Diiodomethane → HCID 58022844, compound

HRID 572631Notes

Reaction equation

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]

Participants

Conditions

Temperature: 38 °C

Procedure

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)

Workup

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

Sources & evidence

ORD record: ord-4d374c4be201472eb2bff1353af90c0f
Source dataset: uspto-grants-2015_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09029411B2

Reaction notes

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