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[ CAS No. 842136-59-8 ]

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2D
Chemical Structure| 842136-59-8
Chemical Structure| 842136-59-8
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CAS No. :842136-59-8MDL No. :MFCD11847367
Formula : C9H9BrClNO2 Boiling Point : -
Linear Structure Formula :-InChI Key :-
M.W :278.53Pubchem ID :-
Synonyms :

Computed Properties of [ 842136-59-8 ]

TPSA : - H-Bond Acceptor Count : -
XLogP3 : - H-Bond Donor Count : -
SP3 : - Rotatable Bond Count : -

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Application In Synthesis of [ 842136-59-8 ]

  • Upstream synthesis route of [ 842136-59-8 ]
  • Downstream synthetic route of [ 842136-59-8 ]

[ 842136-59-8 ] Synthesis Path-Upstream   1~1

  • 1
  • [ 842136-59-8 ]
  • [ 189628-37-3 ]
YieldReaction ConditionsOperation in experiment
95%
Stage #1: With lithium aluminium tetrahydride In tetrahydrofuran at -15 - -10℃; for 1 h;
Stage #2: With water; ammonium chloride In tetrahydrofuran
Preparation Example 5 Synthesis of 2-(5-bromo-2-chlorobenzyl)-1-benzothiophene; Oxalyl chloride (3.78 mL, 0.0441 mmol) and N,N-dimethylformamide (0.06 mL) were added to a chloroform (20 mL) solution of 5-bromo-2-chlorobenzoic acid (10.0 g, 0.0425 mol). After the reaction mixture was stirred at room temperature for one day, the reaction mixture was evaporated under reduced pressure. The obtained yellow oily substance was dissolved in chloroform (20 mL). This solution was added dropwise to a mixture of N,O-dimethoxyhydroxylamine hydrochloride (4.56 g, 0.0468 mol), triethylamine (12.3 mL, 0.0882 mol) and chloroform (50 mL) for 15 minutes, while maintaining the reaction temperature at 5°C to 10°C. After stirred for 15 minutes, the reaction mixture was warmed to room temperature. After water (20 mL) was added to the reaction mixture, the organic layer was separated and the organic layer was washed with a saturated sodium bicarbonate aqueous solution and brine, and then dried with anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was evaporated under reduced pressure to obtain 5-bromo-2-chloro-N-methoxy-N-methylbenzamide (11.8 g, 99.7percent) as a colorless crystal. This was used in the next reaction without purification. LiAlH4(1.47 g, 0.0388 mol) was added little by little to a tetrahydrofuran (108 mL) solution of 5-bromo-2-chloro-N-methoxy-N-methylbenzamide (10.8 g, 0.0388 mol) so that the internal temperature did not exceed -10°C. The reaction mixture was stirred at -15°C for one hour and carefully added with a saturated ammonium chloride aqueous solution and deposited insolubles were filtered off with celite. After the filtrate was extracted with ethyl acetate, the organic layer was washed with 1M hydrochloric acid, a saturated sodium bicarbonate aqueous solution, brine, and then dried with anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was evaporated under reduced pressure to obtain 5-bromo-2-chlorobenzaldehyde (8.1 g, 95percent) as a pale yellow crystal. This was used in the next reaction without purification. 1.6 M n-butylithium hexane solution (26.9 mL) was added to a mixture of benzo[b]thiophene (5.8 g, 0.043 mol) and tetrahydrofuran (58 mL) at -78°C over 20 minutes. After stirred for 0.5 hours, the mixture was added with a tetrahydrofuran (50 mL) solution of 5-bromo-2-chlorobenzaldehyde (9.0 g, 0.041 mol) and stirred for further five minutes. The reaction mixture was warmed to room temperature. After the reaction mixture was added with a saturated ammonium chloride aqueous solution and extracted with ethyl acetate, the organic phase was washed with brine and then dried with anhydrous magnesium sulfate. After the desiccant was filtered off, the residue obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography (hexane:ethyl acetate=10:1) to obtain pale yellow oily (1-benzothien-2-yl)(5-bromo-2-chlorophenyl)methanol (10.3 g, 71percent). Then, Et3SiH (9.2 mL, 0.058 mol) and BF3*Et2O (3.6 mL, 0.029 mol) were added sequentially to a chloroform (110 mL) solution of (1-benzothien-2-yl)(5-bromo-2-chlorophenyl)methanol (10.2 g, 0.0288 mol) at -15°C. The reaction mixture was warmed to room temperature and stirred at the temperature for ten hours. After the reaction mixture was added with a saturated sodium bicarbonate aqueous solution, the organic phase was separated, washed with brine and then dried with anhydrous magnesium sulfate. After the desiccant was filtered off, the residue obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography (hexane:ethyl acetate=60:1) to obtain a colorless oily title compound (5.5 g, 56percent). 1H NMR (300 MHz, CHLOROFORM-d) δ ppm 4.30 (s, 2 H) 6.98 - 7.06 (m, 1 H) 7.22 -7.37 (m, 4 H) 7.43 (d, J=2.3 Hz, 1 H) 7.64 - 7.71 (m, 1 H) 7.72 - 7.80 (m, 1 H). EI 336(M+), 338(M+2), 340(M+4).
65 g With diisobutylaluminium hydride In toluene at -70 - -65℃; for 0.5 h; Amide compound of Formula III (wherein X=bromo; 88 gms) and toluene (440ml) were added in to a round bottom flask at 25-35°C and allowed to cool to -65°C to -70°C. Diisobutyl aluminium hydride (lLt, 25percentsolution in toluene) was added to the reaction mass and stirred for 30 min at same temperature. The reaction mass was quenched with aqueous sodium potassium tartrate solution and heated the reaction mass to 25-35°C. The layers were separated and the aqueous layer was extracted with toluene then the organic layers were combined and washed with aqueous sodium chloride and dried over sodium sulphate. The organic layer was concentrated under reduced pressure at 45 °C and the obtained residue was diluted in heptane (200ml) and allowed to cool to 5-10°C. The reaction mass was stirred for l-2hrs at 5-10°C, filtered, washed with chilled heptane and dried at 30-35 °C to get the title compound. Yield: 65gms.
Reference: [1] Patent: EP1845095, 2007, A1, . Location in patent: Page/Page column 36-37
[2] Patent: US2008/27014, 2008, A1, . Location in patent: Page/Page column 40
[3] Patent: WO2018/29611, 2018, A1, . Location in patent: Page/Page column 60
[4] Patent: WO2007/136116, 2007, A2, . Location in patent: Page/Page column 91-92
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