Ammonium Chloride → 4-(1,2,4-Oxadiazol-3-yl)aniline

HRID 1093701ノート

反応式

HRID 1093701 の反応式
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]2[N:14]=[CH:13][O:12][N:11]=2)=[CH:6][CH:5]=1)([O-])=O.[Cl-].[NH4+]>C1COCC1.O.[Zn]>[O:12]1[CH:13]=[N:14][C:10]([C:7]2[CH:8]=[CH:9][C:4]([NH2:1])=[CH:5][CH:6]=2)=[N:11]1

参加物

6

反応物 2

HCID 25517Ammonium ChlorideHCID 27982883-(4-Nitrophenyl)-1,2,4-oxadiazole

生成物 1

HCID 214837044-(1,2,4-Oxadiazol-3-yl)aniline収率 96.2%

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a stirred solution of 4-nitrobenzonitrile (1 g, 0.0068 mol) in ethanol (20 mL) and water (8 mL) was added hydroxylamine hydrochloride (1.9 g, 0.0272 mol) followed by sodium carbonate (2.2 g, 0.0204 mol). The resulting mixture was heated to reflux at 85° C. under an atmosphere of nitrogen for 2 hours The reaction was monitored by TLC (50% Ethyl acetate in Hexane). The volatiles were evaporated and the residue was extracted with ethyl acetate. The ethyl acetate was washed with brine solution, dried over Na2SO4 and concentrated under reduced pressure to get afford 1.2 g (98%) of N-hydroxy-4-nitro-benzamidine. 1H NMR (DMSO-d6): δ 10.2 (s, 1H), 8.24 (d, 2H), 7.97 (d, 2H), 6.03 (s, 2H). To a stirred solution of N-hydroxy-4-nitro-benzamidine (1.2 g, 0.0066 mol) in THF (15 mL) was added triethyl orthoformate (2.93 g, 0.0198 mol). The resulting mixture was cooled to between 0 and 5° C. Boron trifluoride dimethyl ether (0.9 g, 0.0079 mol) was then added dropwise and the resulting mixture was stirred at ambient temperature for 3 hours. Volatiles were evaporated under reduced pressure and the resulting residue was washed with ether and dried to afford 0.65 g (55%) of 3-(4-nitro-phenyl)-[1, 2, 4]oxadiazole. To a stirred solution of 3-(4-nitro-phenyl)-[1, 2, 4]oxadiazole (0.2 g, 0.001 mol) in THF (15 mL) was added ammonium chloride (0.214 g, 0.004 mol) in water (5 mL) followed by zinc powder (0.262 g, 0.004 mol) portionwise. The resulting mixture was stirred at ambient temperature for 1 hr and then heated to 65° C. for 5 hours. The mixture was then filtered through celite and the organic layers were concentrated under reduced pressure. The residue was extracted with ethyl acetate. The organic layers were washed with brine solution, dried over Na2SO4 and evaporated under reduced pressure to afford 0.155 g (92%) of 4-[1, 2, 4]oxadiazol-3-yl-phenylamine. 1H NMR (DMSO-d6): δ 9.5 (s, 1H), 7.7 (d, 2H), 6.7 (d, 2H), 5.8 (s, 2H).

後処理

  1. temperatureheated to 65° C. for 5 hours
  2. filtrationThe mixture was then filtered through celite
  3. concentrationthe organic layers were concentrated under reduced pressure
  4. extractionThe residue was extracted with ethyl acetate
  5. washThe organic layers were washed with brine solution
  6. dry with materialdried over Na2SO4
  7. customevaporated under reduced pressure

出典と根拠

ORDレコード
ord-149f5ef8ffd94bc484d091546977bb3b
出典データセット
uspto-grants-2012_03
特許番号
US08129376B2

反応ノート

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