Structure of 32412-39-8
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CAS No. : | 32412-39-8 |
Formula : | C7H7BrOS |
M.W : | 219.10 |
SMILES Code : | CCC(C1=CC=C(Br)S1)=O |
MDL No. : | MFCD01993682 |
InChI Key : | JQAYKLHWCBPAEX-UHFFFAOYSA-N |
Pubchem ID : | 255121 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H319 |
Precautionary Statements: | P305+P351+P338 |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | To a stirred solution of AlCl3 (29.44 g, 221 mmol) in EDC (300 mL) at 0C, propionyl chloride (17.02 g, 184 mmol) was added and reaction mixture was stirred for 20 min at 0C. To this solution, compound 231 (30 g, 184 mmol) was added and further stirred at room temperature for overnight. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water and extracted with DCM. The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to afford the title compound 227 (38.20 g, 95%) as brown coloured solid; TLC: 20% EtOAc/ hexane (Rf: 0.4); 1H NMR (400 MHz, DMSO-d6): δ 7.79 (d, J=4.4 Hz, 1H), 7.38 (d, J=4.0 Hz, 1H), 2.97-2.92 (m, 2H), 1.07 (t, J=7.2 Hz, 3H); LCMS Calculated for C7H7BrOS: 217.94; Observed: 220.80 (M + 2)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With titanium tetrachloride; In dichloromethane; toluene; at -50 - 20℃;Cooling with acetonitrile ice bath; | To a nitrogen flushed round bottom flask equipped with a stir bar and addition funnel was added 80 mL methylene chloride. TiC14 (2.3 mL, 21.0 mmol) was added and the mixture cooled with a dry ice-acetonitrile bath to about-50C. To this was added Me2Zn (2M in toluene, 10.5 mL, 21 mmol). The resulting thick slurry was allowed to stir for at least 10 minutes. A solution of 1- (5-bromo-thiophen-2-yl)-propan-1-one [prepared as described in JACS 1950, 3695] (2.191 g, 10.1 mmol) in 20 mL methylene chloride was added to the reaction mixture via addition over a period of 35 minutes. The ice bath was allowed to melt and the reaction was allowed to warm up overnight. The reaction was then carefully poured into 500 mL ice/water and then extracted three times with 100 mL methylene chloride. The combined organics were washed twice with 1 N HCI (100 mL) and once with brine (100 mL). The organics were then dried over Na2SO4, treated with charcoal, filtered and concentrated to a residue that was chromatographed over silica gel eluting with 100% hexanes. Evaporation of the proper fractions yielded the product as a colorless liquid (1.256 g, 5.39 mmol). 1H NMR (CDCI3) : δ 6.85 (d, 1 H), 6.53 (d, 1 H), 1.62 (q, 2H), 1.31 (s, 6H), 0.81 (t, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | With sodium; In ethanol; at 20℃; for 18h;Inert atmosphere; | Under a nitrogen atmosphere, sodium metal (0.103g, 4.47mmol) was added in small portions to dry ethanol (3.3mL) and stirred at room temperature until all sodium was dissolved. Diethyl oxalate (0.9mL, 6.70mmol) was then added, followed by dropwise addition of a solution of the <strong>[32412-39-8]1-(5-bromothiophen-2-yl)propan-1-one</strong> 1 (0.49g, 2.24mmol) in dry ethanol (4mL). The mixture was stirred at room temperature for 18h, then slowly poured into a mixture of ice and 1M HCl. The resulting mixture was extracted with diethyl ether and concentrated. The analytically pure product was isolated by Flash Chromatography (petroleum ether:ethyl acetate, 8:2, Rf=0.44) to afford 2 in 31% yield (0.22g). 2: yellow oil; IR: ν 1748, 1727, 1648cm-1; 1H NMR (400MHz, CDCl3): δ 1.31 (t, 3H, J=7.2Hz), 1.48 (d, 3H, J=7.0Hz), 4.29 (qd, 2H, J=7.1Hz, J=0.8Hz), 4.78 (q, 1H, J=7.2Hz), 7.16 (d, 1H, J=4.3Hz), 7.54 (d, 1H, J=4.0Hz); 13C NMR (100MHz, CDCl3): δ 13.3, 14.0, 51.9, 63.2, 124.3, 131.7, 133.5, 143.9, 160.5, 189.0, 189.7; MS (ESI), calculated m/z C11H11BrO4S 317.9561 [M]+, found m/z (relative intensity) 318 [M+H]+ (100). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | 5.00 g (22.12 mmol) of 5-bromo-1H-indole-2,3-dione were initially charged in 61.2 ml of acetic acid, and 4.85 g (22.12 mmol) of 1-(5-bromo-2-thienyl)propan-1-one were added. The reaction mixture was stirred at 75 C. for 5 min. Subsequently, 20.4 ml (244 mmol) of conc. hydrochloric acid were added, and stirring of the mixture was continued at 105 C. overnight. After cooling to RT, the reaction mixture was concentrated under reduced pressure, 200 ml of toluene were added and the mixture was concentrated again. Addition of toluene and concentration were repeated twice. The resulting residue was dissolved with heating in a mixture of 100 ml of methanol and 50 ml of THF/DMSO/DMF and purified by preparative HPLC [column: Chromatorex Spring Column C18, 10 μm, 290 mm×100 mm; flow rate: 250 ml/min; detection: 210 nm; temperature: 22 C.; injection: 30 ml, gradient methanol/(water+0.1% formic acid) 50:50→90:10; run time 39 min)]. 6.77 g (72% of theory, 100% purity) of the title compound was obtained. 1H-NMR (400 Mhz, DMSO-d6): δ [ppm]=14.50 (br. s, 1H), 7.97-7.88 (m, 2H), 7.86 (d, 1H), 7.63 (d, 1H), 7.36 (d, 1H), 2.66 (s, 3H). LC/MS (Method 9, ESIpos): Rt=2.26 min, m/z=425/427/429 [M+H]+. |
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