Citric Acid → 3-({[(Tert-butoxy)carbonyl]amino}methyl)-5-nitrobenzoic acid

HRID 964487ノート

反応式

HRID 964487 の反応式
[N+:1]([C:4]1[CH:5]=[C:6]([CH2:14][NH2:15])[CH:7]=[C:8]([CH:13]=1)[C:9]([O:11]C)=[O:10])([O-:3])=[O:2].[OH-].[Na+].[O:18](C(OC(C)(C)C)=O)[C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=O.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C(O)(C)(C)C.O>[C:22]([O:21][C:19]([NH:15][CH2:14][C:6]1[CH:7]=[C:8]([CH:13]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1)[C:9]([OH:11])=[O:10])=[O:18])([CH3:25])([CH3:24])[CH3:23]

参加物

7

反応物 4

HCID 311Citric AcidHCID 14798Sodium HydroxideHCID 90495Di-tert-butyl dicarbonateHCID 19077132Methyl 3-(aminomethyl)-5-nitrobenzoate

生成物 1

HCID 190771343-({[(Tert-butoxy)carbonyl]amino}methyl)-5-nitrobenzoic acid収率 88%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6386tert-Butanol溶媒

実験手順

A solution of methyl 5-nitro-3-aminomethybenzoate (1980 mg, 9.4 mmol) in 1N NaOH (28 mL, 28 mmol) and tert-BuOH (20 mL) was stirred at r.t. for 10 hours and then added BOC2O (4100 mg, 18.8 mmol) and stirred for 17 hours. The reaction mixture was added hexanes (50 mL) and water (50 mL). The aqueous layer was acidified with 5% citric acid aq. and extracted with CH2 Cl2 (2×70 mL). The CH2Cl2 layers were combined and washed with water (50 mL). The organic layer was evaporated to give the desired compound (2450 mg, 88%): 1H NMR (300 MHz, DMSO-d6) δ 13.725 (s, 1H), 8.476 (s, 1H), 8.307 (s, 1H), 8.216 (s, 1H), 7.639 (t, J=5.7 Hz, 1H), 4.398 (d, J=5.7 Hz, 2H), 1.385 (s, 9H); 13C NMR (300 MHz, DMSO-d6) δ 165.5, 155.9, 147.9, 143.5, 133.6, 132.5, 125.4, 122.2, 78.3, 42.6, 28.2.

後処理

  1. extractionextracted with CH2 Cl2 (2×70 mL)
  2. washwashed with water (50 mL)
  3. customThe organic layer was evaporated

出典と根拠

ORDレコード
ord-991de5e9c97e490b943c2a4013aaa6de
出典データセット
uspto-grants-1998_06
特許番号
US05770380

反応ノート

読み込み中…