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Preparation and application of mixed nickel(ii) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligands and phosphite ligands

A phosphite ligand, nitrogen heterocyclic carbene technology, applied in the direction of hydrocarbon production from halogen-containing organic compounds, organic compounds/hydrides/coordination complex catalysts, nickel organic compounds, etc., can solve the problem of inability to achieve convenient and efficient synthesis Diarylmethane compounds, inapplicable to cheap and easy-to-obtain chlorinated aromatic hydrocarbons, staged heating or unfavorable feeding in stages, etc., to achieve the effects of improving industrial application value, simple and easy operation, and high yield.

Active Publication Date: 2021-09-28
SUZHOU UNIV
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Problems solved by technology

In 2015, Weix's research group reported that in the presence of zinc powder, nickel(II) bromide trihydrate was used as the main catalyst and cobalt piperazine as the cocatalyst, through the reductive cross-coupling of iodo or bromo arene and benzyl alcohol Synthesis of diarylmethane compounds by joint reaction, but if benzyl alcohol is replaced by benzyl chloride, only the latter's self-coupling product can be obtained. Also requires step-by-step dosing for successful completion (see: Ackerman, L. K. G.; Anka-Lufford, L. L.; Naodovic, M.; Weix, D. J. Chem. Sci. 2015, 6 , 1115)
In 2016, Gong Hegui's research group reported that in the presence of zinc powder, nickel diiodide and bipyridine were used to form a catalytic system to realize the reductive cross-coupling reaction of brominated aromatic hydrocarbons and chlorinated benzylic compounds. The brominated aromatic hydrocarbons based on chlorinated aromatic hydrocarbons also need to add different additives, and they are not suitable for the cheap and low-reactivity chlorinated aromatic hydrocarbons (see: Zhang, Q. C.; Wang, X.; Qian, Q.; Gong, H. G. Synthesis 2016, 48 , 2829)
In 2016, the inventor's research group reported that the mixed nickel(II) complexes of nitrogen-containing heterocyclic carbene ligands and phosphine ligands achieved reductive cross-coupling of chlorinated aromatics and chlorinated benzylic compounds in the presence of magnesium filings. However, this synthesis method needs to be carried out in stages, that is, to react at low temperature for a period of time, and then heat up to the required reaction temperature to complete the subsequent cross-coupling reaction. Reaction at the reaction temperature will lead to the formation of more self-coupling products of chlorinated benzylic compounds, which cannot achieve the purpose of convenient and efficient synthesis of diarylmethane compounds (see: Zhang, J.; Lu, G. S.; Xu, J .; Sun, H. M.; Shen, Q. Org. Lett. 2016, 18 , 2860)
[0004] The complex catalytic reaction system, staged heating or step-by-step feeding conditions of the existing technology are not conducive to large-scale industrial application

Method used

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  • Preparation and application of mixed nickel(ii) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligands and phosphite ligands
  • Preparation and application of mixed nickel(ii) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligands and phosphite ligands
  • Preparation and application of mixed nickel(ii) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligands and phosphite ligands

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Experimental program
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Effect test

Embodiment 1

[0036] Embodiment one: Ni(NHC)[P(OR) 3 ]X 2 (R = CH 2 CH 3 , X = Br) synthesis

[0037] Under argon protection, nitrogen heterocyclic carbene NHC (0.2884 g, 1.0 mmol) was added to di(triethylphosphite) nickel(II) dibromide (0.5508 g, 1.0 mmol) in tetrahydrofuran solution, room temperature The reaction was carried out at low temperature for 3 hours, then the solvent was removed in vacuo, the residue was washed with n-hexane, the residue obtained was extracted with toluene, the clear liquid was transferred and the solvent toluene was removed to obtain an orange-yellow solid with a yield of 87%.

[0038] The product was subjected to elemental analysis, and the results are shown in Table 1:

[0039]

[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), seal the tube, measure and characterize on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, C 6 D. 6 ): δ ...

Embodiment 2

[0042] Embodiment two: Ni(NHC)[P(OR) 3 ]X 2 (R = CH(CH 3 ) 2 , X = Br) synthesis

[0043] Under the protection of argon, nitrogen heterocyclic carbene NHC (0.2884 g, 1.0 mmol) was added to a tetrahydrofuran solution of di(triisopropyl phosphite)nickel(II) bromide (0.6350 g, 1.0 mmol), React at room temperature for 4 hours, remove 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 an orange solid with a yield of 82%.

[0044] Product is carried out elemental analysis, and the result is as shown in table 2:

[0045]

[0046] The product was characterized by NMR, and the results are as follows:

[0047] Dissolve the product in C 6 D. 6 Medium (about 0.4 mL), seal the tube, measure and characterize on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, C 6 D. 6 ): δ 4.91 (s, 4H), 4.79 (dq, J = 12.0, 6.0 Hz, 3H),2.59 – 2.49 (m, 2H), 2.31 – 2.26 ...

Embodiment 3

[0048] Embodiment three: Ni(NHC)[P(OR) 3 ]X 2 (R = CH 2 CH 3 , X = Cl) synthesis

[0049] Under argon protection, nitrogen heterocyclic carbene NHC (0.2884 g, 1.0 mmol) was added to di(triethylphosphite)nickel(II) chloride (0.4619 g, 1.0 mmol) in tetrahydrofuran solution, room temperature The reaction was carried out under vacuum for 3 hours, the solvent was removed in vacuo, the residue was washed with n-hexane, the obtained residue was extracted with tetrahydrofuran, the clear liquid was transferred and the solvent tetrahydrofuran was removed to obtain an orange-yellow solid with a yield of 80%.

[0050] Product is carried out elemental analysis, and the result is as shown in table 3:

[0051]

[0052] The product was characterized by NMR, and the results are as follows:

[0053] Dissolve the product in C 6 D. 6 Medium (about 0.4 mL), seal the tube, measure and characterize on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, C 6 D. 6 ): δ ...

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Abstract

The present invention disclosed a type of nitrogen heterocycopic nitrogen -loop carbin ligand and phosphate ligands containing dual -ovillyrine.Ni (nhc) [p (or) 3 ] X 2 Among them, R is one of the ethyl or isopic base, X is one of the bromine atom or chlorine atom, and NHC is a nitrogen heterocobin ligand derived from bisodoline.Under the existence of magnesium chips, the present invention containing a nitrogen heterolyrine ligand and a mixed nickel (II) parts of the nitrogen heteroid ligand and phosphate ligand in the present invention can catalyze the low -active chlorine aromatics and fluoribal aromatic hydrocarbonsThe restore cross -link reaction with the chlorine chloride compounds at a single temperature, respectively, generates a new method for synthetic die methane compounds.

Description

technical field [0001] The invention relates to a nickel (II) complex, in particular to the preparation of a mixed nickel (II) complex containing bisoxazoline-derived nitrogen heterocyclic carbene ligands and phosphite ligands and its use as The application of the catalyst in the presence of magnesium chips to catalyze the reductive cross-coupling reaction of chlorinated aromatic hydrocarbons, fluorinated aromatic hydrocarbons and chlorinated benzyl compounds at a single temperature to synthesize diarylmethane compounds in one step. Background technique [0002] As important structural units, diarylmethanes widely exist in organic functional materials and pharmaceutical active molecules, and have important synthetic value. Transition metal-catalyzed cross-coupling reactions of nucleophiles and electrophiles are the traditional method for the synthesis of such compounds, but this method usually requires the direct use of metal-organic reagents with flammability hazards, such ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F15/04B01J31/24C07C1/26C07C15/16
CPCC07F15/04B01J31/24C07C1/26B01J2531/847B01J2231/4205C07C15/16B01J31/2273B01J31/185B01J2231/4233
Inventor 孙宏枚沈正旺
Owner SUZHOU UNIV
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