4-Chlorobenzonitrile → 4-Nitrobenzonitrile

In a nitrogen-atmosphere glovebox, a microwave vial equipped with a magnetic stir bar was charged with 4-chlorobenzonitrile (100 mg, 0.727 mmol, 1 equivalent), sodium nitrite (100 mg, 1.45 mmol, 2 equivalents), tris(dibenzylideneacetone)dipalladium(0) (Pd2dba3) (6.7 mg, 0.00727 mmol, 0.01 equivalents) and phosphine ligand (0.017 mmol, 0.024 equivalents). The solids were slurried in t-butyl alcohol (1.3 mL) before adding tris[2-(2-methoxyethoxy)ethyl]amine (TDA-1) (12 μL, 0.036 mmol, 0.05 equivalents). The vial was sealed with a crimp top and placed in a heating block at 130° C. After 24 hours, the reaction vial was cooled to room temperature and brought out of the glovebox. The reaction solution was diluted with tetrahydrofuran (2 mL) and filtered through a pad of diatomaceous earth into a tared 125-mL Erlenmeyer flask. The vial was rinsed with tetrahydrofuran (3×1 mL) before the filter cake was washed with tetrahydrofuran (2 mL). A wt % analysis was performed on the filtrate and an assay yield was measured (literature reference: Fors B P, et al. J. Am. Chem. Soc. 2009; 131: 12898-12899).

1. customIn a nitrogen-atmosphere glovebox, a microwave vial equipped with a magnetic stir bar
2. customThe vial was sealed with a crimp top
3. customplaced in a heating block at 130° C
4. customthe reaction
5. filtrationfiltered through a pad of diatomaceous earth into a tared 125-mL Erlenmeyer flask
6. washThe vial was rinsed with tetrahydrofuran (3×1 mL) before the filter cake
7. washwas washed with tetrahydrofuran (2 mL)
8. customan assay yield

ORD record

ord-fe3998161a0247b085c487b235e08dfe

Source dataset

uspto-grants-2014_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08841487B2