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CAS No. : | 376592-93-7 | MDL No. : | MFCD10001467 |
Formula : | C13H11NO3 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | ZXLYSSHNDUXXIN-UHFFFAOYSA-N |
M.W : | 229.23 | Pubchem ID : | 11492332 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | |
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 |
---|---|---|
95% | With palladium 10% on activated carbon; hydrogen; In ethanol; water; at 50℃; under 3750.38 - 7500.75 Torr; | The above product was added to a hydrogenation vessel, and 2 g of 10% palladium carbon (about 63% aqueous), and 150 ml of ethanol were added.The reaction was carried out by introducing hydrogen gas at 0.5-1.0 MPa/50 C.After the reaction was completed, it was filtered, concentrated, dissolved in 100 ml of water, and adjusted to pH 5.5 with 1 M hydrochloric acid.The solid is precipitated, suction filtered and dried to give a pale yellow solid(9 g, yield: 95%, HPLC purity: 99%). |
72.8% | With palladium on activated charcoal; hydrazine hydrate; In water; at 25 - 85℃; for 2h; | 2) 300g of Intermediate I, 6g of Pd / C, and 1.5L of water were added into a 5L three-necked flask, and 1.5L of hydrazine hydrate (98%) was added to the system dropwise. During this period, exothermic gas was released and the temperature was controlled at 25 C. After the dropwise addition was completed, the temperature was raised to 85 C. After two hours of reaction, the temperature was reduced to room temperature with suction filtration. The filtrate was cooled to 5 C, the pH was adjusted to 7-8 with concentrated hydrochloric acid, and the filtration cake was washed with 500 ml of water and blow dried at 55 C. 193.14 g of light brown solid intermediate II was obtained with a yield of 72.8% and a purity of 97.3%. |
50.5% | With hydrogen;5% Pd(II)/C(eggshell); In methanol; at 20℃; for 8h; | A solution of 2'-hydroxy-3'-nitrobiphenyl-3-carboxylic acid (800 g, 3.2 mol) in methanol (5 L) was hydrogenated over 5% Pd/C (160 g) at room temperature for 8 hours. The reaction mixture was filtered, concentrated and slurried in THF (2.5 L) to give 3'-amino-2'-hydroxybiphenyl-3-carboxylic acid (690 g, 50.5%) as a brown solid. PXRD analysis provided the diffractogram as shown in FIG. 32. |
With hydrogen; potassium acetate;palladium over charcoal; | Scheme I [0137] The process of Scheme I is a mult-step synthetic sequence that commences with the palladium catalyzed cross-coupling of a phenylboronic acid such as structure 2 and an aryl bromide such as structure 1 to form the biaryl structure 3 Deprotection of the methyl ether is followed by nitration and hydrogenation to give the biphenyl ammo acid such as structure 4 The ammo group is then diazotized under standard conditons and is treated with the approp?ate coupling partner to give the final product of structure 6; Example 187: 3 '- ITV-^-Aza- 1 -(3 ,4-dimethylph.enyl)-2-oxo- 1.2-dihvdroindol-3 - ylidenelhvdrazino|-2'-nydroxybiphenyl-3-carbox:ylic acid ("Compound 287) [0371] This compound was prepared as described in Scheme I. 1H NMR (500 MHz, DMSO-4) 13.10 (s, IH), 13.04 (s, IH), 9.36 (s, IH), 8.16 (dd, J= 5.1, 1.6 Hz, IH), 8.12 (t, J= 1.6 Hz, IH), 8.04 (dd, J= 7.4, 1.6 Hz, IH), 7.94 (ddd, J= 7.7, 1.6, 1.2 Hz, IH), 7.80 (ddd, J= 7.7, 1.6, 1.2 Hz, IH), 7.74 (dd, J= 7.8, 1.6 Hz, IH), 7.60 (t, J = 7.7 Hz, IH), 7.34 (d, J= 1.8 Hz, IH), 7.30 (d, J = 8.1 Hz, IH), 7.28 (dd, J = 8.1, 1.8 Hz, I H), 7.21 (dd, J = 7.4, 5.1 Hz, IH), 7.13 (t, J = 7.8 Hz, IH), 7.03 (dd, J= 7.8, 1.6 Hz, IH), 2.30 (s, 3H), 2.29 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74.15% | Methanolic HCl acid (22 ml, 1.25 M), 50 ml methanol and 2.5 g BPCA (2',3'-dihydroxybiphenyl-3-carboxylic acid) were stirred and cooled down to 0-5 C. at which point 0.770 g NaNO2 (dissolved in 3 ml water) was added dropwise. The resulting solution was stirred at 0-5 C. for 30 min., and then 2 ml of conc. HCl acid were added dropwise. The resulting solution was stirred at 0-5 C. for 30 min. followed by addition of 40 mg sulfamic acid (dissolved in 3 ml water). The resulting reaction mixture was stirred for 45 min at 5-25 C. followed by addition 2.2 g of 1-(3,4-dimethylphenyl)-3-methyl-1,2-dihydropyrazol-5-one. The resulting solution was stirred for 10-15 min at room temperature and 4 ml of ethanolamine was added. The resulting suspension was stirred for 45 min, followed by filtration. 4.56 g of purple powder was obtained. Yield 74.15% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.4% | 3'-Amino-2'-hydroxybiphenyl-3-carboxylic acid (?BPCA?) Form I (90 g, 392.6 mmol), was added slowly with stirring at room temperature to a solvent mixture of tech. methanol (1.8 L) and 4 M hydrochloric acid (0.245 L, 981.5 mmol) in 3 L reactor. The resulting red solution was stirred for thirty minutes. The solution was then cooled to 0-5 C. and a cold solution of sodium nitrite (27 g, 391.3 mmol) in 90 mL of water was added over twenty minutes such that the reaction mixture temperature did not rise above 10 C. The reaction mixture was stirred for one hour at 5-10 C. Sulfamic acid (4 g, 41.2 mmol) in 90 mL of water was added at 5 C. and the resulting mixture was stirred for additionally one hour at the same temperature. The reaction mixture was warmed to room temperature and triethylamine (ca 104 mL) was added to adjust pH 7-8. 1-(3,4-dimethylphenyl)-3-methyl-1H-pyrazol-5-ol (?pyrazole?) form I (72 g, 357.8 mmol), was added in one portion to the reaction mixture and the resulting mixture was stirred for additionally two hours at room temperature. Hydrochloric acid (4M, ca 140 mL) was slowly added with stirring over twenty minutes to adjust pH to 1.8. A solid precipitated and was collected by filtration, washed with of mixture MeOH:water (1:1, 100 mL) and dried at 40 C./0 bar in vacuum oven for about 18 hours giving 151 g of crude orange to brown crystals of Eltrombopag crude (XRPD: form III with small percentage (less than 10%) of form I. (HPLC: 98.5%, Yield=95.4%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Scheme I [0137] The process of Scheme I is a mult-step synthetic sequence that commences with the palladium catalyzed cross-coupling of a phenylboronic acid such as structure 2 and an aryl bromide such as structure 1 to form the biaryl structure 3 Deprotection of the methyl ether is followed by nitration and hydrogenation to give the biphenyl ammo acid such as structure 4 The ammo group is then diazotized under standard conditons and is treated with the approp?ate coupling partner to give the final product of structure 6; Example 187: 3 '- ITV-^-Aza- 1 -(3 ,4-dimethylph.enyl)-2-oxo- 1.2-dihvdroindol-3 - ylidenelhvdrazino|-2'-nydroxybiphenyl-3-carbox:ylic acid ("Compound 287) [0371] This compound was prepared as described in Scheme I. 1H NMR (500 MHz, DMSO-4) 13.10 (s, IH), 13.04 (s, IH), 9.36 (s, IH), 8.16 (dd, J= 5.1, 1.6 Hz, IH), 8.12 (t, J= 1.6 Hz, IH), 8.04 (dd, J= 7.4, 1.6 Hz, IH), 7.94 (ddd, J= 7.7, 1.6, 1.2 Hz, IH), 7.80 (ddd, J= 7.7, 1.6, 1.2 Hz, IH), 7.74 (dd, J= 7.8, 1.6 Hz, IH), 7.60 (t, J = 7.7 Hz, IH), 7.34 (d, J= 1.8 Hz, IH), 7.30 (d, J = 8.1 Hz, IH), 7.28 (dd, J = 8.1, 1.8 Hz, I H), 7.21 (dd, J = 7.4, 5.1 Hz, IH), 7.13 (t, J = 7.8 Hz, IH), 7.03 (dd, J= 7.8, 1.6 Hz, IH), 2.30 (s, 3H), 2.29 (s, 3H). |
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