Methanesulfonic Acid → 2,5-Diamino-benzenesulfonamide methanesulfonate

HRID 548286

反応式

HRID 548286 の反応式
[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]

参加物

8

反応物 4

HCID 6395Methanesulfonic AcidHCID 8028TetrahydrofuranHCID 248583972-Benzylamino-5-nitro-benzenesulfonamideHCID 178418361HCID 178418361、化合物

生成物 1

HCID 251646412,5-Diamino-benzenesulfonamide methanesulfonate収率 93%

試薬・触媒・溶媒 3

HCID 23938Palladium触媒2 回HCID 702Ethanol溶媒HCID 962Water溶媒2 回

反応条件

温度
23 °C

実験手順

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+].

後処理

  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.

出典と根拠

ORDレコード
ord-0f9235f946554b58ae9169eb028efa61
出典データセット
uspto-grants-2011_05
特許番号
US07939524B2

関連ノート

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