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

HRID 1917224Notes

Reaction equation

HRID 1917224 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-587975980ff342c18a4da0bfe41d8f2c
Source dataset
uspto-grants-2013_12
Patent number
US08618286B2

Reaction notes

Loading…