Triethylamine → HCID 23653168, compound

HRID 1642596Notes

Reaction equation

HRID 1642596 reaction equation
[CH3:1][S:2]([C:5]1[CH:6]=[CH:7][C:8]([C@@H:11]([OH:21])[C@H:12]([NH:15][C:16]([CH:18]([Cl:20])[Cl:19])=[O:17])[CH2:13][F:14])=[CH:9][CH:10]=1)(=[O:4])=[O:3].C(N(CC)CC)C.Cl[C:30]([O:32][CH2:33][CH3:34])=[O:31]>CN(C)C1C=CN=CC=1.O1CCCC1>[C:30](=[O:31])([O:32][CH2:33][CH3:34])[O:21][C@H:11]([C:8]1[CH:7]=[CH:6][C:5]([S:2]([CH3:1])(=[O:4])=[O:3])=[CH:10][CH:9]=1)[C@H:12]([NH:15][C:16](=[O:17])[CH:18]([Cl:20])[Cl:19])[CH2:13][F:14]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 10928Ethyl chloroformateHCID 114811Florfenicol

Product 1

HCID 23653168HCID 23653168, compoundYield 95%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A solution of florfenicol (250 g, 0.7 mol), 4-dimethylaminopyridine (42 g, 0.35 mol,), triethylamine (130 mL, 0.91 mol) in 1.2 L of tetrahydrofuran was stirred at 0-5° C. while neat ethyl chloroformate (80 mL, 0.83 mol) was added drop-wise with an addition funnel. The reaction proceeded as indicated by the precipitation of triethylamine hydrochloride salt. The mixture was allowed to stir at room temperature for 30 minutes and the salt was removed from the mixture by filtration. The filtrate was concentrated and 600 mL of ethyl acetate was added and the solution was washed with 1 M HCl (2×200 mL) followed by saturated NaCl (200 mL) and filtered through a layer of Na2SO4/silica gel. The filtrate was concentrated and the crude oil was crystallized from 450 mL of isopropanol to give the pure title product (286 g). m.p. 110-112° C.; H1-NMR (DMSO-d6), δ=1.2 ppm (t, 3 H), 3.2 ppm (s, 3H), 4.1 ppm (q, 2H), 4.3-4.7 ppm (m, 3H), 5.9 ppm (d, 1H), 6.4 ppm (s, 1H), 7.6 ppm (d, 2H), 7.9 ppm (d, 2H), 9.2 ppm (d, 1H); mass spectrum 452.0 (M+Na).

Workup

  1. additionwas added drop-wise with an addition funnel
  2. customas indicated by the precipitation of triethylamine hydrochloride salt
  3. customthe salt was removed from the mixture by filtration
  4. concentrationThe filtrate was concentrated
  5. addition600 mL of ethyl acetate was added
  6. washthe solution was washed with 1 M HCl (2×200 mL)
  7. filtrationfiltered through a layer of Na2SO4/silica gel
  8. concentrationThe filtrate was concentrated
  9. customthe crude oil was crystallized from 450 mL of isopropanol

Sources & evidence

ORD record
ord-8759695df6f04c54bff8a5ce498b8c45
Source dataset
uspto-grants-2012_02
Patent number
US08119667B2

Reaction notes

Loading…