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CAS No. : | 18442-22-3 | MDL No. : | MFCD09744055 |
Formula : | C9H7BrO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | DMEAYYYHWLCPCD-UHFFFAOYSA-N |
M.W : | 227.06 | Pubchem ID : | 22335736 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
75% | With triethylamine;tris-(dibenzylideneacetone)dipalladium(0); copper(l) iodide; triphenylphosphine; at 140℃; for 0.333333h;Microwave irradiation; | Example 79C; A mixture of the product from Example 79B (979 mg, 4.33 mmol), tert-butylacetylene (3 mL, 24.4 mmol), CuI (166 mg, 0.872 mmol), triphenyl phosphine (304 mg, 1.16 mmol), and tris(dibenzylideneacetone)dipalladium(0) (789 mg, 0.862 mmol) was heated in triethylamine (8 mL) under microwave power at 140 for 20 min. Evaporation of the volatiles in vacuo, followed by silica gel chromatography, afforded Example 79C as a yellow oil, 741 mg (75%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
13% | In ethylene glycol; for 4h;Heating / reflux; | Example 79B; The product from Example 79A (7.935 g, 32.3 mmol) was refluxed in ethylene glycol for 4 h. The solution was then cooled to rt and poured into water. The mixture was extracted with ether, then the extracts were washed with water and brine. Concentration in vacuo, followed by silica gel chromatography (9:1 hexane-ethyl acetate to 65:35 hexane-ethyl acetate, eluent gradient), afforded Example 79B as a thick yellow oil, 979 mg (13%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With polyphosphoric acid; at 80℃; for 2h; | Weighed compound 7 (5g), added to a three-necked bottle, and weighed 50mL of polyphosphoric acid into a 100mL three-necked bottle.The reaction system was heated in an oil bath and stirred at 80 C for 2 hours. Lower the system temperature to room temperature,The reaction was quenched by adding 100 mL of water and stirring for 10 minutes, and extracted three times with 100 mL of ethyl acetate.The organic phases are combined, then the organic phase is washed with water and the organic phase washed with saturated sodium chloride.Dried over anhydrous sodium sulfate, filtered and concentrated, the crude product was purified by column chromatography (mobile phase:Ethyl acetate: petroleum ether = 1:3) was purified. 3.1 g (60%) of a yellow solid were obtained. |
With phosphorus pentachloride;aluminium chloride; | Example 30 7-Bromo-2,3-dihydro-4H-chromen-4-one 2.45 g (10 mmol) of the compound from Example 5 are added to 3.12 g (15.00 mmol) of phosphorus pentachloride. The mixture is stirred at room temperature for O min, resulting in a clear solution. After addition of 2.67 g (20 mmol) of aluminium chloride, the reaction mixture becomes solid. It is heated at 130 C. for 30 min and, after cooling, added to ice and extracted with ethyl acetate. The organic phase is washed with water and saturated aqueous sodium chloride solution, dried over magnesium sulphate and, after removal of the solvent by distillation, purified by column chromatography on silica gel (V 8:2). Recrystallization from cyclohexane/pentane affords 0.78 g (34%) of colourless crystals. 1H-NMR (200 MHz, CDCl3, delta/ppm): 2.80 (t, 2H), 4.55 (t, 2H), 7.15 (dd, 1H), 7.25 (s, 1H), 7.71 (t, 1H). MS (EI POS): 226 [M+]. | |
With polyphosphoric acid; at 70℃; for 2h;Inert atmosphere; | Into a 3-L 4-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed 3-(3-bromophenoxy)- propanoic acid (195 g, 795.69 mmol, 1.00 equiv), and PPA (2008 g). The reaction was stirred for 2 h at 70C in an oil bath, then slowly poured into 2 L of ice. The resulting solids were collected by filtration, and purified by Prep-SFC (Column, AD-H; mobile phase, (0284) methanol:MeCN=l: l; Detector, UV, 220, 254 nm) to give the title compound |
With polyphosphoric acid; at 70℃; for 2h;Inert atmosphere; | Into a 3-L 4-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed 3-(3-bromophenoxy)-propanoic acid (195 g, 795.69 mmol, 1.00 equiv), and PPA (2008 g). The reaction was stirred for 2 h at 70C in an oil bath, then slowly poured into 2 L of ice. The resulting solids were collected by filtration, and purified by Prep-SFC (Column, AD-H; mobile phase, methanol:MeCN=1:1; Detector, UV, 220, 254 nm) to give the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | The 7-[4-(4-methoxytetrahydropyran-4-yl)thien-2-ylthio]chroman-4-one used as a starting material was obtained as follows: A solution of sodium hydrosulphide hydrate (8.88 g) in NMP (150 ml) was stirred and heated to 140 C. The mixture was partially evaporated under vacuum to remove the water. The mixture was cooled to 45 C. and a solution of <strong>[18442-22-3]7-bromochroman-4-one</strong> (12 g) in NMP (150 ml) was added dropwise. The mixture was stirred and heated to 50 C. for 30 minutes. The mixture was poured onto a mixture of ice and water and extracted with ethyl acetate. The organic phase was dried (MgSO4) and evaporated to give 7-mercaptochroman-4-one (7 g, 73%). A solution of the material so obtained in DMSO (20 ml) was stirred at ambient temperature for 16 hours. The mixture was poured onto a mixture of ice and water. The precipitate was isolated and dried. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | A mixture of the product so obtained and 2N aqueous sodium hydroxide (100 ml) was stirred at ambient temperature. The precipitate was isolated and purified by column chromatography using a 4:1 mixture of petroleum ether and methylene chloride as eluent. There was thus obtained 7-bromochroman-4-one in 39% yield, m.p. 95-97C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | Using analogous procedures to those described in the portion of Example 2 which is concerned with the preparation of starting materials, <strong>[18442-22-3]7-bromochroman-4-one</strong> was converted in turn into:- <strong>[18442-22-3]7-bromochroman-4-one</strong> ethylene acetal in 64% yield; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With bromine; In tetrachloromethane; for 1.58333h; | lnter.med.iate 6; 3,3,7-fribromo-2,3-dihydro-4H-chromen-4-one.; To a vigorously stirring solution of 7-Bromo-2,3-dihydro-4W-chromen-4-oiotaie (20.0 g,88.1 mmoi) in CCI4 (400 mL) was added dropwise a solution of bromine (10 mL, 194 mmoi) in CCI4 {100 mL) over 45 minutes. The resulting solution was stirred for 50 minutes and CHCl3(100 mL) was added to the solution to dissolve the precipitate, The solution was washed with 10% NaHSO3 (75 mL), dried over Na2SC^ and evaporated to dryness to give the title compound (32,5 g, 86%) as a yellowish solid. LC/MS data; 302.9 (M-Br)* (Calculated for C9HsBr3O2 384.85). (calo. monoisotopic mass is 38171, calc. monoisotopio mass (M-Br)+= 302.9). 1H NMR data (DMSO-ddelta): 7.82 (d, 1H, J = 8.6 Hz, Ar-H), 7.51 (d, 1H, J = 2.0 Hz, Ar- H)1 7.42 (dd, 1H1 J1= 8.3, ?4=1.7 Hz, Ar-H)1 5.02 (s, 2H, CH2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | A solution of diisobutylaluminum hydride in heptane (1.0 M, 60 mL, 60.0 mmol) was added dropwise to a solution of 7-bromo-4H-chromen-4-one (4.5 g, 20.0 mmol) in tetrahydrofuran at -78 C under an atmosphere of argon over a period of 30 minutes. After 30 minutes the reaction was quenched with a mixture of silica gel (10 g), and water (10 mL). The mixture was allowed to warm to room temperature and was filter through celite and the tetrahydrofuran was removed under reduced pressure. The residue was taken up in chloroform (100 mL) and washed with sodium hydroxide (IN, 25 mL) and dried over sodium sulfate. The mixture was filtered and the solvent was removed under reduced pressure. The residue was subjected to flash chromatography with eluant of dichloromethane. The product containing fractions were combined and the solvent was removed under reduced pressure to provide 7- bromochroman-4-one (3.57 g, 15.7 mmol, 78 %). | |
69% | Intermediate 5; 7-Bromo-2,3-dhydro-4W-chromen-4-one.;The solution of 7-Bromo-4H-chromen-4-one (26.0 g, 116 mmol) in absolute THF (500 mL) was stirred under argon for 1 h and then it was cooled to -80 0C. To a suspension formed a solution of diisobutylaluminum hydride 1M In heptane (173 mL, 173 mmol) was added during 30 minutes and the resulting mixture was stirred at -80 0C for additional 30 minutes. The solution was quenched by mixture of SiO2 (52 g) and H2O (52 mL), allowed to warm to 00C. Then SiO2 was filtered, washed with EtOAc and the solution was evaporated to dryness. The residue was dissolved in CHCI3 (400 mL), washed with 1 N NaOH (300 mL), dried over Na2SO4 and evaporated. The resulting solid was purified by column chromatography on SiO2 (63-100 mum, 1200 mL) in CHCI3 (80 - 100%) gradient in hexane to afford 101865-076 (18.1 g, 69%) as a pale yellow solid. LC/MS data: 226.9 V(M+Hf (Calculated for C8H7BrO2 227.06) (calc. monoisotopic mass is 225.96, calc. monoisotopic mass (M+Hf = 226.96). 1H NMR data (DMSO-d6): 7.66 (d, 1H1 J=8.3 Hz, Ar-H), 7.33 (d, 1H, J=2.0 Hz, Ar-H), 7.25 (dd, 1H, ^=8.3 Hz1 J2=L 7 Hz, Ar-H), 4.56 (t 2H, CH2 , J=6.6 Hz)1 2.80 (t, 2H, CH2 , J=S,6 Hz). | |
51.7% | With diisobutylaluminium hydride; In tetrahydrofuran; at -78℃; for 0.5h; | A solution of XXV-3 (2.9 g, 12.9 mmol) in THF (10 mL) was cooled to -78 C., DIBAl-H (24 mL, 24 mmol) was added and the resulting solution was stirred at -78 C. for 30 min., Then sat.NH4Cl was added to quench the reaction, extracted with EA, washed with brine, dried over Na2SO4 and concentrated, the residue was purified by flash chromatography (PE/EA=1/1) to give XXV-4 (1.5 g, yield: 51.7%) as a yellow solid. |
With diisobutylaluminium hydride; In tetrahydrofuran; chloroform; toluene; | Example 14c; step 5: A solution of 7-bromo-4H-chromen-4-one (26 g, 116 mmol) in dry THF (500 mL) under nitrogen for 1 hr, cooled to -80 C., and 173 mL of diisobutylaluminium hydride (2M in Toluene) was added over 30 minutes. The reaction was stirred at the same temperature for 30 min, quenched with a SiO2 (52 g)/water (52 mL) suspension, and allowed to warm to 0 C. The solution was filtered, the SiO2 washed with EtOAc, and the combined filtrate was concentrated to dryness. The residue was dissolved in CHCl3 (400 mL), washed with 1N NaOH (300 mL), dried over Na2SO4 and concentrated. Purification by chromatography on SiO2 (60-120 mesh) EtOAc/Pet ether (gradient elution 0-15%) afforded 7-bromochroman-4-one 18.1 g (69%) a pale yellow solid. LCMS 229.0 (M+2H); 1H NMR (DMSO-d6) 7.64-7.67 (d, 1H), 7.32 (s, 1H), 7.22-7.25(d, 1H), 4.53-4.57 (t, 2H), 2.76-2.80 (t, 2H). | |
With diisobutylaluminium hydride; In tetrahydrofuran; toluene; at -78℃; for 1.5h;Inert atmosphere; | To a solution of compound 1D (32.6 g, 145.5 mmol) in THF (600 mL) was added DIBAL (1 M in toluene, 437 mL, 437 mmol) dropwise under nitrogen at -78 for 30 minutes. The mixture was allowed to stir at -78 for 1 hour, then the reaction mixture was poured into 500 mL of 1 M aq. HCl, and extracted with ethyl acetate. The organic extract was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue obtained was purified using flash column chromatography on silica gel (petroleum ether: ethyl acetate 20: 1 to provide compound 1E as a solid. 1H-NMR (CDCl3, 400 MHz) : delta 7.72 (d, J 8.0 Hz, 1H) , 7.13-7.17 (m, 2H) , 4.52 (t, J 6.4 Hz, 1H) , 2.79 (d, J 6.4 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | 7-Bromo-4-chromanone. Into a round bottom flask kept at 0 C., AlCl3 (0.533 g, 3.99 mmol) and, 5 mL of CH2Cl2 was added. The reaction system was put under nitrogen and stirred for about 7 minutes before adding 10 mL of a CH2Cl2 solution of 4-chromanone (0.296 g, 1.99 mmol). After the reaction mixture was stirred for 10 minutes, 10 mL of Br2 (0.352 g, 2.20 mmol) was added and, the reaction mixture was stirred at room temperature for an hour. At the end of this period of time, the reaction mixture was poured into 30 mL of ice-water and, the product was extracted 3 times from the aqueous phase with EtOAc. The resultant organic phase was washed once with brine and dried under Na2SO4. After the solvent was evaporated, the solid formed was filtered and dried to obtain 0.361 g (1.51 mmol) of the product (93% pure) in a 74% yield. 1H NMR (300 MHz, CDCl3, delta): 7.90 (dd, J=2.6, 0.3 ArH, 1H,), 7.47 (dd, J=8.8, 2.5, Ar, 1H,), 6.82 (dd, J=8.8, 0.2, Ar, 1H), 4.48 (t, J=6.5, C2, 2H), 2.75 (t, J=6.5, C2, 2H). |
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