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

HRID 444404ノート

反応式

HRID 444404 の反応式
[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

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 3007855Zincchloride触媒HCID 6212Chloroform溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-a217f4ac4670401bbed60aaadabf7a6d
出典データセット
uspto-grants-1981_04
特許番号
US04264510

反応ノート

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