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[ CAS No. 37074-40-1 ]

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2D
Chemical Structure| 37074-40-1
Chemical Structure| 37074-40-1
Structure of 37074-40-1 *Storage: {[proInfo.prStorage]}

Quality Control of [ 37074-40-1 ]

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Product Details of [ 37074-40-1 ]

CAS No. :37074-40-1MDL No. :MFCD00045017
Formula :C9H9BrOBoiling Point :-
Linear Structure Formula :-InChI Key :QRTFRIPKQPOIPI-UHFFFAOYSA-N
M.W :213.07Pubchem ID :347124
Synonyms :

Computed Properties of [ 37074-40-1 ]

TPSA : 17.1 H-Bond Acceptor Count : 1
XLogP3 : - H-Bond Donor Count : 0
SP3 : 0.22 Rotatable Bond Count : 1

Safety of [ 37074-40-1 ]

Signal Word:WarningClassN/A
Precautionary Statements:P261-P305+P351+P338UN#:N/A
Hazard Statements:H315-H319-H335Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 37074-40-1 ]

  • Upstream synthesis route of [ 37074-40-1 ]
  • Downstream synthetic route of [ 37074-40-1 ]

[ 37074-40-1 ] Synthesis Path-Upstream   1~18

  • 1
  • [ 51930-77-9 ]
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YieldReaction ConditionsOperation in experiment
99% With pyridinium chlorochromate In dichloromethane at 20℃; for 12.00 h; [00494] l-(4-bromo-3-methylphenyl)ethanone. l-(4-bromo-3-methylphenyl)ethanol (2.14 g, 9.9 mmol) and pyridinium chlorochromate (2.62 g, 12 mmol) were added to a solution of dichloromethane (30 mL) under nitrogen atmosphere. And the reaction was stirred at room temperature for 12 hours. The mixture was partitioned between dichloromethane (3 * 20 mL) and brine (20 mL). The organic layer was concentrated to dryness and the residue was purified by column chromatography (silica gel, petroleum ether/ethyl acetate = 30: 1) to give l-(4-bromo- 3-methylphenyl) ethanone (2.08 g, 99percent) as a colorless oil. LRMS (M + H+) mlz: calcd 211.98; found 211. 1H NMR (300 MHz, CDC13): ^ 7.81 (s, 1H), 7.62-7.61 (m, 2H), 2.58 (s, 3H), 2.46 (s, 3H).
99% With pyridinium chlorochromate In dichloromethane at 20℃; for 12.00 h; Inert atmosphere 1-(4-bromo-3-methylphenyl)ethanol (2.14 g, 9.9 mmol) and pyridinium chlorochromate (2.62 g, 12 mmol) were added to a solution of dichloromethane (30 mL) under nitrogen atmosphere. And the reaction was stirred at room temperature for 12 hours. The mixture was partitioned between dichloromethane (3*20 mL) and brine (20 mL). The organic layer was concentrated to dryness and the residue was purified by column chromatography (silica gel, petroleum ether/ethyl acetate=30:1) to give 1-(4-bromo-3-methylphenyl)ethanone (2.08 g, 99percent) as a colorless oil. LRMS (M+H+) m/z: calcd 211.98. found 211. 1H NMR (300 MHz, CDCl3): δ 7.81 (s, 1H), 7.62-7.61 (m, 2H), 2.58 (s, 3H), 2.46 (s, 3H).
Reference: [1] Patent: WO2013/75083, 2013, A1. Location in patent: Paragraph 00492; 00494
[2] Patent: US9206128, 2015, B2. Location in patent: Page/Page column 225; 226
  • 2
  • [ 43230-11-1 ]
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YieldReaction ConditionsOperation in experiment
84%
Stage #1: With sulfuric acid; sodium nitrite In acetonitrile at 0℃;
Stage #2: With urea In water; acetonitrile
Stage #3: With hydrogen bromide; copper(I) bromide In water; acetonitrile at 50℃; for 2.00 h;
Step 2: Synthesis of 4'-bromo-3'-methylacetophenone 27.0 g of acetonitrile was added to a sulfuric acid solution of 27.0 g (181 mmol) of 4-acetyl-2-methylaniline, and the mixture was cooled to 0°C. An aqueous solution in which 13.1 g (190 mmol) of sodium nitrite was dissolved into 26.2 g of water was added in dropwise to the mixture. After reacting the resultant mixture for 1 hour at 0°C, an aqueous solution in which 1.1 g (18 mmol) of urea was dissolved into 2.2 g of water was added in dropwise, and the mixture was further stirred for 30 minutes to obtain an aqueous solution of 4-acetyl-2-methylbenzenediazonium sulfate. 5.18 g (36 mmol) of copper bromide, 62.2 g (362 mmol) of 47percent hydrobromic acid and 81.0 g of acetonitrile were fed into another reactor. The aqueous solution of 4-acetyl-2-methylbenzenediazonium sulfate was added to this mixture in dropwise over 1 hour with stirring at 50°C. After adding in dropwise, the mixture was reacted for 1 hour at 50°C. Then, 81 g of toluene was added and the mixture was stirred for 30 minutes, and the water phase was separated. 54 g of toluene was added to the water phase and extracted again. The combined toluene solution was washed twice with 54 g of 14percent aqueous ammonia and once with 54 g of water to obtain a toluene solution of 4'-bromo-3'-methylacetophenone. After removing the solvent by distilling under reduced pressure, the residue was distilled under reduced pressure of 1.5 kPa. 32.8 g of the obtained fraction which was collected in the range of outflow gas temperature from 130°C to 137°C was analyzed by HPLC. A percentage of relative area of 4'-bromo-3'-methylacetophenone was 99.1 percent (yield 84percent).
81%
Stage #1: With hydrogenchloride; sodium nitrite In water at -10 - -5℃; for 0.50 h;
Stage #2: With copper(I) bromide In water at 70℃; for 2.00 h;
Take 3-methyl-4-aminoacetophenone 149g,Add 500g concentrated hydrochloric acid, -10 ° ~ -5 °,An aqueous solution of sodium nitrite 140g (70g of sodium nitrite + 70g of water) was added dropwise during the addition.The temperature must not exceed -5° after the additionContinue to react for 30min. After the reaction is over,The reaction solution was slowly added dropwise to the aqueous solution of cuprous bromide (150 g copper bromide + 200 g water).The reaction system slowly warms up to 70 degrees for 2 hours. After the reaction is completed, it is filtered and the cake is washed to neutrality.The pale yellow solid was 171 g in a yield of 81percent.
Reference: [1] Patent: EP2172462, 2010, A1. Location in patent: Page/Page column 73-74
[2] Patent: CN107629029, 2018, A. Location in patent: Paragraph 0044; 0045; 0046; 0047; 0048
  • 3
  • [ 41963-20-6 ]
  • [ 75-16-1 ]
  • [ 37074-40-1 ]
YieldReaction ConditionsOperation in experiment
58%
Stage #1: at 60 - 65℃; Inert atmosphere
Stage #2: With sulfuric acid In toluene for 1.50 h;
4-bromo-3-methylacetophenonone 4-bromo-3-methylbenzonitrile (lg, 5.1 mmol) was dissolved in toluene (4 mL) under argon atmosphere. Methyl magnesium bromide (1.3 mL, 1 1.22 mmol) was added to the solution. The mixture was heated at 60-65 °C overnight. The reaction mixture was hydrolyzed with a 5M H2SO4 solution during lh30. The aqueous layer was extracted with EtOAc (5x100 mL). The combined organic layer was washed with 25 mL of water, dried over Na2SO4, filtered and evaporated under vacuum. Purification by silica gel flash chromatography (PE/EtOAc 5: 1) afforded the product (630 mg, 58percent) as a white oil. NMR (300 MHz, CDC13) δ 7.80 (bs, 1H, Har), 7.61 (bs, 2H, Har), 2.56 (s, 3H, CH3), 2.44 (s, 3H, CH3). 13C NMR (75 MHz, CDCb) δ 197.7 (C), 138.7 (C), 136.4 (C), 133.0 (CH), 131.0 (C), 130.7 (CH), 127.4 (CH), 26.9 (CH3), 23.3 (CH3). HRMS (ESI) [M+Na]+ C9H9BrONa: Calcd. 234.9729 found 234.9737.
Reference: [1] Patent: WO2015/1024, 2015, A1. Location in patent: Page/Page column 68-69
  • 4
  • [ 41963-20-6 ]
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YieldReaction ConditionsOperation in experiment
97% With hydrogenchloride In diethyl ether PREPARATION EXAMPLE 16
Preparation of Benzylamine Derivative
A mixture of 32 grams (165 millimoles) of 3-methyl-4-bromocyanobenzene and 27.4 grams (165 millimoles) of CH3 MgI was heated under reflux for 8 hours in 200 milliliters of diethyl ether.
Then, to the reaction product thus obtained, 200 milliliters of 6 Normal hydrochloric acid was added, and the resulting mixture was heated wnder reflux for 6 hours.
A diethyl ether layer was separated, washed with water and then dried over anhydrous sodium sulfate.
Subsequently the diethyl ether was distilled away under reduced pressure.
Thus, as a product, 34.1 grams (160 millimoles) of 3-methyl-4-bromoacetophenone was obtained (yield, 97percent).
Reference: [1] Patent: US4680054, 1987, A
  • 5
  • [ 95-46-5 ]
  • [ 75-36-5 ]
  • [ 37074-40-1 ]
Reference: [1] Chemische Berichte, 1891, vol. 24, p. 3768
[2] Justus Liebigs Annalen der Chemie, 1941, vol. 546, p. 277,291
[3] Journal fuer Praktische Chemie (Leipzig), 1891, vol. <2> 43, p. 359
[4] Patent: WO2017/60820, 2017, A1. Location in patent: Page/Page column 12
  • 6
  • [ 917-64-6 ]
  • [ 41963-20-6 ]
  • [ 37074-40-1 ]
YieldReaction ConditionsOperation in experiment
4.5 g
Stage #1: for 16.00 h; Reflux
Stage #2: With hydrogenchloride In water at 20℃; for 6.00 h; Reflux
At ambient temperature, methylmagnesium iodide (3 M in diethyl ether) (17 mL, 51 mmoles) is added dropwise to a solution of commercial 4-bromo-3-methylbenzonitrile (10 g, 51 mmoles) in diethyl ether (100 mL). The reaction mixture is heated at reflux for 16 hours. After return to ambient temperature, 60 mL of 6N hydrochloric acid are added, and the mixture is then heated at reflux for 6 hours. After cooling, the aqueous and organic phases are separated, and the aqueous phase is extracted with 40 mL of ethyl acetate. The organic phases are combined, washed with a saturated aqueous NaCl solution (2×40 mL), dried over MgSO4 and then concentrated under reduced pressure. 4.5 g of intermediate 9 are obtained in the form of a brown oil. 1H NMR (300 MHz, CDCl3): δ 7.80 (s, 1H), 7.62 (s, 2H), 2.60 (s, 3H), 2.45 (s, 3H) IR (cm−1): 1681
Reference: [1] Justus Liebigs Annalen der Chemie, 1941, vol. 546, p. 277,291
[2] Patent: US2017/137385, 2017, A1. Location in patent: Paragraph 0265; 0266; 0267
  • 7
  • [ 170230-01-0 ]
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Reference: [1] Patent: WO2006/85118, 2006, A2. Location in patent: Page/Page column 32-33
  • 8
  • [ 917-54-4 ]
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  • [ 37074-40-1 ]
Reference: [1] Patent: WO2011/91532, 2011, A1. Location in patent: Page/Page column 20
  • 9
  • [ 75-16-1 ]
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Reference: [1] Patent: WO2017/60820, 2017, A1. Location in patent: Page/Page column 11
  • 10
  • [ 7697-28-1 ]
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Reference: [1] Patent: WO2011/91532, 2011, A1
[2] Patent: WO2017/60820, 2017, A1
  • 11
  • [ 78775-11-8 ]
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Reference: [1] Patent: WO2013/75083, 2013, A1
[2] Patent: US9206128, 2015, B2
  • 12
  • [ 95-53-4 ]
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Reference: [1] Patent: CN107629029, 2018, A
  • 13
  • [ 120-66-1 ]
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Reference: [1] Patent: CN107629029, 2018, A
  • 14
  • [ 40664-73-1 ]
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Reference: [1] Patent: CN107629029, 2018, A
  • 15
  • [ 95-46-5 ]
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Reference: [1] Journal of Organic Chemistry, 1947, vol. 12, p. 617,680
  • 16
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Reference: [1] Justus Liebigs Annalen der Chemie, 1941, vol. 546, p. 277,291
  • 17
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Reference: [1] Journal of Organic Chemistry, 1947, vol. 12, p. 617,680
  • 18
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Reference: [1] Justus Liebigs Annalen der Chemie, 1941, vol. 546, p. 277,291
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