Triphosgene → HCID 58119452, compound

HRID 1854590Notes

Reaction equation

HRID 1854590 reaction equation
[NH2:1][C@@H:2]([CH2:6][S:7][S:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[C:3]([OH:5])=[O:4].Cl[C:16](Cl)([O:18]C(=O)OC(Cl)(Cl)Cl)Cl>C1COCC1>[C:9]1([S:8][S:7][CH2:6][C@H:2]2[C:3](=[O:5])[O:4][C:16](=[O:18])[NH:1]2)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

4

Reactant 2

HCID 94429TriphosgeneHCID 581194503-(Phenyldithio)-L-alanine

Product 1

HCID 58119452HCID 58119452, compoundYield 85%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
47.5 °C

Procedure

To a rapidly stirred (over-head stirrer) suspension of S-thiol-phenyl-L-cysteine (1b) (57.5 g, 0.25 mol) in THF (250 mL) was added solid triphosgene (26 g, 88 mmol) in one portion at 45-50° C. (before addition, remove the heating mantle). When the temperature drops to 45° C., put the heating mantle back on and maintain the inside temperature around 45-50° C. until the solution becomes homogeneous. After the removal of the heating mantle, the solution was purged with argon overnight into a NaOH bubbler to remove any residual phosgene. The solvent was evaporated in vacuo and this provided anhydride 2b (55 g) in 85% yield. 2b: m.p. 217° C. (decomp); 1H NMR (300 MHz, CDCl3) δ 2.90-2.98 (m, 1H), 3.30 (d, 1H, J=12 Hz), 4.68 (d, 1H, J=9 Hz), 6.01 (s, 1H), 7.34-7.58 (m, 5H); 13C NMR (75.5 MHz, CD3Cl3): δ 39.4, 56.5, 128.3, 128.9, 129.5, 135.2, 150.8, 167.7. Due to the unstable nature of this anhydride, it was stored in the refrigerator overnight under an atmosphere of argon and used immediately the next day without further purification.

Workup

  1. additionbefore addition
  2. customremove the heating mantle)
  3. customdrops to 45° C.
  4. customAfter the removal of the heating mantle
  5. customthe solution was purged with argon overnight into a NaOH bubbler
  6. customto remove any residual phosgene
  7. customThe solvent was evaporated in vacuo
  8. customwas stored in the refrigerator overnight under an atmosphere of argon
  9. customwithout further purification

Sources & evidence

ORD record
ord-4317a6c8aac54415adf12b77005fa779
Source dataset
uspto-grants-2015_02
Patent number
US08962692B2

Reaction notes

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