Copper(I)-Mediated Ligand-Accelerated Ullmann-Type Coupling of Anilines with Aryliodides: Ligand Selection and Reaction Kinetics for Synthesis of Tri-<i>p</i>-Tolylamine
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Bibliographic record
Abstract
Screening of eight ligands for the copper-catalyzed ligand-accelerated Ullmann condensation of p -toluidine with 4-iodotoluene to produce tri- p -tolylamine (TTA) revealed that 2,2‘-dipyridyl and 4,4‘-dipyridyl gave the highest conversion to TTA in the shortest time. Based on the ligand-screening results, a mechanistic structure of the active reaction complex between copper and the two fastest ligands was proposed. The TTA synthesis reaction kinetics was followed by an HPLC method, and kinetic parameters of the reaction were determined in temperature range 128−196 °C. The condensation of p -toludine with 4-iodotoluene to give TTA was modeled as a parallel-consecutive reaction system composed of two condensation reactions. Reaction orders for the first condensation reaction to give di- p -tolylamine were determined to be 1.18 and 1.16 with respect to 4-iodotoluene and p -toluidine, respectively. For the second condensation reaction, the reaction orders were determined to be 0.13 and 0.11 with respect to 4-iodotoluene and di- p -tolylamine, respectively. Activation energies for the first and second reaction were determined as 53.6 and 53.8 kJ mol -1, respectively. The preexponential constants ( k o ) in the Arrhenius equation for the first and second reaction were determined as 1774.4 min -1 (mol/L) -1.34 and 5657.8 min -1 (mol/L) 0.76, respectively. Finally, the model predictions gave very good agreement with experimental results for low, medium, and high reaction temperature.
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Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.002 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
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Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
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