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Synonyms: 6-Bromo-3-pyridinemethanol
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CAS No. : | 122306-01-8 |
Formula : | C6H6BrNO |
M.W : | 188.02 |
SMILES Code : | OCC1=CC=C(Br)N=C1 |
Synonyms : |
6-Bromo-3-pyridinemethanol
|
MDL No. : | MFCD04974508 |
InChI Key : | QPPDKOIDAYZUHN-UHFFFAOYSA-N |
Pubchem ID : | 6421249 |
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 |
---|---|---|
1.05 g | With thionyl chloride In dichloromethane at 0 - 20℃; for 2 h; | A solution of (6-bromopyridin-3-yl)methanol (1.000 g) in DCM (10 mL) was cooled to EtOAc. Ethylene was added dropwise thionylchloride (1.260 g) in remove the ice bath after the addition. Stir for 2 hours to allow the solution to naturally warm to room temperature. Direct concentration gave 1.050 g of 2-bromo-5-(chloromethyl)pyridine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With silver nitrate; In water; acetone; | Step E Preparation of 2-bromo-5-(hydroxymethyl)pyridine To a solution of 2-bromo-5-(bromomethyl)pyridine, as described above in Step D, (2.15 g, 8.57 mmol) in acetone (100 mL) was added a solution of silver nitrate (2.18 g, 12.9 mmol) in water (100 mL). The reaction was stirred in the dark at 25 C. for 72 hours. The reaction was filtered and the acetone was removed in vacuo. The residue was partitioned between methylene chloride (100 mL) and water (100 mL). The layers were separated and the aqueous layer was extracted with methylene chloride (1*100 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by column chromatography (40→90% ethyl acetate/hexane) to provide the title compound as a clear oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With thionyl chloride; In dichloromethane; | This compound was synthesised as previously reported and analysis matched with literature values.[30] microscopy of the adjacent tissue immunohistochemically stained with 1E8 antibody. Scale bars indicate 100 mm. (6-Bromopyridin-3-yl)methanol (2) (2.93 g, 11.3mmol) was dissolved in dichloromethane (40mL) and treated with an excess of thionyl chloride (7mL). The reaction was monitored by TLC (33% ethyl acetate in petroleum spirits; Rf 0.81) and once complete, volatiles were removed by evaporation. The residue was then suspended in saturated NaHCO3 (50mL) and extracted with ethyl acetate (2_50mL). The organic extracts were combined, dried over MgSO4, and evaporated to dryness to yield a brown oil, which yielded a crystalline white solid upon standing. The solid was suspended in pentane and isolated by filtration, washed with pentane, and air-dried to give a crystalline colourless solid (2.13 g, 10.3mmol, 91% yield). dH (400MHz, CDCl3) 8.37 (d, 4JHH 1.9, 1H, ArH), 7.60 (dd, 3JHH 8.2, 4JHH 2.4, 1H, ArH), 7.50 (d, 3JHH 8.2, 1H, ArH), 4.54 (s, 2H, CH2). |
With sodium hydroxide; thionyl chloride; In water; toluene; acetonitrile; | To a mechanically-stirred solution of 78.12 g of thionyl chloride in 450 mL of acetonitrile at 15 C. was added a solution of 160.75 g of 3-hydroxymethyl-6-bromopyridine in 446 mL of acetonitrile over 30 minutes. The temperature rose to 22 C. during the addition, and the reaction mixture was stirred for 15 minutes at room temperature. The mixture was cooled in an ice bath, and a solution of 70 g of NaOH in 1.4 L of water was added at such a rate that the temperature did not exceed 15 C. 603 mL of toluene was added to the mixture and stirred rapidly. The layers were separated. The aqueous phase was reextracted with toluene. The combined organic phase was concentrated in vacuo to give 181.61 g of 3-chloromethyl-6-bromopyridine. | |
1.05 g | With thionyl chloride; In dichloromethane; at 0 - 20℃; for 2h; | A solution of (6-bromopyridin-3-yl)methanol (1.000 g) in DCM (10 mL) was cooled to EtOAc. Ethylene was added dropwise thionylchloride (1.260 g) in remove the ice bath after the addition. Stir for 2 hours to allow the solution to naturally warm to room temperature. Direct concentration gave 1.050 g of 2-bromo-5-(chloromethyl)pyridine. |
With thionyl chloride; In chloroform; at 0 - 20℃; for 4h; | SOCI2 (1.26 g, 10.6 mmol, 2 eq) was added drop wise to a stirred solution of compound 77 (1 g, 5.3 mmol, 1 eq) in CHCb (10 mL) at 0 C. The mixture was stirred for 4 h at room temperature. After LC-MS indicated completion, the mixture was poured into ice-water and adjusted pH = 7-8 with saturated NaHCCb, extracted with DCM (10 mL X 3). The combined organic layers was washed with brine (5 mL X 3) and dried over NaiSCU, filtered and concentrated to afford the crude product (870 mg, crude), which was used in next step directly. NMR (300 MHz, CDCb): delta 8.39 (d, J= 1.5 Hz, 1 H), 7.64 - 7.60 (m, 1 H), 7.52 (d, J= 8.1 Hz 1 H), 4.56 (s, 1 H). LCMS: (M+H)+ = 205.9, 207.9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With N-Bromosuccinimide; triphenylphosphine; In dichloromethane; at 20℃; for 3.5h; | A solution of (6-bromo-3-ρyridinyl)methanol (50) (2.503 g, 13.3 mmol) and triphenylphosphine (4.026 g, 15.4 mmol) in anhydrous CH2Cl2 (100 mL) was carefully treated with recrystallized N-bromosuccinimide (2.732 g, 15.4 mmol) (water bath cooling), and the mixture was stirred at room temperature for 3.5 h. The resulting solution was concentrated, and then added to excess petroleum ether at the top of a silica gel column (100 g in petroleum ether), rinsing on with minimal extra CH2Cl2. Elution with petroleum ether firstly gave foreruns, and then further elution with 15-25% Et2O/pentane gave pure 2-bromo-5-(bromomethyl)pyridine (51) (Schubert et al., 1999) (3.045 g, 91%) as a lachrymatory white solid that was used directly in the next step; 1II NMR (CDCl3) δ 8.38 (d, J = 2.5 Hz, 1 H), 7.59 (dd, J - 8.2, 2.6 Hz, 1 H), 7.48 (d, J = 8.2 Hz, 1 H), 4.42 (s, 2 H). |
91% | With N-Bromosuccinimide; triphenylphosphine; In dichloromethane; at 20℃; for 3.5h; | F. Synthesis of (6S)-6-[6-(4-fluorophenyl)-3-pyridinyl]methoxy}-2-nitro-6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazine (5) by the method of Scheme 4 A solution of (6-bromo-3-pyridinyl)methanol (50) (2.503 g, 13.3 mmol) and triphenylphosphine (4.026 g, 15.4 mmol) in anhydrous CH2Cl2 (100 mL) was carefully treated with recrystallized N-bromosuccinimide (2.732 g, 15.4 mmol) (water bath cooling), and the mixture was stirred at room temperature for 3.5 h. The resulting solution was concentrated, and then added to excess petroleum ether at the top of a silica gel column (100 g in petroleum ether), rinsing on with minimal extra CH2Cl2. Elution with petroleum ether firstly gave foreruns, and then further elution with 15-25% Et2O/pentane gave pure 2-bromo-5-(bromomethyl)pyridine (51) (Schubert et al., 1999) (3.045 g, 91%) as a lachrymatory white solid that was used directly in the next step; 1H NMR (CDCl3) δ 8.38 (d, J=2.5 Hz, 1H), 7.59 (dd, J=8.2, 2.6 Hz, 1H), 7.48 (d, J=8.2 Hz, 1H), 4.42 (s, 2H). |
87.0% | With carbon tetrabromide; triphenylphosphine; In dichloromethane; at 0 - 20℃;Inert atmosphere; | To a solution of (6-bromopyridin-3-yl)methanol (3.0 g, 16.0 mmol) in DCM (60 mL) was added triphenylphosphine (4.82 g, 18.4 mmol). After addition was completed, themixture was degassed three times under N2. Then a solution of CBr4 (5.84 g, 17.6 mmol) in DCM (15 mL) was added dropwise at 0C, and the reaction was stirred at room temperature overnight. The mixture was concentrated under reduced pressure to give a crude product, which was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 50: 1 to 15: 1) to give 2-bromo-5-(bromomethyl)pyridine (3.46 g, 87.0% yield) as a white solid. LC10 MS: m/z 252 [M+Hj |
78% | With phosphorus tribromide; In dichloromethane; at 0 - 20℃; for 3h; | To a stirred solution of (6-Bromopyridin-3-yl) methanol (2 g, 0.01 mol) in DCM (40 mL), PBr3 (14.3 g, 0.05 mol)) was added at 0C and allowed to stir RT for 3 h. The reaction was monitored by TLC and LC S. The crude reaction mass was diluted with 20 mL of ice cold water and basified with sat. NaHC03 solution to a pH- 8 extracted with DCM (2 X 20 mL), washed with brine, the organic layer was dried over anhydrous NaaSC^, evaporated to get crude resiude that was purified in 100-200 silica gel in 10 % EtOAc/Hexane to get 2.1 g (78%) of the title compound as an off white gummy solid. (0771) LC-MS (method 23): R, = 1.91 min; m/z = 251.74 (M+H++2). |
62% | With phosphorus tribromide; In diethyl ether; at 20℃; for 1h; | EXAMPLE 474-((6-(2-(2,4-Difluorophenyl)-l,l-difluoro-2-hydroxy-3-(lH-tetrazol-l- yl)propyl)pyridin-3-yl)methoxy)benzonitrile (79) and 4-((6-(2-(2,4-difluorophenyl)-l,l- difluoro-2-hydroxy-3-(2H-tetrazol-2-yl)propyl)pyridin-3-yl)methoxy)benzonitrile (80)To a stirred solution of compound J (prepared as in the first step of Example 17; 2.0 g, 10.75 mmol) in CH3OH (30 mL) was added NaBH4 (0.53 g, 13.97 mmol) portionwise at 0 C and the reaction mixture was stirred at 0 C for 1 h. After completion of the reaction (by TLC), CH3OH was removed under reduced pressure, and the reaction mixture was diluted with ice- cold water (75 mL) and extracted with EtOAc (2 x 75 mL). The combined organic layers were washed with water (75 mL) and brine (75 mL), dried over anhydrous Na2S04 and concentrated under reduced pressure to obtain the crude material. Purification by silica gel column chromatography (eluting with 40% EtOAc/hexanes) afforded compound AV (1.4 g, 7.44 mmol, 69%) as a yellow solid. 1H NMR (400 MHz, CDC13): δ 8.35 (s, 1H), 7.59 (dd, J = 8.0, 2.4 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 4.71 (d, J = 6.0 Hz, 2H), 2.03 (t, J = 6.0 Hz, OH). MS (ESI): m/z 188 [M+] .To a stirred solution of compound AV (1.0 g, 5.31 mmol) in Et20 (20 mL) was added phosphorus tribromide (PBr3; 1.5 mL, 15.95 mmol) at 0 C, and the mixture was stirred for 1 h at RT. After complete consumption of the starting material (by TLC), the reaction mixture was quenched with ice-cold water (30 mL), adjusted to pH~8 using satd NaHC03 and extracted with EtOAc (2 x 100 mL). The combined orgainc extracts were washed with water (100 mL) and brine (100 mL), dried over anhydrous Na2S04 and concentrated under reduced pressure to obtain the crude material. Purification by silica gel column chromatography (10% EtOAc/hexanes) afforded compound AW (0.83 g, 3.30 mmol, 62%) as a colorless liquid. 1H NMR (400 MHz, CDC13): δ 8.38 (d, J = 2.4 Hz, 1H), 7.59 (dd, J = 8.0, 2.4 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 4.41 (s, 2H).To a stirred suspension of 4-hydroxybenzonitrile (0.39 g, 3.30 mmol) and Cs2C03 (1.62 g, 4.96 mmol) in DMF (10 mL) was added compound AW (0.83 g, 3.30 mmol) at RT, and the mixture was stirred for 4 h. After completion of the reaction (by TLC), the reaction mixture was quenched with ice-cold water (25 mL) and extracted with EtOAc (4 x 50 mL). The combined organic extracts were washed with water (50 mL) and brine (50 mL), dried over anhydrous Na2S04 and concentrated under reduced pressure to obtain the crude material. Purification by silica gel column chromatography (eluting with 10% EtOAc/hexanes) afforded compound AX (0.90 g, 3.11 mmol, 94%) as a pale yellow solid. 1H NMR (500 MHz, CDC13): δ 8.44 (d, J = 2.0 Hz, 1H), 7.64-7.61 (m, 3H), 7.54 (d, J = 8.5 Hz, 1H), 7.01 (d, J = 8.5 Hz, 2H), 5.08 (s, 2H). MS (ESI): m/z 291 [M+2]+.To a stirred suspension of copper powder (1.55 g, 6.22 mmol) in DMSO (10 mL) was added ethyl 2-bromo-2,2-difluoroacetate (0.63 g, 3.11 mmol) at RT and the mixture was stirred for 1 h. A solution of compound AX (0.9 g, 3.11 mmol) in DMSO (5 mL) was added to the reaction mixture and stirring was continued for another 16 h at RT. After complete consumption of the starting material (by TLC), the reaction mixture was quenched with satd NH4C1 solution (100 mL) and extracted with EtOAc (2 x 100 mL). The combined organic extracts were washed with water (100 mL) and brine (100 mL), dried over anhydrous Na2S04 and concentrated under reduced pressure to obtain the crude material. Purification by silica gel column chromatography (eluting with 25% EtOAc/hexane) afforded compound AY (0.5 g, 1.5 mmol, 49%) as a pale yellow solid. 1H NMR (500 MHz, CDC13): δ 8.71 (s, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.63 (d, J = 9.0 Hz, 2H), 7.03 (d, J = 9.0 Hz, 2H), 5.18 (s, 2H), 4.38 (q, J = 7.0 Hz, 2H), 1.34 (t, J = 7.0 Hz, 3H). MS (ESI): m/z 334 [M+2]+.To a stirred solution of l-bromo-2,4-difluorobenzene (348 mg, 1.80 mmol) in Et20 (10 mL) was added w-BuLi (1.6 M in hexane; 0.7 mL, 1.80 mmol) at -78 C, and the mixture was stirred for 30 min under inert atmosphere. A solution of compound AY (500 mg, 1.50 mmol) in Et20 (30 mL) was added to the reaction mixture at -78 C and stirring was continued for another 2 h. After completion of the reaction (by TLC), the reaction mixture was quenched with satd NH4C1 solution (100 mL) and extracted with EtOAc (2 x 100 mL). The combined organic extracts were washed with water (100 mL) and brine (100 mL), dried over anhydrous Na2S04 and concentrated under reduced pressure to afford the crude AZ (1.5 g) as a brownish liquid. This crude material was used in the next step without any further purification. MS (ESI): m/z 401 [M+H]+.To a stirred solution of crude AZ (650 mg, crude) in Et20 (100 mL) was added freshly prepared diazomethane [prepared by dissolving NMU (1.67 g, 16.25 mmol) in a 1 : 1 mixture of 10% KOH solution (100 mL) and Et20 (100 mL) at 0 C followed by separation and drying of the organic layer usin... |
With carbon tetrabromide; triphenylphosphine; In dichloromethane; at 0℃; for 0.0833333h; | To a solution of (6-bromopyridin-3 -yl)methanol (5.0 g, 27 mmol) in DCM (50 ml) was added triphenylphosphine (6.3 g, 24 mmol), at 0C. To this reaction mixture was added a solution of carbon tetrabromide (7.1 g, 21 mmol) in 15 ml DCM. The resulting mixture was stirred for 5 minutes, then evaporated, and purified using 0 to 10% ethyl acetate in hexanes toprovide 2-bromo-5-(bromomethyl)pyridine. LC-MS [M+H]: 251.89 |
Tags: (6-Bromopyridin-3-yl)methanol | 6-Bromo-3-pyridinemethanol | Pyridines | Bromides | Alcohols | Organic Building Blocks | Heterocyclic Building Blocks | 122306-01-8
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H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
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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* Country/Region
* Quantity Required :
* Cat. No.:
* CAS No :
* Product Name :
* Additional Information :
Calculate the required mass, volume, or concentration of the solution. The Ambeed Molarity calculator is based on the following equation:
Concentration (mol/L) × Volume (L) × Molecular Weight (g/mol)= Mass (g)
Concentration
Volume
Molecular Weight
Mass
* When preparing stock solution, always refer to the molecular weight of the corresponding batch as shown on the product label or MSDS/COA (available for download on the product page).
Total Compounds: mg
The concentration of the dissolution solution you need to prepare is mg/mL