Dichloromethane → HCID 66685736, compound

HRID 409646Notes

Reaction equation

HRID 409646 reaction equation
[CH2:1]([O:3][C:4](=[O:18])[C:5]([NH:7][CH2:8][C:9]([O:11][CH2:12][CH2:13][CH2:14][CH2:15][CH:16]=[CH2:17])=O)=O)[CH3:2].C(Cl)Cl.O(S(C(F)(F)F)(=O)=O)S(C(F)(F)F)(=O)=O>N1C=CC=CC=1>[O:11]1[C:9]2=[CH:8][N:7]=[C:5]([C:4]([O:3][CH2:1][CH3:2])=[O:18])[CH:17]=[C:16]2[CH2:15][CH2:14][CH2:13][CH2:12]1

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 67749Trifluoromethanesulfonic anhydrideHCID 86683904HCID 86683904, compound

Product 1

HCID 66685736HCID 66685736, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

Ethyl-2-((2-(hex-5-en-1-yloxy)-2-oxoethyl)amino)-2-oxoacetate (0.35 g) and DCM (4 mL) were added to a vessel with stirring followed by the addition of pyridine (0.13 g). Tf2O (0.58 g) was then added to the mixture slowly at ambient temperature. The mixture was stirred at ambient temperature for 4 days after which time the mixture was extracted with 6N HCl (3×10 mL). The combined acid layers were washed with DCM (10 mL) and the pH was adjusted to ˜10 with solid K2CO3. The basic aqueous layer was extracted with DCM (20 mL). The organic layer was concentrated under reduced pressure to provide the title compound (A) and ethyl 2,3,4,5-tetrahydrooxepino[2,3-c]pyridine-7-carboxylate (B) as a 3:1 mixture as based on NMR analysis. 1H NMR (300 MHz, CDCl3) δ ppm 8.38 (s, 0.3H, cmpd B), 8.11 (s, 1H, cmpd A), 7.95 (s, 0.3H, cmpd B), 4.36-4.51 (m, 2.6H, cmpd A/B CH3CH2), 4.17-4.25 (m, 2H, cmpd A OCH2), 4.06-4.13 (m, 0.6H, cmpd B OCH2), 2.85-2.93 (m, 0.6H, cmpd B CH2), 2.71 (t, J=6.53 Hz, 2H, cmpd A CH2), 2.45 (s, 3H, cmpd A CH3), 1.99-2.15 (m, 2.6H, cmpd A/B CH2), 1.54-1.88 (m, 0.6H, cmpd B CH2), 1.44 (t, J=7.12 Hz, 0.9H, cmpd B CH3), 1.44 (t, J=7.12 Hz, 3H, cmpd A CH3); 13C NMR (75 MHz, CDCl3) δ ppm 166.53, 165.01, 162.88, 159.21, 153.21, 143.48, 143.11, 142.72, 139.52, 136.74, 134.94, 130.12, 127.21, 73.82, 65.85, 61.61, 61.21, 33.74, 31.53, 24.97, 22.11, 21.48, 14.56, 14.28; Cmpd A: HRMS (M+Na) m/z, calcd for C12H15NO3Na, 244.0950; found 244.0961; Cmpd B: HRMS (M+H) m/z, calcd for C12H16NO3, 222.1130; found 222.1130.

Workup

  1. stirringThe mixture was stirred at ambient temperature for 4 days after which time the mixture
  2. extractionwas extracted with 6N HCl (3×10 mL)
  3. washThe combined acid layers were washed with DCM (10 mL)
  4. extractionThe basic aqueous layer was extracted with DCM (20 mL)
  5. concentrationThe organic layer was concentrated under reduced pressure

Sources & evidence

ORD record
ord-4b8073bf523b4dce969ce8ed1ff836e6
Source dataset
uspto-grants-2014_06
Patent number
US08759523B2

Reaction notes

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