Hydroquinone → Methyl (1,2,3,4,5,6,7,8-octahydro-2,3-dimethylene-1,4-epoxynaphthalen-6-yl) ketone

HRID 444404노트

반응식

HRID 444404 반응식
[CH2:1]=[C:2]1[C:7](=[CH2:8])[CH:6]2[O:9][CH:3]1[C:4](=[CH2:11])[C:5]2=[CH2:10].[CH:12]([C:14]([CH3:16])=[O:15])=[CH2:13].C1(C=CC(O)=CC=1)O>[Cl-].[Zn+2].[Cl-].C(Cl)(Cl)Cl>[CH2:11]=[C:4]1[C:5](=[CH2:10])[CH:6]2[O:9][CH:3]1[C:2]1[CH2:1][CH2:13][CH:12]([C:14]([CH3:16])=[O:15])[CH2:8][C:7]=12

참가 물질

6

반응물 3

HCID 785HydroquinoneHCID 6570Methyl vinyl ketoneHCID 1429962,3,5,6-Tetramethylidene-7-oxabicyclo[2.2.1]heptane

생성물 1

HCID 54365753Methyl (1,2,3,4,5,6,7,8-octahydro-2,3-dimethylene-1,4-epoxynaphthalen-6-yl) ketone수율 86%

시약·촉매·용매 2

HCID 3007855Zincchloride촉매HCID 6212Chloroform용매

실험 절차

A mixture of 11.4 g of 2,3,5,6-tetramethylene-7-oxabicyclo[2.2.1]heptane, 2 g of anhydrous zinc chloride, 30 ml of methyl vinyl ketone and 75 ml of chloroform, containing 10 mg of hydroquinone, was stirred at room temperature for 20 hours under nitrogen. The mixture was concentrated under reduced pressure (ca 15 mmHg, room temperature) and rapidly eluted with methylene chloride/ethyl acetate (2:1) on a short column filled with 18 g of SiO2 (70-230 mesh). The first fractions contained methyl (1,2,3,4,5,6,7,8-octahydro-2,3-dimethylene-1,4-epoxynaphthalene-6-yl) ketone and unreacted methyl vinyl ketone. After the addition of 5 mg of hydroquinone, the mixture was concentrated to dryness at room temperature under reduced pressure (1 mmHg) until the methyl vinyl ketone had been completely removed. There were obtained 14.5 g (86%) of methyl (1,2,3,4,5,6,7,8-octahydro-2,3-dimethylene-1,4-epoxynaphthalen-6-yl) ketone in sufficient purity for the next step.

후처리

  1. concentrationThe mixture was concentrated under reduced pressure (ca 15 mmHg, room temperature)
  2. washrapidly eluted with methylene chloride/ethyl acetate (2:1) on a short column
  3. additionfilled with 18 g of SiO2 (70-230 mesh)
  4. additionAfter the addition of 5 mg of hydroquinone
  5. concentrationthe mixture was concentrated to dryness at room temperature under reduced pressure (1 mmHg) until the methyl vinyl ketone
  6. customhad been completely removed

출처 및 근거

ORD 기록
ord-a217f4ac4670401bbed60aaadabf7a6d
출처 데이터셋
uspto-grants-1981_04
특허 번호
US04264510

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