tert-Butanol → tert-Butyl (3-Amino-1-phenyl-1H-pyrazol-4-yl)carbamate

HRID 1013488ノート

反応式

HRID 1013488 の反応式
[N+:1]([C:4]1[C:5](C(O)=O)=[N:6][N:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:8]=1)([O-])=O.C([N:20](CC)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.FC(F)(F)[C:44]([OH:46])=[O:45].[C:49](O)([CH3:52])([CH3:51])[CH3:50]>O1CCOCC1>[NH2:20][C:5]1[C:4]([NH:1][C:44](=[O:45])[O:46][C:49]([CH3:52])([CH3:51])[CH3:50])=[CH:8][N:7]([C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=2)[N:6]=1

参加物

7

反応物 5

HCID 6386tert-ButanolHCID 6422Trifluoroacetic acidHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 230849354-Nitro-1-phenyl-1H-pyrazole-3-carboxylic acid

生成物 1

HCID 57717456tert-Butyl (3-Amino-1-phenyl-1H-pyrazol-4-yl)carbamate

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

A solution of 4-nitro-1-phenyl-1H-pyrazole-3-carboxylic acid (20.0 g, 85.8 mmol), triethylamine (36.0 mL, 257.3 mmol), and diphenylphosphoryl azide (37.8 g, 137.2 mmol) in dioxane (400 mL) and tert-butanol (200 mL) was heated to reflux for 16 hours. The reaction was evaporated to dryness in vacuo, diluted with methylene chloride (400 mL) and treated with trifluoroacetic acid (128 g, 857.7 mmol). The solution was stirred at ambient temperature for 16 hours. The reaction was evaporated in vacuo and the resulting oil diluted with hexanes (750 mL), ethyl acetate (150 mL) and methylene chloride (100 mL). The solids were filtered, washed with above solvent system (hexanes:ethyl acetate; methylene chloride 75:15:10), and dried to give 12.0 g of desired product as yellow solid. 1H NMR (CDCl3) δ 8.43 (s, 1H), 7.62 (m, 2H), 7.48 (m, 2H), 7.37 (m, 1H).

後処理

  1. temperatureto reflux for 16 hours
  2. customThe reaction was evaporated to dryness in vacuo
  3. additiondiluted with methylene chloride (400 mL)
  4. customThe reaction was evaporated in vacuo
  5. additionthe resulting oil diluted with hexanes (750 mL), ethyl acetate (150 mL) and methylene chloride (100 mL)
  6. filtrationThe solids were filtered
  7. washwashed with above solvent system (hexanes:ethyl acetate; methylene chloride 75:15:10)
  8. customdried

出典と根拠

ORDレコード
ord-588e3134367d4558b3947923e9a134c5
出典データセット
uspto-grants-2011_07
特許番号
US07981874B2

反応ノート

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