Carbon Dioxide → HCID 86746572, compound

HRID 2082594Notes

Reaction equation

HRID 2082594 reaction equation
[C:1](=[O:3])=O.Cl.[CH2:5]([O:7][C:8](=[O:14])[C@H:9]([CH:11]([CH3:13])[CH3:12])[NH2:10])[CH3:6].C(N(CC)CC)C.P(Cl)(Cl)(Cl)=O>ClCCl.C(OCC)C>[N-:10]=[C:1]=[O:3].[CH2:5]([O:7][C:8](=[O:14])[C@H:9]([CH:11]([CH3:13])[CH3:12])[NH2:10])[CH3:6]

Participants

7

Reactant 4

HCID 280Carbon DioxideHCID 8471TriethylamineHCID 24813Phosphorus oxychlorideHCID 87181Ethyl L-valinate hydrochloride

Product 1

HCID 86746572HCID 86746572, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent2×

Procedure

Carbon dioxide was added subsurface to a dichloromethane (40 mL) solution containing valine ethyl ester hydrochloride salt (0.025 mol, 4.54 g), N-cyclohexyl-N',N',N",N"-tetraethylguanidine (0.023 mol, 5.8 g) and triethylamine (0.10 mol, 10.0 g) at -10° C. (ice and salt bath) for 40 min at a pressure of 0 psig. The reaction mixture was transferred rapidly via cannula under carbon dioxide to the precooled solution of phosphorus oxychloride (0.025 mol, 3.9 g) in 40 mL dichloromethane. After stirring for 20 min at -10° C. diethylether (50 mL) was added to the reaction mixture. A white ppt formed and was filtered off. The filtrate was concentrated in vacuo and the residue was extracted with 3×25 mL diethylether. The ether layers were concentrated and the residue was distilled under vacuum collecting product, valine ethyl ester isocyanate, at 37°-40° C. (2.917 g, 68%) of 99% purity as judged by GC. IR (neat) 2253, 1740 cm-1. 1H NMR (CDCl3) δ 4.28-4.20 (m, 2H), 3.88 (d, 1H, J=3.8), 2.24-2.18 (m, 1H), 1.29 (t, 3H, J=7.2), 1.00 (d, 3H, J=6.9), 0.89 (d, 3H, J=6.8) ppm.

Workup

  1. additionwas added to the reaction mixture
  2. customA white ppt formed
  3. filtrationwas filtered off
  4. concentrationThe filtrate was concentrated in vacuo
  5. extractionthe residue was extracted with 3×25 mL diethylether
  6. concentrationThe ether layers were concentrated
  7. distillationthe residue was distilled under vacuum
  8. customcollecting product, valine ethyl ester isocyanate
  9. customat 37°-40° C.

Sources & evidence

ORD record
ord-13c1d1e78ad14a798956327273f5e7a8
Source dataset
uspto-grants-1993_02
Patent number
US05189205

Reaction notes

Loading…