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CAS No. : | 338454-30-1 | MDL No. : | MFCD06409944 |
Formula : | C14H15BO3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | QPXFEWQLALNXEZ-UHFFFAOYSA-N |
M.W : | 242.08 | Pubchem ID : | 17750522 |
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 |
---|---|---|
65% | 4-Bromo-1-benzyloxy-2-methyl-benzene (6.9 g; 25 mmol) is dissolved in tetrahydrofuran (37.5 ml; dried over a molecular sieve) and the solution is cooled to -78 C. A 1.6 M n-butyllithium solution in n-hexane (17 ml; 27.5 mmol) is added dropwise in the course of 30 minutes such that the temperature does not rise above -70 C. After a further 10 minutes at this temperature, trimethyl borate (8.3 ml; 75 mmol) is added dropwise in the course of 25 minutes at below -70 C. The reaction mixture is allowed to warm slowly to room temperature overnight. It is then cooled to 0 C. and an aqueous 1 N hydrochloric acid solution is added dropwise. The reaction mixture is diluted with water and ethyl acetate, the phases are separated and the aqueous phase is re-extracted with ethyl acetate. The combined organic phases are washed successively with water and a saturated aqueous sodium chloride solution, dried over magnesium sulphate, filtered with suction and concentrated. [00235] Yield: 3.95 g (65%) 4-benzyloxy-3-methyl-phenylboron acid as a white powder. [00236] MS(ISN): 301.2 (M-H)- |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In water; acetonitrile; at 80℃; for 48.0h;Inert atmosphere; | Step E. Ethyl 1-{6-[4'-(benzyloxy-4-chloro-3'-methylbiphenyl-2-yl]pyridin-2-yl}-5-(trifluoromethyl)-1H-pyrazole-4-carboxylate To a flask containing the product from the above Step D (2.11 g, 3.88 mmol) were added <strong>[338454-30-1][4-(benzyloxy)-3-methylphenyl]boronic acid</strong> (1.410 g, 5.83 mmol) and dichloro bis(triphenylphosphine)palladium (0.41 g, 0.58 mmol). Acetonitrile (25 mL) and sodium carbonate (7.77 mL of 1.0 M aqueous solution, 7.77 mmol) were added, and the resulting mixture was degassed via nitrogen sparge. The reaction mixture was stirred at 80 C. for 48 h, then was allowed to cool to room temperature and was poured into water. The mixture was extracted with EtOAc, and the organic phase was concentrated in vacuo. Purification by chromatography on silica gel (0 to 25% EtOAc in hexanes, then 30 to 100% EtOAc in hexanes) provided the title compound: LCMS m/z 591.9 [M+H]+; 1H NMR (500 MHz, CDCl3) delta 8.15 (s, 1H), 7.74 (d, J=2.2 Hz, 1H), 7.59 (t, J=7.9 Hz, 1H), 7.48-7.31 (m, 8H), 6.98 (d, J=1.8 Hz, 1H), 6.93 (d, J=7.7 Hz, 1H), 6.87 (dd, J=8.4, 2.2 Hz, 1H), 6.77 (d, J=8.4 Hz, 1H), 5.06 (s, 2H), 4.40 (q, J=7.1 Hz, 2H), 2.21 (s, 3H), 1.40 (t, J=7.2 Hz, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68.4% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In N,N-dimethyl-formamide; at 120℃; for 0.5h;Inert atmosphere; | This compound was prepared from compound XXIa in accordance with scheme 2 using 4-benzyloxy-3-methylphenylboronic acid (compound VI with R?=H, R?3- CH3). Compound XXIa (445 mg; 1.50 mmol; 1 eq) was dissolved in 10 mL DMF. 4- benzyloxy-3-methylphenylboronic acid (436 mg; 1.80 mmol; 1.2 eq) and sodiumcarbonate (397 mg; 3.75 mmol; 2.5 eq) were added under stirring and the mixtures was degassed with argon for 5 mi Tetrakis(triphenylphosphine)-palladium(0) (87 mg; 0.075 mmol; 0.05 eq) was added and the mixture was stirred for 30 mm at 120C. The mixture was evaporated. The residue was extracted with DCM/water. After phase separation, the organic phase was washed one with water, dried withMgSO4 and evaporated. The oily residue was dissolved in DCM and purified by flash chromatography (silica gel, DMC/MeOH 95:5 giving the product with a yield of 470mg (1.025 mmol; 68.4%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39.9% | With sodium carbonate; In N,N-dimethyl-formamide; at 120℃; for 1.0h;Inert atmosphere; | Compound IXc was prepared in accordance with scheme 2 starting from tert-butyl2-chloro- 7,8- dihydro- 1, 6-naphthyridine- 6(5H)-carboxylate instead of compound IIIusing <strong>[338454-30-1](4-(benzyloxy)-3-methylphenyl)boronic acid</strong> (compound VI with R?=H,R?=CH3). Tert-butyl 2-chloro- 7,8- dihydro- 1,6- naphthyridine- 6(5H) -carboxylate (500mg; 1.86 mmol; 1 eq) and <strong>[338454-30-1](4-(benzyloxy)-3-methylphenyl)boronic acid</strong> (540 mg;2.233 mmol; 1.2 eq) were dissolved in DMF (15 mL) to give a yellow solution.Sodium carbonate (493 mg; 4.65 mmol; 2.5 eq) was added and the mixtures wasdegassed with argon for 30 mm.Tetrakis(triphenylphosphine)-palladium(0) (107 mg; 0.093 mmol; 0.05 eq) was added and the mixture was stirred for lh at 120C. The reaction mixture was evaporated and the residue was dissolved in DCM. The crude product was subsequently washed with water and a saturated NaC1 solution. The organic phasewas dried over Mg504, filtered and evaporated. The residue was absorbed on Celite XTR and purified by flash chromatography (12g silica gel, 0-10% MeOH in DCM) giving tert-butyl 2- (4- (benzyloxy) - 3-methylphenyl) -7,8- dihydro- 1,6- naphthyridine6(5H)-carboxylate with a yield of 320 mg (0.743 mmol; 39.9%). |
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