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[ CAS No. 31462-59-6 ]

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CAS No. :31462-59-6 MDL No. :MFCD00129737
Formula : C5H4N2O2 Boiling Point : 318.7°C at 760 mmHg
Linear Structure Formula :- InChI Key :N/A
M.W :124.10 g/mol Pubchem ID :169306
Synonyms :

Safety of [ 31462-59-6 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P305+P351+P338 UN#:N/A
Hazard Statements:H319 Packing Group:N/A
GHS Pictogram:

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  • Upstream synthesis route of [ 31462-59-6 ]
  • Downstream synthetic route of [ 31462-59-6 ]

[ 31462-59-6 ] Synthesis Path-Upstream   1~17

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YieldReaction ConditionsOperation in experiment
80.5% With selenium(IV) oxide In pyridine at 20 - 80℃; for 5.5 h; To 4-Methyl pyrimidine (5.0 g, 0.053 mol) in pyridine (55ML) was added selenium dioxide (8.82 g, 0.079 mol) at RT with stirring. The reaction mixture was stirred at 55 °C for 2 h and at 80 °C for 3.5 hr. After cooling to RT and stirring over night, the reaction mixture was filtered and the residue was washed with pyridine. The combined pyridine solution was concentrated and the carboxylic acid obtained was washed with water to remove traces of selenium dioxide. Yield : 5.3 g, 80.5 percent. [00157] To Pyrimidine-4-carboxylic acid (5.0 g, 0.04 mol) in methanol (170 ml) was added conc. HCI (2 ML) at RT. After refluxing overnight, the reaction mixture was cooled to RT and neutralized with 10 percent sodium bicarbonate solution and concentrated. The ester was extracted with diethyl ether, dried over NA2SO4 AND concentrated to get the methyl ester as a yellow solid, yield : 3.3 g, 57.55 percent. [00158] TRIMETHYL ACETYLCHLORIDE (11.30 g, 0.093 mol) was added to a benzene (500 ML) solution of triethylamine (15.75 g, 0.155 mol) and 4- CHLOROANILINE (10.0 g, 0.078 mol) at 0°C. The reaction mixture was warmed to RT and stirred for 3h. The reaction mixture was then quenched with water, extracted with ethyl acetate, washed with water, brine solution and dried over NA2SO4. The solid product obtained was crystallized from pet ether. Yield : 14.0 g, 84. 43 percent. [00159] To N- (4-chlorophenyl)-2, 2-dimethyl propanamide (3.5 g, 0.0165 mol) in THF (50 MI) at 0 °C was added n-butyl lithium in hexane (2.64 g, 1.2 M, 0. 041 MOL). Stirring was continued at 0 °C for 2 h, the reaction then cooled to-70 °C, pyrimidine-4-methyl carboxylate (3.18 g, 0.023 mol) in THF (25 ML) was then added slowly and the solution was warmed to RT and stirred overnight. Diethyl ether (50 ml) and water (50 ml) were added and the organic layer was separated. The aqueous layer was further extracted with ether. The combined ether layers were washed with water, brine and dried over NA2SO4. The product obtained upon concentration was purified by column chromatography. Yield : 1.7 g, 32.69 percent. [00160] The protected amino ketone (1.7 g, 0.0054 mol) in sulfuric acid (10 ML, 70 percent) was heated at 95 °C over night. The reaction mixture was cooled to RT and basified with 10percent NAOH, extracted with DCM, washed with water, brine and dried over NA2SO4. The product obtained upon concentration was purified by column chromatography using basic alumina to yield title compound (0.20g, 16percent).
78% at 20 - 85℃; for 41.5 h; Preparation 2: 2-Chloro-1-methyl-1H-[4,4l]bipyrimidinyl-6-oneStep A: Preparation of Pyrimidine-4-carboxylic acid: To a solution of 4-methyl pyrimidine (Aldrich) (10 g, 0.10 mmol) in pyridine (100 ml) was added SeO2 (17.8 g, 0.16 mmol). The mixture was heated to 55°C for 2 hr., then 850C for 3.5 hr. The reaction was allowed to cool to RT and stirred for 36 hr. The solids were filtered through diatomaceous earth. The solvent was evaporated and the residue diluted in 100 ml MeOH. The precipitate was collected to give the title compound as a brown solid (9.7 g, 78percent). 1H-NMR(DMSO-Qf6): δ ppm 13.4-14.0(broad, 1 H), 9.34 (s, 1 H), 9.04 (d, J=4.98 Hz, 1 H) and 8.02((d, J=4.98 Hz, 1H). Mass: (M+1) 125 calculated for C5H4N2O2.
67% With potassium permanganate; potassium hydroxide In water at 75℃; for 1.5 h; (i) To a suspension of4-methylpyrimidine (5.0 g, 0.053 mol) in water (300 mL), KMNO4 (21 g, 0.132 mol) and KOH(20.8 g, 0.372 mol) were added and heated the mixture at 75°C for 1.5 hours. Cooled to roomtemperature and ethanol (300 mL) was added drop wise. Filtered off the solids over Celite andconcentrated the filtrate. The resulting crude was diluted with water (50 mL) and acidified withconc. HCl. Precipitate was collected and dried under vacuum to obtain pyrimidine-4-carboxylicacid (4.5 g, 67percent yield), as a white solid. 1H NMR (400 MHz, DMSO-d6): δ 13.93 (brs, 1H),9.37 (d, J = 1.2HZ, 1H), 9.06 (d, J = 4.8 Hz, 1H), 8.01 (dd, J = 4.8, 1.2 Hz, 1H).
58% With potassium hydroxide; potassium permanganate In water at 75℃; for 1.5 h; Intermediate A; Preparation of pyrimidine 4-carboxylic acid; 4-Methylpyrimidine (1.00 g, 10.6 mmol) was diluted in water (90 ml_). Potassium permanganate (4.20 g, 26.5 mmol) and potassium hydroxide (4.20 g, 74.8 mmol) were added, and the mixture was heated at 75 0C for 1.5 h. Ethanol was added dropwise, and the precipitate was removed by filtration through Celite. The filtrate was concentrated under reduced pressure, diluted in water, and treated with a concentrated HCI solution until acidic. The title compound precipitated as a fine powder, which was collected by vacuum filtration and dried in a vacuum oven (770 mg, 58percent): 1H NMR (DMSO-cfe) δ: 13.92 (1 H, br s), 9.35 (1H, d), 9.05 (1 H1 d), 7.99 (1H, dd).
58% With SeO2 In pyridine To a solution of 4-methylpyrimidine (4 g, 46.5 mmol) in pyridine (20 mL) was added SeO2 (8.7 g, 79.06 mmol) at room temperature.
The reaction mixture was then heated to 60° C. for 2 h, and then stirred at room temperature for 16 h.
The reaction mixture was diluted with DCM (50 mL) and filtered to remove selenium waste.
The filtrate was concentrated to give a residue that was stirred with H2O (20 mL), the precipitated solid was filtered and washed with acetone (2*20 mL) and dried to provide (BB12) (3.1 g, 58percent) as a brown solid. Rf: 0.2 (40percent MeOH/CHCl3).
1H NMR (400 MHz, DMSO-d6): δ 13.8 (1H, br s), 9.37 (1H, s), 9.07 (1H, d, J=5.2 Hz), 8.01 (1H, d, J=4 Hz); m/z 123 (M-H)-.

Reference: [1] Patent: WO2004/46092, 2004, A2, . Location in patent: Page 52-53
[2] Patent: WO2008/23239, 2008, A1, . Location in patent: Page/Page column 21
[3] Heterocycles, 2003, vol. 60, # 4, p. 953 - 957
[4] PLoS ONE, 2016, vol. 11, # 5,
[5] Patent: WO2008/70150, 2008, A1, . Location in patent: Page/Page column 59
[6] Patent: US2012/322722, 2012, A1,
[7] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1991, vol. 27, # 7, p. 768 - 771[8] Khimiya Geterotsiklicheskikh Soedinenii, 1991, # 7, p. 959 - 962
[9] Journal of Medicinal Chemistry, 2017, vol. 60, # 16, p. 6942 - 6990
[10] Chemische Berichte, 1899, vol. 32, p. 1533,2930, 2934
[11] Patent: WO2004/14881, 2004, A2, . Location in patent: Page 135
[12] Patent: WO2010/83384, 2010, A2, . Location in patent: Page/Page column 61
[13] Journal of Organic Chemistry, 2015, vol. 80, # 5, p. 2676 - 2699
[14] Inorganic Chemistry, 2018, vol. 57, # 11, p. 6266 - 6282
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Reference: [1] Tetrahedron, 2001, vol. 57, # 51, p. 10111 - 10117
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Reference: [1] Chemistry - A European Journal, 2008, vol. 14, # 8, p. 2340 - 2348
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Reference: [1] Chemistry - A European Journal, 2008, vol. 14, # 8, p. 2340 - 2348
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Reference: [1] Chemistry - A European Journal, 2008, vol. 14, # 8, p. 2340 - 2348
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Reference: [1] Chemistry - A European Journal, 2008, vol. 14, # 8, p. 2340 - 2348
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Reference: [1] Journal of the Chemical Society, 1953, p. 3129
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Reference: [1] Chemische Berichte, 1899, vol. 32, p. 1533,2930, 2934
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Reference: [1] Chemische Berichte, 1899, vol. 32, p. 1533,2930, 2934
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Reference: [1] Bulletin des Societes Chimiques Belges, 1957, vol. 66, p. 276,289
[2] Journal of Organic Chemistry, 2015, vol. 80, # 5, p. 2676 - 2699
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Reference: [1] Journal of Medicinal Chemistry, 2017, vol. 60, # 16, p. 6942 - 6990
[2] Inorganic Chemistry, 2018, vol. 57, # 11, p. 6266 - 6282
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YieldReaction ConditionsOperation in experiment
77%
Stage #1: for 14 h; Reflux
Stage #2: With sodium hydrogencarbonate In water at 20℃;
General Procedure 8Intermediate 23; [0245] Thionyl chloride (3.55mL, 48.4 mmol, 3 eq) was added drop-wise to a solution of pyrimidine-4-carboxylic acid (2 g, 16.1 mmol) in EtOH (15 mL) and the resulting mixture was heated to reflux for 14 h. The mixture was then cooled to RT and made alkaline with saturated aqueous NaHC03 to pH 8. The basic solution was then extracted with EtOAc (4 x 50 mL). The combined organic layers were washed with brine (30 mL), dried over Na2S04, filtered and concentrated in vacuo to afford Intermediate 23 (1.7g, 77percent). 1H NMR: (DMSO- d6) 5 9.40 (d, J= 1.0 Hz, 1H), 9.10 (d, J= 5.1 Hz, 1H), 8.05 (dd, J= 5.1, 1.3 Hz, 1H), 4.39 (q, J= 7.1 Hz, 2H), 1.35 (t, J= 7.1 Hz, 3H); MS: 153 [M + H]+; TLC: 40percent hexane in EtOAc: Rf: 0.40.
77% for 14 h; Reflux General Procedure 13 was followed in the preparation of Intermediate 19. 2129 General Procedure 13 2131 Intermediate 19 2132 [0243] Thionyl chloride (3.55mL, 48.4 mmol, 3 eq) was added dropwise to a solution of 2133 pyrimidine-4-carboxylic acid (2 g, 16.1 mmol) in EtOH (15 mL) and the resulting mixture 2134 was heated to reflux for 14 h. The mixture was then cooled to RT and made alkaline with 2135 saturated aqueous NaHC03 to pH 8. The basic solution was then extracted with EtOAc (4 x 2136 50 mL). The combined organic layers were washed with brine (30 mL), dried over Na2S04, 2137 filtered and concentrated in vacuo to afford Intermediate 19 (1.7g, 77percent). 1H NMR: (DMSO- 2138 d6) 5 9.40 (d, J= 1.0 Hz, 1H), 9.10 (d, J= 5.1 Hz, 1H), 8.05 (dd, J= 5.1, 1.3 Hz, 1H), 4.39 2139 (q, J= 7.1 Hz, 2H), 1.35 (t, J= 7.1 Hz, 3H); MS: 153 [M + H]+; TLC: 40percent hexane in EtOAc: 2140 Rf: 0.40
77% for 14 h; Reflux General Procedure 8 Thionyl chloride (3.55 mL, 48.4 mmol, 3 eq) was added drop-wise to a solution of pyrimidine-4-carboxylic acid (2 g, 16.1 mmol) in EtOH (15 mL) and the resulting mixture was heated to reflux for 14 h. The mixture was then cooled to RT and made alkaline with saturated aqueous NaHCO3 to pH 8. The basic solution was then extracted with EtOAc (450 mL). The combined organic layers were washed with brine (30 mL), dried over Na2SO4, filtered and concentrated in vacuo to afford Intermediate 23 (1.7g, 77percent). 1H NMR: (DMSO-d6) δ 9.40 (d, J=1.0 Hz, 1H), 9.10 (d,J=5.1Hz, 1H), 8.05 (dd, J=5.1, 1.3 Hz, 1H), 4.39 (q, J=7.1Hz, 2H), 1.35 (t, J=7.1Hz, 3H); MS: 153 [M+H]+; TLC: 40percent hexane in EtOAc: Rf: 0.40.
Reference: [1] Journal of Organic Chemistry, 2015, vol. 80, # 5, p. 2676 - 2699
[2] Patent: WO2011/126903, 2011, A2, . Location in patent: Page/Page column 92
[3] Patent: WO2014/145986, 2014, A1, . Location in patent: Paragraph 0242; 0243
[4] Patent: US2017/326125, 2017, A1, . Location in patent: Paragraph 0359-0361
[5] Bulletin des Societes Chimiques Belges, 1957, vol. 66, p. 276,289
[6] Gazzetta Chimica Italiana, 1952, vol. 82, p. 652,655, 660
[7] Inorganic Chemistry, 2018, vol. 57, # 11, p. 6266 - 6282
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Reference: [1] Zhurnal Obshchei Khimii, 1955, vol. 25, p. 2313,2314, 2315; engl. Ausg. S. 2285, 2286
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Reference: [1] PLoS ONE, 2016, vol. 11, # 5,
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Reference: [1] Tetrahedron, 2001, vol. 57, # 51, p. 10111 - 10117
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Reference: [1] Chemistry - A European Journal, 2008, vol. 14, # 8, p. 2340 - 2348
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Reference: [1] Chemistry - A European Journal, 2008, vol. 14, # 8, p. 2340 - 2348
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