Methanesulfonic Acid → 2,5-Diamino-benzenesulfonamide methanesulfonate

HRID 424178

Reaktionsgleichung

Reaktionsgleichung von HRID 424178
[CH3:1][S:2]([OH:5])(=[O:4])=[O:3].C([NH:13][C:14]1[CH:19]=[CH:18][C:17]([N+:20]([O-])=O)=[CH:16][C:15]=1[S:23]([NH2:26])(=[O:25])=[O:24])C1C=CC=CC=1.O1CCCC1.[H][H]>[Pd].C(O)C.O>[CH3:1][S:2]([OH:5])(=[O:4])=[O:3].[NH2:13][C:14]1[CH:19]=[CH:18][C:17]([NH2:20])=[CH:16][C:15]=1[S:23]([NH2:26])(=[O:24])=[O:25]

Komponenten

8

Edukt 4

HCID 6395Methanesulfonic AcidHCID 8028TetrahydrofuranHCID 248583972-Benzylamino-5-nitro-benzenesulfonamideHCID 178418361HCID 178418361, Verbindung

Produkt 1

HCID 251646412,5-Diamino-benzenesulfonamide methanesulfonateAusbeute 93 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23938PalladiumKatalysator2×HCID 702EthanolLösungsmittelHCID 962WaterLösungsmittel2×

Reaktionsbedingungen

Temperatur
23 °C

Versuchsvorschrift

Methanesulfonic acid (465 mL, 7.16 mol) was added slowly to a solution of 2-benzylamino-5-nitro-benzenesulfonamide (2.20 kg, 7.16 mol) and tetrahydrofuran (11.0 L). The resulting solution was added to a mixture of 10% palladium on carbon (220 g of 50% water wet catalyst) and water (1.1 L) in a hydrogenation reactor. The mixture was further diluted with absolute ethanol (21.0 L) and was then hydrogenated with 55 psi hydrogen at 50° C. for 21 h. Additional 10% palladium on carbon (55 g of 50% water wet catalyst) was added, and hydrogenation at 55 psi and 50° C. was continued for 22 h. The resulting suspension was diluted with water (1.1 L) and the suspension was then filtered through a pad of Celite. The filtrate was partially concentrated in vacuo and was then diluted with acetonitrile (15.4 L). The solution was again partially concentrated in vacuo and diluted with acetonitrile (15.4 L). The resulting suspension was partially concentrated in vacuo and was allowed to stir at 23° C. for 2 h. The suspension was filtered and the solid was then washed with acetonitrile (3 L). The solid was further dried in vacuo at 45° C. to afford the desired product, 2,5-diamino-benzenesulfonamide methanesulfonate (1.88 kg, 6.64 mol, 93%), as a purple solid. 1H NMR (400 MHz, DMSO-d6) δ: 2.34 (3H, s), 6.05 (2H, b), 6.87 (1H, d, J=8.6 Hz), 7.20 (1H, dd, J1=8.6 Hz, J2=2.3 Hz), 7.38 (2H, s), 7.53 (1H, d, J=2.3 Hz), 9.62 (3H, b). LC-MS (ESI) calcd for C6H9NO2S 187.04, found 187.9 [M+H+].

Aufarbeitung

  1. filtrationthe suspension was then filtered through a pad of Celite
  2. concentrationThe filtrate was partially concentrated in vacuo
  3. additionwas then diluted with acetonitrile (15.4 L)
  4. concentrationThe solution was again partially concentrated in vacuo
  5. additiondiluted with acetonitrile (15.4 L)
  6. concentrationThe resulting suspension was partially concentrated in vacuo
  7. filtrationThe suspension was filtered
  8. washthe solid was then washed with acetonitrile (3 L)
  9. customThe solid was further dried in vacuo at 45° C.

Quellen und Nachweise

ORD-Eintrag
ord-4743c1212d804f5fbd8418ebce811d27
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08101800B2

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