Sodium cyanoborohydride → 2,3-Dichloro-N-{2-[formyl(Hydroxy)amino]ethyl}benzamide

HRID 23814

反応式

HRID 23814 の反応式
[Cl:1][C:2]1[C:14]([Cl:15])=[CH:13][CH:12]=[CH:11][C:3]=1[C:4]([NH:6][CH2:7][CH:8]=[N:9][OH:10])=[O:5].[CH3:16][OH:17].Cl.C([BH3-])#N.[Na+]>CO.CN(C1C=CC(N=NC2C=CC(S(O)(=O)=O)=CC=2)=CC=1)C>[Cl:1][C:2]1[C:14]([Cl:15])=[CH:13][CH:12]=[CH:11][C:3]=1[C:4]([NH:6][CH2:7][CH2:8][N:9]([CH:16]=[O:17])[OH:10])=[O:5]

参加物

6

反応物 3

HCID 5003444Sodium cyanoborohydrideHCID 21893726Hydrochloride methanol2 回HCID 854351652,3-dichloro-N-(2-hydroxyimino-ethyl)-benzamide

生成物 1

HCID 98384882,3-Dichloro-N-{2-[formyl(Hydroxy)amino]ethyl}benzamide収率 32%

試薬・触媒・溶媒 2

HCID 11037Benzenesulfonic acid, 4-(2-(4-(dimethylamino)phenyl)diazenyl)-触媒HCID 887Methanol溶媒

実験手順

To a solution of 2,3-dichloro-N-(2-hydroxyimino-ethyl)-benzamide (34.3 g, 0.14 mol) in MeOH (700 mL) under an argon atmosphere at 0° C. was added methyl orange (0.01 g) followed by a saturated solution of MeOH/HCl until a persistent red color was observed. Sodium cyanoborohydride (10.5 g, 0.17 mol) was added sequentially with saturated MeOH/HCl over 0.5 h. The reaction mixture was stirred an additional 1 h and the MeOH was removed in vacuo. The residue was partitioned between 3N HCl (300 mL) and dichloromethane (300 mL). The organic phase was extracted with 3N HCl (2×200 mL). The combined aqueous extracts were washed with dichloromethane, were basidified with cold dilute NaOH and were extracted (7×100 mL) with dichloromethane/MeOH (9:1). The combined organic extracts were washed with brine, were dried (Na2SO4) and were concentrated. The residue was diluted with ether (200 mL) and the precipitate collected by filtration to provide the title compound (11 g, 32%) as a white solid. 1H NMR (400 MHz, CD3OD): δ 7.60 (dd, j=1.7 and 7.8 Hz, 1H); 7.41 (dd, j=1.7 and 7.6 Hz, 1H); 7.35 (t, j=7.7 Hz, 1H); 3.57 (t, j=6.2 Hz, 2H); 3.06 (t, j=6.2 Hz, 1H).

後処理

  1. customthe MeOH was removed in vacuo
  2. customThe residue was partitioned between 3N HCl (300 mL) and dichloromethane (300 mL)
  3. extractionThe organic phase was extracted with 3N HCl (2×200 mL)
  4. washThe combined aqueous extracts were washed with dichloromethane
  5. extractionwere extracted (7×100 mL) with dichloromethane/MeOH (9:1)
  6. washThe combined organic extracts were washed with brine
  7. dry with materialwere dried (Na2SO4)
  8. concentrationwere concentrated
  9. additionThe residue was diluted with ether (200 mL)
  10. filtrationthe precipitate collected by filtration

出典と根拠

ORDレコード
ord-dfc2d82938924a48bd87b35e356b11eb
出典データセット
uspto-grants-2005_02
特許番号
US06852882B2

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