Trimethylsilylacetylene → Cyclopropanecarboxylic acid, 1-[4-amino-3-[2-(trimethylsilyl)ethynyl]phenyl]-, methyl ester

HRID 1908372Notes

Reaction equation

[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([C:11]([O:13][CH3:14])=[O:12])[CH2:10][CH2:9]2)=[CH:4][C:3]=1Br.[C:16]([Si:18]([CH3:21])([CH3:20])[CH3:19])#[CH:17]>CCN(CC)CC.CN(C1C=CN=CC=1)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([C:11]([O:13][CH3:14])=[O:12])[CH2:10][CH2:9]2)=[CH:4][C:3]=1[C:17]#[C:16][Si:18]([CH3:21])([CH3:20])[CH3:19]

Participants

Conditions

Temperature: 70 °C

Procedure

To a degassed solution of methyl 1-(4-amino-3-bromophenyl)cyclopropane carboxylate (8 g, 0.03 mol) in Et3N (100 mL) was added ethynyl-trimethyl-silane (30 g, 0.3 mol), DMAP (5% mol) and Pd(PPh3)2Cl2 (5% mol) under N2. The mixture was refluxed at 70° C. overnight. The insoluble solid was filtered off and washed with EtOAc (100 mL×3). The filtrate was evaporated under reduced pressure to give a residue, which was purified by chromatography column on silica gel (petroleum ether/ethyl acetate=20:1) to give methyl 1-(4-amino-3-((trimethylsilyl)ethynyl)phenyl)cyclopropanecarboxylate (4.8 g, 56%). 1H NMR (300 MHz, CDCl3) δ7.27 (s, 1H), 7.10 (dd, J=2.1, 8.4 Hz, 1H), 6.64 (d, J=8.4 Hz, 1H), 3.60 (s, 3H), 1.55-1.51 (m, 2H), 1.12-1.09 (m, 2H), 0.24 (s, 9H).

Workup

filtrationThe insoluble solid was filtered off
washwashed with EtOAc (100 mL×3)
customThe filtrate was evaporated under reduced pressure
customto give a residue, which
customwas purified by chromatography column on silica gel (petroleum ether/ethyl acetate=20:1)

Sources & evidence

ORD record: ord-1964080c95f6409a93515bed5445063e
Source dataset: uspto-grants-2013_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08598181B2

Reaction notes

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