Ammonium Chloride → HCID 86702148, compound

HRID 1776219Notes

Reaction equation

HRID 1776219 reaction equation
[CH3:1][O:2][C:3]1[CH:18]=[C:17]([O:19][CH3:20])[CH:16]=[CH:15][C:4]=1[CH2:5][N:6]1[CH2:11][CH2:10][CH2:9][CH:8]([F:12])[S:7]1(=[O:14])=[O:13].C([Li])CCC.C1C=CC(S(N(S(C2C=CC=CC=2)(=O)=O)[F:36])(=O)=O)=CC=1.[Cl-].[NH4+]>O1CCCC1>[CH3:1][O:2][C:3]1[CH:18]=[C:17]([O:19][CH3:20])[CH:16]=[CH:15][C:4]=1[CH2:5][N:6]1[CH2:11][CH2:10][CH2:9][C:8]([F:36])([F:12])[S:7]1(=[O:14])=[O:13]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 588007N-FluorobenzenesulfonimideHCID 86702147HCID 86702147, compoundHCID 178418339Butyllithium

Product 1

HCID 86702148HCID 86702148, compoundYield 15.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of 2-(2,4-dimethoxybenzyl)-6-fluoro-1,2-thiazinane-1,1-dioxide (0.500 g, 1.8 mmol) in anhydrous tetrahydrofuran (30 mL), cooled to −78° C., was slowly added 2.5 N n-butyl lithium in hexanes (1.262 mL, 3.2 mmol). The solution was stirred at −78° C. for 1 hr, a solution of N-fluorobenzene sulfonimide (1.243 g, 3.9 mmol) in anhydrous tetrahydrofuran (5 mL) was slowly added over 10 mins, and the mixture stirred at −78° C. for 3 hrs and at room temperature for 3 hrs. The reaction mixture was poured into saturated aqueous ammonium chloride and extracted with ethyl acetate (2×). The combined organic layers were washed with water, saturated aqueous sodium chloride, dried (anhydrous sodium sulfate), filtered, and concentrated in vacuo. The crude product was purified by silica gel chromatography (15-60% ethyl acetate/hexanes) to give a yellow oil (0.09 g). 1H NMR (CDCl3, 300 MHz) δ 7.25-7.21 (d, 1H, J=8.4 Hz), 6.50-6.47 (dd, 1H, J=2.4, 8.4 Hz), 6.45-6.44 (d, 1H, J=2.4 Hz), 4.43 (s, 2H), 3.82 (s, 3H), 3.81 (s, 3H), 3.38-3.37 (t, 2H, J=5.1 Hz), 2.58-2.45 (m, 2H), 2.00-1.92 (m, 2H).

Workup

  1. stirringthe mixture stirred at −78° C. for 3 hrs and at room temperature for 3 hrs
  2. extractionextracted with ethyl acetate (2×)
  3. washThe combined organic layers were washed with water, saturated aqueous sodium chloride
  4. dry with materialdried (anhydrous sodium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe crude product was purified by silica gel chromatography (15-60% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-d0142f5dbd50407fbbff7450878a9398
Source dataset
uspto-grants-2016_02
Patent number
US09265772B2

Reaction notes

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