Hydrochloric Acid → HCID 22272431, compound

HRID 2251392Notes

Reaction equation

HRID 2251392 reaction equation
ClC1C=CC(S(N)(=O)=O)=CC=1.[H-].[Na+].FC1C=C(F)C=CC=1[N+]([O-])=O.Cl.[Cl:26][C:27]1[CH:32]=[CH:31][C:30]([S:33]([NH:36][C:37]2[CH:42]=[C:41](F)[CH:40]=[CH:39][C:38]=2[N+:44]([O-:46])=[O:45])(=[O:35])=[O:34])=[CH:29][CH:28]=1.[CH3:47][N:48]1[CH2:54][CH2:53][CH2:52][NH:51][CH2:50][CH2:49]1>CN(C=O)C.C(Cl)Cl>[Cl:26][C:27]1[CH:32]=[CH:31][C:30]([S:33]([NH:36][C:37]2[CH:42]=[C:41]([N:51]3[CH2:52][CH2:53][CH2:54][N:48]([CH3:47])[CH2:49][CH2:50]3)[CH:40]=[CH:39][C:38]=2[N+:44]([O-:46])=[O:45])(=[O:35])=[O:34])=[CH:29][CH:28]=1

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 668244-ChlorobenzenesulfonamideHCID 679672,4-DifluoronitrobenzeneHCID 2283491-MethylhomopiperazineHCID 22272507HCID 22272507, compound

Product 1

HCID 22272431HCID 22272431, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

4-chlorobenzene sulfonamide (3.5 g, 18.3 mmol) was added slowly to a suspension of sodium hydride (1.6 g, 55% suspension in mineral oil, 36.6 mmol) in anhydrous DMF (50 mL) under an atmosphere of nitrogen. The mixture was warmed to 40° C. for 1 hour and 2,4-difluoronitrobenzene (2 mL) was added dropwise. This mixture was stirred at 60° C. overnight. The cooled reaction mixture was poured into hydrochloric acid (1 N, 250 mL) and extracted with ethyl acetate (2×50 mL). The organic extracts were washed with water, dried over MgSO4 and evaporated to give a yellow solid. The product was re-crystallized from ethanol. Yield 2.4 g (40%). 1H NMR (400 MHz, CDCl3) δ 6.85 (m, 1 H), 7.48 (AB, J=8.3 Hz, 2 H), 7.56 (dd, J=10.01, 2.68 Hz, 1 H), 7.84 (AB, J=8.3 Hz, 2 H), 8.21 (dd, J=5.61 Hz, 1 H), 10 (bs, 1 H). Calculated N 8.47%, C 43.58%, S 9.70%, H 2.44%; Found N 8.54%, C43.89%, S10.10%, H 2.76%. 4-Chloro-N-[5-fluoro-2-nitrophenyl]benzenesulfonamide (1 g, 3 mmol) and N-methylhomopiperazine (0.4 mL) were heated together at 130° C. for 3 hours. The product was allowed to cool, dissolved in CH2Cl2 (50 mL) and washed with aqueous sodium bicarbonate. The organic phase was dried over MgSO4 and evaporated to give 1.05 g of a yellow solid which was re-crystallized from toluene. Yield 0.65 g (51%). 1H NMR (400 MHz, CDCl3) δ 1.98 (q, J=5.62 Hz, 1 H), 2.37 (s, 3 H), 2.52 (t, J=5.62 Hz, 2 H), 2.67 (t, J=5.12 Hz, 2 H), 3.55 (t, J=6.35 Hz, 2 H), 3.60 (t, J=5.12 Hz, 2 H), 6.34 (dd, J=9.77, 2.68 Hz, 1 H), 6.86 (d, J=2.68 Hz, 1 H), 7.43 (ab, J=8.79 Hz, 2H), 7.79 (ab, J=8.79 Hz, 2H), 8.01 (d, J=9.77 Hz, 1 H), 11.6 (brs, 1 H). Calculated N 13.19%, C 50.88%, H 4.98%; Found N 13.27%, C 50.99%, H 4.83%.

Workup

  1. customThe cooled reaction mixture
  2. extractionextracted with ethyl acetate (2×50 mL)
  3. washThe organic extracts were washed with water
  4. dry with materialdried over MgSO4
  5. customevaporated
  6. customto give a yellow solid
  7. customThe product was re-crystallized from ethanol
  8. temperatureto cool
  9. washwashed with aqueous sodium bicarbonate
  10. dry with materialThe organic phase was dried over MgSO4
  11. customevaporated

Sources & evidence

ORD record
ord-1a15c4a3a2d1470aab252eae4e29bc93
Source dataset
uspto-grants-2008_01
Patent number
US07319097B2

Reaction notes

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