CN111454298A - Nickel complex containing m-carborane triazole ligand and preparation method and application thereof - Google Patents
Nickel complex containing m-carborane triazole ligand and preparation method and application thereof Download PDFInfo
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- CN111454298A CN111454298A CN202010263406.4A CN202010263406A CN111454298A CN 111454298 A CN111454298 A CN 111454298A CN 202010263406 A CN202010263406 A CN 202010263406A CN 111454298 A CN111454298 A CN 111454298A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 68
- -1 m-carborane triazole Chemical class 0.000 title claims abstract description 31
- 239000003446 ligand Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 14
- 150000003138 primary alcohols Chemical class 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003852 triazoles Chemical class 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 14
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 claims description 8
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 claims description 4
- JJCKHVUTVOPLBV-UHFFFAOYSA-N 3-Methylbenzyl alcohol Chemical compound CC1=CC=CC(CO)=C1 JJCKHVUTVOPLBV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- PPKDSHDYUBDVKL-UHFFFAOYSA-N diazonio-(4-methoxyphenyl)azanide Chemical compound COC1=CC=C([N-][N+]#N)C=C1 PPKDSHDYUBDVKL-UHFFFAOYSA-N 0.000 claims description 3
- CZZVSJPFJBUBDK-UHFFFAOYSA-N diazonio-(4-nitrophenyl)azanide Chemical compound [O-][N+](=O)C1=CC=C([N-][N+]#N)C=C1 CZZVSJPFJBUBDK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- CTRLRINCMYICJO-UHFFFAOYSA-N phenyl azide Chemical compound [N-]=[N+]=NC1=CC=CC=C1 CTRLRINCMYICJO-UHFFFAOYSA-N 0.000 claims description 3
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000013375 chromatographic separation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 238000000921 elemental analysis Methods 0.000 description 15
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- MFGWMAAZYZSWMY-UHFFFAOYSA-N beta-naphthyl carbinol Natural products C1=CC=CC2=CC(CO)=CC=C21 MFGWMAAZYZSWMY-UHFFFAOYSA-N 0.000 description 5
- JTWJUVSLJRLZFF-UHFFFAOYSA-N 2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},11$l^{2},12$l^{2}-decaborabicyclo[8.1.1]dodecane Chemical compound [B]1C2[B]C1[B][B][B][B][B][B][B][B]2 JTWJUVSLJRLZFF-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 238000005086 pumping Methods 0.000 description 3
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- CDNQOMJEQKBLBN-UHFFFAOYSA-N 3-(hydroxymethyl)benzaldehyde Chemical compound OCC1=CC=CC(C=O)=C1 CDNQOMJEQKBLBN-UHFFFAOYSA-N 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- CZRXLQPVJOJLML-UHFFFAOYSA-N azulene-1-carbaldehyde Chemical compound C1=CC=CC=C2C(C=O)=CC=C21 CZRXLQPVJOJLML-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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 Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a nickel complex containing a meta-carborane triazole ligand, a preparation method and application thereof, and the nickel complexThe compound is prepared by (1) dropwise adding n-Bu L i solution to m-C m-carborane2B10H12Stirring and reacting in the solution; then adding 3-bromopropyne for re-reaction, and separating to obtain 1, 3-dipropargyl m-carborane after the reaction is finished; (2) under the catalysis of CuI catalyst, 1, 3-dipropargyl meta-carborane reacts with aryl azide, and NiCl is added2Adding the mixture into a reaction system for continuous reaction, and separating to obtain the nickel complex containing the m-carborane triazole ligand after the reaction is finished. The nickel complex is applied to catalyzing partial oxidation of primary alcohol to prepare aldehyde. Compared with the prior art, the preparation method is simple and green, the complex can efficiently catalyze the partial oxidation of the primary alcohol to prepare the aldehyde, the reaction condition is mild, the universality is good, the catalysis efficiency is high, and the byproducts are few; and the catalyst has high stability and is insensitive to air and water.
Description
Technical Field
The invention relates to the field of complex synthesis, and particularly relates to a nickel complex containing a meta-carborane triazole ligand, and a preparation method and application thereof.
Background
Since the synthesis of carboranes in the sixties of the twentieth century, the chemistry of carboranes with stable properties has attracted considerable interest and has gradually become an active area in modern chemical research. Due to its special physicochemical properties, carborane derivatives are widely used in molecular recognition, liquid crystal materials, nonlinear optical materials and synthesis of polymer materials. The carborane-based metal complexes are also widely applied to organic synthesis as catalysts. In contrast, the metal complexes with ortho-carborane as a building block have been studied most extensively, while the complexes with meta-carborane structure are relatively rare and lack of understanding of their properties. Therefore, it is necessary to search for a synthesis method of a metal organic compound based on m-carborane as a ligand and an application of the metal organic compound in organic synthesis.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a nickel complex containing a m-carborane triazole ligand, which has the advantages of simple preparation method, good catalytic effect and high stability, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a nickel complex containing a meta carborane triazole ligand, the nickel complex having the formula:
wherein R is H, OMe or NO2One of which, "·" is a boron hydrogen bond.
Preferably, the nickel complex comprises a nickel complex 1, a nickel complex 2 and a nickel complex 3, and the structural formula is as follows:
a process for preparing a nickel complex containing a meta carborane triazole ligand as described above, comprising the steps of:
(1) preparation of 1, 3-dipropargyl m-carborane by dropwise adding n-Bu L i solution to m-C2B10H12Stirring and reacting in the solution; then adding 3-bromopropyne for re-reaction, and separating to obtain 1, 3-dipropargyl m-carborane after the reaction is finished, wherein the reaction formula is as follows:
(2) preparation of nickel complex containing m-carborane triazole ligand: under the catalysis of CuI catalyst, 1, 3-dipropargyl meta-carborane reacts with aryl azide, and NiCl is added2Adding the mixture into a reaction system for continuous reaction, and separating to obtain the nickel complex containing the m-carborane triazole ligand after the reaction is finished, wherein the reaction formula is as follows:
further, n-Bu L i, m-C described in step (1)2B10H12And 3-bromopropyne in a molar ratio of (2.2-2.5) to 1.0 (2.2-2.5); CuI, 1, 3-dipropargyl meta-carborane, aryl azide and NiCl in step (2)2The molar ratio of (0.04-0.06) to (1.0), (1.2-1.5) to (0.8-1.2).
Further, the step (1) is specifically as follows:
(1-1) at a low temperature, dropwise adding the n-Bu L i solution to m-C m-carborane2B10H12Stirring in the solution;
(1-2) heating to room temperature, and continuing to react;
(1-3) adding 3-bromopropyne for re-reaction, draining the solvent after the reaction is finished, and recrystallizing to obtain the 1, 3-dipropargyl m-carborane.
Further, the low-temperature in the step (1-1) is-5 ℃, the n-Bu L i solution is n-Bu L i n-hexane solution, and the m-C solution is2B10H12The solution is m-C2B10H12Ether solution; the stirring time is 20-40 min; the continuous reaction time in the step (1-2) is 20-40 min; and (3) carrying out the re-reaction for 2-4h, and carrying out recrystallization by adopting n-hexane.
Further, the step (2) is specifically as follows:
(2-1) dissolving 1, 3-dipropargyl meta-carborane and aryl azide in a solvent under the catalysis condition of a catalyst CuI, and reacting at room temperature;
(2-2) adding NiCl2Adding the mixture into a reaction system for continuous reaction, standing and filtering after the reaction is finished, decompressing and draining the solvent, and recrystallizing the obtained crude product to obtain the nickel complex containing the m-carborane triazole ligand.
Further, the solvent in the step (2-1) is tetrahydrofuran THF, the aryl azide comprises azidobenzene, 4-methoxy azidobenzene or 4-nitro azidobenzene, and the reaction time at room temperature is 3-6 h; the continuous reaction time in the step (2-2) is 5-6h, and dichloromethane is adopted for recrystallization.
Use of a nickel complex comprising a meta carborane triazole ligand as described above for catalyzing the partial oxidation of a primary alcohol to produce an aldehyde.
Further, the specific application method comprises the following steps: under the condition of taking a nickel complex as a catalyst, dissolving primary alcohol in toluene, reacting at normal temperature and normal pressure by taking air as an oxidant, and after the reaction is finished, carrying out chromatographic separation on concentrated reaction liquid by using a silica gel column to obtain corresponding aldehyde.
Further, the primary alcohol comprises one or more of benzyl alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methoxybenzyl alcohol, 4-chlorobenzyl alcohol, 4-nitrobenzyl alcohol, 1,3, 5-trimethylbenzyl alcohol or 2-naphthylmethyl alcohol, the molar ratio of the nickel complex to the primary alcohol is (0.02-0.05):1.0, and the reaction time is 3-6 h.
The preparation method is simple and green, and the nickel complex can be obtained in high yield by one-pot reaction. The complex can efficiently catalyze the partial oxidation of primary alcohol to prepare aldehyde, has mild reaction conditions, can catalyze more types of substrates, has good universality, high catalysis efficiency, fewer byproducts and lower cost, is easy to separate products, and does not produce a large amount of waste residues. And the catalyst has high stability and is insensitive to air and water.
Compared with the prior art, the invention has the following advantages:
(1) the nickel complex containing the m-carborane triazole ligand is simple in preparation method, can be prepared in high yield through one-pot reaction, and can stably exist in the air;
(2) the nickel complex can efficiently catalyze the partial oxidation of primary alcohol to prepare aldehyde, has good selectivity and mild reaction conditions, and only needs air as an oxidant.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1: synthesis of nickel complex 1 and application thereof in catalytic oxidation of benzyl alcohol
(1) n-Bu L i (22.0mmol) in n-hexane was added dropwise to the m-C m-carborane at 0 deg.C2B10H12(10.0mmol) of ethyl ether solution, stirring for 30 minutes after the dropwise addition is finished, slowly raising the temperature to room temperature, reacting for 30 minutes, and adding 3-bromopropaneAlkyne (21.0mmol) continuously reacts for 3 hours at room temperature, the solvent is pumped out after the reaction is finished, and the product is recrystallized by normal hexane to obtain 1, 3-dipropargyl m-carborane C8B10H16(yield 85%) the reaction equation is:
1H NMR(400MHz,CDCl325 ℃ C.). about.3.55 (s, 2H.), 2.63(s, 4H.) theoretical value of elemental analysis C8B10H16C43.61, H7.32; experimental values: c43.55, H7.30.
(2) CuI (0.05mmol), 1, 3-dipropargylpyrocarbylborane (1.0mmol) and azidobenzene (1.2mmol) were dissolved in THF at room temperature, reacted at that temperature for 3 hours, and then NiCl was added2(1.0mmol) was added to the reaction system and reacted for an additional 6 hours. After the reaction is finished, standing and filtering, decompressing and pumping out the solvent, recrystallizing the obtained crude product by using dichloromethane to obtain a brown target product nickel complex 1 (the yield is 78%), wherein the reaction formula is as follows:
1H NMR(400MHz,CDCl325 ℃ C.: 8.23(s,2H),7.73(d, J ═ 7.2Hz,4H),7.58(d, J ═ 7.5Hz,2H),7.36(t, J ═ 6.4Hz,4H),3.12(s,4H). theoretical value of elemental analysis C20B10H26Cl2N6Ni: c40.84, H4.46, N14.29; experimental values: c40.89, H4.42, N14.26.
(3) Dissolving benzyl alcohol (1.0mmol) and nickel complex 1(0.02mmol) in 2m L of toluene, introducing air at room temperature for reaction for 3 hours, concentrating the reaction solution after the reaction is finished, directly separating by silica gel column chromatography (petroleum ether: dichloromethane ═ 3:1), drying until the mass is unchanged, and obtaining the corresponding product C7H6O (93% yield), reaction formula:
theoretical values of elemental analysis C79.22, H5.70; experimental values: c79.27, H5.72.
Example 2: synthesis of nickel complex 1 and application thereof in catalytic oxidation of 2-methyl benzyl alcohol
The synthesis steps of the nickel complex 1 are the same as those of the example 1, and the difference from the example 1 lies in the application steps, specifically:
dissolving 2-methylbenzyl alcohol (1.0mmol) and nickel complex 1(0.02mmol) in 2m L of toluene, introducing air at room temperature for reacting for 6 hours, concentrating the reaction solution after the reaction is finished, directly separating by silica gel column chromatography (petroleum ether: dichloromethane ═ 3:1), and drying until the mass is unchanged to obtain the corresponding product C8H8O (96% yield) according to the formula:
theoretical value of elemental analysis C79.97, H6.71; experimental values: c80.02 and H6.75.
Example 3: synthesis of nickel complex 1 and application thereof in catalytic oxidation of 3-methyl benzyl alcohol
The synthesis steps of the nickel complex 1 are the same as those of the example 1, and the difference from the example 1 lies in the application steps, specifically:
dissolving 3-methylbenzyl alcohol (1.0mmol) and nickel complex 1(0.03mmol) in 2m L of toluene, introducing air at room temperature for reaction for 5 hours, concentrating the reaction solution after the reaction is finished, directly separating the concentrated reaction solution by silica gel column chromatography (petroleum ether: dichloromethane ═ 3:1), and drying until the mass is unchanged to obtain the corresponding product C8H8O (95% yield) according to the formula:
theoretical value of elemental analysis C79.97, H6.71; experimental values: c80.00, H6.73.
Example 4: synthesis of nickel complex 1 and application thereof in catalytic oxidation of 4-chlorobenzyl alcohol
The synthesis steps of the nickel complex 1 are the same as those of the example 1, and the difference from the example 1 lies in the application steps, specifically:
dissolving 4-chlorobenzyl alcohol (1.0mmol) and nickel complex 1(0.03mmol) in 2m L toluene, introducing air at room temperature for reaction for 4 hours, concentrating the reaction solution after the reaction is finished, directly separating by silica gel column chromatography (petroleum ether: dichloromethane ═ 3:1), drying until the mass is unchanged, and obtaining the corresponding product C7H5ClO (92% yield) having the formula:
theoretical values of elemental analysis C59.81, H3.59; experimental values: c59.77, H3.63.
Example 5: synthesis of nickel complex 2 and application thereof in catalytic oxidation of 4-methyl benzyl alcohol
(1) n-Bu L i (22.0mmol) in n-hexane was added dropwise to the m-C m-carborane at 0 deg.C2B10H12(10.0mmol) of ethyl ether solution, continuously stirring for 30 minutes after the dropwise addition is finished, slowly raising the temperature to room temperature, continuously reacting for 30 minutes, adding 3-bromopropyne (21.0mmol), continuously reacting for 3 hours at room temperature, draining the solvent after the reaction is finished, and recrystallizing the product by n-hexane to obtain the 1, 3-dipropargyl m-carborane C8B10H16(yield 85%) according to the formula:
1H NMR(400MHz,CDCl325 ℃ C.). about.3.55 (s, 2H.), 2.63(s, 4H.) theoretical value of elemental analysis C8B10H16: c43.61, H7.32; experimental values: c43.55, H7.30.
(2) CuI (0.05mmol), 1, 3-dipropargylpyrocarbylborane (1.0mmol) and 4-methoxyazidobenzene (1.3mmol) were dissolved in THF at room temperature, reacted at this temperature for 5 hours, and then NiCl was added2(1.0mmol) was added to the reaction system and reacted for an additional 6 hours. After the reaction is finished, standing and filtering, decompressing and pumping out the solvent, and recrystallizing the obtained crude product with dichloromethane to obtain brownThe target product nickel complex 2 (yield 82%) has the formula:
1H NMR(400MHz,CDCl325 ℃ C.: 8.26(s,2H),7.79(d, J ═ 7.0Hz,4H),7.55(d, J ═ 7.5Hz,4H),3.39(s,6H),3.10(s,4H), theoretical value of elemental analysis C22B10H30Cl2N6NiO2: c40.76, H4.66, N12.96; experimental values: c40.79, H4.57, N13.02.
(3) Dissolving 4-methylbenzyl alcohol (1.0mmol) and nickel complex 2(0.05mmol) in 2m L of toluene, introducing air at room temperature for reaction for 5 hours, concentrating the reaction solution after the reaction is finished, directly separating the concentrated reaction solution by silica gel column chromatography (petroleum ether: dichloromethane ═ 3:1), and drying until the mass is unchanged to obtain the corresponding product C8H8O (96% yield) is given by the equation:
theoretical value of elemental analysis C79.97, H6.71; experimental values: c79.94, H6.75.
Example 6: synthesis of nickel complex 2 and application thereof in catalytic oxidation of 4-methoxybenzene
The synthesis steps of the nickel complex 2 are the same as those of the example 5, and the difference from the example 5 lies in the application steps, specifically:
dissolving 4-methoxybenzyl alcohol (1.0mmol) and nickel complex 2(0.02mmol) in 2m L toluene, introducing air at room temperature for reaction for 3 hours, concentrating the reaction solution after the reaction is finished, separating by silica gel column chromatography (petroleum ether: dichloromethane ═ 3:1), drying until the mass is unchanged, and obtaining the corresponding product C8H8O2(yield 96%) according to the formula:
theoretical values of elemental analysis C79.57, H5.92; experimental values: c79.59, H5.95.
Example 7: synthesis of nickel complex 2 and application thereof in catalytic oxidation of 4-nitrobenzol
The synthesis steps of the nickel complex 2 are the same as those of the example 5, and the difference from the example 5 lies in the application steps, specifically:
dissolving 4-methoxybenzyl alcohol (1.0mmol) and nickel complex 2(0.03mmol) in 2m L toluene, introducing air at room temperature for reaction for 5 hours, concentrating the reaction solution after reaction, separating by silica gel column chromatography (petroleum ether: dichloromethane ═ 3:1), drying until the mass is unchanged to obtain the corresponding product C7H5NO3(yield 91%) according to the formula:
theoretical values of elemental analysis C55.63, H3.33, N9.27; experimental values: c55.70, H3.35, N9.30.
Example 8: synthesis of nickel complex 3 and application thereof in catalytic oxidation of 1,3, 5-trimethyl benzyl alcohol
(1) n-Bu L i (22.0mmol) in n-hexane was added dropwise to the m-C m-carborane at 0 deg.C2B10H12(10.0mmol) of ethyl ether solution, continuously stirring for 30 minutes after the dropwise addition is finished, slowly raising the temperature to room temperature, continuously reacting for 30 minutes, adding 3-bromopropyne (21.0mmol), continuously reacting for 3 hours at room temperature, draining the solvent after the reaction is finished, and recrystallizing the product by n-hexane to obtain the 1, 3-dipropargyl m-carborane C8B10H16(yield 85%) according to the formula:
1H NMR(400MHz,CDCl325 ℃ C.). about.3.55 (s, 2H.), 2.63(s, 4H.) theoretical value of elemental analysis C8B10H16: c43.61, H7.32; experimental values: c43.55, H7.30.
(2) CuI (0.05mmol) and 1, 3-dipropargyl meta-carbon are added at room temperatureBorane (1.0mmol) and 4-Nitro-azidobenzene (1.5mmol) were dissolved in THF, reacted at this temperature for 5 hours, and then NiCl was added2(1.0mmol) was added to the reaction system and reacted for an additional 5 hours. After the reaction is finished, standing and filtering, decompressing and pumping out the solvent, and recrystallizing the obtained crude product by using dichloromethane to obtain a brown target product nickel complex 3 (the yield is 83 percent), wherein the reaction formula is as follows:
1H NMR(400MHz,CDCl325 ℃ C.: 8.25(s,2H),7.83(d, J ═ 7.2Hz,4H),7.60(d, J ═ 7.2Hz,4H),3.19(s,4H). theoretical value of elemental analysis C20B10H24Cl2N8NiO4: c35.42, H3.57, N16.52; experimental values: c35.37, H3.62, N16.59.
(3) Dissolving 1,3, 5-trimethyl benzyl alcohol (1.0mmol) and nickel complex 3(0.05mmol) in 2m L of toluene, introducing air at room temperature for reaction for 6 hours, concentrating the reaction solution after the reaction is finished, directly separating by silica gel column chromatography (petroleum ether: dichloromethane ═ 3:1), drying until the mass is unchanged, and obtaining the corresponding product C10H12O (90% yield) according to the formula:
theoretical value of elemental analysis C81.04, H8.16; experimental values: c81.11, H8.22.
Example 9: synthesis of nickel complex 3 and application thereof in oxidation catalytic oxidation of 2-naphthalene methanol
The synthesis steps of the nickel complex 3 are the same as those in the embodiment 8, and the difference from the embodiment 8 lies in the application steps, specifically:
dissolving 2-naphthylmethanol (1.0mmol) and nickel complex 3(0.02mmol) in toluene 2m L, introducing air at room temperature for reaction for 4 hours, concentrating the reaction solution after the reaction is finished, directly separating by silica gel column chromatography (petroleum ether: dichloromethane ═ 3:1), drying until the mass is unchanged, and obtaining the corresponding product C11H8O (yield 92%), and reaction thereofThe formula is as follows:
theoretical value of elemental analysis C84.59, H5.16; experimental values: c84.65, H5.12.
Claims (10)
1. A nickel complex containing a meta carborane triazole ligand, wherein the nickel complex has the formula:
wherein R is H, OMe or NO2One of which, "·" is a boron hydrogen bond.
2. A process for preparing a nickel complex containing a meta carborane triazole ligand as defined in claim 1, comprising the steps of:
(1) preparation of 1, 3-dipropargyl m-carborane by dropwise adding n-Bu L i solution to m-C2B10H12Stirring and reacting in the solution; then adding 3-bromopropyne for re-reaction, and separating to obtain 1, 3-dipropargyl m-carborane after the reaction is finished;
(2) preparation of nickel complex containing m-carborane triazole ligand: under the catalysis of CuI catalyst, 1, 3-dipropargyl meta-carborane reacts with aryl azide, and NiCl is added2Adding the mixture into a reaction system for continuous reaction, and separating to obtain the nickel complex containing the m-carborane triazole ligand after the reaction is finished.
3. The method for preparing the nickel complex containing the m-carborane triazole ligand as claimed in claim 2, wherein the n-Bu L i, m-C in the step (1)2B10H12And 3-bromopropyne in a molar ratio of (2.2-2.5) to 1.0 (2.2-2.5); CuI, 1, 3-dipropargyl meta-carborane, aryl azide and NiCl in step (2)2In a molar ratio ofThe ratio of (0.04-0.06) to (1.0), (1.2-1.5) to (0.8-1.2).
4. The method for preparing the nickel complex containing the m-carborane triazole ligand according to claim 2, wherein the step (1) is specifically as follows:
(1-1) at a low temperature, dropwise adding the n-Bu L i solution to m-C m-carborane2B10H12Stirring in the solution;
(1-2) heating to room temperature, and continuing to react;
(1-3) adding 3-bromopropyne for re-reaction, draining the solvent after the reaction is finished, and recrystallizing to obtain the 1, 3-dipropargyl m-carborane.
5. The method for preparing the nickel complex containing the m-carborane triazole ligand as claimed in claim 4, wherein the low temperature in the step (1-1) is-5 to 5 ℃, the n-Bu L i solution is n-Bu L i n-hexane solution, and the m-C solution is m-C solution2B10H12The solution is m-C2B10H12Ether solution; the stirring time is 20-40 min; the continuous reaction time in the step (1-2) is 20-40 min; and (3) carrying out the re-reaction for 2-4h, and carrying out recrystallization by adopting n-hexane.
6. The method for preparing the nickel complex containing the m-carborane triazole ligand according to claim 2, wherein the step (2) is specifically as follows:
(2-1) dissolving 1, 3-dipropargyl meta-carborane and aryl azide in a solvent under the catalysis condition of a catalyst CuI, and reacting at room temperature;
(2-2) adding NiCl2Adding the mixture into a reaction system for continuous reaction, standing and filtering after the reaction is finished, decompressing and draining the solvent, and recrystallizing the obtained crude product to obtain the nickel complex containing the m-carborane triazole ligand.
7. The method for preparing the nickel complex containing the m-carborane triazole ligand according to claim 6, wherein the solvent in the step (2-1) is Tetrahydrofuran (THF), the aryl azide comprises azidobenzene, 4-methoxy azidobenzene or 4-nitro azidobenzene, and the room-temperature reaction time is 3-6 h; the continuous reaction time in the step (2-2) is 5-6h, and dichloromethane is adopted for recrystallization.
8. Use of a nickel complex containing a meta carborane triazole ligand according to claim 1, wherein the nickel complex is used to catalyze the partial oxidation of primary alcohols to produce aldehydes.
9. The application of the nickel complex containing the m-carborane triazole ligand as claimed in claim 8, wherein the specific application method comprises: under the condition of taking a nickel complex as a catalyst, dissolving primary alcohol in toluene, reacting at normal temperature and normal pressure by taking air as an oxidant, and after the reaction is finished, carrying out chromatographic separation on concentrated reaction liquid by using a silica gel column to obtain corresponding aldehyde.
10. The use of a nickel complex containing a meta carborane triazole ligand as claimed in claim 9, wherein the primary alcohol comprises one or more of benzyl alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methoxybenzyl alcohol, 4-chlorobenzyl alcohol, 4-nitrobenzyl alcohol, 1,3, 5-trimethylbenzyl alcohol, or 2-naphthalenyl alcohol, the molar ratio of the nickel complex to the primary alcohol is (0.02-0.05):1.0, and the reaction time is 3-6 hours.
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| CN110483581A (en) * | 2019-08-09 | 2019-11-22 | 上海应用技术大学 | It is a kind of containing the palladium complex of carborane ligand and its preparation and application between double phosphines |
| CN110627841A (en) * | 2019-09-28 | 2019-12-31 | 上海应用技术大学 | Iron complex containing m-carborane triazole ligand and preparation and application thereof |
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| CN110483581A (en) * | 2019-08-09 | 2019-11-22 | 上海应用技术大学 | It is a kind of containing the palladium complex of carborane ligand and its preparation and application between double phosphines |
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