Sodium Hydroxide → 4-(3-Chloropropyl)-7-nitro-3,4-dihydro-2H-benzo[b][1,4]thiazine

HRID 424539Notes

Reaction equation

HRID 424539 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[NH:12][CH2:11][CH2:10][S:9][C:8]=2[CH:13]=1)([O-:3])=[O:2].[Cl:14][CH2:15][CH2:16][CH2:17]I.[OH-].[Na+]>C(Cl)Cl.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[Cl:14][CH2:15][CH2:16][CH2:17][N:12]1[CH2:11][CH2:10][S:9][C:8]2[CH:13]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=[CH:6][C:7]1=2

Participants

7

Reactant 3

HCID 14798Sodium HydroxideHCID 813631-Chloro-3-iodopropaneHCID 204961217-Nitro-3,4-dihydro-2H-benzo[b][1,4]thiazine

Product 1

HCID 591440694-(3-Chloropropyl)-7-nitro-3,4-dihydro-2H-benzo[b][1,4]thiazineYield 47%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 7-nitro-3,4-dihydro-2H-benzo[b][1,4]thiazine (1.0 g, 5.10 mmol) and 1-chloro-3-iodopropane (1.075 mL, 10.19 mmol) in CH2Cl2 (10 mL) was treated with 50% NaOH solution (10 mL), followed by tetrabutylammonium bromide (0.082 g, 0.255 mmol) at room temperature. The resulting mixture was stirred overnight (16 hours) at room temperature and then refluxed for 4 hours. The reaction was brought to room temperature and diluted with water (50 mL), and the product was extracted into CH2Cl2 (3×25 mL). The combined CH2Cl2 layers were washed with brine (20 mL) and dried (Na2SO4). The solvent was evaporated, and the crude material was purified by column chromatography (1:4 to 2:3 EtOAc:hexanes) to obtain the title compound (0.65 g, 47%) as a solid. 1H NMR (CDCl3) δ 7.96 (d, 1H, J=2.7 Hz), 7.88 (dd, 1H, J=2.7, 9.3 Hz), 6.64 (d, 1H, J=9.3 Hz), 3.84-3.80 (m, 2H), 3.65-3.60 (m, 4H), 3.05-3.02 (m, 2H), 2.16-2.08 (m, 2H); ESI-MS (m/z, %): 273 (MH+, 100).

Workup

  1. temperaturerefluxed for 4 hours
  2. customwas brought to room temperature
  3. extractionthe product was extracted into CH2Cl2 (3×25 mL)
  4. washThe combined CH2Cl2 layers were washed with brine (20 mL)
  5. dry with materialdried (Na2SO4)
  6. customThe solvent was evaporated
  7. customthe crude material was purified by column chromatography (1:4 to 2:3 EtOAc:hexanes)

Sources & evidence

ORD record
ord-94bffbf5935c4d74873da8af8373d9e8
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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