3,6-dibroMo-1,2-BenzenediaMine

In a flask, Was added 4, 7-dibromobenzothiadiazole (18.6g, 0.1mol), Benzil (21g, 0.1mol) and acetic acid (200ml), The reaction was heated to 90 degrees for 5 hours.cool down, filter, The filter cake was recrystallized from ethanol, To give the product 28g, Yield 78percent.In three 100mL bottle, Was added 4, 7-dibromo-benzothiadiazole (20g, 69mmol) and ethanol (500mL), Under ice-cooling, Sodium borohydride (11.4g, 300mmol), Stirred at room temperature 20h.Spin dry solvent, 100mL of water was added, Ethyl acetate three times, Dried over anhydrous sodium sulfate, concentrate, To give the product 17.2g, 95percent yield.In two 250mL flask, followed by adding ethanol 150ml, 2, 5- dibromo benzothiadiazole (5. 88g, 20mmol), the flask was placed in an ice-water bath, sodium borohydride was slowly added repeatedly (1. 52g, 40mmol after), 0 ° C reaction lOmin, room temperature, the reaction 3h, the reaction was completed. After rotary evaporation to dryness in vacuo purified by column chromatography, petroleum ether: dichloromethane = 1: 1 to giveOff-white product 5. 05g (95percent yield).4, 7-Dibromo-2, 1, 3-benzothiadiazole (2.0 g, 6.8 mmol) was added to a 250 ml three-necked flask, Ethanol (60 mL) was added sodium borohydride (2.58 g, 68 mmol) at 0 & lt; 0 & gt;After stirring for some time, Charge and discharge three times, in the argon gas for the protection of gas at room temperature for 6h, stop the reaction, After cooling to room temperature, extracted with dichloromethane, the organic phase washed several times, Until the water layer is clear, the organic phase is collected, The solvent was removed by distillation under reduced pressure, To give the beige solid compound 2 (1.65 g, yield 91.1percent).2.94 g of compound 2 (10 mmol), 150 mL of ethanol and 50 mL of THF were added to a 250 mL round-bottom flask and stirred for 10 minutes. 1.51 g of Sodium borohydride (10 mmol) was then added and heated to reflux. After reacting overnight, the resulting solution was filtered with a filter paper and extracted using ether and saturated saline. The organic layer was then collected. After removal of water of the collected solution by adding dry magnesium sulfate and concentrated by reducing the pressure, 2.4 g of white solid product (compound 3) was obtained, with a yield of 90percent.To a suspension of 4, 7-dibromo-2, 1, 3-benzothiadiazole (1) (5.88 g, 20 mmol) in ethanol (190 mL), sodium borohydride (14 g, 0.37 mol)was added portionwise at 0 °C, then the mixture was stirred for 20 h atroom temperature. After evaporation of the volatile solvent and water(200 mL) was added, the mixture was extracted with dichloromethane(3 × 30 mL). The extract was dried over anhydrous magnesium sulfateand evaporated to remove the solvents under vacuum. 3, 6-Dibromo-1, 2-phenylenediamine (2) (4.7 g) was obtained as a pale yellow solid in87percent yield. The intermediate 2 was directly used in the following procedure.A solution of selenium dioxide (1.17 g, 10.5 mmol) in hot water(22 mL) was added to a solution of 2 (2.7 g, 10 mmol) in refluxingethanol (55 mL). The reaction mixture was heated under reflux for 2 h.After the mixture had been cooled to room temperature, filtration of theyellow precipitates and recrystallization from ethyl acetate gave 4, 7-dibromo-2, 1, 3-benzoselenadiazole (3) (2.8 g) in 82percent yield as goldenyellow needles. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.65 (s, 2H). mp 285–287 °C. 13C NMR (100 MHz, CDCl3) δ (ppm): 157.2, 132.1, 116.5.Anal. Calcd for C6H2Br2N2Se: C, 21.14; H, 0.59; N, 8.22. Found: C, 21.34; H, 0.92; N, 7.98.1000mL 1--neck flask (one neck flask) in 4, 7-di-bromo-benzo-1, 2, 3-thiadiazole (4, 7-dibromo-1, 2, 3-benzothiadiazole) (25g, 85 mmol) , NaBH4 (16g, mmol) and the mixture was placed 500mL of ethanol was stirred at room temperature for 16 hours. When the reaction is complete, remove the solvents by rotary evaporation the drier and extracted with CHCl3. This oil is extractedThe base layer is washed with brine (brine) solution. Thereafter, the dried organic layer was again put on MgSO4 and the solvent removed by evaporation to give a dry objective compound C-1 (19g, 71.4 mmol, 84percent).To a solution of 1 1.8 g (0.04 mol) of 4, 7-dibromo-2, 1 , 3-benzothiadiazole (prepared as described in Macromolecules 2005, 38, 244-253) in 380 ml of ethanol was added 28.0 g (0.74 mol) of sodium borohydride at 0°C. The mixture was warmed to room temperature and the solvent was evaporated. The residue was taken up in diethyl ether and water. The organic phase was separated. After evaporation of the solvent, 8.86 g (83percent) of a bright yelow solid was obtained.To 500ml three-necked flask, 4, 7-dibromo-2, 1, 3-benzothiadiazole 6.00g of (20.4 mmol) was added and after argon gas substitution, ethanol 190ml was added, and cooled with an ice-bath. Here, after the addition of sodium borohydride 13.6g the (360mmol) little by little, and the mixture was stirred at room temperature overnight. Thereafter, ethanol after distilled off under reduced pressure, after dried over anhydrous magnesium sulfate and the organic layer was washed with saturated brine and transferred to a separatory funnel it after dissolving the solid with diethyl ether and water , and the solvent was evaporated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane) to obtain the desired product. The yield 4.50g, 83percent yield.Into a 500 ml three-necked flask equipped with a refluxing condenser, 10.0 g (FW: 293.96; 34 mmole) of 4, 7-dibromobenzothiadiazole and 400 ml of ethanol as the solvent were placed. Under cooling with ice, 24.2 g (FW: 37.83; 640 mmole) of sodium borohydride was added, and the resultant mixture was sufficiently stirred for about 2 hours. When generation of a gas (hydrogen sulfide) was not observed any more, the temperature was adjusted at the room temperature, and the reaction mixture was left standing for one night (about 14 hours). Then, the solvent was completely removed under a reduced pressure, and about 400 ml of water was added to dissolve the residue. The resultant solution was left standing for one night, and the object product was recrystallized (7.17 g). The obtained product was treated by extraction with ethyl ether three times, washed with a saturated aqueous solution of sodium chloride, dried with anhydrous sodium sulfate and filtered. After diethyl ether was removed by distillation, 0.88 g of the object compound (3, 6-dibromo-1, 2-diaminobenzene) was obtained. The overall yield was 82percent.4, 7-Dibromobenzothiadiazole (5.0 g, 17 mmol) was dissolved in 50 mL ethanol (EtOH) in 1 L-round flask. The reaction mixture was cooled down to 0 °C and NaBHAfter inserting the round bottom flask the compound 1-a (5.0 g), 90 mL ethanol, 30 mL THF and then the insert, respectively, are injected to NaBH4 (3.2 g). After that, if the amount of catalyst injected CoCl2-6H2O, there is changed to black solution and the reaction was performed for 3 hours. After ether to complete the reaction, 50 mL and through the H2O 50 mL, if the solvent, extract the product through ether and aqueous NaCl solution is created, a yellow solid, when the recrystallization through the MC and hexane, a yellow solid product 3, to give the 6-dibromobenzene-1, 2-diamine (compound a-2). (Yield: 78percent).(1) Formula (IIa) the compounds of formula [brief records compound (IIa), the cartridge] (3.50 g, 11 . 91 mmol) dissolved in 200 ml anhydrous alcohol, under stirring at room temperature slowly adding NaBHSynthesis of 3, 6-dibromobenzene-1, 2-diamine: Dibromobenzo[c][1, 2, 5]thiadiazole (2.29 g, 10 mmol) and sodiumborohydride (5.7 g, 150 mmol) were added to ethanol at 0 °Cand stirred at room temperature for 36 h. The solution wasadded water and ethyl acetate then was separated by separatoryfunnel. The organic layer was dried over MgSO4 then concentrated under reduced pressure and purified by chromatographyon a silica column eluting with petroleum ether/ethyl acetate(5:1, v/v) to afford a yellow solid (1.9 g, 71 percent yield). 1H NMR(400 MHz, CDCl3, ppm) δ-aromatic H, 6.86 (d, 2H), 3.92 (s, 4H); 13C NMR (100 MHz, CDCl3, ppm): 133.73, 123.27, 109.70.4, 7-Dibromo-2, 1, 3-benzothiadiazole (1) (8.82 g, 0.03 mol) was dissolved in ethanol (190 ml), to the suspension was added portionwise sodium borohydride (21 g, 0.55 mol) at 0 °C, and the mixture was stirred for 20 h at room temperature. Then evaporation of the solvent, 200 ml water was added, and the mixture was extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous magnesium sulfate. After evaporation of the solvent, the residue was purified by column chromatography on silica gel using hexane/ethyl acetate (25:1) as eluent to afford 3, 6-dibromo-1, 2-phenylenediamine (5.01 g) as a pale solid in 63percent yield. 3 (1 g, 3.40 mmol) was dispersed in ethanol (33 mL) in a 100 mLround-bottomed flask. Sodium borohydride (2.4 g, 63.4 mmol) was added portionwise at 0 °C. The mixture was stirred at room temperature or 20 h. After evaporating the solvent under vacuum, the solid product was dissolved in ether. The ether solution was washed with water several times, dried on sodium sulfate, and was finally removed by evaporation. The product was dried in vacuo. Yield 0.3 g (33percent). EXAMPLE 28 The compound (1-b)5. 56g to ethanol (wako pure chemical industries (strain) made) 180 ml in addition, in a nitrogen atmosphere 5 °C NaBH To have a mechanical stir, Thermometer 5L reaction bottle into N220min, 72 g of 4, 7-dibromobenzo [1, 2, 5] thiadiazole, 720 ml of THF, Ethanol 2160 ml While stirring, NaBH was added to 49.3 g, CoCl2 · 6H2O 0.6g, heated to reflux (67 ) after 2h reaction added NaBH44.7g, After 4 h reaction, add NaBH44.6g, 7h after the start every 1h sampling tracking reaction, When the content of 4, 7-dibromobenzo [1, 2, 5] thiadiazole content of LC 60percent to stop the reaction (see Figure 3, Raw materials 4, 7-dibromobenzo [1, 2, 5] thiadiazole content LC = 13.5047percent, the main content of LC = 64.5831percent); reaction equation is as follows: The reaction solution was spontaneously reduced to room temperature (10 ° C), and the reaction solution was filtered through a silica gel funnel, And rinse with 200mlTHF, The filtrate was concentrated (-0.09 MPa, 45 ° C) to no liquid distillate, A solution of 140 g of a tan solid was added with 720 ml of ethyl acetate and stirred to dissolve.Add 1L water for 30min, The aqueous phase was added to 360 ml of ethyl acetate, The organic phases were combined, washed with water until neutral, and the organic phase was added to 100 g of anhydrous magnesium sulfate for 2 h, Filtration, filtrate concentration (-0.09MPa, 45 )To no liquid distillation to produce 61g of brown solid is high purity 3, 6-dibromobenzene-1, 2-diamine.Method 2

Molecular Weight:265.93
XLogP3:1.9
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:2
Exact Mass:265.88772
Monoisotopic Mass:263.88977
Topological Polar Surface Area:52
Heavy Atom Count:10
Complexity:106
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes