Complete recipeSource: Both
Route 1: Other
pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1
Linker precursors2,3,4-trimethoybenzaldehyde; 2,3-dimethoxycyclohexa-2,5-diene-1,4-dione; 2,3,5,6,8,9,11,12-octamethoxyl-tetraoxa[8]circulene
SolventsCH2Cl2, MeOH, H2O, EtOAc/petroleum ether, EtOAc/DCM, DCM/DMSO-d6 for analysis
Additivesm-CPBA, NaHCO3, Na2S2O3, NaOH, HCl, ceric ammonium nitrate, silica gel, BF3·Et2O, BBr3
Atmospherenot specified for most steps; dry DCM used for BBr3 demethylation
Temperature0 °C to room temperature; reflux for circulene formation; -60 °C then room temperature for BBr3 step
Time3 h warming step; 16 h NaOH step; 1.5 h CAN oxidation; 24 h reflux; 2 h at -60 °C plus overnight at room temperature; 2 h quench
Oxidant / reductantm-CPBA and ceric ammonium nitrate oxidation; BBr3 demethylation reagent
Work-upphase separation, aqueous washes, extraction, drying over salts, evaporation, chromatography; final quench with water and filtration
Activationnot specified
Scalability contextReported millimole-scale precursor synthesis and 0.12 mmol final demethylation.
Show 10 structured reagent records
| Role | Reagent | Amount / concentration | Source |
|---|---|---|---|
| Linker | 2,3,4-trimethoybenzaldehyde 1 | 19.62 g, 100.0 mmol | pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1 |
| Oxidant | m-CPBA | 85 wt%, 21.93 g, 108.0 mmol | pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1 |
| Solvent | CH2Cl2 | 44 mL plus 180 mL plus extraction volumes | pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1 |
| Base | aqueous NaOH | 100 mL · 10% (w/v) | pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1 |
| Acid | aqueous HCl | used to acidify to pH = 1; 100 mL in circulene workup · 6.0 M and 2.0 M | pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1 |
| Oxidant | ceric ammonium nitrate | 138.38 g, 261.0 mmol | pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1 |
| Additive | BF3·Et2O | 31.0 mL | pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1 |
| Linker | 2,3-dimethoxycyclohexa-2,5-diene-1,4-dione (4) | 4.20 g, 25.0 mmol | pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1 |
| Linker | 2,3,5,6,8,9,11,12-octamethoxyl-tetraoxa[8]circulene (5) | 72.06 mg, 0.12 mmol | pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1 |
| Additive | BBr3 in DCM | 11.52 mL, 11.52 mmol · 1.0 M | pp.6-8 · Experimental Section, Synthesis of 8OH-TOC · Scheme S1 |