Dimethylformamide → HCID 11702208, compound

HRID 1016469Notes

Reaction equation

HRID 1016469 reaction equation
[CH2:1]([O:8][C:9]([NH:11][CH:12]([CH2:23][CH:24]([CH3:26])[CH3:25])[C:13]([O:15]N1C(=O)CCC1=O)=O)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.[NH2:28][CH2:29][C:30]#[N:31].C(N(CC)CC)C.CN(C=O)C>C(#N)C>[C:29]([CH2:30][NH:31][C:13]([C@@H:12]([NH:11][C:9](=[O:10])[O:8][CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[CH2:23][CH:24]([CH3:25])[CH3:26])=[O:15])#[N:28]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 1029993397-35-1HCID 11491918Aminoacetonitrile hydrochloride

Product 1

HCID 11702208HCID 11702208, compoundYield 61.5%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A mixture comprised of 2,5-dioxopyrrolidin-1-yl 2-benzyloxycarbonylamino-4-methylvalerate (39.6 g, 0.109 mol), aminoacetonitrile hydrochloride (10.1 g, 0.109 mol), triethylamine (61 mL, 0.436 mol), DMF (40 mL) and acetonitrile (360 mL) was stirred at room temperature for 27 hours. The mixture was filtered, concentrated to a volume of 100 mL and poured into ice water (1000 mL). The mixture was stirred until a precipitate had formed. The precipitate was collected, washed with water and dried. The dry product was recrystallized from 55% ethanol/water (80 mL). The crystals were collected and recrystallized from 65% ethanol/water (70 mL). The crystals were collected and dried to provide benzyl (S)-1-cyanomethylcarbamoyl-3-methylbutylcarbamate (21.1 g, 0.067 mol) as white needles, m.p. 120-121° C. Proton NMR (300 MHz, DMSO-d6): δ 8.68 (t, J=6 Hz, 1H), δ 7.54 (d, J=8 Hz, 1H), δ 7.33 (m, 5H), δ 5.00 (Abq, 2H), δ 4.09 (d, J=6 Hz, 2H, δ 4.03 (m, 1H), δ 1.24-1.64 (m, 3H), δ 0.84 (apparent t, J=7 Hz, 6H). MS (electrospray): mH+ 303.9 (100%). Calcd. for C16H21N3O3: C, 63.35; H, 6.98; N, 13.85. Found: C, 63.55; H, 7.01; N, 13.74.

Workup

  1. filtrationThe mixture was filtered
  2. concentrationconcentrated to a volume of 100 mL
  3. additionpoured into ice water (1000 mL)
  4. stirringThe mixture was stirred until a precipitate
  5. customhad formed
  6. customThe precipitate was collected
  7. washwashed with water
  8. customdried
  9. customThe dry product was recrystallized from 55% ethanol/water (80 mL)
  10. customThe crystals were collected
  11. customrecrystallized from 65% ethanol/water (70 mL)
  12. customThe crystals were collected
  13. customdried

Sources & evidence

ORD record
ord-c57902ae26a04df6a651fa048d90d01f
Source dataset
uspto-grants-2002_11
Patent number
US06476026B1

Reaction notes

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