2-Methylbenzenesulfonic acid → 6-Acetoxy-5-hexadecanolide

HRID 2122098노트

반응식

HRID 2122098 반응식
OO.[C:3](#N)[CH3:4].[C@@H]12O[C@@H]1CCCC2.Cl[C:14]1[CH:15]=[C:16]([CH:21]=[CH:22][CH:23]=1)[C:17]([O:19]O)=[O:18].[C:24]1([CH3:34])[C:25](S(O)(=O)=O)=[CH:26][CH:27]=[CH:28][CH:29]=1.[C:35]([O:38]C(=O)C)(=[O:37])[CH3:36]>[OH-].[K+].C(O)(C)C.C(N(CC)CC)C.C1(C)C=CC=CC=1>[C:35]([O:38][C@@H:22]([CH2:21][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:34][CH2:3][CH3:4])[C@@H:23]1[O:18][C:17](=[O:19])[CH2:16][CH2:15][CH2:14]1)(=[O:37])[CH3:36]

참가 물질

10

반응물 5

HCID 69252-Methylbenzenesulfonic acidHCID 7918Acetic AnhydrideHCID 70297m-Chloroperbenzoic acidHCID 637978Cyclohexene oxideHCID 86584456HCID 86584456, 화합물

생성물 1

HCID 2059926-Acetoxy-5-hexadecanolide

시약·촉매·용매 4

HCID 1140Toluene용매HCID 3776Isopropanol용매HCID 8471Triethylamine용매HCID 14797Potassium Hydroxide용매

반응 조건

온도
100 °C

실험 절차

The metathesis product from above was oxidized to the epoxide as described by Bach et al. in “Epoxidation of Olefins by Hydrogen peroxide-Acetonitrile: cis-Cyclohexene Oxide”, Organic synthesis collective Volume Vii, 1990, p. 126 or with m-chloroperoxybenzoic acid. The glyceride esters were hydrolyzed and the epoxide opened to the diol by warming the epoxide in 2 M KOH and 20 mL of isopropyl alcohol (IPA) to 60° C. for six hours. The solution was concentrated and washed with 50 mL of 1 M HCl. The organic phase was dried with anhydrous sodium sulfate, filtered and used in the next reaction without further purification. Lactonization was accomplished using the following procedure: the crude diol (2.9 g, 9.0 mmol) was dissolved into 50 mL of anhydrous toluene containing 50 mg of toluenesulfonic acid and heated to 100° C. for six hours. The mixture was cooled to room temp and washed with 50 mL of NaHCO3 saturated water. The organic phase was dried with anhydrous sodium sulfate, filtered and used in the next reaction without further purification. The dried solution was acetylated with 1.8 g (0.018 mmol) acetic anhydride and 5 mL of triethylamine. The solution was stirred at room temp overnight. The reaction was worked up by washing with 50 mL of 1 M HCl and 50 mL wash of NaHCO3 saturated water. The organic phase was dried with anhydrous sodium sulfate, filtered, concentrated and to yield (5R,6S)-6-acetoxy-5-hexadecanolide and its stereoisomers, and then purified by column chromatography.

후처리

  1. concentrationThe solution was concentrated
  2. washwashed with 50 mL of 1 M HCl
  3. dry with materialThe organic phase was dried with anhydrous sodium sulfate
  4. filtrationfiltered
  5. customused in the next reaction without further purification
  6. temperatureThe mixture was cooled to room temp
  7. washwashed with 50 mL of NaHCO3 saturated water
  8. dry with materialThe organic phase was dried with anhydrous sodium sulfate
  9. filtrationfiltered
  10. customused in the next reaction without further purification
  11. washby washing with 50 mL of 1 M HCl and 50 mL
  12. washwash of NaHCO3 saturated water
  13. dry with materialThe organic phase was dried with anhydrous sodium sulfate
  14. filtrationfiltered
  15. concentrationconcentrated

출처 및 근거

ORD 기록
ord-487a33da5071424eba8b476ea950df8f
출처 데이터셋
uspto-grants-2004_02
특허 번호
US06696597B2

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