1H-Pyrazole-3-carboxylic acid, 4-bromo-, methyl ester CAS#: 81190-89-8; 凯望编码 (ChemWhat Code): 1188593
Identification
| 英文名 | 1H-Pyrazole-3-carboxylic acid, 4-bromo-, methyl ester |
| IUPAC Name | methyl 4-bromo-1H-pyrazole-5-carboxylate |
| 分子结构 |  |
| CAS编号 | 81190-89-8 |
| MDL Number | MFCD00466326 |
| 别名 | methyl 4-bromo-1H-pyrazole-3-carboxylate 81190-89-8 DTXSID50385177 DTXCID50336200 640-582-9 methyl 4-bromo-1H-pyrazole-5-carboxylate 190263-20-8 4-Bromo-1H-pyrazole-3-carboxylic acid methyl ester 1639902-31-0 methyl 4-bromopyrazole-3-carboxylate MFCD00619124 1H-Pyrazole-3-carboxylic acid, 4-bromo-, methyl ester MFCD00466326 4-bromopyrazole-3-carboxylic acid methyl ester SCHEMBL13726965 SCHEMBL15519155 KWQDACZQHJCUNK-UHFFFAOYSA-N ALBB-010454 BCP23475 BBL013079 methyl 4-bromopyrazole-5-carboxylate SBB022111 STK315331 AKOS000310357 AKOS003744357 AB06264 CS-W019707 FS-2160 SY030486 DB-075744 ST45137494 EN300-138289 O11931 AH-034/11365123 SR-01000390601 SR-01000390601-1 1H-Pyrazole-3-carboxylic acid,4-bromo-,methyl ester 1H-PYRAZOLE-5-CARBOXYLIC ACID, 4-BROMO-, METHYL ESTER |
| 分子式 | C5H5BrN2O2 |
| 分子量 | 205.01 |
| InChI | InChI=1S/C5H5BrN2O2/c1-10-5(9)4-3(6)2-7-8-4/h2H,1H3,(H,7,8) |
| InChI Key | KWQDACZQHJCUNK-UHFFFAOYSA-N |
| SMILES | COC(=O)C1=C(C=NN1)Br |
| Patent Information | ||
| Patent ID | Title | Publication Date |
| US2013/165464 | HETEROARYLS AND USES THEREOF | 2013 |
Physical Data
| Appearance | White powder |
Spectra
| Description (NMR Spectroscopy) | Nucleus (NMR Spectroscopy) | Solvents (NMR Spectroscopy) |
| Chemical shifts, Spectrum | 13C | chloroform-d1 |
Route of Synthesis (ROS)
| Conditions | Yield |
| Stage #1: methyl 4-bromo-1H-pyrazole-3-carboxylate With sodium hydride In tetrahydrofuran at 0℃; for 0.166667h; Stage #2: (2-trimethylethylsilylethoxy)methyl chloride In tetrahydrofuran at 20℃; Experimental Procedure Intermediate 4A. Methyl 4-bromo-1-((2-(trimethylsiliyl)ethoxy)methyl)-1H-pyrazole-3carboxylate To a suspension of methyl 4-brorno-1H-pyrazole-3-carboxylate (2.45 g, 11.9 rnmol) in THF (120 rnL) at () °C, was added 60% Nal-I (0.621 g, 15.5 mrnol) portionwise.The reaction was stirred at 0 °C for 10 mm, then 2-(trirnethylsilyi)ethoxymethyl chloride (254 mL, 14.34 mrnoi) was added dropwise. The suspension was warmed slowly to rt overnight. Then, it was cooled down to 0 °C, MeOH was added and the solvents were removed in vacuo. The residue was diluted with EtOAc and sat. Nal-ICOs. The aqqueous layer was extracted 2x with EtOAc. The organic layer was washed with brine, dried overMgSO4 and concentrated. Purification by flash chromatography (80 g column, 0-50% E:tOAc in Hexanes) afforded intermediate 4A as a colorless oil (3.17 g, 87%). ‘H NMR (400 MHz. CFILOROFORM-d) d 7.73 (s, IH), 5.48 (s, 2H), 3.97 (s, 3H), 3.63 – 3.56 (iii. 2H). 093 (t, .J=8.3 Hz, 2H). 000 (s. 9H). LCMS [M + H] = 337.0, | 87% |
| Stage #1: methyl 4-bromo-1H-pyrazole-3-carboxylate With sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Stage #2: (2-trimethylethylsilylethoxy)methyl chloride In tetrahydrofuran at 0℃; for 5h; Experimental Procedure To a solution of methyl 4-bromo-1H-pyrazole-3-carboxylate (10.0 g, 48.8 mmol) in THF (150.00 mL) was added NaH (2.341 g, 58.5 mmol) portion wise at 0 °C. The reaction mixture was stirred for 30 min, then SEM-Cl (10.38 mL, 58.5 mmol) was added. The reaction mixture was stirred at 0 °C for 5 h. The reaction was quenched with water (30 mL). The reaction mixture separated into two layers, and the aqueous layer was extracted with EtOAc (2 X 50 mL). The combined organic extracts were dried (Na2SO4) and concentrated to yield crude compound. The crude compound was purified by ISCO using 120 g silica column, the compound was eluted in 20% EA in hexanes, the fractions were collected and concentrated to afford methyl 4-bromo-1-((2- (trimethylsilyl)ethoxy)methyl)-1H-pyrazole-3-carboxylate (13.95 g, 41.6 mmol, 85 % yield) as an oil. LCMS Retention time: 1.63 min [A], MS (E+) m/z: 337.1 [M+2H]. | 85% |
| Stage #1: methyl 4-bromo-1H-pyrazole-3-carboxylate With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 0.5h; Inert atmosphere; Stage #2: (2-trimethylethylsilylethoxy)methyl chloride In tetrahydrofuran; mineral oil at 20℃; Experimental Procedure 3 Method C3: SEM Protection of Pyrazoles Illustrative Example 4-Bromo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrazole-3-carboxylic acid methyl ester General procedure: The pyrazole (1 eq) is dissolved in dry THF at 0° C. After addition of NaH (1.5 eq), the mixture is stirred at 0° C. under N2 atmosphere for 30 min. Next, SEM-C1 (1.5 eq) is slowly added and the resulting mixture is stirred at room temperature overnight. Subsequently, the mixture is quenched with water and extracted with EtOAc. The organic phase is isolated, dried over Na2SO4, filtered and evaporated to give a residue that is used as such. The pyrazole (Int 4, 2 g, 9.76 mmol) is dissolved in dry THF (20 mL) at 0° C. After addition of NaH (60 w %, 584 mg, 14.6 mmol), the mixture is stirred at 0° C. under N2 atmosphere for 30 min. Next, SEM-C1 (2.58 mL, 14.6 mmol) is slowly added and the resulting mixture is stirred at room temperature overnight. Subsequently, the mixture is quenched with water and extracted with EtOAc. The organic phase is isolated, dried over Na2SO4, filtered and evaporated to give a residue that is used as such. |
Safety and Hazards
| Pictogram(s) |  |
| Signal | Warning |
| GHS Hazard Statements | H302 (66.7%): Harmful if swallowed [Warning Acute toxicity, oral] H312 (33.3%): Harmful in contact with skin [Warning Acute toxicity, dermal] H315 (100%): Causes skin irritation [Warning Skin corrosion/irritation] H319 (100%): Causes serious eye irritation [Warning Serious eye damage/eye irritation] H332 (66.7%): Harmful if inhaled [Warning Acute toxicity, inhalation] H335 (100%): May cause respiratory irritation [Warning Specific target organ toxicity, single exposure; Respiratory tract irritation] |
| Precautionary Statement Codes | P261, P264, P264+P265, P270, P271, P280, P301+P317, P302+P352, P304+P340, P305+P351+P338, P317, P319, P321, P330, P332+P317, P337+P317, P362+P364, P403+P233, P405, and P501 |
Other Data
| Transportation | Under the room temperature and away from light |
| HS Code | |
| Storage | Under the room temperature and away from light |
| Shelf Life | 2 years |
| Market Price |
| Druglikeness | |
| Lipinski rules component | |
| 分子量 | 205.011 |
| logP | 1.828 |
| HBA | 4 |
| HBD | 1 |
| Matching Lipinski Rules | 4 |
| Veber rules component | |
| Polar Surface Area (PSA) | 54.98 |
| Rotatable Bond (RotB) | 2 |
| Matching Veber Rules | 2 |
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