Methyl 2,6-dimethylbenzoate → Methyl 2-(cis-3-hydroxycyclohexyloxymethyl)-6-methylbenzoate

HRID 10381

반응식

HRID 10381 반응식
[C@H:1]1([OH:8])[CH2:6][CH2:5][CH2:4][C@@H:3]([OH:7])[CH2:2]1.CC(C)([O-])C.[K+].Br[CH2:16][C:17]1[CH:26]=[CH:25][CH:24]=[C:23]([CH3:27])[C:18]=1[C:19]([O:21][CH3:22])=[O:20].CC1C=CC=C(C)C=1C(OC)=O>C(COC)OC.C(OC)(C)(C)C.O>[OH:7][C@@H:3]1[CH2:4][CH2:5][CH2:6][C@H:1]([O:8][CH2:16][C:17]2[CH:26]=[CH:25][CH:24]=[C:23]([CH3:27])[C:18]=2[C:19]([O:21][CH3:22])=[O:20])[CH2:2]1

참가 물질

8

반응물 4

HCID 519028Methyl 2,6-dimethylbenzoateHCID 64327411,3-Cyclohexanediol, cis-HCID 10263795Methyl 2-(bromomethyl)-6-methylbenzoateHCID 23665647Potassium tert-butoxide

생성물 1

HCID 69207297Methyl 2-(cis-3-hydroxycyclohexyloxymethyl)-6-methylbenzoate수율 14.2%

시약·촉매·용매 3

HCID 962Water용매HCID 80711,2-Dimethoxyethane용매HCID 15413tert-Butyl methyl ether용매

반응 조건

온도
5 °C

실험 절차

5 g (42.8 mmol) of cis-1,3-cyclohexanediol were dissolved in 50 ml of dimethoxyethane (DME), admixed at 20–23° C. with 3.36 g (30 mmol) of potassium tert-butoxide (KOtBu) and stirred. After about 30 minutes, the mixture is cooled to 5° C. and 3.7 g (approx. 50%) of methyl 2-bromomethyl-6-methylbenzoate, which may be prepared, for example, by methanolyzing the acid bromide (2-bromomethyl-6-methylbenzoyl bromide) or by brominating methyl 2,6-dimethylbenzoate, are added dropwise. The mixture is stirred at 5–10° C. for 1 h and then at 20–23° C. overnight. Water and methyl tert-butyl ether (MTBE) are added, the mixture is stirred vigorously, the phases are separated, the aqueous phase is washed once more with MTBE and the combined organic phases are concentrated under reduced pressure. The residue is chromatographed on silica gel (1:1 ethyl acetate/n-heptane). 600 mg of the desired compound are obtained as a light yellow oil, 1H NMR (CDCl3), δ =1.27 (m, 1H), 1.45 (m, 1H), 1.55 (m, 1H), 1.74 (m, 1H), 1.83 (m, 1H), 2.05 (m, 1H), 2.34 (s, 3H), 3.47 (m, 1H), 3.72 (m, 1H), 3.91 (s, 3H), 4.58 (dd, 2H), 7.15 (d, 1H), 7.20 (d, 2H), 7.27 (m, 1H).

후처리

  1. additionare added dropwise
  2. stirringThe mixture is stirred at 5–10° C. for 1 h
  3. customat 20–23° C.
  4. customovernight
  5. stirringthe mixture is stirred vigorously
  6. customthe phases are separated
  7. washthe aqueous phase is washed once more with MTBE
  8. concentrationthe combined organic phases are concentrated under reduced pressure
  9. customThe residue is chromatographed on silica gel (1:1 ethyl acetate/n-heptane)

출처 및 근거

ORD 기록
ord-39f6c4bd24b6470583618751582d3aed
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07094795B2

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