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[ CAS No. 67853-37-6 ]

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CAS No. :67853-37-6 MDL No. :MFCD07779272
Formula : C7H6BrNO3 Boiling Point : 273.2°C at 760 mmHg
Linear Structure Formula :- InChI Key :-
M.W :232.03 g/mol Pubchem ID :17750299
Synonyms :

Safety of [ 67853-37-6 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H332-H335 Packing Group:N/A
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Application In Synthesis of [ 67853-37-6 ]

  • Upstream synthesis route of [ 67853-37-6 ]
  • Downstream synthetic route of [ 67853-37-6 ]

[ 67853-37-6 ] Synthesis Path-Upstream   1~7

  • 1
  • [ 101935-40-4 ]
  • [ 74-88-4 ]
  • [ 67853-37-6 ]
YieldReaction ConditionsOperation in experiment
94% With caesium carbonate In DMF (N,N-dimethyl-formamide) at 18 - 22℃; The nitrophenol starting material B2 (3.1 g; 14.2 MMOL) was dissolved in DMF (20 mL) and to the solution was added ground cesium carbonate (5. 58 G ; 17.1 MMOL) followed by Mel (2.6 mL; 42.5 MMOL). The mixture was stirred at room temperature overnight. The DMF was evaporated, the residue taken up in ether (1X 200 mL), washed with water (1X 200 ML), brine (4x 100 mL), dried (MGS04), filtered and evaporated to afford the crude 2-bromo-3-nitroanisole B3 (94percent; 3.1 g) as an orange solid. MS 234 (M+2H) + ; Homogeneity by HPLC (TFA) 220 nm: 98percent.
94% With caesium carbonate In N,N-dimethyl-formamide at 20℃; Step B:; The nitrophenol starting material 1b2 (3.1 g; 14.2 mmol) was dissolved inDMF (20 mL) and to the solution was added ground cesium carbonate (5.58 g; 17.1mmol) followed by Mel (2.6 mL; 42.5 mmol). The mixture was stirred at roomtemperature overnight. The DMF was evaporated, the residue taken up in ether (1 X200 mL), washed with water (1 X 200 mL), brine (4 X 100 mL), dried (MgSO4), filteredand evaporated to afford the crude 2-bromo-3-nitroanisole 1b3 (94percent; 3.1 g) as anorange solid.MS 234 (M+2H)+; Homogeneity by HPLC (TFA) (at) 220nm: 98percent
94% With caesium carbonate In DMF (N,N-dimethyl-formamide) at 20℃; The nitrophenol starting material 1b2 (3.1 g; 14.2 mmol) was dissolved in DMF (20 mL) and to the solution was added ground cesium carbonate (5.58 g; 17.1 mmol) followed by Mel (2.6 mL; 42.5 mmol).
The mixture was stirred at room temperature overnight.
The DMF was evaporated, the residue taken up in ether (1*200 mL), washed with water (1*200 mL), brine (4*100 mL), dried (MgSO4), filtered and evaporated to afford the crude 2-bromo-3-nitroanisole 1b3 (94percent; 3.1 g) as an orange solid.MS 234 (M+2H)+; Homogeneity by HPLC (TFA)at;220 nm: 98percent
94% With caesium carbonate In N,N-dimethyl-formamide at 20℃; The nitrophenol starting material 2b2 (3.1 g; 14.2 mmol) was dissolved inDMF (20 mL) and to the solution was added ground cesium carbonate (5.58 g; 17.1mmol) followed by Mel (2.6 mL; 42.5 mmol). The mixture was stirred at roomtemperature overnight. The DMF was evaporated, the residue taken up in ether (1 X200 mL), washed with water (1 X 200 mL), brine (4 X 100 mL), dried ( MgSO4),filtered and evaporated to afford the crude 2-bromo-3-nitroanisole 2b3 (94percent; 3.1 g)as an orange solid.MS 234 (M+2H)+; Homogeneity by HPLC (TFA) (at) 220nm: 98percent
94% With caesium carbonate In N,N-dimethyl-formamide at 18 - 22℃; Step B; The nitrophenol starting material 2B2 (3.1 g; 14.2 mmol) was dissolved in DMF (20 mL) and to the solution was added ground cesium carbonate (5.58 g; 17.1 mmol) followed by MeI (2.6 mL; 42.5 mmol). The mixture was stirred at room temperature overnight. The DMF was evaporated, the residue taken up in ether (1 X 200 mL), washed with water (1 X 200 mL), brine (4 X 100 mL), dried (MgSO4), filtered and evaporated to afford the crude 2-bromo-3-nitroanisole 2B3 (94percent; 3.1 g) as an orange solid. MS 234 (M+2H)+; Homogeneity by HPLC (TFA) (at) 220nm: 98percent

Reference: [1] Patent: WO2004/103996, 2004, A1, . Location in patent: Page 40-41
[2] Patent: WO2006/7700, 2006, A1, . Location in patent: Page/Page column 62
[3] Patent: US2006/19905, 2006, A1, . Location in patent: Page/Page column 24
[4] Patent: WO2006/85, 2006, A1, . Location in patent: Page/Page column 75-76
[5] Patent: WO2007/9227, 2007, A1, . Location in patent: Page/Page column 35
  • 2
  • [ 16554-45-3 ]
  • [ 67853-37-6 ]
YieldReaction ConditionsOperation in experiment
50%
Stage #1: With hydrogen bromide; sodium nitrite In water at 0℃; for 0.666667 h;
Stage #2: With copper(I) bromide In water at 0 - 60℃; for 2 h; Heating / reflux
A solution of sodium nitrite (1.48 mol) in water (250 mL) was added to a cold (0-5° C.) solution of the nitroaniline (1.08 mol) in hydrobromic acid (4.87 mol) (prepared by heating the reaction mixture at 90° C. for 2 h).
The reaction mixture was maintained for 40 min and was filtered.
The filtrate was added dropwise to a cold (0-5° C.) solution of copper (I) bromide (1.81 mol) in hydrobromic acid (640 mL) and the reaction mixture was maintained for 30 min.
The reaction mixture was warmed to 60° C. and was maintained for 30 min.
The reaction mixture was warmed to reflux and was maintained for 1 h.
The reaction mixture was diluted with water (2 L) and was extracted with dichloromethane (3*1 L).
The combined organic layers were washed with 10percent sodium hydroxide (1.0 L), water (2.0 L), 10percent hydrochloric acid (1.6 L) and water (2.0 L), dried (magnesium sulfate) and concentrated.
The residue was recrystallized from ethanol to provide the bromide in 50percent yield as a yellow solid.
Reference: [1] Patent: US2007/78147, 2007, A1, . Location in patent: Page/Page column 67
[2] Bulletin of the Chemical Society of Japan, 1978, vol. 51, p. 2437 - 2438
[3] Journal of Medicinal Chemistry, 2006, vol. 49, # 17, p. 5352 - 5362
  • 3
  • [ 603-85-0 ]
  • [ 67853-37-6 ]
Reference: [1] Journal of Medicinal Chemistry, 2006, vol. 49, # 17, p. 5352 - 5362
[2] Journal of Organic Chemistry, 1988, vol. 53, # 6, p. 1170 - 1176
  • 4
  • [ 101935-40-4 ]
  • [ 77-78-1 ]
  • [ 67853-37-6 ]
Reference: [1] Journal of Organic Chemistry, 1988, vol. 53, # 6, p. 1170 - 1176
  • 5
  • [ 67853-37-6 ]
  • [ 112970-44-2 ]
YieldReaction ConditionsOperation in experiment
100% With hydrogenchloride; iron In ethanol for 1.5 h; Reflux Step 1.
Synthesis of 2-bromo-3-methoxyaniline (C23)
Iron (1.94 g, 34 mmol) was added to a solution of 2-bromo-1-methoxy-3-nitrobenzene (2.50 g, 10.77 mmol) in ethanol (18 mL) and concentrated hydrochloric acid (1 mL), and the reaction was heated at reflux for 1.5 hours.
The mixture was cooled to room temperature, filtered through Celite and concentrated in vacuo to afford the title compound as a solid. Yield: 2.57 g, 10.77 mmol, 100percent. LCMS m/z 202.1 (M+1).
1H NMR (400 MHz, CD3OD) δ 3.77 (s, 3H), 6.30 (d, J=8.0 Hz, 1H), 6.43 (d, J=8.0 Hz, 1H), 6.98 (dd, J=8.0, 8.0 Hz, 1H).
96% With iron; ammonium chloride In ethanol; water for 1 h; Heating / reflux Iron powder (1.08 mol) and ammonium chloride (862 mmol) were added to a solution of the bromide (216 mmol) in ethanol (200 mL) and water (140 mL) and the reaction mixture was heated at reflux for 1 h.
The suspension was filtered and concentrated and the residue was extracted with ethyl acetate (3*200 mL).
The combined organic layers were dried (sodium sulfate) and concentrated to give the bromoaniline in 96percent yield as a yellow liquid.
96% With hydrogenchloride; iron In ethanol; water at 85℃; for 2 h; To a suspension of 2-bromo-1-methoxy-3-nitrobenzene (3.90 g, 16.81 mmol) and iron powder (2.82 g, 50.4 mmol) in EtOH (50 mL) was added concentrated HC1 (3.08 mL, 37.0 mmol). The mixture was heated at 85 °C for 2.0 h. HPLC indicated a completion of the reaction. After cooled to room temperature, the solvent was removed under vacuum. The residue was suspended in EtOAc and saturated sodium bicarbonate.The insoluble material was removed by filtration through a pad of wet celite. The organic layer of the filtrate was collected, washed with brine, dried over sodium sulfate. After evaporation of solvent, Intermediate iSA (3.25 g, 16.09 mmol, 96 percentyield) was obtained as brown oil. It was used for the next step without further purification. ‘H NMR (500MHz, chloroform-d) 7.08 (t, J=8.1 Hz, 1H), 6.45 (dd, J8.0, 1.4 Hz, 1H), 6.34 (dd,J=8.3, 1.1 Hz, 1H), 3.89 (s, 2H); LC-MS: method A, RT = 1.21 mm, MS (ESI) m/z: 202.0 and 204.0 (M+H)
95% With iron; ammonium chloride In tetrahydrofuran; methanol; water for 1 h; Reflux 2-bromo-1-methoxy-3-nitrobenzene (1 g, 4.31 mmol), Fe (1.68 g, 30.17 mmol) and NH4Cl (1.61 g, 30.17 mmol)were dissolved in THF (4 mL)/MeOH (4 mL)/H2O (2 mL) solution and stirred for 1 hour under reflux. After terminationof the reaction, the reaction solution was cooled to room temperature, diluted with saturated NaHCO3 solution andextracted with EtOAc. The extract solution was concentrated under reduced pressure and purified by column chromatography(eluent, EtOAc/Hex = 1/5) to obtain the title compound (0.83 g, 95 percent yield).1H NMR (500 MHz, CDCl3) δ 7.05(dd, 1H), 6.42(d, 1H), 6.31(d, 1H), 3.86(s, 3H)
91% With acetic acid In ethanol for 3.5 h; Heating / reflux 2-Bromo-3-nitroanisole B3 (1.00 g; 4.31 MMOL) was dissolved in glacial acetic acid (11.0 mL) and ethanol (11.0 mL). To this solution was added iron powder (0.98 g; 17.5 MMOL). The mixture was stirred at reflux for 3.5 h and worked up. The reaction mixture was diluted with water (35 mL), neutralized with solid Na2CO3 and the product extracted with CH2CI2 (3X 50 mL). The extracts were dried (NA2SO4), filtered and CONCENTRATED IN VACUO to afford the crude product, 2-bromo-3 methoxyaniline B4 (91 percent; 0. 79 g) as a pale yellow oil. MS 201.8 (MH) + ; Homogeneity by HPLC (TFA) 220 nm: 95percent.
91% With iron; acetic acid In ethanol for 3.5 h; Heating / reflux Step C:; 2-Bromo-3-nitroanisole 1b3 (1.00 g; 4.31 mmol) was dissolved in glacialacetic acid (11.0 mL)/ethanol (11.0 mL) and to the solution was added iron powder(0.98 g; 17.5 mmol). The mixture was stirred at reflux for 3.5 hr and worked up. Thereaction mixture was diluted with water (35 mL), neutralized with solid Na2CO3 and theproduct extracted with CH2CI2 (3X 50 mL). The extracts were dried (Na2SO4), filteredand concentrated in vacua to afford the crude product, 2-bromo-3 methoxyaniline 1b4(91percent; 0.79 g) as a pale yellow oil. MS 201.8 (MH)+; Homogeneity by HPLC (TFA) (at)220nm: 95percent
91% With iron; acetic acid In ethanol for 3.5 h; Heating / reflux 2-Bromo-3-nitroanisole 1b3 (1.00 g; 4.31 mmol) was dissolved in glacial acetic acid (11.0 mL)/ethanol (11.0 mL) and to the solution was added iron powder (0.98 g; 17.5 mmol).
The mixture was stirred at reflux for 3.5 hr and worked up.
The reaction mixture was diluted with water (35 mL), neutralized with solid Na2CO3 and the product extracted with CH2Cl2(3*50 mL).
The extracts were dried (Na2SO4), filtered and concentrated in vacuo to afford the crude product, 2-bromo-3 methoxyaniline 1b4 (91percent; 0.79 g) as a pale yellow oil. MS 201.8 (MH)+; Homogeneity by HPLC (TFA)at;220 nm: 95percent
91% With iron; acetic acid In ethanol for 3.5 h; Heating / reflux 2-Bromo-3-nitroanisole 2b3 (1.00 g; 4.31 mmol) was dissolved in glacialacetic acid (11.0 mL )/ethanol (11.0 mL) and to the solution was added iron powder(0.98 g; 17.5 mmol). The mixture was stirred at reflux for 3.5 hr and worked up. Thereaction mixture was diluted with water (35 mL), neutralized with solid Na2CO3 andthe product extracted with CH2CI2( 3X 50 mL). The extracts were dried (Na2SO4),filtered and concentrated in vacuo to afford the crude product, 2-bromo-3methoxyaniline 2b4 (91percent; 0.79 g) as a pale yellow oil. MS 201.8 (MH)+;Homogeneity by HPLC (TFA) (at) 220nm: 95percent
91%
Stage #1: With iron; acetic acid In ethanol for 3.5 h; Heating / reflux
Stage #2: With sodium carbonate In ethanol; water
Step C; 2-Bromo-3-nitroanisole 2B3 (1.00 g; 4.31 mmol) was dissolved in glacial acetic acid (11.0 mL)/ethanol (11.0 mL) and to the solution was added iron powder (0.98 g; 17.5 mmol). The mixture was stirred at reflux for 3.5 h and worked up. The reaction mixture was diluted with water (35 mL), neutralized with solid Na2CO3 and the product extracted with CH2CI2 (3X 50 mL). The extracts were dried (Na2SO4), filtered and concentrated in vacuo to afford the crude product, 2-bromo-3 methoxyaniline 2B4 (91percent; 0.79 g) as a pale yellow oil. MS 201.8 (MH)+; Homogeneity by HPLC (TFA) (at) 220nm: 95percent
89% With water; iron; ammonium chloride In tetrahydrofuran at 70℃; for 2.5 h; A solution of 2-bromo-l-methoxy-3 -nitrobenzene (500 mg, 2.16 mmol) in CH3OH (5 mL) and THF (5 mL) was added to a solution OfNH4Cl (572 mg, 10.7 mmol) in water (5 mL). Then, iron (325 mesh, 601 mg, 10.7 mmol) was added and the resulting mixture was heated to 70 °C under nitrogen. After 2.5 h, the reaction mixture was cooled to room temperature, filtered over kieselguhr, diluted with AcOEt, and successively washed with a saturated solution OfNaHCO3 in water and brine. The organic layer was dried (Na2SO4) and evaporated. The residue was triturated in CH2Cl2, the filtered to give 390 mg (89 percent) of the target product 37 as a beige solid.

Reference: [1] Patent: US2012/252758, 2012, A1, . Location in patent: Page/Page column 27
[2] Journal of Medicinal Chemistry, 2015, vol. 58, # 23, p. 9287 - 9295
[3] Patent: US2007/78147, 2007, A1, . Location in patent: Page/Page column 67
[4] Patent: WO2018/13774, 2018, A1, . Location in patent: Page/Page column 318
[5] Patent: EP3239143, 2017, A2, . Location in patent: Paragraph 0441
[6] Patent: WO2004/103996, 2004, A1, . Location in patent: Page 40-41
[7] Patent: WO2006/7700, 2006, A1, . Location in patent: Page/Page column 62
[8] Patent: US2006/19905, 2006, A1, . Location in patent: Page/Page column 24-25
[9] Patent: WO2006/85, 2006, A1, . Location in patent: Page/Page column 75-76
[10] Patent: WO2007/9227, 2007, A1, . Location in patent: Page/Page column 35
[11] Patent: WO2007/14919, 2007, A1, . Location in patent: Page/Page column 91
[12] Journal of Organic Chemistry, 1988, vol. 53, # 6, p. 1170 - 1176
[13] Synthetic Communications, 2007, vol. 37, # 16, p. 2777 - 2786
[14] Bulletin of the Chemical Society of Japan, 1978, vol. 51, p. 2437 - 2438
[15] Journal of Medicinal Chemistry, 2006, vol. 49, # 17, p. 5352 - 5362
  • 6
  • [ 67853-37-6 ]
  • [ 101935-40-4 ]
YieldReaction ConditionsOperation in experiment
98% With boron tribromide In dichloromethane at -70 - 20℃; for 26 h; Inert atmosphere SSynthesis of 2-f2'-Nitro-6'-pyridin-4-yl-biphenyl-4-yloxymethyl)-αuinoline (Example 384)2-Bromo-3-nitrophenol Error. Objects cannot be created from editing field codes.BBr3 (1.0M in CH2Cl2, 88 mL, 88 mmol) was added dropwise over 1 h to a stirred solution of 2-bromo-3-nitroanisole in CH2Cl2 (35 mL) under argon at -70 0C. The resulting deep burgundy-colored reaction mixture was allowed to warm up to RT slowly (over 2 h) and stirred at RT for 23 h. The reaction mixture was poured onto 35O g crushed ice and extracted with EtOAc (300 mL). The organic phase was separated, washed with brine (75 mL), and dried over MgSO4. Concentration and purification by chromatography (5-70percent EtO Ac/heptane) gave the title compound 2-bromo-3-nitrophenol (5.36 g, 98percent) as a yellow solid. 1H NMR (300 MHz, CDCI3/TMS) δ 7.48 (d, J= 8.1 Hz, IH), 7.37 (t, J = 8.1 Hz, IH), 7.27 (d, J= 8.4 Hz, IH), 6.13 (br s, IH); 13C NMR (75 MHz, CDCI3/TMS) δ 153.7, 128.7, 119.8, 117.5, 102.9.
Reference: [1] Patent: WO2009/158467, 2009, A2, . Location in patent: Page/Page column 59-60; 91
  • 7
  • [ 67853-37-6 ]
  • [ 1175277-80-1 ]
Reference: [1] Patent: WO2018/13774, 2018, A1,
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