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[ CAS No. 153505-36-3 ]

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Chemical Structure| 153505-36-3
Chemical Structure| 153505-36-3
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CAS No. :153505-36-3 MDL No. :MFCD11101433
Formula : C6H4BrFN2O2 Boiling Point : 313.9°C at 760 mmHg
Linear Structure Formula :- InChI Key :N/A
M.W :235.01 g/mol Pubchem ID :21911928
Synonyms :

Safety of [ 153505-36-3 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P280-P301+P312-P302+P352-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H320-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 153505-36-3 ]

  • Upstream synthesis route of [ 153505-36-3 ]
  • Downstream synthetic route of [ 153505-36-3 ]

[ 153505-36-3 ] Synthesis Path-Upstream   1~10

  • 1
  • [ 153505-36-3 ]
  • [ 366496-33-5 ]
YieldReaction ConditionsOperation in experiment
76%
Stage #1: With tert.-butylnitrite; copper(ll) bromide In acetonitrile at 60℃; for 0.416667 h;
Stage #2: With hydrogenchloride In water; acetonitrile
Copper (II) bromide (6.37 g, 28.5 mmol) was dissolved in acetonitrile (40 mL) with stirring. /-Butyl nitrite (5.0 mL, 42 mmol) was added via syringe, and the reaction was heated to 602C. 4-Bromo-5-fluoro-2-nitroaniline (4.46 g, 19.0 mmol) was dissolved in acetonitrile (60 mL) and added via addition funnel over 15 minutes. The reaction was stirred an additional 10 minutes and cooled to room temperature. The reaction was poured onto aqueous 2 N HCI EPO <DP n="123"/>(400 ml_). The mixture was extracted with diethyl ether, and the organic layer was washed with brine. The combined aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered, and concentrated in vacuo. Purification by flash chromatography afforded 4.46 g (76percent) of the title compound. 1H NMR (300 MHz, DMSO-αfe): δ 8.59 (d, 1 H1 J= 6.5 Hz)1 8.17 (d, 1 H, J= 8.1 Hz).
Reference: [1] Tetrahedron Letters, 2008, vol. 49, # 44, p. 6348 - 6351
[2] Patent: WO2007/30366, 2007, A1, . Location in patent: Page/Page column 121-122
  • 2
  • [ 153505-36-3 ]
  • [ 153505-37-4 ]
YieldReaction ConditionsOperation in experiment
82% With ammonium formate; zinc In methanol at 0 - 20℃; Inert atmosphere To a flask was added 5-fluoro-2-nitroaniline (8.9 g, 57 mmol), NBS (10 g, 56 mmol), and acetic acid (500 mL), and the reaction was heated to 110 °C.
Once complete it was cooled to room temperature and poured into 3 L of water.
The resulting suspension was filtered and the solid was washed with 500 mL of water.
Solid was air dried overnight (12.7 g, 91 percent).
1H NMR (400 MHz, DMSO-d6) δ 8.27 (d, J = 7.3 Hz, 1H), 7.73 (br. S., 2H), 6.94 (d, J = 11.0 Hz, 1H).
4-bromo-5-fluoro-2-nitroaniline (0.53 g, 2.255 mmol), zinc (0.89 g, 13.5 mmol), and methanol (32 ml) were added to the flask and argon was bubbled through the solution for 1 hour.
Ammonium formate (1.42 g, 22.6 mmol) was then added in several portions.
The reaction was then stirred at room temperature overnight and was complete by LCMS in the morning.
It was filtered through a pad of celite and the filtrate was concentrated.
The residue was partitioned between water and EtOAc and the organic layer was collected.
The aqueous layer was back-extracted using EtOAc (2 x 50 mL).
The combined organics were dried over sodium sulfate, filtered, and concentrated (378 mg, 82 percent). MS (m/z) 205.0, 207.0 (M+, M+2+).
81% With iron; ammonium chloride In tetrahydrofuran; ethanol; water at 95℃; for 4 h; Intermediate 11C; 4-bromo-5 -fluorobenzene- 1 ,2-diamine; To a solution of 4-bromo-5-fluoro-2-nitroaniline (1.0 g, 4.3 mmol) in THF (9.0 mL), EtOH (9.0 mL) and H20 (3 mL) was added iron powder (1.2 g, 21.3 mmol) and ammonium chloride (0.34 g, 6.4 mmol), and the mixture was heated at 95 °C for 4 hours. The cooled mixture was diluted with EtOH, filtered through diatomaceous earth until no further color came through the filter, and concentrated. The residue was dissolved in EtOAc, washed with H20, brine, dried (Na2S04), filtered and concentrated. Hexane was added and the resulting solid collected by filtration to give the title compound (710 mg, 3.5 mmol, 81percent).
43% With tin(ll) chloride In ethanol for 14 h; Reflux step 2: To a suspension of 96 (1.57 g, 6.74 mmol) in EtOH (16 mL) was added SnC¾ (3.82 g, 20.2 mmol). The reaction mixture was heated at reflux for 14 h, cooled to RT and concentrated in vacuo. The residue was partitioned between EtOAc (100 mL) and sat'd. aq. NaHCC>3 (200 mL). The resulting slurry was filtered through a pad of Celite® and the wet cake was washed with EtOAc (3 x 50 mL). The organic layer was washed sequentially with saturated NaHC03, water, and brine, dried (MgSO i), filtered and concentrated in vacuo to afford 600 mg (43percent) of 44oromo-5-fluorobenzene-l,2-diamine (98) as yellow solid: MS (ESI) m/z = 205 [M+l]
Reference: [1] Patent: EP2566477, 2015, B1, . Location in patent: Paragraph 0172; 0173
[2] Patent: WO2012/83170, 2012, A1, . Location in patent: Page/Page column 155
[3] Patent: WO2013/26914, 2013, A1, . Location in patent: Page/Page column 134
[4] Patent: US2007/259936, 2007, A1, . Location in patent: Page/Page column 175
[5] Patent: US2010/222345, 2010, A1, . Location in patent: Page/Page column 69
  • 3
  • [ 153505-36-3 ]
  • [ 153505-37-4 ]
Reference: [1] Patent: US5514680, 1996, A,
  • 4
  • [ 929279-27-6 ]
  • [ 153505-36-3 ]
YieldReaction ConditionsOperation in experiment
84% With potassium carbonate In methanol for 0.5 h; Intermediate 1 IB; 4-bromo-5 -fluoro-2-nitroaniline; To A^-(4-bromo-5-fluoro-2-nitrophenyl)-2,2,2-trifluoroacetamide (3.5 g, 10.5 mmol) was added CH3OH (30mL) followed by 1.0 K2CO3 (10.5mL, 10.5 mmol), and the solution was stirred for 30 minutes (Charifson, P.S.; et al. J. Med. Chem. 2008, 51, 5243-5263). The solution was diluted with H20 and stirred for 1 hour. The resulting orange solid was collected by filtration and dried in a vacuum oven to give the title compound (2.1,g, 8.8 mmol, 84percent).
76% With sodium hydroxide; water In 1,4-dioxane at 20 - 50℃; for 5.75 h; ΛA(4-Bromo-5-fluoro-2-nitrophenyl)-2,2,2-trifluoroacetamide was dissolved in1 ,4-dioxane (80 mL) with stirring. Aqueous 1 N sodium hydroxide solution (50 ml_) was added, and the mixture was stirred for 45 minutes. The reaction was heated to 50 2C and was stirred at that temperature for 5 h. The reaction was cooled to room temperature and poured into diethyl ether and brine. The layers were separated, and the aqueous was extracted further with ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered, and concentrated in vacuo. Purification by flash chromatography afforded 4.46 g (76percent) of the title compound. 1H NMR (300 MHz, DMSO-flfe): δ 8.29 (d, 1 H, J= 7.30 Hz), 7.74 (br s, 2H), 6.97 (d, 1 H, J= 10.7 Hz).
Reference: [1] Patent: WO2012/83170, 2012, A1, . Location in patent: Page/Page column 154-155
[2] Tetrahedron Letters, 2008, vol. 49, # 44, p. 6348 - 6351
[3] Patent: WO2007/30366, 2007, A1, . Location in patent: Page/Page column 121
[4] Patent: US2007/259936, 2007, A1, . Location in patent: Page/Page column 175
  • 5
  • [ 2369-11-1 ]
  • [ 153505-36-3 ]
YieldReaction ConditionsOperation in experiment
91% at 110℃; To a flask was added 5-fluoro-2-nitroaniline (8.9 g, 57 mmol), NBS (10 g, 56 mmol), and acetic acid (500 mL), and the reaction was heated to 110 °C.
Once complete it was cooled to room temperature and poured into 3 L of water.
The resulting suspension was filtered and the solid was washed with 500 mL of water.
Solid was air dried overnight (12.7 g, 91 percent).
1H NMR (400 MHz, DMSO-d6) δ 8.27 (d, J = 7.3 Hz, 1H), 7.73 (br. S., 2H), 6.94 (d, J = 11.0 Hz, 1H).
4-bromo-5-fluoro-2-nitroaniline (0.53 g, 2.255 mmol), zinc (0.89 g, 13.5 mmol), and methanol (32 ml) were added to the flask and argon was bubbled through the solution for 1 hour.
Ammonium formate (1.42 g, 22.6 mmol) was then added in several portions.
The reaction was then stirred at room temperature overnight and was complete by LCMS in the morning.
It was filtered through a pad of celite and the filtrate was concentrated.
The residue was partitioned between water and EtOAc and the organic layer was collected.
The aqueous layer was back-extracted using EtOAc (2 x 50 mL).
The combined organics were dried over sodium sulfate, filtered, and concentrated (378 mg, 82 percent). MS (m/z) 205.0, 207.0 (M+, M+2+).
76% for 1.5 h; Reflux Example 10 N4 -(5-Cyclopropyl-lH-pyrazol-3-yl)- N2 -((6-fluoro-lH-benzo[d]imidazol-5-yl)methyl)pyrimidine-2,4- diamine (1-28) step 1 : A solution of 5-fluoro-2-nitroaniline (1.5 g, 9.61 mmol) and NBS (1.7 g, 9.55 mmol) in HO Ac (75 mL) was heated at reflux for 90 min. The reaction mixture was then poured into ice water (300 mL) and stirred for 10 min. A bright yellow precipitate was collected by filtration and dried in vacuo overnight to afford 1.57 g (76percent) of 4-bromo-5-fluoro-2-nitroaniline (96): MS (ESI) m/z = 235 [M+l] +.
Reference: [1] Patent: EP2566477, 2015, B1, . Location in patent: Paragraph 0172; 0173
[2] Chemical Science, 2016, vol. 8, # 1, p. 734 - 741
[3] Patent: WO2013/26914, 2013, A1, . Location in patent: Page/Page column 133
[4] Patent: US2010/222345, 2010, A1, . Location in patent: Page/Page column 69
[5] Patent: KR2017/1093, 2017, A, . Location in patent: Paragraph 0107-0110
[6] Patent: KR2017/59925, 2017, A, . Location in patent: Paragraph 0075; 0076; 0077; 0078
  • 6
  • [ 351-30-4 ]
  • [ 153505-36-3 ]
YieldReaction ConditionsOperation in experiment
45%
Stage #1: at 20℃;
Stage #2: With hydrogenchloride In tetrahydrofuran; water at 120℃; for 0.333333 h; Microwave irradiation
Stage #3: With sodium hydrogencarbonate In tetrahydrofuran; water
INTERMEDIATE 16; 4-Bromo-5-fluoro-2-nitrophenylaminePotassium nitrate (914 mg, 9.05 mmol) was added to a stirred solution of 4-bromo- 3-fluoroacetanilide (2 g, 8.6 mmol) in sulfuric acid (10 mL) at r.t. After 1.5 h the mixture was poured onto ice (approximately 100 g) and extracted with EtOAc (100 mL). The organic phase was dried (MgSO4) and the solvent removed in vacuo to give a brown solid (2.48 g). 1.9 g of this material was dissolved/suspended in THF (10 mL). Hydrochloric acid (2M, 10 mL) was added, and the mixture heated in a microwave for 20 minutes at 12O0C. The mixture was partitioned between EtOAc and sodium hydrogencarbonate solution (100 mL each) and the aqueous phase extracted with EtOAc (50 mL). The combined organic phases were dried (MgSO4) and the solvent removed in vacuo. The residue was purified by column chromatography (SiO2, 10 to 100percent EtOAc in heptane) to give an orange-brown solid (1.5 g) which was washed with 9:1 heptane:diethyl ether to give, after air-drying, the title compound (900 mg, 45percent) as an orange-yellow solid. 6H (CDCl3) 8.39 (d, IH), 6.59 (d, IH), 6.21 (br, 2H).
Reference: [1] Patent: WO2010/52448, 2010, A2, . Location in patent: Page/Page column 40-41
  • 7
  • [ 2369-11-1 ]
  • [ 7732-18-5 ]
  • [ 153505-36-3 ]
Reference: [1] Patent: US5514680, 1996, A,
  • 8
  • [ 345-24-4 ]
  • [ 153505-36-3 ]
Reference: [1] Journal of Medicinal Chemistry, 2008, vol. 51, # 17, p. 5243 - 5263
  • 9
  • [ 656-65-5 ]
  • [ 153505-36-3 ]
Reference: [1] Patent: WO2012/83170, 2012, A1,
  • 10
  • [ 153505-36-3 ]
  • [ 1008360-84-6 ]
Reference: [1] Patent: WO2013/26914, 2013, A1,
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