Dimethylformamide → [(Z)-1-aminoethylideneamino] 2-fluoro-6-iodobenzoate

HRID 243859

反応式

HRID 243859 の反応式
[F:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]([I:11])[C:3]=1[C:4]([OH:6])=[O:5].C(Cl)(=O)C(Cl)=O.CN(C=O)C.O[NH:24][C:25](=[NH:27])[CH3:26]>C(Cl)Cl>[F:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]([I:11])[C:3]=1[C:4]([O:6]/[N:24]=[C:25](\[NH2:27])/[CH3:26])=[O:5]

参加物

6

反応物 4

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 27333022-Fluoro-6-iodobenzoic acidHCID 178465666HCID 178465666、化合物

生成物 1

HCID 87262981[(Z)-1-aminoethylideneamino] 2-fluoro-6-iodobenzoate収率 86.1%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a heterogeneous mixture of 2-fluoro-6-iodobenzoic acid (1.51 g, 5.66 mmol) at 0° C. in DCM (28 mL) was added oxalyl chloride (0.635 mL, 7.36 mmol) followed by DMF (0.15 mL). Gas evolution commenced immediately and after 5 min the ice bath was removed. When gas evolution had ceased and the mixture was homogeneous an aliquot was removed and quenched with MeOH. Formation of the methyl ester was confirmed by HPLC and the mixture was concentrated in vacuo. The viscous liquid was dissolved in fresh DCM (28 mL) and treated with solid N-hydroxyacetamidine (503 mg, 6.79 mmol) in several portions followed by TEA (1.2 mL, 8.49 mmol) at 0° C. After stirring for 14 h at ambient temperature the mixture was washed with saturated aqueous NaHCO3 solution. The combined organic extracts were dried over Na2SO4, filtered and concentrated in vacuo. Chromatography (Hex to 100% EtOAc/Hex) afforded the desired product as a colorless oil (1.57 g, 86%). MS (ESI) mass calculated for C9H8FIN2O2, 321.96; m/z found, 323.0. 1H NMR (500 MHz, CDCl3): 7.70-7.65 (m, 1H), 7.15-7.11 (m, 2H), 4.87 (br s, 2H), 2.06 (s, 3H).

後処理

  1. customthe ice bath was removed
  2. customwas removed
  3. customquenched with MeOH
  4. concentrationthe mixture was concentrated in vacuo
  5. dissolutionThe viscous liquid was dissolved in fresh DCM (28 mL)
  6. washwas washed with saturated aqueous NaHCO3 solution
  7. dry with materialThe combined organic extracts were dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-729f9215e02a4be5b013386035700ad5
出典データセット
uspto-grants-2014_02
特許番号
US08653263B2

関連ノート

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