3-Hydroxyanthranilic Acid → Methyl 2-(4-chlorophenyl)benzoxazole-4-carboxylate

HRID 506235ノート

反応式

HRID 506235 の反応式
[OH:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:4]([C:5]([OH:7])=[O:6])[C:3]=1[NH2:11].[Cl:12][C:13]1[CH:21]=[CH:20][C:16]([C:17](Cl)=[O:18])=[CH:15][CH:14]=1.[CH3:22]CN(C(C)C)C(C)C.CI>CN(C=O)C.C(OCC)(=O)C.Cl>[Cl:12][C:13]1[CH:21]=[CH:20][C:16]([C:17]2[O:1][C:2]3[C:3](=[C:4]([C:5]([OH:7])=[O:6])[CH:8]=[CH:9][CH:10]=3)[N:11]=2)=[CH:15][CH:14]=1.[Cl:12][C:13]1[CH:21]=[CH:20][C:16]([C:17]2[O:18][C:2]3[C:3](=[C:4]([C:5]([O:7][CH3:22])=[O:6])[CH:8]=[CH:9][CH:10]=3)[N:11]=2)=[CH:15][CH:14]=1

参加物

9

反応物 4

HCID 863-Hydroxyanthranilic AcidHCID 6328Methyl iodideHCID 85014-Chlorobenzoyl chlorideHCID 81531Diisopropylethylamine

生成物 2

HCID 596258542-(4-Chlorophenyl)benzoxazole-4-carboxylic acidHCID 68459315Methyl 2-(4-chlorophenyl)benzoxazole-4-carboxylate収率 30%

試薬・触媒・溶媒 3

HCID 313Hydrochloric Acid溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

実験手順

2-(4-Chlorophenyl)benzoxazole-4-carboxylic acid was prepared from 3-hydroxyanthranilic acid and 4-chlorobenzoyl chloride using the method described in Step A of Example 1. This crude material (2.90 g, 10.6 mmol) was directly dissolved in DMF (40 mL), DIPEA (5.46 g, 42.4 mmol) and methyl iodide (5.93 g, 42.4 mmol) added and the reaction stirred at room temperature for 18 h. After this time the reaction was diluted with ethyl acetate (100 mL) and 2 N HCl (50 mL). The organic layer was separated and then washed with 2 N HCl (25 mL), water (50 mL) and brine (50 mL). The organic layer was then dried over sodium sulfate, filtered and concentrated to dryness to yield light yellow oil. This material was purified using silica gel chromatography to afford 0.532 g (30% yield) of methyl 2-(4-chlorophenyl)benzoxazole-4-carboxylate as a white solid: 1H NMR (300 MHz, CDCl3) δ 8.28 (dd, J=6.9, 1.8 Hz, 2H), 8.04 (d, J=8.1 Hz, 1H), 7.78 (d, J=8.1 Hz, 1H), 7.52 (d, J=8.7 Hz, 2H), 7.43 (t, J=7.8 Hz, 1H), 4.06 (s, 3H); MS (ESI) m/z 288 [M+H]+

後処理

  1. customThe organic layer was separated
  2. washwashed with 2 N HCl (25 mL), water (50 mL) and brine (50 mL)
  3. dry with materialThe organic layer was then dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated to dryness
  6. customto yield light yellow oil
  7. customThis material was purified

出典と根拠

ORDレコード
ord-b859a37d311a44c79c378c77da9715d0
出典データセット
uspto-grants-2010_08
特許番号
US07781430B2

反応ノート

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