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CAS No. : | 21543-49-7 | MDL No. : | MFCD01075226 |
Formula : | C6H6ClNO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | GOXYBEXWMJZLJB-UHFFFAOYSA-N |
M.W : | 143.57 | Pubchem ID : | 177161 |
Synonyms : |
|
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: |
* 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 hydrogenchloride; borane; In tetrahydrofuran; | EXAMPLE 1 6-Chloronicotinic acid (3.0 g, 18.98 mmol) is dissolved in 30 ml of tetrahydrofuran (THF), with the temperature of the solution maintained below 30. A 1 M solution of borane/TMF (19 ml, 19.0 mmol) is added at a rate to maintain a slow evolution of gas. This mixture is stirred at RT overnight. The reaction is poured onto approximately 50 g ice with 2 ml concentrated hydrochloric acid and is stirred for 1 hour. The pH of the reaction is adjusted to 5. The reaction is then extracted with chloroform, washed with water, dried and stripped to give 6-chloro-3-pyridinemethanol. | |
With lithium aluminium tetrahydride; In tetrahydrofuran; at 0℃; for 4h;Reflux; | 2-Ch-oropyridinyI-4-mcthylcncdicthylphbsphonatc. 2-Chloronicotinic acid (3.00 g, 19.0 mmol) was dissolved in dry THF (60 mL) and cooled to 0C. Lithium aluminiumhydride (870 mg, 23.0 mmol) was charged into the stirred reaction (CAUTION: gas evolution) followed by gradual warming to reflux for 4 hours. The reaction was quenched with sequential addition of wet THF (5 mL) and water (50 ml.., cautiously) before filtration through celite and removal of volatilcs in vacuo gave yellow oil that was purified by flash chromatography (Si02, CH2CI2 followed by F,t()Ac). The crystalline alcohol was dissolved in CH2C12 (20 mL) and excess thionylchloride (5-10 mL) before refluxing for 1 hour. On cooling to room temperature, volatiles were removed in vacuo and the residue was neutralised with sat. NallCO before extraction with CH2CI2 (3 x 40 mL). Organics were combined, dried over MgSO^, filtered and concentrated to 3-5 mL before purification through a silica plug (eluting with CH2CI2). Removal of volatiles in vacuo gave yellow oil as the desired 2-chloropyridyl-5-methylcnechloride. The alky chloride was dissolved in triethylphosphite ( 10 mL) and heated to 140C for 2 hours. On cooling to room temperature, volatiles were removed in vacuo and the residue purified by flash chromatography (Si02, CFLC^ followed by EtOAc) to give a light yellow oil (). NMR (500 MHz; CDCI3): S/ppm 8.28-8.26 (m, I II, Vy-H), 7.64 (dl. 1 H, 3./?? - 8.2, 4Jm = 2.5, Py-//), 7.28 (d, 1 H, 3J,?i - 8.2, Py-H), 4.09-4.02 (m, 4H, 0-C//j), 3.09 (d, 211. 3JHi> = 21.6, 0=?-C/), 1.28- 1.25 (m, 6H, C//3). ,3C{ 'H} NMR (125.7 MHz; CDCIj): S/ppm 150.4 (d, 3Jci> = 7.7, PyCH), 150.3 (d, FontWeight="Bold" FontSize="10" JCP = 4, PyC-Cl), 140.0 (d, 3JCl> - 5.5, PyCH), 127.1 (d, 2Ja> = 9, PyQ, 124.2 (d, VCI> - 2.9, PyCH), 62.6 (d, 2,/a> = 6.8, 0-CH2), 30.5 (d, 'Jcp = 140,0, O-P-CHz), 16.5 (d, = 5.9, CH2-CH3). Λ ,Ρ{} NMR (202.5 MHz; CDCh): S/ppm 24.8 (s, 0=P) | |
With lithium aluminium tetrahydride; In tetrahydrofuran; at 0℃; for 3h; | To a solution of LiAIH4 (25 g, 0.65 mol) in THF (1500 ml) was added a solution of 6- chloropyridine-3-carboxylic acid (50 g, 0.323 mol) in THF drop-wise at 0C, and the mixture was stirred for 3h at 0C. THF and Na2S04 x 5H2O was added slowly. After stirring for 20 min, the mixture was filtered and the filtrate was concentrated to give crude product (26 g, yield: 57.1 %). |
0.55 g | With lithium aluminium tetrahydride; In tetrahydrofuran; at 0 - 30℃; for 3h;Inert atmosphere; | To a solution of methyl 6-chloronicotinate (1.08 g, 0.009 mole) in THF (30 mL) at 0 C under N2, was added lithium aluminum hydride (1 M in THF, 7.5 mL, 0.0075 mole) drop wise. Reaction mixture was warmed to RT and stirred for 3 hours. The reaction mixture was cooled to 0 C, diluted with ethyl acetate and treated with water (2 mL). The mixture was filtered through celite bed and concentrated under vacuum to obtain the crude compound which was further purified by flash chromatography using ethyl acetate: n-hexane (40: 60) to afford 2-chloro-5-hydroxymethylpyridine. Yield: 0.55 g; lH - NMR (CDC13, 400 MHz) δ ppm: 2.09 (bs, 1H), 4.72 (s, 2H), 7.31 - 7.34 (d, J = 8.1 Hz, 1H), 7.68 - 7.71 (dd, J = 2.2, 8.4 Hz, 1H), 8.36 (s, 1H); Mass (m/z): 144.1, 146.0 (M+H)+. |
615 mg (75%) | With BH3; In tetrahydrofuran; ethyl acetate; | 9-Chloro-5-{3-[2-(6-chloropyridin-3-yl)-2-hydroxyethylamino]cyclohexyl}-3-methyl-5H-isoxazolo[4,3-c]quinolin4one To a stirred solution of 6-chloronicotinic acid (900 mg, 5.7 mmol) in THF (7 mL) was added BH3 (16 mL, 17.1 mmol, 1M in THF) under N2 atmosphere. The reaction mixture was stirred for 5 h. It was quenched with methanol (5 mL) and then concentrated. The crude was dissolved in EtOAc (30 mL), washed with 1N NaOH (15 mL*3), brine, dried and concentrated. Yield: 615 mg (75%) of 6-chloro-pyridin-3-yl-methanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With oxalyl dichloride; triethylamine; In dimethyl sulfoxide; at -78 - 20℃; for 2.5h; | According to a procedure of Lee et al. [22] oxalylchloride (3.81 g, 30.0 mmol, 3.0 eq) was dissolved in CH2Cl2 (35 mL) at -78C (dry ice/acetone). Then DMSO (46.9 g, 0.60 mol, 60.0 eq.)was added dropwise under stirring and the reaction mixture was stirred for additional 30 min at -78C. Then 2-chloro-5-(hydroxymethyl)pyridine (1.44 g, 10.0 mmol, 1.00 eq) was dissolved in CH2Cl2(10 mL) and added dropwise with a syringe to the cold reaction mixture. Afterwards, the reaction mixture was stirred for 40 min at -78C and NEt3 (91.9 g, 0.90 mol, 90.0 eq) was added to the reaction mixture at a rate of 2.0 mL/min. The reaction mixture was stirred for 1 h at -78C, followed by another 1.5 h stirring at r.t. The reaction mixture was then diluted with Et2O (60 mL) and the organic phase was washed successively withNaHCO3(sat., aq., 2 × 30 mL), KHSO4(1 M, aq., 60 mL) and NaHCO3(sat., aq., 30 mL). After phase separation the organic phase was dried over Na2SO4, the solid removed by filtration and the solvent was removed in vacuum. Further cleaning with liquid chromatography(LC) (SiO2, n-pentane/EtOAc/NEt3= 200/100/6) gave the desired product as yellowish solid (1.35 g, 96%). |
94% | With Br3(1-)*C10H15NPol(1+); dimethyl sulfoxide; at 20℃; for 6h; | General procedure: To a mixture of alcohol in dry DMSO (10 volume) was added 1 equiv of polymer bromide and the reaction mixture was stirred at room temperature for a given period of time (Table 1). After the completion of the reaction, the reaction mixture was filtered and the polymer bed washed with DMSO. Combined DMSO layers were quenched with ice-water mixture and extracted with ether. The ether layer was given water wash, brine wash, dried over anhydrous sodium sulphate, and concentrated to get the pure carbonyl compounds. All the products were characterized by NMR and MS analysis. |
87% | With manganese(IV) oxide; In chloroform; at 60℃; | To a solution of the alcohol from above (481 mg, 3.35 mmol) in CHCl3 (25 mL) was added MnO2 (85%, 3.14 g, 30.7 mmol) and the suspension stirred at 60 0C overnight. The reaction was cooled, filtered through Celite, washing the cake with CH2Cl2 and MeOH and the resultant filtrate concentrated to afford the desired aldehyde (0.41 g, 87%) as a yellow solid. To a solution of 6-chloro-3-pyridinecarboxaldehyde (210 mg, 1.48 mmol) and ρyrimidine-5-boronic acid (207 mg, 1.67 mmol) in THF/DME/2 M Na2CO3 (1:2:1, 4 mL) was added Pd(PPh3)4 (154 mg, 0.13 mmol) and the reaction stirred under argon at 90 0C overnight. Standard work-up and purification by column chromatography on silica gel (CH2Cl2ZMeOH, 95:5) afforded -pyrimidm-S-yl-pyridme-S-carbaldehyde (80 mg, 29%) as a yellow solid. 1H NMR (CDCl3) δ 7.96 (d, IH, J= 8.1 Hz), 8.32 (dd, IH, J= 8.1, 1.5 Hz), 9.20 (d, IH, J = 1.5 Hz), 9.32 (s, IH), 9.42 (s, 2H), 10.18 (s, IH). |
89%Chromat. | With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione; In dichloromethane; at 25℃; for 0.5h; | General procedure: DBDMH (1 mmol) was added to a mixture of 1b (1 mmol) and dichloromethane (20ml). The reaction was kept at room temperature. After the mixture was stirred for0.5h, the mixture was washed with water (330 ml),dried with anhydrous MgSO4,filtered, and vacuum evaporated. The residue was purified by column chromatography (silica gel: petroleum ether/ethyl acetate, 30:1) to afford the product as light yellowsolid (93% yield). |
15 g | With pyridinium chlorochromate; In dichloromethane; at 0 - 20℃; for 2h; | To a solution of PCC (58 g, 0.27 mol) in DCM (1500 ml) was added the product of the proceeding step (26 g, 0.184mol) as a solution in DCM drop wise at 0C. The mixture was then stirred for 2h at 20C. It was filtered through diatomaceous earth and the filter contents were washed with DCM. The organic phase was concentrated to give the crude product, which was purified by column chromatography to give the product (15 g, yield: 60.1 %). 1H NMR (400 MHz, CDCI3): δ 10.067 (s, 1 H), 8.874 (s, 1 H, J=3Hz), 8.158-8.138 (d, 1 H, J=8Hz), 7.534-7.513 (d, 1 H, J=8Hz) |
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione; water-d2; alpha cyclodextrin; at 60℃; for 3h;Green chemistry; | General procedure: To a clean and dry small vial, a solution of substrate 1 (15.0 μmol, 1.0 equivalent) was added using an aqueous cyclodextrin solution (1.0 mL) of the specified concentration in D2O. DBDMH 3 (4.3 mg, 15.0 μmol, 1.0 equivalent) was added to the reaction mixture and sonicated to make sure that the reagents were well suspended. The reaction mixture was heated at 60 C with occasional shaking to maintain the homogeneity of the solution. After the desired period of time, the 1H NMR spectrum of the reaction mixture was recorded to determine the percent conversion. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With phosphorus tribromide; at 0 - 160℃; for 2.5h; | Phosphorous tribromide (100 mmol, 27. 1 g, 2. 0 eq.) was added carefully to 2- CHLORO-5-HYDROXYMETHYL pyridine (50. 0 mmol, 7. 18 g, 1. 0 eq.). The pyridine clumped together and the mixture was heated to 160 degrees C. Within 5 minutes of stirring at > 150 degrees C the mixture was seen to go very dark in color with gas evolution. The mixture was stirred at this same temperature for approximately 2. 5 hours at which point it was cooled to room temperature. The mixture was cooled further to 0 degrees C whereupon saturated sodium bicarbonate was added very cautiously (highly exothermic .). As foaming became less vigorous, ice was added to the mixture until foaming subsided. Solid sodium bicarbonate was then carefully added to achieve a pH of-8-9. The mixture was extracted with ethyl acetate and the organic layer was washed with brine and dried over anhydrous magnesium sulfate. Concentrated in vacuo to afford a dark solid. This material was dissolved in a minimal amount of DCM and purified using a Biotage Sp4 65i over a gradient of 0-100 % ethyl acetate in hexanes to afford the title compound as a pale yellow solid (5. 57 g, 44%). LRMS : 252 (M+H) +. 'H NMR (DMSO-d6, 400 MHz) ; 8. 39 (1H, s) 7. 59 (1H, D, J = 8. 5 Hz) 7. 48 (1H, d, J = 8. 5 Hz) 4. 46 (2H, s) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | <strong>[21543-49-7]2-Chloro-5-hydroxymethylpyridine</strong> (3.8 g, 26.7 mmol) was dissolved in 40 mL of dichloromethane under nitrogen.Triethylamine (5.8 mL, 40.1 mmol) was added dropwise thereto.Stir at -40 C for 15 minutes. Then add MsCl (2.5 mL,32.3 mmol) and continue the reaction at -40 C,After 1 hour, TLC detection showed the end of the reaction. After cooling the reaction solution to room temperature,The reaction solution was quenched by adding 20 mL of water and 20 mL of dichloromethane.The organic phase was collected in layers and the aqueous phase was extracted three times with dichloromethane.The combined organic layers were washed with brine and dried over anhydrous sodium sulfate.The desiccant is filtered off, and the filtrate is dehydrated to remove the solvent.Obtained as a white solid, recrystallized,Obtaining 6.0 g of a white crystalline compound D,The yield was 99%. | |
88% | With triethylamine; In dichloromethane; at -9 - 20℃; for 1.75h; | To a solution of (6-chloro-3-pyridyl) methanol (4.5 g, 31.3 mmol) and triethylamine (13.2 ml, 94.7 mmol) in dichloromethane (90 ml) was dropwise added methanesulfonyl chloride (3.6 ml, 46.5 mmol) over 45 minutes at -9C to 4C under an atmosphere of nitrogen gas, followed by stirring as it was. After 1 hour, the reaction mixture was elevated to room temperature. The reaction mixture was washed with an aqueous saturated sodium bicarbonate solution and a saturated aqueous ammonium chloride solution, dried over anhydrous sodium sulfate and concentrated, to give the title compound (6.14 g, 88%) as a pale brown solid.1H NMR (400 MHz, DMSO-d6) δ ppm; 3.30 (3H, s), 5.34 (2H, s), 7.61 (1H, dd, J = 0.6, 8. 0 Hz), 7.97 (1H, dd, J=2.4, 8.0 Hz), 8.53 (1H, dd, J = 0.6, 2.4 Hz). |
58.3% | With triethylamine; In tetrahydrofuran; at 0 - 20℃; for 3h; | (5) 6-chloro-3-methylhydroxypyridine (formula (6-1), 600 mg, 4.18 mmol) obtained in the step (4) was placed in tetrahydrofuran (12 mL), and triethylamine (TEA) was added at 0 C. , 1.06g, 10.45mmol) and MsCl (methanesulfonyl chloride, 527mg,4.60 mmol), the reaction mixture was stirred at room temperature for 3 h.After a solution of NH4Cl (5 mL), EtOAc (EtOAc (EtOAc)EtOAc.The organic phase is dried to give an oily product6-chloro-3-methanesulfonate pyridine(8-1), 540 mg, 2.3 mmol, yield 58.3%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | (4) 6-chloronicotinate methyl ester(7-1), 1.0 g, 5.85 mmol) was placed in THF (10 mL) and the temperature was dropped to 0 C.A solution of LiAlH4 (LAH, 244 mg, 6.44 mmol) in THF (10 mL) was obtained. After the dropwise addition, the reaction mixture was reacted at 20 C for 2 h.After completion of the reaction, it was quenched with NaOH solution (6.25 mol), then extracted twice with ethyl acetate (2×50 mL) and dried over anhydrous Na2SO4.Filter to dry to give a white solid6-chloro-3-methylhydroxypyridine(6-1), 780 mg, 5.59 mmol, yield 96%),Used directly in the next step. | |
95% | To a solution of methyl 6-chloronicotinate (0.60 g, 3.50 mmol) in THF (10 niL) at - 78 C was added a solution of DIBAL-H (1 M in toluene, 10.5 m-L, 10.5 mmol) and the reaction stirred from -78 0C to room temperature for 1 h. The reaction was diluted with a saturated aqueous solution of sodium potassium tartrate (25 mL) and CH2Cl2 (30 mL) and stirred vigorously overnight. The layers were separated and the aqueous layer was extracted with CH2Cl2 (2 x 15 mL). The combined organic extracts were dried (Na2SO4) and concentrated to afford the desired alcohol (0.48 g, 95%) as a white solid. | |
70% | With lithium aluminium tetrahydride; In tetrahydrofuran; at 0 - 20℃; for 3h;Inert atmosphere; | a) (6-chloropyridin-3-yl)methanol To a suspension of LiAIH4(1.5 g, 40 mmol) in THF(80 mL) was added methyl 6-chloronicotinate (1.56 g, 10 mmol) slowly at 0-5 Π under N2atmosphere. The reaction mixture was stirred at rt for 3h before it was quenched with 15% NaOH and water. The mixture was filtered through Celite and the cake was washed with EtOAc (100 ml_x3). Thefiltrate was washed with brine (200 mL), dried and concentrated to give the desired product as yellow oil (1 g, 70%). [LCMS: RtA = 0.88 min, m/z 144.2 [M+H]+]. |
70% | With lithium aluminium tetrahydride; In tetrahydrofuran; at 0 - 20℃; for 3h;Inert atmosphere; | a) (6-chloropyridin-3-yl)methanol To a suspension of LiAlH4 (1.5 g, 40 mmol) in THF (80 mL) was added methyl 6-chloronicotinate (1.56 g, 10 mmol) slowly at 0-5□ under N2 atmosphere. The reaction mixture was stirred at rt for 3 h before it was quenched with 15% NaOH and water. The mixture was filtered through Celite and the cake was washed with EtOAc (100 mL*3). The filtrate was washed with brine (200 mL), dried and concentrated to give the desired product as yellow oil (1 g, 70%). [LCMS: RtA=0.88 min, m/z 144.2 [M+H]+]. |
With sodium sulfate; In tetrahydrofuran; | Reference example 1. 6-chloropyridine-3-carboaldehyde 0.20g (1.17mmol) of methyl 6-chloronicotinate (Lancaster) was dissolved in 4ml of tetrahydrofuran anhydrous, and 0.045g (1.17mmol) of lithium aluminum hydride was added thereto under ice bath cooling, followed by stirring for 30 minutes. Sodium sulfate 10 hydrate was added to the reaction mixture until no foam appeared, and after stirring for 2 hours, filtration with Celite was performed. The filtrate was evaporated, and the residue was purified with silica gel column chromatography (ethyl acetate) to obtain 0.090g of 6-chloropyridine-3-methyl alcohol. 1H NMR (CDCl3, 300MHz) δ 3.79(1H, brs), 4.70 (2H, s), 7.31 (1H, d, J = 8.3Hz), 7.69 (1H, dd, J = 2.4, 8.3Hz), 8.28 (1H,d, J= 2.4Hz) mass spectrum EIMS, m/z:143(M+) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With thionyl chloride; In chloroform; | (b) Preparation of 2-chloro-5-chloromethylpyridine Thionyl chloride (14.6 ml, 0.2 mol) was added extremely carefully in dropwise manner to a rapidly stirred mixture of 2-chloro-5-hydroxymethylpyridine (18.6 g, 0.13 mol) and chloroform (150 ml) at ambient temperature (20 C.). After addition was complete the resulting mixture was heated under reflux for 12 hours. The reaction mixture was then allowed to cool to ambient temperature (20 C.) and chloroform was evaporated off under reduced pressure to give a brown oil. The product, 2-chloro-5-chloromethyl-pyridine was isolated from this brown oil by flash chromatography using silica gel, 230 to 400 US mesh (0.062 mm to 0.037 mm), with dichloromethane as eluent, as a yellow oil which solidified on standing (17.45 g, 82.9%). | |
With pyridine; thionyl chloride; | (1.2) 2-Chloro-5-chloromethyl-pyridine 85 ml of thionyl chloride are added cautiously to 14.4 g (0.1 mol) of 6-chloro-pyridine-3-methanol. 8.1 g (0.1 mol) of pyridine are then added dropwise and the mixture is heated under reflux until gas evolution is complete. Excess thionyl chloride is removed in vacuo and the residue is poured onto ice. The precipitate is filtered off with suction and dried. Yield 10.6 g (65.5% of theory), m.p.: 38-40 C. The crude product can be used further without purification. | |
With thionyl chloride; In dichloromethane; for 1h;Reflux; | 2-Ch-oropyridinyI-4-mcthylcncdicthylphbsphonatc. 2-Chloronicotinic acid (3.00 g, 19.0 mmol) was dissolved in dry THF (60 mL) and cooled to 0C. Lithium aluminiumhydride (870 mg, 23.0 mmol) was charged into the stirred reaction (CAUTION: gas evolution) followed by gradual warming to reflux for 4 hours. The reaction was quenched with sequential addition of wet THF (5 mL) and water (50 ml.., cautiously) before filtration through celite and removal of volatilcs in vacuo gave yellow oil that was purified by flash chromatography (Si02, CH2CI2 followed by F,t()Ac). The crystalline alcohol was dissolved in CH2C12 (20 mL) and excess thionylchloride (5-10 mL) before refluxing for 1 hour. On cooling to room temperature, volatiles were removed in vacuo and the residue was neutralised with sat. NallCO before extraction with CH2CI2 (3 x 40 mL). Organics were combined, dried over MgSO^, filtered and concentrated to 3-5 mL before purification through a silica plug (eluting with CH2CI2). Removal of volatiles in vacuo gave yellow oil as the desired 2-chloropyridyl-5-methylcnechloride. The alky chloride was dissolved in triethylphosphite ( 10 mL) and heated to 140C for 2 hours. On cooling to room temperature, volatiles were removed in vacuo and the residue purified by flash chromatography (Si02, CFLC^ followed by EtOAc) to give a light yellow oil (). NMR (500 MHz; CDCI3): S/ppm 8.28-8.26 (m, I II, Vy-H), 7.64 (dl. 1 H, 3./?? - 8.2, 4Jm = 2.5, Py-//), 7.28 (d, 1 H, 3J,?i - 8.2, Py-H), 4.09-4.02 (m, 4H, 0-C//j), 3.09 (d, 211. 3JHi> = 21.6, 0=?-C/), 1.28- 1.25 (m, 6H, C//3). ,3C{ 'H} NMR (125.7 MHz; CDCIj): S/ppm 150.4 (d, 3Jci> = 7.7, PyCH), 150.3 (d, FontWeight="Bold" FontSize="10" JCP = 4, PyC-Cl), 140.0 (d, 3JCl> - 5.5, PyCH), 127.1 (d, 2Ja> = 9, PyQ, 124.2 (d, VCI> - 2.9, PyCH), 62.6 (d, 2,/a> = 6.8, 0-CH2), 30.5 (d, 'Jcp = 140,0, O-P-CHz), 16.5 (d, = 5.9, CH2-CH3). Λ ,Ρ{} NMR (202.5 MHz; CDCh): S/ppm 24.8 (s, 0=P) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With carbon tetrabromide; triphenylphosphine; In dichloromethane; at 0 - 20℃; for 4.75h;Inert atmosphere; | Synthesis 265-(Bromomethyl)-2-chloropyridine (26).To a solution of (6-chloropyridin-3-yl)methanol (1 .005 g, 7.0 mmol, 1 eq) in dry DCM(20 ml.) CBr4 (99%, 2.885 g, 8.6 mmol, 1 .2 eq) was added. This solution was cooled to 0C and then Ph3P (2.297 g, 8.7 mmol, 1 .2 eq) was added. The reaction mixture was stirred at 0C for 15 minutes under nitrogen atmosphere and then it was allowed to warm to room temperature. After 4.5 hours the reaction mixture was treated with 20 ml. of water and extracted with DCM. The combined organic extracts were dried over anhydrous Na2S04, filtered and the solvent was removed in vacuo. The residue was purified by flash chromatography on silica gel (n-Hex/EtOAc 9: 1 ) to afford 1 .231 g of 26 as white solid (85%).0.33 (n-Hex/EtOAc 9:1 ). 1 H NMR (400 MHz, CDCI3) δ 8.40 (d, J = 2.5 Hz, 1 H), 7.70 J = 8.2, 2.6 Hz, 1 H), 7.33 (d, J = 8.3 Hz, 1 H), 4.44 (s, 2H); 13C NMR (100 MHz, CDCI3) 5 151.4, 149.6, 139.5, 132.8, 124.6, 28.5; ESI MS m/z: calcd. for C6H6BrCIN [/W+H]+ 205.9, found: 205.9, 207.9, 209.9. |
76.65% | With phosphorus tribromide; In dichloromethane; at 0 - 20℃; for 3h; | To a stirred solution of (6-chloropyridin-3-yl)methanol (2 g, 13.93 mmol) in dry DCM (40 ml), PBr3 (1.6 ml, 16.71 mmol) was added dropwise at 0C. The reaction mixture was stirred at ambient temperature for 3h. The progress of the reaction was monitored by TLC (3:7, Ethyl acetate: pet. ether). After completion of the reaction the reactionmixture was cooled o room temperature and quenched with aqueous 10% NaHCO3 solution (30 ml) and extracted with DCM (3 X 50 ml). The combined organic layer was dried over anhydrous sodium sulfate and removed under reduced pressure. The crude was purified by column chromatography (60-120 mesh silica gel) using 8% Ethyl acetate in pet ether as eluent to yield pure 5-(bromomethyl)-2-chloropyridine (2.2 g,76.65%) as a yellow oil. |
62% | With carbon tetrabromide; 1,3-bis-(diphenylphosphino)propane; In dichloromethane; | (6-chloro-3-pyridinyl)-methanol (1.0 eq.) was taken up in dichloromethane and stirred overnight with carbon tetrabromide (1.5 eq.) and 1,3-bis(diphenylphosphino)propane (0.75 eq.) Ether was added to the solution and filtration followed by concentration of the filtrate afforded (6-chloro-3-bromomethyl) pyridine in 62% yield. |
62% | With carbon tetrabromide; 1,3-bis-(diphenylphosphino)propane; In dichloromethane; | (6-Chloro-3-pyridinyl)-methanol (1.0 eq.) was taken up in dichloromethane and stirred overnight with carbon tetrabromide (1.5 eq.) and 1,3-bis(diphenylphosphino)propane (0.75 eq.). Ether was added to the solution and filtration followed by concentration of the filtrate afforded (6-chloro-3-bromomethyl)pyridine in 62% yield. |
60% | With carbon tetrabromide; triphenylphosphine; In dichloromethane; at 0 - 20℃; for 16h; | To a solution of 19-3B (115 mg, 0.804 mmol) in DCM (3 mL) was added carbon tetrabromide (320 mg, 0.965 mmol), triphenylphosphine (210 mg, 0.965 mmol), and stirred at 0 C to RT for 16 hr. The reaction mixture was diluted with excess DCM (20 mL), washed with water (20 mL), brine (10 mL) and dried over Na2S04, and the organic phase was concentrated under reduced pressure. Obtained crude compound was purified using silica gel chromatography (8% EtOAc in hexanes) to afford 19- 4B (100 mg, 0.48 mmol, yield 60%). MS (ESI): m/z 206.0 (M-l)+. |
0.49 g | With phosphorus tribromide; In dichloromethane; at 0 - 30℃; for 1.5h;Inert atmosphere; | To a solution of 2-chloro-5-hydroxymethylpyridine (0.45 g, 0.003 mole) in DCM (10 mL) at 0 C under N2, was added phosphorus tribromide (0.44 mL, 0.0037 mole) drop wise. Reaction mixture was warmed to RT and stirred for 1.5 hours. The reaction mixture was diluted with DCM (75 mL), treated with saturated aqueous sodium bicarbonate (20 mL). Organic layer was washed with water (20 mL), brine solution (20 mL) and dried over Na2S04 and concentrated under vacuum to obtain the title compound. Yield: 0.49 g; lH - NMR (CDC13, 400 MHz) δ ppm: 4.35 (s, 2H), 7.32 - 7.34 (d, J = 8.2 Hz, 1H), 7.69 - 7.71 (dd, J = 2.2, 7.9 Hz, 1H), 8.40 - 8.41 (d, J = 1.7 Hz, 1H); Mass (m/z): 205.9, 208.0 (M+H)+. |
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