2-Chloro-1,4-naphthoquinone → 2-Chloro-3-(4-methoxycyclohexyl)-1,4-naphthoquinone

HRID 344774

반응식

HRID 344774 반응식
[Cl:1][C:2]1[C:3](=[O:13])[C:4]2[C:9]([C:10](=[O:12])[CH:11]=1)=[CH:8][CH:7]=[CH:6][CH:5]=2.[CH3:14][O:15][CH:16]1[CH2:21][CH2:20][CH:19](C(O)=O)[CH2:18][CH2:17]1.S1(CCCC1)(=O)=O.S(OOS([O-])(=O)=O)([O-])(=O)=O.[NH4+].[NH4+]>C(#N)C.O.[N+]([O-])([O-])=O.[Ag+]>[Cl:1][C:2]1[C:3](=[O:13])[C:4]2[C:9]([C:10](=[O:12])[C:11]=1[CH:19]1[CH2:20][CH2:21][CH:16]([O:15][CH3:14])[CH2:17][CH2:18]1)=[CH:8][CH:7]=[CH:6][CH:5]=2

참가 물질

8

반응물 4

HCID 138912-Chloro-1,4-naphthoquinoneHCID 31347SulfolaneHCID 62648Ammonium PersulfateHCID 736153Rac-(1r,4r)-4-methoxycyclohexane-1-carboxylic acid

생성물 1

HCID 198048602-Chloro-3-(4-methoxycyclohexyl)-1,4-naphthoquinone

시약·촉매·용매 3

HCID 24470Silver Nitrate촉매HCID 962Water용매2회HCID 6342Acetonitrile용매

반응 조건

온도
65 °C

실험 절차

A mixture of 2-chloro-1,4-naphthoquinone (1.16 g), 4-methoxycyclohexane-1-carboxylic acid (1.3 g) and silver nitrate (0.3 g) were stirred at 65° C. in a mixture of acetonitrile (2.5 ml), sulpholane (7.5 ml) and water (17.5 ml) while a solution of ammonium persulphate (2.3 g) in water (5 ml) was added dropwise during 15 minutes. The reaction mixture was stirred for a further 15 minutes at 65° C., cooled in ice and extracted with ether. The ether extracts were washed with sodium bicarbonate solution, dried and evaporated. The crude product was recrystallised from acetonitrile to yield 2-chloro-3-(4-methoxycyclohexyl)-1,4-naphthoquinone, m.p. 110°-113° C.; the product so obtained (0.9 g) was dissolved in boiling methanol (25 ml) and a solution of potassium hydroxide (0.9 g) in water (9 ml) added dropwise during 10 minutes. The reaction mixture was then refluxed for a further 30 minutes, concentrated hydrochloric acid (5 ml) added dropwise and the mixture cooled in ice. Addition of an equal volume of water precipitated an oil which slowly turned to a semi-solid. Recrystallisation from acetonitrile yielded 2-hydroxy-3-(4-methoxycyclohexyl)-1,4-naphthoquinone, m.p. 152°-155°, shown by n.m.r. to be the pure trans isomer.

후처리

  1. additionwas added dropwise during 15 minutes
  2. temperaturecooled in ice
  3. extractionextracted with ether
  4. washThe ether extracts were washed with sodium bicarbonate solution
  5. customdried
  6. customevaporated
  7. customThe crude product was recrystallised from acetonitrile

출처 및 근거

ORD 기록
ord-611660a3f11d4094bac937779ac45559
출처 데이터셋
uspto-grants-1991_10
특허 번호
US05053432

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