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CAS No. : | 56525-63-4 | MDL No. : | MFCD00205141 |
Formula : | C9H9ClO2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | KTFQDZCNPGFKAH-UHFFFAOYSA-N |
M.W : | 184.62 | Pubchem ID : | 2801405 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H315-H319-H335 | Packing Group: | |
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 |
---|---|---|
92% | With tert.-butylhydroperoxide; cetyltrimethylammonim bromide; potassium bromide; In water; at 120℃; under 750.075 Torr;Microwave irradiation; | General procedure: The reaction mixture was treated in a controlled microwavesynthesizer (Biotage Initiator+SP Wave model, 0-200 W at2.45 GHz, capped at 60 W during steady state) for severalminutes (the reaction attained 120 C at 1 bar pressure). Thefinal products were isolated by column chromatographyusing an EtOAc-hexane gradient |
84% | With 2,2'-azobis(2-methylpropionitrile); N-Bromosuccinimide; In tetrachloromethane; for 18h;Heating / reflux; | To a solution of methyl 3-chloro-4-methylbenzoate (5.0 g, 27.1 mmol) in carbon tetrachloride (50 ml) were added N-bromosuccinimide (5.8 g, 32.0 mmol) and 2,2'-azo-bis(2-methylpropionitrile) (0.442 g, 2.70 mmol). The mixture was heated at reflux for 18 h, then allowed to cool to room temperature and concentrated in vacuo. The residue was purified by flash chromatography on silica (eluant pet. ether ? 5% ethyl acetate/95% pet. ether) to give an oil identified as methyl 4-bromomethyl-3-chlorobenzoate (5.96 g, 84%). |
84% | With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 18h;Heating / reflux; | To a solution of methyl 3-chloro-4-methylbenzoate (5.0g, 27.1mmol) in carbon tetrachloride (50ml) were added NBS (5.8g, 32.0mmol) and AIBN (0.442g, 2.70mmol). The mixture was stirred at reflux for 18h. The mixture was al-lowed to cool to room temperature and then concentrated in vacuo. The residue was purified by flash chromatography on silica (eluant EtOAc:pet. ether 0:100 to 5:95); yield 5.96g (84%). |
84% | With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 18h;Heating / reflux; | To a solution of methyl 3-chloro-4-methylbenzoate (5.0 g, 27.1 mmol) in carbon tetrachloride (50 ml) were added NBS (5.8 g, 32.0 mmol) and AIBN (0.442 g, 2.70 mmol).. The mixture was stirred at reflux for 18 h.. The mixture was allowed to cool to room temperature and then concentrated in vacuo.. The residue was purified by flash chromatography on silica (eluant EtOAc:pet. ether 0:100 to 5:95); yield 5.96 g (84%). |
75% | With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 4h;Heating / reflux; | step 1-A mixture of 184a (2 mmol), NBS (2.2 mmol) and AIBN (100 mg) in CCl4 (20 mL) was heated at reflux for 4 h. The mixture was cooled, filtered and the filtrate was concentrated in vacuo. The residue was purified by SiO2 chromatography to afford 0.395 g (75%) of 184b. |
5.96 g (84%) | With N-Bromosuccinimide; azobisisobutyronitrile; In tetrachloromethane; | A1. Methyl 4bromomethyl-3-chlorobenzoate To a solution of methyl 3-chloro-4-methylbenzoate (5.0 g, 27.1 mmol) in carbon tetrachloride (50 ml) were added NBS (5.8 g, 32.0 mmol) and AIBN (0.442 g, 2.70 mmol). The mixture was stirred at reflux for 18 h. The mixture was allowed to cool to room temperature and then concentrated in vacuo. The residue was purified by flash chromatography on silica (eluant EtOAc:pet. ether 0:100 to 5:95); yield 5.96 g (84%). |
With N-Bromosuccinimide;benzoic peroxyanhydride; In tetrachloromethane; | (2) Preparation of methyl 4-bromomethyl-3-chlorobenzoate Methyl 4-methyl-3-chlorobenzoate (4.5 g, 0.024 mol) was dissolved in carbon tetrachloride (100 ml), and thereto were added N-bromosuccinimide (4.8 g, 0.026 mol) and a catalytic amount of perbenzoic anhydride. The mixture was heated and refluxed under nitrogen atmosphere for 2 hours, allowed to cool, and the precipitate was separated by filtration. The filtrate was concentrated, and separated and purified by using a silica-gel column chromatography (ethyl acetate:n-hexane=1:20) to give the title compound (4.7 g, 0.018 mol) (yield 75%). NMR (CDCl3) delta: 8.04 (s, 1H), 7.91 (bd, J=8.13Hz, 1H), 7.50 (d, J=7.92Hz, 1H), 4.58 (s, 2H), 3.92 (s, 3H) | |
5.96 g (84%) | With N-Bromosuccinimide; azobisisobutyronitrile; In tetrachloromethane; | A1. Methyl 4-bromomethyl-3-chlorobenzoate To a solution of methyl 3-chloro-4-methylbenzoate (5.0 g, 27.1 mmol) in carbon tetrachloride (50 ml) were added NBS (5.8 g, 32.0 mmol) and AIBN (0.442 g, 2.70 mmol). The mixture was stirred at reflux for 18 h. The mixture was allowed to cool to room temperature and then concentrated in vacuo. The residue was purified by flash chromatography on silica (eluant EtOAc:pet. ether 0:100 to 5:95); yield 5.96 g (84%). |
With N-Bromosuccinimide;dibenzoyl peroxide; In tetrachloromethane; for 6h;Reflux; | (2-Chloro-4-(methoxycarbonyl)benzyl)triphenylphosphonium bromideMethyl 3-chloro-4-methylbenzoate (2.20 g, 11.96 mmol) was dissolved in carbon tetrachloride (30 mL) and N-bromosuccinimide (2.10 g, 11.80 mmol) was added followed by a catalytic amount of benzoyl peroxide (25 mg). The reaction mixture was refluxed for 6h. (ca. 90% conversion). After cooling to room temperature, a precipitate was filtered. The filtrate was concentrated to give crude brominated intermediate (3.20 g), which was used for the next step without further purification. | |
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 6h;Reflux; | Methyl 3-chloro-4-methylbenzoate (2.20 g, 11.96 mmol) was dissolved in carbon tetrachloride (30 mL) and N-bromosuccinimide (2.10 g, 11.80 mmol) was added followed by a catalytic amount of benzoyl peroxide (25 mg). The reaction mixture was refluxed for 6 h. (ca. 90% conversion). After cooling to room temperature, a precipitate was filtered. The filtrate was concentrated to give crude brominated intermediate (3.20 g), which was used for the next step without further purification. | |
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; at 80℃; | Methyl 3-chloro-4-methylbenzoate (0.30 mL, 2.0 mmol) was dissolved in carbon tetrachloride (5 mL), N-bromosuccinimide (0.39 g, 2.2 mmol) and benzoyl peroxide (48 mg, 0.20 mmol) were added, and the mixture was stirred at 80 C. overnight. The reaction mixture was filtered and concentrated under reduced pressure, 8 mol/L ammonia-methanol solution was added to the obtained residue, and the mixture was stirred at room temperature for 90 min. The reaction mixture was concentrated under reduced pressure, and the obtained residue was dissolved in dichloromethane (5 mL). A-1 (0.36 g, 1.2 mmol), WSC hydrochloride (0.29 g, 1.5 mmol) and HOAt (0.16 g, 1.2 mmol) were added, and the mixture was stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure, and the obtained residue was purified by reversed-phase high performance liquid chromatography (water-acetonitrile, each containing 0.1% trifluoroacetic acid) to give the title compound (0.40 g, 0.84 mmol, 42%). | |
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; at 100℃; for 15h; | To a solution of methyl 3-chloro-4-methyl-benzoate (22.5 g, 121 mmol) and 2,2- azobisisobutyronitrile (2.00 g, 12.2 mmol) in carbon tetrachloride (300 mL) was added 1- bromopyrrolidine-2,5-dione (23.8 g, 134 mmol) portion wise. The mixture was heated to 100 C and stirred at 100 C for 15 hours. On completion, the mixture was concentrated in vacuo to give a solid. The solid was washed with water (200 mL) and extracted with DCM (2 X 150 mL). The combined organic layer was dried over anhydrous sodium sulfate, filtered and concentrated in vacuum to give a residue. The residue was purified with silica gel chromatograph (petroleum ether: ethyl acetate = 100: 1) to give the title compound. NMR (400MHz, CDCh) delta = 7.99 (d, J = 1.5 Hz, 1H), 7.84 (dd, 7= 1.6, 8.0 Hz, 1H), 7.45 (d, J= 8.0 Hz, 1H), 4.53 (s, 2H), 3.86 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; at 20℃; | Chloro-trimethyl-silane (6.0 mL, 46.9 mmol) was added to a stirring solution of 3-chloro- 4-methyl-benzoic acid (2.0 g, 11.7 mmol) in methanol (40 mL). After stirring at RT overnight the solvent was removed in vacuo to give the title compound, which was used in the following step without further purification. GC/MS (m/z): 184 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With N-Bromosuccinimide;dibenzoyl peroxide; In tetrachloromethane; at 80℃; | After stirring a suspension of 3-chloro-4-methyl-benzoic acid methyl ester (1.04 g, 5.61 mmol), l-bromo-pyrtauolidine-2,5-dione (3.26 g, 15.7 mmol) and benzoyl peroxide (100.2 mg, 0.88 mmol) in tetrachloromethane (68 mL) at 800C overnight the mixture was concentrated in vacuo and the residue was partitioned between EA (300 mL) and water (200 mL). The organic layer was washed with sat. NaHCtheta3 solution (1 x 200 mL), water (1 x 200 mL) and sat. NaCl solution (1 x 200 mL). The organic layer was dried over Na2SO4, filtered and <n="99"/>concentrated in vacuo. The residue, a mix of 4-bromomethyl-3-chloro-benzoic acid methyl ester and 4-dibromomethyl-3-chloro-benzoic acid methyl ester, was used in the following step without further purification. The residue (1.48 g, 5.61 mmol) was dissolved in acetone (45 mL) and water (9 mL) and AgNO3 (3.22 g, 16.3 mmol) were added. The flask was covered with aluminum foil to avoid decomposition of the AgNU3. The mixture was stirred at RT overnight. After filtration of the mixture and evaporation of the solvent, the residue was partitioned between EA (700 mL) and sat. NaHCC>3 solution (350 mL). The organic layer was washed with water (1 x 350 mL) and sat. NaCl solution (1 x 350 mL), dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (elution with n-hexane/EA 9:1) to give the title compound. GC/MS (m/z): 198 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With sulfuric acid; at 60℃; for 48h; | Concentrated sulfuric acid (4.00 mL, 73.3 mmol) was added to a solution of 3-chloro-4- methylbenzoic acid (1, 25.0 g, 147 mmol) in methanol (200 mL) and the reaction mix- ture was allowed to stir at 60 C for 2 days. The solution was cooled to room temperature, sodium hydrogencarbonate (6.80 g, 80.0 mmol) was added, and the mixture was evaporated under reduced pressure. The residue was partitioned between ethyl acetate (300 mL) and water (250 mL). The organic layer was separated; washed with 0.5 M aqueous solution of sodium hydroxide (2 x 250 mL), 0.5 M aqueous solution of hydro- chloric acid (200 mL) and brine (150 mL); dried over anhydrous sodium sulfate and evaporated in vacuo to give methyl 3-chloro-4-methylbenzoate (2) as orange oil. Yield : 27.0 g (98%). RF (Si02, dichlormethane/methanol 95: 5) : 0.80. JH NMR spectrum (300 MHz, CDCI3, deltaEta) : 8.00 (d, J = 1.65 Hz, 1 H); 7.80 (dd, J = 7.9 and 1.5 Hz, 1 H); 7.28 (d, J = 8.1 Hz, 1 H); 3.90 (s, 3 H); 2.42 (s, 3 H). |
96% | With thionyl chloride; at 0 - 20℃; for 120h; | To a solution of3- chloro-4-methylbenzoic acid (20 g, 117 mmol) in MeOH (200 mL) was added drop wise thionyl chloride (25.6 mL, 352 mmol) at 0C with stirring. The mixture was stirred at room temperature for 5 days. The reaction was concentrated. The residue was dissolved in EA (500 mL), washed with 10% Na2C03 (250 mLx2), water (250 mL) and brine (250 mL), dried over Na2S04, filtered and concentrated to afford product as a yellow solid (20. 8 g, 96%). |
With thionyl chloride; at 100℃; for 16h; | To a solution of <strong>[5162-82-3]3-chloro-4-methyl-benzoic acid</strong> (20.0 g, 117 mmol) in methanol (200 mL) was added thionyl chloride (65.6 g, 551 mmol). The mixture was heated to 100 C and stirred at 100 C for 16 hours. On completion, the mixture was concentrated in vacuo to give a residue. The residue was purified with silica gel chromatography (petroleum ethenethyl acetate = 80: 1) to give the title compound. 1H NMR (400MHz, CDCh) delta = 8.01 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.30 (d, J= 8.0 Hz, 1H), 3.91 (s, 3H), 2.43 (s, 3H). |