Structure of 79802-71-4
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CAS No. : | 79802-71-4 |
Formula : | C30H16N4 |
M.W : | 432.47 |
SMILES Code : | N#CC1=CC=C(/C(C2=CC=C(C=C2)C#N)=C(C3=CC=C(C=C3)C#N)/C4=CC=C(C=C4)C#N)C=C1 |
MDL No. : | N/A |
InChI Key : | MKUUESUDECITIV-UHFFFAOYSA-N |
Pubchem ID : | 102492274 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501 |
* 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 |
---|---|---|
3.1 g | In N,N-dimethyl-formamide; for 60h;Reflux; Inert atmosphere; | TPE-4Br (6.67 g) , CuCN (5.0 g, 56 mmol) , and DMF (50 mL) were added into a two-necked round bottom flask. The mixture was heated at reflux for 60 hours under nitrogen conditions and then suspended into 300 mL of water. After ethylenediamine (10 mL) was added, the resulting mixture was stirred at 100 for 1 hour and was then filtered. The precipitated solid was extracted with dichloromethane (3 × 150 mL) and the combined organic phase was dried with anhydrous magnesium sulfate. After filtration and solvent evaporation, the residue was repeatedly purified by silica gel column chromatography with hexane and dichloromethane (v/v, 1/1) as eluent to give TPE-4CN 3.1 g in 70%yield as a white solid.1H NMR (CDCl3, 500 MHz) : δ (ppm) 7.48 (t, J = 5.0 Hz, 8H) and 7.08 (t, J = 5.0 Hz, 8H) . HRMS (MALDI-TOF) , m/z calcd. for C30H16N4: 432.1375; found 432.1379. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With sodium azide; zinc dibromide; In 1-methyl-pyrrolidin-2-one; water; at 150℃; for 24h; | Into a 25 mL round-bottomed flask were added sodium azide (1.12 g, 16 mmol) , zinc bromide (450 mg, 2 eq. ) and 2 mL of water. TPE-4CN (2 mmol) was dissolved in 10 mL of N-Methylpyrrolidone (NMP) and injected into the solution. The reaction mixture was refluxed for 24 hours with vigorous stirring at 150 . The mixture was acidified to pH 1 with aqueous HCl solution (3 M) and was extracted into an organic layer with ethyl acetate (20 mL) . The organic phase was washed with 3M HCl (2 x 10 mL) and solvent was evaporated to yield a crude product. This crude product was added into NaOH solution (0.25 M, 40 mL) and stirred vigorously until a white precipitate of zinc hydroxide was observed. The resulting suspension was filtered to remove zinc hydroxide. The filtrate was washed with ethylacetate (10 mL x 2) and acidified to pH 1 with 3 M HCl. The tetrazole product precipitated upon stirring, which was again extracted into 20 mL ethyl acetate and the organic layer was separated. The aqueous layer was washed with ethyl acetate (20 mL x 2) . The organic layers were combined, concentrated and dried under vacuum to yield TPE-4TTZ (71%) as a yellowish solid.1H NMR (400 MHz, DMSO) : δ 7.89 (d, 8H, J = 8.2 Hz) , 7.31 (d, 8H, J = 8.2 Hz) . HRMS (MALDI-TOF) , m/z calcd. for C30H20N16Na+: 627.1949; found 627.1986 (M + Na+) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With potassium phosphate; 18-crown-6 ether; copper diacetate; In N,N-dimethyl acetamide; at 120℃; for 12h;Inert atmosphere; Schlenk technique; Sealed tube; | In a dry Schlenck tube, add bis(4-cyanophenyl)methane (65 mg, 0.3 mmol), anhydrous copper acetate (136 mg, 0.75 mmol), potassium phosphate (150 mg, 0.75 mmol) and 18-crown-6 (16mg, 0.06mmol), then anhydrous N,N-dimethylacetamide (5 mL) was added under nitrogen atmosphere and the tube was sealed and heated for 12 hours. After the reaction mixture was cooled, 50 mL dilute hydrochloric acid (3 M) was added, the aqueous phase was extracted three times with ethyl acetate (50 mL), and the organic phases were combined and washed with saturated sodium carbonate and saturated brine each time. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed in vacuo, and then separated by silica gel chromatography column chromatography to obtain 62 mg of tetrakis(4-cyanophenyl)ethylene with a yield of 96%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With lithium hexamethyldisilazane; In tetrahydrofuran; at -78 - 20℃;Inert atmosphere; | To a 15.0mL dry tetrahydrofunan (THF) solution containing <strong>[79802-71-4]tetra(4-cyanophenyl)ethylene</strong> (500mg, 1.2mmol) at -78C under a nitrogen atmosphere, a tetrahydrofuran (THF) solution of lithium hexamethyldisilazide (LiHMDS, 1.0M, 8.5mL, 8.5mmol) was added. After 20min, the resultant mixture was warmed to room temperature, giving a clear yellow solution. This reaction was further stirred overnight. The resulting pale yellow reaction solution was added 30mL water. Then, the organic phase was removed under vaccum. The precipatate was seprated by filtration and transfered to a 50mL flask. Then, 15mL concentrated HCl was added. The mixture was stirred for 2.0h. The product was obtained by centrifugation, which was further purified by evaporation of acqueous solution containig solid sample, affording L·4Cl- as a white crystals with yield of 420mg (56%). 1H NMR (400MHz, D2O): 7.64 (d, J=8.0Hz, 8H), 7.41 (d, J=8.0Hz, 8H), 4.79 (s, 16H) ppm. 13C NMR (100MHz, D2O): 166.2, 147.4, 144.8, 141.6, 131.9, 127.6, 126.8ppm. It is worth noting that the present synthesis is diffrerent the recent reported method [33]. |