Phenyl chloroformate → Phenyl methyl(2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethyl)carbamate

HRID 424486Notes

Reaction equation

HRID 424486 reaction equation
[CH3:1][N:2](C)[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:19](Cl)(=[O:27])[O:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>ClCCl.C(N(CC)CC)C.O.C(=O)([O-])[O-].[Na+].[Na+]>[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)[C:19](=[O:27])[O:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

7

Reactant 2

HCID 15891Phenyl chloroformateHCID 59144138N,N-Dimethyl-2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethanamine

Product 1

HCID 59144104Phenyl methyl(2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethyl)carbamateYield 100%

Reagents, catalysts & solvents 4

HCID 8471TriethylamineCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 10340Sodium CarbonateSolvent

Procedure

To a stirred solution of N,N-dimethyl-2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethanamine (100 mg, 0.374 mmol) in dichloromethane (5 mL) under argon was added phenyl carbonochloridate (0.094 mL, 0.748 mmol). The resulting mixture was stirred at room temperature. A precipitate was observed, and triethylamine (3 drops) was added to aid dissolution (reaction turned clear). The mixture was then stirred over the weekend. The clear yellow mixture was then diluted with water and sodium carbonate and then extracted with dichloromethane (3×). The combined organics were dried, filtered, concentrated, and then chromatographed in ethyl acetate, giving the desired product (139 mg, 100%). 1H NMR (DMSO-d6) δ 7.84-7.74 (m, 2H), 7.39-7.31 (m, 2H), 7.23-7.16 (m, 1H), 7.03-6.93 (m, 3H), 3.85-3.78 (m, 3H), 3.73-3.65 (m, 2H), 3.55-3.50 (m, 1H), 3.09, 2.97 (2s, 3H), 3.09-3.05 (m, 2H); MS-EI: (m/z, %) 373 (M+, 4), 209 (31), 179 (100), 151 (28).

Workup

  1. stirringThe mixture was then stirred over the weekend
  2. extractionextracted with dichloromethane (3×)
  3. customThe combined organics were dried
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customchromatographed in ethyl acetate

Sources & evidence

ORD record
ord-f4793b1fce8a4e689f04c252fe267283
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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