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

HRID 276873

반응식

HRID 276873 반응식
[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]

참가 물질

5

반응물 2

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

생성물 1

HCID 105641445-tert-Butoxycarbonylamino-2-chloroisonicotinic acid

시약·촉매·용매 2

HCID 3283Diethyl Ether용매HCID 8037N,N,N',N'-Tetramethylethylenediamine용매

반응 조건

온도
-15 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-670b7db6796640bcb4d6faf0637650bb
출처 데이터셋
uspto-grants-2002_03
특허 번호
US06355636B1

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