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Chemical Structure| 878207-91-1 Chemical Structure| 878207-91-1

Structure of 878207-91-1

Chemical Structure| 878207-91-1

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Product Details of [ 878207-91-1 ]

CAS No. :878207-91-1
Formula : C8H9NO3
M.W : 167.16
SMILES Code : CC1=C(C(OC)=O)[N+]([O-])=CC=C1
MDL No. :MFCD21604097

Safety of [ 878207-91-1 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P264-P271-P280-P302+P352-P304+P340-P305+P351+P338-P312-P362-P403+P233-P501

Application In Synthesis of [ 878207-91-1 ]

* 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.

  • Downstream synthetic route of [ 878207-91-1 ]

[ 878207-91-1 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 878207-91-1 ]
  • [ 878207-92-2 ]
YieldReaction ConditionsOperation in experiment
41% With trichlorophosphate; at 110℃; for 4h; A solution of 2-(methoxycarbonyl)-3-methylpyridin-1-ium-1-olate (500 mg, 2.99 mmol, 1.00 equiv) in phosphorus oxychloride (2 mL) was stirred for 4 hours at 110 C. The reaction was quenched with water, adjusted pH to 7, and extracted with ethyl acetate. The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated under vacuum. The residue was purified by a silica gel column eluting with ethyl acetate/petroleum ether (1:5) to give the title compound (230 mg, 41%) as a white solid. LC-MS (ES, m/z): 186 [M+H]+.
40% With trichlorophosphate; In 1,2-dichloro-ethane; for 4h;Reflux; A solution of 2-(methoxycarbonyl)-3-methylpyridine 1-oxide (500 mg, 2.99 mmol) and phosphorus oxychloride (0.55 mL, 5.98 mmol) in 1,2-dichloroethane (10 ml) was refluxed for 4 h. After completion of reaction, the reaction mixture was combined with 100 ml of ice water and extracted with dichoromethane (50 ml x 2) being washed with water and sodium bicarbonate solution, and then the combined organic layer was dried over anhydrous sodium sulfate, and filtered. The solvent was removed under reduced pressure, and the resulting residue was purified by silica gel column chromatography (10% EA/Hexnae) to give 223 mg (yield 40%) of the title compound. 1H NMR(300MHz, CDCl3) delta 7.59 (dd, J = 8.1, 0.5 Hz, 1H), 7.38 (d, J = 8.1 Hz, 1H), 3.97 (s, 3H), 2.57 (s, 3H).
37% With trichlorophosphate; at 100℃; for 3h; A solution of 2-(methoxycarbonyl)-3-methylpyridine 1-oxide (2 g, 6.0 mmol) in POCI3 (5 mL) was stirred at 100C for 3 hours. After being concentrated, the residue was purified by column chromatography (PE : EtOAc = 1 : 1) to give the product of methyl 6-chloro- 3-methylpicolinate (380 mg, yield: 37%). -NMR (CDCI3, 400 MHz) delta 7.59 (d, J= 8.0 Hz, 1H), 7.38 (d, J= 8.0 Hz, 1H), 3.96 (s, 3H), 2.56 (s, 3H). MS (M+H)+: 186 / 188.
37% With trichlorophosphate; at 100℃; for 3h; solution of 2-(methoxycarbonyl)-3-methylpyridine 1-oxide (2 g, 6.0 mmol) in POd3 (5 mL) was stirred at 100C for 3 hours. After being concentrated, the residue was purified by column chromatography (PE : EtOAc = 1: 1) to give the product of methyl 6-chloro-3- methylpicolinate (380 mg, yield: 37%). ?H-NMR (CDC13, 400 MHz) 7.59 (d, J 8.0 Hz, 1H),7.38 (d, J= 8.0 Hz, 1H), 3.96 (s, 3H), 2.56 (s, 3H). MS (M+H): 186 / 188.
20.9% With trichlorophosphate; at 0 - 20℃; for 16.75h; POCl3 (30.0 mL) is added slowly to methyl 3 -methyl- 1 -oxido- pyridin- l-ium-2-carboxylate (13.0 g, 0.077 mol) at 0 C over 30 minutes. The reaction mixture is stirred for 15 minutes at 0 C and then gradually warmed to ambient temperature. After 16 hours, the reaction mixture is cooled to 0 C and excess POCl3 is removed under reduced pressure. The crude residue is then quenched by addition of ice and diluted with water and CH2CI2 (50 mL). The organic layer is washed sequentially with saturated NaHC03 solution, water, and brine; dried over sodium sulfate; filtered; and concentrated under reduced pressure. The crude product is purified by silica gel flash chromatography, eluting 5-10% EtOAc in hexanes to afford methyl 6-chloro-3 -methyl - pyridine-2-carboxylate as a white solid (3.00 g, 20.9%). Mass spectrum (m/z): 186.2 (M+H)+.
With trichlorophosphate; at 60℃; for 16h;Neat (no solvent); b) 6-Chloro-3-methyl-2-pyridmecarboxylic acid, methyl esterA solution of 3-methyl-2-pyridinecarboxylic acid 1-oxide, methyl ester (Example 71 (a))(300 mg) in phosphorous oxychloride (1 mL) was heated at 60C for 16 hours. Thereaction mixture was then poured into water (10 mL) and extracted with dichloromethane(2x10 mL). The organics were dried over magnesium sulphate, filtered and concentratedto dryness to give the sub-title compound as a colourless oil (300 mg).MS: APCI(+ve) 185/187

  • 2
  • [ 59718-84-2 ]
  • [ 878207-91-1 ]
YieldReaction ConditionsOperation in experiment
98% With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 0 - 20℃; for 4h; To a solution of <strong>[59718-84-2]methyl 3-methylpicolinate</strong> (5.0 g, 33.1 mmol) in dichloromethane (100 ml) was added of m-chloroperbenzoic acid (8.9 g, 39.7 mmol) at 0oC. After being stirred for 4 h at room temperature, the reaction mixture was combined with 100 ml of water, extracted with dichoromethane (50 ml x 2), and washed with water and sat. sodium bicarbonate solution. The combined organic layer was dried over anhydrous sodium sulfate, and filtered. The solvent was removed from the filtrate under reduced pressure, and the resulting residue was refined by silica gel column chromatography (5% MeOH/CH2Cl2) to give 5.3g (yield 98%) of the title compound. 1H NMR(300MHz, CDCl3) δ 8.09 (d, J = 6.3 Hz, 1H), 7.12 (m, 1H), 7.13 (d, J = 7.9 Hz, 1H), 4.03 (s, 3H), 2.30 (s, 3H).
96% With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 45℃; for 4h; A solution of <strong>[59718-84-2]methyl 3-methylpyridine-2-carboxylate</strong> (800 mg, 5.29 mmol, 1.00 equiv) and 3-chloroperoxybenzoic acid (1826 mg, 10.58 mmol, 2.00 equiv) in dichloromethane (20 mL) was stirred for 4 hours at 45 C. The resulting solution was concentrated under vacuum and the residue was purified by a silica gel column eluting with ethyl acetate/petroleum ether (1:3). This resulted in the title compound (850 mg, 96%) as yellow oil. LC-MS (ES, m/z): 168 [M+H]+.
96% With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 45℃; for 4h; A solution of <strong>[59718-84-2]methyl 3-methylpyridine-2-carboxylate</strong> (800 mg, 5.29 mmol, 1.00 equiv) and 3-chloroperoxybenzoic acid (1826 mg, 10.58 mmol, 2.00 equiv) in dichloromethane (20 mL) was stirred for 4 hours at 45 C. The resulting solution was concentrated under vacuum and the residue was purified by a silica gel column eluting with ethyl acetate/petroleum ether (1:3). This resulted in the title compound (850 mg, 96%) as yellow oil. LC-MS (ES, mlz): 168 [M+H]+
89.9% With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 0 - 20℃; for 16.25h; To a solution of <strong>[59718-84-2]methyl 3-methylpyridine-2-carboxylate</strong> (13.0 g, 0.086 mol) in CH2CI2 (130 mL) is added meta-chloroperoxybenzoic acid (89.05 g, 0.258 mol, 50 % w/w) portionwise at 0 C. The reaction mixture is stirred for 15 minutes at 0C and then gradually warmed to ambient temperature. After 16 hours, saturated NaHC03 solution (100 mL) is added. The mixture is stirred for 30 minutes and is extracted with CH2CI2. The combined organic layers are washed with 0.5M NaOH aqueous solution (2 χ 50 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure to give methyl 3 -methyl- 1 -oxido-pyridin- 1 -ium-2-carboxylate as an off- white solid (13.0 g, 89.9%). The residue is used in the next step without further purification. Mass spectrum (m z): 168.2 (M+H)+.
85% With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 20℃; for 24h;Inert atmosphere; To a solution of ethyl 2-methyl-3-pyridinecarboxylate (1.86 ml_, 12.1 mmol) in DCM (50 ml_) mCPBA was added (4.18 g, 24.2 mmol) at RT. The solution was stirred at RT for 24 hrs. The solution was filtered and concentrated. The residue was purified by FC on silica (eluent: DCM to 15% MeOH) to a solid still containing mCBA that was dissolved with DCM and washed with NaHC03, the organic phase was dried and evaporated to afford 2- (methoxycarbonyl)-3-methylpyridin-N oxide (p134, 1.9 g, y=85%). MS (m/z): 168.1 [M]+.
79% With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 20℃; A mixture of <strong>[59718-84-2]methyl 3-methylpicolinate</strong> (2 g, 14.8 mmol) and m-CPBA (3 g, 17.8 mmol) in DCM (35 mL) was stirred at RT overnight. Then the mixture was washed with NaHSC (a.q.) and concentrated in vacuum. The residue was purified by column chromatography (DCM : MeOH = 200 : 1) to give the product of 2-(methoxycarbonyl)-3- methylpyridine 1-oxide (1.89 g, yield: 79%). -NMR (CDC13> 400 MHz) δ 8.05 (d, J= 6.0 Hz, 1H), 7.18 (t, J= 8.4 Hz, 1H), 7.10 (d, J= 8.0 Hz, 1H), 3.95 (s, 3H), 2.23 (s, 3H). MS (M+H)+: 168.
79% With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 25℃; A mixture of <strong>[59718-84-2]methyl 3-methylpicolinate</strong> (2 g, 14.8 mmol) and m-CPBA (3 g, 17.8mmol) in DCM (35 mE) was stirred at RT overnight. Then the mixture was washed with NaHSO3 (a.q.) and concentrated in vacuum. The residue was purified by column chromatography (DCM:MeOH = 200: 1) to give the product of 2-(methoxycarbonyl)-3-methylpyridine 1-oxide (1.89 g, yield: 79%). ‘H-NMR (CDC13, 400 MHz) 8.05 (d, J 6.0 Hz, 1H), 7.18 (t, J 8.4 Hz, 1H), 7.10 (d, J= 8.0 Hz, 1H), 3.95 (s, 3H), 2.23 (s, 3H). MS (M+H): 168.
With dihydrogen peroxide; In water; acetic acid; at 20 - 60℃; Example 716-[4-Chloro-3-[[(tricyclo[3.3.1.13'7]dec-l-ylmethyl)amino]carbonyl]phenyl]-3-methyl-2-pyridinecarboxylic acidCla) 3-Methyl-2-pyridinecarboxyIic acid 1-oxide, methyl esterA solution of 3-methyl 2-pyridinecarboxylic acid, methyl ester (340 mg) in acetic acid (5mL) and 35% aqueous hydrogen peroxide (5 mL) was heated at 60C for 5 hours beforebeing stirred at room temperature overnight. The reaction mixture was quenched bypouring into a sodium sulfite/ ice water mixture (50 mL) and then extracted intodichloromethane (3 x 25 mL). The organics were dried over magnesium sulphate, filteredand concentrated to dryness to give the sub-title compound as a colourless oil (300 mg).MS: APCI(+ve) 168 (M+H4).

 

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