Ethanethiol → HCID 54302492, compound

HRID 2416686Notes

Reaction equation

HRID 2416686 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].C[O:6][C:7]1[CH:24]=[CH:23][C:10]2[CH2:11][CH:12]([CH2:18][C:19]([O:21][CH3:22])=[O:20])[C:13](=[O:17])[N:14]([CH3:16])[CH2:15][C:9]=2[CH:8]=1.C(S)C>C(Cl)Cl>[OH:6][C:7]1[CH:24]=[CH:23][C:10]2[CH2:11][CH:12]([CH2:18][C:19]([O:21][CH3:22])=[O:20])[C:13](=[O:17])[N:14]([CH3:16])[CH2:15][C:9]=2[CH:8]=1

Participants

5

Reactant 3

HCID 6343EthanethiolHCID 6451240Aluminum(III) ChlorideHCID 54244036HCID 54244036, compound

Product 1

HCID 54302492HCID 54302492, compoundYield 88%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Anhydrous aluminum chloride (1.35 g, 10.15 mmole) was added all at once to a solution of methyl (±)-8-methoxy-2-methyl-3-oxo-2,3,4,5-tetrahydro-1H-2-benzazepine-4-acetate (562 mg, 2.03 mmole) and ethanethiol (0.75 mL, 10.15 mmole) in anhydrous CH2Cl2 (20 mL) at 0° C. under argon. The mixture was warmed to RT and stirred for 4.5 hr, then was recooled to 0° C. Ice cold H2O (20 mL) was added, and the mixture was stirred briskly for 5 min, then was extracted with CHCl3 (3×20 mL). The combined CHCl3 layers were dried (MgSO4) and concentrated to leave a residue. The aqueous layer was suction filtered to collect a solid precipitate. This precipitate and the residue from the CHCl3 layer were combined in 1:1 MeOH/CHCl3, and the solution was concentrated to leave an off-white solid. This was triturated with hot MeOH, and the mixture was allowed to cool to RT. The solid was collected by suction filtration and washed sequentially with cold MeOH and Et2O. Drying in high vacuum at 40° C. gave the title compound (467.9 mg, 88%) as a colorless solid: TLC (5% MeOH/CHCl3) Rf 0.17; 1H NMR (250, DMSO-d6) δ 9.29(s, 1 H), 6.89 (d, J=8.1 Hz, 1 H), 6.50-6.70 (m, 2 H), 5.16 (d, J=16.4 Hz, 1 H), 3.84 (d, J=16.4 Hz, 1 H), 3.60-3.85 (m, 1 H), 3.56 (s, 3 H), 2.30-3.00 (m, 4 H), 2.86 (s, 3 H); MS (ES) m/e 286 (M+Na)+, 264 (M+H)+.

Workup

  1. customwas recooled to 0° C
  2. stirringthe mixture was stirred briskly for 5 min
  3. extractionwas extracted with CHCl3 (3×20 mL)
  4. dry with materialThe combined CHCl3 layers were dried (MgSO4)
  5. concentrationconcentrated
  6. customto leave a residue
  7. filtrationThe aqueous layer was suction filtered
  8. customto collect a solid precipitate
  9. concentrationthe solution was concentrated
  10. customto leave an off-white solid
  11. customThis was triturated with hot MeOH
  12. temperatureto cool to RT
  13. filtrationThe solid was collected by suction filtration
  14. washwashed sequentially with cold MeOH and Et2O
  15. customDrying in high vacuum at 40° C.

Sources & evidence

ORD record
ord-20971bbcf379424aa4acf7786f2393f2
Source dataset
uspto-grants-2004_11
Patent number
US06825188B2

Reaction notes

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