1,2-Dibromoethane → [1,1':2',1''-Terphenyl]-2-yldi-tert-butylphosphane

HRID 1354963

Reaction equation

HRID 1354963 reaction equation
[Mg].Br[CH2:3][CH2:4]Br.CN([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1P(C1CCCCC1)C1CCCCC1)C.[C:34]([P:38]([C:40]([CH3:43])([CH3:42])[CH3:41])Cl)([CH3:37])([CH3:36])[CH3:35]>C1COCC1.[Cu]Cl>[C:34]([P:38]([C:40]([CH3:43])([CH3:42])[CH3:41])[C:4]1[CH:3]=[CH:11][CH:10]=[CH:9][C:14]=1[C:9]1[C:10]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[CH:11][CH:12]=[CH:13][CH:14]=1)([CH3:37])([CH3:36])[CH3:35]

Participants

7

Reactant 4

HCID 78391,2-DibromoethaneHCID 139566Di-tert-butylchlorophosphineHCID 27342172-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenylHCID 5462224Magnesium

Product 1

HCID 9951497[1,1':2',1''-Terphenyl]-2-yldi-tert-butylphosphaneYield 26%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

An oven-dried Schlenk tube was cooled to room temperature under an argon purge, and was charged with magnesium turnings (54 mg, 2.2 mmol), THF (2 mL), and 1,2-dibromoethane (9 μL). The mixture was stirred at room temperature for 15 min, then a solution of 2 (618 mg, 2.0 mmol) in 1 mL THF was added dropwise. The mixture was stirred at rt for 1 h, then the septum was removed from the flask, and copper (I) chloride (283 mg, 2.1 mmol) was added. The tube was capped with the septum and purged with argon for 1 min. The tube was charged with di-t-butylchlorophosphine (0.46 mL, 2.4 mmol) and additional THF (1 mL). The mixture was heated to 60° C. with stirring for 26 h. The mixture was cooled to room temperature and filtered, and the solids were washed with ether/hexanes (50 mL, 1/1 v/v). The organic solution was poured into a separatory funnel and washed with ammonium hydroxide solution (3×50 mL), and brine (50 mL). The organic phase was then dried over anhydrous sodium sulfate, filtered, and concentrated. The crude material was recrystallized from hot methanol to afford 191 mg (26%) of 3 as a white, crystalline solid.

Workup

  1. custompurge
  2. stirringThe mixture was stirred at rt for 1 h
  3. additionwas added
  4. customThe tube was capped with the septum
  5. custompurged with argon for 1 min
  6. temperatureThe mixture was heated to 60° C.
  7. stirringwith stirring for 26 h
  8. temperatureThe mixture was cooled to room temperature
  9. filtrationfiltered
  10. washthe solids were washed with ether/hexanes (50 mL, 1/1 v/v)
  11. additionThe organic solution was poured into a separatory funnel
  12. washwashed with ammonium hydroxide solution (3×50 mL), and brine (50 mL)
  13. dry with materialThe organic phase was then dried over anhydrous sodium sulfate
  14. filtrationfiltered
  15. concentrationconcentrated
  16. customThe crude material was recrystallized from hot methanol

Sources & evidence

ORD record
ord-8c618f70bf3048f0bac5f5deb636808e
Source dataset
uspto-grants-2007_05
Patent number
US07223879B2

Linked notes

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