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[ CAS No. 18699-87-1 ]

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2D
Chemical Structure| 18699-87-1
Chemical Structure| 18699-87-1
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Product Details of [ 18699-87-1 ]

CAS No. :18699-87-1MDL No. :MFCD04114137
Formula : C6H6N2O2 Boiling Point : 213.8°C at 760 mmHg
Linear Structure Formula :-InChI Key :-
M.W :138.12Pubchem ID :329360
Synonyms :

Computed Properties of [ 18699-87-1 ]

TPSA : 58.7 H-Bond Acceptor Count : 3
XLogP3 : 1.1 H-Bond Donor Count : 0
SP3 : 0.17 Rotatable Bond Count : 0

Safety of [ 18699-87-1 ]

Signal Word:WarningClass:N/A
Precautionary Statements:P280-P305+P351+P338UN#:N/A
Hazard Statements:H302Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 18699-87-1 ]

  • Upstream synthesis route of [ 18699-87-1 ]
  • Downstream synthetic route of [ 18699-87-1 ]

[ 18699-87-1 ] Synthesis Path-Upstream   1~25

  • 1
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  • [ 3430-10-2 ]
Reference: [1] Bulletin de la Societe Chimique de France, 1992, # 1, p. 79 - 84
[2] Patent: EP1510516, 2005, A1, . Location in patent: Page/Page column 134
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  • [ 272-49-1 ]
Reference: [1] Organic Letters, 2009, vol. 11, # 6, p. 1357 - 1360
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  • [ 109-06-8 ]
  • [ 21203-68-9 ]
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YieldReaction ConditionsOperation in experiment
0.1 g With oxygen; nitrogen(II) oxide In acetonitrile at 90℃; for 10 h; Into the reactor, 0.93 g (10.0 mmol) of 2-methylpyridine, 5 mL of acetonitrile, 0.15 g of sulfonated graphene was added, and the reaction was stirred under an oxygen atmosphere at 5.0 MPa of nitrogen monoxide and a temperature of 90 ° C for 10 h. After the end of the reaction, nitrogen gas was introduced into the reaction mixture at a normal pressure until the nitrogen oxides completely escaped to the cold trap reaction receiver, and the catalyst was filtered off. The filtrate was washed with a 5percent (m/m) aqueous solution of sodium hydrogencarbonate to near neutral, and then washed with distilled water until the organic phase was neutral and concentrated by evaporation in vacuo. Separating the product components by column chromatography,The mass of 2-methylnitropyridine is 0.67g,Wherein 2-methyl-3-nitropyridine 0.10 g (mass fraction 16percent),2-methyl-5-nitropyridine 0.57 g (mass fraction 84percent), yield 49percent.
Reference: [1] Acta Chemica Scandinavica, 1994, vol. 48, # 2, p. 181 - 182
[2] Acta Chemica Scandinavica, 1994, vol. 48, # 12, p. 1001 - 1006
[3] Patent: CN108003029, 2018, A, . Location in patent: Paragraph 0043; 0044
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YieldReaction ConditionsOperation in experiment
80%
Stage #1: With sodium t-butanolate In 1-methyl-pyrrolidin-2-one at 16 - 35℃; for 2 h;
Stage #2: at 29 - 50℃; for 1.16667 h;
Stage #3: With sulfuric acid In water at 50 - 100℃; for 0.75 h;
Add NMP (2.0 L) to a 12-L, 3-neck flask fitted with a stirrer, a temperature probe and a reflux condenser fitted with a gas adapter for N2 and cool to 16° C.. Add sodium tert-butoxide (0.675 kg, 6.81 mol, 2.2 equiv., corrected for 97percent purity) in one portion whereupon one observes an immediate exotherm to 29° C. Stir the mixture for 30 min to partially dissolve the NaOt-Bu and then add diethyl malonate (0.943 L, 6.19 mol, 2.0 equiv.) at 20° C. to 35° C. over 70 min with continual cooling whereupon a homogeneous solution forms. Stir for 20 min and add a solution of 2-chloro-3-nitropyridine (1a-1, 0.491 kg, 3.09 mol, 1.0 equiv.) and NMP (1.0 L) to the reaction mixture at 29° C. to 44° C. over 70 min. Heat the reaction mixture to 50° C. Monitor the progress of the reaction HPLC (Agilent series 1100; Waters Symmetry C8 (5μ) column (3.9.x.150 mm), flow rate at 1.0 mL/min. Isocratic: CH3CN/0.1percent aq. TFA, 50/50; λ=220 nm. RT: diethyl malonate=2.6 min, 2-chloro-3-nitropyridine=2.7 min, 2-(3-nitro-pyridin-2-yl)-malonic acid diethyl ester =3.9 min). Typically >99percent conversion occurs within 1-2 h. Discontinue heating and add 6M H2SO4 (2.17 L) at 50° C. to 59° C. over 45 min. A thick solid precipitate forms during the addition. Heat the mixture to 100° C. The evolution of gas occurs. Monitor the progress of the reaction by HPLC as previously described (RT: 2-methyl-3-nitropyridine 2a-1=2.0 min, 2-(3-nitro-pyridin-2-yl)-malonic acid diethyl ester=3.9 min). Typically one observes >99percent conversion within 12 h. Allow the mixture to cool to 40° C. and pour into ice water (20 kg, pH 1.5). Add 25percent aq. NaOH (2.65 L) at -11° C. to -6° C. over 20 min to pH 11. Add toluene (4.0 L) and stir the mixture for 10 min. Filter the mixture through Celite.(R). to remove inorganic solids and wash the filtercake with toluene (6.0 L). Separate the phases and extract the aqueous phase twice with toluene (6.0 L and 4.0 L). Filter the combined toluene phases through Celite.(R). and wash the filter cake with toluene (1.0 L). Combine the toluene filtrates and wash with water (2.x.3.0 L). Dry (MgSO4) the toluene phase, filter and concentrate to give 2-methyl-3-nitropyridine 2a-1 (0.34 kg, 80percent yield, correct for residual NMP and toluene) as an oil. HPLC analysis shows the material to be 96percent pure. 1H NMR (CDCl3) δ 2.87 (s, 3H), 7.35 (dd, 1H, J=4.8, 8.1 Hz), 8.27 (dd, 1H, J=1.4, 8.1 Hz), δ 8.72 (dd, 1H, J=1.4, 4.8 Hz).
Reference: [1] Patent: US2005/131012, 2005, A1, . Location in patent: Page/Page column 13-14
[2] Organic and Biomolecular Chemistry, 2005, vol. 3, # 20, p. 3701 - 3706
[3] Synthetic Communications, 1990, vol. 20, # 19, p. 2965 - 2970
[4] Patent: WO2011/73092, 2011, A1,
[5] Organic Process Research and Development, 2011, vol. 15, # 5, p. 1040 - 1045
[6] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 1, p. 339 - 342
[7] Journal of Medicinal Chemistry, 2012, vol. 55, # 22, p. 9531 - 9540
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YieldReaction ConditionsOperation in experiment
55% With potassium carbonate In 1,4-dioxane for 24 h; Heating / reflux A mixture of 2-chloro-3-nitropyridine (1.6g, 10.09mmol), Pallac tetrakis(triphenylphosphine) (1170mg, 1.01 mmol), methylboronic acid (665mg, mmol ) and potassium carbonate (4180mg, 30.3 mmol) was refluxed in dioxane 1 days. The reaction was cooled to room temperature, and then filtered. The filtrate concentrated and the residue was purified by flash column chromatography (? EtOAc/Hexanes) to afford 760mg (55percent) of 2-methyl-3-nitropyridine. 1H NMR (CDC 8.71 (tetra, 1.7Hz, 5.0Hz, 1H), 8.26 (tetra, 1.7Hz, 8.3Hz, 1H)1 7.34 (dd, 5.( 8.3Hz, 1 H), 2.85 (s, 3H). MS m/z 139.1(M+H)+.
Reference: [1] Tetrahedron, 1998, vol. 54, # 23, p. 6311 - 6318
[2] Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 15, p. 4232 - 4241
[3] Patent: WO2009/1214, 2008, A2, . Location in patent: Page/Page column 52
[4] Organic and Biomolecular Chemistry, 2005, vol. 3, # 20, p. 3701 - 3706
[5] Patent: US2005/131012, 2005, A1, . Location in patent: Page/Page column 13
[6] Patent: WO2006/25716, 2006, A1, . Location in patent: Page/Page column 12
[7] Patent: WO2006/25717, 2006, A1, . Location in patent: Page/Page column 9
[8] Patent: US2011/152296, 2011, A1, . Location in patent: Page/Page column 12
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YieldReaction ConditionsOperation in experiment
60% With sodium In sulfuric acid; toluene Method 1
Into a flask containing diethyl malonate (20 g, 0.125 mol) was added sodium (2.0 g, 0.087 mol).
The reaction mixture was stirred for 1 h at room temperature and then allowed to warm to 120° C. (oil bath temperature) for 50 min.
To this yellow suspension of the solid mass was added toluene (120 mL) followed by addition of a solution of 2-chloro-3-nitropyridine 1 (12.8 g, 0.08 mol) in 40 mL of toluene.
The reaction mixture was refluxed for 8 h, and then stirred overnight at room temperature.
The solvent was removed under reduced pressure and the residue was dissolved in 30percent H2 SO4 (60 mL).
This reaction mixture was heated to 125° C. (oil bath) for 7 h, cooled and poured into ice (200 g).
The reaction mixture was neutralized with saturated NaHCO3 solution, filtered through Celite, extracted several times with ether.
The combined extracts were dried over anhydrous Na2 SO4.
The solvent was evaporated and the residue was distilled under reduced pressure to provide 6.65 g (60percent) of the desired product 3.
Reference: [1] Organic Letters, 2009, vol. 11, # 6, p. 1357 - 1360
[2] Patent: US5869676, 1999, A,
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Reference: [1] Patent: EP1510516, 2005, A1, . Location in patent: Page/Page column 134
  • 8
  • [ 64362-41-0 ]
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Reference: [1] Organic and Biomolecular Chemistry, 2005, vol. 3, # 20, p. 3701 - 3706
[2] Synthetic Communications, 1990, vol. 20, # 19, p. 2965 - 2970
[3] Synthesis, 2003, # 11, p. 1671 - 1678
[4] Patent: US2005/131012, 2005, A1, . Location in patent: Page/Page column 13
[5] Patent: WO2009/23844, 2009, A2, . Location in patent: Page/Page column 136-137
[6] Organic Process Research and Development, 2011, vol. 15, # 5, p. 1040 - 1045
[7] Organic Letters, 2011, vol. 13, # 22, p. 6102 - 6105
[8] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 1, p. 339 - 342
  • 9
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YieldReaction ConditionsOperation in experiment
42% With potassium carbonate In 1,4-dioxane for 24 - 48 h; Heating / reflux Example 77; N-Methyl-3-(2-(2-oxoindolin-5-ylamino)-5-(trifluoromethvπpyridin-4-ylamino)picolinamide; 2-Methyl-3-nitropyridine; Reference: Gray, M.; Andrews, I.P.; Hook, D. F.; Kitteringham, J.; Voyle, M.; Tetrahedron Lett.; 2000, 41, 6237 - 6240.The mixture of 2-chloro-3-nitropyridine (50 g, 0.315mol, 1.0 eq), TMB (50 mL, 1.1 eq), (PPh3)4Pd (0) (36.4 g, 0.1 eq), K2CO3 (130.6 g, 3.0 eq) and dioxane (1500 mL) was refluxed under argon for 2 days. The mixture was cooled to room temperature and filtered through a celite pad to remove K2CO3 and catalyst. The celite pad was washed with EtOAc. The organic solutions were combined and concentrated to get the crude which was purified by silica gel chromatography (0percent~40percent EtO Ac/Hex) to obtain the desired product 2-methyl-3-nitropyridine (30.5g, isolated yield 70percent) (Note: isolated yield 42percent was obtained when the reaction was refluxed for 24 h).
Reference: [1] Tetrahedron Letters, 2000, vol. 41, # 32, p. 6237 - 6240
[2] Patent: WO2008/115369, 2008, A2, . Location in patent: Page/Page column 117
[3] Patent: WO2004/104001, 2004, A2, . Location in patent: Page 41
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Reference: [1] Patent: US5869676, 1999, A,
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Reference: [1] Journal of the American Chemical Society, 1954, vol. 76, p. 596,598
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Reference: [1] Journal of Organic Chemistry, 2003, vol. 68, # 14, p. 5534 - 5539
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Reference: [1] Journal of the American Chemical Society, 1952, vol. 74, p. 3828,3830
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  • [ 68-12-2 ]
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  • [ 5028-23-9 ]
Reference: [1] Tetrahedron Letters, 2000, vol. 41, # 32, p. 6237 - 6240
  • 15
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Reference: [1] Tetrahedron Letters, 1980, vol. 21, p. 2433 - 2434
  • 16
  • [ 2530-26-9 ]
  • [ 105-39-5 ]
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  • [ 5832-44-0 ]
Reference: [1] Journal of Organic Chemistry, 2008, vol. 73, # 17, p. 6793 - 6799
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Reference: [1] Journal of Organic Chemistry, 2012, vol. 77, # 9, p. 4402 - 4413
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Reference: [1] Journal of Heterocyclic Chemistry, 1992, vol. 29, # 2, p. 359 - 367
[2] Tetrahedron Letters, 1980, vol. 21, p. 2433 - 2434
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Reference: [1] Tetrahedron Letters, 1980, vol. 21, p. 2433 - 2434
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Reference: [1] Journal of Heterocyclic Chemistry, 1992, vol. 29, # 2, p. 359 - 367
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Reference: [1] Journal of Organic Chemistry, 2008, vol. 73, # 17, p. 6793 - 6799
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Reference: [1] Organic Process Research and Development, 2011, vol. 15, # 5, p. 1040 - 1045
[2] Patent: WO2004/104001, 2004, A2,
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Reference: [1] Organic Process Research and Development, 2011, vol. 15, # 5, p. 1040 - 1045
  • 24
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  • [ 17288-32-3 ]
Reference: [1] Organic Process Research and Development, 2011, vol. 15, # 5, p. 1040 - 1045
[2] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 1, p. 339 - 342
[3] Patent: WO2004/104001, 2004, A2,
[4] Patent: US2007/259910, 2007, A1,
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Reference: [1] Tetrahedron, 1998, vol. 54, # 23, p. 6311 - 6318
[2] Tetrahedron, 1998, vol. 54, # 23, p. 6311 - 6318
[3] Journal of Medicinal Chemistry, 1992, vol. 35, # 20, p. 3672 - 3677
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