Carbon Dioxide → 5-tert-Butoxycarbonylamino-2-chloroisonicotinic acid

HRID 276873

反応式

HRID 276873 の反応式
[Cl:1][C:2]1[N:7]=[CH:6][C:5]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[CH:4][CH:3]=1.[C:16](=[O:18])=[O:17]>CN(C)CCN(C)C.CCOCC>[C:11]([O:10][C:9]([NH:8][C:5]1[C:4]([C:16]([OH:18])=[O:17])=[CH:3][C:2]([Cl:1])=[N:7][CH:6]=1)=[O:15])([CH3:12])([CH3:14])[CH3:13]

参加物

5

反応物 2

HCID 280Carbon DioxideHCID 7330593(6-Chloro-pyridin-3-yl)-carbamic acid tert-butyl ester

生成物 1

HCID 105641445-tert-Butoxycarbonylamino-2-chloroisonicotinic acid

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 8037N,N,N',N'-Tetramethylethylenediamine溶媒

反応条件

温度
-15 °C

実験手順

To 13 g of (6-chloro-pyridin-3-yl)-carbamic acid, tert-butyl ester in 24 mL of tetramethylethylenediamine and 300 mL of ether at −78° C. under an inert atmosphere was added slowly 68 mL of 2.5 M n-butyllithium/hexanes (3 eq). After the addition was complete, the reaction was allowed to warm to −15° C. for two hours then recooled to −78° C. Dry ice was allowed to sublime in a separate flask and the vapor was passed over the rapidly stirred reaction mixture while the cooling bath was removed and the reaction allowed to warm to 0° C. Sufficient water was added to dissolve the precipitated product and the resultant aqueous phase was washed twice with ether before acidifying with concentrated HCl. The precipitate was filtered, washed with water, and dried in vacuo to give 10.9 g of 5-tert-butoxycarbonylamino-2-chloro-isonicotinic acid, which was used as is for the next step: melting point 250° C. and higher (slowly decomposed); mass spectrum (negative mode, m/e): M−H 271.1.

後処理

  1. additionAfter the addition
  2. customthen recooled to −78° C
  3. customto sublime in a separate flask
  4. customthe vapor was passed over the rapidly stirred reaction mixture while the cooling bath
  5. customwas removed
  6. temperatureto warm to 0° C
  7. additionSufficient water was added
  8. dissolutionto dissolve the precipitated product
  9. washthe resultant aqueous phase was washed twice with ether
  10. filtrationThe precipitate was filtered
  11. washwashed with water
  12. customdried in vacuo

出典と根拠

ORDレコード
ord-670b7db6796640bcb4d6faf0637650bb
出典データセット
uspto-grants-2002_03
特許番号
US06355636B1

関連ノート

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