Water → tert-Butyl (2-(5-chloropicolinoyl)-6-methoxyphenyl)carbamate

HRID 921265ノート

反応式

HRID 921265 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13].[Li]C(C)(C)C.[Cl:22][C:23]1[CH:24]=[CH:25][C:26]([C:29](OCC)=[O:30])=[N:27][CH:28]=1.O>CCOCC.CCOC(C)=O>[C:12]([O:11][C:10](=[O:16])[NH:9][C:4]1[C:3]([O:2][CH3:1])=[CH:8][CH:7]=[CH:6][C:5]=1[C:29](=[O:30])[C:26]1[CH:25]=[CH:24][C:23]([Cl:22])=[CH:28][N:27]=1)([CH3:13])([CH3:15])[CH3:14]

参加物

7

反応物 4

HCID 962WaterHCID 4935494tert-butyl N-(2-methoxyphenyl)carbamateHCID 15414989Ethyl 5-Chloropyridine-2-carboxylateHCID 178418306HCID 178418306、化合物

生成物 1

HCID 86713384tert-Butyl (2-(5-chloropicolinoyl)-6-methoxyphenyl)carbamate収率 57.4%

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
-78 °C

実験手順

To a cold (−23° C.), stirred solution of tert-butyl 2-methoxyphenylcarbamate (548 mg, 2.454 mmol) in ether (6 mL) under N2 was added t-BuLi (3.2 mL, 5.44 mmol). After stirring for 2.5 h, the reaction mixture was cooled to −78° C. To the reaction mixture was added a solution of ethyl 5-chloropicolinate (564.5 mg, 3.04 mmol) in ether (12 mL) dropwise via cannula over 5 min. The reaction mixture was stirred for 60 min, and then warmed to room temperature. After 1.5 h, to the reaction mixture was added H2O with vigorous stirring. The reaction mixture was diluted with EtOAc, and the organic phase was separated, washed with sat NaCl then dried (Na2SO4), filtered and concentrated to yield the product Intermediate A-29A (511.5 mg, 57.4% yield)) as a yellow solid: 1H NMR (400 MHz, chloroform-d) δ ppm 8.55 (1H, dd, J=2.3, 0.6 Hz), 8.08 (1H, dd, J=8.4, 0.7 Hz), 7.80 (1H, dd, J=8.4, 2.4 Hz), 7.16-7.25 (2H, m), 7.06 (1H, dd, J=7.5, 2.2 Hz), 6.90 (1H, s), 3.92 (3H, s), 1.28 (9H, s).

後処理

  1. stirringThe reaction mixture was stirred for 60 min
  2. temperaturewarmed to room temperature
  3. waitAfter 1.5 h
  4. customthe organic phase was separated
  5. washwashed with sat NaCl
  6. dry with materialthen dried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto yield the product Intermediate A-29A (511.5 mg, 57.4% yield)) as a yellow solid

出典と根拠

ORDレコード
ord-8c3d6cd24fdd4ab08499c8223dd680c4
出典データセット
uspto-grants-2016_03
特許番号
US09273014B2

反応ノート

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