Diethyl Ether → beta-Ethenylidene-2-thiopeneethanamine

HRID 1195825ノート

反応式

HRID 1195825 の反応式
CC[O:3]CC.C[Si](C)(C)[N:8]([CH2:13][C:14]#[C:15][CH2:16]OC)[Si](C)(C)C.[S:21]1[CH:25]=[CH:24][CH:23]=[C:22]1[Mg]Br.[NH4+].[OH-]>Cl[Ni]Cl.C(OC(=O)C)C>[NH4+:8].[OH-:3].[C:15](=[C:14]([C:22]1[S:21][CH:25]=[CH:24][CH:23]=1)[CH2:13][NH2:8])=[CH2:16]

参加物

8

反応物 4

HCID 3283Diethyl EtherHCID 14923Ammonium HydroxideHCID 13161121N,N-bis(trimethylsilyl)-4-methoxy-2-butynylamineHCID 178418438HCID 178418438、化合物

生成物 2

HCID 14923Ammonium HydroxideHCID 14518110beta-Ethenylidene-2-thiopeneethanamine収率 87%

試薬・触媒・溶媒 2

HCID 24385Nickel Dichloride触媒HCID 8857Ethyl Acetate溶媒

実験手順

NiCl2 (dppp) catalyst (170 mg; 3M %) was added to dry ether (30 ml) in a 100 ml 3-necked flask with mechanical stirrer, thermometer and nitrogen bubbler. III (2.47 g, 10.2 mM) was added via syringe with stirring and immediately thereafter 3M thienylmagnesium bromide (7 ml, 21 mM) was added via syringe. After stirring at room temperature for 20 hours the reaction was complete as shown by G C analysis. The silylated product was isolated by shaking with dilute NH4OH and extraction into ethylacetate (three times, each into 100 ml). After drying over K2CO3 and concentration, 2.68 g crude product was obtained. Purification and desilylation by flash chromatography (300 g silica gel, eluted with CHCl3, then CHCl3 :MeOH:conc. NH4OH 100:10:1) gave 1.22 g (87%) of the desired product as a light tan oil after drying under high vacuum.

後処理

  1. stirringAfter stirring at room temperature for 20 hours the reaction
  2. customThe silylated product was isolated
  3. dry with materialAfter drying over K2CO3 and concentration
  4. custom2.68 g crude product was obtained
  5. customPurification and desilylation by flash chromatography (300 g silica gel
  6. washeluted with CHCl3

出典と根拠

ORDレコード
ord-b6098608db7a4f1a9b8de21ce01d3dc0
出典データセット
uspto-grants-1992_05
特許番号
US05112852

反応ノート

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