Phenyl phosphorus dichloride → HCID 178419207, compound

HRID 564286Notes

Reaction equation

HRID 564286 reaction equation
I[C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[C:4]([CH3:9])[C:3]=1[O:10][CH3:11].[CH:12]([Mg]Cl)(C)C.[Li+].[Cl-].[C:19]1([P:25](Cl)Cl)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C[Mg]Cl.[BH3:31].C1COCC1>C1COCC1>[CH3:11][O:10][C:3]1[C:4]([CH3:9])=[CH:5][C:6]([CH3:8])=[CH:7][C:2]=1[P:25]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[CH3:12].[BH3:31]

Participants

8

Reactant 6

HCID 12573Phenyl phosphorus dichlorideHCID 433294Lithium ChlorideHCID 2723981Borane;tetrahydrofuranHCID 14112611HCID 14112611, compoundHCID 178418332HCID 178418332, compoundHCID 178418918HCID 178418918, compound

Product 1

HCID 178419207HCID 178419207, compoundYield 29%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Procedure

To a solution of 12.5 g (47.7 mmol) 1-Iodo-2-methoxy-3,5-dimethylbenzene in 150 ml dry THF are added under a nitrogen atmosphere 47.7 ml of a 1.0 M solution of isopropylmagnesiumchloride.LiCl in THF at −78° C. The Grignard solution is allowed to warm to room temperature (2 h) and then added via a dropping funnel to a cooled (−78° C.) solution of 8.1 g (45 mmol) PhPCl2 in 100 ml dry THF over a period of ca. 1 h. The solution is allowed to warm to room temperature and stirred for 3 h (a colour change to orange is observed during this time). The reaction mixture is then treated with 20 ml of a 3.0 M solution of MeMgCl in THF (60 mmol) and stirred at room temperature for 1 h (orange colour disappears). Borane-THF complex (1.0 M in THF, 75 ml) is then added and the solution left stirring overnight. The reaction is then carefully quenched with water (100 ml), the organic layer separated and the aqueous layer extracted with CH2Cl2 (2×100 ml). The combined organic layers are washed with brine (2×200 ml), dried over Na2SO4, filtered and evaporated to dryness in vacuo. The oily crude product is purified on a silica column (30×5 cm, eluent cyclohexane: EtOAc—4:1) to yield 3.6 g (13.2 mmol, 29%) of pure racemic product.

Workup

  1. customat −78° C
  2. additionadded via a dropping funnel to
  3. temperatureto warm to room temperature
  4. stirringstirred at room temperature for 1 h (orange colour disappears)
  5. waitthe solution left
  6. stirringstirring overnight
  7. customThe reaction is then carefully quenched with water (100 ml)
  8. customthe organic layer separated
  9. extractionthe aqueous layer extracted with CH2Cl2 (2×100 ml)
  10. washThe combined organic layers are washed with brine (2×200 ml)
  11. dry with materialdried over Na2SO4
  12. filtrationfiltered
  13. customevaporated to dryness in vacuo
  14. customThe oily crude product is purified on a silica column (30×5 cm, eluent cyclohexane: EtOAc—4:1)

Sources & evidence

ORD record
ord-5e1a3d9f5fc34c6b854b8caeb858f4aa
Source dataset
uspto-grants-2011_11
Patent number
US08067642B2

Reaction notes

Loading…