HCID 68524438, compound → 3-(4-Iodophenyl)-4-cyano-5-ethyl-thiophene-2-carboxylic acid ethyl ester

HRID 1990079Notes

Reaction equation

C([Zn][CH2:4][CH3:5])C.[CH2:6]([O:8][C:9]([C:11]1[S:12][C:13](SC)=[C:14]([C:23]#[N:24])[C:15]=1[C:16]1[CH:21]=[CH:20][C:19]([I:22])=[CH:18][CH:17]=1)=[O:10])[CH3:7]>C1COCC1.[Ni](Cl)Cl.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:6]([O:8][C:9]([C:11]1[S:12][C:13]([CH2:4][CH3:5])=[C:14]([C:23]#[N:24])[C:15]=1[C:16]1[CH:21]=[CH:20][C:19]([I:22])=[CH:18][CH:17]=1)=[O:10])[CH3:7]

Participants

Conditions

Temperature: 60 °C

Procedure

Add dropwise diethylzinc (1.0M in hexanes, 7 ml, 6.99 mmol, 3 eq) to a mechanically stirring suspension of 4-cyano-3-(4-iodo-phenyl)-5-methylsulfanyl-thiophene-2-carboxylic acid ethyl ester (1 gr, 2.33 mmol) and 1,3-bis-(diphenylphosphino)propane nickel (II) chloride (24 mg, 0.0466 mmol, 0.02 eq) in dry THF (12 ml) and heat the resulting mixture 60° C. for 30 min. Cool the reaction to room temperature and remove solvents in vacuo. Purify the solid by chromatography on silica gel (eluting with 10-80% Ethyl acetate/hexane) to provide the title compound in 60% yield: Mass spectrum (EI+): m/z 412 (M++1); 1H NMR (CDCl3, 200 MHz): δ 7.72 (d, 2H, J=8.5); 7.05 (d, 2H, J=8.5); 4.14 (q, 2H, J=7.2); 3.01 (q, 2H, J=7.2); 1.36 (t, 3H, J=7.5); 1.17 (t, 3H, J=7.2).

Workup

temperatureCool
customthe reaction to room temperature
customremove solvents in vacuo
customPurify the solid by chromatography on silica gel (eluting with 10-80% Ethyl acetate/hexane)

Sources & evidence

ORD record: ord-342028d74a334548af1b64c7965f58d5
Source dataset: uspto-grants-2010_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07642361B2

Reaction notes

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