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CAS No. : | 14047-29-1 |
Formula : | C7H7BO4 |
M.W : | 165.94 |
SMILES Code : | C1=CC(=CC=C1B(O)O)C(=O)O |
MDL No. : | MFCD00151801 |
InChI Key : | SIAVMDKGVRXFAX-UHFFFAOYSA-N |
Pubchem ID : | 312183 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H303-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 |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In toluene; for 10h; | 35.144 mmol of 4-bromopyridine hydrochloride, 35.144 mmol, were weighed separately4-carboxyphenylboronic acid and 10 mmol of sodium carbonate were added to a toluene solution, and 0.08 mmol was addedOf tetraprophenylphosphonium palladium, in the catalyst tetrasthenyl phosphorus palladium under the action,Reaction for 10 h to obtain a white intermediate.The intermediate product is dried,Adding thionyl chloride,inReflux at 80 ° C,After completion of the reaction, the excess solvent was evaporated to dryness to give a yellow solid.The yellow solid was mixed with 5-aminoisophthalic acid in DMF and reacted at room temperature for 3 h. The reaction solution was added to 500 mL of distilled water,Precipitation of a large number of solid, that is, H2PYBI ligand. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; triethylamine; In dichloromethane; at 20℃; | To a mixture of 4-carboxyphenyl boronic acid (0.200 g, 1. 21 mmol), aniline (0.13 mL, 1. 45 mmol) and triethylamine (0.34 ML, 2.41 mmol) in dichloromethane (3 mL) was added benzotriazole-l-yl-oxy-tris (pyrrolidine) -phosphonium hexafluoro- phosphate (0.753 g, 1.45 mmol) at room temperature, and the stirring was continued overnight. The mixture was diluted with water and extracted with ethyl acetate. The separated organic phase was washed with saturated sodium carbonate solution and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by recrystallization from ethyl acetate to give [4- (anilinocarbonyl) phenyl] boronic acid (0.183 g, 63%) as a colorless solid. |
42% | General procedure: Toluene (25 mL) and activated 4A molecular sieve beads (0.5 g) were added to a solution of 3-CPBA or 4-CPBA (166 mg, 1 mmol) in MeOH (3 mL) and the mixture was magnetically stirred at 60 C for 1h. APTES (0.468 mL, 2 mmol) was then added and the mixture was stirred at 60 C for additional 24 h followed by the filtration through a pad of Celite 545 and evaporation of the solvent on a rotary evaporator. The oily residue was suspended in 0.5 M aqueous HCl (20 mL) and the product was extracted with EtOAc (3×30 mL). The combined organic layers were washed with distilled water (3 ×20 mL) until neutral pH, dried with anhydrous MgSO4, filtered and the solvent was evaporated to afford I (292 mg, 79 %) or II (306 mg, 83 %) as white solid with purity higher than 95 % (according to 1H NMR data) | |
40.8% | With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; triethylamine; In N,N-dimethyl-formamide; at 20℃; for 12h; | General procedure: A suspension of 3-boronobenzoic acid (1.0 g, 5.9 mmol), aniline (0.65 g, 7 mmol), Et3N (1.29 g, 12 mmol) and PyBop (3.6 g, 7 mmol) in DMF(10 mL) was stirred for 12 h at r t. After completion of reaction, the solution was diluted with H2O (15 mL), and then the product was extracted three times with EtOAc (50 mL). The combined organic layer was dried over Na2SO4, and the solvent was removed in vacuo, the crude product was purified on a silica gel column using (1-5%) CH3OH/DCM as eluent to afford 16a (1.47 g, 75%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Production Example 22 4-[6-(Difluoromethyl)-3-pyridyl]benzenecarboxylic acid Operations similar to those of Production Example 14 were conducted using 4-carboxyphenylboronic acid and 5-bromo-2- (difluoromethyl)pyridine, to provide the title compound as white solid. ESI-MS Found:m/z 248[M-H]- |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | To a suspension of 4-carboxyphenylboronic acid (5.0 g, 30 mmol) in DMF (5 mL) and dichloromethane (200 mL) at 0C was added oxalylchloride (5.9 mL, 66 mmol) dropwise. <n="54"/>When gas evolution slowed, the ice bath was removed and the reaction allowed to warm to room temperature over 30 min. The reaction was then heated at 4O0C for 3 h by which time all solids had dissolved. The dichloromethane was removed by distillation and the DMF solution cooled to 00C. A solution of aminoacetonitrile hydrochloride (3.05 g, 33 mmol) in DMF (80 rnL) and DIPEA (13 mL, 75 mmol) was then added dropwise. After the addition was complete the ice bath was removed and the solution allowed to stir at room temperature for 16 h. Most of the DMF was then removed in vacuo and the reaction was partitioned between ethyl acetate and 2 M aqueous hydrochloric acid. The aqueous layer was extracted twice further with ethyl acetate and the combined organic fractions dried (Na2SO4) filtered and concentrated under reduced pressure to afford 4-(cyanomethylcarbamoyl)phenylboronic acid as a waxy pale yellow solid (5.34 g, 87%). 1HNMR (J6-DMSO, 300 MHz) delta 9.18 (IH, br. t, J= 5.1Hz), 7.8-7.9 (4H, m), 4.31 (2H, d, J= 5.4 Hz). LC-MS: rt 0.9 min.; m/z 203.3 [M-H]". | |
87% | Example 3 - Synthesis of Compound 90; To a suspension of 4-carboxyphenylboronic acid (5.0 g, 30 mmol) in DMF (5 mL) and dichloromethane (200 mL) at 0C was added oxalylchloride (5.9 mL, 66 mmol) dropwise. When gas evolution slowed, the ice bath was removed and the reaction allowed to warm to room temperature over 30 min. The reaction was then heated at 400C for three hours by which time all solids had dissolved. The dichloromethane was removed by distillation and the DMF solution cooled to 0C. A solution of aminoacetonitrile hydrochloride (3.05 g, 33 mmol) in DMF (80 mL) and DIPEA (13 mL, 75 mmol) was then added dropwise. After the addition was complete the ice bath was removed and the solution allowed to stir at room temperature for 16 h. Most of the DMF was then removed in vacuo and the reaction was partitioned between ethyl acetate and 2 M aqueous hydrochloric acid. The aqueous layer was extracted twice further with ethyl acetate and the combined organic fractions dried (Na2SO4) filtered and concentrated under reduced pressure to afford 4-(cyanomethylcarbamoyl)phenylboronic acid as a waxy pale yellow solid (5.34 g, 87%). 1H NMR (300 MHz, J6-DMSO): 9.18 (br. t, J- 5.1Hz, IH), 7.8-7.9 (m, 4H), 4.31 (d, J= 5.4 Hz, 2H); LC-ESI-MS (method B): rt 0.9 min.; m/z 203.3 [M-H]-. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In water; acetonitrile; at 100℃; for 24h;Inert atmosphere; | Example 159 A4-(pyridin-4-yl)benzoic acid; To a solution of 4-boronobenzoic acid (1.66 g, 10 mmol) and 4-bromopyridine (1.72 g, 11 mmol) in acetonitrile (40 mL) and water (40 mL), potassium carbonate (5.5 g, 40 mmol), Bis(triphenylphosphine)palladium(II) chloride (400 mg, 0.37 mmol) was added. The mixture was degassed and purged withed nitrogen. The mixture was stirred at 100° C. for 24 h. Then the hot suspension was filtered and concentrated to half of the original volume and washed with dichloromethane. The aquatic phase was adjusted to pH=3 with hydrochloric acid (1 M) and filtrated, washed with water. The residue was dried in vacuum to obtain 1.8 g of white solid of 4-(pyridin-4-yl)benzoic acid. Yield: 90percent. LC-MS (ESI) m/z: 200 (M+1)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
29.1% | To a mixture of <strong>[959121-99-4]3-bromo-7-methoxyquinoline</strong> (Intermediate 13, 380 mg, 1.6 mmol), 4-boronobenzoic acid (266 mg, 1.6 mmol) and Na2C03 (848 mg, 8.0 mmol) in DME/H20/EtOH (5 mL, V/V/V = 1/1/0.5) was added Pd(dppf)Cl2 (585 mg, 0.8 mmol). The mixture was heated to 120C by microwave for 1 h. The mixture was partitioned between water (20 mL) and ethyl acetate (20 mL). The aqueous phase was separated and acidified to pH = 3 with 1 N HC1. The precipitate was filtered and dried in vacuo to afford product as a powder (130 mg, 29.1%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9.25% | With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In 1,4-dioxane; ethanol; water; at 80℃; for 9h;Inert atmosphere; | A solution of 4-boronobenzoic acid (22.2, 2.0 g, 12.0 mmol) and <strong>[131747-63-2]4-bromopicolinaldehyde</strong> (22.2a, 2.24 g 12.0 mmol) in dioxane (30 mL), ethanol (30 mL) and a solution of sodium carbonate in water (8 mL) was purged with argon for 15 minutes followed by addition of PdC12 (PPh3)2 (0.42 g, 0.60 mmol). The mixture was again purged with argon for 10 minutes and then heated at 80°C for 9 h. After completion, solvents were removed under reduced pressure and the mixture was diluted with ice cold water (100 mL) and extracted with ethyl acetate (450 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to get crude. The crude was purified by silica gel (100-200 mesh) column chromatography eluting with 5-10percent methanol in dichloromethane to afford 4-(2- formylpyridin-4-yl)benzoic acid (22.1). Yield: 0.250 g, 9.25percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sodium carbonate; In ethanol; water; at 20℃; for 1.25h;Green chemistry; | General procedure: To a solution of aryl halide (1 equiv.), aryl boronic acid (1.1 equiv.) and sodium carbonate (2.5 equiv.) in ethanol (EtOH):water (H2O) (1:1) (5mL), hexagonal boron nitride tethered N-heterocyclic carbene-palladium(II) complex (h-BN(at)NHC-Pd) (0.02mol% Pd) was added and stirred at room temperature for required period of time. On completionof the reaction monitored by TLC, the h-BN(at)NHC-Pd heterogeneous catalyst was separated from the reaction massby centrifugation. DCM (20mL) was added to the residual reaction mixture. Then DCM layer was separated using a separatory funnel. The DCM layer was washed with water, brine solution and dried over anhydrous Na2SO4.The driedDCM layer was concentrated in vacuum and purified through column chromatography using hexane and ethyl acetate as eluents to get the corresponding products in good to excellent yields. All the cross-coupled products were analyzed by 1H NMR spectroscopy and compared with the standards. |
88% | With potassium carbonate; In ethanol; water; at 20℃; for 1h;Green chemistry;Quantum yield; | General procedure: In a 10 mL glass vial equipped with a cap containing 5 mL of ethanol:water (1:1) mixture, aryl halide (1 equiv), phenylboronic acid (1.1 equiv), K2CO3 (2.5 equiv) were added followed by dipping of the dip catalyst into the reaction mixture which was then stirred magnetically at room temperature for required time. The progress of the reaction was monitored by thin layer chromatography (TLC). After reaction completion, the dip catalyst was simply removed from the reaction mass and washed with ethanol (1 x 5 mL) and water (1 x 5 mL) and was reused without purifying further. The product was extracted using dichloromethane (2 x 10 mL) and the combined organic layer was subjected to water wash (2 x 10 mL) followed by drying of the organic layer over Na2SO4. The dried organic layer was concentrated in vacuo, and the product was purified by column chromatography using n-hexane and ethyl acetate as eluents to afford the corresponding products in good to excellent yields. All the coupled products were known molecules and were confirmed by comparing with our previous standards (Kandathil et al., 2017; Vishal et al., 2017). |
Tags: 4-Boronobenzoic acid | Organoboron | Carboxylic Acids | Aryls | Boronic Acids | Fluorinated Building Blocks | Organic Building Blocks | Boronic Acids/Esters | Organometallic Reagents | 14047-29-1
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