ChemicalBook CAS DataBase List 2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl synthesis

6synthesis methods

Product Name:2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl
CAS Number:657408-07-6
Molecular formula:C26H35O2P
Molecular Weight:410.53

694-80-4

151-10-0

16523-54-9

2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

657408-07-6

To a solution of 1,3-dimethoxybenzene (2 mL, 15.30 mmol) in anhydrous THF (35 mL) was slowly added n-butyllithium (nBuLi, 6.2 mL, 15.50 mmol) through a dropping funnel over 5 min at 0 °C. The reaction mixture was stirred at room temperature for 3.5 h. After stirring, 2-bromochlorobenzene (1.6 mL, 13.70 mmol) was added slowly dropwise through a syringe at 0 °C for 30 min. After stirring for 15 min, the reaction mixture was cooled to -78 °C and n-butyllithium (6.20 mL, 15.50 mmol) was again added slowly through a dropping funnel over 5 min. 30 min later, chlorodicyclohexylphosphine (3.03 mL, 13.70 mmol) was added. The reaction mixture was kept at -78 °C for 1 h, during which rapid mechanical stirring was performed. Subsequently, the reaction mixture was warmed to room temperature and the resulting precipitate was filtered through a silica gel sintered disc covered with a cellulose acetate layer and washed with 600 mL of ethyl acetate. The filtrate was concentrated by rotary evaporation and the resulting orange oil was recrystallized in acetone to give white crystalline S-Phos ligand in 36% yield (1.22 g, 2.97 mmol). Melting point: 163-165 °C (literature value 162.0-162.5 °C); Thin layer chromatography (TLC) conditions: ethyl acetate/cyclohexane (10/90), Rf = 0.65; 1H-NMR (CDCl3): δ = 0.99-1.26 (m, 10H, H(Cy)), 1.60-1.77 (m, 12H, H(Cy)), and 3.67 (s, 6H, Me), 6.58 (d, 2H, J = 8.2 Hz, H3' and H5'), 7.15-7.18 (m, 1H, H(Ar)), 7.18-7.42 (m, 3H, H(Ar)), 7.57 (d, 1H, J = 7.4 Hz, H(Ar)) ppm; 13C-NMR (CDCl3): δ = 26.5, 27.3, 27.4, 27.6, 29.0, 29.1, 29.8, 30.1, 33.8, 34.0 (C(Cy)), 55.3 (Cb), 103.1 (Ca), 126.2, 128.2, 128.8 (C3', C4', C5'), 130.9, 131.00, 132.4. 135.8 (C3, C4, C5, C6), 135.8, 136.1, 142.7, 143.1, 157.4 (C2', C6') ppm; IR (KBr): υ = 3000, 2923, 2851, 1588, 1471, 1442, 1428, 1108 cm-1.

694-80-4 Synthesis

694-80-4
400 suppliers
$5.00/10g

151-10-0
463 suppliers
$5.00/10g

16523-54-9 Synthesis

16523-54-9
274 suppliers
$8.00/1g

657408-07-6
345 suppliers
$6.00/1g

Yield:657408-07-6 36%

Reaction Conditions:

Stage #1: 1,3-Dimethoxybenzenewith n-butyllithium in tetrahydrofuran at 0 - 20; for 3.5 h;
Stage #2: 2-bromo-1-chlorobenzene in tetrahydrofuran at 0; for 0.5 h;
Stage #3: chlorodicyclohexylphosphane

Steps:

To a solution of 1,3-dimethoxybenzene (2 ml, 15.30 mmol) in anhydrous THF (35 ml) at 0° C., nBuLi (6.2 ml, 15.50 mmol) is added to the dropping funnel for 5 min. The reaction medium is stirred at room temperature for 3.5 h, then 2-bromochlorobenzene (1.6 ml, 13.70 mmol) is added by syringe, dropwise, at 0° C., for 30 min. After 15 min of stirring, the reaction medium is cooled to -78° C. and nBuLi (6.20 ml, 15.50 mmol) is added to the dropping funnel dropwise for 5 min. After 30 min, chlorodicyclohexylphosphine (3.03 ml, 13.70 mmol) is added. The reaction medium is maintained at -78° C. for 1 h, under rapid stirring (mechanical stirring). After returning to room temperature, the precipitate obtained is filtered on a fritted disc containing silica topped with a layer of cellulose acetate, with 600 ml ethyl acetate. The solvents are evaporated with a rotary evaporator, and the orange oil obtained is recrystallized in acetone to obtain S-Phos ligand in the form of white crystals with a yield of 36% (1.22 g, 2.97 mmol). MP: 163-165° C. (Lit. MP 162.0-162.5° C.); TLC: (AcOEt/cyclohexane 10/90). R_f=0.65; ¹H-NMR (CDCl₃): δ=0.99-1.26 (m, 10H, H(Cy)), 1.60-1.77 (m, 12H, H(Cy)), 3.67 (s, 6H, Me), 6.58 (d, 2H, J=8.2 Hz, H_3' and H_5'), 7.15-7.18 (m, 1H, H(Ar)), 7.18-7.42 (m, 3H, H(Ar)), 7.57 (d, 1H, J=7.4 Hz, H(Ar)) ppm; ¹³C-NMR (CDCl₃): δ=26.5, 27.3, 27.4, 27.6, 29.0, 29.1, 29.8, 30.1, 33.8, 34.0 (C(Cy)), 55.3 (Cb), 103.1 (Ca), 126.2, 128.2, 128.8 (C_3', C_4', C_5'), 130.9, 131.00, 132.4, 135.8 (C₃, C₄, C₅, C₆), 135.8, 136.1, 142.7, 143.1, 157.4 (C_2', C_6') ppm; IR (KBr): υ=3000, 2923, 2851, 1588, 1471, 1442, 1428, 1108 cm^-1.