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Triphenylphosphine → Tert-butyl 4-(5-chloro-2-oxo-1,2-dihydropyridin-4-yloxy)piperidine-1-carboxylate

HRID 1962276
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HRID 1962276 반응식
[Cl:1][C:2]1[C:3]([OH:9])=[CH:4][C:5](=[O:8])[NH:6][CH:7]=1.O[CH:11]1[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C(Cl)(Cl)Cl.CN(C=O)C>[Cl:1][C:2]1[C:3]([O:9][CH:11]2[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]2)=[CH:4][C:5](=[O:8])[NH:6][CH:7]=1
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참가 물질

7

반응물 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 643502Tert-butyl 4-hydroxypiperidine-1-carboxylateHCID 54679224Gimeracil

생성물 1

HCID 58467944Tert-butyl 4-(5-chloro-2-oxo-1,2-dihydropyridin-4-yloxy)piperidine-1-carboxylate수율 58.4%

시약·촉매·용매 2

HCID 6212
Chloroform
용매
HCID 6228Dimethylformamide용매

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온도
0 °C

실험 절차

A one liter round bottom flask was charged with 5-chloro-4-hydroxypyridin-2(1H)-one (10 g, 68.7 mmol), t-butyl 4-hydroxypiperidine-1-carboxylate (16.59 g, 82 mmol), triphenylphosphine (27.0 g, 103 mmol) and DMF (200 ml). This mixture was stirred for 40 minutes to form a clear and homogeneous solution. The solution was then cooled to 0° C. and diisopropyl azodicarboxylate (16.23 mL, 82 mmol) was added drop-wise while maintaining the temperature below 20° C. during the addition. After the addition, the reaction mixture was allowed to warm to room temperature overnight. The reaction was then heated to 60° C. for 0.5 hours. After cooling the reaction mixture to room temperature, the DMF was distilled from the reaction under high vacuum at 50° C. to yield a brownish, viscous oil. The oil was dissolved in 300 mL of chloroform and then was washed with dilute sodium bicarbonate (pH 8-10) (3×50 mL) The chloroform layer was directly concentrated to afford a light yellow viscous oil, which was partitioned between 250 mL of diethyl ether and 70 mL of 1 N NaOH. The aqueous phase was extracted thoroughly with diethyl ether until LCMS showed no triphenylphosphine oxide or other impurities in the aqueous layer. The aqueous layer was purged with nitrogen to remove residual ether and then acidified slowly with 1 N HCl (˜70 mL) to pH 5 followed by cooling to 0° C. for 2 hours. The precipitates were collected by filtration, washed with ice water (2×20 mL), and air dried overnight. The light yellow solid was further vacuum dried at 40° C. to a constant weight to yield t-butyl 4-(5-chloro-2-oxo-1,2-dihydropyridin-4-yloxy)piperidine-1-carboxylate (13.2 g, 40.1 mmol, 58.4% yield) as a light yellow solid. 1H-NMR (CDCl3, 400 MHz) δ 12.5 (br, s, 1H), 7.19 (s, 1H), 5.75 (s, 1H), 4.34-4.41 (m, 1H), 3.40-3.48 (m, 2H), 3.26-3.37 (m, 2H), 1.71-1.83 (m, 2H), 1.60-1.71 (m, 2H), 1.32 (s, 9H); MS m/e 329.3 (M+H+), 273.20 (M+H+-t-butyl).

후처리

  1. customto form a clear and homogeneous solution
  2. temperaturewhile maintaining the temperature below 20° C.
  3. additionduring the addition
  4. additionAfter the addition
  5. temperatureto warm to room temperature overnight
  6. temperatureThe reaction was then heated to 60° C. for 0.5 hours
  7. temperatureAfter cooling the reaction mixture to room temperature
  8. distillationthe DMF was distilled from the reaction under high vacuum at 50° C.
  9. customto yield a brownish, viscous oil
  10. washwas washed with dilute sodium bicarbonate (pH 8-10) (3×50 mL) The chloroform layer
  11. concentrationwas directly concentrated
  12. customto afford a light yellow viscous oil, which
  13. customwas partitioned between 250 mL of diethyl ether and 70 mL of 1 N NaOH
  14. extractionThe aqueous phase was extracted thoroughly with diethyl ether until LCMS
  15. customThe aqueous layer was purged with nitrogen
  16. customto remove residual ether
  17. temperatureby cooling to 0° C. for 2 hours
  18. filtrationThe precipitates were collected by filtration
  19. washwashed with ice water (2×20 mL), and air
  20. customdried overnight
  21. customdried at 40° C. to a constant weight

출처 및 근거

ORD 기록
ord-4960a233fd914ecd9881d7e55d30cd03
출처 데이터셋
uspto-grants-2013_04
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08415367B2

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