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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
Synonyms: 4,4'-Dimethyl-2,2'-bipyridine
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Revisiting hexakis (azulen-2-yl) benzenes: A new synthetic approach using Suzuki cross-coupling
Borkowski, Maksymilan ; Różyło, Lidia ; Szafert, Sławomir ; Pigulski, Bartłomiej ;
Abstract: Here, we present a novel and significantly shorter synthetic approach to hexakis(azulen-2-yl)benzenes, compared to previously reported strategies. A six-fold Suzuki cross-coupling reaction between hexabromobenzene and borylated azulenes afforded the propeller-shaped hexakis(azulen-2-yl)benzenes 1c and 1d in yields ranging from 46% to 81%. The resulting azulene-containing hydrocarbons were fully characterized, including X-ray single-crystal diffraction analysis. We believe, that these hexakis(azulen-2-yl)benzenes hold great potential as building blocks for larger, conjugated polycyclic aromatic hydrocarbons.
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CAS No. : | 1134-35-6 |
Formula : | C12H12N2 |
M.W : | 184.24 |
SMILES Code : | CC1=CC(C2=NC=CC(C)=C2)=NC=C1 |
Synonyms : |
4,4'-Dimethyl-2,2'-bipyridine
|
MDL No. : | MFCD00006441 |
InChI Key : | NBPGPQJFYXNFKN-UHFFFAOYSA-N |
Pubchem ID : | 14338 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With selenium(IV) oxide; In 1,4-dioxane; for 44h;Inert atmosphere; Reflux; | General procedure: To a 100ml two-necked RB, dimethyl bipyridine 1 (500 mg, 0.00271 mol, 1.0 equiv.)was taken, added 100 mL of 1,4-dioxane drop wise and stirred to get a homogenous mixtureand the solution was purged with nitrogen for 15 min bubbling nitrogen into the dioxane withstirring. 0. 663 mg of SeO2 (2.2 equiv) was added and refluxed under N2 atmosphere for 44hours. After the completion of the reaction (Monitored by TLC), the reaction mixture waswashed with warm 1,4-dioxane for 2 to 3 minutes and filtered and 1, 4-dioxane was removedunder reduced pressure. The residue was then dissolved in hot distilled ethyl acetate, filteredand again washed with hot ethyl acetate. The ethyl acetate layer was washed with 1MNa2CO3 (250ml) to remove additional carboxylic acid. The organic layer was dried withanhydrous Na2SO4 and concentrated and the residue was purified on alumina using 60% ethylacetate in petroleum ether to afford the newly synthesized 2,2'-bipyridine 4,4'-dicarbaldehyde was thoroughly characterized by spectroscopic technique such as IR, 1HNMR, 13C NMR and HRMS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With chloro-trimethyl-silane; In N,N-dimethyl-formamide; at 100℃; for 48h; | The antenna ligand for NC-11 was synthesized in a pressure tube containing 4,4'- dimethyl-2,2'-bipyridine (2g, 0.0108 mol) and 9-benzyl- H-carbazole-3-carbaldehyde (6.19g, 0.0217mol) and 0.065mol of trimethylchlorosilane, and magnetic stirrer bar in 70ml DMF. The reaction temperature was raised to 100C and allowed to run for 48 hours with continuous stirring. During the course of the reaction, the color of the reaction mixture changed to yellow and turned orange on cooling and release of pressure from the tube. The solvent was removed using rotary evaporator, and the orange product was recovered by addition of water and filtration under vacuum to furnish the ancillary ligand in 84% yield. Scheme 3 shows a schematic of the synthesis of the antenna ligand for NC-11. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium sulfate; dibenzoyl peroxide; In tetrachloromethane; water; | 3. Synthesis of a mono-anionic ligand (salt form): sodium (4'-methyl-2,2'-bipyridin-4-yl)methanesulfonate (6) To 4,4'-dimethyl-2,2'-bipyridine (20 g, 108.5 mmol) in 400 mL of anhydrous tetrachloromethane was added 19 g (106.8 mmol) of N-Bromosuccinimide and 2.6 g of benzoyl peroxide. The mixture was refluxed overnight and cooled to room temperature. The solid was removed by filtration and the filtrate concentrated by rotary-evaporation. The column chromatography with triethylamine treated silica column afforded 6 g of 4-(bromomethyl)-4'-methyl-2,2'-bipyridine (5), which was mixed with 4.9 g (38.9 mmol) of Na2SO3 in 100 mL of water. The cloudy mixture was refluxed for six hours. When it was still hot, the supernatant was concentrated to about 30 mL and cooled to room temperature. The yellow precipitate was collected by filtration and washed with dichloromethane to afford 3.6 g of 4'-methyl-2,2'-bipyridin-4-yl)methanesulfonate (6). 1H NMR (D2O, 400 MHz, See ) delta 8.81 (1H), 8.67 (1H), 8.44 (1H), 8.30 (1H), 7.88 (1H), 7.76 (1H), 4.42 (2H), 2.73 (3H). |