3-Chloroaniline → HCID 89442503, compound

HRID 2205469Notes

Reaction equation

HRID 2205469 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][CH:8]=1)[NH2:5].O.C1COCC1.[Cl:15][C:16]1[CH:17]=[C:18](/[CH:22]=[CH:23]/[S:24](Cl)(=[O:26])=[O:25])[CH:19]=[CH:20][CH:21]=1.C([O-])([O-])=O.[Na+].[Na+]>O>[Cl:1][C:2]1[CH:3]=[C:4]([NH:5][S:24](/[CH:23]=[CH:22]/[C:18]2[CH:19]=[CH:20][CH:21]=[C:16]([Cl:15])[CH:17]=2)(=[O:25])=[O:26])[CH:6]=[CH:7][CH:8]=1

Participants

6

Reactant 4

HCID 79323-ChloroanilineHCID 10340Sodium CarbonateHCID 21881883Oxolane--water (1/1)HCID 22628233(1E)-2-(3-Chlorophenyl)ethenesulfonyl chloride

Product 1

HCID 89442503HCID 89442503, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a well-stirred solution of 3-chloroaniline (367.9 mg, 2.87 mmol, 1 eq.) in a solvent system of H2O-THF (14 mL, 1:1 ratio) was sequentially added first compound 1 (676.6 mg, 2.87 mmol, 1 eq.) and then a 1M-solution of Na2CO3 (2.2 mL, 0.77 mmol, 0.77 eq.) until the pH was about 8. After the reaction mixture was stirred for 22 hours at room temperature, water was added and the product was extracted 3 times with EtOAc from the aqueous phase. The resulting organic phase was washed with brine, dried under Na2SO4 and the solvent evaporated. After the product was purified from the crude by flash column chromatography (10% EtOAc/hexanes), compound 2 (808.5 mg, 2.46 mmol) was obtained in an 86% yield. 1H NMR (400 MHz, CDCl3) δ 7.48 (d, J=15.4 Hz, C═CH, 1H), 7.43 (s, ArH, 1H), 7.39 (dt, J=6.8, 2.3 Hz, ArH, 1H), 7.33 (m, ArH, 2H), 7.25 (t, J=8.0, ArH, 1H), 7.22 (t, J=2.1, ArH, 1H), 7.13 (ddd, J=8.0, 1.9, 0.9 Hz, ArH, 1H), 7.07 (ddd, J=8.0, 2.1, 0.9 Hz, ArH, 1H), 6.79 (d, J=15.4 Hz, C═CH, 1H), 6.61 (s, NH, 1H). 13C NMR (100 MHz, CDCl3, δ): 142.03 (CH), 137.53 (C), 135.17 (C), 133.76 (C), 131.14 (CH), 130.55 (CH), 130.36 (CH), 128.11 (CH), 126.67 (CH), 125.38 (CH), 125.30 (CH), 120.49 (CH), 118.46 (CH). GC-MS m/z (% relative intensity, ion): 330.85 (0.8, M+4), 328.95 (4, M+2), 326.90 (6, M+), 262.95 (28), 151.95 (48), 136.95 (99), 126.95 (54), 102.00 (100), 98.80 (51), 90.95 (19).

Workup

  1. extractionthe product was extracted 3 times with EtOAc from the aqueous phase
  2. washThe resulting organic phase was washed with brine
  3. customdried under Na2SO4
  4. customthe solvent evaporated
  5. customAfter the product was purified from the crude by flash column chromatography (10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-903532d92b9b42f4bf573ff63c274d12
Source dataset
uspto-grants-2016_06
Patent number
US09371307B2

Reaction notes

Loading…