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[ CAS No. 53078-85-6 ]

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CAS No. :53078-85-6 MDL No. :MFCD01806278
Formula : C7H8BrN Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W :186.05 g/mol Pubchem ID :6422065
Synonyms :

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Signal Word:Warning Class:N/A
Precautionary Statements:P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302 Packing Group:N/A
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[ 53078-85-6 ] Synthesis Path-Upstream   1~15

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Reference: [1] Journal of Organic Chemistry, 1980, vol. 45, # 8, p. 1546 - 1547
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  • [ 149-30-4 ]
  • [ 21303-50-4 ]
Reference: [1] Patent: US2003/139390, 2003, A1,
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YieldReaction ConditionsOperation in experiment
59% With tert.-butyl lithium In hydrogenchloride; diethyl ether; water; pentane a.
2-Amino-4-methylbenzoic acid
To a cold (-78° C.) stirred solution of 2-bromo-5-methylaniline (10.0 g, 53.7 mM) in anhydrous ethyl ether (500 mL) under a nitrogen atmosphere was added t-butyllithium (127 mL of 1.7M solution, 214.8 mM) in pentane over a 15 min period during which time the temperature of the reaction was not allowed to exceed -65° C.
After stirring at -78° C. for an additional 1.5 hr, the reaction mixture was quenched with an excess of crushed Dry Ice (solid CO2).
After the Dry Ice had evaporated, water was added to the reaction mixture and the organic layer was separated and discarded.
The aqueous layer was acidified with iN hydrochloric acid and then extracted with two portions of ethyl acetate.
The combined extracts were dried (MgSO4), filtered and concentrated to provide the title amino acid (4.8 g, 59percent) as a tan crystalline solid; MS(CI): 152 (M+H).
Reference: [1] Patent: US5599814, 1997, A,
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  • [ 7697-23-6 ]
Reference: [1] Journal of Fluorine Chemistry, 2002, vol. 116, # 2, p. 173 - 179
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  • [ 60956-23-2 ]
Reference: [1] Journal of the Chemical Society, 1914, vol. 105, p. 514
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YieldReaction ConditionsOperation in experiment
99% at 100℃; for 12.3333 h; Production Example 1
Synthesis of 2-bromo-5-methylaniline
4-Bromo-3-nitrotoluene (60.35 g, 279 mmol), 5percent by weight platinum carbon (1.09 g, 0.28 mmol) and triethylamine (112.93 g, 1116 mmol) were stirred under heating at 100° C., to which formic acid (99percent) (42.39 g, 921 mmol) was added dropwise over 20 minutes.
After stirring for 12 hours, it was brought back to room temperature, and then 100 ml of ethyl acetate and 100 ml of water were added thereto.
After stirring well, it was filtered through celite to remove platinum carbon.
By further adding 200 ml of ethyl acetate and 100 ml of water, it was extracted, the organic phase was washed with water (300 ml*3 times), and dried on magnesium sulfate.
The solvent was evaporated to obtain 2-bromo-5-methylaniline (51.30 g, 276 mmol).
The yield was 99percent.
1H-NMR (270 MHz, CDCl3) δ(ppm): 7.260 (1H, d), 6.583 (1h
97.5% With hydrogenchloride; sodium hydroxide; stannous chloride In ethanol Reference Example 36
A conc. hydrochloric acid solution (45 mL) containing stannous chloride (21.6 g, 114 mmol) was added to an ethanol solution (60 mL) containing 4-bromo-3-nitrotoluene (5 g, 23.1 mmol) while the mixture was cooled on an ice bath.
The reaction solution was stirred at 60°C for 0.5 hour.
After the reaction was completed, ethanol was evaporated under reduced pressure, and 12 N aqueous sodium hydroxide solution was added to the aqueous solution until pH 12 or more.
The aqueous solution was extracted with ether; the organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure, to obtain 2-bromo-5-methylaniline (4.21 g, 97.5percent) as a pale yellow solid.
1H-NMR (CDCl3) δ: 2.22 (3H, s), 2.73-4.79 (2H,br), 6.44 (1H, dd, J=8.06, 2.2Hz), 6.59 (1H, d, J=1.5Hz), 7.23-7.29(1H,m) ppm
FABMS:187(M+1)
97.4% With hydrazine hydrate In methanol at 20℃; for 2 h; Example 123[0328] (S)-2-(2-(3-ethyl-2,4-dimethyl- lH-indol- 1 -yl)acetamido)-N-(6-methoxypyridin-3- yl)-N-methyl-3-phenylpropanamideExample 123A. Preparation of 2-bromo-5-methylbenzenamine[0329] To a solution of bromo-4-methyl-2-nitrobenzene (5 g, 23.3 mmol, 1.0 eq) in MeOH, was added Ranney Nickel (2 mL). The mixture was stirred for 15 minutes, and hydrazine hydrate (2.33 g, 46.6 mmol, 2 eq) was added dropwise. The resulting mixture was stirred for 2 hours at room temperature Then the reaction mixture was filtered, the filtrate was concentrated under vacuum. The residue was washed with H20 (2x30 mL), extracted with EtOAc (2x20 mL). The combined organic extracts were evaporated to afford 2-bromo- 5-methylbenzenamine (4.2 g, 22.7 mmol, yield: 97.4percent), LC/MS: m/z M++l = 186.
78%
Stage #1: With tin(ll) chloride In ethyl acetate at 70 - 100℃; for 2 h;
Stage #2: With sodium hydrogencarbonate In water; ethyl acetate
Step 1 :4-bromo-3-nitrotoluene 36a (5.0 g, 22.9 mmol) is dissolved in 50 ml_ ethyl acetate and solid tin(ll) chloride dihydrate (20.0 g, 86.9 mmol) is added. The mixture is heated under nitrogen atmosphere at 7O0C for 2 h (note: temporary overheating to 1000C is observed. Caution should be exercised.). The mixture is cooled down and is poured into 200 ml. of ice-water. 50 ml. of 5percent aqueous NaHCO3 solution is <n="91"/>added (rapid foaming.), followed by 10 N aqueous NaOH to bring the pH ~ 7-8. Large volume of gelatinous yellowish precipitate is formed. This heterogeneous mixture is shaken with EtOAc (200 ml_) and the mixture is centrifuged in 50 mL portions, resulting in good separation of a yellowish solid. The clear supernatant is decanted and is extracted with EtOAc. Combined organic phase is washed with brine, dried over sodium sulphate, filtered and concentrated under vacuum to give an orange oily residue. This residue is re-dissolved in 100 mL of ether and the solution is washed with 10percent Na2CO3 (20 mL) followed by 2.5 M aqueous NaOH (20 mL). The dark brown organic solution is then stirred with MgSO4 and active charcoal and filtered to give a light yellow solution, which darkened rapidly on standing in open flask. The solvent is removed under vacuum to give the desired compound 36b as a brown-red oil which is used in the next step without further purification (3.31 g, 78percent yield).
78% With water; tin(ll) chloride In ethyl acetate at 70℃; for 2 h; 4-bromo-3-nitrotoluene 36a (5.0 g, 22.9 mmol) is dissolved in 50 mL ethyl acetate and solid tin(ll) chloride dihydrate (20.0 g, 86.9 mmol) is added. The mixture is heated under nitrogen atmosphere at 700C for about 2 h (note: temporary overheating to 1000C is observed. Caution should be exercised.). The mixture is cooled down and is poured into 200 mL of ice-water. 50 mL of 5percent aqueous NaHCO3 solution is added (rapid foaming.), followed by 10 N aqueous NaOH to bring the pH to about 7-8. Large volume of gelatinous yellowish precipitate is formed. This heterogeneous mixture is shaken with 200 mL EtOAc and the mixture is centrifuged in 50 mL portions, resulting in good separation of a yellowish solid. The clear supernatant is decanted and is extracted with EtOAc. Combined organic phase is washed with brine, dried over sodium sulphate, filtered and concentrated under vacuum to give an orange oily residue. This residue is re-dissolved in 100 mL of ether and the solution is washed with 10percent Na2CO3 (20 mL) followed by 2.5 M aqueous NaOH (20 mL). The dark brown organic solution is then stirred with MgSO4 and active charcoal and filtered to give a light yellow solution, which <n="101"/>13-152darkened rapidly on standing in open flask. The solvent is removed under vacuum to give the desired compound 36b as a brown-red oil which is used in the next step without further purification (3.31 g, 78percent yield).
78%
Stage #1: With tin(ll) chloride In ethyl acetate at 70 - 100℃; for 2 h;
Stage #2: With sodium hydroxide; water; sodium hydrogencarbonate In ethyl acetate
4-bromo-3-nιtrotoluene 36a (5 0 g, 22 9 mmol) is dissolved in ethyl acetate (50 mL) and solid tιn(ll) chloride dihydrate (20 0 g, 86 9 mmol) is added The mixture is heated under nitrogen atmosphere at 700C for 2 h (note temporary overheating to 1000C is observed) The mixture is cooled down and is poured into ice-water (200 mL) 5percent aqueous NaHCO3 (50 mL) solution is added (rapid foaming), followed by 10 N aqueous NaOH to bring the pH ~ 7-8 Large volume of gelatinous yellowish precipitate is formed This heterogeneous mixture is shaken with EtOAc (200 mL) and the mixture is centrifuged in 50 mL portions, resulting in good separation of a yellowish solid The clear supernatant is decanted and is extracted with EtOAc Combined organic phase is washed with brine, dried over sodium sulphate, filtered and concentrated under vacuum to give an orange oily residue This residue is re- dissolved in 100 mL of ether and the solution is washed with 10percent Na2CO3 (20 mL) followed by 2 5 M aqueous NaOH (20 mL) The dark brown organic solution is then stirred with MgSO4 and active charcoal and filtered to give a light yellow solution, which darkened rapidly on standing in open flask The solvent is removed under vacuum to give the desired compound 36b as a brown-red oil which is used in the next step without further purification (3 31 g, 78percent yield)
78%
Stage #1: With tin(ll) chloride In ethyl acetate at 70℃; for 2 h;
Stage #2: With sodium hydroxide; sodium hydrogencarbonate In water; ethyl acetate
4-bromo-3-nitrotoluene 36a (5.0 g, 22.9 mmol) is dissolved in 50 ml. ethyl acetate and solid tin(ll) chloride dihydrate (20.0 g, 86.9 mmol) is added. The mixture is heated under nitrogen atmosphere at 7O0C for 2 h (note: temporary overheating to 1000C is observed. Caution should be exercised.). The mixture is cooled down and is poured into 200 ml_ of ice-water. 5percent aqueous NaHCO3 (50 ml.) solution is added (rapid foaming.), followed by 10 N aqueous NaOH to bring the pH ~ 7-8. Large volume of gelatinous yellowish precipitate is formed. This heterogeneous mixture is shaken with EtOAc (200 ml_) and the mixture is centrifuged in 50 ml. portions, resulting in good separation of a yellowish solid. The clear supernatant is decanted and is extracted with EtOAc. Combined organic phase is washed with brine, dried over sodium sulphate, filtered and concentrated under vacuum to give an orange oily residue. This residue is re-dissolved in 100 mL of ether and the solution is washed with 10percent Na2CO3 (20 mL) followed by 2.5 M aqueous NaOH (20 mL). The dark brown organic solution is then stirred with MgSO4 and active charcoal and filtered to give a light yellow solution, which darkened rapidly on standing in open flask. The <n="104"/>solvent is removed under vacuum to give the desired compound 36b as a brown-red oil which is used in the next step without further purification (3.31 g, 78percent yield).
77% With ammonium chloride; zinc In 1,4-dioxane; water at 20℃; for 3 h; 2-bromo-5-methylaniline (1): To a solution of l-bromo-4-methyl-2-nitrobenzene (3.0 g, 13.8 mmol) in dioxane/water (1 : 1; 60 mL), zinc dust (9 g, 138.8 mmol) was added followed by the addition of ammonium chloride (7.3 g, 138.8 mmol). The reaction mixture was stirred at room temperature for 3 h. After completion of the reaction, the reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to afford 2 (2 g, 77percent) as a pale yellow liquid. 1H NMR (400 MHz, DMSO-d6): δ 2.12 (s, 3H), 5.14 (s, 2H), 6.28 (dd, J = 1.7, 8.0 Hz, 1H), 6.58 (s, 1H), .16 (d, J = 8.0 Hz, 1H). MS m/z (M+H): 186.3
68% With hydrogenchloride; iron In methanol; water at 20℃; for 168 h; Heating / reflux Add iron powder (7.75 g, 138 mmol), concentrated HC1 (1 mL) and water (10 mL) to a solution of commercially available 4- bromo-3-nitrotoluene (10 g, 46 mmol) in methanol (200 mL) at room temperature under nitrogen and heat the mixture at reflux for 168 h. Remove the solvents under reduced pressure, suspend the residue in 0.1 N NAOH (350 mL) and extract with chloroform (3 x 300 mL). Dry the combined organic extracts over MGS04 and remove the solvents under reduced pressure to afford to afford 2-bromo-5- methylphenylamine (Step 1) as an amber oil (5.87 g, 68percent): 1H NMR (CDC13) 5 2.20 (s, 3H), 4.00 (br s, 2H), 6.40 (d, 1H), 6.60 (s, 1H), 7.20 (d, 1H).

Reference: [1] Patent: US2003/191325, 2003, A1, . Location in patent: Page/Page column 8
[2] Patent: EP1820799, 2007, A1,
[3] Patent: WO2006/51851, 2006, A1, . Location in patent: Page/Page column 59-60
[4] Patent: WO2012/65062, 2012, A1, . Location in patent: Page/Page column 89-90
[5] Journal of Fluorine Chemistry, 2002, vol. 116, # 2, p. 173 - 179
[6] Patent: WO2009/62285, 2009, A1, . Location in patent: Page/Page column 89-90
[7] Patent: WO2009/62308, 2009, A1, . Location in patent: Page/Page column 99-100
[8] Patent: WO2009/62288, 2009, A1, . Location in patent: Page/Page column 97
[9] Patent: WO2009/62289, 2009, A1, . Location in patent: Page/Page column 102-103
[10] Patent: WO2014/149164, 2014, A1, . Location in patent: Paragraph 001109
[11] Patent: WO2004/63155, 2004, A1, . Location in patent: Page 134-135
[12] Justus Liebigs Annalen der Chemie, 1939, vol. 541, p. 283,290
[13] Justus Liebigs Annalen der Chemie, 1942, vol. 550, p. 67,83
[14] Journal of the American Chemical Society, 1933, vol. 55, p. 1212,1215
[15] Chemische Berichte, 1880, vol. 13, p. 963[16] Chemische Berichte, 1881, vol. 14, p. 417
[17] Patent: US2003/139390, 2003, A1,
[18] Angewandte Chemie - International Edition, 2007, vol. 46, # 39, p. 7509 - 7512
[19] Journal of the American Chemical Society, 2011, vol. 133, # 16, p. 6166 - 6169
[20] Dalton Transactions, 2018, vol. 47, # 48, p. 17401 - 17411
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Reference: [1] Patent: US5202356, 1993, A,
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Reference: [1] Justus Liebigs Annalen der Chemie, 1942, vol. 550, p. 67,83
[2] Journal of the American Chemical Society, 1933, vol. 55, p. 1212,1215
[3] Justus Liebigs Annalen der Chemie, 1939, vol. 541, p. 283,290
[4] Journal of the American Chemical Society, 2011, vol. 133, # 16, p. 6166 - 6169
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Reference: [1] Patent: WO2003/99275, 2003, A1, . Location in patent: Page 52
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Reference: [1] Chinese Journal of Chemistry, 2018, vol. 36, # 9, p. 815 - 818
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Reference: [1] Journal of Fluorine Chemistry, 2002, vol. 116, # 2, p. 173 - 179
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Reference: [1] Journal fuer Praktische Chemie (Leipzig), 1892, vol. &lt;2&gt; 46, p. 26
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Reference: [1] Journal of the Chemical Society, 1926, p. 2038
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Reference: [1] Journal of Fluorine Chemistry, 2002, vol. 116, # 2, p. 173 - 179
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Reference: [1] Justus Liebigs Annalen der Chemie, 1939, vol. 541, p. 283,290
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