl2Adding 27.2242g (0.19mmol) of 2-amino-6-methylpyridine into a triethylamine mixed solvent, stirring until the mixture is dissolved, then dropwise adding 33.1595g (0.275mmol) of pivaloyl chloride, and reacting for 12 hours at room temperature under the stirring condition; after the reaction is finished, filtering the obtained reaction product, removing the precipitate, and removing the solvent from the obtained filtrate by adopting a vacuum rotary drying method to obtain a light yellow crude product of 2-pivaloyl-6-methylpyridine; the crude 2-pivaloylamino-6-methylpyridine was recrystallized from diethyl ether, the obtained crystals were washed with n-hexane and dried to obtain 28.6307g of white needle-like crystals, i.e. 2-pivaloylamino-6-methylpyridine, in a yield of 59.14%.
(1.2) taking 15.3832g (0.08mmol) of 2-pivaloylamino-6-methylpyridine obtained in the step (1.1), dissolving in 200mL of carbon tetrachloride with air removed, adding 14.2384g (0.08mmol) of N-bromosuccinimide (NBS) and 0.6568g (0.004mmol) of azobisisobutyronitrile, and carrying out reflux reaction for 6h under the protection of nitrogen; after the reaction is finished, cooling the reaction product to room temperature, and removing the solvent by using a vacuum rotary drying method to obtain a brown oily mixture (crude 2-pivaloylamino-6-bromomethylpyridine); the crude product of 2-pivaloyl-6-bromomethylpyridine was chromatographically separated by silica column using petroleum ether/ethyl acetate at a ratio of 8: 1 as eluent to give 4.9723g of yellow crystalline 2-pivaloyl-6-bromomethylpyridine with a yield of 22.99%.
(1.3) 0.3514g (3.25mmol) of 2-picolylamine and 2.0336g (7.5mmol) of 2-pivaloylamino-6-bromomethylpyridine obtained in step (1.2) were dissolved in 75mL of 1, 4-dioxane/H2O mixed solvent (1, 4-dioxane and H in the mixed solvent)2O volume ratio of 4: 1), adding 0.7294g (13mmol) of KOH, and reacting the obtained mixed solution at room temperature for 2 days under stirring; after the reaction is finished, 1 mol. L is used-1Neutralizing the obtained reaction product solution with HCl solution, evaporating under vacuum condition, and removing solvent to obtain brown oily crude product (crude product of bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine); the crude bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine was recrystallized from diethyl ether to give 2.1539g of the aimed product as colorless needle crystals, bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine, abbreviated as bppa.
(1.4) 2.1539g (3.25mmol) of bppa obtained in step (1.3) was dissolved in 163mL of ethanol, a KOH solution (prepared by dissolving KOH in a small amount of water and containing 8.9776g of KOH (160mmol)) was added, and the resulting mixed solution was reacted at 60 ℃ for 4 days with stirring. During the reaction, thin layer chromatography (CHCl) is used3MeOH 7/1, Rf 0.05) was detected for the reaction product. After the reaction is finished, carrying out reduced pressure evaporation on the obtained reaction liquid, removing the solvent, and dissolving the obtained solid substance in 4mL of water; using 40mL CH2Cl2Extracting the target product in water for at least 5 times; after the extraction is complete, CH is combined2Cl2Phase, reduced pressure rotary evaporation of CH2Cl2Evaporating to dry to obtain crude bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine; the crude bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine was dissolved in 4mL of methanol solution, and activated carbon was added to remove impurities, the activated carbon was removed by filtration, and the solvent in the filtrate obtained by filtration was evaporated to give 0.8384g of the objective product, bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine, abbreviated to bapa, in a reddish brown viscous state, in 80.51% yield.
(2) Preparation of [ Co (H)2O)6](ClO4)2And bapa mixed solution:
(2.1) 1.519g (4.06mmol) of [ Co (H)2O)6](ClO4)2Dissolved in 24mL of H2In a mixed solvent of O/methanol to obtain [ Co (H)2O)6](ClO4)2A solution; 1.270g (3.96mmol) of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa) prepared in step (1) was weighed out and dissolved in 72mL of H2In the mixed solvent of O/methanol, the solution of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine is obtained. In this step, H is used2H in O/methanol mixed solvent2The volume ratio of O to methanol is 1: 1.
(2.2) mixing [ Co (H) in step (2.1) ]2O)6](ClO4)2The solution was added to a solution of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine, and 0.333g (3.96mmol) of NaHCO was added3Stirring and uniformly mixing to obtain a mixed solution.
(3) Preparation of a cobalt carbonyl complex: and (3) introducing air into the mixed solution obtained in the step (2) by using a commercially available low-power small-sized air pump for bubbling, wherein the bubbling rate of the air is controlled to emit 1 to 2 bubbles per second in the bubbling process, and stirring the mixed solution at room temperature for 6 days to enable the mixed solution to react to generate a cobalt carbonyl complex (namely, the dihydrate perchloric acid bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine cobalt carbonyl (III) complex). After the reaction is stopped, filtering the reaction product after the reaction to obtain red filtrate and brown filter residue; carrying out vacuum rotary drying on the red filtrate to obtain 1.9568g of a crude product (namely a carbonyl cobalt complex crude product); dissolving the crude product in deionized water to obtain a light red solution; and (3) separating and purifying the light red solution by using a Sephadex SP-C25 type cation exchange column, recrystallizing and drying to obtain the cobalt carbonyl complex.
By high resolution mass spectrometry,1HNMR showed structural characterization of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa) prepared in this example, as shown in FIGS. 1 and 2.
FIG. 1 is a drawing showing bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (ba) prepared in example 1 of the present inventionpa) high resolution mass spectrum. Bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa) has the formula: c18H20N6Molecular weight 320.17, [ bapaH ] formed by binding a proton]+Has a theoretical charge-to-mass ratio m/z of 321.18. As can be seen from FIG. 1, the maximum m/z peak in the mass spectrum test chart of the sample of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa) prepared in example 1 of the present invention is 321.21, corresponding to [ bapaH ]]+ charge to mass ratio, indicating that the product is bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa).
FIG. 2 shows NMR spectra of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa) prepared in example 1 of the present invention1H NMR spectrum. In fig. 2: 1H NMR (400MHz, DMSO). delta. (ppm): 8.49(d, J ═ 4.4Hz,1H),7.78(t, J ═ 7.6Hz,1H),7.60(d, J ═ 7.8Hz,1H),7.34(t, J ═ 7.7Hz,2H),7.27-7.23(m,1H),6.72(d, J ═ 7.2Hz,2H),6.29(d, J ═ 8.1Hz,2H),3.71(s,2H),3.49(s, 4H). As can be seen from FIG. 2, the chemical shift of the hydrogen of the methylene group attached to the aminopyridine ring corresponds to 3.49ppm, and the chemical shifts of the hydrogen on the two amino-substituted pyridine rings are 6.29ppm, 6.72ppm and 7.34ppm in this order; the chemical shift of the methylene hydrogen attached to the pyridine ring is 3.71ppm, and the chemical shifts of the hydrogen on the pyridine ring correspond to 7.27-7.23 ppm, 7.60ppm, 7.78ppm and 8.49ppm, respectively; -NH2No peak was observed in polar DMSO. 3.31ppm and 2.51ppm are solvent peaks for water in DMSO, and 1.20 and 0.96 are solvent peaks for residual small amounts of solvent ethanol and dichloroethane.1The chemical shift and peak area ratio of the H peak shown in the H NMR spectrum are consistent with the structural features of the bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa) molecule.
From the above results, it was found that bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine (bapa) was successfully synthesized in the present invention.
By high resolution mass spectrometry, X-ray single crystal diffraction,1The cobalt carbonyl complex prepared in this example was subjected to structural and compositional measurements by HNMR, uv-vis spectroscopy, and elemental analysis, and the results are shown in fig. 3 to 7.
The carbonyl prepared in example 1 of the present invention was tested using a Waters Xevo G2-XS QTof high resolution Mass Spectrometry InstrumentThe cobalt complex was tested and the results are shown in FIG. 3. FIG. 3 is a high resolution mass spectrum of a cobalt carbonyl complex prepared in example 1 of the present invention. The cobalt carbonyl complex prepared in the embodiment 1 of the invention has a molecular formula of [ Co (bapa)) (O2CO)]ClO4·2H2O, wherein the cation [ Co (bapa) (O)2CoO)]+The composition formula of (A) is as follows: c19H20CoN6O3，[Co(bapa)(O2CoO)]+Has a theoretical charge-to-mass ratio m/z of 439.09. As can be seen from FIG. 3, the maximum m/z peak in the mass spectrum test chart of the cobalt carbonyl complex crystal sample is 439.09, corresponding to the cation [ Co (bapa) (O)2CoO)]+The charge-to-mass ratio of (a) indicates that the product is the target product.
The cobalt carbonyl complex crystal prepared by the volatile solvent method in the embodiment 1 of the invention adopts a Bruker Kappa APEX-II X-ray diffractometer for crystal structure determination, Mo K α ray which is monochromatized by graphite is used as incident radiation, diffraction points are collected in an omega-2 theta scanning mode, HELXL-97 is used for obtaining unit cell parameters through least square correction, WinGXv1.80 is used for obtaining crystal structure, all H atoms are synthesized by difference Fourier and calculated by ideal position, detailed crystallography determination data are shown in Table 1:
TABLE 1 [ Co (bapa) (O) obtained in inventive example 12CO)]ClO4·2H2X-ray single crystal diffraction test crystallography data table of O
FIG. 4 is a compound asymmetry structural diagram of a cobalt carbonyl complex plotted using X-ray single crystal diffraction test data in example 1 of the present invention. The results of single crystal testing from the cobalt carbonyl complex sample show: the probability of two substituted amino groups of the cobalt carbonylcomplex at the positions numbered 6N and 6N' shown in fig. 4 is 50% each.
FIG. 5 is a crystal packing diagram of a cobalt carbonyl complex plotted using X-ray single crystal diffraction test data in example 1 of the present invention. As can be seen from fig. 5, the crystal of the cobalt carbonylide complex has a disordered structure.
The cobalt carbonyl complex obtained in example 1 of the present invention was tested at 25 ℃ using a 400MHz NMR spectrometer, and the results are shown in FIG. 6. FIG. 6 shows NMR of cobalt carbonyl complex prepared in example 1 of the present invention1H NMR spectrum. In fig. 6:1h NMR (400MHz, dmso) δ 9.61(s, 1H), 8.59(s, 1H), 8.16-8.06 (m,1H), 8.06-7.96 (m,1H), 7.74-7.33 (m, 6H), 7.24(s, 1H), 6.81-6.34 (m, 6H), 5.33(d, J ═ 17.0Hz, 1H), 4.96(ddd, J ═ 72.6, 41.7, 17.0Hz, 5H), 4.59(dd, J ═ 31.4, 19.1Hz, 3H). The type of hydrogen in the molecule and the data shown in the test results of fig. 6 indicate that the crystal composition should contain two isomers. Meanwhile, as can be seen from the results in table 1 and fig. 6, the nuclear magnetic and single crystal diffraction test results at the tested temperature indicate that the content of each of the two isomers in the cobalt carbonyl complex prepared by the preparation method of the present invention is 50%.
The cobalt carbonyl complex prepared in example 1 of the present invention was tested at 25 ℃ using a blueStarA UV instrument from Leiberttaceae instruments, Inc. of Beijing, and the results are shown in FIG. 7. FIG. 7 is a UV-Vis spectrum of a cobalt carbonyl complex prepared in example 1 of the present invention. As can be seen from FIG. 7, the maximum absorption wavelength λ of the coordination center atom ComaxTwo, 516nm and 517nm, respectively, correspond to an absorbance value of 0.3024, indicating that coordination bonds are indeed formed in the product.
The chemical formula of the carbonyl cobalt complex prepared by the invention is [ Co (bapa)) (O2CO)]ClO4·2H2O or C19H24ClCoN6O9Wherein the theoretical calculation value of the content of each element is as follows: c, 39.70; h, 4.21; cl, 6.17; co, 10.25; n, 14.62; o, 25.05; the elemental analysis and determination result of the cobalt carbonyl complex crystal prepared by the invention is C, 39.33; h, 4.247; n, 14.88, corresponds to the theoretical value.
According to the detection results, the carbonyl cobalt complex prepared by the preparation method is successfully prepared, and the product prepared by the preparation method contains two isomers of an axial isomer and an isomerA cobalt carbonyl complex, with the two isomers each at a 50% level. The different precipitation sequences are carried out on the products under different temperature conditions and in the chromatographic column separation process for many times1In H NMR test, the type and data of H shown in the spectrogram are unchanged by comparing with the spectrogram shown in FIG. 6, which shows that the components of two isomers in the crystal and corresponding solution of the product cannot change with temperature and cannot be separated by a chromatographic column method.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. The cobalt carbonyl complex is characterized in that the molecular formula of the cobalt carbonyl complex is [ Co (bapa) (O)2CO)]ClO4·2H2O, wherein bapa represents bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine.
2. A cobalt carbonyl complex according to claim 1, wherein the structural formula of the cobalt carbonyl complex is represented by formula (i) or formula (ii):
3. a cobalt carbonylide complex according to claim 1 or 2, wherein the cobalt carbonylide complex is of a triclinic system, the space point group is P-1, and the unit cell parameters are:
α＝79.9350(10)°，β＝77.5380(10)°，γ＝86.4720(10)°，z＝2。
4. a method of preparing a cobalt carbonyl complex according to any one of claims 1 to 3, comprising the steps of:
(1) will [ Co (H) ]2O)6](ClO4)2Bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine, NaHCO3And H2Mixing the O/methanol mixed solvent to obtain a mixed solution;
(2) and (2) introducing air into the mixed solution obtained in the step (1) for bubbling, stirring to enable the mixed solution to react, and carrying out aftertreatment on the obtained reaction product to obtain the cobalt carbonyl complex.
5. The method according to claim 4, wherein said bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine comprises the steps of:
(a) dissolving 2-amino-6-methylpyridine in CH2Cl2Adding pivaloyl chloride dropwise into a triethylamine mixed solvent for reaction, and carrying out aftertreatment on an obtained reaction product to obtain 2-pivaloyl amido-6-methylpyridine;
(b) dissolving the 2-pivaloyl-6-methylpyridine obtained in the step (a) in carbon tetrachloride without air, adding N-bromosuccinimide and azobisisobutyronitrile, reacting under the protection of nitrogen, and carrying out aftertreatment on the obtained reaction product to obtain 2-pivaloyl-6-bromomethylpyridine;
(c) dissolving the 2-pivaloylamino-6-bromomethylpyridine and 2-picolylamine obtained in step (b) in 1, 4-dioxane/H2Adding KOH into a mixed solvent of O for reaction, and carrying out aftertreatment on an obtained reaction product to obtain bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine;
(d) dissolving the bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine obtained in the step (c) in ethanol, adding KOH for reaction, and carrying out aftertreatment on the obtained reaction product to obtain the bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine.
6. The method according to claim 5, wherein in the step (a): the 2-amino-6-methylpyridine and CH2Cl2The ratio of the triethylamine mixed solvent is 0.07 mmol-0.08 mmol: 100 mL; the pivaloyl chloride and CH2Cl2The ratio of the triethylamine mixed solvent is 0.10 mmol-0.12 mmol: 100 mL; the CH2Cl2CH in triethylamine mixed solvent2Cl2The ratio of triethylamine to triethylamine is 6-8 mL: 1 g;
in the step (b): the mol ratio of the 2-pivaloyl amido-6-methylpyridine, the N-bromosuccinimide and the azobisisobutyronitrile is 1: 0.05;
in the step (c): the mol ratio of the 2-picolylamine, the 2-pivaloylamino-6-bromomethylpyridine and the KOH is 3.25: 7.50: 13.00; the 1, 4-dioxane/H21, 4-dioxane and H in O mixed solvent2The volume ratio of O is 4: 1;
in the step (d): the proportion of the bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine, ethanol and KOH is 3.25mmol, 163mL, 160 mmol.
7. The method according to claim 6, wherein in the step (a): the reaction is carried out under stirring conditions; the reaction time is 12-24 h; the post-treatment comprises the following steps: filtering the reaction product, removing the precipitate, and removing the solvent in the obtained filtrate to obtain a crude product of 2-pivaloyl-6-methylpyridine; recrystallizing the crude product of the 2-pivaloyl-6-methylpyridine by using ether, washing and drying to obtain the 2-pivaloyl-6-methylpyridine;
in the step (b): the reaction time is 6-12 h; the post-treatment comprises the following steps: removing the solvent in the reaction product to obtain a crude product of 2-pivaloylamino-6-bromomethylpyridine; taking petroleum ether/ethyl acetate as eluent, and carrying out chromatographic separation on the crude product of the 2-pivaloyl-6-bromomethylpyridine by adopting a silicon dioxide column to obtain the 2-pivaloyl-6-bromomethylpyridine; the volume ratio of petroleum ether to ethyl acetate in the eluent is 8: 1;
in the step (c): the reaction is carried out under stirring conditions; the reaction time is 2 to 4 days; the post-treatment comprises the following steps: neutralizing the reaction product by adopting 1mol/L HCl solution, and evaporating the reaction product under the vacuum condition to obtain a crude product of bis (6-pivaloylamino-2-pyridylmethyl) (2-pyridylmethyl) amine; recrystallizing the crude product of bis (6-pivaloyl-2-pyridylmethyl) (2-pyridylmethyl) amine with diethyl ether to obtain bis (6-pivaloyl-2-pyridylmethyl) (2-pyridylmethyl) amine;
in the step (d): the reaction is carried out under stirring conditions; the temperature of the reaction is 60 ℃; the reaction time is 4 to 7 days; the post-treatment comprises the following steps: removing solvent from the reaction product, dissolving the obtained solid substance in water, and using CH2Cl2Extracting for at least 5 times; after the extraction is completed, removing CH in the solid substance obtained by extraction2Cl2Obtaining crude product of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine; dissolving bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine in methanol, adding activated carbon to remove impurities, filtering, and evaporating to obtain bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine.
8. The method according to any one of claims 4 to 7, wherein the step (1) comprises the steps of:
(1.1) mixing [ Co (H)2O)6](ClO4)2Dissolved in H2In a mixed solvent of O/methanol to obtain [ Co (H)2O)6](ClO4)2A solution; dissolving bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine in H2Obtaining a solution of bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine in an O/methanol mixed solvent;
(1.2) mixing [ Co (H)2O)6](ClO4)2Adding the solution into bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine solution, and adding NaHCO3And stirring to obtain a mixed solution.
9. The method of claim 8, wherein [ Co (H) is used as the catalyst2O)6](ClO4)2Bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine and NaHCO3The molar ratio of (A) to (B) is 1-1.03: 1; said [ Co (H) ]2O)6](ClO4)2And H2The proportion of the O/methanol mixed solvent is 4.06 mmol: 24 mL; said bis (6-amino-2-pyridylmethyl) (2-pyridylmethyl) amine and H2The proportion of the O/methanol mixed solvent is 3.96 mmol: 72 mL; said H2H in O/methanol mixed solvent2The volume ratio of O to methanol is 1: 1.
10. The production method according to any one of claims 4 to 7, wherein in the step (2), the bubbling rate of air in the bubbling process is controlled to emit 1 to 2 bubbles per second; the stirring time is 36-144 h; the post-treatment comprises the following steps: filtering the reaction product, and removing the solvent in the filtrate obtained by filtering by adopting a vacuum rotary drying method to obtain a carbonyl cobalt complex crude product; and dissolving the crude cobalt carbonyl complex in deionized water, purifying the cobalt carbonyl complex by using SP-C25 type cation exchange resin, removing the solvent, crystallizing, and drying to obtain the cobalt carbonyl complex.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114031647A (en) * | 2021-12-06 | 2022-02-11 | 广西师范大学 | Binuclear cobalt complex and preparation method and application thereof |
| CN116282240A (en) * | 2023-05-12 | 2023-06-23 | 研峰科技(北京)有限公司 | Purification method of triruthenium laurcarbonyl |
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| CN104086602A (en) * | 2014-07-21 | 2014-10-08 | 中国人民解放军国防科学技术大学 | Carbonyl cobalt complex with three-legged ligand and preparation method of carbonyl cobalt complex |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114031647A (en) * | 2021-12-06 | 2022-02-11 | 广西师范大学 | Binuclear cobalt complex and preparation method and application thereof |
| CN116282240A (en) * | 2023-05-12 | 2023-06-23 | 研峰科技(北京)有限公司 | Purification method of triruthenium laurcarbonyl |
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