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Mixed nickel (II) complex based on phosphite and unsaturated n-heterocyclic carbene as well as preparation method and application thereof

A nitrogen-heterocyclic carbene and phosphite technology, which is applied in the field of nickel complexes and their organic synthesis, can solve the problems of no hydrogenation addition reaction, etc., and achieve the effect of improving operability, low toxicity, and facilitating coordination

Active Publication Date: 2017-01-04
东营悦来湖园区运营管理有限公司
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  • Abstract
  • Description
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Problems solved by technology

[0004] Phosphites are less expensive and less toxic than traditional phosphine ligands (e.g., triphenylphosphine, tricyclohexylphosphine), but so far, phosphites and nitrogen-heterocyclic carbene-containing The research on mixed nickel(II) complexes is still very little, and only the first case of mixed nickel(II) complexes containing phosphite and saturated nitrogen heterocyclic carbene has been reported, and they were found to be highly effective in catalyzing chlorine The reaction of substituted hydrocarbons with neopentyl glycol diboronate has not been reported on mixed nickel (II) complexes based on phosphite esters and unsaturated azacyclic carbenes, nor have they been used to catalyze styrene or Report on the Hydroaddition Reaction of Substituted Styrenes to Electron-deficient Heteroaromatics

Method used

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  • Mixed nickel (II) complex based on phosphite and unsaturated n-heterocyclic carbene as well as preparation method and application thereof

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Experimental program
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Effect test

Embodiment 1

[0028] Embodiment one: Ni[P(OR 1 ) 3 ][(R 2 NCHCHNR 2 )C]X 2 (R 1 = ethyl, R 2 =2,4,6-trimethylphenyl, X=bromine) synthesis

[0029] The unsaturated nitrogen heterocyclic carbene (R 2 NCHCHNR 2 )C (0.3042g, 1.0 mmol) was added into a tetrahydrofuran solution of bis(triethylphosphite)nickel(II) bromide (0.5500 g, 1.0 mmol), reacted at room temperature for 2 hours, and removed the solvent in vacuo, Wash the residue with n-hexane, extract the residue with toluene, transfer the clear liquid and remove the solvent toluene to obtain a red solid with a yield of 68%.

[0030] The product was subjected to elemental analysis, and the results are shown in Table 1:

[0031] Table 1 Elemental analysis results

[0032] C：（%） H：（%） N：（%） theoretical value 46.99 5.84 4.06 actual value 47.16 5.93 4.01

[0033] The product was characterized by NMR, and the results are as follows:

[0034] Dissolve the product in C 6 D. 6 Medium (about 0.4 mL), seal...

Embodiment 2

[0035] Embodiment two: Ni[P(OR 1 ) 3 ][(R 2 NCHCHNR 2 )C]X 2 (R 1 = isopropyl, R 2 = 2,4,6-trimethylphenyl, X = bromine) synthesis

[0036] The unsaturated nitrogen heterocyclic carbene (R 2 NCHCHNR 2 )C (0.3042g, 1.0 mmol) was added to a tetrahydrofuran solution of bis(triisopropyl phosphite)nickel(II) bromide (0.6350 g, 1.0 mmol), reacted at room temperature for 3 hours, and removed the solvent in vacuo , wash the residue with n-hexane, extract the residue with toluene, transfer the clear liquid and remove the solvent toluene to obtain a red solid with a yield of 72%.

[0037] Product is carried out elemental analysis, and the result is as shown in table 2:

[0038] Table 2 Elemental analysis results

[0039] C：（%） H：（%） N：（%） theoretical value 49.21 6.33 3.83 actual value 49.43 6.39 3.72

[0040] The product was characterized by NMR, and the results are as follows:

[0041] Dissolve the product in C 6 D. 6 Medium (about 0.4 mL)...

Embodiment 3

[0042] Embodiment three: Ni[P(OR 1 ) 3 ][(R 2 NCHCHNR 2 )C]X 2 (R 1 = ethyl, R 2 =2,6-diisopropylphenyl, X=bromine) synthesis

[0043] The unsaturated nitrogen heterocyclic carbene (R 2 NCHCHNR 2 )C (0.3883g, 1.0 mmol) was added into a tetrahydrofuran solution of bis(triethylphosphite)nickel(II) bromide (0.5500 g, 1.0 mmol), reacted at room temperature for 1 hour, and removed the solvent in vacuo, Wash the residue with n-hexane, extract the residue with toluene, transfer the clear liquid and remove the solvent toluene to obtain a red solid with a yield of 73%.

[0044] Product is carried out elemental analysis, and the result is as shown in table 3:

[0045] Table 3 Elemental analysis results

[0046] C：（%） H：（%） N：（%） theoretical value 51.19 6.77 3.62 actual value 51.31 6.80 3.57

[0047] The product was characterized by NMR, and the results are as follows:

[0048] Dissolve the product in C 6 D. 6 Medium (about 0.4 mL), seal the...

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Abstract

The invention discloses a mixed nickel (II) complex based on phosphite and unsaturated n-heterocyclic carbene as well as a preparation method and application thereof. The chemical compound of the mixed nickel (II) complex is Ni[P(OR1)3][(R2NCHCHNR2)C]X2. In the mixed nickel (II) complex based on phosphite and unsaturated n-heterocyclic carbene disclosed by the invention, a hydrogenation addition reaction of styrene or substituted styrene against electron-deficient heterocyclic aromatic can be efficiently catalyzed in the presence of magnesium to synthesize a 1,1-diphenylethylane compound, which is the first case of the mixed nickel (II) complex catalyzing the hydrogenation addition reaction by adopting phosphite and unsaturated n-heterocyclic carbene as assistant ligands.

Description

technical field [0001] The invention relates to a nickel (II) complex and its application in the field of organic synthesis, in particular to a mixed nickel (II) complex based on phosphite and unsaturated nitrogen heterocyclic carbene, and its preparation method and its application. Background technique [0002] As important structural units, 1,1-diarylethanes widely exist in drug molecules and biologically active molecules, and the hydrogenation addition reaction of arylethenes to aromatic hydrocarbons catalyzed by transition metal catalysts is the key to the synthesis of 1,1- A highly atom-economical approach to diarylethanoids. Among transition metal catalysts, compared with noble metal catalyst systems such as palladium, ruthenium, and gold, nickel-based catalysts have significant cost advantages in industrial applications due to their low price. Therefore, the development of nickel-based catalysts to realize the hydrogenation addition reaction of arylethenes to aromat...

Claims

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Application Information

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IPC IPC(8): C07F15/04B01J31/22C07D277/64C07D235/12C07D235/10C07D235/08
CPCB01J31/2273B01J2231/32B01J2531/0233B01J2531/847C07D235/08C07D235/10C07D235/12C07D277/64C07F15/04
Inventor 孙宏枚许槿张杰陆谷生
Owner 东营悦来湖园区运营管理有限公司
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