Triphenylphosphine → HCID 86671497, compound

HRID 2043374Notes

Reaction equation

Br[C:2]1[C:3]([C:7]2[CH:14]=[CH:13][C:10]([C:11]#[N:12])=[CH:9][C:8]=2[CH3:15])=[CH:4][S:5][CH:6]=1.C(P(=[CH:37][C:38]([O:40][CH2:41][CH3:42])=[O:39])=O)(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH:43]1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>CN(C=O)C.CCOC(C)=O.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:11]([C:10]1[CH:13]=[CH:14][C:7]([C:3]2[C:2](/[CH:43]=[CH:37]/[C:38]([O:40][CH2:41][CH3:42])=[O:39])=[CH:6][S:5][CH:4]=2)=[C:8]([CH3:15])[CH:9]=1)#[N:12]

Participants

Conditions

Temperature: 150 °C

Procedure

To a solution of 4-(4-bromothiophen-3-yl)-3-methylbenzonitrile (2.4 g, 8.7 mmol) and ethyl 2-(tritylphosphinylidene)acetate (2.6 g, 26 mmol) in DMF (10 mL) was added Pd(OAc)2 (194 mg, 0.87 mmol) and PPh3 (228 mg, 0.87 mmol), and the mixture was stirred at 150° C. under nitrogen overnight. The mixture was diluted with EtOAc. The organic layer was washed with water and brine, dried over Na2SO4, concentrated in vacuo, and purified on silica gel column (PE: EtOAc=20:1) to give (E)-ethyl 3-(4-(4-cyano-2-methylphenyl)thiophen-3-yl)acrylate (Scheme III, 14, X1=4-cyano-2-methylphenyl) (1 g, yield 39%) as yellow oil. 1H NMR (CD3OD 400 MHz): δ 8.03 (d, J=2.8 Hz, 1H), 7.71 (s, 1H), 7.64 (d, J=7.6 Hz, 1H), 7.39-7.34 (m, 2H), 7.28 (d, J=16 Hz, 1H), 6.06 (d, J=16.4 Hz, 1H), 4.15 (q, J=7.2 Hz, 2H), 2.15 (s, 3H), 1.24 (t, J=7.2 Hz, 3H).

Workup

washThe organic layer was washed with water and brine
dry with materialdried over Na2SO4
concentrationconcentrated in vacuo
custompurified on silica gel column (PE: EtOAc=20:1)

Sources & evidence

ORD record: ord-dafe27e2f16b4c2d8ef05ebd4f0f3276
Source dataset: uspto-grants-2013_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08586624B2

Reaction notes

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