Structure of 145369-29-5
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CAS No. : | 145369-29-5 |
Formula : | C12H6F3NO3S |
M.W : | 301.24 |
SMILES Code : | O=S(C(F)(F)F)(OC1=CC=C2C=C(C#N)C=CC2=C1)=O |
MDL No. : | MFCD11505953 |
InChI Key : | HCBCJAFWOBCSRJ-UHFFFAOYSA-N |
Pubchem ID : | 15541822 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H302-H318 |
Precautionary Statements: | P264-P270-P280-P301+P312-P305+P351+P338-P310-P330-P501 |
Class: | 9 |
UN#: | 3077 |
Packing Group: | Ⅲ |
* 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 |
---|---|---|
With triethylamine; triphenylphosphine;palladium diacetate; In ethyl acetate; acetonitrile; | EXAMPLE 13C 6-((trimethylsilyl)ethynyl)-2-naphthonitrile A solution of Example 13B (350 mg, 1.16 mmol), trimethylsilylacetylene(148 mg, 1.51 mmol), Pd(OAc)2 (26 mg, 0.12 mmol), triphenylphosphine (61 mg, 0.23 mmol), and triethylamine (2 mL) in acetonitrile (1 mL) in a sealed was heated to 100 C., stirred for 19 hours, diluted with ethyl acetate (20 mL), washed with water, dried (MgSO4), filtered, treated with silica gel (4 g), and concentrated. The concentrated was purified by flash column chromatography on silica gel with 10% ethyl acetate/hexanes to provide the desired product. MS (DCI/NH3) m/e 267 (M+NH4)+. |
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 |
---|---|---|
With caesium carbonate; In ethyl acetate; N,N-dimethyl-formamide; | EXAMPLE 47A 6-(3-Methoxyphenyl)-2-naphthalenecarbonitrile A solution of Example 28B (300 mg, 1 mmol), palladium (II) acetate (22 mg, 0.1 mmol) and 1-1'-bis(diphenyphosphino)ferrocene (111 mg, 0.2 mmol) was stirred in DMF (3 mL) for 15 min, treated with Cs2CO3 (813 mg, 2.5 mmol) and 3-methoxyphenylboronic acid (228 mg, 1.5 mmol), stirred for 20 min at 80 C., cooled, treated with pH 7 buffer (10 mL) and extracted with diethyl ether. The ether extracts were dried (MgSO4), concentrated and purified on silica gel with 10% ethyl acetate/hexane to provide 140 mg of the title compound as a white solid. MS (DCI/NH3) m/e 277 (M+NH4)+. | |
With caesium carbonate; In ethyl acetate; N,N-dimethyl-formamide; | EXAMPLE 47A 6-(3-Methoxyphenyl)-2-naphthalenecarbonitrile A solution of Example 28B (300 mg, 1 mmol), palladium (II) acetate (22 mg, 0.1 mmol) and 1-1'-bis(diphenyphosphino)ferrocene (111 mg, 0.2 mmol) was stirred in DMF (3 mL) for 15 min, treated with Cs2CO3 (813 mg, 2.5 mmol) and 3-methoxyphenylboronic acid (228 mg, 1.5 mmol), stirred for 20 min at 80 C., cooled, treated with pH 7 buffer (10 mL) and extracted with diethyl ether. The ether extracts were dried (MgSO4), concentrated and purified on silica gel with 10% ethyl acetate/haexane to provide 140 mg of the title compound as a white solid. MS (DCI/NH3) m/e 277 (M+NH4)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With triethylamine; triphenylphosphine;palladium diacetate; In methanol; hexane; ethyl acetate; N,N-dimethyl-formamide; | EXAMPLE 96 6-Cyano-naphthalene-2-carboxylic acid methyl ester To a solution of <strong>[145369-29-5]trifluoromethanesulfonic acid 6-cyano-naphthalen-2-yl ester</strong> from Example 95 (1.50 g, 4.98 mmol) in 20 mL of anhydrous DMF was added palladium(II) acetate (33.53 mg, 0.15 mmol), triphenylphosphine (78.36 mg, 0.30 mmol), triethylamine (1.39 mL, 9.96 mmol) and 5 mL of methanol. This mixture was purged with carbon monoxide for ten minutes. The reaction mixture was then placed under balloon pressure of carbon monoxide and heated to 60 C. for 16 hours. The mixture was then diluted with brine, extracted with EtOAc (3*100 mL), extracts washed with 1N HCl (2*100 mL), dried over MgSO4, and concentrated under reduced pressure. Flash chromatography (hexane to 20% EtOAc/hexane) afforded the desired product as a white solid (525 mg, 50%). LRMS (electrospray) m/z: 229 (M+18) 1H NMR (CDCl3): δ8.66 (s, 1H), 8.29 (s, 1H), 8.20 (dd, 1H, J=8.54, 1.51 Hz), 8.06 (d, 1H, J=8.54 Hz), 7.98 (d, 1H, J=8.53 Hz), 7.70 (dd, 1H, J=8.53, 1.50 Hz), 4.03 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With potassium phosphate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; for 17h;Heating / reflux;Product distribution / selectivity; | Preparation of 6-[3-(1 -adamantyl)-4-methoxyphenyl1-2- cvanonaphthalene2,4,6-Tris[3-(1 -adamantyl)-4-methoxyphenyl]-1 ,3,5,2,4,6-trioxatriborinane (889 mg, 1.11 mmol), 6-cyanonaphthalenyl thfluoromethanesulfonate (500 mg, 1.66 mmol), K3PO4 (1 ,41 g, 6.64 mmol), THF (10 ml) and H2O (2 ml) were placed in a Schlenk flask and the reaction mixture was deoxygenated (3 freeze-thaw cycles). Immediately after, Pd(PPh3)4 (96 mg, 0.083 mmol) was added and the mixture was deoxygenated again (2 freeze-thaw cycles). After heating to reflux for 17 h, the reaction mixture was diluted, while still hot, in toluene (50 ml). The mixture was filtered through celite which was washed with hot toluene (2 x 50 ml). The combined organic phases were washed with hot H2O (2 x 50 ml). The organic phase was evaporated and a crude product (906 mg) was obtained that was recrystallized with a minimum volume of <n="24"/>toluene at reflux (6.2 ml), leading to the title compound (541 mg, 83%) as a gray powder. The spectroscopic data coincide with those of Example 11. |
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