Sulfuric Acid → Sodium 2'-(dicyclohexylphosphino)-2,6-diisopropyl-[1,1'-biphenyl]-4-sulfonate

HRID 227922Notes

Reaction equation

HRID 227922 reaction equation
[CH:1]1([P:7]([CH:29]2[CH2:34][CH2:33][CH2:32][CH2:31][CH2:30]2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[C:14]2[C:19]([CH:20]([CH3:22])[CH3:21])=[CH:18][C:17](C(C)C)=[CH:16][C:15]=2[CH:26]([CH3:28])[CH3:27])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.C(Cl)Cl.[OH:38][S:39](O)(=[O:41])=[O:40].[OH-].[Na+:44]>CO>[CH:1]1([P:7]([CH:29]2[CH2:34][CH2:33][CH2:32][CH2:31][CH2:30]2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[C:14]2[C:19]([CH:20]([CH3:22])[CH3:21])=[CH:18][C:17]([S:39]([O-:41])(=[O:40])=[O:38])=[CH:16][C:15]=2[CH:26]([CH3:28])[CH3:27])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[Na+:44]

Participants

6

Reactant 4

HCID 1118Sulfuric Acid2×HCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl

Product 1

HCID 23674066Sodium 2'-(dicyclohexylphosphino)-2,6-diisopropyl-[1,1'-biphenyl]-4-sulfonateYield 94%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

To an oven-dried 25 mL round bottom flask equipped with a Teflon-coated magnetic stir bar and rubber septum was added dicyclohexyl-(2′,4′,6′-triisopropyl-biphenyl-2-yl)-phosphane (476 mg, 1.00 mmol) and CH2Cl2 (1.0 mL). The solution was cooled to 0° C. using an ice/water bath and then concentrated H2SO4 (1.00 mL) and fuming sulfuric acid (3.0 mL, 20% SO3) were added dropwise. The solution was allowed to warm to room temperature and stir for 24 h. At this time it was cooled to 0° C. using an ice/water bath and crushed ice (˜10 g) was added. The solution turned cloudy and white in color. An aqueous solution of NaOH (6.0 M, ˜20.0 mL) was then added dropwise to the cooled solution until it became neutral (pH ˜7.0 as judged by pH paper). The aqueous solution was extracted with CH2Cl2 (3×50 mL) and concentrated under reduced pressure to give a beige solid. The crude material was then dissolved in a minimum amount of cold methanol (˜20 mL), filtered and concentrated (this cycle was repeated) to give sodium 2′-(dicyclohexyl-phosphanyl)-2,6-diisopropyl-biphenyl-4-sulfonate (4) as a beige solid (503 mg, 94%). Mp=>250° C. 1H NMR (400 MHz, CD3OD) δ: 7.52 (s, 2H), 7.46 (m, 1H), 7.22 (m, 2H), 6.90 (m, 1H), 2.24 (m, 1H), 0.71-1.83 (34H). 13C NMR (125 MHz, CD3OD) δ: 148.4, 147.9, 147.8, 147.5, 145.6, 142.8, 137.4, 137.2, 133.92, 133.91, 132.43, 132.42, 129.3, 128.1, 121.3, 121.0, 40.1, 39.9, 39.7, 39.5, 39.3, 38.8, 35.8, 35.7, 32.5, 32.3, 31.9, 30.8, 30.6, 28.7, 28.6, 28.4, 28.3, 27.7, 26.0, 25.9, 23.3, 23.1. 31P NMR (162 MHz, CD3OD) δ: −10.7. IR (neat, cm−1): 3459, 2927, 2851, 1634, 1463, 1447, 1184, 1078, 1040. Anal. Calcd for C30H42NaO3PS: C, 67.14; H, 7.89. Found: C, 66.93; H, 7.77.

Workup

  1. customTo an oven-dried 25 mL round bottom flask equipped with a Teflon-coated magnetic stir bar
  2. temperatureto warm to room temperature
  3. temperatureAt this time it was cooled to 0° C.
  4. additionwas added
  5. extractionThe aqueous solution was extracted with CH2Cl2 (3×50 mL)
  6. concentrationconcentrated under reduced pressure
  7. customto give a beige solid
  8. filtrationfiltered
  9. concentrationconcentrated (this cycle

Sources & evidence

ORD record
ord-4304840afd5a47e9b7b2f906d1897c2a
Source dataset
uspto-grants-2009_07
Patent number
US07560596B2

Reaction notes

Loading…