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CAS No. : | 4334-88-7 | MDL No. : | MFCD02179441 |
Formula : | C9H11BO4 | Boiling Point : | - |
Linear Structure Formula : | C2H5OCOC6H4B(OH)2 | InChI Key : | ZLNFACCFYUFTLD-UHFFFAOYSA-N |
M.W : | 193.99 | Pubchem ID : | 2734350 |
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: |
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* 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 caesium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; for 18h;Heating / reflux; | Intermediate 44; 5 ' -Cyano-2 ' -methyl-biphenyl-4-carboxylic acid ethyl ester; A mixture of <strong>[42872-74-2]3-bromo-4-methyl-benzonitrile</strong> (600mg), 4-(ethoxycarbonylphenyl) boronic acid (594mg), cesium carbonate (995mg) and tetrakis(triphenylphosphine) palladium (0), 5 mol% (180mg) was heated to reflux under nitrogen in DME (30 ml) and water (15ml) for 18 h. The reaction mixture was then cooled to room temperature and filtered. The resulting filtrate was then evaporated and purified on silica gel, gradient elution with 10-20% ethyl acetate in petrol gave the title compound as a pale yellow solid (867mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In toluene; at 75 - 100℃; | Example 1 - Synthesis of Compound 3; A mixture of 4-ethoxycarbonylphenyl boronic acid (23.11 g, 119 mmol), 2,4- dichloropyrimidine (16.90 g, 113 mmol), toluene (230 mL) and aqueous sodium carbonate (2 M, 56 mL) was stirred vigorously and nitrogen was bubbled through the suspension for 15 minutes. Tetrakis(triphenylphosphine)palladium[0] (2.61 g, 2.26 mmol) was added. Nitrogen was bubbled through for another 10 min., the mixture was heated to 100C, then at 75C overnight. The mixture was cooled, diluted with ethyl acetate (200 mL), water (100 mL) was added and the layers were separated. The aqueous layer was extracted with ethyl acetate (100 ml) and the two organic extracts were combined. The organics were washed with brine, filtered through sodium sulfate, <n="58"/>concentrated, and the resultant solid was triturated with methanol (100 niL) and filtered. The solids were washed with methanol (2 x 30 mL) and air dried. This material was dissolved in acetonitrile (150 mL) and dichloromethane (200 mL), stirred with MP.TMT Pd-scavenging resin (Agronaut part number 800471) (7.5 g) over 2 days. The solution was filtered, the solids were washed with dichloromethane (2 x 100 mL), and the filtrate concentrated to give ethyl 4-(2-chloropyrimidin-4-yl)benzoate as anoff-white solid (17.73 g, 60%) - additional washing with dichloromethane yielded a further 1.38 g and 0.5 g of product. 1H NMR (300 MHz, J6-DMSO) delta 8.89 (IH, d, J= 5.0 Hz); 8.32 (2H, d, J= 8.7 Hz); 8.22 (IH, d, J= 5.5 Hz); 8.12 (2H, d, J= 8.7 Hz); 4.35 (2H, q, J= 7.1 Hz); 1.34 (3H, t, J= 7.1 Hz); LC-ESI-MS (method B): rt 7.3 min.; m/z 263.0 / 265.0 [M+H]+. |
37% | Ester 1 : Preparation of Ethyl 4-(2-chloropyrimidin-4-yl)benzoate. To a solution of 2,4-dichloropyrimidine [70 g, 470 mmol] in DMF [600 mL] was added (PPh3)2PdCl2 [9.9 g, 14 mmol] and mixture was heated to 90C for 1 h. To this, (4-(ethoxycarbonyl)phenyl)boronic acid [91 g, 470 mmol] was added and mixture was heated to 90C for additional 0.5 h. A solution of potassium bicarbonate [282 g, 2.8 mol] in 200 mL of water was added to reaction mixture and stirred for 0.5 h at 90C. After completion of reaction, mixture was quanched in ice cooled water [500 mL]. The off white solid obtained was filtered, washed with water and dried under vacuum to get title compound. [45 g, 37%]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 140℃; under 7757.43 Torr; for 1h;Microwave irradiation; | 4-Ethoxycarbonyl-phenylboronic acid (2eq.) was added to a solution of 5-bromo-[l,2,4]triazolo[l,5-a]pyridin-2-ylamine in dioxane/water (5:1) K2CO3 (2 eq.) and PdCl2dppf (cat.) were added to the mixture. The resultion mixture was subjected to macrowave: T: 1400C, 60 min, Wmax: 150, Pmax: 150 PSI. The crude of the reaction was diluted with water. The product was extracted with ethyl acetate (3 times). The organic layers were dried with MgSO4. The solvent was removed under high vacuum to afford a brown solid used in the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃; for 4.0h;Inert atmosphere; | To a solution of <strong>[1159981-95-9]5-bromopyrazolo[1,5-a]pyrimidine</strong> (300 mg, 1.5 mmol) in 1,4-dioxane (10 mL) and water (2 mL), were sequentially added 4-ethoxycarbonyl phenyl boronic acid (380 mg, 1.95 mmol), K3PO4 (955 mg, 4.5 mmol) and Pd(PPh3)4 (52 mg, 0.04 mmol). The reaction mixture was heated at 90° C. for 4 h under argon atmosphere then, was diluted with EtOAc and washed with water and brine solution. The organic layer was dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel, eluent petroleumether/EtOAc 9:1 to 1:1) to afford ethyl 4-(pyrazolo[1,5-a]pyrimidin-5-yl)benzoate (200 mg, 49percent) of as a yellow solid. 1H NMR (400 MHz, CDCl3) delta (ppm): 8.77 (d, J=8.0, 1H), 8.18-8.15 (m, 4H), 7.33 (d, J=7.5 Hz, 2H), 7.12 (d, J=4.4 Hz, 1H), 6.77 (d, J=2.2 Hz, 1H), 4.45 (q, J=6.8 Hz, 2H), 1.44 (t, J=7.2 Hz, 3H); MS (ESI) m/z 268 [C15H13N3O2+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; caesium carbonate; In 1,4-dioxane; water; at 18 - 85℃; for 4h; | Water (160 mL) was added dropwise at room temperature to a mixture of 4-ethoxycarbonylphenylboronic acid (50 g, 0.26 mol), <strong>[55405-67-9]3-bromopyrazolo[1,5-a]pyrimidine</strong> (56.25 g, 0.28 mol), Pd(ddpf)Cl2.CH2Cl2 (4.25 g, 5.21 mmol), and Cs2CO3 (169.42 g, 0.52 mol) in 1,4-dioxane (1 L). The reaction mixture was then heated 85 C. for 4 h. The reaction mixture was cooled, poured into water and extracted with EtOAc (2×300 mL). The combined organic layers were dried over Na2SO4, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel chromatography eluting with a gradient of petroleum ether: EtOAc (100:10 to 3:1) to deliver the title compound (64 g, 93%) as a yellow solid. [0400] 1H NMR (400 MHz, CDCl3) delta 8.73 (d, 1H), 8.63 (d, 1H), 8.52 (s, 1H), 8.20-8.09 (m, 4H), 6.92 (dd, 1H), 4.41 (q, 2H), 1.43 (t, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; silver(l) oxide; In tert-Amyl alcohol; at 50℃; for 20h;Inert atmosphere; | General procedure: Amixture of phenylboronic acid (1a) (1 mmol, 122 mg), alpha-trifluoromethylacrylicacid (2) (0.5 mmol, 70 mg), [Cp*RhCl2]2 (0.01 mmol, 6 mg), AgSbF6 (0.1 mmol, 34mg), Ag2O (1 mmol, 232 mg), and 1-methylnaphthalene (ca. 40 mg) as internal standard was stirred in tert-amylalcohol (3 ml) under argon at 50 C for 20 h.Then the reaction mixture was diluted by ethyl acetate (30 ml). The organiclayer was washed by 1 N HCl(30 ml), water 30 (ml), and brine (30 ml) and driedover Na2SO4. After evaporation of the solvents under vacuum, product 3a? (101 mg,93%) was isolated by column chromatography on silica gel usinghexane/EtOAc/AcOH=90/9/1 (v/v/v) as eluent. |
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