4-[Bis(1,1-dimethylethyl)phosphino]-N,N-dimethylbenzenamine

Under argon protection, To the drying reactor was added 1 L of toluene, Followed by the addition of N, N-dimethylaniline (121 g, 1 mol)4-dimethylaminopyridine (122 g, 1 mol), Cuprous acetate (1.2 g, 0.01 mmol)And di-tert-butylphosphonium chloride (181 g, 1 mol)And then heated to 120 C for 8 hours.After completion of the reaction, 1 L of water was added to the quenching reaction, Then extracted, The organic layer was dried over anhydrous magnesium sulfate, filter, After distillation under reduced pressure to give a yellow solid, This was lyophilized in 1 L of n-hexane to recrystallize to give a white solid [4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine 254 g, Yield 96percent.The reaction flask was replaced with a nitrogen atmosphere, and 32 g of di-tert-butylphosphine and 200 mL of toluene were added to 1 L of the reaction flask, Start the magnetic stirrer, add 0.1M 2.5M n-butyllithium at -10 ° C, drip to 50 ° C for 12 hours, drop the temperature of the reaction solution to -10 ° C, A solution of 40 g of N, N-dimethyl-p-bromoaniline in toluene was added dropwise to the reaction at 50 ° C for 12 hours, after which the reaction solution was lowered to room temperature, 10 mL of triethylamine aqueous solution was added dropwise under ice-cooling, and the upper organic phase was depiltrated under nitrogen protection, Distillation under reduced pressure, collecting 120 ° C (15 mm Hg) di-tert-butyl-4-dimethylaminophenylphosphine 49.2 gUnder argon protection, To the drying reactor was added 1 L of toluene, Followed by the addition of N, N-dimethylaniline (121 g, 1 mol)4-dimethylaminopyridine (122 g, 1 mol), Cuprous acetate (1.2 g, 0.01 mmol)And di-tert-butylphosphonium chloride (181 g, 1 mol)And then heated to 120 C for 8 hours.After completion of the reaction, 1 L of water was added to the quenching reaction, Then extracted, The organic layer was dried over anhydrous magnesium sulfate, filter, After distillation under reduced pressure to give a yellow solid, This was lyophilized in 1 L of n-hexane to recrystallize to give a white solid [4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine 254 g, Yield 96percent.The reaction system is cooled to -30 ° C, under the protection of nitrogen flow, Adding catalyst to remove water by vacuum dryingAfter the powder was 10.2 g, the reaction was stirred for 10 min.Further, 930 g of di-tert-butylphosphonium chloride was added dropwise.The dropping process controls the reaction temperature below -30 ° C, and the dropwise addition is completed, and the temperature is raised to 50 ° C for 3 hours to obtain di-tert-butyl-4-dimethylaminophenylphosphine. The reaction system was again cooled to -30 ° C, and 1.5 L of a saturated aqueous solution of ammonium chloride was added dropwise with stirring.After stirring for 0.5 h, the mixture was allowed to stand for stratification under the protection of a nitrogen stream.The liquid is separated, and the upper organic phase is concentrated and concentrated to obtain a yellow viscous material for high vacuum distillation under reduced pressure.The degree of vacuum is 0.3-0.5 mmHg, and the fraction of 120 ° C - 140 ° C is collected, and after cooling, it is an off-white solid.That is, the ligand di-tert-butyl-4-dimethylaminophenylphosphine has a yield of 1145-1160 g, a purity of not less than 97percent, and a yield of 81.5percent to 85.0percent.The reaction system is cooled to -60 ° C under the protection of nitrogen flow.Adding catalyst to the vacuum drying to remove water, copper bromideAfter the powder was 14.8 g, the reaction was stirred for 8 min, and 930 g of di-tert-butylphosphonium chloride was added dropwise.The dropping process controls the reaction temperature below -60 ° C, and the dropwise addition is completed, and the temperature is raised to 55 ° C for 4 hours to obtain di-tert-butyl-4-dimethylaminophenylphosphine. The reaction system was again cooled to below -60 ° C, and 1.5 L of a saturated aqueous solution of ammonium chloride was added dropwise with stirring, and the mixture was stirred for 0.5 h.After standing and layering, The liquid is separated under the protection of a nitrogen stream, and the upper organic phase is concentrated and concentrated to obtain a yellow viscous material for high vacuum distillation under reduced pressure.The degree of vacuum is 0.3-0.5 mmHg, and the fraction of 120 ° C - 140 ° C is collected, and after cooling, it is an off-white solid.It is a ligand of di-tert-butyl-4-dimethylaminophenylphosphine, and the yield is 1145-1160 g, the purity is not less than 97percent, and the yield is 81.5percent to 85.0percent.The reaction flask was replaced with a nitrogen atmosphere, and 32 g of di-tert-butylphosphine and 200 mL of toluene were added to 1 L of the reaction flask, Start the magnetic stirrer, add 0.1M 2.5M n-butyllithium at -10 ° C, drip to 50 ° C for 12 hours, drop the temperature of the reaction solution to -10 ° C, A solution of 40 g of N, N-dimethyl-p-bromoaniline in toluene was added dropwise to the reaction at 50 ° C for 12 hours, after which the reaction solution was lowered to room temperature, 10 mL of triethylamine aqueous solution was added dropwise under ice-cooling, and the upper organic phase was depiltrated under nitrogen protection, Distillation under reduced pressure, collecting 120 ° C (15 mm Hg) di-tert-butyl-4-dimethylaminophenylphosphine 49.2 gTo a solution of {Te((2, 6-OCH3)2C6H3)}2 (0.053 g, 0.1 mmol) inacetonitrile (5 mL), PdI2 (0.036 g, 0.1 mmol) was added and thesolution was stirred for 2.5 h. In the next step, The reaction system is cooled to -60 C under the protection of nitrogen flow.Adding catalyst to the vacuum drying to remove water, copper bromideAfter the powder was 14.8 g, the reaction was stirred for 8 min, and 930 g of di-tert-butylphosphonium chloride was added dropwise.The dropping process controls the reaction temperature below -60 C, and the dropwise addition is completed, and the temperature is raised to 55 C for 4 hours to obtain di-tert-butyl-4-dimethylaminophenylphosphine. The reaction system was again cooled to below -60 C, and 1.5 L of a saturated aqueous solution of ammonium chloride was added dropwise with stirring, and the mixture was stirred for 0.5 h.After standing and layering, The liquid is separated under the protection of a nitrogen stream, and the upper organic phase is concentrated and concentrated to obtain a yellow viscous material for high vacuum distillation under reduced pressure.The degree of vacuum is 0.3-0.5 mmHg, and the fraction of 120 C - 140 C is collected, and after cooling, it is an off-white solid.It is a ligand of di-tert-butyl-4-dimethylaminophenylphosphine, and the yield is 1145-1160 g, the purity is not less than 97%, and the yield is 81.5% to 85.0%.The reaction system is cooled to -30 C, under the protection of nitrogen flow, Adding catalyst to remove water by vacuum dryingAfter the powder was 10.2 g, the reaction was stirred for 10 min.Further, 930 g of di-tert-butylphosphonium chloride was added dropwise.The dropping process controls the reaction temperature below -30 C, and the dropwise addition is completed, and the temperature is raised to 50 C for 3 hours to obtain di-tert-butyl-4-dimethylaminophenylphosphine. The reaction system was again cooled to -30 C, and 1.5 L of a saturated aqueous solution of ammonium chloride was added dropwise with stirring.After stirring for 0.5 h, the mixture was allowed to stand for stratification under the protection of a nitrogen stream.The liquid is separated, and the upper organic phase is concentrated and concentrated to obtain a yellow viscous material for high vacuum distillation under reduced pressure.The degree of vacuum is 0.3-0.5 mmHg, and the fraction of 120 C - 140 C is collected, and after cooling, it is an off-white solid.That is, the ligand di-tert-butyl-4-dimethylaminophenylphosphine has a yield of 1145-1160 g, a purity of not less than 97%, and a yield of 81.5% to 85.0%.Take a dry 10L three-neck reaction flask, dry nitrogen is fully replaced and under nitrogen flow protection, Add 5.5 L of anhydrous tetrahydrofuran, stir and add 540 g of bis(acetonitrile)palladium dichloride.The obtained ligand di-tert-butyl-4-dimethylaminophenylphosphine was further reacted for 30 minutes, and a yellow solid was precipitated. After the reaction was continued for 9 hours at room temperature, After filtration, the filter cake was dipped in anhydrous tetrahydrofuran, drained and dried in a vacuum oven at 60 C.Obtaining a yellow crystalline powdery target product, namely dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium, yielding 1440 g to 1445 g, Elemental analysis showed that the product content exceeded 98.0%, the palladium content exceeded 15.0%, and the palladium calculated yield was 97.7% to 98.1%.

Molecular Weight:265.37
XLogP3:3.6
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:4
Exact Mass:265.195936895
Monoisotopic Mass:265.195936895
Topological Polar Surface Area:3.2
Heavy Atom Count:18
Complexity:237
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes