tert-Butyl acrylate → Tert-butyl 3-(4-cyano-3-methylphenyl)acrylate

HRID 1820949Notes

Reaction equation

Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([CH3:10])[CH:3]=1.[C:11]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])(=[O:14])[CH:12]=[CH2:13].CN(C1CCCCC1)C1CCCCC1.C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1)(C)(C)C>O1CCOCC1>[CH3:10][C:4]1[CH:3]=[C:2]([CH:13]=[CH:12][C:11]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH:9]=[CH:8][C:5]=1[C:6]#[N:7]

Participants

Conditions

Temperature: 70 °C

Procedure

A solution of 10.0 g (51.0 mmol) of 4-bromo-2-methylbenzonitrile in 80 mL of 1,4-dioxane was treated with 7.19 g (56.1 mmol) of tert-butyl acrylate, 10.96 g (56.1 mol) of N-methyldicyclohexylamine, 228 mg (0.76 mol) of 2-(di-tert-butylphosphino) biphenyl, and 396 mg (0.38 mol) of tris(dibenzylideneacetone)dipalladium(0)-chloroforin adduct. The resulting mixture was heated at 70° C. for 16 h and cooled to rt. The reaction mixture was filtered though a filter paper, and the filtrate was concentrated. The crude product was partitioned into four portions. Chromatography on four Biotage 40M cartridges using 19:1 v/v hexanes/EtOAc as the eluant followed by pooling of product fractions afforded 10.0 g of the title compound: 1H NMR (500 MHz, CDCl3) δ 1.55 (s, 9H), 2.58 (s, 3H), 6.44 (d, J=16.0, 1H), 7.41 (d, J=8.0, 1H), 7.45 (s, 1H), 7.53 (d, J=16.0, 1H), 7.61 (d, J=8.0, 1H).

Workup

temperaturecooled to rt
filtrationThe reaction mixture was filtered though a filter paper
concentrationthe filtrate was concentrated
customThe crude product was partitioned into four portions

Sources & evidence

ORD record: ord-6b43ac07abe54773802a453d049c3e15
Source dataset: uspto-grants-2009_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07605171B2

Reaction notes

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