2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → Ethyl 4-cyano-3-(4-methoxyphenyl)-5-morpholin-4-ylthiophene-2-carboxylate

HRID 572606Notes

Reaction equation

[C:1]([C:3]1[CH:4]([C:19]2[CH:24]=[CH:23][C:22]([O:25][CH3:26])=[CH:21][CH:20]=2)[CH:5]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[S:6][C:7]=1[N:8]1[CH2:13][CH2:12][O:11][CH2:10][CH2:9]1)#[N:2].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1(C)C=CC=CC=1>[C:1]([C:3]1[C:4]([C:19]2[CH:20]=[CH:21][C:22]([O:25][CH3:26])=[CH:23][CH:24]=2)=[C:5]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[S:6][C:7]=1[N:8]1[CH2:13][CH2:12][O:11][CH2:10][CH2:9]1)#[N:2]

Participants

Conditions

Temperature: 90 °C

Procedure

To a solution of ethyl 4-cyano-3-(4-methoxyphenyl)-5-morpholin-4-yl-2,3-dihydrothiophene-2-carboxylate (0.168 g, 0.45 mmol) in toluene (5 mL) was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.102 g, 0.45 mmol). The mixture was allowed to stir at 90° C. for 90 min and allowed to cool before filtration through Celite, eluting with toluene. The filtrate was concentrated and the residue was purified by column chromatography. The resulting orange solid was recrystallized from ethyl acetate/40-60 petroleum ether to give ethyl 4-cyano-3-(4-methoxyphenyl)-5-morpholin-4-ylthiophene-2-carboxylate (0.11 g, 66%). LCMS: (FA) ES+ 373. 1H NMR (400 MHz, d6-DMSO) δ: 7.28-7.31 (m, 2H), 6.96-7.00 (m, 2H), 4.06 (q, 2H), 3.81 (s, 3H), 3.76-3.79 (m, 4H), 3.59-3.61 (m, 4H) and 1.08 (t, 3H).

Workup

temperatureto cool before filtration through Celite
washeluting with toluene
concentrationThe filtrate was concentrated
customthe residue was purified by column chromatography
customThe resulting orange solid was recrystallized from ethyl acetate/40-60 petroleum ether

Sources & evidence

ORD record: ord-cccd66a5e0314c4ebaf93aa4cb9e8bd9
Source dataset: uspto-grants-2015_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09029411B2

Reaction notes

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