4-broMo-1,2-bis(broMoMethyl)benzene

To a solution of 11 (103 mg, 0.474 mM) in Et2O (3 mL) was slowly added a solution of PBr3 (0.16 mL, 1.66 mM) in Et2O (0.25 mL) at 0 °C. The whole was refluxed for 7 h, poured to ice (ca 30 mL), andextracted with Et2O (20 mL × 3). The organic solutions were washed with brine (10 mL), dried, andevaporated. Purification of the residue by column chromatography (SiO2, hexane) gave 12 (154 mg, 95percent) as colorless plates, mp 42-44 °C (lit [20]. mp 40-44 °C).After dissolving Compound 3 (5.2 g, 23.9 mmol) in methylene chloride (50 milliliter), followed by adding N-bromosuccinimide (12.8 g, 71.7 mmol) at room temperature, and then the resultant solution was stirred for 6 hours. Water (200 milliliter) was poured in the resultant reaction solution, and the deposited solid was washed by ethanol, and as a result, Compound 4 was obtained. Product Amount: 6.9 g, Yield: 84 percent4-bromo-l, 2-bis(bromomethyl)benzene (Q22). To a 1000 mL round bottom flask was added 4-brmo-oe-xylene <21) (0.0811 mol, 15.0Og), NBS (0.0426 mol, 7.580 g), 2, 2 -azobisisobutyronitrile (0.00405 mol, 0.6650 g) and 500 mL of CClStep A : 4-bromo-l, 2-bis(bromomethyl)benzene A solution of 4-bromo-l, 2-dimethylbenzene (2.0 g, 10.81 mmol) in carbon tetrachloride (70 mL) in a 250 mL round bottom flask was stirred at room temperature until all solids were dissolved. N-bromosuccinimide (4.81 g, 27.0 mmol) and 2, 2'- azobis(2-methylpropionitrile) (0.044 g, 0.270 mmol) were added and mixture was heated to 70°C for 1 h. After cooling to room temperature, the mixture was filtered through celite bed. Celite bed was rinsed with carbon tetrachloride (3x50 mL). Combined filtrate was dried (sodium sulphate), filtered and concentrated under reduced pressure. The crude material was purified by combi- flash column chromatography (Column: 120 gm Red- Sep; eluent: hexane). The fractions were collected and concentrated under reduced pressure to yield 4-bromo-l, 2-bis(bromomethyl) benzene (2.1 g, 56.7percent yield) as colorless gummy oil. 1H NMR (400 MHz, CDC1To a solution of 11 (103 mg, 0.474 mM) in Et2O (3 mL) was slowly added a solution of PBr3 (0.16 mL, 1.66 mM) in Et2O (0.25 mL) at 0 °C. The whole was refluxed for 7 h, poured to ice (ca 30 mL), andextracted with Et2O (20 mL × 3). The organic solutions were washed with brine (10 mL), dried, andevaporated. Purification of the residue by column chromatography (SiO2, hexane) gave 12 (154 mg, 95percent) as colorless plates, mp 42-44 °C (lit [20]. mp 40-44 °C).After dissolving Compound 3 (5.2 g, 23.9 mmol) in methylene chloride (50 milliliter), followed by adding N-bromosuccinimide (12.8 g, 71.7 mmol) at room temperature, and then the resultant solution was stirred for 6 hours. Water (200 milliliter) was poured in the resultant reaction solution, and the deposited solid was washed by ethanol, and as a result, Compound 4 was obtained. Product Amount: 6.9 g, Yield: 84 percent4-bromo-l, 2-bis(bromomethyl)benzene (Q22). To a 1000 mL round bottom flask was added 4-brmo-oe-xylene <21) (0.0811 mol, 15.0Og), NBS (0.0426 mol, 7.580 g), 2, 2 -azobisisobutyronitrile (0.00405 mol, 0.6650 g) and 500 mL of CClStep A : 4-bromo-l, 2-bis(bromomethyl)benzene A solution of 4-bromo-l, 2-dimethylbenzene (2.0 g, 10.81 mmol) in carbon tetrachloride (70 mL) in a 250 mL round bottom flask was stirred at room temperature until all solids were dissolved. N-bromosuccinimide (4.81 g, 27.0 mmol) and 2, 2'- azobis(2-methylpropionitrile) (0.044 g, 0.270 mmol) were added and mixture was heated to 70°C for 1 h. After cooling to room temperature, the mixture was filtered through celite bed. Celite bed was rinsed with carbon tetrachloride (3x50 mL). Combined filtrate was dried (sodium sulphate), filtered and concentrated under reduced pressure. The crude material was purified by combi- flash column chromatography (Column: 120 gm Red- Sep; eluent: hexane). The fractions were collected and concentrated under reduced pressure to yield 4-bromo-l, 2-bis(bromomethyl) benzene (2.1 g, 56.7percent yield) as colorless gummy oil. 1H NMR (400 MHz, CDC11.66 g (10 mmol) of Compound 9 was placed in a round flask, and 20 mL of dimethyl sulfoxide was added to dissolve the solution. A solution of 2 g (50 mmol) of sodium hydroxide in water at a ratio of 50 wtpercent was added and heated to 80 ° C. After 30 minutes, when the reaction solution turned red, 3.77 g (11 mmol) of Compound 10 was added and the mixture was stirred at 80° C for 12 hours. After cooling to room temperature, 20 ml of water was added, extracted with dichloromethane in a separating funnel, and then the solvent was removed by a rotary evaporator. Column chromatography afforded 1.53 g (yield: 44percent) of Compound 11.4-Bromo-l , 2-bis(bromomethyl)benzene (250 mg) and 2-(2-(2-methoxyethoxy)ethoxy)ethanol (263 mg) were dissolved in dioxane (8 mL). Sodium hydride (60percent, 64.2 mg) was added, and the solution was mixed at ambient temperature. After 20 minutes, the solvent was removed under vacuum. The residue was suspended in ethyl acetate (20 mL), washed with brine (5 mL) and dried over anhydrous sodium sulfate. The solution was concentrated and syringe filtered. The remaining solvent was then removed under vacuum, and the material was utilized without further purification. NMR (500 MHz, dimethylsulfoxide-efe) delta ppm 7.57 (d, IH), 7.48 (dd, IH), 7.33 (d, IH), 4.54 (s, 2H), 4.50 (s, 2H), 3.60- 3.55 (m, 8H), 3.53-3.50 (m, 12H), 3.44-3.40 (m, 4H), 3.24-3.23 (m, 6H). MS (ESI) m/z 526.2 (M+H)+.

Molecular Weight:342.85
XLogP3:3.7
Rotatable Bond Count:2
Exact Mass:341.80774
Monoisotopic Mass:339.80979
Heavy Atom Count:11
Complexity:116
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes