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Chemical Structure| 1235142-25-2
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CAS No. :1235142-25-2 MDL No. :
Formula : C14H12BrNO3 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W :322.15 Pubchem ID :-
Synonyms :

Safety of [ 1235142-25-2 ]

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Application In Synthesis of [ 1235142-25-2 ]

* 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 [ 1235142-25-2 ]

[ 1235142-25-2 ] Synthesis Path-Downstream   1~5

  • 1
  • [ 321601-48-3 ]
  • [ 100-39-0 ]
  • [ 1235142-25-2 ]
YieldReaction ConditionsOperation in experiment
95% With potassium carbonate In acetone Reflux; 2.2.3. Synthesis of methyl 3-(benzyloxy)-6-bromopicolinate (Compound 4) To a solution of methyl 3-hydroxy-6-bromopicolinate 3 (11.6 g,49.8 mmol), in acetone (200 mL, 0.25 M) was added successively K2CO3(21 g, 149 mmol, 3 equiv) and benzyl bromide (12 mL, 100 mmol, 2.0equiv). The heterogeneous reaction mixture was reflux overnight. Saltswere removed by filtration and the crude product was concentratedunder reduced pressure. Purification by flash chromatography (Petroleum ether/EtOAc 95/5 to 3/2, v/v) afforded the desired product4 as a white solid (15.2 g, 95%). Rf=0.4 (Petroleum ether/EtOAc 8/2,v/v). 1H NMR (300 MHz, CDCl3): δ (ppm)=3.97 (s, 3H), 5.21 (s, 2H),7.24 (d, J=8.7 Hz, 1H), 7.47-7.34 (m, 5H), 7.51 (d, J=8.7 Hz, 1H).13C NMR (75 MHz, CDCl3): δ (ppm)=52.9, 71.2, 125.0, 126.9, 128.4,128.8, 131.2, 131.4, 135.2, 139.8, 154.0, 164.0. MS (ESI+): m/z (%):324 (85) and 322 (100) [M+H]+.
95% With potassium carbonate In acetone Reflux; 1 Methyl 3-(benzyloxy)-6-bromopicolinate - 4a To a solution of methyl 3-hydroxy-6-bromopicolinate 9a (11.6 g, 49.8 mmol), in acetone (200 mL, 0.25 M) was added successively potassium carbonate (21 g, 149 mmol, 3 equiv.) and benzyl bromide (12 mL, 100 mmol, 2.0 equiv.). The heterogeneous reaction mixture was reflux overnight. Salts were removed by filtration and the crude product was concentrated under reduced pressure. Purification by flash chromatography on silica gel (Petroleum ether/EtOAc 95/5 to 60/40, v/v) afforded the desired product 4a as a white solid (15.2 g, 95%). Rf = 0.4 (Petroleum ether/EtOAc 8/2, v/v). 1H NMR (300 MHz, CDCl3): δ (ppm) 3.97 (s, 3H), 5.21 (s, 2H), 7.24 (d, J = 8.7 Hz, 1H), 7.47-7.34 (m, 5H), 7.51 (d, J = 8.7 Hz, 1H). 13C NMR (75 MHz, CDCl3): δ (ppm) 52.9, 71.2, 125.0, 126.9, 128.4, 128.8, 131.2, 131.4, 135.2, 139.8, 154.0, 164.0. MS (ESI+): m/z (%): 324 (85) and 322 (100) [M+H] +.
95% With potassium carbonate In acetone Reflux; 1 Methyl 3-(benzyloxy)-6-bromopicolinate - 4a To a solution of methyl 3-hydroxy-6-bromopicolinate 9a (11.6 g, 49.8 mmol), in acetone (200 mL, 0.25 M) was added successively potassium carbonate (21 g, 149 mmol, 3 equiv.) and benzyl bromide (12 mL, 100 mmol, 2.0 equiv.). The heterogeneous reaction mixture was reflux overnight. Salts were removed by filtration and the crude product was concentrated under reduced pressure. Purification by flash chromatography on silica gel (Petroleum ether/EtOAc 95/5 to 60/40, v/v) afforded the desired product 4a as a white solid (15.2 g, 95%). Rf = 0.4 (Petroleum ether/EtOAc 8/2, v/v). 1H NMR (300 MHz, CDCl3): δ (ppm) 3.97 (s, 3H), 5.21 (s, 2H), 7.24 (d, J = 8.7 Hz, 1H), 7.47-7.34 (m, 5H), 7.51 (d, J = 8.7 Hz, 1H). 13C NMR (75 MHz, CDCl3): δ (ppm) 52.9, 71.2, 125.0, 126.9, 128.4, 128.8, 131.2, 131.4, 135.2, 139.8, 154.0, 164.0. MS (ESI+): m/z (%): 324 (85) and 322 (100) [M+H] +.
93% With potassium carbonate In acetone for 15h; Reflux;
93% With potassium carbonate In acetone for 15h; Reflux;
With potassium carbonate In tetrahydrofuran at 20℃; for 3h; 1.2 Step 2 - Synthesis of methyl 3-(benzyloxy)-6-bromopicolinate A mixture of methyl 6-bromo-3-hydroxypicolinate (500 mg, 2.15 mmol), BnBr (443 mg, 3.25 mmol) and K2C03 (595 mg, 4.31 mmol) in THF (5 mL) was stirred at RT for 3 h. Then water was added and the mixture was extracted with EtOAc (20 mL * 3). The organic layer was dried over Na2S04 and concentrated to give crude methyl 3-(benzyloxy)-6- bromopicolinate (500 mg, yield 72%), which was used for the next step without further purification. MS (M+H)+: 322 / 324.
With potassium carbonate In tetrahydrofuran at 25℃; for 3h; 1.2 Synthesis of methyl 3-(benzyloxy)-6-bromopicolinate A mixture of methyl 6-bromo-3-hydroxypicolinate (500 mg, 2.15 mmol), BnBr (443 mg, 3.25 mmol) and K2C03 (595 mg, 4.31 mmol) in THF (5 mL) was stirred at RT for 3 h. Then water was added and the mixture was extracted with EtOAc (20 mL * 3). The organic layer was dried over Na2504 and concentrated to give crude methyl 3-(benzyloxy)-6-bromopicolinate (500 mg, yield 72%), which was used for the next step without further purification. MS (M+H): 322 / 324.

Reference: [1]Pashirova, Tatiana N.; Braïki, Anissa; Zueva, Irina V.; Petrov, Konstantin A.; Babaev, Vasily M.; Burilova, Evgenia A.; Samarkina, Darya A.; Rizvanov, Ildar Kh.; Souto, Eliana B.; Jean, Ludovic; Renard, Pierre-Yves; Masson, Patrick; Zakharova, Lucia Ya.; Sinyashin, Oleg G. [Journal of Controlled Release, 2018, vol. 290, p. 102 - 111]
[2]Current Patent Assignee: NATIONAL INSTITUTE OF APPLIED SCIENCES; UNIVERSITY OF ROUEN NORMANDIE; ETAT FRANCAIS REPRESENTE PAR LA DIRECTION CENTRALE DU SERVICE DE SANTE DES ARMEES; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE - EP3945092, 2022, A1 Location in patent: Paragraph 0086; 0103-0104
[3]Current Patent Assignee: NATIONAL INSTITUTE OF APPLIED SCIENCES; UNIVERSITY OF ROUEN NORMANDIE; ETAT FRANCAIS REPRESENTE PAR LA DIRECTION CENTRALE DU SERVICE DE SANTE DES ARMEES; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE - EP3945092, 2022, A1 Location in patent: Paragraph 0086; 0103-0104
[4]Mercey, Guillaume; Verdelet, Tristan; Saint-Andre, Geraldine; Gillon, Emilie; Wagner, Alain; Baati, Rachid; Jean, Ludovic; Nachon, Florian; Renard, Pierre-Yves [Chemical Communications, 2011, vol. 47, # 18, p. 5295 - 5297]
[5]Renou, Julien; Loiodice, Mélanie; Arboléas, Mélanie; Baati, Rachid; Jean, Ludovic; Nachon, Florian; Renard, Pierre-Yves [Chemical Communications, 2014, vol. 50, # 30, p. 3947 - 3950]
[6]Current Patent Assignee: WUXI APPTEC CO., LTD. - WO2014/209727, 2014, A1 Location in patent: Page/Page column 32-33
[7]Current Patent Assignee: WUXI APPTEC CO., LTD. - WO2014/205593, 2014, A1 Location in patent: Page/Page column 34
  • 2
  • [ 321596-55-8 ]
  • [ 1235142-25-2 ]
  • 3
  • [ 321596-56-9 ]
  • [ 1235142-25-2 ]
  • [ 1342906-73-3 ]
YieldReaction ConditionsOperation in experiment
70% With tetrakis(triphenylphosphine) palladium(0); sodium formate; In N,N-dimethyl-formamide; at 80℃; for 20.0h; Pd(PPh3)4 (140 mg, 0.05 equiv) was added to a degassed solution of 5 (1.0 g, 2.5 mmol) and sodium formate (190 mg, 1.1 equiv) in DMF (20 mL, 50 g/L). The mixture was stirred for 20 h at 80 C. DMF was removed under vacuum and the crude mixture was directly absorbed on silica gel and purified by flash chromatography (cyclohexane/EtOAc 7/3, v/v) to give 10 (560 mg, 70%) as a beige solid. Rf=0.3 (cyclohexane/EtOAc 7/3, v/v). Mp 78 C. 1H NMR (300 MHz, CDCl3) delta (ppm) 3.95 (s, 3H), 5.16 (s, 2H), 7.36-7.45 (m, 3H), 7.53-7.56 (m, 2H), 7.71 (d, J=5.1 Hz, 1H), 8.27 (d, J=5.1 Hz, 1H). 13C NMR (75 MHz, CDCl3) delta 53.1, 76.8, 128.5, 128.6, 128.7, 130.1, 131.3, 135.9, 145.3, 145.4, 152.5, 164.4. MS (ESI+) m/z (%): 324 (95), 322 (100). Anal. Calcd for C14H12BrNO3: C, 52.20; H, 3.75; N, 4.35. Found: C, 52.33; H, 3.89; N, 3.81.
  • 4
  • [ 5390-04-5 ]
  • [ 1235142-25-2 ]
  • [ 1585949-24-1 ]
YieldReaction ConditionsOperation in experiment
99% With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In dichloromethane at 20℃; Inert atmosphere;
99% With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In acetonitrile at 40℃; for 0.0833333h; Microwave irradiation;
96% Stage #1: pent-1-yn-5-ol; methyl 3-(benzyloxy)-6-bromopyridine-2-carboxylate With triethylamine In dichloromethane for 0.333333h; Inert atmosphere; Stage #2: With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0) In dichloromethane at 20℃; Inert atmosphere; 2.2.4. Synthesis of methyl 3-(benzyloxy)-6-(5-hydroxypent-1-ynyl)picolinate (Compound 5) To a solution of methyl 3-(benzyloxy)-6-bromopicolinate 4 (3.19 g,9.90 mmol) in dichloromethane (66 mL) and triethylamine (33 mL) wasadded 4-pentyn-1-ol (650 μL, 9.93 mmol, 1 equiv). The resulting mixturewas degassed for 20 min with argon. CuI (200 mg, 1.02 mmol, 0.1equiv.) and Pd(PPh3)4 (527 mg, 0.50 mmol, 0.05 equiv.) were thenpoured and the solution was stirred under argon at room temperatureovernight. The reaction mixture was concentrated under reducedpressure. Purification by flash chromatography (Petroleum ether/EtOAc 7/3 to 3/7, v/v) afforded the desired product 5 as a yellow oilthat crystallized upon standing (3.1 g, 96%). Rf=0.33 (Petroleumether/EtOAc 3/7, v/v). 1H NMR (300 MHz, CDCl3) δ (ppm)=1.86 (qt,J=6.4 Hz, 2H), 2.38 (br s, 1H), 2.54 (t, J=7.0 Hz, 2H), 3.78 (t,J=6.2 Hz, 2H), 3.96 (s, 3H), 5.20 (s, 2H), 7.30-7.45 (m, 7H). 13C NMR(75 MHz, CDCl3) δ (ppm)=15.9, 31.0, 52.7, 61.4, 70.9, 79.6, 89.8,121.9, 127.0, 128.3, 128.8, 130.1, 135.4, 135.6, 140.0, 153.0, 164.9.MS (ESI+): m/z (%): 673 (100) [2M+Na]+, 348 (95) [M+Na]+ and326 (100) [M+H]+.
  • 5
  • [ 5390-04-5 ]
  • [ 1235142-25-2 ]
  • [ 1585949-22-9 ]
YieldReaction ConditionsOperation in experiment
94% Stage #1: pent-1-yn-5-ol; methyl 3-(benzyloxy)-6-bromopyridine-2-carboxylate With copper(l) iodide; triethylamine In dichloromethane for 0.333333h; Inert atmosphere; Stage #2: With tetrakis(triphenylphosphine) palladium(0) In dichloromethane at 20℃; Inert atmosphere; 1 Methyl 3-(benzyloxy)-6-(4-hydroxybut-1-yn-1-yl)picolinate - 14b To a solution of methyl 3-(benzyloxy)-6-bromopicolinate 4a (2.0 g, 6.20 mmol, 1 equiv) in dry dichloromethane (53 mL) and triethylamine (27 mL) was added 4-pentyn-1-ol (485 µL, 6.21 mmol, 1 equiv). The resulting mixture was degassed for 20 min with argon. CuI (200 mg, 0.1 equiv.) and Pd(PPh3)4 (330 mg, 0.05 equiv.) were then poured and the solution was stirred under argon at rt overnight. The reaction mixture was concentrated under reduced pressure. Purification by flash chromatography (Petroleum ether/EtOAc 7/3 to 3/7, v/v) afforded the desired product 14b as a yellow oil that crystallized upon standing (1.8 g, 94%). Rf = 0.3 (Petroleum ether/EtOAc 4/6, v/v). 1H NMR (300 MHz, CDCl3) δ (ppm) 2.66 (t, J = 6.6 Hz, 2H), 3.00 (br s, 1H), 3.82 (t, J = 6.6 Hz, 2H), 3.96 (s, 3H), 4.29-4.35 (m, 1H), 5.18 (s, 2H), 7.28-7.44 (m, 7H). 13C NMR (75 MHz, CDCl3) δ (ppm) 23.8, 52.7, 60.7, 70.9, 80.6, 87.4, 121.9, 126.9, 128.3, 128.8, 130.1, 135.0, 135.5, 139.9, 153.2, 164.8. MS (ESI+): m/z (%): 312 (100) [M+H]+.
94% Stage #1: pent-1-yn-5-ol; methyl 3-(benzyloxy)-6-bromopyridine-2-carboxylate With copper(l) iodide; triethylamine In dichloromethane for 0.333333h; Inert atmosphere; Stage #2: With tetrakis(triphenylphosphine) palladium(0) In dichloromethane at 20℃; Inert atmosphere; 1 Methyl 3-(benzyloxy)-6-(4-hydroxybut-1-yn-1-yl)picolinate - 14b To a solution of methyl 3-(benzyloxy)-6-bromopicolinate 4a (2.0 g, 6.20 mmol, 1 equiv) in dry dichloromethane (53 mL) and triethylamine (27 mL) was added 4-pentyn-1-ol (485 µL, 6.21 mmol, 1 equiv). The resulting mixture was degassed for 20 min with argon. CuI (200 mg, 0.1 equiv.) and Pd(PPh3)4 (330 mg, 0.05 equiv.) were then poured and the solution was stirred under argon at rt overnight. The reaction mixture was concentrated under reduced pressure. Purification by flash chromatography (Petroleum ether/EtOAc 7/3 to 3/7, v/v) afforded the desired product 14b as a yellow oil that crystallized upon standing (1.8 g, 94%). Rf = 0.3 (Petroleum ether/EtOAc 4/6, v/v). 1H NMR (300 MHz, CDCl3) δ (ppm) 2.66 (t, J = 6.6 Hz, 2H), 3.00 (br s, 1H), 3.82 (t, J = 6.6 Hz, 2H), 3.96 (s, 3H), 4.29-4.35 (m, 1H), 5.18 (s, 2H), 7.28-7.44 (m, 7H). 13C NMR (75 MHz, CDCl3) δ (ppm) 23.8, 52.7, 60.7, 70.9, 80.6, 87.4, 121.9, 126.9, 128.3, 128.8, 130.1, 135.0, 135.5, 139.9, 153.2, 164.8. MS (ESI+): m/z (%): 312 (100) [M+H]+.
Methyl 3-(benzyloxy)-6-(4-hydroxybut-1-yn-1-yl)picolinate - 14b Methyl 3-(benzyloxy)-6-(4-hydroxybut-1-yn-1-yl)picolinate - 14b To a solution of methyl 3-(benzyloxy)-6-bromopicolinate 4a (2.0 g, 6.20 mmol, 1 equiv) in dry dichloromethane (53 mL) and triethylamine (27 mL) was added 4-pentyn-1-ol (485 μL, 6.21 mmol, 1 equiv). The resulting mixture was degassed for 20 min with argon. CuI (200 mg, 0.1 equiv.) and Pd(PPh3)4 (330 mg, 0.05 equiv.) were then poured and the solution was stirred under argon at rt overnight. The reaction mixture was concentrated under reduced pressure. Purification by flash chromatography (Petroleum ether/EtOAc 7/3 to 3/7, v/v) afforded the desired product 14b as a yellow oil that crystallized upon standing (1.8 g, 94%). Rf = 0.3 (Petroleum ether/EtOAc 4/6, v/v). 1H NMR (300 MHz, CDCl3) δ (ppm) 2.66 (t, J = 6.6 Hz, 2H), 3.00 (br s, 1H), 3.82 (t, J = 6.6 Hz, 2H), 3.96 (s, 3H), 4.29-4.35 (m, 1H), 5.18 (s, 2H), 7.28-7.44 (m, 7H). 13C NMR (75 MHz, CDCl3) δ (ppm) 23.8, 52.7, 60.7, 70.9, 80.6, 87.4, 121.9, 126.9, 128.3, 128.8, 130.1, 135.0, 135.5, 139.9, 153.2, 164.8. MS (ESI+): m/z (%): 312 (100) [M+H]+.
Methyl 3-(benzyloxy)-6-(4-hydroxybut-1-yn-1-yl)picolinate - 14b Methyl 3-(benzyloxy)-6-(4-hydroxybut-1-yn-1-yl)picolinate - 14b To a solution of methyl 3-(benzyloxy)-6-bromopicolinate 4a (2.0 g, 6.20 mmol, 1 equiv) in dry dichloromethane (53 mL) and triethylamine (27 mL) was added 4-pentyn-1-ol (485 μL, 6.21 mmol, 1 equiv). The resulting mixture was degassed for 20 min with argon. CuI (200 mg, 0.1 equiv.) and Pd(PPh3)4 (330 mg, 0.05 equiv.) were then poured and the solution was stirred under argon at rt overnight. The reaction mixture was concentrated under reduced pressure. Purification by flash chromatography (Petroleum ether/EtOAc 7/3 to 3/7, v/v) afforded the desired product 14b as a yellow oil that crystallized upon standing (1.8 g, 94%). Rf = 0.3 (Petroleum ether/EtOAc 4/6, v/v). 1H NMR (300 MHz, CDCl3) δ (ppm) 2.66 (t, J = 6.6 Hz, 2H), 3.00 (br s, 1H), 3.82 (t, J = 6.6 Hz, 2H), 3.96 (s, 3H), 4.29-4.35 (m, 1H), 5.18 (s, 2H), 7.28-7.44 (m, 7H). 13C NMR (75 MHz, CDCl3) δ (ppm) 23.8, 52.7, 60.7, 70.9, 80.6, 87.4, 121.9, 126.9, 128.3, 128.8, 130.1, 135.0, 135.5, 139.9, 153.2, 164.8. MS (ESI+): m/z (%): 312 (100) [M+H]+.

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