Dichloromethane → 3-(Tert-butyldiphenylsilyloxy)propanamidine

HRID 1432014Notes

Reaction equation

HRID 1432014 reaction equation
[NH4+:1].[Cl-].C[Al](C)C.[Si:7]([O:24][CH2:25][CH2:26][C:27]#[N:28])([C:20]([CH3:23])([CH3:22])[CH3:21])([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.C(Cl)Cl>C1C=CC=CC=1.C1(C)C=CC=CC=1>[Si:7]([O:24][CH2:25][CH2:26][C:27]([NH2:1])=[NH:28])([C:20]([CH3:22])([CH3:23])[CH3:21])([C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)[C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 25517Ammonium ChlorideHCID 108287163-(Tert-butyldiphenylsilyloxy)propanenitrileHCID 16682925Trimethylaluminum

Product 1

HCID 588414073-(Tert-butyldiphenylsilyloxy)propanamidine

Reagents, catalysts & solvents 2

HCID 241BenzeneSolvent2×HCID 1140TolueneSolvent

Procedure

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

Workup

  1. additionAfter the addition
  2. temperaturethe resulting mixture was heated up to 80° C. for 20 h
  3. temperatureThe reaction mixture was slowly cooled to room temperature
  4. filtrationIt was then filtered
  5. washwashed thoroughly with MeOH/DCM (1:2)
  6. concentrationAfter concentration, flash chomatography (SiO2, EtOAc to EtOAc/MeOH=100:20 to 100:30 to EtOAc/2M NH3 in MeOH=100:30)

Sources & evidence

ORD record
ord-36f971ecd60f4468a284b89b15308914
Source dataset
uspto-grants-2009_11
Patent number
US07612060B2

Reaction notes

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