Dimethylformamide → Methyl 6-formyl-1-naphthoate

HRID 472786

반응식

HRID 472786 반응식
[C]=O.FC(F)(F)S(O[C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[C:15]([C:19]([O:21][CH3:22])=[O:20])=[CH:14][CH:13]=[CH:12]2)(=O)=O.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.C([SiH](CCCCCCCC)CCCCCCCC)CCCCCCC.CN([CH:89]=[O:90])C>CC([O-])=O.CC([O-])=O.[Pd+2]>[CH:89]([C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[C:15]([C:19]([O:21][CH3:22])=[O:20])=[CH:14][CH:13]=[CH:12]2)=[O:90]

참가 물질

8

반응물 6

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 812191,3-Bis(diphenylphosphino)propaneHCID 87780Trioctylsilane, 95%HCID 22622428Methyl 6-(((trifluoromethyl)sulfonyl)oxy)-1-naphthoateHCID 178418416HCID 178418416, 화합물

생성물 1

HCID 58056979Methyl 6-formyl-1-naphthoate수율 36%

시약·촉매·용매 1

HCID 167845palladium(II) acetate촉매

반응 조건

온도
70 °C

실험 절차

Carbon monoxide (CO) gas was slowly bubbled through a solution of methyl 6-(((trifluoromethyl)sulfonyl)oxy)-1-naphthoate (334 mg, 1.0 mmol), Pd(OAc)2 (22 mg, 0.10 mmol), 1,3-bis-(diphenylphosphino)propane (40 mg, 0.10 mmol) and triethylamine (0.28 mL, 2.0 mmol) an DMF (8.3 mL). After 15 min, trioctylsilane (0.90 mL, 2.0 mmol) was added as bubbling continued. The mixture was heated at 70° C., continuing to bubble CO into the solution. After 6 h at 70 the bubbling CO was replaced with a balloon of CO and the reaction mixture was stirred overnight. After 18 h at 70° C., the reaction was cooled to room temperature, diluted with EtOAc (150 mL) and washed with water (3×50 mL) and brine (50 mL). The organic phase was dried (Na2SO4), filtered and concentrated in vacuo. The resulting residue was purified on 40 g silica gel (100% hexanes→25% EtOAc/hexanes, gradient) to afford 78 mg (36%) of methyl 6-formyl-1-naphthoate.

후처리

  1. customas bubbling
  2. customto bubble CO into the solution
  3. waitAfter 6 h at 70 the bubbling CO was replaced with a balloon of CO
  4. waitAfter 18 h at 70° C.
  5. temperaturethe reaction was cooled to room temperature
  6. additiondiluted with EtOAc (150 mL)
  7. washwashed with water (3×50 mL) and brine (50 mL)
  8. dry with materialThe organic phase was dried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe resulting residue was purified on 40 g silica gel (100% hexanes→25% EtOAc/hexanes, gradient)

출처 및 근거

ORD 기록
ord-f1f9697f468c45b4bb16255818f39e02
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08633220B2

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