Potassium Iodide → 7-Nitro-4-(3-(pyrrolidin-1-yl)propyl)-3,4-dihydro-2H-benzo[b][1,4]thiazine

HRID 424540Notes

Reaction equation

HRID 424540 reaction equation
Cl[CH2:2][CH2:3][CH2:4][N:5]1[CH2:10][CH2:9][S:8][C:7]2[CH:11]=[C:12]([N+:15]([O-:17])=[O:16])[CH:13]=[CH:14][C:6]1=2.[NH:18]1[CH2:22][CH2:21][CH2:20][CH2:19]1.C(=O)([O-])[O-].[K+].[K+].[I-].[K+]>C(#N)C.O>[N+:15]([C:12]1[CH:13]=[CH:14][C:6]2[N:5]([CH2:4][CH2:3][CH2:2][N:18]3[CH2:22][CH2:21][CH2:20][CH2:19]3)[CH2:10][CH2:9][S:8][C:7]=2[CH:11]=1)([O-:17])=[O:16]

Participants

7

Reactant 4

HCID 4875Potassium IodideHCID 11430Potassium CarbonateHCID 31268PyrrolidineHCID 591440694-(3-Chloropropyl)-7-nitro-3,4-dihydro-2H-benzo[b][1,4]thiazine

Product 1

HCID 591441447-Nitro-4-(3-(pyrrolidin-1-yl)propyl)-3,4-dihydro-2H-benzo[b][1,4]thiazineYield 94%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
60 °C

Procedure

A solution of 4-(3-chloropropyl)-7-nitro-3,4-dihydro-2H-benzo[b][1,4]thiazine (0.54 g, 1.980 mmol) in dry acetonitrile (20 mL) was treated with pyrrolidine (1.637 mL, 19.80 mmol), potassium carbonate (2.74 g, 19.80 mmol), and potassium iodide (0.657 g, 3.96 mmol) at room temperature. The resulting mixture was stirred at 60° C. overnight (18 hours). The reaction was brought to room temperature and diluted with water (50 mL), and the product was extracted into ethyl acetate (2×25 mL). The combined ethyl acetate layers were washed with brine (20 mL) and then dried (Na2SO4). The solvent was evaporated, and the crude material was purified by flash column chromatography (5:95 (2 M NH3 in MeOH):CH2Cl2) to obtain the title product (0.57 g, 94%) as a syrup. 1H NMR (DMSO-d6) δ 7.84-7.80 (m, 2H), 6.87 (d, 1H, J=9.6 Hz), 3.79-3.75 (m, 2H), 3.49 (t, 2H, J=6.9 Hz), 3.08-3.05 (m, 2H), 2.44-2.40 (m, 6H), 1.76-1.69 (m, 6H); ESI-MS (m/z, %): 308 (MH+, 100).

Workup

  1. customwas brought to room temperature
  2. extractionthe product was extracted into ethyl acetate (2×25 mL)
  3. washThe combined ethyl acetate layers were washed with brine (20 mL)
  4. dry with materialdried (Na2SO4)
  5. customThe solvent was evaporated
  6. customthe crude material was purified by flash column chromatography (5:95 (2 M NH3 in MeOH):CH2Cl2)

Sources & evidence

ORD record
ord-824314184ea544178e5c090b1bc09439
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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