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CAS No. : | 52927-22-7 | MDL No. : | MFCD01863480 |
Formula : | C11H7NO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | WKTNIBWKHNIPQR-UHFFFAOYSA-N |
M.W : | 169.18 | Pubchem ID : | 4589476 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
93% | With triethylamine; In dichloromethane; at 20℃; | To a solution of 6-hydroxy-2-naphthonitrile (1.0 g, 5.92 mmol)and Et3N (896 mg, 8.88 mmol) in DCM (1.5 mL) was added Tf2O (2.5 g, 8.88 mmol). After stirring at room temperature overnight, H2O (30 mL) was added and the mixture was extracted with ethyl acetate (30 mL x 3). The combined organic layers were washed with brine (30 mL x 3) and dried over Na2SO4. After concentration and purification by column chromatography (petroleum ether/ethyl acetate = 30:1), 59 was obtained as a white solid (1.65 g, 93%). 1H NMR (400 MHz, CDCl3) d 8.30 (s, 1H), 8.03 (d, J = 9.2 Hz,1H), 7.99 (d, J = 8.4 Hz, 1H), 7.83 (d, J = 1.6 Hz, 1H), 7.73 (d,J = 8.4 Hz, 1H), 7.52 (dd, J = 9.2, 2.4 Hz, 1H). |
79.1% | With pyridine; In dichloromethane; at 20℃; | Step 1: 6-cyanonaphthalen-2-yl trifluoromethanesulfonate [004451 To a mixture of 6-hydroxy-2-naphthonitrile (2.13 g, 12.59 mmol), pyridine (1.29 g, 16.37 mmol) and DCM (30 mL) was added trifluoromethanesulfonic anhydride (3.91 g, 13.85 mmol) via syring in 10 minutes. The reaction mixture was stirred at ft overnight. After the reaction was finished, the reaction mixture was quenched with water (20 mL), and the mixture was poured into DCM (100 mL). The resulting mixture was washed with water (100 mL x 2) and saturated brine (100 mL). The orgaic phase was dried over anhydrous Na2SO4 (15 g), filtered and concentrated in vacuo. The crude was purified by silica column chromatography (PE/EtOAc (v/v) = 4/1) to give the title compound as a white solid (3.00 g, 79.1 %). |
78% | With triethylamine; In dichloromethane; at 0℃; for 1h; | To a stirred solution of 6-hydroxy-2-naphthonitrile N (3.0 g, 17.7 mmol) in DCM (90 mL) were added triethylamine (2.68 g, 26.5 mmol) and triflic anhydride (7.5 g, 26.5 mmol) at 0 C and stirring was continued for an additional 1 h at 0 C. The reaction mixture was partitioned between water and DCM; the organic phase was separated, dried over anhydrous Na2S04, and concentrated under reduced pressure to give crude material. The crude material was purified by column chromatography (Si02, 100-200 mesh) eluting with 3% EtOAc/hexane to afford alcohol O (4.2 g, 13.9 mmol, 78%) as a solid. 1H NMR (200 MHz, CDC13): 58.30 (s, 1 H), 8.00 (app t, 2 H), 7.83 (d, J = 2.6 Hz, 1 H), 7.74 (dd, J = 8.8, 1.8 Hz, 1 H), 7.51 (dd, J = 8.8, 2.2 Hz, 1 H). |
78% | With triethylamine; In dichloromethane; at 0℃; for 1h; | To a stirred solution of 6-hydroxy-2-naphthonitrile N (3.0 g, 17.7 mmol) in DCM (90 mL) were added triethylamine (2.68 g, 26.5 mmol) and triflic anhydride (7.5 g, 26.5 mmol) at 0 C and stirring was continued for an additional 1 h at 0 C. The reaction mixture was partitioned between water and DCM; the organic phase was separated, dried over anhydrous Na2S04, and concentrated under reduced pressure to give crude material. The crude material was purified by column chromatography (Si02, 100-200 mesh) eluting with 3% EtOAc/hexane to afford alcohol O (4.2 g, 13.9 mmol, 78%) as a solid. 1H NMR (200 MHz, CDCb): 5D8.30 (s, 1 H), 8.00 (app t, 2 H), 7.83 (d, 7 = 2.6 Hz, 1 H), 7.74 (dd, 7 = 8.8, 1.8 Hz, 1 H), 7.51 (dd, 7 = 8.8, 2.2 Hz, 1 H). |
78% | With triethylamine; In dichloromethane; at 0℃; for 1h; | To a stirred solution of 6-hydroxy-2-naphthonitrile N (3.0 g, 17.7 mmol) in DCM (90 mL) were added triethylamine (2.68 g, 26.5 mmol) and triflic anhydride (7.5 g, 26.5 mmol) at 0 C and stirring was continued for an additional 1 h at 0 C. The reaction mixture was partitioned between water and DCM; the organic phase was separated, dried over anhydrous Na2S04, and concentrated under reduced pressure to give crude material. The crude material was purified by column chromatography (Si02, 100-200 mesh) eluting with 3% EtOAc/hexane to afford alcohol O (4.2 g, 13.9 mmol, 78%) as a solid. 1H NMR (200 MHz, CDCb): 5D8.30 (s, 1 H), 8.00 (app t, 2 H), 7.83 (d, 7 = 2.6 Hz, 1 H), 7.74 (dd, 7 = 8.8, 1.8 Hz, 1 H), 7.51 (dd, 7 = 8.8, 2.2 Hz, 1 H). |
With triethylamine; In ethanol; dichloromethane; | EXAMPLE 28B 6-(Trifluoromethanesulfonyloxy)-2-naphthalenecarbonitrile A solution of Example 28A (14.01 g, 82.8 mmol) and triethylamine (9.2 g, 91.1 mmol) in methylene chloride (40 mL) at 0 C. was treated dropwise with trifluoromethylsulfonic anhydride (28 g, 99.4 mmol), warmed to 25 C. for 48 h, concentrated, redissolved in ethanol (50 mL) and triturated with water to precipitate 8.4 g of the title compound. MS (DCI/NH3) m/e 319 (M+NH4)+. | |
With triethylamine; In dichloromethane; at 0 - 20℃; for 48h; | Preparation of 6-cvano-2-naphthalenyl thfluoromethanesulfonateTo a solution of 6-cyano-2-naphthol (1 g, 5.91 mmol) and anhydrous NEt3 (anh.) (1 ml, 7.09 mmol) in CH2CI2 anh. (20 ml) and under an inert atmosphere at 0 0C, triflic anhydride [(CF3SO2)2O, 1.20 ml, 7.09 mmol] was added, dropwise. The reaction was brought to room temperature and was then left to react until there was no starting product observed (48 h). The <n="19"/>reaction mixture was concentrated to dryness and the crude product obtained was suspended in EtOH (5 ml_). Water (5 ml_) was added, the mixture was triturated and the resulting suspension was filtered to give a crude product (1.74 g) as a brownish solid. Purification by column chromatography (SiO2, CH2CI2: cyclohexane, 6/4) yielded the compound of the title (1.56 g, 88%) in the form of a white solid IR (KBr) 3058, 2240, 1809, 1630, 1604, 1425, 1152, 964, 932. 1H NMR (400 MHz, CDCI3) 8.30 (d, J = 0.4 Hz, 1 H), 8.03 (d, J = 8.8 Hz, 1 H), 7.99 (d, J = 8.4 Hz, 1 H), 7.83 (d, J = 2.4 Hz, 1 H), 7.73 (dd, J = 8.8 and 1.4 Hz, 1 H) and 7.52 (dd, J = 8.8 and 2.4 Hz, 1 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With pyridine; hydrogenchloride; trifluoromethylsulfonic anhydride; In hexane; ethyl acetate; | EXAMPLE 95 Trifluoromethanesulfonic acid 6-cyano -naphthalen-2-yl ester A flame dried flask equipped with a stir bar and rubber septum was charged with dry dichlorornethane (35 mL) and 6-cyano-2-naphthol (3.00 g, 17.73 mmol) fromn Example 94 under an argon atmosphere. To this mixture was added pyridine (7.17 mL, 88.61 mmol), and the resulting solution was chilled to 0 C. Triflic anhydride (3.59 mL, 21.28 mmol) was added slowly by syringe, and the reaction mixture was stirred at 0 C. for 1.5 hours. one half equivalent of triflic anhydride was then added and the reaction mixture was allowed to gradually warm to room temperature over a 16 hour period. The solvents were then removed by rotary evaporation, and the residue was taken up in 200 mL of 1:1 EtOAc and 1N HCl. The organics were washed once more with 1N HCl (100 mL), dried over MgSO4 ,and concentrated. Flash chromatography (hexane to 15% EtOAc/hexane) afforded the desired product as a white solid (3.98 g, 75%). LRMS (electrospray) m/z: 319 (M+18) 1H NMR (CDCl3) δ8.32 (s, 1H), 8.05 (d, 1H, J=9.04 Hz), 8.01 (d, 1H, J=8.54 Hz), 7.85 (d, 1H, J=2.51 Hz), 7.76 (dd, 1H, J=9.04, 1.51 Hz), 7.54 (dd, 1H, J=9.03, 2.51 Hz). |
With trifluoromethanesulfonic acid anhydride; triethylamine; In ethanol; dichloromethane; | EXAMPLE 13B 6-cyano-2-naphthyl trifluoromethanesulfonate A solution of Example 13A (14.01 g, 82.8 mmol) and triethylamine (9.2 g, 91.1 mmol) in dichloromethane (40 mL) at 0 C. was treated dropwise with trifluoromethanesulfonic anhydride (28 g, 99.4 mmol), warmed to room temperature, stirred for 48 hours, concentrated, dissolved in ethanol, (50 mL) triturated with water, and filtered to provide the desired product. MS (DCI/NH3) m/e 319 (M+NH4)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With triethylamine; In dichloromethane; at 20℃; | The A42-1 (1.0g, 5.92mmol) was dissolved in dichloromethane (30mL), followed by triethylamine (896mg, 8.88mmol), trifluoromethanesulfonateAnhydride (2.5g, 8.88mmol), stirred at room temperature overnight, quenched with water was added, extracted three times with ethyl acetate, the organic phase was washed with brine, dried over anhydrous sodium sulfateDry, the solvent was distilled off, the residue was purified by column chromatography (petroleum ether: ethyl acetate = 30: 1) to give a white solid (1.65g, 93%). |
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