Dimethylformamide → tert-Butyl (2-chloro-3-formylpyridin-4-yl)carbamate

HRID 604983ノート

反応式

HRID 604983 の反応式
[Cl:1][C:2]1[CH:7]=[C:6]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=[CH:4][N:3]=1.C([Li])(C)(C)C.CCCCC.CN([CH:29]=[O:30])C>C1COCC1>[Cl:1][C:2]1[C:7]([CH:29]=[O:30])=[C:6]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:12])([CH3:14])[CH3:13])[CH:5]=[CH:4][N:3]=1

参加物

5

反応物 3

HCID 6228DimethylformamideHCID 21858447tert-butyl N-(2-chloropyridin-4-yl)carbamateHCID 178446069HCID 178446069、化合物

生成物 1

HCID 52987944tert-Butyl (2-chloro-3-formylpyridin-4-yl)carbamate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of tert-butyl (2-chloropyridin-4-yl)carbamate (1.14 gm, 5 mmol) in dry THF (20 mL) was cooled to −70° C. under an inert atmosphere and 1.7 M t-butyl lithium/pentane (8 mL, 13.5 mmol) was slowly added. The reaction was stirred for two hours and then dry DMF (1.2 mL, 15.5 mmol) was added. The reaction was allowed to slowly warm to room temperature over a three hour period. The reaction mixture was quenched with 3 N HCl (12 mL) and diluted with diethyl ether. The ether layer was washed with aqueous NaHCO3, dried (over Na2SO4), filtered and evaporated. The residue was triturated with cold diethyl ether to give pure t-butyl (2-chloro-3-formylpyridine-4-yl)carbamate. The mother liquors were chromatographed on silica gel eluting with 15-20% ethyl acetate/hexane to give additional product. 1H-NMR (500 MHz, CDCl3): δ 11.0 (1H, br s), 10.52 (1H, s), 8.38 (1H, d, J=6 Hz), 8.31 (1H, d, J=6 Hz), 1.54 (9H, s); m/e (m+1): 257.2.

後処理

  1. additionwas slowly added
  2. customThe reaction mixture was quenched with 3 N HCl (12 mL)
  3. additiondiluted with diethyl ether
  4. washThe ether layer was washed with aqueous NaHCO3
  5. dry with materialdried (over Na2SO4)
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was triturated with cold diethyl ether

出典と根拠

ORDレコード
ord-6fd43be77bb74deda481ae6eb9976e73
出典データセット
uspto-grants-2011_03
特許番号
US07910561B2

反応ノート

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