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CAS No. : | 169126-64-1 | MDL No. : | MFCD08436043 |
Formula : | C15H23BO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | CHQAGZBOYKWZNW-UHFFFAOYSA-N |
M.W : | 246.15 | Pubchem ID : | 10037535 |
Synonyms : |
|
Num. heavy atoms : | 18 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.6 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 77.66 |
TPSA : | 40.46 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | Yes |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.73 cm/s |
Log Po/w (iLOGP) : | 0.0 |
Log Po/w (XLOGP3) : | 4.32 |
Log Po/w (WLOGP) : | 2.02 |
Log Po/w (MLOGP) : | 2.54 |
Log Po/w (SILICOS-IT) : | 2.26 |
Consensus Log Po/w : | 2.23 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -4.27 |
Solubility : | 0.0133 mg/ml ; 0.0000539 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -4.88 |
Solubility : | 0.00322 mg/ml ; 0.0000131 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -4.32 |
Solubility : | 0.0119 mg/ml ; 0.0000482 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 2.49 |
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 |
---|---|---|
0.8838 mg | Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.166667 h; Inert atmosphere Stage #2: With Triisopropyl borate In tetrahydrofuran; hexane at -78 - 20℃; for 3.33333 h; Inert atmosphere Stage #3: With hydrogenchloride; water In tetrahydrofuran; hexane for 2 h; |
The method of Faul et al. was used. To a 100 mL round bottom flask containing THF (30 mL) was added a 1.6 M solution of «-BuLi in hexanes (8.0 mL, 12.8 mmol), and the resulting solution was cooled in a dry-ice acetone bath to -78 °C with stirring, under nitrogen. To this solution was added a solution of the 2:1 mixture of 32:12 (3.3587 g, 7.88 mmol) in THF (8 mL) over 20 min and the reaction was stirred at -78 °C for 10 min, and a mixture of triisopropylborate (4.9 mL, 21.3 mmol) in THF (10 mL) was added dropwise over 20 min. The reaction was stirred at -78 °C for 1 h and then warmed to room temperature and stirred for 2 h. The reaction was then quenched with 3 N HC1 (35 mL), and after stirring for 2 h, it was poured into ethyl acetate, the layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo to give a crude product that was purified by column chromatography (150 mL Si02, ethyl acetate:hexanes 1 :3) to give 33 (0.8838 g, 45percent) as a white crystalline solid: 1H NMR (400 MHz, CDC13) ? 8.29 (s, 1H), 7.21 (s, 1H), 2.82 (s, 3H), 1.72 (s, 4H), 1.34 (s, 6H), 1.33 (s, 6H); 13C NMR (100.6 MHz, CDC13) ? 149.4, 142.8, 141.4, 136.3, 128.5, 35.1, 35.0, 34.3, 33.8, 31.8, 31.5, 22.6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(a) 3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydro-2-naphthylboronic acid, In a similar manner to Example 3(a), starting with 5 g (17.8 mmol) of <strong>[119999-22-3]3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-bromonaphthalene</strong>, 4.22 g (100%) of boronic acid are obtained. | ||
0.8838 mg | The method of Faul et al. was used. To a 100 mL round bottom flask containing THF (30 mL) was added a 1.6 M solution of «-BuLi in hexanes (8.0 mL, 12.8 mmol), and the resulting solution was cooled in a dry-ice acetone bath to -78 C with stirring, under nitrogen. To this solution was added a solution of the 2:1 mixture of 32:12 (3.3587 g, 7.88 mmol) in THF (8 mL) over 20 min and the reaction was stirred at -78 C for 10 min, and a mixture of triisopropylborate (4.9 mL, 21.3 mmol) in THF (10 mL) was added dropwise over 20 min. The reaction was stirred at -78 C for 1 h and then warmed to room temperature and stirred for 2 h. The reaction was then quenched with 3 N HC1 (35 mL), and after stirring for 2 h, it was poured into ethyl acetate, the layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo to give a crude product that was purified by column chromatography (150 mL Si02, ethyl acetate:hexanes 1 :3) to give 33 (0.8838 g, 45%) as a white crystalline solid: 1H NMR (400 MHz, CDC13) ? 8.29 (s, 1H), 7.21 (s, 1H), 2.82 (s, 3H), 1.72 (s, 4H), 1.34 (s, 6H), 1.33 (s, 6H); 13C NMR (100.6 MHz, CDC13) ? 149.4, 142.8, 141.4, 136.3, 128.5, 35.1, 35.0, 34.3, 33.8, 31.8, 31.5, 22.6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(b) 5,6,7,8-Tetrahydro-3,5,5,8,8-pentamethyl-2-naphthylboronic Acid. In a manner similar to that of Example 1(a), starting with 14.00 g (49.8 mmol) of the compound obtained in Example 36(a), 7.36 mg (60%) of the expected product are obtained in the form of a colourless oil. 1H NMR (CDCl3) delta 1.32 (s, 6H), 1.34 (s, 6H), 1.72 (s, 4H), 2.81 (s, 3H), 7.21 (s, 1H), 8.28 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With ammonium chloride; potassium carbonate;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; water; | d. 2-Methoxy-3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)pyridine-5-carboxaldehyde. A mixture of 2-methoxy-3-bromo-pyridine-5-carboxyaldehyde (319 mg, 1.48 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl) <strong>[169126-64-1]boronic acid</strong> (545 mg, 2.22 mmol), potassium carbonate (817 mg, 5.91 mmol) and water (2 mL) in anhydrous 1,2-dimethoxyethane (30 mL) was degassed with argon for 15 minutes prior to the addition of tetrakis(triphenylphosphine)palladium (0) (342 mg, 0.30 mmol). The reaction mixture was heated under reflux for 15 hours, allowed to cool to room temperature and extracted with ethyl acetate (2*100 mL). The organic extracts were successively washed with water (100 mL), a saturated aqueous solution of NH4Cl (100 mL), brine (100 mL), dried over MgSO4 and filtered. Removal of the solvent under reduced pressure gave an oil which was purified by column chromatography, Biotage 12M cartridge, eluding with 5% ethyl acetate/95% hexane, to give 2-methoxy-3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)pyridine-5-carboxaldehyde (100% yield). 1H NMR (500 MHz, CDCl3): delta 1.24 (s, 6 H), 1.27 (s, 6 H), 1.70 (s, 4 H), 2.09 (s, 3 H), 4.09 (s, 3 H), 7.07 (s, 1 H), 7.17 (s, 1 H), 7.94 (d, J=2.0 Hz, 1 H), 8.64 (d, J=2.0 Hz, 1 H), 10.01 (s, 1 H). |
With ammonium chloride; potassium carbonate; sodium chloride;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; water; | d. 2-Methoxy-3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)pyridine-5-carboxaldehyde. A mixture of 2-methoxy-3-bromo-pyridine-5-carboxyaldehyde (319 mg, 1.48 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl) <strong>[169126-64-1]boronic acid</strong> (545 mg, 2.22 mmol), potassium carbonate (817 mg, 5.91 mmol) and water (2 mL) in anhydrous 1,2-dimethoxyethane (30 mL) was degassed with argon for 15 minutes prior to the addition of tetrakis(triphenylphosphine)palladium(0) (342 mg, 0.30 mmol). The reaction mixture was heated under reflux for 15 hours, allowed to cool to room temperature and extracted with ethyl acetate (2*100 mL). The organic extracts were successively washed with water (100 mL), a saturated aqueous solution of NH4Cl (100 mL), a saturated aqueous solution of NaCl (100 mL), dried over MgSO4 and filtered. Removal of the solvent under reduced pressure gave an oil which was purified by column chromatography, using a Biotage 12M cartridge, eluding with 5% ethyl acetate/95% hexane. The title compound was isolated in quantitative yield. 1H NMR (500 MHz, CDCl3): delta1.24 (s, 6 H), 1.27 (s, 6 H), 1.70 (s, 4 H), 2.09 (s, 3 H), 4.09 (s, 3 H), 7.07 (s, 1 H), 7.17 (s, 1 H), 7.94 (d, J=2.0 Hz, 1 H), 8.64 (d, J=2.0 Hz, 1 H), 10.01 (s, 1 H). | |
With ammonium chloride; potassium carbonate; sodium chloride;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; water; | d. 2-Methoxy-3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)pyridine-5-carboxaldehyde A mixture of 2-methoxy-3-bromo-pyridine-5-carboxyaldehyde (319 mg, 1.48 mmol), <strong>[169126-64-1](3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)<strong>[169126-64-1]boronic acid</strong></strong> (545 mg, 2.22 mmol), potassium carbonate (817 mg, 5.91 mmol) and water (2 mL) in anhydrous 1,2-dimethoxyethane (30 mL) was degassed with argon for 15 minutes prior to the addition of tetrakis(triphenylphosphine)palladium (0) (342 mg, 0.30 mmol). The reaction mixture was heated under reflux for 15 hours, allowed to cool to room temperature and extracted with ethyl acetate (2*100 mL). The organic extracts were successively washed with water (100 mL), a saturated aqueous solution of NH4Cl (100 mL), a saturated aqueous solution of NaCl (100 mL), dried over MgSO4 and filtered. Removal of the solvent under reduced pressure gave an oil which was purified by column chromatography, using a Biotage 12M cartridge, eluding with 5% ethyl acetate/95% hexane. The title compound was isolated in quantitative yield. 1H NMR (500 MHz, CDCl3): delta1.24 (s, 6H), 1.27 (s, 6H), 1.70 (s, 4H), 2.09 (s, 3H), 4.09 (s, 3H), 7.07 (s, 1H), 7.17 (s, 1H), 7.94 (d, J=2.0 Hz, 1H), 8.64 (d, J=2.0 Hz, 1H), 10.01 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With potassium carbonate;tetrakis(triphenylphosphine)palladium (0); In ethanol; water; toluene; | b. 3-Trifluoromethoxy-4-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl) benzaldehyde. To a solution of <strong>[85366-66-1]3-bromo-4-trifluoromethoxybenzaldehyde</strong> (10.0 g, 37.2 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl) boronic acid (11.0 g, 44.68 mmol, 1.2 eq) in a mixture of toluene (100 mL), ethanol (20 mL) and water (15 mL) was added potassium carbonate (10.28 g, 74.4 mmol, 2 eq). The mixture was degased with argon for 40 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.86 g, 0.74 mmol, 0.02 eq) was added and the mixture heated at reflux under argon for 22 hours. The mixture was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over MgSO4, filtered and evaporated. The residue was chromatographed on silica gel (eluent: ethyl acetate/hexane 5:95) to give 3-trifluoromethoxy-4-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl) benzaldehyde (11.1 g, 76%), 1H NMR (300 MHz; CDCl3) 1.25 (s, 6 H); 1.32 (s, 6 H); 1.70 (s, 4 H); 2.08 (s, 3 H); 7.06 (s, 1 H); 7.18 (s, 1 H); 7.48 (dd, J1=8.4 Hz, J2=1.5 Hz, 1 H); 7.84 (d, J=2.0 Hz, 1 H); 7.88 (dd, J1=2.0 Hz, J2=8.5 Hz, 1 H), 9.91 (s, 1 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With ammonium chloride; potassium carbonate; sodium chloride;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; water; | b. 3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)-4-methoxy-6-hydroxybenzaldehyde. A mixture of <strong>[57543-36-9]3-bromo-6-hydroxy-4-methoxy-benzaldehyde</strong> (2 g, 8.66 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl) boronic acid (3.18 g, 12.99 mmol), potassium carbonate (4.79 g, 34.63 mmol) and water (4 mL) in anhydrous 1,2-dimethoxyethane (140 mL) was degassed with argon for 15 minutes prior to the addition of tetrakis(triphenylphosphine)palladium(0) (2.0 g, 1.73 mmol). The reaction mixture was heated under reflux for 15 hours, allowed to cool to room temperature and extracted with ethyl acetate (2*100 mL). The organic extracts were successively washed with water (100 mL), a saturated aqueous solution of NH4Cl (100 mL), a saturated aqueous solution of NaCl (100 mL), dried over MgSO4 and filtered. Removal of the solvent under reduced pressure gave an oil which was purified by column chromatography, using a Biotage 40M cartridge, eluding with 5% ethyl acetate/95% hexane, to give 3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)-4-methoxy-6-hydroxybenzaldehyde as a white solid (2.2 g, 73%). 1H NMR (500 MHz; CDCl3): delta1.28 (s, 6 H), 1.33 (s, 6 H), 1.70 (s, 4 H), 2.08 (s, 3 H), 3.84 (s, 3 H), 6.51 (s, 1 H), 7.07 (s, 1 H), 7.15 (s, 1 H), 7.31 (s, 1 H), 9.73 (s, 1 H), 11.53 (s, 1 H). |
73% | With ammonium chloride; potassium carbonate; sodium chloride;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; water; | b. 3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)-4-methoxy-6-hydroxybenzaldehyde A mixture of <strong>[57543-36-9]3-bromo-6-hydroxy-4-methoxy-benzaldehyde</strong> (2 g, 8.66 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)boronic acid (3.18 g, 12.99 mmol), potassium carbonate (4.79 g, 34.63 mmol) and water (4 mL) in anhydrous 1,2-dimethoxyethane (140 mL) was degassed with argon for 15 minutes prior to the addition of tetrakis(triphenylphosphine)palladium(0) (2.0 g, 1.73 mmol). The reaction mixture was heated under reflux for 15 hours, allowed to cool to room temperature and extracted with ethyl acetate (2*100 mL). The organic extracts were successively washed with water (100 mL), a saturated aqueous solution of NH4Cl (100 mL), a saturated aqueous solution of NaCl (100 mL), dried over MgSO4 and filtered. Removal of the solvent under reduced pressure gave an oil which was purified by column chromatography, using a Biotage 40M cartridge, eluding with 5% ethyl acetate/95% hexane, to give 3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)-4-methoxy-6-hydroxybenzaldehyde as a white solid (2.2 g, 73%). 1H NMR (500 MHz; CDCl3): delta1.28 (s, 6H), 1.33 (s, 6H), 1.70 (s, 4H), 2.08 (s, 3H), 3.84 (s, 3H), 6.51 (s, 1H), 7.07 (s, 1H), 7.15 (s, 1H), 7.31 (s, 1H), 9.73 (s, 1H), 11.53 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With potassium carbonate;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; hexane; water; | b. A mixture of 3-methoxy-4-trifluoromethanesulfonyl benzaldehyde (0.50 g, 1.76 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) <strong>[169126-64-1]boronic acid</strong> (0.43 g, 1.76 mmol) and potassium carbonate (0.97 g, 7.04 mmol) in 1,2-dimethoxyethane (15 mL) and water (1 mL) was degassed with argon for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.20 g, 0.17 mmol) was added and the mixture heated at reflux under argon for 5 hours. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (Biotage, eluent: 0-30% ethyl acetate in hexane) to give 0.40 g of 4-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)-3-methoxybenzaldehyde (67%). 1H NMR (500 MHz; CDCl3) delta1.27 (s, 6 H), 1.32 (s, 6 H), 1.70 (s, 4 H), 2.09 (s, 3 H), 3.85 (s, 3 H), 7.09(s, 1 H), 7.16 (s, 1 H), 7.26 (s, 1 H), 7.35 (d, J=7.5 Hz, 1 H); 7.47 (s, 1 H), 7.50 (d, J=7.5 Hz, 1 H), 10.02 (s, 1 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With potassium carbonate;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; water; | A mixture of 2-fluoro-4-methoxy-3-trifluoromethanesulfonyl benzaldehyde (1.21 g, 4.01 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl) <strong>[169126-64-1]boronic acid</strong> (1.08 g, 4.41 mmol) and potassium carbonate (2.22 g, 16.04 mmol) in 1,2-dimethoxyethane (30 mL) and water (2 mL) was degassed with argon for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.23 g, 0.2 mmol) was added and the mixture heated at reflux under argon for 16 hours. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (Biotage, eluent: ethyl acetate/hexane, 0.5:8.5) to give 0.87 g of 4-methoxy-2-fluoro-3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl) benzaldehyde (62%). 1H NMR (500 MHz; CDCl3): delta1.26 (s, 6 H), 1.32 (s, 6 H), 1.69 (s, 4 H), 2.07 (s, 3 H), 3.85 (s, 3 H), 7.07 (d, J=8.8 Hz, 1 H), 7.07 (s, 1 H), 7.19 (s, 1 H), 7.90 (t, J=8.8 Hz, 1 H), 10.25 (s, 1 H). |
62% | With potassium carbonate;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; water; | A mixture of 2-fluoro-4-methoxy-3-trifluoromethanesulfonyl benzaldehyde (1.21 g, 4.01 mmol), <strong>[169126-64-1](3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)<strong>[169126-64-1]boronic acid</strong></strong> (1.08 g, 4.41 mmol) and potassium carbonate (2.22 g, 16.04 mmol) in 1,2-dimethoxyethane (30 mL) and water (2 mL) was degassed with argon for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.23 g, 0.2 mmol) was added and the mixture heated at reflux under argon for 16 hours. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (Biotage, eluent: ethyl acetate/hexane, 0.5:8.5) to give 0.87 g of 4-methoxy-2-fluoro-3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)benzaldehyde (62%). 1H NMR (500 MHz; CDCl3): delta1.26 (s, 6H), 1.32 (s, 6H), 1.69 (s, 4H), 2.07 (s, 3H), 3.85 (s, 3H), 7.07 (d, J=8.8 Hz, 1H), 7.07 (s, 1H), 7.19 (s, 1H), 7.90 (t, J=8.8 Hz, 1H), 10.25 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; water; | b. A mixture of 3-methoxy-2-trifluoromethanesulfonyl benzaldehyde (0.430 g, 1.51 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) <strong>[169126-64-1]boronic acid</strong> (0.740 g, 3.00 mmol) and potassium carbonate (0.835 g) in 1,2-dimethoxyethane (20 mL) and water (1 mL) was degassed with argon for 15 minutes. To this mixture was added tetrakis(triphenylphosphine)palladium(0) (0.35 g, 0.3 mmol) and the resulting mixture was heated at reflux under argon for 4 hours. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (ethyl acetate/hexane, 1:9) to give 0.48 g of 3-methoxy-2-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)benzaldehyde. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With sodium acetate;dichlorobis(triphenylphosphine)palladium[II]; In methanol; | Step 1 To a mixture of dichlorobis(triphenylphosphine)palladium(II) (220 mg, 0.3 mmol), sodium acetate (2.1 g, 15 mmol) and 3-chloro-cyclopentpent-2-enone (1.2 g, 10.3 mmol) in methanol (35 mL) at room temperature under nitrogen was added <strong>[169126-64-1]5,6,7,8-tetrahydro-3,5,5,8,8-pentamethyl-2-naphthalene<strong>[169126-64-1]boronic acid</strong></strong> (2.7 g, 11 mmol) and the mixture heated at reflux for 3 h, cooled to room temperature and filtered through a plug of Celite. Concentration under reduced pressure gave a residue which was purified by flash chromatography to give 3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)-cyclopent-2-enone (2.0 g, 73%). 1H NMR (CDCl3, 300 MHz): 1.27 (12H, s), 1.65 (4H, s), 2.47 (3H, s), 2.53 (2H, m), 3.03 (2H, m), 6.32 (6H, m), 7.18 (1H, s), 7.42 (1H, s). 13C NMR (CDCl3, 75 MHz): 209.9, 175.7, 147.1, 142.8, 133.3, 132.5, 131.6, 129.6, 125.6, 34.9, 34.2, 34.0, 31.9, 31.8, 31.6, 21.6. MS Calcd for C20H26O: 282.4. Found: 282.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; water; | b. 3-(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-4-methoxybenzaldehyde A mixture of <strong>[34841-06-0]3-bromo-4-methoxybenzaldehyde</strong> (19.0 g, 88.4 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)boronic acid (23.8 g, 97.2 mmol) and potassium carbonate (48.8 g, 353.6 mmol) in 1,2-dimethoxyethane (500 mL) and water (40 mL) was degassed with argon for 60 minutes. Tetrakis(triphenylphosphine)palladium(0) (5.0 g, 4.3 mmol) was added and the mixture heated at reflux under argon for 16 hours. The solution was cooled to room temperature, diluted with ethyl acetate (200 mL) and washed successively with water (100 mL) and brine (100 mL), dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (eluent: ethyl acetate/hexane, 1:9) to give 26.8 g of 3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-4-methoxy-benzaldehyde (90%). 1H NMR (500 MHz; CDCl3): delta1.26 (s, 6H); 1.32 (s, 6H); 1.70 (s, 4H); 2.08 (s, 3H); 3.89 (s, 3H); 7.06 (d, J=8.5 Hz, 1H); 7.09 (s, 1H); 7.16 (s, 1H); 7.71 (d, J=2.0 Hz, 1H); 7.88 (dd, J1=2.0 Hz, J2=8.5H (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; n-butyllithium; In tetrahydrofuran; hexane; | (a) 3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydro-2-naphthylboronic acid, 100 g (0.356 mol) of 2-bromo-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthalene and 1 litre of THF are introduced into a two-litre reactor under a stream of nitrogen, and the solution is cooled to -60 C. 157 ml (0.392 mol) of n-butyllithium (2.5 M in hexane) are added dropwise and the mixture is stirred for one hour. 121 ml (1.07 mol) of trimethyl borate are added dropwise at -70 C. and the mixture is stirred for one hour. 500 ml of hydrochloric acid (1 N) are added at -35 C. and the mixture is allowed to return to room temperature. The reaction medium is extracted with ethyl acetate and the organic phase is separated out after settling has taken place, washed twice with 500 ml of hydrochloric acid (1 N), dried over magnesium sulphate and evaporated. 83 g (95%) of the expected boronic acid are collected. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In a similar manner to Example 9(b), by reaction of 15 g (61 mmol) of 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl<strong>[169126-64-1]boronic acid</strong> with 8.16 g (41 mmol) of 5-bromo-2-hydroxybenzaldehyde, 11.7 g (89%) of 2-hydroxy-5-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)benzaldehyde are obtained, with a melting point of 138-9 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(b) 5-(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)-2-thiophenecarboxaldehyde In a similar manner to Example 3(b), by reaction of 4.2 g (17 mmol) of 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl<strong>[169126-64-1]boronic acid</strong> with 2.17 g (11.3 mmol) of 5-bromo-2-thiophenecarboxaldehyde, 2.1 g (60%) of the expected aldehyde are obtained, with a melting point of 130-5 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;tetrakis(triphenylphosphine)palladium (0); In 1,2-dimethoxyethane; ethanol; | (b) 3-(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)benzaldehyde 700 ml of DME, 2.4 g (2 mmol) of tetrakistriphenylphosphinepalladium(0) and 8.44 g (45.6 mmol) of 3-bromobenzaldehyde are introduced into a three-necked flask under a stream of nitrogen and the mixture is stirred for 10 minutes. A solution of 17 g (69.1 mmol) of 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl<strong>[169126-64-1]boronic acid</strong> in 25 ml of ethanol are then added, followed by 46 ml (91 mmol) of potassium carbonate solution (2 M) and the mixture is refluxed for four hours. The reaction medium is cooled and filtered and the solid is washed with bicarbonate solution and then with ethyl acetate. The solid obtained is recrystallized from ethanol and 7 g (50%) of the expected aldehyde are collected, with a melting point of 104-5 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(a) 4-(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)-2-pyrrolecarboxaldehyde In a similar manner to Example 3(b), by reaction of 2.47 g (10 mmol) of 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthylboronic acid with 1.5 g (8.4 mmol) of <strong>[931-33-9]4-bromo-2-pyrrolecarboxaldehyde</strong>, 950 mg (38.5%) of the expected aldehyde are obtained, with a melting point of 128-9 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(b) N-Methyl-4-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)-2-pyrrolecarboxaldehyde In a similar manner to Example 3(b), by reaction of 3 g (12.1 mmol) of 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl<strong>[169126-64-1]boronic acid</strong> with 1.9 g (10.1 mmol) of N-methyl-4-bromo-2-pyrrolecarboxaldehyde, 1.85 g (59%) of the expected product are obtained in the form of a pale yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(a) 4-(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)-2-thiophenecarboxaldehyde In a similar manner to Example 3(b), by reaction of 4.2 g (17 mmol) of 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl<strong>[169126-64-1]boronic acid</strong> with 2.17 g (11.3 mmol) of 4-bromo-2-thiophenecarboxaldehyde, 2.75 g (78%) of the expected aldehyde are obtained, with a melting point of 144-6 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 14 3-(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)phenylacrylic acid In a similar manner to Example 9(b), by reaction of 73.4 g (0.30 mol) of 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl<strong>[169126-64-1]boronic acid</strong> with 44.7 g (0.20 mol) of 4-bromophenylacrylic acid, and after recrystallization from ethanol, 48 g (61%) of 3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)phenylacrylic acid are obtained, with a melting point of 207-8 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrabutylammomium bromide; palladium diacetate; sodium carbonate; In water; at 20 - 150℃; for 0.333333h;Inert atmosphere; | To a 50 mL Schlenk flask charged with bromide 36 (0.4317 g, 1.60 mmol), <strong>[169126-64-1]boronic acid</strong> 33 (0.4010 g, 1.63 mmol), TBAB (0.52 g), Na2C03 (0.51 g, 4.81 mmol), and water (3.7 mL), was added Pd(OAc)2 (0.0203 g, 0.09 mmol), and the flask was evacuated and back-filled with nitrogen three times. The reaction was stirred at room temperature for 15 min and then placed in an oil bath pre-heated to 150 C and stirred for 5 min. The reaction was allowed to cool to room temperature, and the black residue was taken up in ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give a crude product that was purified by column chromatography (150 mL Si02, ethyl acetate:hexanes 1 :9) to give 37 (0.5032 g, 80%) as a colorless oil: ? NMR (400 MHz, CDC13) ? 7.68 (d, J= 16.0, 1H), 7.41 (dd, J= 8.0, 2.0, 1H), 7.33 (d, J= 1.6, 1H), 7.27 (d, J= 8.0, 1H), 7.16 (s, 1H), 7.00 (s, 1H), 6.39, (d, J= 16.0, 1H), 4.25 (q, J= 7.2, 2H), 2.09 (s, 3H), 2.01 (s, 3H), 1.70 (s, 4H), 1.33 (t, J= 7.2, 3H), 1.32 (s, 6H), 1.26 (s, 3H), 1.24 (s, 3H); 13C NMR (100.6 MHz, CDC13) ? 171.1, 167.2, 144.6, 143.8, 143.1, 142.5, 142.1, 141.6, 139.0, 138.8, 137.7, 132.8, 132.3, 131.7, 130.3, 129.3, 127.9, 127.6, 127.4, 127.2, 126.6, 1 17.2, 60.4, 60.3, 35.2, 35.1, 34.0, 33.9, 32.0, 31.9, 31.8, 31.8, 21.0, 20.0, 19.8, 19.5, 14.3, 14.1 ; LC-MS (M+H)+ calcd for C27H3502 391.2637, found 391.2655. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With tetrabutylammomium bromide; palladium diacetate; sodium carbonate; In water; at 20 - 150℃; for 0.333333h;Inert atmosphere; | To a 50 mL Schlenk flask charged with bromide 45 (1.03 g, 3.20 mmol), <strong>[169126-64-1]boronic acid</strong> 33 (0.8040 g, 3.27 mmol), TBAB (1.04 g), Na2C03 (1.02 g, 9.62 mmol), and water (7.4 mL), was added Pd(OAc)2 (0.0406 g, 0.18 mmol), and the flask was evacuated and back-filled with nitrogen three times. The reaction was stirred at room temperature for 15 min and then placed in an oil bath pre-heated to 150 C and stirred for 5 min. The reaction was allowed to cool to room temperature, and the black residue was taken up in ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give a crude product that was purified by column chromatography (150 mL Si02, ethyl acetate:hexanes 1 :9) to give 46 (1.0138 g, 71%) as a colorless oil: 1H NMR (400 MHz, CDC13) ? 7.75 (d, J= 8.4, 1H), 7.68 (d, J= 16.0, 1H), 7.57 (d, J= 8.0, 1H), 7.45 (s, 1H), 7.13 (s, 1H), 7.02 (s, 1H), 6.51 (d, J= 16.0, 1H), 4.26 (q, J= 7.2, 2H), 1.98 (s, 3H), 1.69 (s, 4H), 1.32 (t, J = 7.2, 3H), 1.31 (s, 6H), 1.24 (s, 3H), 1.22 (s, 3H); 13C NMR(100.6 MHz, CDC13) ? 166.4, 144.5, 142.6, 141.9, 141.3, 137.1, 135.1, 132.3, 131.1, 130.2, 129.9, 127.6, 127.3, 126.7, 126.6, 126.3, 125.0, 122.3, 120.8, 60.7, 35.1, 35.0, 33.9, 33.8, 31.9, 31.8, 31.7, 19.7, 14.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With tetrabutylammomium bromide; palladium diacetate; sodium carbonate; In water; at 20 - 150℃; for 0.333333h;Inert atmosphere; | To a 50 mL Schlenk flask charged with bromide 65 (0.434 g, 1.61 mmol), <strong>[169126-64-1]boronic acid</strong> 33 (0.4010 g, 1.63 mmol), TBAB (0.52 g), Na2C03 (0.51 g, 4.81 mmol), and water (3.7 mL), was added Pd(OAc)2 (0.0203 g, 0.09 mmol), and the flask was evacuated and back-filled with nitrogen three times. The reaction was stirred at room temperature for 15 min and then placed in an oil bath pre-heated to 150 C and stirred for 5 min. The reaction was allowed to cool to room temperature, and the black residue was taken up in ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give a crude product that was purified by column chromatography (150 mL Si02, ethyl acetate :hexanes 1 :9) to give 66 (0.4602 g, 73%) as a white solid: ? NMR (400 MHz, CDC13) ? 8.52 (s, 1H), 7.69 (d, J= 16.0, 1H), 7.24 (s, 1H), 7.18 (s, 1H), 6.95 (s, 1H), 6.90 (d, J= 16.0, 1H), 4.25 (q, J= 7.2, 2H), 2.10 (s, 3H), 2.00 (s, 3H), 1.69 (s, 4H), 1.33 (t, J= 7.2, 3H), 1.32 (s, 6H), 1.24 (s, 6H); 13C NMR (100.6 MHz, CDC13) ? 166.8, 151.2, 150.6, 150.3, 144.7, 143.3, 142.5, 135.2, 132.9, 131.6, 128.0, 126.4, 124.8, 121.5, 60.5, 35.1, 35.0, 34.0, 33.9, 31.9, 31.8, 19.3, 16.8, 14.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With tetrabutylammomium bromide; palladium diacetate; sodium carbonate; In water; at 20 - 150℃; for 0.333333h;Inert atmosphere; | To a 50 mL Schlenk flask charged with bromide69 (0.434 g, 1.61 mmol), <strong>[169126-64-1]boronic acid</strong> 33 (0.4010 g, 1.63 mmol), TBAB (0.52 g), Na2C03 (0.51 g, 4.81 mmol), and water (3.7 mL), was added Pd(OAc)2 (0.0203 g, 0.09 mmol), and the flask was evacuated and back-filled with nitrogen three times. The reaction was stirred at room temperature for 15 min and then placed in an oil bath pre-heated to 150 C and stirred for 5 min. The reaction was allowed to cool to room temperature, and the black residue was taken up in ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give a crude product that was purified by column chromatography (150 mL Si02, ethyl acetate :hexanes 1 :9) to give 70 (0.323 g, 51%) as a white solid: 1H NMR (400 MHz, CDC13) ? 8.61 (d, J= 2.0, 1H), 7.79 (d, J= 16.0, 1H), 7.63 (d, J= 2.4, 1H), 7.18 (s, 1H), 6.99 (s, 1H), 6.48 (d, J= 16.0, 1H), 4.25 (q, J= 7.2, 2H), 2.34 (s, 3H), 2.01 (s, 3H), 1.70 (s, 4H), 1.32 (t, J= 7.2, 3H), 1.31 (s, 6H), 1.25 (d, J= 7.2, 6H); 13C NMR (100.6 MHz, CDC13) ? 166.4, 158.6, 147.5, 144.7, 142.5, 140.9, 137.2, 135.5, 135.3, 132.2, 128.0, 127.5, 127.2, 1 19.4, 60.6, 35.1, 35.0, 34.0, 33.9, 31.9, 31.8, 31.8, 22.9, 19.5, 14.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With tetrabutylammomium bromide; palladium diacetate; sodium carbonate; In water; at 20 - 150℃; for 0.333333h;Schlenk technique; Inert atmosphere; | b. (E)-Ethyl 3-(4-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)pyridin-2- yl)acrylate (68). To a 50 mL Schienk flask charged with bromide 67 (0.4 125 g, 1.61 mmol), <strong>[169126-64-1]boronic acid</strong> 82 (0.411 g, 1.67 mmol), TBAB (0.52 g), Na2CO3 (0.51 g, 4.81 mmol), and water (3.7 mL), was added Pd(OAc)2 (0.0203 g, 0.09 mmol), and the flask was evacuated and back-filled with nitrogen three times. The reaction was stirred at room temperature for 15 mm and then placed in an oil bath pre-heated to 150 C and stirred for 5 mm. The reaction was allowed to cool to room temperature, and the black residue was taken up in ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give a crude product that was purified by column chromatography (150 mL Si02, 5% ethyl acetate:hexanes) to give 68 (0.56 g, 92%) as a white solid: ?H NMR (400 MHz, CDCI3) oe 8.65 (d, J 5.2, 1H), 7.73 (d, J 16.0, 1H),7.41 (d,J 0.8, 1H), 7.27 (dd,J= 5.2, 1.6, 1H), 7.22, (s, 1H), 7.14(s, 1H), 6.97 (d,J= 16.0, 1H),4.28 (q, J= 6.8, 2H), 2.25 (s, 3H), 1.71 (s, 4H), 1.34 (t, J= 7.2, 3H), 1.32 (s, 6H), 1.29 (s, 6H); ?3C NMR (100.6 MHz, CDC13) oe 166.7, 152.5, 151.2, 149.5, 145.6, 143.1, 143.0, 135.8, 131.8, 128.8, 127.4, 124.9, 124.8, 122.6, 60.6, 34.9, 34.0, 33.9, 31.8, 31.7, 19.9, 14.2; JR (neat) oe 2970, 1694, 1593 cm?; LC-FAB-MS (M+Na)+ calcd for C25H31NO2Na 400.2253, found 400.2237. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrabutylammomium bromide; palladium diacetate; sodium carbonate; In water; at 20 - 150℃; for 0.333333h;Schlenk technique; Inert atmosphere; | b. (E)-Ethyl 3-(5-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yI)pyridin-3- yl)acrylate (72). To a 50 mL Schienk flask charged with bromide 71(0.434 g, 1.61 mmol), <strong>[169126-64-1]boronic acid</strong> 82 (0.409 g, 1.66 mmol), TBAB (0.52 g), Na2CO3 (0.51 g, 4.81 mmol), and water (3.7 mL), was added Pd(OAc)2 (0.0203 g, 0.09 mmol), and the flask was evacuated and back-filled with nitrogen three times. The reaction was stirred at room temperature for 15 mm and then placed in an oil bath pre-heated to 150 C and stirred for 5 mm. The reaction was allowed to cool to room temperature, and the black residue was taken up in ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give a crude product that was purified by column chromatography (150 mL Si02, 6% ethyl acetate:hexanes to 8% ethyl acetate:hexanes) to give 72 (0.535 8 g, 88%) as a white solid, m.p. 114-1 19 C: 1H NMR (400 MHz, CDC13) oe 8.71 (d, J= 2.0, 1H), 8.60 (d, J= 2.0, 1H), 7.85 (t, J= 2.0, 111), 7.72 (d, J= 16.4, 111), 7.23 (s, 1H), 7.13 (s, 1H), 6.54 (d, J= 16.4, 1H), 4.25 (q, J= 7.2, 2H), 2.24 (s, 3H), 1.71 (s, 4H), 1.35 (t, J = 7.2, 311), 1.33 (s, 6H), 1.29 (s, 6H); ?3C NMR (100.6 MHz, CDC13) oe 166.1, 150.2, 146.6, 145.4, 143.1, 140.5, 138.2, 135.4, 134.1, 132.2, 129.9, 128.7, 127.9, 120.9, 60.8, 34.9, 34.0, 33.9, 31.8,31.7, 20.0, 14.2; IR (neat) oe 2956, 1709, 1644 cm?; LC-FAB-MS (M+H)+ calcd for C25H32N02378.2433, found 378.2441. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With tetrabutylammomium bromide; palladium diacetate; sodium carbonate; In water; at 20 - 150℃; for 0.333333h;Schlenk technique; Inert atmosphere; | b. (E)-Ethyl 3-(5-methyl-6-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2- yl)pyridin-2-yl)acrylate (76). To a 50 mL Schienk flask charged with bromide 75 (0.4355 g, 1.61 mmol), <strong>[169126-64-1]boronic acid</strong> 82(0.411 g, 1.67 mmol), TBAB (0.52 g), Na2CO3 (0.51 g, 4.81 mmol), and water (3.7 mL), was added Pd(OAc)2 (0.0203 g, 0.09 mmol), and the flask was evacuated and back- filled with nitrogen three times. The reaction was stirred at room temperature for 15 mm and then placed in an oil bath pre-heated to 150 C and stirred for 5 mm. The reaction was allowed to cool to room temperature, and the black residue was taken up in ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give a crude product that was purified by column chromatography (150 mL Si02, 5% ethyl acetate:hexanes) to give 76 (0.3 59 g, 57%) as a white solid, m.p. 127-130 C: ?H NMR (400 MHz, CDC13) (5 7.75 (d, J15.6, 1H), 7.59 (d,J= 8.0, 1H), 7.36 (d,J= 8.0, 1H), 7.17 (s, 1H), 7.08, (s, 1H), 6.83 (d,J= 15.6,1H), 4.25 (q, J= 7.2, 2H), 2.16, (s, 3H), 2.07 (s, 3H), 1.68 (s, 4H), 1.30 (t, J= 7.2, 3H), 1.30 (s, 6H),1.25 (s,6H); ?3CNMR(100.6MHz,CDC13)oe 166.9, 160.4,149.9,144.4,143.9,141.9,138.3,136.6,132.8, 128.3, 126.7, 121.6, 121.3, 60.4, 35.2, 35.1, 34.0, 33.9, 31.8, 19.4, 19.3, 14.2; JR (neat) (52957, 1713, 1646 1569 cm?; LC-FAB-MS (M+Na)+ calcd for C26H33NO2Na 414.2409, found414.2408. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With tetrabutylammomium bromide; palladium diacetate; sodium carbonate; In water; at 20 - 150℃; for 0.333333h;Schlenk technique; Inert atmosphere; | b. (E)-Ethyl 3-(6-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahyd ronaphthalen-2-yl)pyridin-2- yl)acrylate (80). To a 50 mL Schienk flask charged with bromide 79 (0.4 125 g, 1.61 mmol), <strong>[169126-64-1]boronic acid</strong> 82 (0.409 g, 1.66 mmol), TBAB (0.52 g), Na2CO3 (0.51 g, 4.81 mmol), and water (3.7 mL), was added Pd(OAc)2 (0.0203 g, 0.09 mmol), and the flask was evacuated and back-filled with nitrogen three times. The reaction was stirred at room temperature for 15 mm and then placed in an oil bath pre-heated to 150 C and stirred for 5 mm. The reaction was allowed to cool to room temperature, and the black residue was taken up in ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give a crude product that was purified by column chromatography (150 mL Si02, 3% ethyl acetate:hexanes) to give 80 (0.2723 g, 44%) as a white solid, m.p. 107-110 C: ?H NMR (400 MHz, CDC13) oe 7.77 (dd, J 15.6, 2.0, 1H),7.76 (d, J= 7.6, 1H), 7.41 (dd, J= 7.6, 0.8, 1H), 7.36 (dd, J= 7.6, 0.8, 1H), 7.35 (s, 111), 7.22 (s, 1H), 6.97 (d,J= 15.6, 1H), 4.27 (q,J= 7.2, 2H), 2.38 (s, 3H), 1.70 (s, 4H), 1.33 (t,J= 7.2, 3H), 1.30 (s, 12H); ?3CNMR (100.6 MHz, CDC13)6 166.9, 160.6, 151.9, 145.3, 143.4, 142.5, 137.0, 136.9, 132.9, 129.0, 127.9, 124.5, 122.3, 121.7, 60.5, 35.0, 34.0, 33.9, 31.9, 31.8, 20.2, 14.2; JR (neat) oe2956, 1710, 1645 cm?; LC-FAB-MS (M+Na)+ calcd for C25H3,NO2Na 400.2253, found 400.2247. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In 1,2-dimethoxyethane; at 120℃; for 1.25h;Microwave irradiation; Inert atmosphere; Sealed tube; | The following were introduced into a conical- bottomed 10 mE microwave reaction vessel 182 mg of (1,1,1 ,4,4,7-pentamethyltetralin-6-yl)<strong>[169126-64-1]boronic acid</strong> (o.74 mmol; 1.25 eq); 160 mg of methyl 1-(3-bromophenyl) azetidine-3-carboxylate (preparation 3; 0.59 mmol; 1 eq), then 4 mE of DME. The medium was placed under argon, then 556 pL ofa solution ofK2CO3 at 2.6 mol/E (1.18 mmol; 2 eq) and 24mg of Pd(dppf)C12,CH2C12 (0.029 mmol; 0.05 eq) were added. The reaction vessel was sealed and the soluble reaction mixture was stirred with a vortex and was then irradiated with microwaves for 1 h 15 at 120 C. The reaction medium was diluted with 1 N HC1 to pH 6. It was then extracted with EtOAc, and then washed with brine. The organic phase was dried over MgSO4, then filtered and concentrated under reduced pressure. The residue was purified by flash chromatography or silica using a cyclohexane/ 0% to 10% ethyl acetate gradient. 162 mg of the title compound were obtained in the form of a colorless paste.j1127] Yld: 70%.?H NMR (300 MHz, CHC13-d) oeppm 1.28 (s, 6H)1.32 (s, 6H) 1.70 (s, 4H) 2.22 (s, 3H) 3.49-3.63 (m, 1H) 3.75 (s, 3H) 3.98-4.15 (m, 4H) 6.44-6.47 (m, 2H) 6.75 (m, 1H) 7.16 (s, 2H) 7.20-7.23 (m, 1H). EC-MS: mlz (M+H): 392. |
Tags: 169126-64-1 synthesis path| 169126-64-1 SDS| 169126-64-1 COA| 169126-64-1 purity| 169126-64-1 application| 169126-64-1 NMR| 169126-64-1 COA| 169126-64-1 structure
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P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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