Sodium Azide → 1-Fluoro-2-isocyanato-4-methoxybenzene

HRID 391699

反応式

HRID 391699 の反応式
N/C(/C#N)=C(\N[C:7]([NH:9][C:10]1[CH:15]=[C:14]([O:16][CH3:17])[CH:13]=[CH:12][C:11]=1[F:18])=[O:8])/C#N.FC1C=CC(OC)=CC=1C(O)=O.C(Cl)(=O)C(Cl)=O.[N-]=[N+]=[N-].[Na+]>C(Cl)Cl.CN(C=O)C.O.O1CCOCC1>[F:18][C:11]1[CH:12]=[CH:13][C:14]([O:16][CH3:17])=[CH:15][C:10]=1[N:9]=[C:7]=[O:8]

参加物

8

反応物 4

HCID 33557Sodium AzideHCID 65578Oxalyl chlorideHCID 27745432-Fluoro-5-methoxybenzoic acidHCID 57474799HCID 57474799、化合物

生成物 1

HCID 221509931-Fluoro-2-isocyanato-4-methoxybenzene

試薬・触媒・溶媒 3

HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒HCID 218864351,4-Dioxane--water (1/1)溶媒

実験手順

(Z)-1-(2-Amino-1,2-dicyanovinyl)-3-(2-fluoro-5-methoxyphenyl)urea. 2-Fluoro-5-methoxybenzoic acid (0.62 g, 3.62 mmol) was dissolved in CH2Cl2 (15 mL) and DMF (0.5 mL). Oxalyl chloride (0.38 mL, 4.32 mmol) was added dropwise. The mixture was stirred for another 15 min. The reaction was concentrated and then taken up in dioxane (10 mL). Sodium azide (0.26 g, 3.96 mmol) in water/dioxane (1:1 v/v, 10 mL) was added to the acid chloride at 0° C. The mixture was stirred for 10 min. The reaction was partitioned between EtOAc and water. The layers were shaken and separated. The organic layer was dried over sodium sulfate, filtered, and concentrated. The crude acyl azide was filtered through a silica gel plug (90% Hexanes in EtOAc. The filtrate was concentrated. The purified acyl azide was dissolved in toluene and stirred at 100° C. for 1 h. The toluene solution was concentrated to afford 1-fluoro-2-isocyanato-4-methoxybenzene in quantitative yield. 1-Fluoro-2-isocyanato-4-methoxybenzene (0.6 g, 3.62 mmol) was reacted with 2,3-diaminomaleonitrile (0.39 g, 3.62 mmol) according to General Procedure A to afford the title compound. MS (ESI) m/z 276.4 [M+1]+.

後処理

  1. concentrationThe reaction was concentrated
  2. stirringThe mixture was stirred for 10 min
  3. customThe reaction was partitioned between EtOAc and water
  4. stirringThe layers were shaken
  5. customseparated
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. filtrationThe crude acyl azide was filtered through a silica gel plug (90% Hexanes in EtOAc
  10. concentrationThe filtrate was concentrated
  11. dissolutionThe purified acyl azide was dissolved in toluene
  12. stirringstirred at 100° C. for 1 h
  13. concentrationThe toluene solution was concentrated

出典と根拠

ORDレコード
ord-81bf7fa3d1c3454da3e25ffe2c2865cc
出典データセット
uspto-grants-2013_02
特許番号
US08383634B2

関連ノート

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