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

HRID 572631노트

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HRID 572631 반응식
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]

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 6342Acetonitrile용매

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온도
38 °C

실험 절차

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)

후처리

  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)

출처 및 근거

ORD 기록
ord-4d374c4be201472eb2bff1353af90c0f
출처 데이터셋
uspto-grants-2015_05
특허 번호
US09029411B2

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