Alternatived Products of [ 62224-25-3 ]
Product Details of [ 62224-25-3 ]
CAS No. : | 62224-25-3 |
MDL No. : | N/A |
Formula : |
C7H6Br2O2S
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Boiling Point : |
- |
Linear Structure Formula : | - |
InChI Key : | - |
M.W : |
313.99
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Pubchem ID : | - |
Synonyms : |
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Safety of [ 62224-25-3 ]
Signal Word: | |
Class: | |
Precautionary Statements: | |
UN#: | |
Hazard Statements: | |
Packing Group: | |
Application In Synthesis of [ 62224-25-3 ]
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
- Upstream synthesis route of [ 62224-25-3 ]
- Downstream synthetic route of [ 62224-25-3 ]
- 1
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[ 2810-04-0 ]
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[ 62224-25-3 ]
Yield | Reaction Conditions | Operation in experiment |
92% |
With N-Bromosuccinimide; sulfuric acid; trifluoroacetic acid; at 20℃; |
Ethyl 4,5-dibromothiophene-2-carboxylate To a stirred solution of ethyl thiophene-2-caroxylate (12.62g, 80.8mmol) in 12 mL of sulfuric acid and 40 mL of TFA was added NBS (32.0Og, 177.8mmol) in portions during 2-3 hours. After stirring overnight at room temperature, the reaction mixture was poured into ice water. The white precipitate formed was collected by suction filtration, and purified by recrystallization in methanol. 23.38g (92%) of product was obtained as a white solid, mp: 47.0 - 48.0 (lit. mp 48.0 - 49.0 0C, Bull. Chem. Soc. Jpn. 1991 , 64 (8), 2566-8) |
92% |
With N-Bromosuccinimide; sulfuric acid; trifluoroacetic acid; at 20℃; |
To a stirred solution of ethyl thiophene-2-carox late (12.62g, 80.8mmol) in 12 mL of sulfuric acid and 40 mL of TFA was added NBS (32.00g, 177.8mmol) in portions during 2-3 hours. After stirred overnight at room temperature, the reaction mixture was poured onto ice. The white precipitate formed was collected by suction filtration, and purified by recrystallization in methanol. 23.38g (92%) of product was obtained as a white solid, mp: 47.0 - 48.0 (lit. mp 48.0 - 49.0 C, Bull. Chem. Soc. Jpn. 1991, 64 (8), 2566-8). |
39% |
With bromine; acetic acid; at 60℃; |
Example 8A Ethyl 4,5-dibromothiophene-2-carboxylate 16.5 ml (320 mmol) of bromine are provided in 120 ml of acetic acid, and 10.0 g (64.0 mmol) of ethyl thiophene-2-carboxylate, dissolved in 40 ml of acetic acid, are added dropwise. The mixture is stirred at 60 C. overnight. The reaction mixture is concentrated, a saturated aqueous sodium bicarbonate solution is added to the residue and the mixture is extracted with dichloromethane. The organic phase is dried over magnesium sulfate, filtered and concentrated. The crude product is recrystallized from diethyl ether. 7.80 g (39% of theory) of the title compound are obtained. 1H-NMR (400 MHz, DMSO-d6): delta=7.79 (s, 1H), 4.30 (q, 2H), 1.29 (t, 3H). GC-MS (Method 11): Rt=5.55 min; MS (EIpos): m/z=314 [M]+. |
Reference:
[1]Patent: WO2006/92059,2006,A1 .Location in patent: Page/Page column 27; 16/21
[2]Patent: WO2012/116452,2012,A1 .Location in patent: Page/Page column 62; 63
[3]Synthesis,2010,p. 2965 - 2968
[4]Bulletin of the Chemical Society of Japan,1991,vol. 64,p. 2566 - 2568
[5]Patent: US2012/22123,2012,A1 .Location in patent: Page/Page column 13
[6]Patent: WO2019/169479,2019,A1 .Location in patent: Page/Page column 22; 23
- 2
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[ 62224-25-3 ]
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[ 62224-17-3 ]
- 3
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[ 2810-04-0 ]
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[ 62224-17-3 ]
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[ 62224-25-3 ]
- 4
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[ 62224-25-3 ]
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[ 328956-61-2 ]
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[ 1232068-87-9 ]
Yield | Reaction Conditions | Operation in experiment |
27% |
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; at 60℃;Inert atmosphere; |
Example 9A Ethyl 4-bromo-5-(3-chloro-5-fluorophenyl)thiophene-2-carboxylate Under argon, 3.71 g (11.8 mmol) of the compound from Example 8A and 2.16 g (12.4 mmol) of <strong>[328956-61-2]3-chloro-5-fluorophenylboronic acid</strong> are provided in 125 ml of degassed toluene/water (2.2/1), and 6.75 g (63.7 mmol) of sodium carbonate and 409 mg (0.35 mmol) of tetrakis(triphenylphosphine)palladium(0) are added. The mixture is stirred at 60 C. overnight. Water is added to the reaction mixture, the phases are separated, the aqueous phase is extracted with dichloromethane and the combined organic phases are dried over sodium sulfate, filtered and concentrated. The crude product is purified by preparative HPLC (RP18 column; eluent: acetonitrile/water gradient). This gives 1.17 g (27% of theory) of the title compound are obtained. 1H-NMR (400 MHz, DMSO-d6): delta=7.90 (s, 1H), 7.66-7.54 (m, 3H), 4.34 (q, 2H), 1.31 (t, 3H). LC-MS (Method 1): Rt=3.22 min; MS (ESIpos): m/z=363 [M+H]+. |
- 5
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[ 62224-25-3 ]
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[ 935685-88-4 ]
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[ 1232069-34-9 ]
Yield | Reaction Conditions | Operation in experiment |
|
With caesium carbonate In 1,2-dimethoxyethane at 50℃; Inert atmosphere; |
10 3-{3-(3-Chloro-4-fluorophenyl)-5-[(4-oxoimidazolidin-1-yl)carbonyl]thiophen-2-yl}-5-fluorobenzenecarbonitrile
Example 10 3-{3-(3-Chloro-4-fluorophenyl)-5-[(4-oxoimidazolidin-1-yl)carbonyl]thiophen-2-yl}-5-fluorobenzenecarbonitrile Under argon, 1.50 g (4.78 mmol) of the compound from Example 8A are provided in 75 ml of 1,2-dimethoxyethane, and 1.30 g (5.26 mmol) of the compound from Example 5A, 4.67 g (14.3 mmol) of cesium carbonate, 159 mg (0.33 mmol) of dicyclohexyl[2',4',6'-tri(propan-2-yl)biphenyl-2-yl]phosphane and 32.0 mg (0.14 mmol) of palladium(II) acetate are added. The mixture is stirred at 50° C. overnight. Water is subsequently added, the mixture is extracted with ethyl acetate and the extract is dried over sodium sulfate, filtered and concentrated. The crude product is purified by preparative HPLC (RP18 column; eluent: acetonitrile/water gradient with addition of 0.1% formic acid). 1.05 g of ethyl 4-bromo-5-(3-cyano-5-fluorophenyl)thiophene-2-carboxylate are obtained. LC-MS (Method 1): Rt=2.91 min; MS (ESIpos): m/z=354 [M+H]+. |
- 6
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[ 62224-25-3 ]
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[ 209919-30-2 ]
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C21H18Cl2O2S
[ No CAS ]