Iodine → HCID 66660749, compound

HRID 2196820Notes

Reaction equation

HRID 2196820 reaction equation
[NH2:1][CH2:2][CH2:3][NH:4][C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:9])[CH3:8].[CH3:12][C:13]([CH3:18])([CH3:17])[CH2:14][CH:15]=O.[S-:19][C:20]#[N:21].[K+].II>C(#N)C>[C:13]([C:14]1[S:19][C:20](=[NH:21])[N:1]([CH2:2][CH2:3][NH:4][C:5](=[O:11])[O:6][C:7]([CH3:8])([CH3:10])[CH3:9])[CH:15]=1)([CH3:18])([CH3:17])[CH3:12]

Participants

6

Reactant 4

HCID 807IodineHCID 763353,3-DimethylbutanalHCID 187201N-BOC-ethylenediamineHCID 516872Potassium thiocyanate

Product 1

HCID 66660749HCID 66660749, compoundYield 32%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

A mixture of tert-butyl 2-aminoethylcarbamate (5.9 g, 37 mmol) and 3,3-dimethylbutanal (4.9 mL 95%, 37 mmol) in 30 mL of dry acetonitrile with 4 g of 4 Å (8-12 mesh beads) molecular sieves was stirred at ambient temperature for 24 hours. The mixture was filtered through Celite and washed with 5 mL of acetonitrile. Potassium thiocyanate (4.8 g, 49 mmol) was added and the mixture warmed to 50° C. for 10 minutes. Iodine (9.3 g, 37 mmol) was added and the reaction stirred at 50° C. for 6 hours. Acetonitrile (30 mL) was added followed by 10 mL of 20% Na2S2O5. The layers were separated and the organic layer was dried with Na2SO4, filtered, and the solvent removed. The residue was chromatographed by equilibrating the column with CH2Cl2, loading the sample, and eluting with 5% methanol in CH2Cl2 (0.1% NH4OH) isocratically to afford the title compound (3.5 g, 11.7 mmol, 32% yield). MS (DCI/NH3) m/z 300.2 (M+H)+. 1H NMR (300 MHz, CHLOROFORM-D) δ ppm 1.31 (s, 9 H) 1.42 (s, 9 H) 3.57 (q, J=6.78 Hz, 2 H) 4.26 (t, J=6.95 Hz, 2 H) 5.63 (t, J=5.76 Hz, 1 H) 6.58 (s, 1 H).

Workup

  1. filtrationThe mixture was filtered through Celite
  2. washwashed with 5 mL of acetonitrile
  3. temperaturethe mixture warmed to 50° C. for 10 minutes
  4. stirringthe reaction stirred at 50° C. for 6 hours
  5. customThe layers were separated
  6. dry with materialthe organic layer was dried with Na2SO4
  7. filtrationfiltered
  8. customthe solvent removed
  9. customThe residue was chromatographed
  10. washeluting with 5% methanol in CH2Cl2 (0.1% NH4OH) isocratically

Sources & evidence

ORD record
ord-be342f5a8f4241faaa595579f4947014
Source dataset
uspto-grants-2012_12
Patent number
US08338467B2

Reaction notes

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