Buchwald–Hartwig amination: 5-Chloro-2-nitroanisole → Tert-butyl 4-(3-methoxy-4-nitrophenyl)-3-oxopiperazine-1-carboxylate
68% yield, run at 90 °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 | 5-Chloro-2-nitroanisole | C₇H₆ClNO₃ | |
| Reactant | Tert-butyl 3-oxopiperazine-1-carboxylate | C₉H₁₆N₂O₃ | |
| Reagent | Cesium carbonate | CCs₂O₃ | |
| Catalyst | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) | C₃₉H₃₂OP₂ | |
| Catalyst | Palladium (II) acetate | C₄H₈O₄Pd | |
| Solvent | 1,4-Dioxane | C₄H₈O₂ | |
| Product | Tert-butyl 4-(3-methoxy-4-nitrophenyl)-3-oxopiperazine-1-carboxylate | C₁₆H₂₁N₃O₆ | 68.39% |
Conditions
- Temperature
- 90 °C
Yield
- 68% of Tert-butyl 4-(3-methoxy-4-nitrophenyl)-3-oxopiperazine-1-carboxylate.
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.
| Catalyst | Reagents | Solvent | Temp. | Time | Yield |
|---|---|---|---|---|---|
| 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Bis(dibenzylideneacetone)palladium | Cesium carbonate | 1,4-Dioxane | 90 °C | — | 100% |
| 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Palladium (II) acetate | Cesium carbonate | 1,4-Dioxane | 90 °C | — | 68% (this run) |
Procedure
Copied from the source record, unedited
A mixture of tert-butyl 3-oxopiperazine-1-carboxylate (100 mg, 0.50 mmol), 4-chloro-2-methoxy-1-nitrobenzene (94 mg, 0.50 mmol), cesium carbonate (244 mg, 0.75 mmol), (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (17.34 mg, 0.03 mmol) and diacetoxypalladium (4.48 mg, 0.02 mmol) was dried for 15 min under HV. Degassed dioxane (1,0-1,2 ml) was added and the resulting mixture was stirred at 90°c for 16 hours under inert atmosphere. TLC showed consumption of both SM and new spot (UV active). Reaction combined with EN02378-08 (same TLC profile).LC-MS of crude: EN02378-07-01 Extraction: AE/2M Na2CO3 sol. Purification by chromatography: eluent AE/hexane 20/80 to 60/40. **Isolated: m= 240 mg** ; orange foam. FLA 02378-07-02: 1H NMR, LC-MS: OK. Estimated yield: 68%.
The source
This record comes from experimental reaction archive (ord-dc9ab726462a4f469bd87d2f3adfc402). Open the source and check it against what is on this page.
experimental reaction archive record ord-dc9ab726462a4f469bd87d2f3adfc402 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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