Buchwald–Hartwig amination: Methyl 3-bromo-5-iodobenzoate → Methyl 3-anilino-5-bromobenzoate
41% yield, run at 110 °C, as recorded by experimental reaction archive. The written procedure is below. One of 2 recorded runs making this product; all of them are compared below.
The atoms, from reactants to products
What was in the flask
| Role | Species | Formula | Yield |
|---|---|---|---|
| Reactant | Methyl 3-bromo-5-iodobenzoate | C₈H₆BrIO₂ | |
| Reactant | Aniline | C₆H₇N | |
| Reagent | Cesium carbonate | CCs₂O₃ | |
| Catalyst | Binap, (A+-)- | C₄₄H₃₂P₂ | |
| Catalyst | Palladium (II) acetate | C₄H₈O₄Pd | |
| Solvent | Toluene | C₇H₈ | |
| Product | Methyl 3-anilino-5-bromobenzoate | C₁₄H₁₂BrNO₂ | 40.51% |
Conditions
- Temperature
- 110 °C
Yield
- 41% of Methyl 3-anilino-5-bromobenzoate.
Every recorded run making this product
2 runs of this class made the same product and differed in what else was in the flask. They are listed from the highest yield down, with this page's run marked.
| Reactants | Catalyst | Reagents | Solvent | Temp. | Time | Yield |
|---|---|---|---|---|---|---|
| Methyl 3-bromo-5-iodobenzoate; Aniline | Binap, (A+-)-; Palladium (II) acetate | Cesium carbonate | Toluene | 110 °C | — | 41% (this run) |
| Methyl 3,5-Dibromobenzoate; Aniline | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Palladium (II) acetate | Cesium carbonate | Toluene | 110 °C | — | 0% |
Procedure
Copied from the source record, unedited
diacetoxypalladium (0.314 g, 1.40 mmol) and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (0.871 g, 1.40 mmol) were added to a degassed mixture of methyl 3-bromo-5-iodobenzoate (4.77 g, 13.99 mmol), aniline (2.55 ml, 13.99 mmol) and cesium carbonate (3.87 g, 11.89 mmol) in toluene (137 ml) under nitrogen. The resulting mixture was stirred at 110 °C for 18 hours. The resulting mixture was evaporated to dryness and the residue was diluted with EtOAc (150 mL), and washed with water (100 mL), the organic layer was dried over MgSO4, filtered and evaporated to afford crude product. The crude product was purified by flash silica chromatography, elution gradient 0 to 15% EtOAc in heptane. Pure fractions were evaporated to dryness to afford methyl 3-bromo-5-(phenylamino)benzoate (1.735 g, 40.5 %) as
The source
This record comes from experimental reaction archive (ord-6368febfb34940ba908b28066b8fb22a). Open the source and check it against what is on this page.
experimental reaction archive record ord-6368febfb34940ba908b28066b8fb22a from dataset "750 AstraZeneca ELN dataset" (url: https://chemrxiv.org/engage/chemrxiv/article-details/60c9e3f37792a23bfdb2d471). No atom mapping is provided by the source.
How to read this record
This is one experiment, not a rule. It says that on one occasion these species were combined under these conditions and this came out. It does not say the reaction will give the same result on your substrate, and nothing on the page has been generalised into a claim that it would.
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