(Methoxycarbonylsulfamoyl)triethylammonium hydroxide → HCID 58467997, compound

HRID 1879380Notes

Reaction equation

HRID 1879380 reaction equation
[F:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1[C@@H:9]1[CH2:19][CH2:18][C@@H:17](O)[C:12]2=[N:13][CH:14]=[CH:15][CH:16]=[C:11]2[CH2:10]1.[OH-].COC(NS([N+](CC)(CC)CC)(=O)=O)=O>C1C=CC=CC=1>[F:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1[C@@H:9]1[CH2:19][CH:18]=[CH:17][C:12]2=[N:13][CH:14]=[CH:15][CH:16]=[C:11]2[CH2:10]1

Participants

4

Reactant 2

HCID 11032497(Methoxycarbonylsulfamoyl)triethylammonium hydroxideHCID 57911431HCID 57911431, compound

Product 1

HCID 58467997HCID 58467997, compoundYield 45%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Conditions

Temperature
85 °C

Procedure

In an oven-dried 250 mL round-bottom flask was mixed (6R,9R)-6-(2,3-difluorophenyl)-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-9-ol (1.93 g, 7.01 mmol) and (methoxycarbonylsulfamoyl)triethylammonium hydroxide, inner salt (2.005 g, 8.41 mmol) in benzene (60 mL) to give a suspension. It was heated at 85° C. with stirring under nitrogen for 1 h (color quickly changed to deep red). LCMS showed desired MW. TLC (1/1 ethyl acetate/hexanes) showed only a trace of SM left and a major, more polar component. Benzene was removed in vacuo and the residue was partitioned between ethyl acetate and water. The layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried and concentrated to give a tan oil. Purification by FCC up to 80% ethyl acetate/hexane afforded the desired product (0.81 g, 45%) as a light yellow oil. MS(ESI)[M+H+]=258.16, 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 8.45 (dd, J=4.78, 1.51 Hz, 1H) 7.35 (d, J=7.55 Hz, 1H) 6.92-7.09 (m, 4H) 6.77 (dt, J=12.53, 1.92 Hz, 1H) 6.20 (dt, J=12.59, 4.53 Hz, 1H) 3.43-3.58 (m, 1H) 3.22 (dd, J=14.10, 9.57 Hz, 1H) 2.96 (d, J=14.35 Hz, 1H) 2.69 (td, J=5.29, 2.01 Hz, 2H); 13C NMR (101 MHz, CHLOROFORM-d) δ ppm 154.90 (s, 1C) 151.94-149.34 (dd, J=13.10 and 249.47 Hz, 1C) 149.43-146.86 (dd, J=12.33 and 247.45 Hz, 1C) 147.31 (s, 2C) 136.93 (s, 2C) 135.63 (d, J=11.56 Hz, 1C) 134.74 (s, 1C) 133.74 (s, 2C) 131.83 (s, 2C) 123.95-124.47 (m, 2C) 122.61 (t, J=3.47 Hz, 2C) 121.44 (s, 2C) 115.15 (d, J=16.96 Hz, 2C) 40.28 (s, 2C) 38.53 (s, 2C) 37.70 (s, 1C); 19F NMR (376 MHz, CHLOROFORM-d) δ ppm −138.33-−137.90 (m, 1F) −144.07-−143.71 (m, 1F).

Workup

  1. customto give a suspension
  2. waitleft
  3. customBenzene was removed in vacuo
  4. customthe residue was partitioned between ethyl acetate and water
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with ethyl acetate
  7. washThe combined organic layers were washed with brine
  8. customdried
  9. concentrationconcentrated
  10. customto give a tan oil
  11. customPurification by FCC up to 80% ethyl acetate/hexane

Sources & evidence

ORD record
ord-81ba8d7f39b64f41965f39dce417adb8
Source dataset
uspto-grants-2012_11
Patent number
US08314117B2

Reaction notes

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