(Trimethylsilyl)acetonitrile → HCID 86709946, compound

Temperature

90 °C

To a screw-capped vial containing 2-(3,5-dibromophenyl)-1,3-dioxolane (4.g, 12.99 mmol), Xantphos (0.15 g, 0.26 mmol), Pd2(dba)3 in anhydrous DMF (5.0 mL) was added trimethylsilyl acetonitrile (2.20 mL, 16.07 mmol) and the reaction mixture was degassed with nitrogen for 15 min to give an orange-red suspension. To the above mixture was added ZnF2 under nitrogen atmosphere and the vial sealed with a cap containing a PTFE/silicone septum under nitrogen. The heterogeneous mixture was heated with stirring at 90° C. in an oil bath to give an olive green suspension. The reaction mixture was let stirred at 90° C. for 22 h to give a dark brown suspension/solution. The reaction mixture cooled to room temperature and diluted with diethyl ether (100 mL). The resulting solution was washed with water (2×75 mL). The organic layer was removed and evaporated in vacuo and the residue was dissolved in ethyl acetate (50 mL), dried over anhydrous Na2SO4, filtered and evaporated in vacuo to afford an orange-red viscous liquid (3.65 g). Purification of the crude product by Silica-gel flash chromatography on silica gel column and elution with 10-80% ethyl acetate in hexanes afforded the desired product as a pale yellow viscous liquid (1.95 g). LC-MS analysis of the liquid shows the desired product's mass: m/z 268 (79BrM+H), m/z 270 (81BrM+H), m/z 290 (79BrM+Na), and m/z 292 (81BrM+Na); GC-MS (EI mode) analysis also shows the desired product's mass: m/z 266 (79BrM+) and m/z 268 (81BrM+), Calcd for C11H10BrNO2: 268.11. 1H NMR (400 MHz, CDCl3): δ 3.72 (s, 2H, —CH2CN), 3.98-4.05 (M, 2H, —CH2—O—), 4.06-4.13 (M, 2H, —CH2—O—), 5.75 (s, 1H, O—CH—O), 7.36 (s, 1H), 7.47 (s, 1H), 7.58 (s, 1H). 1H NMR spectrum of the liquid was consistent with the suggested structure of the product.

1. customthe reaction mixture was degassed with nitrogen for 15 min
2. customto give an orange-red suspension
3. customthe vial sealed with a cap
4. temperatureThe heterogeneous mixture was heated
5. customto give an olive green suspension
6. stirringThe reaction mixture was let stirred at 90° C. for 22 h
7. customto give a dark brown suspension/solution
8. temperatureThe reaction mixture cooled to room temperature
9. washThe resulting solution was washed with water (2×75 mL)
10. customThe organic layer was removed
11. customevaporated in vacuo
12. dissolutionthe residue was dissolved in ethyl acetate (50 mL)
13. dry with materialdried over anhydrous Na2SO4
14. filtrationfiltered
15. customevaporated in vacuo

ORD record

ord-3dba37d9a5aa45de9d9dc5b424300921

Source dataset

uspto-grants-2015_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09085606B2