4-Methylbenzenethiol → 2-Cyano-3-(4-methylphenyl)thio-1-cyclopentanone

HRID 2294094ノート

反応式

HRID 2294094 の反応式
[C:1]1([CH3:8])[CH:6]=[CH:5][C:4]([SH:7])=[CH:3][CH:2]=1.C[Al](C)C.[C:13]1(=[O:18])[CH2:17][CH2:16][CH:15]=[CH:14]1.C1(C)C=CC(S([C:28]#[N:29])(=O)=O)=CC=1>C(Cl)Cl.CCCCCC.O1CCCC1.C(OCC)C.CO>[C:28]([CH:14]1[CH:15]([S:7][C:4]2[CH:5]=[CH:6][C:1]([CH3:8])=[CH:2][CH:3]=2)[CH2:16][CH2:17][C:13]1=[O:18])#[N:29]

参加物

10

反応物 4

HCID 78114-MethylbenzenethiolHCID 135882-Cyclopenten-1-oneHCID 87946p-Toluenesulphonyl cyanideHCID 16682925Trimethylaluminum

生成物 1

HCID 104439012-Cyano-3-(4-methylphenyl)thio-1-cyclopentanone

試薬・触媒・溶媒 5

HCID 887Methanol溶媒HCID 3283Diethyl Ether溶媒HCID 6344Dichloromethane溶媒2 回HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒

実験手順

A solution of p-toluenethiol (13.7 g, 0.11 mol) in anhydrous methylene chloride was stirred under cooling with ice in a nitrogen stream, followed by the addition of a solution of trimethylaluminium (7.9 g, 0.11 mol) in hexane. The obtained mixture was stirred for about 20 minutes and cooled in a dry ice-acetone bath, followed by the dropwise addition of a solution of 2-cyclopentenone (8.41 g, 0.10 mol) in methylene chloride. The obtained mixture was further stirred for 80 minutes and diluted with anhydrous tetrahydrofuran, followed by the addition of a solution of p-toluenesulfonyl cyanide (22.9 g, 0.12 mol) in tetrahydrofuran at -50° C. or below. The mixture thus obtained was stirred for about 30 minutes and further in an ice bath for about 60 minutes. About 40 ml of methanol was dropped into the resulting mixture, followed by the addition of diethyl ether. The obtained mixture was washed with aqueous hydrochloric acid, an aqueous solution of sodium hydrogencarbonate and an aqueous solution of common salt, dehydrated and concentrated. The concentrated solution gave 2-cyano-3-(4-methylphenyl)thio-1-cyclopentanone as a crystalline powder by allowing the solution as such to stand or by adding a small amount of an n-hexane/ethyl acetate (1:1) mixture to the solution and allowing the obtained mixture to stand. yield: 22 g

後処理

  1. temperatureunder cooling with ice in a nitrogen stream
  2. temperaturecooled in a dry ice-acetone bath
  3. stirringThe obtained mixture was further stirred for 80 minutes
  4. customThe mixture thus obtained
  5. stirringwas stirred for about 30 minutes and further in an ice bath for about 60 minutes
  6. washThe obtained mixture was washed with aqueous hydrochloric acid
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-3eb5023fd6834266a47dc00943dcc69a
出典データセット
uspto-grants-1997_11
特許番号
US05688800

反応ノート

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