Dichloromethane → 3-(Tert-butyldiphenylsilyloxy)propanamidine

HRID 1444725Notes

Reaction equation

HRID 1444725 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>C1(C)C=CC=CC=1.C1C=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 241BenzeneSolventHCID 1140TolueneSolvent

Procedure

To a suspension of NH4Cl (5.35 g, 0.1 mol) in 60 mL of dry benzend at 0° C. was slowly added 50 mL of 2M solution of trimethylaluminum in toluene. 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 20 mL of dry benzene 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 product 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-09db8a4c6f3143188b4f3a5c6d057be2
Source dataset
uspto-grants-2010_02
Patent number
US07662811B2

Reaction notes

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