Methanol → tert-Butyl 2-(methyl(2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethyl)amino)acetate

HRID 424523Notes

Reaction equation

HRID 424523 reaction equation
[CH3:1][NH: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.C(N(C(C)C)CC)(C)C.Br[CH2:28][C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30].CO>CN(C=O)C.[Cl-].[Na+].O.C(Cl)Cl>[CH3:1][N: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)[CH2:28][C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30]

Participants

8

Reactant 4

HCID 887MethanolHCID 79177tert-Butyl bromoacetateHCID 81531DiisopropylethylamineHCID 59144162N-Methyl-2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethanamine

Product 1

HCID 59144161tert-Butyl 2-(methyl(2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethyl)amino)acetate

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A solution of N-methyl-2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethanamine (0.95 g, 3.75 mmol), diisopropylethyl amine (1.960 mL, 11.25 mmol), and tert-butyl bromoacetate (0.61 mL, 4.13 mmol) in DMF (20 mL) was heated at 55° C. for 17 hours (overnight). The yellow solution was diluted with brine (40 mL) and extracted with EtOAc (100 mL). The organic extract was separated and rinsed with brine (20 mL). The organic layer was dried (Na2SO4), filtered, and concentrated to give a yellow residue. This residue was subjected to flash chromatography on silica gel using 2.5:97.5 MeOH:CH2Cl2 to give a yellow brown residue. Two fractions were collected, with the latter containing a non-polar yellow spot (950 mg, 68.9%). 1H-NMR (CDCl3) δ 7.96 (d, J=2.7 Hz, 1H), 7.88 (d, J=2.7, 9.3 Hz, 1H), 6.65 (d, J=9.3 Hz, 1H), 3.88-3.83 (m, 2H), 3.55 (t, J=7.2 Hz, 2H), 3.20 (s, 2H), 3.02-2.99 (m, 2H), 2.76 (t, J=7.2 Hz, 2H), 2.44 (s, 3H), 1.46 (s, 9H); ESI-MS (m/z, %): 368 (MH+, 20), 312 (100).

Workup

  1. extractionextracted with EtOAc (100 mL)
  2. extractionThe organic extract
  3. customwas separated
  4. washrinsed with brine (20 mL)
  5. dry with materialThe organic layer was dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give a yellow residue
  9. customTwo fractions were collected, with the latter
  10. additioncontaining a non-polar yellow spot (950 mg, 68.9%)

Sources & evidence

ORD record
ord-7a148961a1294837948aaf3bd078274a
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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