Preparation and application of mixed-ligand nickel(II) complex containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand

Abstract

The invention discloses a mixed Ni(II) complex containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand and application thereof; the chemical formula of the mixed Ni(II) complex is Ni(NHC)[P(OR).sub.3]X.sub.2, wherein R is ethyl or isopropyl, X is bromine or chlorine, and NHC is a bisoxazoline-derived nitrogen heterocyclic carbene ligand. In the presence of magnesium shavings, the mixed Ni(II) complex containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand of the present invention can catalyze low-activity chlorinated aromatic hydrocarbons and fluorinated aromatic hydrocarbons with chlorinated benzyl compounds, respectively, reductive cross-coupling reaction at a single temperature, generating a diarylmethane compound in one step, providing a new method for the synthesis of diarylmethane compounds.

Claims

1. A mixed Ni(II) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand, having the following structure: ##STR00005## wherein, R is ethyl or isopropyl; X is bromine or chlorine.

2. The mixed Ni(II) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand according to claim 1, wherein a preparation method therefor comprises the following steps: reacting bis(phosphite) Ni(II) dibromide with NHC to obtain the mixed Ni(II) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand, reacting bis(phosphite) Ni(II) dichloride with NHC to obtain the mixed Ni(II) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand, the NHC has the following structural formula: ##STR00006##

3. The mixed Ni(II) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand according to claim 2, wherein the reaction is carried out in a solvent without active hydrogen.

4. The mixed Ni(II) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand according to claim 2, wherein the bis(phosphite) Ni(II) dibromide is di(triethyl phosphite) nickel dibromide (II) or di(triisopropyl phosphite) nickel dibromide (II); the bis(phosphite) Ni(II) dichloride is di(triethyl phosphite) nickel dichloride (II) or di(triisopropyl phosphite) nickel dichloride (II).

5. The mixed Ni(II) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand according to claim 2, wherein the reaction is conducted at room temperature for 3 to 5 hours.

6. The mixed Ni(II) complexes containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand according to claim 2, wherein a molar ratio of bis(phosphite) Ni(II) dibromide to NHC is 1 to 1; a molar ratio of bis(phosphite) Ni(II) dichloride to NHC is 1 to 1.

Description

EMBODIMENTS OF THE INVENTION

(1) The method provided by the present invention uses the air-stable new nickel (II) complex Ni(NHC)[P(OR).sub.3]X.sub.2 as a catalyst for the first time at a single temperature, and directly uses two halogenated hydrocarbons under the action of magnesium chips as a substrate, diarylmethane compounds are synthesized efficiently through a one-step reaction. Compared with the prior art, the synthesis method provided by this patent does not require staged heating reaction, that is, the reaction is performed at a temperature of zero or lower for a period of time, and then the temperature is raised to a specific temperature to complete the reaction, but can be performed in a gentle single reaction At temperature, a new mixed nickel (II) complex is as a catalyst, and diarylmethane compounds are directly generated in one step through the reduction cross-coupling reaction of two halogenated hydrocarbons in the presence of magnesium chips. The mixed nickel (II) complex provided by the present invention can not only effectively inhibit the self-coupling reaction of two halogenated hydrocarbons, but also efficiently catalyze their reductive cross-coupling reaction. The activity is equivalent or higher. This is based on a mixed-type nickel (II) complex containing a bisoxazoline-derived nitrogen heterocyclic carbene ligand and a phosphite ligand as a catalyst, passing through two halogenated hydrocarbons at a single temperature in the presence of magnesium shavings The reductive cross-coupling reaction is the first example of one-step synthesis of diarylmethanes compounds.

(2) The present invention will be further described below in conjunction with examples. The raw materials involved are all from the prior art, purchased commercially or prepared according to the existing literature:

(3) ##STR00003##

Example 1: Synthesis of Ni (NHC)[P(OR).SUB.3.]X.SUB.2.(R═CH.SUB.2.CH.SUB.3., X═Br)

(4) Under argon protection, added NHC (0.2884 g, 1.0 mmol) to di(triethyl phosphite) nickel dibromide (II) (0.5508 g, 1.0 mmol) in tetrahydrofuran had reacted at room temperature for 3 hours. Then the solvent had been removed in vacuum, the residue had been washed with n-hexane, and the obtained residue had been extracted by toluene, and the clear liquid had been transferred, and solvent toluene had been removed to obtain the yellow solid, wherein the yield is 87%.

(5) The results of elemental analysis of the product are shown in Table 1:

(6) TABLE-US-00001 TABLE 1 Elemental analysis results C: (%) H: (%) N: (%) Theoretical value 41.04 5.84 4.16 Actual value 41.11 5.88 4.13

(7) The product was subjected to nuclear magnetic characterization and the results are as follows:

(8) The product was dissolved in C.sub.6D.sub.6 (ca. 0.4 mL), sealed, and characterized by Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, C.sub.6D.sub.6): δ 4.86. (s, 4H), 4.31 (q, J=6.8 Hz, 6H), 2.54-2.48 (m, 2H), 2.28-2.24 (m, 2H), 2.12-1.97 (m, 8H), 1.70-1.39 (m, 4H), 1.28-1.25 (m, 4H), 1.26 (t, J=7.0 Hz, 9H) ppm.

Example 2: Synthesis of Ni(NHC)[P(OR).SUB.3.]X.SUB.2.(R═CH(CH.SUB.3.).SUB.2., X═Br)

(9) Under argon protection, added NHC (0.2884 g, 1.0 mmol) to di(triisopropyl phosphite) nickel dibromide (II) (0.6350 g, 1.0 mmol) in tetrahydrofuran had reacted at room temperature for 4 hours. Then the solvent had been removed in vacuum, the residue had been washed with n-hexane, and the obtained residue had been extracted by toluene, and the clear liquid had been transferred, and solvent toluene had been removed to obtain the yellow solid, wherein the yield is 82%.

(10) The results of elemental analysis of the product are shown in Table 2:

(11) TABLE-US-00002 TABLE 2 Elemental analysis C: (%) H: (%) N: (%) Theoretical value 43.67 6.34 3.92 Actual value 43.74 6.39 3.89

(12) The product was subjected to nuclear magnetic characterization and the results are as follows:

(13) The product was dissolved in C.sub.6D.sub.6 (ca. 0.4 mL), sealed, and characterized by Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, C.sub.6D.sub.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(m, 2H), 2.18-2.01 (m, 8H), 1.79-1.50 (m, 4H), 1.30-1.25(m, 4H), 1.18 (d, J=6.5 Hz, 18H) ppm.

Example 3: Synthesis of Ni(NHC)[P(OR).SUB.3.]X.SUB.2.(R═CH.SUB.2.CH.SUB.3., X═Cl)

(14) Under argon protection, added NHC (0.2884 g, 1.0 mmol) to di(triethyl phosphite) nickel dichloride (II) (0.4619 g, 1.0 mmol) in tetrahydrofuran had reacted at room temperature for 3 hours. Then the solvent had been removed in vacuum, the residue had been washed with n-hexane, and the obtained residue had been extracted by toluene, and the clear liquid had been transferred, and solvent toluene had been removed to obtain the yellow solid, wherein the yield is 80%.

(15) The results of elemental analysis of the product are shown in Table 3:

(16) TABLE-US-00003 TABLE 3 Elemental analysis C: (%) H: (%) N: (%) Theoretical value 47.29 6.73 4.80 Actual value 47.39 6.78 4.76

(17) The product was subjected to nuclear magnetic characterization and the results are as follows:

(18) The product was dissolved in C.sub.6D.sub.6 (ca. 0.4 mL), sealed, and characterized by Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, C.sub.6D.sub.6): δ 4.97 (s, 4H), 4.39 (q, J=6.0 Hz, 6H), 2.50-2.44 (m, 2H), 2.30-2.23 (m, 2H), 2.03-1.89 (m, 8H), 1.71-1.38 (m, 4H), 1.29-1.23(m, 4H), 1.19 (t, J=6.9 Hz, 9H) ppm.

Example 4: Synthesis of Ni(NHC)[P(OR).SUB.3.]X.SUB.2.(R═CH(CH.SUB.3.).SUB.2., X═Cl)

(19) Under argon protection, added NHC (0.2884 g, 1.0 mmol) to di(triisopropyl phosphite) nickel dichloride (II) (0.5460 g, 1.0 mmol) in tetrahydrofuran had reacted at room temperature for 5 hours. Then the solvent had been removed in vacuum, the residue had been washed with n-hexane, and the obtained residue had been extracted by toluene, and the clear liquid had been transferred, and solvent toluene had been removed to obtain the yellow solid, wherein the yield is 80%.

(20) The results of elemental analysis of the product are shown in Table 4:

(21) TABLE-US-00004 TABLE 4 Elemental analysis C: (%) H: (%) N: (%) Theoretical value 49.87 7.24 4.47 Actual value 49.98 7.29 4.42

(22) The product was subjected to nuclear magnetic characterization and the results are as follows:

(23) The product was dissolved in C.sub.6D.sub.6 (ca. 0.4 mL), sealed, and characterized by Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, C.sub.6D.sub.6): δ 4.99 (s, 4H), 4.90 (dq, J=12.80, 5.4 Hz, 3H), 2.62-2.48 (m, 2H), 2.30-2.26 (m, 2H), 2.21-2.00 (m, 8H), 1.74-1.51 (m, 4H), 1.35-1.26 (m, 4H), 1.15 (d, J=7.0 Hz, 18H) ppm.

Example 5: Ni(NHC)[P(OR).SUB.3.]X.SUB.2.(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of Chlorobenzene and p-methylbenzyl chloride

(24) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), chlorobenzene (51 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the separation yield was 94%, and the gas phase yield was 99%. The following examples were all separation yields.

(25) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.30-7.21 (m, 2H), 7.19-7.12(m, 3H), 7.07 (s, 4H), 3.92 (s, 2H), 2.29 (s, 3H) ppm.

Example 6: Ni(NHC)[P(OR).SUB.3.]X.SUB.2.(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of p-methylchlorobenzene and p-methylbenzyl chloride

(26) Under argon protection, catalyst (3.6 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), p-methylchlorobenzene (54 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), the yield was 92%.

(27) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.06 (s, 8H), 3.88 (s, 2H), 2.29 (s, 6H) ppm.

Example 7: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of p-methoxychlorobenzene and p-methylbenzyl chloride

(28) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), p-methoxychlorobenzene (61 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), the yield was 95%.

(29) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.15-7.00 (m, 6H), 6.81 (d, J=8.6 Hz, 2H), 3.87 (s, 2H), 3.75 (s, 3H), 2.30 (s, 3H) ppm.

Example 8: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of p-tert-butylchlorobenzene and p-methylbenzyl chloride

(30) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), p-tert-butylchlorobenzene (84 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (the mixed solvent with the volume ratio of ethyl acetate/petroleum was 1:100 as developing solvent), and the yield was 94%.

(31) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.28 (d, J=8.3 Hz, 2H), 7.13-7.06 (m, 6H), 3.90 (s, 2H), 2.30 (s, 3H), 1.29 (s, 9H) ppm.

Example 9: Ni(NHC)[P(OR).SUB.3.]X.SUB.2.(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of p-fluorochlorobenzene and p-methylbenzyl chloride

(32) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), p-fluorochlorobenzene (54 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the yield was 93%.

(33) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.15-6.99 (m, 6H), 6.98-6.89 (m, 2H), 3.88 (s, 2H), 2.30 (s, 3H) ppm.

Example 10: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of p-trifluoromethylchlorobenzene and p-methylbenzyl chloride

(34) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), p-trifluoromethylchlorobenzene (67 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the yield was 88%.

(35) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.51 (d, J=8.0 Hz, 2H), 7.27 (d, J=7.9 Hz, 2H), 7.15-6.99 (m, 4H), 3.98 (s, 2H), 2.31 (s, 3H) ppm.

Example 11: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of o-methylchlorobenzene and p-methylbenzyl chloride

(36) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), o-methylchlorobenzene (58 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the yield was 94%.

(37) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.16-7.02 (m, 6H), 7.00-6.96(m, 2H), 3.92 (s, 2H), 2.29 (s, 3H), 2.22 (s, 3H) ppm.

Example 12: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of o-fluorochlorobenzene and p-methylbenzyl chloride

(38) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), o-fluorochlorobenzene (53 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the yield was 89%.

(39) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.19-7.06 (m, 6H), 7.04-6.96 (m, 2H), 3.98-3.89 (m, 2H), 2.29 (s, 3H) ppm.

Example 13: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of 2,6-dimethylchlorobenzene and p-methylbenzyl chloride

(40) Under argon protection, catalyst (6.8 mg, 0.010 mmol, 2 mol %), magnesium chips (14.5 mg, 0.6 mmol), 2,6-dimethylchlorobenzene (66 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 8 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the yield was 95%.

(41) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.11-6.99 (m, 5H), 6.89 (d, J=7.6 Hz, 2H), 4.00 (s, 2H), 2.28 (s, 3H), 2.23 (s, 6H) ppm.

Example 14: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of 2,6-diethylchlorobenzene and p-methylbenzyl chloride

(42) Under argon protection, catalyst (6.8 mg, 0.010 mmol, 2 mol %), magnesium chips (14.5 mg, 0.6 mmol), 2,6-diethylchlorobenzene (84.3 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 10 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the yield was 89%.

(43) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.19 (t, J=7.5 Hz, 1H), 7.06 (dd, J=27.9, 7.6 Hz, 4H), 6.88 (d, J=7.6 Hz, 2H), 4.06 (s, 2H), 2.57 (q, J=7.7 Hz, 4H), 2.28 (s, 3H), 1.12 (t, J=7.5 Hz, 6H) ppm.

Example 15: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of meta-dimethylaminochlorobenzene and p-methylbenzyl chloride

(44) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), meta-dimethylaminochlorobenzene (70 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (the mixed solvent with the volume ratio of ethyl acetate/petroleum was 1:100 as developing solvent), and the yield was 96%.

(45) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.15-7.02 (m, 5H), 6.60-6.50 (m, 3H), 3.88 (s, 2H), 2.86 (s, 6H), 2.28 (s, 3H) ppm.

Example 16: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of 4-(2-methyl-1,3-dioxolane-2-yl) chlorobenzene and p-methylbenzyl chloride

(46) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), 4-(2-methyl-1,3-dioxolane-2-yl) chlorobenzene (99 mg, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (the mixed solvent with the volume ratio of ethyl acetate/petroleum was 1:100 as developing solvent), and the yield was 93%.

(47) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.38 (d, J=8.1 Hz, 2H), 7.15 (d, J=8.1 Hz, 2H), 7.09 (s, 4H), 4.01 (t, J=6.8 Hz, 2H), 3.92 (s, 2H), 3.76 (t, J=6.8 Hz, 2H), 2.31 (s, 3H), 1.63(s, 3H) ppm.

Example 17: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of 1-chloronaphthalene and p-methylbenzyl chloride

(48) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), 1-chloronaphthalene (68 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (the mixed solvent with the volume ratio of ethyl acetate/petroleum was 1:50 as developing solvent), and the yield was 97%.

(49) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.03-7.94 (m, 1H), 7.88-7.78(m, 1H), 7.74-7.72 (m, 1H), 7.48-7.35 (m, 3H), 7.26-7.25(m, 1H), 7.11-7.07 (m, 2H), 6.81-6.78 (m, 2H), 4.37 (s, 2H), 2.29 (s, 3H) ppm.

Example 18: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of 6-chloro-N-methylindole and p-methylbenzyl chloride

(50) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), 6-chloro-N-methylindole (82.8 mg, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (the mixed solvent with the volume ratio of ethyl acetate/petroleum was 1:10 as developing solvent), and the yield was 93%.

(51) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.50 (d, J=8.1 Hz, 1H), 7.24-7.14 (m, 4H), 7.09 (s, 1H), 6.95-6.92 (m, 2H), 6.38 (d, J=3.0 Hz, 1H), 4.10 (s, 2H), 3.67 (s, 3H)), 2.35 (s, 3H) ppm.

Example 19: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Cl) Catalyzed Cross-Coupling Reaction of chlorobenzene and p-methylbenzyl chloride

(52) Under argon protection, catalyst (2.9 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), chlorobenzene (51 μl, 0.5 mmol), p-methylbenzyl chloride (82 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (the mixed solvent with the volume ratio of ethyl acetate/petroleum was 1:100 as developing solvent), the yield was 85%.

(53) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.30-7.20 (m, 2H), 7.15 (t, J=6.6 Hz, 3H), 7.07 (d, J=8.7 Hz, 2H), 6.84-6.75 (m, 2H), 3.89(s, 2H), 3.72 (s, 3H) ppm.

Example 20: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Cl) Catalyzed Cross-Coupling Reaction of chlorobenzene and p-tert-butylbenzyl chloride

(54) Under argon protection, catalyst (3.2 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), chlorobenzene (51 μl, 0.5 mmol), p-tert-butylbenzyl chloride (97 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), the yield was 84%.

(55) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.31-7.20 (m, 4H), 7.19-7.10 (m, 3H), 7.13-7.06 (m, 2H), 3.93 (s, 2H), 1.29 (s, 9H) ppm.

Example 21: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of chlorobenzene and o-methylbenzyl chloride

(56) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), chlorobenzene (51 μl, 0.5 mmol), o-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), the yield was 88%.

(57) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.25 (t, J=7.4 Hz, 2H), 7.21-7.05 (m, 7H), 3.98 (s, 2H), 2.23 (s, 3H) ppm.

Example 22: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of p-tert-butylchlorobenzene and benzyl chloride

(58) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), p-tert-butylchlorobenzene (84 μl, 0.5 mmol), benzyl chloride (69 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), the yield was 95%.

(59) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.28 (dd, J=12.4, 7.8 Hz, 4H), 7.23-7.15(m, 3H), 7.11 (d, J=8.1 Hz, 2H), 3.95 (s, 2H), 1.30 (s, 9H) ppm.

Example 23: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of p-tert-butylchlorobenzene and p-fluorochlorobenzyl

(60) Under argon protection, catalyst (3.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), p-tert-butylchlorobenzene (84 μl, 0.5 mmol), p-fluorochlorobenzyl (72 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), the yield was 92%.

(61) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.30 (d, J=8.2 Hz, 2H), 7.17-7.05 (m, 4H), 6.96 (t, J=8.7 Hz, 2H), 3.91 (s, 2H), 1.30 (s, 9H) ppm.

Example 24: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of fluorobenzene and p-methylbenzyl chloride

(62) Under argon protection, catalyst (6.8 mg, 0.010 mmol, 2 mol %), magnesium chips (14.5 mg, 0.6 mmol), fluorobenzene (47 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 10 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the yield was 92%.

(63) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.30-7.21 (m, 2H), 7.19-7.12 (m, 3H), 7.07 (s, 4H), 3.92 (s, 2H), 2.29 (s, 3H) ppm.

Example 25: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of p-methylfluorobenzene and p-methylbenzyl chloride

(64) Under argon protection, catalyst (6.8 mg, 0.010 mmol, 2 mol %), magnesium chips (14.5 mg, 0.6 mmol), p-methylfluorobenzene (55 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 10 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the yield was 92%.

(65) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.06 (s, 8H), 3.88 (s, 2H), 2.30 (s, 6H) ppm.

Example 26: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of p-methoxyfluorobenzene and p-methylbenzyl chloride

(66) Under argon protection, catalyst (6.8 mg, 0.010 mmol, 2 mol %), magnesium chips (14.5 mg, 0.6 mmol), p-methoxyfluorobenzene (57 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 40° C. for 12 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the yield was 90%.

(67) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.15-7.00 (m, 6H), 6.81 (d, J=8.6 Hz, 2H), 3.87 (s, 2H), 3.75 (s, 3H), 2.30 (s, 3H) ppm.

Example 27: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of o-methylfluorobenzene and p-methylbenzyl chloride

(68) Under argon protection, catalyst (6.8 mg, 0.010 mmol, 2 mol %), magnesium chips (14.5 mg, 0.6 mmol), o-methylfluorobenzene (55 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 60° C. for 12 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the yield was 95%.

(69) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.16-7.02 (m, 6H), 7.00-6.96(m, 2H), 3.92 (s, 2H), 2.29 (s, 3H), 2.22 (s, 3H) ppm.

Example 28: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of 1-fluoronaphthalene and p-methylbenzyl chloride

(70) Under argon protection, catalyst (6.8 mg, 0.010 mmol, 2 mol %), magnesium chips (14.5 mg, 0.6 mmol), 1-fluoronaphthalene (56 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 65° C. for 10 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (the mixed solvent with the volume ratio of ethyl acetate/petroleum was 1:50 as developing solvent), and the yield was 98%.

(71) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.03-7.94 (m, 1H), 7.88-7.78 (m, 1H), 7.74-7.72 (m, 1H), 7.48-7.35 (m, 3H), 7.26-7.25(m, 1H), 7.11-7.07 (m, 2H), 6.81-6.78 (m, 2H), 4.37 (s, 2H), 2.29 (s, 3H) ppm.

Example 29: Ni(NHC)[P(OR).SUB.3.]X.SUB.2 .(R═CH.SUB.2.CH.SUB.3., X═Br) Catalyzed Cross-Coupling Reaction of fluorobenzene and p-tert-butylbenzyl chloride

(72) Under argon protection, catalyst (6.8 mg, 0.010 mmol, 2 mol %), magnesium chips (14.5 mg, 0.6 mmol), fluorobenzene (47 μl, 0.5 mmol), p-tert-butylbenzyl chloride (97 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 10 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), the yield was 93%.

(73) The product had been dissolved in CDCl.sub.3 (ca. 0.4 mL), sealed, and characterized on Unity Inova-400 NMR apparatus at room temperature: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.31-7.21 (m, 4H), 7.17-7.10 (m, 3H), 7.13-7.07 (m, 2H), 3.96 (s, 2H), 1.28 (s, 9H) ppm.

Example 30: Ni(IPr)(PPh.SUB.3.)X.SUB.2 .(X═Br) Catalyzed Cross-Coupling Reaction of chlorobenzene and p-methylbenzyl chloride

(74) Under argon protection, catalyst (4.4 mg, 0.005 mmol, 1 mol %), magnesium chips (14.5 mg, 0.6 mmol), chlorobenzene (51 μl, 0.5 mmol), p-methylbenzyl chloride (80 μl, 0.6 mmol), tetrahydrofuran (1.0 ml) were sequentially added to the reaction flask, and had reacted at 50° C. for 1 h, then had quenched with saturated ammonium chloride solution. The product was extracted with ethyl acetate and purified by column chromatography (with petroleum as a developing solvent), and the separation yield was 49%, and the separation yield of the self-coupling by-product of p-methylbenzyl chloride was 40%.

(75) The structure of the catalyst Ni(IPr)(PPh.sub.3)X.sub.2 (X═Br) is shown below.

(76) ##STR00004##

(77) Bisoxazoline-derived nitrogen heterocyclic carbene, which has special structural characteristic. It has not been reported as a ligand in nickel complexes, especially the mixed Ni(II) complex containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand is a new type of Ni(II) complex, which has not been reported in the literature so far. At the first time the invention discloses a mixed Ni(II) complex containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand, which can catalyze at a single temperature in the presence of magnesium shavings reductive cross-coupling reactions of low-activity chlorinated aromatic hydrocarbons and fluorinated aromatic hydrocarbons with chlorinated benzyl compounds to synthesize diarylmethane compounds in one step. Its catalytic activity and substrate applicability are equivalent to or higher than those of the prior art. The operability is also significantly better than the existing technology.