Buchwald–Hartwig amination: 1-Bromo-2-nitrobenzene → 2-Nitrodiphenylamine
85% yield, run at 100 °C, as recorded by experimental reaction archive. The written procedure is below.
The atoms, from reactants to products
What was in the flask
| Role | Species | Formula | Yield |
|---|---|---|---|
| Reactant | 1-Bromo-2-nitrobenzene | C₆H₄BrNO₂ | |
| Reactant | Aniline | C₆H₇N | |
| Reagent | Cesium carbonate | CCs₂O₃ | |
| Catalyst | Binap, (A+-)- | C₄₄H₃₂P₂ | |
| Catalyst | Bis(dibenzylideneacetone)palladium | C₅₁H₄₂O₃Pd₂ | |
| Solvent | Toluene | C₇H₈ | |
| Product | 2-Nitrodiphenylamine | C₁₂H₁₀N₂O₂ | 84.87% |
Conditions
- Temperature
- 100 °C
Yield
- 85% of 2-Nitrodiphenylamine.
Other recorded runs with the same starting material
No other run in the library makes this product. These runs of the same class start from one of the same reactants, which is the nearest company this record has.
- 6-chloro-N-phenylpyridin-2-amine53%
- Methyl 3-anilino-5-bromobenzoate41%
- Methyl 3-anilino-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate2%
- Phenyl-pyridin-3-yl-aminenot recorded
- Methyl 3-anilino-5-bromobenzoate0%
- Phenyl-pyridin-3-yl-aminenot recorded
- Phenyl-pyridin-3-yl-aminenot recorded
- Phenyl-pyridin-3-yl-aminenot recorded
- Phenyl-pyridin-3-yl-aminenot recorded
- Phenyl-pyridin-3-yl-aminenot recorded
- Phenyl-pyridin-3-yl-aminenot recorded
- Phenyl-pyridin-3-yl-aminenot recorded
Procedure
Copied from the source record, unedited
A 200 mL roundbottom flask was charged with 1-bromo-2-nitrobenzene (Alfa Aesar; 2.10 g, 10.40 mmol), Pd2(dba)3 (Aldrich; 119.6 mg, 2.5 mol%), racemic BINAP (Strem; 197.8 mg, 3.1 mol%), and cesium carbonate (Aldrich; 4.87 g, 14.95 mmol). The flask was evacuated and backfilled with N2 (3x), and then anhydrous toluene (20 mL) was added. Aniline (Acros; 1.20 mL, 13.2 mmol) was added followed by additional toluene (30 mL), and the mixture was allowed to stir at room temperature for 5 minutes before being placed in a 100 °C oil bath. After heating overnight, the reaction was allowed to cool and was partitioned between EtOAc and water. The aqueous layer was extracted with EtOAc (2x), and the combined organics were concentrated under reduced pressure. The crude material was purified by silica gel
The source
This record comes from experimental reaction archive (ord-2c85deae4d144af0a18fb548e5e9eabd). Open the source and check it against what is on this page.
experimental reaction archive record ord-2c85deae4d144af0a18fb548e5e9eabd 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.
The pathway is a separate question, kept on separate pages. A mechanism here is the canonical arrow pushing for a class, run on real structures and labelled rule-derived. It is not evidence, and this record is not a mechanism.
Where to next
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