Methylhydrazine → HCID 18606041, compound

HRID 979957Notes

Reaction equation

HRID 979957 reaction equation
C([N:3](CC)CC)C.Cl.[C:9]([O:13][C:14](=[O:24])[C@H:15]([CH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[NH2:16])([CH3:12])([CH3:11])[CH3:10].[C:25](N1C=CN=C1)([N:27]1[CH:31]=CN=C1)=[O:26].CNN>C(Cl)Cl.C(Cl)(Cl)Cl.CO>[C:9]([O:13][C:14](=[O:24])[C@H:15]([CH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[NH:16][C:25](=[O:26])[N:27]([CH3:31])[NH2:3])([CH3:12])([CH3:10])[CH3:11]

Participants

8

Reactant 4

HCID 6061MethylhydrazineHCID 8471TriethylamineHCID 682631,1'-CarbonyldiimidazoleHCID 11459563L-Phenylalanine, 1,1-dimethylethyl ester, hydrochloride (1:1)

Product 1

HCID 18606041HCID 18606041, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolvent2×HCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent3×

Procedure

Triethylamine (0.28 ml; 2 mmol) was added to a slurry of (L)-phenylalanine t-butyl ester hydrochloride (0.50 g; 1.94 mmol) in methylene chloride (4 ml). Carbonyldiimidazole (0.325 g; 2 mmol) was added, and stirring was continued for 30 minutes. Then methylhydrazine (0.11 ml; 2 mmol) was added over 5 minutes. Stirring was continued for 18 hours. Solvent was removed, and the resulting solid residue was partitioned between ether and water. The ether layer was washed twice with water and once with brine, and dried (MgSO4). Removal of solvent gave crude carbazide 11 as a colorless oil. Flash chromatography on silica gel (E. Merck No. 9385; 2×12 cm) in 100:1 methylene chloride: methanol gave pure 11 (0.480 g; 1.63 mmol; 84%): TLC (20:1 CH2Cl2 :CH3OH) Rf=0.3. MS m/e 294 (M+). Analysis: Calculated for C15H24N3O3 : C, 61.20 H, 8.22 N, 14.27. Found: C, 61.75 H, 8.28 N, 14.00. NMR (CDCl3) δ1.33 (9H,s); 3.00 (3H,s); 3.05 (2H,d,J=6); 3.6 (2H,bs); 4.63 (1H,d of t; J=8,6); 6.7-7.0 (1H, m); 7.25 (5H,s); IR (CHCl3): 3450, 3000, 1730, 1650 cm-1.

Workup

  1. stirringStirring
  2. waitwas continued for 18 hours
  3. customSolvent was removed
  4. customthe resulting solid residue was partitioned between ether and water
  5. washThe ether layer was washed twice with water and once with brine
  6. dry with materialdried (MgSO4)
  7. customRemoval of solvent
  8. customgave crude carbazide 11 as a colorless oil

Sources & evidence

ORD record
ord-01e1c2e39aaa49f98e2e0ef330250bdd
Source dataset
uspto-grants-1987_01
Patent number
US04634715

Reaction notes

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