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

HRID 391699

반응식

HRID 391699 반응식
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]

참가 물질

8

반응물 4

HCID 33557Sodium AzideHCID 65578Oxalyl chlorideHCID 27745432-Fluoro-5-methoxybenzoic acidHCID 57474799HCID 57474799, 화합물

생성물 1

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

시약·촉매·용매 3

HCID 6228Dimethylformamide용매HCID 6344Dichloromethane용매HCID 218864351,4-Dioxane--water (1/1)용매

실험 절차

(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]+.

후처리

  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

출처 및 근거

ORD 기록
ord-81bf7fa3d1c3454da3e25ffe2c2865cc
출처 데이터셋
uspto-grants-2013_02
특허 번호
US08383634B2

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