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[ CAS No. 99-05-8 ]

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Chemical Structure| 99-05-8
Chemical Structure| 99-05-8
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CAS No. :99-05-8MDL No. :MFCD00007795
Formula : C7H7NO2 Boiling Point : -
Linear Structure Formula :-InChI Key :N/A
M.W :137.14Pubchem ID :7419
Synonyms :

Computed Properties of [ 99-05-8 ]

TPSA : 63.3 H-Bond Acceptor Count : 3
XLogP3 : - H-Bond Donor Count : 2
SP3 : 0.00 Rotatable Bond Count : 1

Safety of [ 99-05-8 ]

Signal Word:WarningClass:N/A
Precautionary Statements:P261-P264-P270-P271-P280-P280-P301+P312+P330-P302+P352-P304+P340+P312-P305+P351+P338-P332+P313-P337+P313-P362+P364-P403+P233-P405-P501UN#:N/A
Hazard Statements:H302-H315-H319-H335Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 99-05-8 ]

  • Upstream synthesis route of [ 99-05-8 ]
  • Downstream synthetic route of [ 99-05-8 ]

[ 99-05-8 ] Synthesis Path-Upstream   1~12

  • 1
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  • [ 56-81-5 ]
  • [ 1078-30-4 ]
  • [ 7250-53-5 ]
Reference: [1] Chemistry of Natural Compounds, 1982, vol. 18, p. 604 - 605[2] Khimiya Prirodnykh Soedinenii, 1982, vol. 18, # 5, p. 638 - 640
[3] Chemistry of Natural Compounds, 1982, vol. 18, p. 604 - 605[4] Khimiya Prirodnykh Soedinenii, 1982, vol. 18, # 5, p. 638 - 640
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  • [ 16675-62-0 ]
YieldReaction ConditionsOperation in experiment
21 g
Stage #1: at 150℃; for 7 h;
Stage #2: for 12 h; Reflux
Synthesis of methyl quinoline-5-carboxylate (intermediate-97):A 500mL RB flask fitted with magnetic stirrer was charged with Starting Material-32 (60g,435mmo1), Starting material-33 (168g, 1824mmo1), 3-nitrobenzoic acid (30g, i79mmol) in9OmL of conc.H2S04. Then reaction mixture was heated at 150 CC for 7 h. After reactioncooled to RT and added MeOH (600 mL) and refluxed for 12 hours. Then cooled to 0 °C quenched with ice and concentrated. Crude reaction mixture was basif led with NaHCO3, extracted with DCM and concentrated. Resulted crude material was purified by silica gel column chromatography eluting with Petroleum ether (60-80), ethyl acetate and 0.5percent of triethylamine as eluent. The product (intermediate-97) was obtained as a brown liquid (21g).
21 g
Stage #1: at 150℃; for 7 h; Reflux
Stage #2: at 20℃; for 12 h; Reflux
Synthesis of methyl quinoline-5-carboxylate (intermediate-97) [0751] A 500 mL RB flask fitted with magnetic stirrer was charged with Starting Material-32 (60 g, 435 mmol), Starting material-33 (168 g, 1824 mmol), 3-nitrobenzoic acid (30 g, 179 mmol) in 90 mL of conc.H2SO4. Then reaction mixture was heated at 150° C. for 7 h. After reaction cooled to RT and added MeOH (600 mL) and refluxed for 12 hours. Then cooled to 0° C. quenched with ice and concentrated. Crude reaction mixture was basified with NaHCO3, extracted with DCM and concentrated. Resulted crude material was purified by silica gel column chromatography eluting with Petroleum ether (60-80), ethyl acetate and 0.5percent of triethylamine as eluent. The product (intermediate-97) was obtained as a brown liquid (21 g).
Reference: [1] Patent: WO2013/128465, 2013, A1, . Location in patent: Page/Page column 203
[2] Patent: US2015/158860, 2015, A1, . Location in patent: Paragraph 0750; 0751
  • 3
  • [ 99-05-8 ]
  • [ 14192-26-8 ]
Reference: [1] Patent: CN106854173, 2017, A,
  • 4
  • [ 99-05-8 ]
  • [ 1877-77-6 ]
Reference: [1] Chemistry - A European Journal, 2017, vol. 23, # 41, p. 9908 - 9918
[2] Bioorganic and Medicinal Chemistry, 2010, vol. 18, # 17, p. 6340 - 6350
[3] Journal of the American Chemical Society, 1950, vol. 72, p. 3586
[4] Chemische Berichte, 1905, vol. 38, p. 2063
[5] Journal of Medicinal Chemistry, 1976, vol. 19, p. 1362 - 1366
[6] Patent: US2009/258905, 2009, A1, . Location in patent: Page/Page column 8
[7] Patent: WO2007/18941, 2007, A2, . Location in patent: Page/Page column 98-99
  • 5
  • [ 99-05-8 ]
  • [ 107922-46-3 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2011, vol. 21, # 15, p. 4436 - 4440
  • 6
  • [ 99-05-8 ]
  • [ 16636-51-4 ]
Reference: [1] Patent: US6331640, 2001, B1,
[2] Justus Liebigs Annalen der Chemie, 1901, vol. 319, p. 336
[3] Justus Liebigs Annalen der Chemie, 1901, vol. 319, p. 336
  • 7
  • [ 99-05-8 ]
  • [ 16636-51-4 ]
Reference: [1] Patent: US4407746, 1983, A,
  • 8
  • [ 24424-99-5 ]
  • [ 99-05-8 ]
  • [ 111331-82-9 ]
YieldReaction ConditionsOperation in experiment
98% With sodium hydroxide In 1,4-dioxane; water at 0 - 20℃; General procedure: To a stirred solution of 4-aminobenzoic acid 6a (5.00 g, 36.5 mmol) and sodium hydroxide (1.56 g, 39.3 mmol) in 1:1 water/dioxane (60 mL) at 0 °C was added di-tert-butyl dicarbonate (14.3 g, 65.4 mmol). The resulting mixture was stirred for 3 h, then warmed to room temperature and stirred overnight. The aqueous mixture was then washed with ethyl acetate (60 mL) before further ethyl acetate (60 mL) was added and the resulting mixture neutralised with 1 M aqueous KHSO4. The organic layer was separated, washed with water (60 mL), dried (MgSO4) and the solvent removed in vacuo to give the title product 73a (7.53 g, 87percent) as an off-white solid, which was used without further purification.
97% With triethylamine In 1,4-dioxane; water at 20℃; for 16 h; To a solution of 3-aminobenzoic acid (6 g, 0.043 mmol), Triethyl amine (12.1 mL, 87.6 mmol), water (50 mL) in 1-4 Dioxane (100 mL) was added Boc anhydride (15 mL, 65.7 mmol) at room temperature. Reaction mixture was allowed to stir for 16 h at room temperature. TLC showed absence of starting material (Rf=0.7, 70percent ethyl acetate/n-hexane). 1-4 Dioxane was removed under reduced pressure and 3N HCl solutions (60 mL) was added drop wise in the reaction mixture. White precipitate obtained was filter out, washed with hexane and dried. [0509] Yield: 10 g (97percent) [0510] 1H NMR (400 MHz, CDCl3): δ 1.47 (s, 9H), 7.35 (t, J=8 Hz, 1H), 7.53 (d, J=8 Hz, 1H), 7.61 (d, J=8 Hz, 1H), 8.14 (s, 1H), 9.53 (s, 1H), 12.9 (br, 1H).
94%
Stage #1: With triethylamine In 1,4-dioxane; water at 20℃; for 0.0833333 h;
Stage #2: at 20℃; for 26 h;
General procedure: To a solution of 12a (2.0 g, 14.6 mmol) in 67percent 1.4-dioxane/water(48 mL) was added triethylamine (4.07 mL, 29.2 mmol) at room temperature and allowed to stir for 5 min. Di-tert-butyl decarbonate(6.37 mL, 29.2 mmol) was then added to the solution. After beingstirred for 26 h, the reaction mixture was concentrated and acidified with 2M hydrochronic acid to yield a white precipitate. The slurry wasthen filtered, washed with water and dried over in vacuo to afford 13a(2.94 g, 86percent) as a white solid.
92.5% With triethylamine In methanol at 0 - 20℃; for 10 h; Inert atmosphere :[0145]The mixture of 3-aminobenzoic acid (500 mg, 3.65 mmol) and triethylamine (1.11 g, 10.97 mmol) in methanol (6 mL) was allowed to cool to 0 before di-tert-butyl dicarbonate (880 mg, 4.03mmol) was added. Then, the resulting mixture was stirred at room temperature for 10 h before quenched with water. The solvent was removed under reduced pressure. The residue was purified by column chromatography (silica gel, dichloromethane/methanol 100: 1 to 10: 1) to give 3- ( (tert-butoxycarbonyl) amino) benzoic acid (1) as a white solid (800 mg, yield 92.5) . Mass spectrum (ESI) m/z calc. for C12H15NO4[M-H]-236.10, found 236.10.1H NMR (400 MHz, d6-DMSO) δ 12.90 (s, 1H) , 9.55 (s, 1H) , 8.14 (s, 1H) , 7.62 (d, J 8.5 Hz, 1H) , 7.53 (d, J 7.8 Hz, 1H) , 7.36 (t, J 7.9 Hz, 1H) , 1.48 (s, 9H) .
84%
Stage #1: With sodium hydroxide In 1,4-dioxane; water at 20℃;
Stage #2: With hydrogenchloride In water
Commercially available 3-amino benzoic acid (5 g, 36 mmol) was dissolved in 1 M sodium hydroxide solution (40 mL, 40 mmol) and 1,4-dioxane (30 mL). After the addition of di-tert-butyl dicarbonate (7.85 g, 36 mmol), the mixture was stirred at room temperature over the weekend. The dioxane was removed in vacuo and the residue was diluted with water (100 mL). Then concentrated hydrochloric acid (37percent) was added until pH3. The precipitate was collected by filtration, washed with water (100 mL) and air-dried to afford the title compound as a white solid (7.3 g, 84percent).
82% With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; 3-aminobenzoic acid (4.4 g, 32.1 mmol) and di-tert-butyl dicarbonate (10.5 g, 48.2 mmol) were dissolved in anhydrous THF (60 mL) . Then N-ethyl-N-isopropylpropan-2-amine (8.3 g, 64.2 mmol) was added. The reaction mixture was stirred at room temperature. After the completion of the reaction, it was concentrated in vacco and the residue was extracted with ethyl acetate. The organic layer was concentrated and the residue was purified by column chromatograph to provide the desired product (6.2 g, 82) MS [MH] -calcd for C12H14NO4 236.10, found 236.10.
7.2 g With sodium hydroxide In 1,4-dioxane; water at 20℃; for 12 h; Cooling with ice To a stirred solution of 3-aminobenzoic acid (5 g, 36.5 mmol) in water (40.0 ml) was added aq. solution of sodium hydroxide (2.187 g, 54.7 mmol) followed by (BOC)20 (10.16 ml, 43.8 mmol) in dioxane (20.0 ml) under ice cooling. The mixture was stirred under ice cooling for 30 min and further at room temperature for 12 hrs. To the reaction mixture ethyl acetate (50.0 ml) was added and the aq. layer was separated. The aq. layer was acidified up to pH 4 using 2N HC1 and precipitated crystals were collected by filtration (7.2 gm). iH NMR (400 MHz, DMSO-c 8 12.80 (brs, 1H), 9.54 (s, 1H), 8.14 (s, 1H), 7.62 (dd, 1H, J=0.8Hz, J=8Hz), 7.54-7.52 (m, 1H), 7.35 (t, 1H, J= 7.6Hz), 1.48 (s, 9H).
7.2 g With sodium hydroxide In 1,4-dioxane; water at 22 - 26℃; for 12.5 h; Cooling with ice Step a:
Synthesis of 3-((tert-butoxycarbonyl)amino)benzoic acid
To a stirred solution of 3-aminobenzoic acid (5 g, 36.5 mmol) in water (40.0 ml) was added aq. solution of sodium hydroxide (2.187 g, 54.7 mmol) followed by (BOC)2O (10.16 ml, 43.8 mmol) in dioxane (20.0 ml) under ice cooling.
The mixture was stirred under ice cooling for 30 min and further at room temperature for 12 hrs.
To the reaction mixture ethyl acetate (50.0 ml) was added and the aq. layer was separated.
The aq.
layer was acidified up to pH 4 using 2N HCl and precipitated crystals were collected by filtration (7.2 gm).
1H NMR (400 MHz, DMSO-d6) δ 12.80 (brs, 1H), 9.54 (s, 1H), 8.14 (s, 1H), 7.62 (dd, 1H, J=0.8 Hz, J=8 Hz), 7.54-7.52 (m, 1H), 7.35 (t, 1H, J=7.6 Hz), 1.48 (s, 9H).

Reference: [1] Journal of Medicinal Chemistry, 2001, vol. 44, # 3, p. 441 - 452
[2] Tetrahedron, 2012, vol. 68, # 6, p. 1790 - 1801
[3] Patent: US2014/194383, 2014, A1, . Location in patent: Paragraph 0500; 0507-0508
[4] Chemical Communications, 2013, vol. 49, # 66, p. 7340 - 7342
[5] Bioorganic and Medicinal Chemistry, 2018,
[6] Patent: US5179125, 1993, A,
[7] Patent: US5210266, 1993, A,
[8] Patent: WO2017/152842, 2017, A1, . Location in patent: Paragraph 0129; 0130
[9] Journal of Medicinal Chemistry, 2018, vol. 61, # 3, p. 834 - 864
[10] Journal of Medicinal Chemistry, 1997, vol. 40, # 3, p. 331 - 341
[11] Patent: US5728829, 1998, A,
[12] Chemical Communications, 2014, vol. 50, # 20, p. 2638 - 2641
[13] Chemistry - A European Journal, 2015, vol. 21, # 32, p. 11340 - 11343
[14] Journal of Medicinal Chemistry, 1996, vol. 39, # 5, p. 1172 - 1188
[15] Patent: US2011/280808, 2011, A1, . Location in patent: Page/Page column 53
[16] Patent: WO2015/158214, 2015, A1, . Location in patent: Paragraph 073; 074
[17] Journal of Medicinal Chemistry, 2016, vol. 59, # 2, p. 707 - 720
[18] New Journal of Chemistry, 2005, vol. 29, # 5, p. 673 - 680
[19] Journal of Organic Chemistry, 2006, vol. 71, # 21, p. 8283 - 8286
[20] Chemical Communications, 2012, vol. 48, # 5, p. 711 - 713
[21] Synlett, 2004, # 10, p. 1794 - 1798
[22] Journal of Medicinal Chemistry, 1992, vol. 35, # 21, p. 3774 - 3783
[23] Chemical and Pharmaceutical Bulletin, 2000, vol. 48, # 12, p. 1964 - 1972
[24] Bioorganic and Medicinal Chemistry Letters, 1998, vol. 8, # 6, p. 647 - 652
[25] Patent: US2003/55009, 2003, A1,
[26] Patent: US5728829, 1998, A,
[27] Patent: EP1144365, 2004, B1, . Location in patent: Page 34
[28] Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 15, p. 4460 - 4472
[29] Medicinal Chemistry Research, 2013, vol. 22, # 1, p. 134 - 146
[30] ACS Medicinal Chemistry Letters, 2013, vol. 4, # 7, p. 590 - 595
[31] RSC Advances, 2014, vol. 4, # 76, p. 40444 - 40448
[32] Patent: WO2013/136249, 2013, A1, . Location in patent: Page/Page column 43
[33] Archives of Pharmacal Research, 2014, vol. 37, # 5, p. 588 - 599
[34] Patent: WO2014/100734, 2014, A1, . Location in patent: Paragraph 00331
[35] Journal of Medicinal Chemistry, 2014, vol. 57, # 13, p. 5664 - 5678
[36] Patent: US2015/133424, 2015, A1, . Location in patent: Paragraph 0215-0216
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  • [ 99-05-8 ]
  • [ 111331-82-9 ]
YieldReaction ConditionsOperation in experiment
65% With sodium hydroxide In water; N,N-dimethyl-formamide at 0 - 20℃; for 16 h; Step A:; Di-tert-Butyl carbonate (1.28 g, 58.4 mmol) was added to solution of m-aminobenzoic acid (0.5 g, 36.5 mmol), sodium hydroxide (0.21 g, 51.4 mmol), DMF (10 mL) and water (10 mL) at 0° C. The reaction mixture was allowed to reach ambient temperature while stirring for 16 h. A 6 mL of 1 N HCl was added to the solution to bring it to pH 6. The precipitate was collected to yield the tBoc protected aminobenzoic acid (0.5 6 g, 23.6 mmol, 65percent) as a white solid. 1HNMR (CDCl3). HRMS calculated for C12H19N2O4 (M+NH+): 255.1345. Found: 255.1356. HPLC: tR=11.9 min.
Reference: [1] Patent: US2006/228325, 2006, A1, . Location in patent: Page/Page column 65
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Reference: [1] Patent: US2003/232815, 2003, A1, . Location in patent: Page 11
[2] Journal of Medicinal Chemistry, 2016, vol. 59, # 22, p. 10299 - 10314
[3] Patent: US6639107, 2003, B1,
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Reference: [1] European Journal of Medicinal Chemistry, 2013, vol. 63, p. 231 - 238
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  • [ 151072-00-3 ]
  • [ 202467-69-4 ]
YieldReaction ConditionsOperation in experiment
97% With hydrogenchloride; tributylphosphine In methanol at 60℃; for 3 h; In 60 °C conditions, containing m-aminobenzoic acid to (9.45g, 68 . 9mmol) methanol solution of 200g in, added tributylphosphine 1g and 4MHCl/methanol solution 400 ml, then slowly adding raw material I (19.8g, 64 . 28mmol) methanol solution of 220g, stirring reaction at the same temperature and 3h, the slurry reaction cooling and filtering, to obtain white crystal, white crystal washing with methanol, vacuum drying, get compound 127.8g, molar yield 97percent, HPLC purity 99.2percent
80 g at 20℃; Inert atmosphere Under nitrogen protection,Nitro (1S, 4S) -3-oxo-2-thia-5- azabicyclo [2.2.1] heptane-5-carboxylic anhydride (3)Add 700mL glacial acetic acid,50g m-aminobenzoic acid (room temperature),The color of the solution changes from cloudy to slightly clear and finally becomes turbid,Stir overnight. The next day filtration,Drying afforded 80 g of a white solid (10).
Reference: [1] Patent: CN105566193, 2016, A, . Location in patent: Paragraph 0014; 0015
[2] Patent: CN104130262, 2017, B, . Location in patent: Paragraph 0132; 0133; 0134
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