Tributylamine → N,N-Diisopropyl-3-(2-thienyl)propenamide

HRID 428343

Reaction equation

Br[C:2]1[S:3][CH:4]=[CH:5][CH:6]=1.[CH:7]([N:10]([CH:15]([CH3:17])[CH3:16])[C:11](=[O:14])[CH:12]=[CH2:13])([CH3:9])[CH3:8].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CCCC)CCCC)CCC>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C(OCC)C.CN(C=O)C>[CH:15]([N:10]([CH:7]([CH3:9])[CH3:8])[C:11](=[O:14])[CH:12]=[CH:13][C:2]1[S:3][CH:4]=[CH:5][CH:6]=1)([CH3:17])[CH3:16]

Participants

Conditions

Temperature: 130 °C

Procedure

2-Bromothiophene (2.28 g, 14.0 mmol), N,N-diisopropylacrylamide (1.55 g, 10.0 mmol), palladium(II)acetate (34 mg, 0.15 mmol), tri-o-tolylphosphine (183 mg, 0.6 mmol), tri-n-butyl amine (2.04 g, 11.0 mmol) and dry DMF (5 mL) were mixed under a N2-atmosphere. The mixture was heated to 130° C. for 9 hours. Diethyl ether and H2O was added to the somewhat cooled mixture. The aqueous phase was extracted twice with diethyl ether. The combined organic phases were washed twice with 2 M HCl, once with water, once with brine, and dried (MgSO4), and the solvent was then evaporated. The crude product was chromatographed on silica (petroleum ether-ethyl acetate 4:1), affording a yellow oil, 1.58 g (66%): 1H NMR (CDCl3) 67 1.35 (br, 12H), 3.9 (br, 1H), 4.1 (br 1H), 6.65 (d, 1H), 7.00-7.30 (m, 3H), 7.72 (d, 1H).

Workup

extractionThe aqueous phase was extracted twice with diethyl ether
washThe combined organic phases were washed twice with 2 M HCl, once with water, once with brine
dry with materialdried (MgSO4)
customthe solvent was then evaporated
customThe crude product was chromatographed on silica (petroleum ether-ethyl acetate 4:1)
customaffording a yellow oil, 1.58 g (66%)

Sources & evidence

ORD record: ord-bd6dd6ada6b640f69bd0ffc231d41bb5
Source dataset: uspto-grants-2001_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06313132B1

Linked notes

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