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

HRID 344774

反応式

HRID 344774 の反応式
[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

参加物

8

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 24470Silver Nitrate触媒HCID 962Water溶媒2 回HCID 6342Acetonitrile溶媒

反応条件

温度
65 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-611660a3f11d4094bac937779ac45559
出典データセット
uspto-grants-1991_10
特許番号
US05053432

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