Ammonium Chloride → 3-(Tert-butyldiphenylsilyloxy)propanamidine

HRID 32126Notes

Reaction equation

HRID 32126 reaction equation
[NH4+:1].[Cl-].C[Al](C)C.[C:7]([Si:11]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[O:12][CH2:13][CH2:14][C:15]#[N:16])([CH3:10])([CH3:9])[CH3:8]>C1(C)C=CC=CC=1.C1C=CC=CC=1>[C:7]([Si:11]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[O:12][CH2:13][CH2:14][C:15]([NH2:1])=[NH:16])([CH3:10])([CH3:8])[CH3:9]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 108287163-(Tert-butyldiphenylsilyloxy)propanenitrileHCID 16682925Trimethylaluminum

Product 1

HCID 588414073-(Tert-butyldiphenylsilyloxy)propanamidine

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 1140TolueneSolvent

Procedure

To a suspension of NH4Cl (5.35 g, 0.1 mmol) in 60 mL of dry benzend at 0 C was slowly added 50 mL of 2 M solution of trimethylaluminum in toluene. After the addition was complete, the reaction was warmed to RT and was stirred for 2 h until gas evolution had ceased. A solution of 3-(tert-butyl-diphenyl-silanyloxy)-propionitrile (9.27 g, 0.03 mol) in 20 mL of dry benzene was added to the aluminum amide reagent and the resulting was heated up to 80° C. for 20 h. The reaction was slowly cooled to RT and then carefully poured into a slurry of 300 mL of Ch2Cl2 and 200 g of silica gel. It was then filtered and washed thoroughly with MeOH/CH2Cl2 (1:2). After concentration, flash chromatography (SiO2, EtOAc to EtOAc/MeOH=100:20 to 100:30 to EtOAc/2 M NH3 in MeOH=100:30) gave the desired compound as a white solid.

Workup

  1. additionAfter the addition
  2. temperaturethe resulting was heated up to 80° C. for 20 h
  3. temperatureThe reaction was slowly cooled to RT
  4. additioncarefully poured into a slurry of 300 mL of Ch2Cl2 and 200 g of silica gel
  5. filtrationIt was then filtered
  6. washwashed thoroughly with MeOH/CH2Cl2 (1:2)
  7. concentrationAfter concentration, flash chromatography (SiO2, EtOAc to EtOAc/MeOH=100:20 to 100:30 to EtOAc/2 M NH3 in MeOH=100:30)

Sources & evidence

ORD record
ord-9fb4692a82b2400faed082a9859d43e3
Source dataset
uspto-grants-2008_09
Patent number
US07425631B2

Reaction notes

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