CN110252404B - Organic-inorganic compound based on Zn-substituted Keggin type heteropolytungstates, synthetic method and application - Google Patents
Organic-inorganic compound based on Zn-substituted Keggin type heteropolytungstates, synthetic method and application Download PDFInfo
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- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 12
- 238000010189 synthetic method Methods 0.000 title description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 86
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005859 coupling reaction Methods 0.000 claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008878 coupling Effects 0.000 claims abstract description 10
- 238000010168 coupling process Methods 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- QRXMUCSWCMTJGU-UHFFFAOYSA-N 5-bromo-4-chloro-3-indolyl phosphate Chemical compound C1=C(Br)C(Cl)=C2C(OP(O)(=O)O)=CNC2=C1 QRXMUCSWCMTJGU-UHFFFAOYSA-N 0.000 claims abstract 3
- 230000001376 precipitating effect Effects 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 28
- 230000001699 photocatalysis Effects 0.000 claims description 11
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- 238000010523 cascade reaction Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910021432 inorganic complex Inorganic materials 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 150000003939 benzylamines Chemical class 0.000 abstract description 4
- 239000012621 metal-organic framework Substances 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 150000002466 imines Chemical class 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 238000004458 analytical method Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000007210 heterogeneous catalysis Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005691 oxidative coupling reaction Methods 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910003471 inorganic composite material Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 benzylamine compound Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
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- 239000013067 intermediate product Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical group [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UVRGCSVAFSXZCJ-UHFFFAOYSA-N phenylmethanamine styrene Chemical compound C(C1=CC=CC=C1)N.C=CC1=CC=CC=C1 UVRGCSVAFSXZCJ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- QQWYQAQQADNEIC-RVDMUPIBSA-N tert-butyl [(z)-[cyano(phenyl)methylidene]amino] carbonate Chemical compound CC(C)(C)OC(=O)O\N=C(/C#N)C1=CC=CC=C1 QQWYQAQQADNEIC-RVDMUPIBSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Abstract
The invention relates to an organic-inorganic compound based on Zn-substituted Keggin type heteropolytungstates, which has the molecular formula as follows: c32H61N12Zn2PW11O42Of the formula [ Zn (HPYI ]3][Zn(PYI)PW11O39]·3H2O, abbreviated as ZnW-PYI. The compound belongs to an orthorhombic system,P2(1)2(1)2(1)and (4) space group. The synthesis method specifically comprises the following steps: adding Zn (CH)3COO)2·2H2O、K4PW11VO40·2H2O andL‑mixing BCIP in a mixed solvent of distilled water and methanol, adjusting pH to 2-3, transferring to a reaction kettle, reacting at 110 + -10 deg.C for 4-6 days, cooling to room temperature, precipitating crystal, filtering, washing, and drying to obtain the final product. The metal organic framework compound can be used as a photocatalyst to catalyze the self-coupling reaction of benzylamine or benzylamine derivatives and the application research of styrene and benzylamine coupling through the series reaction, and provides a theoretical basis.
Description
Technical Field
The invention belongs to the technical field of preparation of heteropolytungstate-based compounds, and particularly relates to an organic-inorganic compound based on Zn-substituted Keggin-type heteropolytungstates, a synthetic method and application of the organic-inorganic compound as a photocatalyst in catalyzing self-coupling reaction of benzylamine or benzylamine derivatives and coupling cascade reaction of styrene and benzylamine.
Background
Imines are important nitrogen-containing intermediates in various fields such as biology, medicine, chemical synthesis and the like, and can be used not only as a guide group for C-H bond activation reaction, but also as electrophilic reactants. Therefore, efficient reaction systems for the preparation of imines are still a subject of high demand. Conventional methods include secondary amine oxidation, in situ amine oxidation, coupling of alcohols with amines, condensation of amines with carbonyl compounds, and the like. However, the above methods all have certain limitations, such as: harsh reaction conditions, complex catalyst preparation, narrow substrate range and the like. Therefore, further development of economical heterogeneous catalysts remains challenging.
Polyoxometallates (POMs) are similar to TiO2Compared with the traditional photocatalyst, the POMs as a novel photocatalyst have wide application prospect. POMs have strong absorption capacity to ultraviolet light and near ultraviolet light, and can carry out effective charge transfer under illumination while maintaining the structure. In addition, the redox potential of POMs can be controlled at the molecular level by adjusting the structure and constituent elements of the polyacid. The Metal Organic Framework (MOFs) material is an excellent heterogeneous catalysis carrier, and the POMOFs material prepared by introducing organic ligands with a photocatalytic function and POMs into a MOFs structure through careful design can carry out heterogeneous catalysis while carrying out high-activity photocatalysis. The present application contemplates that the introduction of electron donors and electron acceptors can be effective devices for charge transfer in photocatalytic processes, and the addition of polyacid anions further enhances redox conversion and selectivity. Under visible light irradiation, POMOFs typically undergo different charge transfer processes, such as ligand-metal charge transfer (LMCT), metal-ligand charge transfer (MLCT), pi-pi transition of delocalized ligands, and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an organic-inorganic compound based on Zn-substituted Keggin type heteropolytungstates, a synthetic method and application of the organic-inorganic compound as a photocatalyst in catalyzing oxidative coupling of benzylamine and derivatives thereof and catalyzing coupling series reaction of styrene and benzylamine.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic-inorganic compound based on Zn-substituted Keggin type heteropolytungstates has a molecular formula as follows: c32H61N12Zn2PW11O42(ii) a The chemical formula is: [ Zn (HPYI)3][Zn(PYI)PW11O39]·3H2O; abbreviated as ZnW-PYI. The compound belongs to an orthorhombic system, P2(1), 2(1) and space group. The compound can be used as a catalyst for efficiently carrying out photocatalysis on the self-coupling reaction of benzylamine or aniline derivatives and catalyzing the coupling of styrene and benzylamine through a series reaction.
The synthesis method of the organic-inorganic compound based on Zn-substituted Keggin type heteropolytungstates comprises the following specific steps: adding Zn (CH)3COO)2·2H2O、K4PW11VO40·2H2And uniformly mixing the O and the L-BCIP in a mixed solvent of distilled water and methanol, adjusting the pH to 2-3, then transferring the mixture into a reaction kettle, reacting for 4-6 days at 110 +/-10 ℃, cooling to room temperature, separating out crystals, and filtering, washing and drying the crystals to obtain the catalyst.
Further, Zn (CH)3COO)2·2H2O、K4PW11VO40·2H2The mass ratio of O to L-BCIP is 2-4: 2-3: 1.
the invention provides application of the organic-inorganic compound based on Zn-substituted Keggin type heteropolytungstates as a catalyst in photocatalysis benzylamine or aniline derivative self-coupling reaction.
The invention also provides application of the organic-inorganic compound based on Zn-substituted Keggin type heteropoly tungstate as a catalyst in catalyzing coupling of styrene and benzylamine through a series reaction.
Compared with the prior art, the invention has the following beneficial effects:
1) the organic-inorganic composite material of the heteropolytungstate can accurately analyze the crystal structure characteristics through X-ray single crystal diffraction, and provides theoretical support for further conjecturing the interaction between an active center and a reaction substrate and researching the catalytic reaction mechanism of the heteropolytungstate;
2) the pore channel structure in the organic-inorganic composite material of the heteropolytungstate has hydrophilicity and hydrophobicity, the reasonable distribution of the pore channel in the crystal structure and the synergistic effect between the ligand and the polyacid effectively improve the heterogeneous catalysis efficiency of the material. The research of catalyzing the self-coupling reaction of benzylamine or benzylamine derivatives and catalyzing the coupling series reaction of styrene and benzylamine is realized, and the development space is provided for the future practical application;
3) the invention is beneficial to developing a series reaction synthesis strategy with the characteristics of atom economy, high efficiency and the like. The traditional strong oxidation catalyst with strong corrosivity and high equipment requirement is abandoned by the catalytic system, and the catalytic reaction is carried out under the irradiation of visible light by using clean energy oxygen as an oxidant, so that the catalytic system conforms to the development concept of green chemistry. The development of a catalytic system to the direction of energy conservation and environmental protection is realized while striving to realize the optimal reaction time, the maximum conversion rate and the maximum yield of the series reaction;
4) efficient catalysis is realized by designing and adjusting reasonable matching of three-dimensional and electronic effects between the catalytic active sites and the substrate. The catalysis process is heterogeneous, the catalyst can be recovered through filtration or centrifugal separation, the cyclic utilization is realized, and the catalysis efficiency is not obviously reduced after the repeated cycle, so that the organic-inorganic composite material of the multifunctional heteropolytungstate provides a good theoretical basis for the development of the fields of fine chemical engineering, drug synthesis and the like in China.
Drawings
FIG. 1 is a schematic of the synthesis and catalytic reaction of compound ZnW-PYI;
FIG. 2 is a scheme for the synthesis of the compounds L-BCIP (A) and L-PYI (B);
FIG. 3(a) the unit cell structure diagram of compound ZnW-PYI; (b) a Zn (2) atom coordination environment diagram; (c) a one-dimensional chain structure of compound ZnW-PYI; (d) the three-dimensional network structure of compound ZnW-PYI;
FIG. 4(a) shows that the N atom in ligand L-PYI and [ PW ] in compound ZnW-PYI structure11ZnO39]6-A schematic representation of the formation of hydrogen bonds by the terminal oxygens of (a); (b) two-dimensional plan view of compound ZnW-PYI formed by hydrogen bonding stacking;
FIG. 5 is an infrared spectrum of compound ZnW-PYI;
FIG. 6 XRD spectrum of compound ZnW-PYI;
FIG. 7 thermal analysis graph of compound ZnW-PYI;
FIG. 8(a) Black curve is the UV-VIS diffuse reflectance spectrum of compound ZnW-PYI before illumination; the red curve is the ultraviolet-visible diffuse reflectance spectrum of compound ZnW-PYI after 10 minutes of illumination; (b) the blue curve is the ultraviolet-visible diffuse reflectance spectrum of the compound ZnW-PYI soaked with the substrate benzylamine before illumination; the orange curve is the ultraviolet-visible diffuse reflectance spectrum of the substrate benzylamine compound ZnW-PYI after being soaked for 10 minutes;
FIG. 9(a) PXRD pattern of the catalyst after three cycles of catalysis by compound ZnW-PYI; (b) cyclic test pattern of coupling reaction of olefin and benzylamine.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1
A method for synthesizing an organic-inorganic composite of heteropolytungstates comprises the following steps:
polyacid precursor, ligand and catalyst [ Zn (HPYI) ]3][Zn(PYI)PW11O39]·3H2Synthesis of O
(1) Polyacid precursor K4PW11VO40·2H2Synthesis of O (see Chenweilin, Wanengbo. polyacid chemistry [ M ]]Beijing: scientific press, 2013,100.), as follows:
54g of H are weighed out3[PW12O40]Dissolved in 50mL of distilled water, and solid LiCO was slowly added with stirring3Until the pH of the solution became 4.9, at which time the solution had a volume of about 75 mL. Then, stirringSlowly adding 100 mL0.2mol.L under the stirring condition-1NaVO (NaVO)3Using 6 mol. L-1The pH of the well stirred mixture was adjusted to 2 with HCl solution. Heating the solution to 60 deg.C, maintaining for 10min, cooling to room temperature, and adding 6 mol/L-1The pH of the uniformly stirred mixture was adjusted to 2 with HCl solution, heated to 60 ℃ and 20g of solid KCl was added to the solution and kept at 60 ℃ for 10 min. After the reaction was completed, it was cooled to room temperature to obtain a pale yellow product with a yield of about 40 g.
(2) The ligand L-N-tert-butyl-carbonyl-2- (imidazole) -1-pyrrolidinine (L-BCIP) can be synthesized by the literature (S.Z.Luo, X.L.Mi, L.Zhang, et al.functional chromatographic methods for microbial addition, etc. [ J ]. Angew Chem Int Ed.,2006,45:3093 + 3097 ]), and the synthetic route is shown in FIG. 2.
(3) Synthesis of Compound ZnW-PYI
The compound ZnW-PYI is prepared by self-assembly under hydrothermal conditions, and specifically comprises the following steps: 30mg (0.164mmol) of Zn (CH) are weighed out separately3COO)2·2H2O，27.6mg(0.01mmol)K4PW11VO40·2H2O, 9.8mg (0.039mmol) L-BCIP in 25mL of Teflon reaction lining, 4.0mL of prepared mixed solvent of distilled water and 2.0mL of methanol was added, and the mixture was placed on a magnetic stirrer and stirred for 10-12 hours to mix uniformly. Subsequently, 1 mol. L-1HCl adjusts the pH of the turbid solution to 2.35. Then the mixture is transferred to a stainless steel high-pressure reaction kettle and is put into a constant-temperature oven at 110 ℃ for four days. After the reaction is finished, cooling to room temperature, separating out pink transparent crystal which is compound ZnW-PYI, filtering, washing with distilled water for 3-5 times, and drying to obtain 38% yield (based on K)4PW11VO40·2H2O)。
The chemical formula of the compound ZnW-PYI is as follows: c32H61N12Zn2PW11O42Elemental analysis and ICP (%): calculated for compound 4: h, 1.77; c, 11.07; n, 4.84; o, 19.36; p, 0.89; zn, 3.77; w, 58.30. Experimental values: h, 1.76; c, 11.04；N，4.89；O，19.41；P，0.92；Zn，3.74；W，58.24。
Crystal structure analysis: the compound ZnW-PYI was subjected to crystal test and analysis, and the results were as follows.
TABLE 1 crystallographic data for Compound ZnW-PYI
As can be seen in table 1: compound ZnW-PYI belongs to the orthorhombic system, P2(1)2(1) space group. As can be seen from FIG. 3a, the unit cell of compound ZnW-PYI is a Keggin type polyacid anion substituted with one Zn [ PW11ZnO39]6-Four L-PYI ligands and two crystallographically independent Zn (II) atoms, wherein the Zn (1) atom is located in the polyacid anion [ PW11ZnO39]6-Inside. L-PYI is generated in situ by L-BCIP after acidification in the reaction process, and nitrogen atoms on pyrrolidine are protonated. Both Zn atoms are hexa-coordinated to form a distorted octahedral structure. On the equatorial plane, Zn (2) atom is connected with nitrogen atom in three L-PYI ligands respectively, and the three L-PYI ligands are spirally arranged and shaped like a fan; on the longitudinal axis, the Zn (2) atom is attached to two terminal oxygens from the polyacid anion, respectively, see FIG. 3 b.
As can be seen from FIG. 3c, the Zn (2) atom as a junction is bonded to the polyacid anion [ PW11ZnO39]6-The L-PYI ligands connected with the Zn (2) atoms are densely arranged in the middle of the one-dimensional chain. The Zn (1) atom-bound L-PYI ligand is distributed regularly in the polyacid anion [ PW11ZnO39]6-Two sides. The naked pyrrole nitrogen atom is protonated due to the removal of Boc on ligand L-BCIP during the reaction to generate L-PYI. N atom in ligand L-PYI and [ PW11ZnO39]6-Form hydrogen bonds, see FIG. 4a, where N (3) · O (29) and N (6) · O (23) and N (9) · O (37) are separated by distances, respectively
And
the one-dimensional chains are stacked into a two-dimensional layered planar structure by the action of hydrogen bonds, as shown in fig. 4 b. The two-dimensional layers are stacked through the hydrogen bonding of the ligand and the polyacid to form a three-dimensional network structure, so that the existence of the hydrogen bonding consolidates the whole three-dimensional framework, which is shown in fig. 3 d. In addition, as the ligand L-PYI activates W ═ O through a hydrogen bond, the chiral pyrrolidine molecule can be used as a synergistic catalytic site, so that the oxidation activity of POMs is improved, and the reaction of benzaldehyde as an intermediate product of tandem catalysis and benzylamine can be promoted.
TABLE 2 major bond lengths of compounds ZnW-PYI
Angle of harmony key (°)
Infrared spectrum: the infrared spectrum of compound ZnW-PYI is shown in FIG. 5. As can be seen from the figure: the main absorption peaks of the compound are respectively: 3400(m), 3127(w), 1618(s), 1531(s), 1453(m), 1100(s), 947(s), 898(s), 768(s). Wherein, 3400cm-1The left and right broadband absorption peaks are attributed to H2And O stretching and contracting vibration. 1700-1100 cm-1Four characteristic absorption peaks of the region are respectively assigned to the L-PYI ligand. Furthermore, 950 + 750cm-1Three characteristic absorption peaks of the region are respectively assigned to the polyacid anion [ PW ] after Zn substitution11ZnO39]6-Middle W-Od、W–Oa、W–ObAnd W-OcThe stretching and contracting of the keys.
X-ray powder diffraction: the X-ray powder diffraction pattern of compound ZnW-PYI is shown in FIG. 6, Simulated represents the pattern obtained by simulation, and Experimental represents the pattern determined by experiment. The comparison shows that the peak types and the peak positions of the two are basically completely matched, which indicates that the sample is pure and has few impurities.
Thermal stability: the thermogravimetric analysis curve of compound ZnW-PYI is shown in FIG. 7. It can be seen in the figure that: the weight loss is 4% before 314 ℃, free water molecules in pore channels and crystal water on a skeleton are mainly lost, and the analysis is basically consistent with the crystal structure analysis; 314 ℃ and 800 ℃, mainly corresponding to the decomposition of partial polyacid and ligand in the framework; after 800 ℃, the skeleton completely collapsed. Therefore, the compound has higher thermal stability, completely meets the requirements of heterogeneous catalysis, and can be used as a heterogeneous catalyst for catalytic reaction.
Ultraviolet-visible diffuse reflectance spectrum: FIG. 8 shows the UV-visible diffuse reflectance results for compound ZnW-PYI. It can be seen in the figure that: two absorption peaks at 200-400nm respectively correspond to n-pi and pi-pi transition of ligand L-PYI and Keggin type Zn substituted polyacid anion [ PW11ZnO39]6-Characteristic absorption peak of (1). Furthermore, the relatively weak broad absorption band at 500nm is probably due to electron transfer between the organic ligand L-PYI inside the framework and the polyacid. As can be seen in FIG. 8a, after compound ZnW-PYI was exposed to 200W xenon for 10 minutes, the compound slightly increased in UV absorption intensity, but no new absorption peak appeared. Considering that the compound ZnW-PYI can successfully catalyze the coupling reaction of benzylamine under illumination, the test is continued by using the compound ZnW-PYI which is soaked in the reaction substrate benzylamine, and the result is that: the absorption intensity of the compound at 500nm is obviously enhanced, and the figure 8b shows that the reaction substrate has good auxiliary effect on the electron transfer of the system. Subsequently, after placing compound ZnW-PYI under 200W xenon lamp for 10 minutes, it was found that a new absorption peak was generated at 765nm, which should be attributed to W6+→W5+The transition between charge transfer (IVCT) probably due to benzylamine electron transfer to the absent polyacid while hydrogen atoms are pulled off to form benzylamine free radical (PhCH)2NH). The sample soaked with the substrate benzylamine after illumination is put intoAnd (3) carrying out dark treatment, wherein after the system is placed for 2 hours under dark conditions, the absorption peak at 765nm disappears, and the intensity of the absorption peak can be basically restored to the position before illumination, which proves that the electron transfer in the system is reversible.
Example 2: experiment of photocatalytic application
Catalyzing the oxidation coupling reaction of benzylamine: at room temperature, 1mmol benzylamine and 0.5mL acetonitrile are added as solvent in a 10mL heat-resistant glass container with a circulating water condensing device. 10mg (0.01mmol) of compound ZnW-PYI as a catalyst was added to the above mixed solution, and high-purity oxygen gas was introduced under one atmosphere, followed by magnetic stirring with the addition of magnetons. Then, the reaction was carried out for 16 hours under the irradiation of white light with a wavelength range of 420-500nm by using a 10W LED lamp. After the reaction, separating the reacted catalyst, collecting the residual filtrate, adding anhydrous Na2SO4The powder was dried and left to stand for 24 hours. The next day, the dried filtrate was filtered off and rotary evaporated under reduced pressure to give the product. Dissolving a small amount of product in CDCl3Or d6Nuclear magnetic tests in DMSO.
Catalyzing styrene and benzylamine to perform oxidative coupling series reaction: at room temperature, 2mmol benzylamine and 1mmol styrene as substrates and 0.5mL acetonitrile as solvent are added into a 10mL heat-resistant glass container with a circulating water condensing device. 10mg (0.01mmol) of compound ZnW-PYI as a catalyst was added to the above mixed solution, and high-purity oxygen gas was introduced under one atmosphere, followed by magnetic stirring with the addition of magnetons. Then, the reaction was carried out for 16 hours under the irradiation of white light with a wavelength range of 420-500nm by using a 10W LED lamp. After the reaction, separating the reacted catalyst, collecting the residual filtrate, adding anhydrous Na2SO4The powder was dried and left to stand for 24 hours. The next day, the dried filtrate was filtered off and rotary evaporated under reduced pressure to give the product. Dissolving a small amount of product in CDCl3Or d6Nuclear magnetic tests in DMSO.
Study of photocatalytic Properties
It is contemplated that during the reaction of the olefin with benzylamine, a self-coupling reaction of benzylamine may occur. Based on this, the activity of the photocatalytic benzylamine self-coupling reaction of compound ZnW-PYI was initially studied, as shown in Table 3. Benzylamine as substrate at room temperatureWith O2As an oxidizing agent, compound ZnW-PYI was used as a catalyst, and the yield of the target imine product reached 99% after 16 hours of reaction under irradiation with white light (10W LED lamp), Table 2-3 (entry 1). In addition, control experiments showed that only the ligand L-BCIP or the polyacid K was used4PW11VO40·2H2When O is used as a catalyst, almost no target product is generated. Mixing polyacid K4PW11VO40·2H2The O and the ligand L-BCIP are simply mixed to be used as a catalyst, and the target product is hardly generated. Meanwhile, the research on the extension of the substrate variety shows that the substrate is para-position with an electron donating group (-CH)3) The yield of benzylamine was substantially unchanged and the yield of the desired product reached 99%, see table 3 (entry 2). When the substrate was a benzylamine having an electron-withdrawing group (-F, -Cl) at the para-position, the yield of the obtained objective product was slightly decreased, and the yields were 80% and 91%, respectively, as shown in Table 3 (entries 3 and 4). However, when the substrate was replaced with aniline having no H atom on the α -C, no target product was formed, as shown in Table 3 (entry 5), indicating that the H atom on the α -C of benzylamine had to be pulled off during the self-coupling reaction to form a transition intermediate (PhCH)2NH·)。
TABLE 3 Compound ZnW-PYI photocatalytic benzylamine self-coupling reaction[a]
[a]Reaction conditions are as follows: benzylamine and derivatives, 1 mmol; compound 4, 0.01 mmol; acetonitrile, 0.5 mL; o is21 atmosphere; white light, 10W LED; at normal temperature for 36 hours. [ b ] a]By using1The yield of the product was determined by H nmr spectroscopy.
Subsequently, the substrate was replaced and the tandem reaction for the synthesis of imines starting from olefins was explored. At room temperature, using styrene benzylamine as substrate and O2Is oxidant, compound ZnW-PYI is used as catalyst, white light(10W LED lamp) the yield of the imine target product reached 99% after 16 hours of reaction, Table 4 (entry 1). Control experiments show that essentially no target product is formed in the absence of light or catalyst. Furthermore, only the ligand L-BCIP or the polyacid K is used4PW11VO40·2H2O as catalyst gave yields of 0% and 30%, respectively. Mixing polyacid K4PW11VO40·2H2Simple mixing of O and ligand L-BCIP as catalyst only yields about 20%. The following results were obtained by control experiments: the combination of the polyacid and the ligand can not only promote the synergistic catalytic action of the catalytic site, but also better realize the catalytic advantages of each component. Polyacid anion [ PW ] in the course of tandem catalysis of the reaction of styrene with benzylamine11ZnO39]6-Styrene can be oxidized into benzaldehyde, and the ligand L-PYI serving as a synergistic catalytic center can catalyze the intermediate product benzaldehyde to further react with benzylamine to generate an imine product. In addition, oxidative coupling reactions of benzylamines and styrene with different substituents have also been explored. As can be seen from Table 4 (entries 2, 3), the electron donating group (-CH) is present in either of the para positions of the substrates3) The yield of benzylamine of electron-withdrawing groups (-F, -Cl) is up to 99%; it is shown that the type of benzylamine has little effect on the reaction during the tandem catalysis. Next, the oxidative coupling reaction of styrene and benzylamine having various substituents was investigated. When using a compound having a strong electron-donating group (-OCH)3) The yield of the corresponding imine was 99% when styrene as a substrate. When 4-chlorostyrene and 2-chlorostyrene with electron withdrawing groups are used as substrates, 91% and 90% of the corresponding imine products are obtained, respectively, probably due to the greater influence of the electron withdrawing substituents at the ortho position on the benzene ring electron cloud. In addition, when 4-tert-butylstyrene containing steric hindrance is used as a substrate, 80% of corresponding imine can still be obtained, and the reaction is not greatly influenced by smaller steric hindrance.
TABLE 4 Compound ZnW-PYI coupling tandem reaction of a photocatalytic styrene with benzylamine[a]
[a]Reaction conditions are as follows: styrene and derivatives, 1 mmol; benzylamine and derivatives, 2 mmol; compound 4, 0.01 mmol; 3mL of acetonitrile; o is21 atmosphere; white light, 10W LED; at normal temperature for 18 hours. [ b ] a]By using1The yield of the product was determined by H nmr spectroscopy.
In order to investigate the heterogeneous nature of the coupling serial catalytic reaction of styrene and benzylamine, after the catalytic reaction is carried out for 16h, the compound ZnW-PYI is separated from the reaction system, and the remaining solution is continuously stirred for reaction for 16h, so that the result shows that the remaining solution hardly reacts after the catalyst is removed. At room temperature, using styrene and benzylamine as substrates and O2As an oxidant, compound ZnW-PYI was used as a catalyst, and the catalyst was tested for recyclability under irradiation with white light (10W LED lamp). The results show that the catalyst can be used repeatedly at least 3 times, the forms of the initial reaction sample and the recovered sample are almost unchanged after three reaction cycles, the PXRD pattern of the catalyst is shown in figure 9a, and as can be seen from the figure, the peak pattern and the peak position after three cycles are basically completely matched with the peak pattern and the peak position of the initial sample, which indicates that the compound ZnW-PYI can still maintain the original structure after three reactions. The yield of the target product of the three cycles still maintained a yield of more than 92%, see fig. 9 b. The results show that the catalyst has higher stability and heterogeneous catalytic capability.
Claims (5)
1. An organic-inorganic compound based on Zn-substituted Keggin-type heteropolytungstates is characterized in that the molecular formula is as follows: c32H61N12Zn2PW11O42；
The organic-inorganic compositeThe compound is obtained by the following steps: adding Zn (CH)3COO)2·2H2O、K4PW11VO40·2H2O andL-and uniformly mixing BCIP in a mixed solvent of distilled water and methanol, adjusting the pH value to 2-3, transferring the mixture into a reaction kettle, reacting at 110 +/-10 ℃ for 4-6 days, cooling to room temperature, separating out crystals, and filtering, washing and drying the crystals to obtain the BCIP.
2. A synthesis method of organic-inorganic composite based on Zn-substituted Keggin-type heteropolytungstates as claimed in claim 1, characterized in that Zn (CH) is added3COO)2·2H2O、K4PW11VO40·2H2And (2) uniformly mixing O and L-N-tert-butyloxycarbonyl-2-imidazole-1-pyrrolidine (L-BCIP) in a mixed solvent of distilled water and methanol, adjusting the pH to 2-3, then transferring the mixture into a reaction kettle, reacting at 110 +/-10 ℃ for 4-6 days, cooling to room temperature, precipitating crystals, and filtering, washing and drying the crystals to obtain the compound.
3. The method for synthesizing an organic-inorganic composite based on Zn-substituted Keggin-type heteropolytungstates as claimed in claim 2, wherein Zn (CH)3COO)2·2H2O、K4PW11VO40·2H2The mass ratio of O to L-N-tert-butyloxycarbonyl-2-imidazole-1-pyrrolidine (L-BCIP) is 2-4: 2-3: 1.
4. the use of the organic-inorganic composite based on Zn-substituted Keggin-type heteropolytungstates of claim 1 as a catalyst for photocatalytic benzylamine or aniline derivative self-coupling reactions.
5. The use of the organic-inorganic complex based on Zn-substituted Keggin-type heteropolytungstates of claim 1 as a catalyst for the coupling of styrene and benzylamine by a tandem reaction.
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