Acetone → HCID 57428805, compound

HRID 2267277Notes

Reaction equation

HRID 2267277 reaction equation
[C:1]([O:5][C:6](=[O:11])[NH:7][CH2:8][CH2:9][NH2:10])([CH3:4])([CH3:3])[CH3:2].[CH3:12][C:13]([CH3:15])=O.[Si]([C:20]#[N:21])(C)(C)C>CCO.CCOC(C)=O>[C:1]([O:5][C:6](=[O:11])[NH:7][CH2:8][CH2:9][NH:10][C:13]([C:20]#[N:21])([CH3:15])[CH3:12])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 3

HCID 180AcetoneHCID 82115Trimethylsilyl cyanideHCID 187201N-BOC-ethylenediamine

Product 1

HCID 57428805HCID 57428805, compoundYield 14.1%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

(2-Aminoethyl)carbamic acid tert-butyl ester (25.07 g, 156.5 mmol) was dissolved in EtOH (500 mL), treated with acetone (13.75 mL, 187 mmol), and the stirred solution was cooled in an ice bath. After stirring for 30 min, TMS-CN (62 mL, 465 mmol; CAUTION—toxic) was added dropwise over 1 h. The solution was stirred for 16 h, allowing to warm gradually to room temperature. The solution was concentrated in vacuo [caution: HCN gas evolved: a dry pump venting to the back of the fume hood was used] resulting in a pale yellow solid. This was dissolved in EtOAc (100 mL) and concentrated to a viscous oil. Hexane (500 mL) was added rapidly and the resulting mixture was swirled vigorously until a thick white crystalline precipitate formed. The mixture was allowed to stand for 30 min, and the crystallized product (30.0 g) was collected by filtration, washing with a small amount of hexane to give a white crystalline solid. The filtrate was concentrated in vacuo to give a viscous gum (5 g). This was quickly purified by flash chromatography eluting with EtOAc [N.B. the product is somewhat unstable to silica gel and decomposes if allowed to stay on the column for a long time] resulting in an additional 1.7 g of product, which was combined with the recrystallized material. Total yield=31.7 g, 89%. 1H NMR: δ (d6-DMSO, 400 MHz) 6.64 (1 H, t), 2.83 (2 H, m), 2.60 (1 H, t), 2.41 (2 H, m), 1.21 (9 H, s), 1.17 (6 H, s).

Workup

  1. temperaturethe stirred solution was cooled in an ice bath
  2. stirringThe solution was stirred for 16 h
  3. concentrationThe solution was concentrated in vacuo [
  4. customresulting in a pale yellow solid
  5. concentrationconcentrated to a viscous oil
  6. additionHexane (500 mL) was added rapidly
  7. customformed
  8. waitto stand for 30 min
  9. filtrationthe crystallized product (30.0 g) was collected by filtration
  10. washwashing with a small amount of hexane
  11. customto give a white crystalline solid
  12. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-20f1db532d174b0ca761cb7f65d8aea8
Source dataset
uspto-grants-2010_12
Patent number
US07858785B2

Reaction notes

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