Dichloromethane → 2-(4-Methanesulfmyl-phenyl)-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one

HRID 33341Notes

Reaction equation

HRID 33341 reaction equation
[CH3:1][S:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[NH:10][C:11]3[CH:12]=[CH:13][CH:14]=[C:15]4[C:21](=[O:22])[NH:20][CH2:19][CH2:18][C:17]=2[C:16]=34)=[CH:5][CH:4]=1.C(Cl)Cl.[OH:26]OS([O-])=O.[K+]>CO.O>[CH3:1][S:2]([C:3]1[CH:8]=[CH:7][C:6]([C:9]2[NH:10][C:11]3[CH:12]=[CH:13][CH:14]=[C:15]4[C:21](=[O:22])[NH:20][CH2:19][CH2:18][C:17]=2[C:16]=34)=[CH:5][CH:4]=1)=[O:26]

Participants

6

Reactant 3

HCID 6344DichloromethaneHCID 222666992-(4-Methylsulfanyl-phenyl)-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-oneHCID 23707502Potassium hydroxy sulfite

Product 1

HCID 222666912-(4-Methanesulfmyl-phenyl)-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

2-(4-methylsulfanyl-phenyl)-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one (100 mg, 0.32 mmol) was dissolved in 10 mL 1:1 MeOH:CH2Cl2. The solution was cooled to 0° C. and oxone (259 mg, 0.42 mmol) was added dropwise as a solution in 1.5 mL H2O). The bright yellow reaction mixture was stirred at 0° C. for 15 min. Saturated Na2S2O5(aq) (4 mL) was added. The layers were separated and the aqueous layer extracted twice with 25% iPrPH/CHCl3. The combined organic layers were dried (MgSO4), concentrated in vacuo, and the two products (2-(4-methanesulfinyl-phenyl)-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one and 2-(4-methanesulfonyl-phenyl)-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one) separated by radial chromatography eluting with 5% MeOH/CHCl3. Each was then crystallized from CH2Cl2/MeOH. 2-(4-Methanesulfinyl-phenyl)-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one, 39 mg (37%), was isolated as a white solid: m.p. 316-317° C. (dec); 1H NMR (300 MHz, d6-DMSO) δ 2.81 (s, 3H), 3.09 (m, 2H), 3.40 (m, 2H), 7.25 (t, J=7.8 Hz, 1H), 7.59 (dd, J=8.1, 0.9 Hz, 1H), 7.71 (dd, J=7.5, 0.9 Hz, 1H), 7.84 (m, 4H), 8.08 (br t, 1H), 11.68 (br s, 1H). MS (electrospray, MH+) 325. Anal. (C18H16N2O2S) C, H, N, S.

Workup

  1. customThe layers were separated
  2. extractionthe aqueous layer extracted twice with 25% iPrPH/CHCl3
  3. dry with materialThe combined organic layers were dried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customthe two products (2-(4-methanesulfinyl-phenyl)-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one and 2-(4-methanesulfonyl-phenyl)-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one) separated by radial chromatography
  6. washeluting with 5% MeOH/CHCl3
  7. customEach was then crystallized from CH2Cl2/MeOH

Sources & evidence

ORD record
ord-fc41944a01704471ab2dfada1a1b45db
Source dataset
uspto-grants-2008_09
Patent number
US07429578B2

Reaction notes

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