Water → 1-(p-chlorophenyl)-1,4-dihydro-beta,beta,1-trimethyl-3,1-benzazasiline-3(2H)-ethanol

HRID 46750Notes

Reaction equation

HRID 46750 reaction equation
[Cl-].[NH+]1C2C=CC=CC=2C=C[SiH]=1.[Cl-].[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([Si:20]2([CH3:35])[C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][C:24]=3[C:23]3[O:30][CH2:31][C:32]([CH3:34])([CH3:33])[N+:22]=3[CH2:21]2)=[CH:16][CH:15]=1.O.[BH4-].[Na+]>CO>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]([Si:20]2([CH3:35])[C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][C:24]=3[CH2:23][N:22]([C:32]([CH3:33])([CH3:34])[CH2:31][OH:30])[CH2:21]2)=[CH:18][CH:19]=1

Participants

6

Reactant 4

HCID 962WaterHCID 4311764Sodium borohydrideHCID 70603445HCID 70603445, compoundHCID 131711657HCID 131711657, compound

Product 1

HCID 203854771-(p-chlorophenyl)-1,4-dihydro-beta,beta,1-trimethyl-3,1-benzazasiline-3(2H)-ethanol

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

The crude benzazasilinium chloride (34.8 g., 92 m mol) obtained in part (a) above is dissolved in 20 ml. of water and 10 ml. of methanol and the solution is added with stirring to 52.6 g. (1.38 mol) of sodium borohydride in 500 ml. of peroxide free 1,2-dimethoxyethane between 20° and 30° C. After stirring 16 hours, the reaction mixture is poured into an ice-toluene-sodium potassium tartrate-water mixture. The organic phase is washed with water, dried with sodium sulfate and concentrated to an oil. The latter is passed in chloroform through a short silica gel column. The main portion of the effluent is concentrated to yield the title product as an oil. When dissolved in acetone and upon adding 2 g. of HCl gas with cooling and addition of ethyl ether, the free base is converted into the hydrochloride salt. The resultant crystals (m.p. 197°-198° C.) are recrystallized from ethanol-acetone-ether (ca. 1:2:5) and methanol-acetone-ether (ca. 1:3:5) and then acetone to obtain the purified salt (199°-200.5° C.).

Workup

  1. dissolutionabove is dissolved in 20 ml
  2. stirringAfter stirring 16 hours
  3. washThe organic phase is washed with water
  4. dry with materialdried with sodium sulfate
  5. concentrationconcentrated to an oil
  6. concentrationThe main portion of the effluent is concentrated

Sources & evidence

ORD record
ord-8325bd6bf75f49d4b01143df957fac07
Source dataset
uspto-grants-1979_11
Patent number
US04175091

Reaction notes

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