Ethyl chloroformate → N-carbonylethoxy-N-{4-chloro-2-[1-(4-fluorophenoxyimino)ethyl]phenyl}trifluoromethanesulfonamide

HRID 970887Notes

Reaction equation

HRID 970887 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][S:9]([C:12]([F:15])([F:14])[F:13])(=[O:11])=[O:10])=[C:4]([C:16](=[N:18][O:19][C:20]2[CH:25]=[CH:24][C:23]([F:26])=[CH:22][CH:21]=2)[CH3:17])[CH:3]=1.[C:27]([O-:30])([O-])=O.[K+].[K+].ClC([O:36][CH2:37][CH3:38])=O>CC(C)=O>[C:37](=[CH:38][CH2:27][O:30][N:8]([C:5]1[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][C:4]=1[C:16](=[N:18][O:19][C:20]1[CH:21]=[CH:22][C:23]([F:26])=[CH:24][CH:25]=1)[CH3:17])[S:9]([C:12]([F:15])([F:13])[F:14])(=[O:11])=[O:10])=[O:36]

Participants

5

Reactant 3

HCID 10928Ethyl chloroformateHCID 11430Potassium CarbonateHCID 86603997N-{4-chloro-2-[1-(4-fluorophenoxyimino)ethyl]phenyl}trifluoromethanesulfonamide2×

Product 1

HCID 86604012N-carbonylethoxy-N-{4-chloro-2-[1-(4-fluorophenoxyimino)ethyl]phenyl}trifluoromethanesulfonamideYield 63%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To a mixture of N{4-chloro-2-[1-(4-fluorophenoxyimino)ethyl]phenyl}trifluoromethanesulfonamide (compound 129) (150 mg, 0.37 mmol) and K2CO3(151 mg, 1.10 mmol) in acetone (5 mL) was added ethyl chloroformate (105 μL, 1.10 mmol), and the reaction allowed to stir at RT for 21 hours. The reaction mixture was concentrated under vacuum and the residue dissolved in Et2O (50 mL), washed with H2O (40 mL) then brine (40 mL), dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by radial thin layer chromatography (eluting with EtOAc/PE, 1:19) to afford N-carbonylethoxy-N-{4-chloro-2-[1-(4-fluorophenoxyimino)ethyl]phenyl}trifluoromethanesulfonamide 310 (85 mg, 63% based on recovered starting material), as a pale yellow oil. 1H n.m.r. (400 MHz, CDCl3) δ 7.52, d, J=2.4 Hz, 1H; 7.45, dd, J=2.4 and 8.8 Hz, 1H; 7.26, d, J=2.4 Hz, 1H; 7.14, m, 2H; 6.98, m, 2H; 4.24, m, 1H; 4.15, m, 1H; 2.41,s, 3H; 1.15, t, J=7.2 Hz, 3H. HRMS (M+) 482.0316.

Workup

  1. concentrationThe reaction mixture was concentrated under vacuum
  2. dissolutionthe residue dissolved in Et2O (50 mL)
  3. washwashed with H2O (40 mL)
  4. dry with materialbrine (40 mL), dried over Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by radial thin layer chromatography (eluting with EtOAc/PE, 1:19)

Sources & evidence

ORD record
ord-2edf1b62edba465e897dcc5cbc34bb68
Source dataset
uspto-grants-2007_12
Patent number
US07312248B2

Reaction notes

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