Diethyl Ether → Stannane, trimethyl(4-methylphenyl)-

HRID 1740242Notes

Reaction equation

HRID 1740242 reaction equation
[CH3:1][Sn:2](Cl)([CH3:4])[CH3:3].[C:6]1([CH3:14])[CH:11]=[CH:10][C:9]([Mg]Br)=[CH:8][CH:7]=1.C(OCC)C.[Cl-].[NH4+].CC1C=CC(C2C=CC(C)=CC=2)=CC=1>O1CCCC1.O>[CH3:14][C:6]1[CH:11]=[CH:10][C:9]([Sn:2]([CH3:4])([CH3:3])[CH3:1])=[CH:8][CH:7]=1

Participants

8

Reactant 5

HCID 3283Diethyl EtherHCID 11941Di-p-tolylHCID 14016Trimethyltin chlorideHCID 25517Ammonium ChlorideHCID 178418370HCID 178418370, compound

Product 1

HCID 617834Stannane, trimethyl(4-methylphenyl)-Yield 100%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 546 g (2.74 mol) of trimethyltin chloride in tetrahydrofuran (4L) under nitrogen at -10° C. was added dropwise, maintaining the temperature below -5° C. over 4 hours, 4.14 L of 1.0 M p-tolylmagnesium bromide in diethyl ether (4.14 mol, 1.5 eq.). The suspension was allowed to warm slowly to room temperature over 12 hours then saturated ammonium chloride solution (1 L) was added followed by sufficient water (approximately 1 L) to dissolve the precipitate. The solution was extracted with ether-hexane (1:1) (1×4 L, 3×2 L). The combined organic phases were washed with brine, dried over magnesium sulfate and the solvents removed under vacuum. Purification by flash chromatography on silica gel eluting with hexane/ethyl acetate (95:5) gave a pale yellow oil containing white crystals of 4,4'-dimethylbiphenyl which were removed by filtration to leave 698 g (100%) of product. 1H NMR (300 MHz, CDCl3): δ 0.30 (s, 9H), 2.34 (s, 3H), 7.19 (d, 7.7 Hz, 2H), 7.40 (d, 7.7 Hz, 2H).

Workup

  1. temperaturemaintaining the temperature below -5° C. over 4 hours
  2. dissolutionto dissolve the precipitate
  3. extractionThe solution was extracted with ether-hexane (1:1) (1×4 L, 3×2 L)
  4. washThe combined organic phases were washed with brine
  5. dry with materialdried over magnesium sulfate
  6. customthe solvents removed under vacuum
  7. customPurification by flash chromatography on silica gel eluting with hexane/ethyl acetate (95:5)
  8. customgave a pale yellow oil
  9. customwere removed by filtration

Sources & evidence

ORD record
ord-9adeea1407f249e0bb11ef85ba8a8fd1
Source dataset
uspto-grants-1999_10
Patent number
US05968924

Reaction notes

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