Buchwald–Hartwig amination: 2,4-Dichloropyridine → N-(4-chloro-2-pyridinyl)-1,3-oxazol-2-amine
0% yield, run at 160 °C, as recorded by experimental reaction archive. The written procedure is below. One of 11 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 | 2,4-Dichloropyridine | C₅H₃Cl₂N | |
| Reactant | 2-Aminooxazole | C₃H₄N₂O | |
| Reagent | Potassium Phosphate, Tribasic | K₃O₄P | |
| Catalyst | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) | C₃₉H₃₂OP₂ | |
| Catalyst | Bis(dibenzylideneacetone)palladium | C₅₁H₄₂O₃Pd₂ | |
| Solvent | 1,4-Dioxane | C₄H₈O₂ | |
| Product | N-(4-chloro-2-pyridinyl)-1,3-oxazol-2-amine | C₈H₆ClN₃O | 0% |
Conditions
- Temperature
- 160 °C
Yield
- 0% of N-(4-chloro-2-pyridinyl)-1,3-oxazol-2-amine.
Every recorded run making this product
11 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 |
|---|---|---|---|---|---|---|
| 2,4-Dichloropyridine; 2-Aminooxazole | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Bis(dibenzylideneacetone)palladium | Potassium Carbonate | Anisole | 120 °C | — | 50% |
| 2,4-Dichloropyridine; 2-Aminooxazole | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Palladium (II) acetate | Cesium carbonate | 1,4-Dioxane | 100 °C | — | 11% |
| 2-Bromo-4-chloropyridine; 2-Aminooxazole | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Bis(dibenzylideneacetone)palladium | Cesium carbonate | 1,4-Dioxane | 140 °C | — | 8% |
| 2,4-Dichloropyridine; 2-Aminooxazole | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Bis(dibenzylideneacetone)palladium | Sodium hydride | 1,4-Dioxane | 140 °C | — | 3% |
| 2,4-Dichloropyridine; 2-Aminooxazole | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Bis(dibenzylideneacetone)palladium | sodium phenoxide | 1,4-Dioxane | 80 °C | — | 3% |
| 2,4-Dichloropyridine; 2-Aminooxazole | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Bis(dibenzylideneacetone)palladium | Cesium carbonate | 1,4-Dioxane | 140 °C | — | 2% |
| 2,4-Dichloropyridine; 2-Aminooxazole | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Palladium (II) acetate | Cesium carbonate | Dimethylacetamide | 100 °C | — | 2% |
| 2-Bromo-4-chloropyridine; 2-Aminooxazole | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Bis(dibenzylideneacetone)palladium | sodium phenoxide | 1,4-Dioxane | 170 °C | — | 1% |
| 2,4-Dichloropyridine; 2-Aminooxazole | Bis(3,5-bis(trifluoromethyl)phenyl)(3,6-dimethoxy-2',4',6'-tri(propan-2-yl)(1,1'-biphenyl)-2-yl)phosphane; Bis(dibenzylideneacetone)palladium | Cesium carbonate | 1,4-Dioxane | 140 °C | — | 0% |
| 2,4-Dichloropyridine; 2-Aminooxazole | 1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine); Bis(dibenzylideneacetone)palladium | Potassium Phosphate, Tribasic | 1,4-Dioxane | 160 °C | — | 0% (this run) |
| 2,4-Dichloropyridine; 2-Aminooxazole | Binap, (A+-)-; Bis(dibenzylideneacetone)palladium | sodium 2-methylpropan-2-olate | Toluene | 100 °C | — | 0% |
Procedure
Copied from the source record, unedited
Objective: Will increased catalyst loading lead to increased isolated yield of the desired product? 2,4-dichloropyridine (0.109 mL, 1.01 mmol), oxazol-2-amine (102 mg, 1.22 mmol), TRIS(DIBENZYLIDENEACETONE)DIPALLADIUM(0) (186 mg, 0.20 mmol), (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (352 mg, 0.61 mmol) (Xantphos) and potassium phosphate (430 mg, 2.03 mmol) were added to a microwave vail and the vial was purged with nitrogen. Degassed dioxane (4mL) was then added and the reaction mixture was heated to 160 °C for 6 h under microwave irradiation. Dichloromethane (10 mL) was added to the crude reaction mixture and the mixture was adsorbed onto silica gel. The crude product was purified by flash silica chromatography, elution gradient 0 to 20% EtOAc in heptane. Unfortunately a
The source
This record comes from experimental reaction archive (ord-4973899cb35d49cd8a53a56048cd33f7). Open the source and check it against what is on this page.
experimental reaction archive record ord-4973899cb35d49cd8a53a56048cd33f7 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
More Buchwald–Hartwig amination records
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