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CAS No. : | 13061-96-6 |
Formula : | CH5BO2 |
M.W : | 59.86 |
SMILES Code : | CB(O)O |
MDL No. : | MFCD00002105 |
InChI Key : | KTMKRRPZPWUYKK-UHFFFAOYSA-N |
Pubchem ID : | 139377 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
77% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate In N,N-dimethyl-formamide at 100℃; for 2 h; | A solution of ethyl 5-bromopyrazolo[1,5-ajpyridine-3-carboxylate (1.0 g, 3.73 mmol),methylboronic acid (448 mg, 7.46 mmol), Pd(dppf)C12 (545 mg, 0.746 mmol) and C52CO3(2.42 g, 7.46 mmol) was dissolved in DMF (5.0 mL), then the mixture was stirred at 100 °Cfor two hours. It was concentrated, and purified by silica gel chromatography with PE:EA=5: 1to obtain the desired compound as an orange solid (589 mg, 77percent). ESI MS m/z = 204.5[M+Hj. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.2% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate In 1,4-dioxane; water at 105℃; for 16 h; Inert atmosphere | To a mixture of 6-bromo-3,4-dihydro-2H-isoquinolin-1-one (19.0 g, 82.4 mmol),CH3B(OH)2 (20.8 g, 329 mmol) and Na2CO3 (18.4 g, 165 mmol) in 1,4-dioxane (200 mL)and water (10.0 mL) is added [1,1’-bis(diphenylphosphino)ferrocene]dichloropalladium (II) (2.46 g, 3.29 mmol) under a nitrogen atmosphere and the mixture is stirred at 105 °C for 16 hours under a nitrogen atmosphere. The suspension is filtered through a pad of diatomaceous earth and the filter cake is washed with DCM (3 x250 mL). The combined filtrates are washed with water (100 mL) and brine (80 mL), dried over Na2SO4, and the solvent isevaporated under reduced pressure. The crude product is purified by silica gel flash chromatography, eluting with a gradient of 0percent to 50percent EtOAc in PE to give the title compound (13.0 g, 95.2percent) as a yellow solid. ES/MS (m/z): 162.0 (M+H), ‘H NIVIR (400MHz, CDC13) 7.94 (d, J=8.0 Hz, 1H), 7.15 (d, J=7.8 Hz, 1H), 7.02 (s, 1H), 6.89 (br s, 1H),3.55 (dt, J=2.9, 6.6 Hz, 2H), 2.94 (t, J=6.5 Hz, 2H), 2.37 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydrogencarbonate;tetrakis(triphenylphosphine) palladium(0); In monoethylene glycol diethyl ether; water;Heating / reflux; | The procedure described by Lisowski et al. (see J. Org. Chem., 2000, 65: 4193) was followed. Intermediate 79 (1.12 g, 3.28 mmol) and tetrakis(triphenylphosphine)palladium (190 mg, 0.16 mmol) were taken up in 100 mL of ethylene glycol dimethyl ether in a 500 mL round-bottom flask. This solution was purged three times by opening to vacuum followed by backfilling with nitrogen. Methylboronic acid (390 mg, 6.6 mmol) was added, followed by a solution of sodium bicarbonate (0.55 g, 6.6 mmol) in 100 mL of water, and the evacuation/nitrogen backfill procedure was repeated once more. The mixture was heated at reflux temperature and monitored for product appearance/starting material disappearance by LC-MS analysis. After 1.5 hours, an additional 190 mg (0.16 mmol) of the palladium catalyst was added and the reaction allowed to be heated at reflux temperature overnight. The organic solvent was removed and the remaining aqueous mixture was partitioned between 100 mL each of 2 M hydrochloric acid and ethyl acetate. The aqueous layer was extracted with additional ethyl acetate and the combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated to give the crude product, which was purified by flash chromatography over silica gel (0-6% ethyl acetate in dichloromethane) to give intermediate 80 of sufficient purity (the product contained about 20% of the deiodinated side-product, 7-(trifluoromethyl)isatin). 1H NMR (400 MHz, DMSO-d6) delta 3.33 (s, 3H), 7.62 (s, 1H), 7.68 (s, 1H), 11.35 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100 mg | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate; In 1,4-dioxane; water; at 100℃; for 18.0h; | A suspension of 4,6-dichloropyridin-2-amine (1.63 g, 10 mmol), methylboronic acid (0.6 g, 10 mmol), Cs2C03 (9.75 g, 30 mmol), and Pd(dppf)Cl2 (400 mg) in dioxane/water (4: 1, 50 mL) was stirred for 18 hours at 100 C. The reaction was diluted with water and extracted with EtOAc (50 mLx3). The combined organic layer was washed with water and brine. The resulting solution was concentrated under reduced pressure and the residue was purified via prep-HPLC to afford 4-chloro-6-methylpyridin-2-amine (100 mg) as brown solid. MS ESI calcd. For C6H7C1N2 [M + H]+ 143, found 143. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With potassium phosphate; palladium diacetate; triphenylphosphine; In tetrahydrofuran;Inert atmosphere; Reflux; | A solution of 19 (1.4 g, 6.1 mmol), methyl boronic acid (0.6 g, 9.3 mmol), Pd(OAc)2 (0.07 g, 0.31 mmol), PPh3 (0.16 g, 0.61 mmol), and K3PO4 (5.2 g, 24 mmol) in dry THF were stirred at reflux under N2 atm overnight. After cooling at room temperature, crude was filtered through celite, concentrated by rotary evaporation, and purified by column chromatography to give 6-methyl-3,4-dihydronaphthalen-1(2H)-one (20) (88%). 1H NMR (600 MHz, CDCl3) delta 7.93 (d, J=12.0 Hz, 1H), 7.11 (d, J=12.0 Hz, 1H), 7.06 (s, 1H), 2.92 (t, J=6.0 Hz, 2H), 2.63 (t, J=12.0 Hz, 2H), 2.37 (s, 3H), 2.13-2.10 (m, 2H). GC-MS (ES) for C11H12O [M]+ 160 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.8% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In 1,4-dioxane; at 90℃; for 5h;Inert atmosphere; | A mixture of bromide 1 (1.0 g, 4.78 mmol), methyl boronic acid (860 mg, 14.3 mmol), Pd(dppf)2Cl2 (194 mg, 0.239 mmol), and K2CO3 (1.32 g, 9.56 mmol) in dioxane (20 mL) was degassed and stirred at 90 C. for 5 h under nitrogen. The reaction mixture was concentrated, and the residue was purified by silica gel chromatography (EtOAc/petroleum ether=1/4) to give the desired product (636 mg, 4.39 mmol, 91.8%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In 1,4-dioxane; at 80℃; | Step 2: 5-methyl-2-(trifluoromethoxy) aniline 5-bromo-2-(trifluoromethoxy) aniline (1.14g, 4.46mmol) obtained from the last step, methyl boronic acid (0.72g, 12mmol), potassium carbonate (1.66g, 12mmmol), [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (0.29g, 0.4mmol) and 1,4-dioxane (25mL) were added to a 100mL reaction flask. The reaction mixture was heated up to 80 C and stirred overnight. After completion of the reaction, the reaction solution was concentrated and dissolved in ethyl acetate. The organic phase was washed with saturated ammonium chloride and saturated brine, dried, concentrated and purified by column chromatography (ethyl acetate/petroleum ether=1:15) to obtain the title compound (yellow oil, 0.61g, 72%). (MS: [M+1] 192.1) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
344 mg | With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In 1,4-dioxane; at 100.0℃; for 6.0h; | Cesium carbonate (338 mg), methylboronic acid (47 mg), and tetrakis(triphenylphosphine)palladium (60 mg) were added to a 1,4-dioxane (3 ml) solution containing 2,3-dichloro-5-nitropyridine (100 mg), followed by stirring at 100C for 6 hours. The reaction solution was adjusted to room temperature, and water was added, followed by extraction with ethyl acetate. The resultant was washed with saturated saline and dried over anhydrous sodium sulfate, the solvent was distilled away under reduced pressure, and 3-chloro-2-methyl-5-nitropyridine (344 mg) was thus obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 100℃;Inert atmosphere; | Methyl boronic acid (2.30 g, 38.4 mmol), c2 (7.95 g, 30.7 mmol) and K2CO3(8.48 G, 61.4 mmol) dissolved in toluene (150 ml) and water (30 ml) in. The mixture through the degassing by bubbling by nitrogen for 30 minutes, and add four trityl phosphorus palladium Pd (PPh3)4(1.78G,1 . 53 mmol). The mixture is then maintained at 100 C lower overnight. After the completion of the reaction, the mixture is cooled to room temperature, toluene extraction, and for brine and washed. The organic solution is filtered and evaporation. The crude product by column chromatography, using ethyl acetate in heptane gradient mixture (20% to 65%) purification. The white powder product by the heptane recrystallized three times, to get to the colorless crystal e2. In a 1 L three-opening in the bottle, adding hydration iridous chloride (14.1 g, 40 mmol) and compound e2 (33.02 g, 170 mmol), then add 300 mL2 - ethoxy ethanol and 100 ml of water, the mixture at reflux overnight under a nitrogen atmosphere. After the reaction, cooling to room temperature, the methanol precipitation and filtration and washing, drying to obtain intermediate A2 (24.00 g, yield 90%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In N,N-dimethyl-formamide; at 120℃; | A mixture of <strong>[953039-63-9]8-bromo-2-chloro-6-fluoroquinazoline</strong> (500 mg, 1.91 mmol, 1 equiv), methylboronic acid (114.5 mg, 1.91 mmol, 1 equiv), K2CO3 (528.6 mg, 3.82 mmol, 2 equiv), Pd(dppf)Cl2 (139.9 mg, 0.19 mmol, 0.1 equiv) in 20 mL of DMF was stirred overnight at 120C. The reaction was then quenched by the addition of 50 mL of water, extracted with ethyl acetate (2x20 mL) and the combined organic layers concentrated. The residue was purified by silica gel chromatography with ethyl acetate/petroleum ether (1 :3) to afford the desired product as a yellow solid in 53% yield. |
53% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In N,N-dimethyl-formamide; at 120℃; | A mixture of <strong>[953039-63-9]8-bromo-2-chloro-6-fluoroquinazoline</strong> (500 mg, 1.91 mmol, 1 equiv), methylboronic acid (114.5 mg, 1.91 mmol, 1 equiv), K2C03 (528.6 mg, 3.82 mmol, 2 equiv), Pd(dppf)Cl2 (139.9 mg, 0.19 mmol, 0.1 equiv) in 20 mL of DMF was stirred overnight at l20C. The reaction was then quenched by the addition of 50 mL of water, extracted with ethyl acetate (2x20 mL) and the combined organic layers concentrated. The residue was purified by silica gel chromatography with ethyl acetate/petroleum ether (1 :3) to afford the desired product as a yellow solid in 53% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium phosphate; palladium diacetate; tricyclohexylphosphine; In water; toluene; at 100℃; for 10h;Inert atmosphere; | Example 66A 3-methylisonicotinonitrile To a mixture of 3-chloroisonicotinonitrile (50 g) in toluene (1.5 L) was added K3PO4 (306 g), and the mixture was stirred for 10 minutes at 25 C. Methylboronic acid (32.4 g) and tricyclohexylphosphine (10.12 g) were added. After 5 minutes, 150 mL of water was added, and the mixture was stirred for 5 minutes at 25 C. Diacetoxypalladium (2.431 g) was added under a nitrogen atmosphere. The resulting mixture was stirred for 10 hours at 100 C. Eleven additional reactions were set up as described above. After cooling to 20 C., all twelve reaction mixtures were combined. 5 L of water was added to the mixture, and the layers were separated. The organic phase was dried over sodium sulfate, filtered and concentrated under reduced pressure to give a residue, which was purified by silica gel chromatography using 1-20% ethyl acetate in heptanes as the eluent to provide the title compound. 1H NMR (400 MHz, chloroform-d) delta ppm 8.68 (s, 1H), 8.60 (d, 1H), 7.46 (d, 1H), 2.56 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In 1,4-dioxane; water; at 95.0℃;Inert atmosphere; | A flask charged with 8-bromo-9H-purin-6-ylamine (500 mg, 2.3 mmol), methylboronic (200 mg, 3.5mmol), Pd(dppf)Cl2 (84 mg, 0.115 mmol) and K2C03 (938 mg, 0.9 mmol) in dioxane/H20 (50 mL/l0 mL) was degassed and filled with N2. The mixture was stirred at 95 C overnight. Solvent was removed and the residue was purified with prep-TLC (DCM/MeOH = 10/1) to give 8-methyl-9H-purin-6-ylamine (150 mg, yield: 43 %) as yellow solid. MS: m/z 150.0 (M+H+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(II) chloride; triethylamine; In methanol; at 20℃; for 12h; | General procedure: A flame-dried 25 mL reaction tube was placed with a stirring bar. Then, Nmethylisatoicanhydride (2 mmol), amine compounds (1.0 equiv) and EtOAc (4.0 mL)were added. The resulting mixture was stirred at 70 for 24 hours. Then, the reactionmixture was concentrated and purified by column chromatography (silica gel) to givethe target product A. A flame-dried 100 mL round-bottom flask was placed with a stirring bar. Then, A(1.5 mol), R2B(OH)2 (1.5 equiv), CuCl (20 mol%), Et3N (50 mol%) and MeOH (30 mL)were added, The resulting mixture was stirred at room temperature for 12 hours. Then,the reaction mixture was filtered, concentrated, and purified by columnchromatography (silica gel) to give the target product B. |
Tags: Methylboronic acid | Organoboron | Aliphatic Chain Hydrocarbons | Boronic Acids | Organic Building Blocks | Boronic Acids/Esters | Organometallic Reagents | 13061-96-6
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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 |
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