Dichlorodimethylsilane → 10,10-Dimethyl-10H-phenoxasiline

HRID 399286Notes

Reaction equation

HRID 399286 reaction equation
[C:1]1([O:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([Li])CCC.CCCCCC.CN(CCN(C)C)C.[CH3:33][Si:34]([CH3:37])(Cl)Cl>C1COCC1.CCOCC.O>[CH3:33][Si:34]1([CH3:37])[C:6]2[CH:5]=[CH:4][CH:3]=[CH:2][C:1]=2[O:7][C:8]2[C:9]1=[CH:10][CH:11]=[CH:12][CH:13]=2

Participants

9

Reactant 5

HCID 6398DichlorodimethylsilaneHCID 7583Diphenyl Ether2×HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 8058HexaneHCID 178418339Butyllithium

Product 1

HCID 14038410,10-Dimethyl-10H-phenoxasiline

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

At room temperature a solution of 8.00 g of diphenylether (47.0 mmol) in 35 ml of THF was added dropwise to a mixture of 41.4 ml of 2.5M n-butyllithium in hexane (103.4 mmol) and 16.7 ml of TMEDA (103.4 mmol). When all phenylether was added, the reaction mixture was stirred for 16 h. The ethereal solution of 2,2'-dilithiodiphenylether and a solution of 5.7 ml of dimethyldichlorosilane (47.0 mmol) in 75 ml of ether were added simultaneously to 40 ml of ether over 1 h. The reaction mixture was stirred for 16 hr. then hydrolyzed by addition of 30 ml of water. The hydrolyzed mixture was stirred for 2 hr. The organic layer was separated, and the aqueous layer was extracted with 30 ml of ether. The combined organic layers were treated with Norit, and dried with MgSO4. The solvent was removed in vacuo. Small crystals formed during the concentration. The semisolid oil was crystallized form methanol, resulting in white crystals of 10,10-dimethylphenoxasilin with a grassy odour. Yield: 4.82 g (45%).

Workup

  1. stirringThe reaction mixture was stirred for 16 hr
  2. stirringThe hydrolyzed mixture was stirred for 2 hr
  3. customThe organic layer was separated
  4. extractionthe aqueous layer was extracted with 30 ml of ether
  5. additionThe combined organic layers were treated with Norit
  6. dry with materialdried with MgSO4
  7. customThe solvent was removed in vacuo
  8. customSmall crystals formed during the concentration
  9. customThe semisolid oil was crystallized form methanol

Sources & evidence

ORD record
ord-2e2c6dc0cf0e46e8959b930a4e3142d6
Source dataset
uspto-grants-1998_10
Patent number
US05817848

Reaction notes

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