855-38-9 Tris(4-methoxyphenyl)phosphine 70071, achiral-phosphine-ligands compound, is more and more widely used in various fields.
855-38-9, Tris(4-methoxyphenyl)phosphine is a chiral-phosphine-ligands compound, ?involved in a variety of chemical synthesis. Rlated chemical reaction is continuously updated,855-38-9
Catalyst Preparation Example 2; Preparation of R,R-(4-methoxyphenyl)2P-CH(methyl)CH(methyl)-P(4-methoxyphenyl)2 ligand An R,R-(4-methoxyphenyl)2P-CH(methyl)CH(methyl)-P(4-methoxyphenyl)2 ligand was prepared as disclosed in the thesis ?B. Bosnich et al, J. Am. Chem. Soc. 99(19) (1977) 6262?.The preparation of (2R,3R)-dibutanediol di-p-toluenesulfonate from (2R,3R)-dibutanediol was conducted using the same method as in Catalyst Preparation Example 1.The preparation of tri(4-methoxyphenyl)phosphorus was conducted as follows. Magnesium pieces (91.1 g, 3.75 mol) were dropped into 95 ml (0.75 mol) of 4-bromo-anisole in 2 L of tetrahydrofuran (THF). The mixture reacted strongly, and was then refluxed and heated for 2 hours to obtain a Grignard reagent. This Grignard reagent was dropped into 17.5 ml (0.2 mol) of a PCl3 solution in 2 L of tetrahydrofuran (THF) at a temperature of -78 C. for 2 hours, while being stirred therein. Thereafter, dry ice and acetone were removed from the reaction product, and then the reaction product was heated to room temperature. The reaction product was stirred overnight, and then the solvent was removed therefrom in a vacuum to form phosphine. The entire reaction product was used in subsequent processes, without removing the phosphine therefrom.Meanwhile, 70 g of recrystallized tri(4-methoxyphenyl)phosphorus and 300 ml of dried tetrahydrofuran (THF) were put into a 1 L three-neck flask equipped with a 250 ml funnel for dropping, a condenser for reflux cooling and a nitrogen injector to form a solution. 2.8 g of lithium pieces were added to the solution in a nitrogen atmosphere at a temperature of 25 C. with stirring. Thereafter, simultaneously, LiP(4-OMe-Ph)2 was formed in the solution, heat was generated in the solution, and the solution became dark reddish yellow. The solution was slowly heated for 1 hour to a temperature of 55 C. and was then cooled for 2 hours to a temperature of 25 C., while being stirred. The 4-methoxyphenyllithium thus formed was decomposed by dropping 18.5 g of distilled and refined t-butyl chloride thereinto for 45 minutes. The reddish yellow solution was heated for 5 minutes and then cooled to a temperature of -4 C.Subsequently, 19.6 g of the (2R,3R)-dibutanediol di-p-toluenesulfonate thus obtained was dissolved in 100 ml of dried tetrahydrofuran (THF), and was then dropped into the reddish yellow solution over 1 hour to form a mixed solution. The mixed solution was slowly heated to room temperature and then stirred for 30 minutes. 300 ml of nitrogen-containing water was added to the mixed solution, and then tetrahydrofuran (THF) was removed therefrom through vacuum distillation, thereby extracting a colorless oily product therefrom. The oily product was extracted twice using 150 ml of ether, and was then dried by Na2SO4 to form an ether extract. The ether extract was filtered in a solution of 50 ml of ethanol and 8.4 g of nickel perchlorate hexahydrate in a nitrogen atmosphere. Na2SO4 remaining in the filtered ether extract was completely washed to form an ether solution, and then the ether solution was added to a nickel solution. As a result, a reddish brown oily product having yellow crystals, [Ni((2S,3S)-bis(di-p-methoxyphenyl)phosphorous butane)2](ClO4)2, was formed. This oily crystalline mixture was added to a solution in which 8.4 g of sodium thiocyanate is dissolved in 50 mL of ethanol to form a mixture solution, and then the mixture solution was vigorously stirred for several hours to form a yellowish brown solid product, [Ni((2S,3S)-bis(di-p-methoxyphenyl)phosphorous butane)2NCS]NCS. This solid product was completely washed with ethanol and was then finally washed with ether to form a nickel complex.17 g of this nickel complex was floated with 150 ml of ethanol in a nitrogen atmosphere, and was then stirred and heated. 20 g of water and 4 g of sodium cyanate (NaCN) were added to the nickel complex. Thus, the nickel complex was slowly dissolved, and was thus formed into a red solution, [Ni((2S,3S)-bis(di-p-methoxyphenyl)phosphorous butane)2CN3]-, and then the red solution was changed into a turbid beige solution. The turbid solution was stirred to form a yellow slurry solution. The slurry solution was cooled to form it into a solid, and then the solid was washed with 25 ml of water twice and then rapidly cooled using ethanol, cooled using ice, to form a beige solid containing impurities. The beige solid containing impurities was dried at a temperature of 25 C., was added to 125 ml of boiling anhydrous ethanol, and was then filtered using a Fritz filter at room temperature for 12 hours. As a result, only a colorless glossy solid remained. Finally, the colorless glossy solid was recrystallized using 60 ml of anhydrous ethanol to obtain 6.2 g of colorless pure S,S-(4-methoxyphenyl)2PCH(methyl)CH(methyl)P(4-methoxyphenyl)2.
855-38-9 Tris(4-methoxyphenyl)phosphine 70071, achiral-phosphine-ligands compound, is more and more widely used in various fields.
Reference£º
Patent; Han, Taek Kyu; Ok, Myung Ahn; Chae, Sung Seok; Kang, Sang Ook; Jung, Jae Ho; US2010/137669; (2010); A1;,
Phosphine ligand
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate