There will be a HazMat fee per item when shipping a dangerous goods. The HazMat fee will be charged to your UPS/DHL/FedEx collect account or added to the invoice unless the package is shipped via Ground service. Ship by air in Excepted Quantity (each bottle), which is up to 1g/1mL for class 6.1 packing group I or II, and up to 25g/25ml for all other HazMat items.
Type
HazMat fee for 500 gram (Estimated)
Excepted Quantity
USD 0.00
Limited Quantity
USD 15-60
Inaccessible (Haz class 6.1), Domestic
USD 80+
Inaccessible (Haz class 6.1), International
USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic
USD 100+
Accessible (Haz class 3, 4, 5 or 8), International
USD 200+
Structure of 452-77-7 * Storage: {[proInfo.prStorage]}
* 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.
Preparation of 3-fluoro-4-methylphenol: 3-Fluoro-4-methylaniline (5g, 39.95 lmmol) was dissolved in 10percent sulfuric acid aqueous solution (100ml). Thereafter, the temperature was lowered to O°C. thereto sodium nitrate (5.5g, 79.902mmol) was added, and the reaction mixture was stirred at same temperature for 30 minutes. Then the reaction mixture was stirred at 500C for 30 minutes, and the last time, stirred at 8O°C for 5 hours. Ice water was added to quench the reaction, and aqueous layer was extracted with ethyl acetate. Combined organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography (n-hexane:ethyl acetate = 8:1) to give 2.26g (yield: 44.8percent, colorless oil) of the target compound.1H NMR(400MHz, CDCl3): 6.98(t, J=8.6Hz, IH), 6.52(m, 2H), 5.82(br, IH),2.12(s, 3H).
Reference：
[1] Patent: WO2007/8037, 2007, A1, . Location in patent: Page/Page column 34-35
[2] Journal of the Chemical Society, 1949, p. Spl. 113
[3] Journal of the American Chemical Society, 1950, vol. 72, p. 1806
2
[ 452-77-7 ]
[ 202865-78-9 ]
Yield
Reaction Conditions
Operation in experiment
100%
With bromine; potassium carbonate In dichloromethane at -15℃; for 1 h;
Example 28; Preparation of Intermediate Compound 28G; 28G; Step A - Synthesis of Compound 9B; 28A 28B; A mixture of compound 28A (6.00 g, 47.9 mmol) and anhydrous potassium carbonate (6.70 g, 48.5 mmol) in anhydrous dichloromethane (130 mL) was cooled to -15 0C in a salt-ice bath and then added dropwise to a solution of bromine (7.70 g, 48.2 mmol) in anhydrous dichloromethane (80 mL). After addition was complete, the reaction was allowed to stir at -15 0C for 1 hour. Ice water (100 mL) was added to the reaction mixture and the aqueous layer was extracted with dichloromethane (2 x 100 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo to provide compound 28B (11.0 g, quant.), which was used without further purification.
100%
With bromine; potassium carbonate In dichloromethane at -15℃; for 1 h;
Example 9; Preparation of Intermediate Compound 9G; 9G; Step A - Synthesis of Compound 9B; A mixture of compound 9A (6.00 g, 47.9 mmol) and anhydrous potassium carbonate (6.70 g, 48.5 mmol) in anhydrous dichloromethane (130 mL) was cooled to -15 0C in a salt-ice bath and then added dropwise to a solution of bromine (7.70 g, 48.2 mmol) in anhydrous dichloromethane (80 mL). After addition was complete, the reaction was allowed to stir at -15 0C for 1 hour. Ice water (100 mL) was added to the reaction mixture and the aqueous layer was extracted with dichloromethane (2 x 100 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo to provide compound 9B (11.0 g, quant.), which was used without further purification.
100%
With bromine; potassium carbonate In dichloromethane at -15℃; for 1 h;
Example 28; Preparation of Intermediate Compound 28G <n="200"/>; 28G; Step A - Synthesis of Compound 28B; 28A 28B; A mixture of compound 28 A (6.00 g, 47.9 mmol) and anhydrous potassium carbonate (6.70 g, 48.5 mmol) in anhydrous dichloromethane (130 mL) was cooled to -15 0C in a salt-ice bath and then added dropwise to a solution of bromine (7.70 g, 48.2 mmol) in anhydrous dichloromethane (80 mL). After addition was complete, the reaction was allowed to stir at -15 0C for 1 hour. Ice water (100 mL) was added to the reaction mixture and the aqueous layer was extracted with dichloromethane (2 x 100 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo to provide compound 28B (11.0 g, quant.), which was used without further purification.
100%
With bromine In dichloromethane at -15℃; for 1 h; Cooling with salt-ice
A mixture of compound SA (6,00 g, 47.9 mrnol) and anhydrous potassium carbonate (6.70 g, 48.5 mmoi) in anhydrous dichloromethane (130 mL) was cooled to -15 0C in a salt-ice bath and then added dropwise to a solution of bromine (7.70 g, 48.2 mmol) in anhydrous dichloromethane (80 mL). After addition was complete, the reaction was allowed to stir at -15 0C for 1 hour. Ice water (100 mL) was added to the reaction mixture and the aqueous layer was extracted with dichloromethane (2 x 100 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo to provide compound SB (1 1.0 g. quant. ). which was used without further purification.
100%
With bromine; potassium carbonate In dichloromethane at -15℃; for 1 h;
Example 9; Preparation of Intermediate Compound AA7; Step A - Synthesis of Compound AA2; A mixture of compound AAl (6.00 g, 47.9 mmol) and anhydrous potassium carbonate (6.70 g, 48.5 mmol) in anhydrous dichloromethane (130 mL) was cooled to -15 0C in a salt-ice bath and then added dropwise to a solution of bromine (7.70 g, 48.2 mmol) in anhydrous dichloromethane (80 mL). After addition was complete, the reaction was allowed to stir at -15 0C for 1 hour. Ice water (100 mL) was added to the reaction mixture and the aqueous layer was extracted with dichloromethane (2 x 100 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo to provide compound AA2 (11.0 g, quant.), which was used without further purification.
100%
With bromine; potassium carbonate In dichloromethane at -15℃; for 1 h;
Example 19; Preparation of Intermediate Compound AA7; Step A - Synthesis of Compound AA2; A mixture of compound AAl (6.00 g, 47.9 mmol) and anhydrous potassium carbonate (6.70 g, 48.5 mmol) in anhydrous dichloromethane (130 mL) was cooled to -15 0C in a salt-ice bath and then added dropwise to a solution of bromine (7.70 g, 48.2 mmol) in anhydrous dichloromethane (80 mL). After addition was complete, the reaction was allowed to stir at -15 0C for 1 hour. Ice water (100 mL) was added to the reaction mixture and the aqueous layer was extracted with dichloromethane (2 x 100 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo to provide compound AA2 (11.0 g, quant.), which was used without further purification.
100%
With bromine; potassium carbonate In dichloromethane at -15℃;
A mixture of compound AA1 (6.00 g, 47.9 mmol) and anhydrous potassium carbonate (6.70 g, 48.5 mmol) in anhydrous dichloromethane (130 mL) was cooled to -15° C. in a salt-ice bath and then added dropwise to a solution of bromine (7.70 g, 48.2 mmol) in anhydrous dichloromethane (80 mL). After addition was complete, the reaction was allowed to stir at -15° C. for 1 hour. Ice water (100 mL) was added to the reaction mixture and the aqueous layer was extracted with dichloromethane (2.x.100 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo to provide compound AA2 (11.0 g, quant.), which was used without further purification.
33%
With bromine; potassium carbonate In dichloromethane at -15℃; for 1 h;
To a suspension of 3-fluoro-4-methylaniline (6.0 g, 48mmol) and K2C03 (6.6 g, 48 mmol) in DCM (80 mL) at -15 °C was added Br2 (2.4 mL, 48mmol) in DCM (20 mL) slowly. The reaction mixture was stirred at -15 °C for 1 h. Themixture was then quenched with ice water (30 mL), diluted with water (80 mL), andextracted with DCM (3 x 50 mL), dried and concentrated. The residue was purified via silica gel chromatography (0 - 10 percent EtOAc in petroleum ether) to give the title compound (3.2 g, 33percent) as a white solid. MS (ES+) C7H7BrFN requires: 203, found: 204 [M+Hf’
Reference：
[1] Patent: WO2009/32123, 2009, A2, . Location in patent: Page/Page column 158
[2] Patent: WO2009/32125, 2009, A1, . Location in patent: Page/Page column 98
[3] Patent: WO2009/32124, 2009, A1, . Location in patent: Page/Page column 198-199
[4] Patent: WO2009/152200, 2009, A1, . Location in patent: Page/Page column 65
[5] ACS Medicinal Chemistry Letters, 2014, vol. 5, # 3, p. 244 - 248
[6] Patent: WO2008/82488, 2008, A1, . Location in patent: Page/Page column 153
[7] Patent: WO2008/82484, 2008, A1, . Location in patent: Page/Page column 194-195
[8] Patent: US2010/322901, 2010, A1, . Location in patent: Page/Page column 64
[9] Patent: WO2018/81276, 2018, A1, . Location in patent: Page/Page column 159
[10] Journal of the American Chemical Society, 2016, vol. 138, # 40, p. 13147 - 13150
4-chloro-2-(3-fluoro-4-methylphenyl)isoindoline-1,3-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
With acetic acid; at 110℃; for 4h;
General procedure: The starting materials 1 and 2 were commercially available (Energy Chemical, Shanghai, China).Compound 2 (3.72 mmol) was added to a stirred solution of compound 1 (3.38 mmol) in glacial aceticacid (10 mL). The reaction mixture was then stirred at 110 C for 4 h. After completion of the reaction,the solvent was evaporated, and the residue was purified on a silica gel column chromatography andeluted with ethyl acetate/petroleum ether (bp 60-90 C) (1:3, v/v) to give compounds 3.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
HazMat Fee +
For Research Only
120K+ Compounds
Competitive Price
1-2 Day Shipping
