JP2013245178A - Method for producing triarylamine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a triarylamine compound by coupling an N, N-dialkyl sulfamate compound and a diaryl amide compound in the presence of a nickel catalyst.SOLUTION: A triarylamine is produced by allowing an N, N-dialkyl sulfamate represented by formula (1) (in the formula, Arrepresents a phenyl group or the like, and Rand Reach independently represents a 1-4C alkyl group that may be substituted with a fluorine atom) to react with a diarylamide in the presence of a nickel catalyst.

Description

  The present invention relates to a method for producing triarylamines.

  Triarylamines are industrially important compounds used for organic EL materials and the like.

  As a method for producing triarylamines, a reaction in which an aryl halide and a diarylamine are directly coupled is known. Specifically, a Backwald-Hartwig reaction using a palladium catalyst or an Ullmann reaction using a copper catalyst is known. Are known. Furthermore, with the aim of synthesizing more diverse triarylamines and improving functional group resistance, triarylamines by coupling reactions using sulfonic acid or sulfamic acid aryl esters derived from phenols inexpensively and easily are used as raw materials. Kinds are being considered. The production of triarylamines using these esters as raw materials so far is a method for producing diphenyl (4-tert-butylphenyl) amine from phenyl (4-tert-butylphenyl) sulfonate and diphenylamine. Is disclosed, and an expensive palladium catalyst is used as the catalyst (Non-patent Document 1).

  On the other hand, there has been no report on a method for producing triarylamines by a coupling reaction using a sulfonic acid or sulfamic acid aryl ester as a raw material, which uses nickel which is cheaper than palladium and less toxic than copper. As a similar reaction, Non-Patent Document 2 discloses a method for producing triarylamines by using dichlorobis (triphenylphosphine) nickel as a catalyst and coupling reaction of aryl halide and diarylamide.

Journal of the American Chemical Society, 2003, 125, 6653. Organic Letters, 2005, vol. 7, p. 2209.

  Production of (2-naphthyl) diphenylamine by the coupling reaction of 2-naphthyl N, N-dimethylsulfamylate with diphenylamide using dichlorobis (triphenylphosphine) nickel used in Non-Patent Document 2 as a catalyst. When performed using (triphenylphosphine) nickel, the yield remained at 40% (Comparative Example-1).

  An object of the present invention is to provide a method for producing triarylamines by a coupling reaction using a sulfonic acid or a sulfamic acid aryl ester as a raw material in the presence of a nickel catalyst.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have made triarylamines by reacting N, N-dialkylsulfamic acid esters with diarylamides in the presence of a nickel catalyst. We found that it can be manufactured. That is, the present invention provides a compound represented by the general formula (1) in the presence of a nickel catalyst.

(In the formula, Ar ¹ represents a phenyl group, biphenylyl group or naphthyl group, they have the general formula (2) -NAr ² Ar ³ (wherein, Ar ² and Ar ³ are each independently a phenyl group, A naphthyl group or a biphenylyl group.) R ¹ and R ² each independently has 1 to 4 carbon atoms which may be substituted with a fluorine atom N, N-dialkylsulfamic acid esters represented by general formula (3)

(In the formula, Ar ⁴ and Ar ⁵ each independently represent a phenyl group, a biphenylyl group, or a naphthyl group, which may be substituted with a methyl group or a methoxy group. M is an alkali metal, or A general formula (5) characterized by reacting a diarylamide represented by the general formula (4) MgX (wherein X represents a halogen atom).

(Wherein Ar ¹ , Ar ⁴ and Ar ⁵ have the same contents as described above).

  According to the present invention, industrially useful triarylamines (5) can be obtained in good yield.

  The present invention is described in further detail below. First, the substituents of N, N-dialkylsulfamic acid esters (1), diarylamides (3) and triarylamines (5) will be described.

Specific examples of Ar ¹ include a phenyl group, a 4-biphenylyl group, a 3-biphenylyl group, a 2-biphenylyl group, a 1-naphthyl group, and a 2-naphthyl group.

Examples of Ar ² and Ar ³ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 4-biphenylyl group, a 3-biphenylyl group, and a 2-biphenylyl group. More specifically, the diarylamino group (2) is a diphenylamino group, (1-naphthyl) phenylamino group, (2-naphthyl) phenylamino group, (4-biphenylyl) phenylamino group, (3-biphenylyl) Phenylamino group, di (1-naphthyl) amino group, di (2-naphthyl) amino group, (4-biphenylyl) (1-naphthyl) amino group, (4-biphenylyl) (2-naphthyl) amino group, (3 -Biphenylyl) (1-naphthyl) amino group, (3-biphenylyl) (2-naphthyl) amino group, di (4-biphenylyl) amino group and the like can be exemplified.

Specific examples of the alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, a butyl group, a trifluoromethyl group, Examples include 2,2,2-trifluoroethyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, perfluorobutyl group and the like. A methyl group is preferred because it is easily available and yields are good.

  Specific examples of the alkali metal represented by M include a lithium atom, a sodium atom, and a potassium atom. A sodium atom is preferable in terms of easy availability and good yield.

  Specific examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom. A bromine atom is preferable in terms of easy availability and good yield.

Specific examples of Ar ⁴ and Ar ⁵ include phenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 1-naphthyl group, and 2-naphthyl group. These may be substituted with a methyl group or a methoxy group, and specifically include o-tolyl group, m-tolyl group, p-tolyl group, 3,5-dimethylphenyl group, mesityl group, 2-methoxy group. Phenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,4-dimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 8-methylnaphthalen-1-yl group, 6-methylnaphthalene-2 -Yl group, 8-methoxynaphthalen-1-yl group, 6-methoxynaphthalen-2-yl group, 4'-methylbiphenyl-4-yl group, 4'-methylbiphenyl-3-yl group, 4'-methyl Biphenyl-2-yl group, 4′-methoxybiphenyl-4-yl group, 4′-methoxybiphenyl-3-yl group, 4′-methoxybiphenyl-2-yl group and the like can be exemplified.

  Next, the manufacturing method of triarylamine (5) is demonstrated.

  It is essential to carry out the production method of the present invention in the presence of a nickel catalyst. As the nickel catalyst, a nickel catalyst comprising a nickel compound and 4-imidazoline-2-ylidene, a nickel catalyst comprising a nickel compound and 1,2-bis (substituted phenyl) benzenes, 1,2-bis (substituted phenyl) benzene Analogous coordination nickel complexes are preferred.

  Specific examples of nickel compounds that can be used include nickel metal such as nickel black, nickel fluoride, nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel nitrate, nickel oxide, nickel sulfate, and hydroxide. Nickel salts such as nickel, nickel carbonate, nickel stearate, bis (acetylacetonato) nickel, bis (hexafluoroacetylacetonato) nickel, allyl (cyclopentadienyl) nickel, bis (1,5-cyclooctadiene) Nickel, bis (cyclopentadienyl) nickel, bis (methylcyclopentadienyl) nickel, bis (ethylcyclopentadienyl) nickel, bis (tetramethylcyclopentadienyl) nickel, bis (pentamethylcyclopentadienyl) ) Nickel, screw ( , N'-diethylethylenediamine) nickel dithiocyanate, (cyclopentadienyl) (carbonyl) nickel dimer, hexaamminenickel dichloride, potassium hexafluoronickelate, tetraethylammonium tetrachloronickelate, tris (ethylenediamine) nickel dichloride Bis (N, N′-diisopropylacetamidinato) nickel, tetrakis (triphenylphosphite) nickel, dichloro [1-methoxy-2- (2-methoxyethoxy) ethane] nickel, dibromo [1-methoxy- Examples include nickel complex salts or complex compounds such as 2- (2-methoxyethoxy) ethane] nickel, dichloro (dimethoxyethane) nickel, and dibromo (dimethoxyethane) nickel. From the viewpoint of good yield, bis (1,5-cyclooctadiene) nickel, bis (acetylacetonato) nickel, nickel chloride, nickel bromide and nickel nitrate are preferred.

  Specific examples of 4-imidazoline-2-ylidene that can be used include 1,3-bis (2,6-diisopropylphenyl) -4-imidazoline-2-ylidene and 1,3-diphenyl-4- Imidazoline-2-ylidene, 1,3-bis (2-methylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (3-methylphenyl) -4-imidazoline-2-ylidene, 1,3- Bis (4-methylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (2-ethylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (3-ethylphenyl) -4- Imidazoline-2-ylidene, 1,3-bis (4-ethylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (2-propylphenyl) -4-imidazoline 2-Ilidene, 1,3-bis (3-propylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (4-propylphenyl) -4-imidazoline-2-ylidene, 1,3-bis ( 2-Isopropylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (3-isopropylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (4-isopropylphenyl) -4-imidazoline- 2-ylidene, 1,3-bis (2,4-dimethylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (3,5-dimethylphenyl) -4-imidazoline-2-ylidene, 1, 3-bis (2,4-diethylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (3,5-diethylphenyl) -4-imidazoline-2-y 1,3-bis (2,4-dipropylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (3,5-dipropylphenyl) -4-imidazoline-2-ylidene, 1, 3-bis (2,4-diisopropylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (3,5-diisopropylphenyl) -4-imidazoline-2-ylidene, 1,3-bis (2, 6-Diisopropyl-4-methylphenyl) -4-imidazoline-2-ylidene and the like can be exemplified. In view of good yield, 1,3-bis (2,6-diisopropylphenyl) -4-imidazoline-2-ylidene is preferable.

  The molar ratio of the nickel compound and 4-imidazoline-2-ylidene in the nickel catalyst comprising the nickel compound and 4-imidazoline-2-ylidene is preferably 1:10 to 1: 0.1, and the yield is good. More preferably, it is 1: 5 to 1: 1.

  Specific examples of 1,2-bis (substituted phosphino) benzenes include 1,2-bis (diphenylphosphino) benzene, 1,2-bis (dicyclohexylphosphino) benzene, 1,2-bis [bis ( 3,4,5-trimethoxyphenyl) phosphino] benzene, 1,2-bis [bis (3,5-di-tert-butyl-4-methoxyphenyl) phosphino] benzene, 1,2-bis [bis (3 , 5-dimethoxyphenyl) phosphino] benzene, 1,2-bis [bis (4-methoxyphenyl) phosphino] benzene, 1,2-bis [bis (3,4,5-triethoxyphenyl) phosphino] benzene, , 2-bis [bis (3,4,5-triisopropoxyphenyl) phosphino] benzene, 1,2-bis [bis [3,5-bis (trifluoro Til) phenyl] phosphino] benzene, 1,2-bis [bis (3,5-dimethoxy-4-methylphenyl) phosphino] benzene, 1,2-bis [bis (3,5-dimethylphenyl) phosphino] benzene, 1,2-bis [bis (4-methoxy-3,5-dimethylphenyl) phosphino] benzene, 1,2-bis [bis (3,5-di-tert-butylphenyl) phosphino] benzene, 1,2- Bis (di-p-tolylphosphino) benzene and the like can be exemplified. In terms of good yield, 1,2-bis (diphenylphosphino) benzene, 1,2-bis (dicyclohexylphosphino) benzene, 1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino Benzene, 1,2-bis [bis (3,5-dimethoxyphenyl) phosphino] benzene, 1,2-bis [bis (3,4,5-triethoxyphenyl) phosphino] benzene, 1,2-bis [ Bis (3,4,5-triisopropoxyphenyl) phosphino] benzene, 1,2-bis [bis [3,5-bis (trifluoromethyl) phenyl] phosphino] benzene, 1,2-bis [bis (3 , 5-Dimethoxy-4-methylphenyl) phosphino] benzene, 1,2-bis [bis (3,5-dimethylphenyl) phosphino] benzene, 1,2-bis Bis (3,5-di -tert- butylphenyl) phosphino] benzene are preferred.

  The molar ratio of nickel compound and 1,2-bis (substituted phenyl) benzene nickel compound to 1,2-bis (substituted phosphino) benzenes is preferably 1:10 to 1: 0.1, and the yield is good. The point is more preferably 1: 5 to 1: 1.

  Specific examples of 1,2-bis (substituted phosphino) benzene coordinated nickel complexes include dichloro [1,2-bis (diphenylphosphino) benzene] nickel, dichloro [1,2-bis (dicyclohexylphenylphosphine). Fino) benzene] nickel, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel, dichloro [1,2-bis [bis (3,5-dimethoxyphenyl) phosphino Benzene] nickel, dichloro [1,2-bis [bis (3,4,5-triethoxyphenyl) phosphino] benzene] nickel, dichloro [1,2-bis [bis (3,4,5-triisopropoxy) Phenyl) phosphino] benzene] nickel, dichloro [1,2-bis [bis [3,5-bis (trifluorome] L) phenyl] phosphino] benzene] nickel, dichloro [1,2-bis [bis (3,5-dimethoxy-4-methylphenyl) phosphino] benzene] nickel, dichloro [1,2-bis [bis (3,5) -Dimethylphenyl) phosphino] benzene] nickel, dichloro [1,2-bis [bis (3,5-di-tert-butylphenyl) phosphino] benzene] nickel, dibromo [1,2-bis (diphenylphosphino) benzene ] Nickel, dibromo [1,2-bis (dicyclohexylphenylphosphino) benzene] nickel, dibromo [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel, dibromo [1, 2-bis [bis (3,5-dimethoxyphenyl) phosphino] benzene] nicke Dibromo [1,2-bis [bis (3,4,5-triethoxyphenyl) phosphino] benzene] nickel, dibromo [1,2-bis [bis (3,4,5-triisopropoxyphenyl) phosphino] Benzene] nickel, dibromo [1,2-bis [bis [3,5-bis (trifluoromethyl) phenyl] phosphino] benzene] nickel, dibromo [1,2-bis [bis (3,5-dimethoxy-4-) Methylphenyl) phosphino] benzene] nickel, dibromo [1,2-bis [bis (3,5-dimethylphenyl) phosphino] benzene] nickel, dibromo [1,2-bis [bis (3,5-di-tert-) Examples include butylphenyl) phosphino] benzene] nickel and the like.

  The above 1,2-bis (substituted phosphino) benzenes coordinated nickel complex is prepared by using, for example, a method described in Non-Patent Document 3, using nickel halide and 1,2-bis (substituted phosphino) benzenes as raw materials. Can be synthesized.

Organic Letters, 2009, Vol. 11, p. 741. In the production method of the present invention, the nickel compound and 4-imidazoline-2-ylidene, or the nickel compound and 1,2-bis (substituted phenyl) benzene may be added together with the raw materials, or mixed in advance. You may add to a raw material later.

  Although there is no restriction | limiting in particular in the usage-amount of a nickel catalyst, Reaction advances fully with what is called a catalyst amount. Specifically, the molar ratio of the nickel catalyst to the N, N-dialkylsulfamic acid esters (1) is preferably 0.005 to 0.5, and 0.01 to 0.25 in terms of yield and efficiency. Is more preferable.

  The N, N-dialkylsulfamic acid esters (1) which are raw materials in this production method are prepared from the corresponding phenols and N, N-dialkylsulfamoyl halides, for example, according to the method described in Non-Patent Document 4. Can be manufactured.

Journal of the American Chemical Society, 2009, 131, 17748. There is no restriction | limiting in particular in the usage-amount of diarylamides (3), A target object can be obtained with a sufficient yield by using more than an equivalent with respect to N, N- dialkyl sulfamic acid ester (1).

  In the manufacturing method of this invention, the raw material and nickel catalyst which concern on reaction can be melt | dissolved in an organic solvent, and it can implement. Examples of organic solvents that can be used include hydrocarbon solvents such as pentane, xylene, hexane, benzene, and toluene, halogen solvents such as dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, diethyl ether, 1, Examples include ether solvents such as 4-dioxane and tetrahydrofuran, amide solvents such as N, N-dimethylformamide, and the like. Furthermore, these mixed solvents etc. can be illustrated. From the viewpoint of good yield, ether solvents or amide solvents are preferable, and 1,4-dioxane or N, N-dimethylformamide is more preferable. There is no restriction | limiting in particular in the usage-amount of a solvent.

  The reaction can be carried out at a temperature appropriately selected from 30 to 250 ° C, but preferably 50 to 200 ° C in terms of good yield.

  Although there is no restriction | limiting in particular in reaction time, A target object can be obtained with a sufficient yield by performing reaction for 0.5 to 100 hours. From the viewpoint of efficiency, 1 to 50 hours is more preferable.

  The reaction may be carried out in either a closed system or an open system depending on the boiling point of the solvent. When performed in a closed system, it can be performed at a pressure appropriately selected from the range of atmospheric pressure (0.1 MPa) to 5.0 MPa. The atmosphere during the reaction is preferably an inert gas such as argon or nitrogen.

  The method for isolating the triarylamines (5) from the solution after the reaction is not particularly limited, but solvent extraction, column chromatography, preparative thin layer chromatography, preparative liquid chromatography, recrystallization, distillation or sublimation. The object can be obtained by a general-purpose method such as

  EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to these.

  Example-1

After replacing the inside of the reaction vessel with argon, bis (1,5-cyclooctadiene) nickel (6.3 mg, 0.023 mmol), N, N-dimethylsulfamyl acid 2-naphthyl (62 mg, 0.25 mmol) and 1,3-bis (2,6-diisopropylphenyl) -4-imidazoline-2-ylidene in 1,4-dioxane (23.5 mM, 2.1 mL) was added. Further, a tetrahydrofuran solution (1.0 M, 0.5 mL) of bromo (diphenylamido) magnesium was added and heated at 110 ° C. for 24 hours. After the reaction, purification was performed using silica gel column chromatography to obtain white solid (2-naphthyl) diphenylamine (57 mg, 78%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 7.04 (2H, tt, J = 7.3 Hz, 1.1 Hz), 7.11-7.14 (4H, m), 7.24-7 .29 (5H, m), 7.32-7.42 (3H, m), 7.58 (1H, d, J = 8.0 Hz), 7.71 (1H, d, J = 8.9 Hz) , 7.75 (1H, d, J = 8.0 Hz).
Example-2

After replacing the inside of the reaction vessel with argon, bis (1,5-cyclooctadiene) nickel (6.6 mg, 0.024 mmol), 4-biphenylyl N, N-dimethylsulfamylate (71 mg, 0.26 mmol) and 1,3-bis (2,6-diisopropylphenyl) -4-imidazoline-2-ylidene in 1,4-dioxane (23.5 mM, 2.2 mL) was added. Further, a tetrahydrofuran solution (1.0 M, 0.5 mL) of bromo (diphenylamido) magnesium was added and heated at 150 ° C. for 43 hours. After the reaction, purification was performed using silica gel column chromatography to obtain white solid (4-biphenylyl) diphenylamine (59 mg, 76%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 7.03 (2H, tt, J = 7.0 Hz, 1.3 Hz), 7.12-7.15 (5H, m) 7.24-7. 32 (6H, m), 7.41 (2H, tt, J = 8.4 Hz, 1.6 Hz), 7.47 (2H, dt, J = 8.4 Hz, 2.7 Hz), 7.57 (2H , Dd, J = 8.4 Hz, 1.3 Hz).
Example-3

After purging the inside of the reaction vessel with argon, bis (1,5-cyclooctadiene) nickel (7.8 mg, 0.028 mmol), 1-naphthyl N, N-dimethylsulfamylate (76 mg, 0.30 mmol) and 1,3-bis (2,6-diisopropylphenyl) -4-imidazoline-2-ylidene in 1,4-dioxane (23.5 mM, 2.6 mL) was added. Further, a tetrahydrofuran solution (1.0 M, 0.6 mL) of bromo (diphenylamido) magnesium was added and heated at 150 ° C. for 24 hours. After the reaction, purification was performed using silica gel column chromatography to obtain yellow solid (1-naphthyl) diphenylamine (76 mg, 84%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 6.92 (2H, tt, J = 7.4 Hz, 1.1 Hz), 7.02 (4H, dt, J = 7.6 Hz, 1.1 Hz) , 7.16-7.20 (4H, m), 7.31-7.36 (2H, m), 7.42-7.47 (2H, m), 7.76 (1H, d, J = 8.2 Hz), 7.87 (1H, d, J = 8.2 Hz), 7.93 (1H, d, J = 8.6 Hz).
Example-4

After purging the inside of the reaction vessel with argon, bis (1,5-cyclooctadiene) nickel (9.5 mg, 0.035 mmol), 4-biphenylyl N, N-dimethylsulfamylate (102 mg, 0.37 mmol) and 1,3-bis (2,6-diisopropylphenyl) -4-imidazoline-2-ylidene in 1,4-dioxane (23.5 mM, 3.2 mL) was added. Further, a tetrahydrofuran solution (1.0 M, 0.8 mL) of bromo [bis (4-methoxyphenyl) amido] magnesium was added and heated at 150 ° C. for 24 hours. After the reaction, purification was performed by silica gel column chromatography to obtain yellow solid (4-biphenylyl) bis (4-methoxyphenyl) amine (78 mg, 55%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 3.80 (6H, s), 6.82-6.86 (4H, m), 6.96-7.00 (2H, m), 7. 06-7.11 (4H, m), 7.26-7.30 (1H, m), 7.37-7.42 (4H, m), 7.53-7.56 (2H, m).
Example-5

After the atmosphere in the reaction vessel was replaced with argon, bis (1,5-cyclooctadiene) nickel (6.6 mg, 0.024 mmol), N, N-dimethylsulfamyl acid [4- (4′-diphenylamino) biphenylyl ] (116 mg, 0.26 mmol) and 1,3-bis (2,6-diisopropylphenyl) -4-imidazoline-2-ylidene in 1,4-dioxane (23.5 mM, 2.2 mL) were added. Further, a tetrahydrofuran solution (1.0 M, 0.51 mL) of bromo (diphenylamido) magnesium was added and heated at 150 ° C. for 43 hours. After the reaction, purification was performed using silica gel column chromatography to obtain N, N, N ′, N′-tetraphenyl-1,1′-biphenyl-4,4′-diamine as a white solid (70 mg, 55%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 7.01 (4H, t, J = 7.2 Hz), 7.10-7.13 (12H, m), 7.23-7.27 (8H M), 7.44 (4H, d, J = 8.5 Hz).
Example-6

After substituting the inside of the reaction vessel with argon, bis (1,5-cyclooctadiene) nickel (11 mg, 0.040 mmol), N, N-dimethylsulfamyl acid [4- (4′-diphenylaminobiphenylyl)] (94 mg, 0.21 mmol) and 1,3-bis (2,6-diisopropylphenyl) -4-imidazoline-2-ylidene in 1,4-dioxane (23.5 mM, 3.6 mL) were added. Further, a tetrahydrofuran solution (1.0 M, 0.5 mL) of bromo [bis (4-methoxyphenyl) amido] magnesium was added and heated at 150 ° C. for 24 hours. After the reaction, purification by silica gel column chromatography gave N, N-bis (4-methoxyphenyl) -N ′, N′-diphenyl-1,1′-biphenylyl-4,4′-diamine as a yellow solid. Obtained (64 mg, 55%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 3.80 (6H, s), 6.81-6.85 (4H, m), 6.95-7.03 (4H, m), 7. 05-7.13 (10H, m), 7.23-7.27 (4H, m), 7.36-7.44 (4H, m).
Example-7

After purging the inside of the reaction vessel with argon, bis (1,5-cyclooctadiene) nickel (8.6 mg, 0.031 mmol), 1-naphthyl N, N-dimethylsulfamylate (84 mg, 0.33 mmol) and 1,3-bis (2,6-diisopropylphenyl) -4-imidazoline-2-ylidene in 1,4-dioxane (23.5 mM, 2.8 mL) was added. Further, a tetrahydrofuran solution (0.5 M, 1.4 mL) of bromo [(1-naphthyl) phenylamido] magnesium was added and heated at 150 ° C. for 24 hours. After the reaction, purification was performed using silica gel column chromatography to obtain di (1-naphthyl) phenylamine as a yellow solid (68 mg, 59%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 6.71 (2H, dd, J = 8.7 Hz, 1.1 Hz), 6.86 (1H, tt, J = 7.4 Hz, 1.1 Hz) 7.09-7.13 (2H, m), 7.22 (2H, dd, J = 7.4 Hz, 1.1 Hz), 7.30-7.37 (4H, m), 7.42- 7.46 (2H, m), 7.68 (2H, d, J = 8.2 Hz), 7.86 (2H, d, J = 8.3 Hz), 8.04 (2H, d, J = 8) .5 Hz).
Example-8

  After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid 2-naphthyl (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 99%). The reaction mixture was purified by silica gel column chromatography to obtain white solid (2-naphthyl) diphenylamine (79 mg, 89%).

Example-9
After replacing the inside of the reaction vessel with argon, dichloro [1,2-bis (dicyclohexylphosphino) benzene] nickel (18 mg, 0.030 mmol), 2-naphthyl N, N-dimethylsulfamylate (75 mg, 0.30 mmol). ) And 1,4-dioxane (1.0 mL). Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 54%).

Example-10
After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,5-dimethoxyphenyl) phosphino] benzene] nickel (33 mg, 0.040 mmol), N, N-dimethylsulfamyl acid 2- Naphthyl (100 mg, 0.40 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 2.4 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 84%).

Example-11
After replacing the inside of the reaction vessel with argon, dichloro [1,2-bis [bis (3,4,5-triethoxyphenyl) phosphino] benzene] nickel (33 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid 2-naphthyl (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 94%).

Example-12
After the inside of the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-triisopropoxyphenyl) phosphino] benzene] nickel (34 mg, 0.027 mmol), N, N-dimethylsulfami 2-naphthyl formate (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 68%).

Example-13
After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis [3,5-bis (trifluoromethyl) phenyl] phosphino] benzene] nickel (34 mg, 0.030 mmol), N, N-dimethylsulfur 2-Naphthyl famylate (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 69%).

Example-14
After replacing the inside of the reaction vessel with argon, dichloro [1,2-bis [bis (3,5-dimethoxy-4-methylphenyl) phosphino] benzene] nickel (26 mg, 0.030 mmol), N, N-dimethylsulfami 2-naphthyl formate (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 99%).

Example-15
After replacing the inside of the reaction vessel with argon, dichloro [1,2-bis [bis (3,5-dimethylphenyl) phosphino] benzene] nickel (28 mg, 0.040 mmol), N, N-dimethylsulfamyl acid 2- Naphthyl (100 mg, 0.40 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 2.4 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 56%).

Example-16
After replacing the inside of the reaction vessel with argon, dichloro [1,2-bis [bis (3,5-di-tert-butylphenyl) phosphino] benzene] nickel (41 mg, 0.040 mmol), N, N-dimethylsulfami 2-naphthyl formate (100 mg, 0.40 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 2.4 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 51%).

Example-17
The inside of the reaction vessel was purged with argon, and then dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (8.4 mg, 0.0090 mmol), N, N-dimethylsulfate. 2-Naphthyl famylate (75 mg, 0.30 mmol) and 1,4-dioxane (1 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 55%).

Example-18
After replacing the inside of the reaction vessel with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (14 mg, 0.015 mmol), N, N-dimethylsulfamyl Acid 2-naphthyl (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 63%).

Example-19
After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid 2-naphthyl (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Furthermore, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added, and the mixture was heated at 120 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 90%).

  Example-20

After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid 2-naphthyl (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Furthermore, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (di-p-tolylamide) was added, and the mixture was heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain a white solid (2-naphthyl) di (p-tolyl) amine (93 mg, 96%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 2.32 (6H, s), 7.02 (4H, d, J = 8.5 Hz), 7.08 (4H, d, J = 8.5 Hz) ), 7.24 (1H, dd, J = 8.9, 2.2 Hz), 7.28-7.38 (3H, m), 7.55 (1H, d, J = 8.1 Hz), 7 .66 (1H, d, J = 8.9 Hz), 7.72 (1H, d, J = 8.1 Hz).
Example-21

After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid 2-naphthyl (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium [bis (4-methoxyphenyl) amide] was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain yellow oily (2-naphthyl) bis (4-methoxyphenyl) amine (103 mg, 96%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 3.81 (6H, s), 7.08 (4H, d, J = 8.6 Hz), 7.18-7.36 (4H, m), 7.52 (1H, d, J = 8.0 Hz), 7.64 (1H, d, J = 8.9 Hz), 7.70 (1H, d, J = 8.2 Hz).
Example-22

After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid 2-naphthyl (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Furthermore, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium [di (4-biphenylyl) amide] was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain white solid di (4-biphenylyl) (2-naphthyl) amine (85 mg, 63%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 7.24 (4H, d, J = 8.7 Hz), 7.29-7.45 (10 H, m), 7.52 (4H, d, J = 8.7 Hz), 7.60 (4H, dd, J = 8.4, 1.3 Hz), 7.64 (1H, d, J = 8.1 Hz), 7.76 (1H, d, J = 6.4 Hz), 7.78 (1H, d, J = 6.4 Hz).
Example-23

After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid 2-naphthyl (75 mg, 0.30 mmol) and N, N-dimethylformamide (1.0 mL) were added. Sodium [(1-naphthyl) phenylamide] in N, N-dimethylformamide (0.25 M, 1.8 mL) was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain yellow solid (1-naphthyl) (2-naphthyl) phenylamine (62 mg, 60%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 6.96 (1H, tt, J = 7.2 Hz, 1.1 Hz), 7.06-7.09 (2H, m), 7.19-7 .24 (2H, m), 7.27-7.36 (6H, m), 7.42-7.51 (3H, m), 7.67 (1H, d, J = 9.5 Hz), 7 .72 (1H, d, J = 7.4 Hz), 7.79 (1H, d, J = 8.2 Hz), 7.89 (1H, d, J = 8.4 Hz), 7.96 (1H, d, J = 8.5 Hz).
Example-24
After substituting the inside of the reaction vessel with argon, dichloro [1,2-bis (diphenylphosphino) benzene] nickel (17 mg, 0.030 mmol), N, N-dimethylsulfamyl acid-2-naphthyl (75 mg, .0. 30 mmol) and N, N-dimethylformamide (1 mL) were added. Further, an N, N-dimethylformamide solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added, and the mixture was heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain white solid (2-naphthyl) diphenylamine (58 mg, 58%).

  Example-25

  After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid 4-biphenylyl (83 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain white solid (4-biphenylyl) diphenylamine (74 mg, 81%).

Example-26
After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid-4-biphenylyl (83 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Furthermore, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added, and the mixture was heated at 120 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain white solid (4-biphenylyl) diphenylamine (80 mg, 83%).

Example-27
After replacing the inside of the reaction vessel with argon, dichloro [1,2-bis [bis (3,4,5-triethoxyphenyl) phosphino] benzene] nickel (33 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid 4-biphenylyl (83 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain white solid (4-biphenylyl) diphenylamine (63 mg, 65%).

Example-28
After the inside of the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-triisopropoxyphenyl) phosphino] benzene] nickel (34 mg, 0.027 mmol), N, N-dimethylsulfami 4-biphenylyl formate (83 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain white solid (4-biphenylyl) diphenylamine (62 mg, 65%).

Example-29
After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl Acid 1-naphthyl (75 mg, 0.30 mmol) and 1,4-dioxane (1.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain white solid (1-naphthyl) diphenylamine (42 mg, 64%).

  Example-30

After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl The acid 4- [4 ′-[(1-naphthyl) phenylamino] biphenylyl] (74 mg, 0.15 mmol) and 1,4-dioxane (2.0 mL) were added. Further, a 1,4-dioxane solution (0.25 M, 0.9 mL) of sodium (diphenylamide) amide was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain white solid 4-[(1-naphthyl) phenylamino] -4 ′-(diphenylamino) biphenylyl (85 mg, 96%).
¹ H-NMR (400 MHz, deuterated chloroform, ppm): δ 6.90 (2H, dd, J = 7.5, 1.0 Hz), 6.99 (4H, d, J = 7.8 Hz), 7.35 (2H, t, J = 8.1 Hz), 7.48-7.72 (10H, m), 7.84 (2H, d, J = 8.3 Hz), 7.91 (2H, d, J = 8.2 Hz), 8.03 (2H, d, J = 8.2 Hz), 8.08 (2H, d, J = 8.5 Hz), 8.31 (2H, d, J = 8.5 Hz), 8.61 (2H, d, J = 8.3 Hz).
Example-31

  After the atmosphere in the reaction vessel was replaced with argon, dichloro [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (28 mg, 0.030 mmol), N, N-dimethylsulfamyl The acid 4- (4′-diphenylaminobiphenylyl) (67 mg, 0.15 mmol) and 1,4-dioxane (2.0 mL) were added. Furthermore, a 1,4-dioxane solution (0.25 M, 0.9 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain N, N, N ′, N′-tetraphenyl-1,1′-biphenyl-4,4′-diamine (39 mg, 54%) as a white solid. ).

Example-32
After the atmosphere in the reaction vessel was replaced with argon, bis (acetylacetonato) nickel (7.7 mg, 0.030 mmol), 1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene (24 mg, 0.03 mmol), 2-naphthyl N, N-dimethylsulfamylate (75 mg, 0.30 mmol) and 1,4-dioxane (1.5 mL) were added, and the mixture was stirred at room temperature for 10 minutes. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain white solid (2-naphthyl) diphenylamine (75 mg, 85%).

Example-33
After the atmosphere in the reaction vessel was replaced with argon, nickel nitrate hexahydrate (8.7 mg, 0.030 mmol), 1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene (24 mg, 0 0.03 mmol), 2-naphthyl N, N-dimethylsulfamylate (75 mg, 0.30 mmol) and 1,4-dioxane (1.5 mL) were added, and the mixture was stirred at room temperature for 10 minutes. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain white solid (2-naphthyl) diphenylamine (54 mg, 62%).

Example-34
After the atmosphere in the reaction vessel was replaced with argon, nickel chloride hexahydrate (7.1 mg, 0.030 mmol), 1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene (24 mg, 0 0.030 mmol), 2-naphthyl N, N-dimethylsulfamylate (75 mg, 0.30 mmol) and 1,4-dioxane (1.5 mL) were added, and the mixture was stirred at room temperature for 10 minutes. Further, a 1,4-dioxane solution (0.25 M, 1.8 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. The reaction mixture was purified by silica gel column chromatography to obtain a white solid (2-naphthyl) diphenylamine (63 mg, 71%).

Example-35
After the reaction vessel was purged with argon, dibromo [1,2-bis [bis (3,4,5-trimethoxyphenyl) phosphino] benzene] nickel (21 mg, 0.020 mmol), N, N-dimethylsulfamyl Acid-2-naphthyl (50 mg, 0.20 mmol) and 1,4-dioxane (1.0 mL) were added. Furthermore, a 1,4-dioxane solution (0.25 M, 1.2 mL) of sodium (diphenylamide) was added and heated at 80 ° C. for 3 hours. After the reaction, purification was performed by silica gel column chromatography to obtain 2-naphthyldiphenylamine as a white solid (yield 97%).

Comparative Example-1
After replacing the inside of the reaction vessel with argon, dichlorobis (triphenylphosphine) nickel (33 mg, 0.050 mmol), 2-naphthyl N, N-dimethylsulfamylate (126 mg, 0.50 mmol) and 1,4-dioxane ( 1.0 mL) was added. Furthermore, a 1,4-dioxane solution (0.25 M, 3.0 mL) of sodium (diphenylamide) was added and heated at 150 ° C. for 3 hours. After the reaction, formation of (2-naphthyl) diphenylamine was confirmed by gas chromatography (yield 40%).

Claims (8)

In the presence of a nickel catalyst, the general formula (1)

(In the formula, Ar ¹ represents a phenyl group, biphenylyl group or naphthyl group, they have the general formula (2) -NAr ² Ar ³ (wherein, Ar ² and Ar ³ are each independently a phenyl group, A naphthyl group or a biphenylyl group.) R ¹ and R ² each independently has 1 to 4 carbon atoms which may be substituted with a fluorine atom Represents an alkyl group.)
N, N-dialkylsulfamic acid esters represented by the general formula (3)

(In the formula, Ar ⁴ and Ar ⁵ each independently represent a phenyl group, a biphenylyl group, or a naphthyl group, which may be substituted with a methyl group or a methoxy group. M is an alkali metal, or General formula (4) MgX (X represents a halogen atom.)
A diarylamide represented by the general formula (5)

(In the formula, Ar ¹ represents a phenyl group, biphenylyl group or naphthyl group, they have the general formula (2) -NAr ² Ar ³ (wherein, Ar ² and Ar ³ are each independently a phenyl group, Ar ⁴ and Ar ⁵ each independently represents a phenyl group, a biphenylyl group, or a naphthyl group, which are substituted with a diarylamino group represented by a naphthyl group or a biphenylyl group. And may be substituted with a group or a methoxy group.)
The manufacturing method of triarylamine represented by these.   The nickel catalyst is a nickel catalyst comprising a nickel compound and 4-imidazoline-2-ylidene, a nickel catalyst comprising a nickel compound and 1,2-bis (substituted phosphino) benzene, or 1,2-bis (substituted phosphino) The production method according to claim 1, which is a benzene coordinated nickel complex.   The production method according to claim 1 or 2, wherein the nickel compound is bis (1,5-cyclooctadiene) nickel, bis (acetylacetonato) nickel, nickel chloride, nickel bromide, or nickel nitrate.   The process according to claim 2 or 3, wherein the 4-imidazoline-2-ylidene is 1,3-bis (2,6-diisopropylphenyl) -4-imidazoline-2-ylidene.   1,2-bis (substituted phosphino) benzenes are 1,2-bis (diphenylphosphino) benzene, 1,2-bis (dicyclohexylphosphino) benzene, 1,2-bis [bis (3,4,5 -Trimethoxyphenyl) phosphino] benzene, 1,2-bis [bis (3,5-dimethoxyphenyl) phosphino] benzene, 1,2-bis [bis (3,4,5-triethoxyphenyl) phosphino] benzene, 1,2-bis [bis (3,4,5-triisopropoxyphenyl) phosphino] benzene, 1,2-bis [bis [3,5-bis (trifluoromethyl) phenyl] phosphino] benzene, 1,2 -Bis [bis (3,5-dimethoxy-4-methylphenyl) phosphino] benzene, 1,2-bis [bis (3,5-dimethylphenyl) phosphine Roh] benzene or 1,2-bis [bis (3,5-di -tert- butylphenyl) phosphino] The method according to claim 2 or claim 3 is benzene. The production method according to any one of claims 1 to 5, wherein R ¹ and R ² are methyl groups.   The manufacturing method according to any one of claims 1 to 5, wherein M is a sodium atom.   The manufacturing method according to any one of claims 1 to 7, wherein M is MgBr.