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Triphenylphosphine → 2,6,6-Trimethyl-2-cyclohexen-1-one

HRID 371516
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HRID 371516 반응식
[CH3:1][C:2]12[O:8][CH:7]1[CH2:6][CH2:5][C:4]([CH3:10])([CH3:9])[C:3]2=[O:11].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)CCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>>[OH:8][C:7]1[CH2:6][CH2:5][C:4]([CH3:9])([CH3:10])[C:3](=[O:11])[C:2]=1[CH3:1].[CH3:1][C:2]1[C:3](=[O:11])[C:4]([CH3:10])([CH3:9])[CH2:5][CH2:6][CH:7]=1
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

5

반응물 3

HCID 11776TriphenylphosphineHCID 742671,2-Bis(diphenylphosphino)ethaneHCID 144916931,3,3-Trimethyl-7-oxabicyclo[4.1.0]heptan-2-one

생성물 2

HCID 883322,6,6-Trimethyl-2-cyclohexen-1-oneHCID 178431408HCID 178431408, 화합물

실험 절차

15.4 g of 1,3,3-trimethyl-7-oxabicyclo-[4.1.0]heptan-2-one, 1.8 g of triphenylphosphine and 2.76 g of 1,2-bis-(diphenylphosphino)-ethane were placed under argon gasification in a round flask equipped with a thermometer and a reflux condenser and the mixture was treated with 2.0 g of bis-(dibenzylidene acetone)palladium(O). The reaction vessel was then immersed in an oil-bath preheated to 150° C. and the reaction mixture was stirred at this temperature with a magnetic stirrer for 1 hour under continued argon gasification. A gas-chromatographical analysis of the mixture obtained without an internal standard gave peaks for 3-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-one (81.9 area %) and 2,6,6-trimethyl-2-cyclohexen-1-one (18 area %). For the working-up, the reaction mixture, cooled to room temperature, was taken up in 20 ml of ethyl acetate and filtered over silica gel in a sintered glass suction filter. The content of the suction filter was rinsed three times with 150 ml of ethyl acetate each time. The filtrate was evaporated to constant weight in a rotary evaporator under a water-jet vacuum at a bath temperature of 40° C. The residue (21.5 g of a yellowish oil) was dissolved in 100 ml of diethyl ether and the solution was added to a separating funnel S1. Two further separating funnels S2 and S3 were each charged with 100 ml of diethyl ether. Then, three 150 ml portions of 3N sodium hydroxide solution were passed in succession and with good intermixing through the three extraction vessels S1 -S3. The ether phases were discarded. The combined alkaline extracts were acidified cautiously (pH about 1) with about 300 ml of concentrated hydrochloric acid while cooling with ice and then saturated with 500 g of sodium chloride while stirring. Three separating funnels S4 -S6 were each charged with 200 ml of ethyl acetate. Thereafter, the aqueous product solution and subsequently three 150 ml portions of saturated sodium chloride solution were passed in succession and with good intermixing through the three extraction vessels S4 -S6. The combined organic phases were dried over sodium sulphate. The drying agent was filtered off under suction and rinsed on the suction filter twice with 100 ml of ethyl acetate each time. The filtrate was evaporated in a rotary evaporator under a water-jet vacuum at a bath temperature of 40° C. and the residue was dried in a high vacuum. There were obtained 10.1 g (65.6%) of 3-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-one in the form of colourless crystals with a purity of 99.6%: m.p. 112°-114° C. after recrystallization from diisopropyl ether.

후처리

  1. customequipped with a thermometer and a reflux condenser
  2. customThe reaction vessel was then immersed in an oil-bath
  3. custompreheated to 150° C.
  4. customA gas-chromatographical analysis of the mixture obtained without an internal

출처 및 근거

ORD 기록
ord-5ca78f863f54468193fea174ba7c736a
출처 데이터셋
uspto-grants-1985_07
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US04532358

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