Diiodomethane → Methyl 4-cyano-3-iodo-5-(methylsulfanyl)thiophene-2-carboxylate

HRID 572631ノート

反応式

HRID 572631 の反応式
N[C:2]1[C:6]([C:7]#[N:8])=[C:5]([S:9][CH3:10])[S:4][C:3]=1[C:11]([O:13][CH3:14])=[O:12].[I:15]CI.[N+]([O-])(OCCC(C)C)=O.[N+]([O-])(OCCCCC)=O>C(#N)C>[C:7]([C:6]1[C:2]([I:15])=[C:3]([C:11]([O:13][CH3:14])=[O:12])[S:4][C:5]=1[S:9][CH3:10])#[N:8]

参加物

6

反応物 4

HCID 6346DiiodomethaneHCID 10985Isoamyl nitrateHCID 61250Amyl NitrateHCID 2778604Methyl 3-amino-4-cyano-5-(methylsulfanyl)thiophene-2-carboxylate

生成物 1

HCID 58022844Methyl 4-cyano-3-iodo-5-(methylsulfanyl)thiophene-2-carboxylate収率 57.3%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

反応条件

温度
38 °C

実験手順

To a suspension of methyl 3-amino-4-cyano-5-(methylthio)thiophene-2-carboxylate (4.0 g, 17.5 mmol) in acetonitrile (20 mL) was added diiodomethane (4.94 mL, 61.3 mmol). The reaction mixture was heated at 38° C. Isoamyl nitrate (5.13 g, 43.8 mmol) was added dropwise over five minutes. After the addition of amyl nitrate, the reaction mixture was allowed to cool to room temperature and stirred for two hours. The reaction mixture was cooled in an ice bath and hexanes (20 mL) were added. The resultant precipitate was filtered and washed with a solution of 90% hexanes in acetonitrile (10 mL), 75% hexanes in diethyl ether (10 mL) and 100% hexanes (20 mL) to give methyl 4-cyano-3-iodo-5-(methylsulfanyl)thiophene-2-carboxylate (3.4 g, 57%) as a light orange solid. 1H NMR (400 MHz, CDCl3) δ: 3.91 (s, 3H), 2.70 (s, 3H)

後処理

  1. temperatureto cool to room temperature
  2. temperatureThe reaction mixture was cooled in an ice bath
  3. filtrationThe resultant precipitate was filtered
  4. washwashed with a solution of 90% hexanes in acetonitrile (10 mL), 75% hexanes in diethyl ether (10 mL)

出典と根拠

ORDレコード
ord-4d374c4be201472eb2bff1353af90c0f
出典データセット
uspto-grants-2015_05
特許番号
US09029411B2

反応ノート

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