Dimethylformamide → Methyl 6-formyl-1-naphthoate

HRID 472786

反応式

HRID 472786 の反応式
[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]

参加物

8

反応物 6

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

生成物 1

HCID 58056979Methyl 6-formyl-1-naphthoate収率 36%

試薬・触媒・溶媒 1

HCID 167845palladium(II) acetate触媒

反応条件

温度
70 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-f1f9697f468c45b4bb16255818f39e02
出典データセット
uspto-grants-2014_01
特許番号
US08633220B2

関連ノート

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