Diethyl Ether → Ethyl 9-(2,6,6-trimethylcyclohex-1-en-1-yl)nonanoate

HRID 1055183

반응식

HRID 1055183 반응식
Br[Zn][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12].FC(F)(F)S(O[C:22]1[C:27]([CH3:29])([CH3:28])[CH2:26][CH2:25][CH2:24][C:23]=1[CH3:30])(=O)=O.C(OCC)C>CC(N(C)C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:30][C:23]1[CH2:24][CH2:25][CH2:26][C:27]([CH3:29])([CH3:28])[C:22]=1[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12]

참가 물질

6

반응물 3

HCID 3283Diethyl EtherHCID 110438992,6,6-Trimethylcyclohex-1-en-1-yl trifluoromethanesulfonateHCID 178471365HCID 178471365, 화합물

생성물 1

HCID 71089603Ethyl 9-(2,6,6-trimethylcyclohex-1-en-1-yl)nonanoate수율 53%

시약·촉매·용매 2

HCID 178418397HCID 178418397, 화합물촉매HCID 31374Dimethylacetamide용매

반응 조건

온도
95 °C

실험 절차

To freshly prepared ethyl 9-(bromozincio)nonanoate (37.7 mmol) in dimethylacetamide under nitrogen in a reaction tube was added 2,6,6-trimethylcyclohex-1-en-1-yl trifluoromethanesulfonate (10.8 g, 39.6 mmol) followed by tetrakis(triphenylphosphine)palladium(0) (872 mg, 0.754 mmol). The tube was sealed and the mixture was stirred at 95° C. for 2 h. The reaction mixture was allowed to cool and was then poured into diethyl ether (100 mL). The upper layer was decanted and the lower layer was washed twice with diethyl ether (2×25 mL). The combined ether layers were washed with sat NH4Cl and brine, dried (MgSO4) and concentrated to give crude material (˜12 g). The material was purified by flash chromatography (silica, 0 to 1.5% EtOAc in hexane). The obtained oil was stirred under vacuum for 8 h in order to remove most of the side-product, ethyl nonanoate, and was then purified by a second flash chromatography (silica, 0 to 15% toluene in hexane). The fractions were analyzed by LCMS and GCMS. The purest fractions were collected and concentrated at a temperature below 25° C. to give ethyl 9-(2,6,6-trimethylcyclohex-1-en-1-yl)nonanoate as a colorless oil (6.16 g, 53% yield over two steps). LCMS ESI+m/z 309 [M+H]+; GCMS m/z 308 [M]+.

후처리

  1. customThe tube was sealed
  2. temperatureto cool
  3. customThe upper layer was decanted
  4. washthe lower layer was washed twice with diethyl ether (2×25 mL)
  5. washThe combined ether layers were washed with sat NH4Cl and brine
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. customto give crude material (˜12 g)
  9. customThe material was purified by flash chromatography (silica, 0 to 1.5% EtOAc in hexane)
  10. stirringThe obtained oil was stirred under vacuum for 8 h in order
  11. customto remove most of the side-product, ethyl nonanoate
  12. customwas then purified by a second flash chromatography (silica, 0 to 15% toluene in hexane)
  13. customThe purest fractions were collected
  14. concentrationconcentrated at a temperature below 25° C.

출처 및 근거

ORD 기록
ord-e28793b2fd55434793b4dca98be9eb7a
출처 데이터셋
uspto-grants-2016_07
특허 번호
US09393315B2

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