Environmentally Benign Route for Scalable Preparation of 1-Imino-3-thioisoindolines−The Key Building Blocks for the Synthesis of Dithio- and Diamino-β-isoindigo Derivatives
Bibliographic record
Abstract
A one-step, gram-scale protocol for the preparation of 1-imino-3-thioisoindolines and a novel one-pot two-step methodology of the synthesis of dithio- or diamino-β-isoindigo derivatives starting from phthalonitriles and sodium hydrosulfide in an aprotic dipolar solvent have been developed. It was demonstrated that the electronic properties of the substituent(s) in the phthalonitrile core play a critical role in β-isoindigo synthesis resulting either in the selective formation of dithio- or diamino-β-isoindigo chromophores. The N-acylated 1-imino-3-thioisoindolines can be used for the direct, easily scalable, and chromatography-free procedure for the preparation of a new class of N,N′-diacylamino-β-isoindigoid compounds. Properties of the monomeric as well as J-aggregated forms of dithio- and diamino-β-isoindigo were probed by the absorption and fluorescence spectroscopies. It was demonstrated that the tetracyano-diamino-β-isoindigo 3f can form a J-aggregate that absorbs at 793 nm and fluoresces at 824 nm. This aggregate is stable in N,N-dimethylformamide solution; however, it slowly dissociates in tetrahydrofuran or under sonication conditions. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to elucidate the electronic structures, spectroscopic properties, and aggregation of new dithio- and diamino-β-isoindigo derivatives.
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How this classification was reachedexpand
Full frame distilled prediction
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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".