Sodium Hydroxide → N,N-Dimethyl-2-(6-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethanamine

HRID 424570Notes

Reaction equation

HRID 424570 reaction equation
[N+:1]([C:4]1[CH:13]=[CH:12][C:7]2[S:8][CH2:9][CH2:10][NH:11][C:6]=2[CH:5]=1)([O-:3])=[O:2].Cl.Cl[CH2:16][CH2:17][N:18]([CH3:20])[CH3:19].[OH-].[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.ClCCl.O>[CH3:19][N:18]([CH3:20])[CH2:17][CH2:16][N:11]1[CH2:10][CH2:9][S:8][C:7]2[CH:12]=[CH:13][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][C:6]1=2

Participants

7

Reactant 3

HCID 14798Sodium HydroxideHCID 11636816N,N-Dimethylaminoethyl chloride hydrochlorideHCID 457916016-Nitro-3,4-dihydro-2H-benzo[b][1,4]thiazine

Product 1

HCID 59144147N,N-Dimethyl-2-(6-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethanamineYield 11.74%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred suspension of 6-nitro-3,4-dihydro-2H-benzo[b][1,4]thiazine (500 mg, 2.55 mmol), 2-chloro-N,N-dimethylethanamine hydrochloride (734 mg, 5.10 mmol), and tetrabutylammonium bromide (41.1 mg, 0.127 mmol) in dichloromethane (5 mL) was added 50% aqueous NaOH (5 mL). The reaction vessel was then sealed, and the mixture was stirred vigorously overnight at room temperature. The mixture was then diluted with water and extracted with dichloromethane (3×). The combined organics were dried, filtered, concentrated, and then chromatographed in 1:4:5 (2M NH3 in methanol):ethyl acetate:dichloromethane, giving the desired product (80 mg, 11.74%) and significant amounts of starting material. 1H NMR (DMSO-d6) δ 7.44 (d, J=2.4 Hz, 1H), 7.36 (dd, J=8.4, 2.4 Hz, 1H), 7.19 (d, J=8.4 Hz, 1H), 3.69-3.64 (m, 2H), 3.48 (t, J=6.9 Hz, 2H), 3.14-3.09 (m, 2H), 2.45 (t, J=6.9 Hz, 2H), 2.22 (s, 6H); ESI-MS (m/z, %): 268 (MH+, 100).

Workup

  1. customThe reaction vessel was then sealed
  2. extractionextracted with dichloromethane (3×)
  3. customThe combined organics were dried
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customchromatographed in 1:4:5 (2M NH3 in methanol)

Sources & evidence

ORD record
ord-1b6443c0e7a3417e9954851acbbf0573
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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