Ethyl phosphorochloridite → Diethyl 2-[bis(3,5-di-t-butyl-4-methoxyphenyl)phosphino]phenylphosphonite

HRID 1581625Notes

Reaction equation

HRID 1581625 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([P:17]([C:25]2[CH:30]=[C:29]([C:31]([CH3:34])([CH3:33])[CH3:32])[C:28]([O:35][CH3:36])=[C:27]([C:37]([CH3:40])([CH3:39])[CH3:38])[CH:26]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2Br)[CH:8]=[C:9]([C:13]([CH3:16])([CH3:15])[CH3:14])[C:10]=1[O:11][CH3:12])([CH3:4])([CH3:3])[CH3:2].Cl[P:42]([O:46][CH2:47][CH3:48])[O:43][CH2:44][CH3:45]>O1CCCC1>[C:1]([C:5]1[CH:6]=[C:7]([P:17]([C:25]2[CH:30]=[C:29]([C:31]([CH3:34])([CH3:33])[CH3:32])[C:28]([O:35][CH3:36])=[C:27]([C:37]([CH3:40])([CH3:39])[CH3:38])[CH:26]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[P:42]([O:46][CH2:47][CH3:48])[O:43][CH2:44][CH3:45])[CH:8]=[C:9]([C:13]([CH3:16])([CH3:15])[CH3:14])[C:10]=1[O:11][CH3:12])([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 2

HCID 68530Ethyl phosphorochloriditeHCID 12115810Bis(3,5-di-t-butyl-4-methoxyphenyl)(2-bromophenyl)phosphine

Product 1

HCID 12115811Diethyl 2-[bis(3,5-di-t-butyl-4-methoxyphenyl)phosphino]phenylphosphoniteYield 91.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

Into a four-neck flask was weighed 15.00 g (24.0 mmol) of the bis(3,5-di-t-butyl-4-methoxyphenyl)(2-bromophenyl)phosphine (7). The atmosphere of the reaction vessel which was fitted with a thermometer, a condenser tube, and a dropping funnel with a pressure-equalizing tube was completely replaced with nitrogen, and 150 mL of anhydrous tetrahydrofuran (hereinafter referred to as THF) was added thereto. Thereto was added dropwise 16.2 mL (25.2 mmol) of n-butyllithium-hexane (1.6 M) solution at −78° C. over a period of 30 minutes, followed by 1 hour of stirring at the same temperature. The resulting mixed solution was cooled to −78° C. and thereto was added dropwise a 10 mL THF solution of 4.15 g (25.2 mmol) of diethyl chlorophosphonite (manufactured by Aldrich) over a period of 30 minutes. After the dropwise addition, a cooling bath was removed and the whole was further stirred at room temperature for 15 hours. After the completion of the reaction, THF was removed by evaporation, the residue was dissolved in 50 mL of diethyl ether, and insoluble matter was removed by filtration. The solvent was removed by evaporation and the residue was purified by active alumina column chromatography (eluent: hexane/ethyl acetate 4/1) to obtain the title compound (14.03 g, a pale yellow solid) Yield 91.5%.

Workup

  1. customInto a four-neck flask was weighed
  2. customThe atmosphere of the reaction vessel which was fitted with a thermometer, a condenser tube, and a dropping funnel with a pressure-equalizing tube
  3. additionwas added
  4. additionThereto was added dropwise 16.2 mL (25.2 mmol) of n-butyllithium-hexane (1.6 M) solution at −78° C. over a period of 30 minutes
  5. additionThe resulting mixed solution
  6. additionAfter the dropwise addition, a cooling bath
  7. customwas removed
  8. stirringthe whole was further stirred at room temperature for 15 hours
  9. customAfter the completion of the reaction, THF
  10. customwas removed by evaporation
  11. dissolutionthe residue was dissolved in 50 mL of diethyl ether
  12. custominsoluble matter was removed by filtration
  13. customThe solvent was removed by evaporation
  14. customthe residue was purified by active alumina column chromatography (eluent: hexane/ethyl acetate 4/1)

Sources & evidence

ORD record
ord-1da3f246a0f442a1ac6adc79eb50eda3
Source dataset
uspto-grants-2004_05
Patent number
US06730629B2

Reaction notes

Loading…