Hydracrylonitrile → 3-(Tert-butyldiphenylsilyloxy)propanenitrile

HRID 747052Notes

Reaction equation

HRID 747052 reaction equation
[OH:1][CH2:2][CH2:3][C:4]#[N:5].CCN(CC)CC.[C:13]([Si:17](Cl)([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)([CH3:16])([CH3:15])[CH3:14]>CN(C1C=CN=CC=1)C.C(Cl)Cl>[C:13]([Si:17]([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)[O:1][CH2:2][CH2:3][C:4]#[N:5])([CH3:16])([CH3:14])[CH3:15]

Participants

6

Reactant 3

HCID 8011HydracrylonitrileHCID 8471TriethylamineHCID 94078tert-Butyldiphenylchlorosilane

Product 1

HCID 108287163-(Tert-butyldiphenylsilyloxy)propanenitrile

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 3-hydroxypropanenitrile (7.1 g, 0.1 mol) and DMAP (1.22 g, 0.01 mmol) in 30 mL of dry DCM at room temperature was added NEt3 (30.3 g, 0.3 mol), followed by tert-butyldiphenyl-silylchloride (27.5 g, 0.1 mol). A lot of white solid appeared. After stirring at room temperature overnight, the reaction mixture was quenched with Sat. NH4Cl solution, extracted with DCM, dried over Na2SO4, and evaporated in vaco. Flash chromatography (SiO2, hexane/EtOAc=100:2 to 100:5 to 100:10) gave the title compound as a white solid. B. Preparation 3-(tert-butyldiphenylsilyloxy)propanamidine. 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 2 M 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 the above nitrile 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 chromatography (SiO2, EtOAc to EtOAc/MeOH=100:20 to 100:30 to EtOAc/2 m NH3 in MeOH=100:30) gave the product as a white solid. C. Preparation of 3-(tert-butyldiphenylsilyloxy)propanamidine2-(2-(tert-butyldiphenylsilyloxy)ethyl)-7,8-dihydroquinazolin-5(6H)-one.

Workup

  1. customthe reaction mixture was quenched with Sat. NH4Cl solution
  2. extractionextracted with DCM
  3. dry with materialdried over Na2SO4
  4. customevaporated in vaco

Sources & evidence

ORD record
ord-db7a4b530aab47e5b33e969aa2de4ff6
Source dataset
uspto-grants-2008_07
Patent number
US07393852B2

Reaction notes

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