Dimethylformamide → {[3-(1,3-Dioxolan-2-yl)phenyl]ethynyl}-(trimethyl)silane

HRID 30549

Reaction equation

[C:1]([Si:3]([CH3:6])([CH3:5])[CH3:4])#[CH:2].Br[C:8]1[CH:9]=[C:10]([CH:14]2[O:18][CH2:17][CH2:16][O:15]2)[CH:11]=[CH:12][CH:13]=1.CN(C)C=O.C(N(CC)CC)C>[Cu](I)I.O>[O:15]1[CH2:16][CH2:17][O:18][CH:14]1[C:10]1[CH:9]=[C:8]([C:2]#[C:1][Si:3]([CH3:6])([CH3:5])[CH3:4])[CH:13]=[CH:12][CH:11]=1

Participants

Conditions

Temperature: 60 °C

Procedure

A mixture of ethynyl(trimethyl)silane (36 g, 367 mmol), 2-(3-bromophenyl)-1,3-dioxolane (78 g, 342 mmol), N,N-dimethylformamide (400 mL), and triethylamine (1.1 81 mL, mmol) was bubbled with anhydrous argon for 5 minutes, treated with copper iodide (0.94 g, 4.96 mmol) and dichlorobis(triphenylphosphine) palladium(II) (7.7 g, 11.01 mmol), stirred at 60° C. for 3 hours, cooled to room temperature, poured into water and extracted with ethyl ether. The organic extracts were combined, dried over MgSO4 and concentrated in vacuo to give {[3-(1,3-dioxolan-2-yl)phenyl]ethynyl}-(trimethyl)silane as a yellow oil (63 g, 256 mmol). The yellow oil was dissolved in MeOH (600 mL) and CH2Cl2 (600 mL), treated with cesium carbonate (91.8 g, 281.6 mmol), stirred at room temperature for 10 h, poured into water and extracted with ethyl ether. The ether extracts were combined, dried over MgSO4, concentrated in vacuo and distilled to give 2-(3-ethynylphenyl)-1,3-dioxolane as a yellow oil (42 g, 71% yield), MS m/e M+ 174; 1H NMR (400 MHz, DMSO-d6) 3.9-4.05 (m, 4H), 4.15 (s, 1H), 5.7 (s, 1H), 7.35-7.45 (m, 4H).

Workup

customwas bubbled with anhydrous argon for 5 minutes
temperaturecooled to room temperature
extractionextracted with ethyl ether
dry with materialdried over MgSO4
concentrationconcentrated in vacuo

Sources & evidence

ORD record: ord-edf0b5c159e345ddb1cb5a2483a44d0c
Source dataset: uspto-grants-2008_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07423158B2

Linked notes

Loading…