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Chemical Structure| 15155-41-6
Chemical Structure| 15155-41-6
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Product Details of [ 15155-41-6 ]

CAS No. :15155-41-6 MDL No. :MFCD00658844
Formula : C6H2Br2N2S Boiling Point : -
Linear Structure Formula :- InChI Key :FEOWHLLJXAECMU-UHFFFAOYSA-N
M.W : 293.97 Pubchem ID :626361
Synonyms :

Calculated chemistry of [ 15155-41-6 ]

Physicochemical Properties

Num. heavy atoms : 11
Num. arom. heavy atoms : 9
Fraction Csp3 : 0.0
Num. rotatable bonds : 0
Num. H-bond acceptors : 2.0
Num. H-bond donors : 0.0
Molar Refractivity : 52.82
TPSA : 54.02 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.84 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.27
Log Po/w (XLOGP3) : 3.17
Log Po/w (WLOGP) : 3.22
Log Po/w (MLOGP) : 2.17
Log Po/w (SILICOS-IT) : 4.04
Consensus Log Po/w : 2.97

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 0.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -4.27
Solubility : 0.016 mg/ml ; 0.0000543 mol/l
Class : Moderately soluble
Log S (Ali) : -3.98
Solubility : 0.0311 mg/ml ; 0.000106 mol/l
Class : Soluble
Log S (SILICOS-IT) : -4.29
Solubility : 0.015 mg/ml ; 0.0000509 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 0.0
Synthetic accessibility : 1.97

Safety of [ 15155-41-6 ]

Signal Word:Danger Class:6.1
Precautionary Statements:P264-P270-P301+P310+P330-P405-P501 UN#:2811
Hazard Statements:H301 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 15155-41-6 ]

* 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.

  • Upstream synthesis route of [ 15155-41-6 ]
  • Downstream synthetic route of [ 15155-41-6 ]

[ 15155-41-6 ] Synthesis Path-Upstream   1~24

  • 1
  • [ 273-13-2 ]
  • [ 15155-41-6 ]
YieldReaction ConditionsOperation in experiment
96% for 6 h; Reflux 10 g (73.4 mmol) of the intermediate and 100 ml of 48percent hydrobromic acid were mixed,35 g (22.3 mmol) of bromine was added dropwise at room temperature and the reaction was heated under reflux for 6 hours,Cooled to room temperature, add 100ml of saturated aqueous sodium bisulfite solution, filter, filter cake and then washed with water, ethanol recrystallization, 20.7g yellow solid, the yield of 96percent.
94% With hydrogen bromide; bromine In water at 100℃; for 6 h; Compound 4 (3g, 22.03mmol) and 100 mL of HBr (48percent) were added toa 500 mL flask. A solution containing Br2 (5 mL, 97.55 mmol) in 50mL of HBr was added dropwise slowly. Then the solution was refluxed at 100 °Cfor 6 h. After the solution was cooled to room temperature, sufficient NaHSO3solution (1M) was added to consume excess Br2. The mixture wasfiltered and washed exhaustively with water. The crude product waschromatographed on silica gel eluting with petroleum ether/dichloromethane (2:1).Further purification was conductedby recrystallization in ethanol to obtain compound 5 as a white needled solid (6.10g,94percent). 1H NMR (500 MHz, CDCl3): δ (ppm) 7.73 (s, 2H).
93% at 120℃; for 15 h; Inert atmosphere 2,1,3-Benzothiadiazole (3g, 22.0mmol) was dissolved in 65mL of HBr (47percent). On the other hand, Br2(3.5mL, 68.3mmol) was diluted with 45mL of HBr. A solution containing Br2was added dropwise to the 2,1,3-benzothiadiazole solution. Then, extra 30mL of HBr was added to the solution and the solution was stirred at 120°C under an argon atmosphere for 15h. Then, the mixture was cooled to room temperature and a sufficient amount of saturated solution of NaHSO3was added to the solution to remove the excess Br2completely. The solution was filtered off and then washed withEt2O. The yellow solid was purified by column chromatography on silica gel using dichloromethane:n-hexane (3:2) as an eluent. Yield: 93percent, FT-IR (KBr pellet, cm1): 3078, 3045, 1574, 1498, 1476, 1310, 1273, 1184, 937, 875, 826, 587, 488cm−1.1H NMR (400MHz, DMSO-d6δ2.48ppm):δ=7.92 (s) ppm.13C NMR [100MHz, DMSO-d6δ40.2ppm (7 peaks)]:δ=162.9, 133.4, 113.7ppm.
92% With hydrogen bromide; bromine In water at 125 - 130℃; Benzothiadiazole (25 g, 184 mmol) was reacted overnight with 20.8 mL bromine (2.2 eq) in 400 mL of 48percent HBr (in water) at 125-130 °C. After cooling the reaction mixture (heavy suspension of reddish-brown solid) was poured into 1 liter of crushed ice and left to stir for 30 minutes. Filtration, washing with water, followed by washing with sodium sulfite solution and water gave 4,7-dibromobenzothiadiazole as brick colored needles, (50.1 g, 92percent, after drying in vacuum oven). This material was used for nitration with fuming nitric acid in trifluoromethanesulfonic acid (TFMSA) as follows: nitric acid (10.0 mL) was added dropwise to TFMSA (150 g) which was cooled below 5 °C. with intensive stirring (white solid formed). 4,7-Dibromobenzothiadiazole (as solid) was added portionwise to the above reaction mixture and, after it became homogenous, the flask was placed in an oil bath and left to stir at 50 °C. for 16-24 hours. The reaction was monitored by13C NMR (110.4, 145.0, and 151.4 ppm). Pouring the solution into 500 mL of ice/water afforded Intermediate A (4,7-dibromo-5,6-dinitrobenzothiadiazole) as a yellowish solid which was thoroughly washed with water and dried in vacuum oven (30.6 g, 94percent).
91.3% at 120℃; for 36 h; Synthesis of dibromobenzo[c][1,2,5]thiadiazole (M1):Bromine was added drop wise over a period of 5 min to avigorously stirred suspension of benzo[c][1,2,5]thiadizole inhydrobromic acid (30 mL) at 120 °C. The reaction was left tostir for 36 h during which a canary yellow precipitate formed.Water (100 mL) was added, the suspension left to stir for 10min, then filtered and washed with a little water. The yellow solid was dried in vacuo for 24 h to give the pure product. (25g, 91.3 percent) 1H NMR (400 MHz, CDCl3, ppm): δ-aromatic H,7.73 (s, 2H)
91% for 2.5 h; Reflux; Inert atmosphere A mixture of 2,1,3-benzothiadiazole (13.6 g, 0.1 mol) in 45percent hydrobromicacid (30 mL) was heated under reflux with stirring while48 g (0.3 mol, 15.3 mL) of bromine was added slowly. The reactionmixture became a suspension of solid in hydrobromic acid and 15 mL ofhydrobromic acid was added, then the mixture was refluxed for another2.5 h. After cooling to room temperature, the precipitate formed andcollected, washed with water, then recrystallized from chloroform togive yellow needle crystals (26.8 g, 91percent). mp 186–188 °C. 1H NMR(400 MHz, CDCl3) δ (ppm): 7.73 (s, 2H). 13C NMR (100 MHz, CDCl3) δ(ppm): 153.34, 132.67, 114.31. Anal. Calcd for C6H2Br2N2S: C, 24.51;H, 0.69; N, 9.53. Found: C, 24.12; H, 0.72; N, 9.66.
90% at 130℃; 1.1
The synthesis of 4,7-dibromo-2,1,3-benzothiadiazole
2,1,3-benzothiadiazole (0.9992 g, 7.34 mmole) was mixed with HBr (2 ml) in a tri-necked flask, and the mixture was refluxed at 130°C in an oil bath.
About 1.5 ml of Br2 was added slowly into the flask through a feeding funnel under vigorous stirring.
Upon formation of a solid, additional amount of HBr (1 ml) was added to help mixing.
The reaction was conducted for about 3 hours, then the oil bath was removed, and the resulted solid was washed with distilled water for several times.
The solid was re-crystallized in MeOH/H2O, and a white powder was obtained (1.942 g, yield: 90percent).
1H NMR (ppm, CDCl3).box.7.70(s, 2H)
13C NMR (ppm, CDCl3).box.113.89, 132.34, 152.94
88.05% at 120℃; for 12 h; Cooling with ice Compound 1c (1.360 g, 9.988 mmol) was dissolved in the solution of HBr (35 mL, 40percent), then a solution of Br2 (1.6 mL, 31.20 mmol) in HBr (35 mL, 40percent) was added dropwise under the ice-water bath. The mixture was stirred for 12 h at 120 °C. After removal of the solvent, the residue was purified by column chromatography on silica (petroleum ether/CH2Cl2 = 7:1 v/v) to give a pink solid (2.580 g) [34] . Yield: 88.05percent. Mp: 184-185 °C. 1H NMR (CDCl3, 400 MHz, TMS) δ: 7.73 (s, 2H).
88% at 135℃; Inert atmosphere Benzo-1,2,5-thiadiazole (5.0 g, 36.7 mmol) was dissolved in 40 mL HBr (47percent) in room temperature. Later, a solution of Br2 (17.6 g, 110 mmol) in 30 mL HBr was added drop wise to reaction mixture. After the addition of Br2, the reaction mixture was heated to 135 °C and refluxed for overnight. Then the mixture was cooled down to room temperature and NaHSO3 solution was added to get rid of excess Br2. The mixture was filtered and orange solid was washed with cold diethyl ether and water several times to obtain 4,7-dibromobenzo[c][1,2,5]thiadiazole (9.53 g, yield 88percent) as a yellow solid. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.66 (s, 2H). 13C NMR (100 MHz, CDCl3) δ (ppm): 152.9, 132.3, 113.9.
87% at 60℃; for 3 h; Reflux To a stirredsuspension of benzo[c][1,2,5]thiadiazole (14; 10 g, 73.4 mmol) in30 mL of hydrobromic acid (48percent), bromine (11.4 mL,222.5 mmol, 3 eq.) was added slowly, while the temperature raised to 60°C.The resulting reaction mixture was heated to reflux for additional 3 h andwas then allowed to cool to room temperature, while a white precipitate wasformed. The mixture was diluted with saturated Na2S2O3-solutionand filtrated. The crude product was washed with water and recrystallized fromethanol to afford 12 as pale yellowneedles (18.5 g, 63 mmol, 87percent). m.p.: 187-188°C. 1H-NMR(250 MHz, CDCl3): δ = 7.70 (s, 2H) ppm. 13C-NMR (63 MHz,CDCl3): δ = 153.06, 132.46, 114.03, 77.16 ppm. MS (EI):m/z = 294 [(M+2)+], 296 [(M+4)+], 292 [M+].EA calc. for C6H2Br2N2S: C, 24.51;H, 0.69; N, 9.53; found: C, 24.71; H, 0.67; N, 9.67.
86% With hydrogen bromide; bromine In waterReflux 13.6 g of benzothiadiazole (100 mmol) (compound 1) and 300 mL of HBr aqueous solution (48percent) were added to a 1,000 mL round-bottom flask and heated to reflux. 15.4 mL of bromine (300 mmol) was then slowly dropped and reacted overnight. After adding sodium thiosulfate aqueous solution to quench the reaction, the resulting solution was filtered. The filtered solid was then washed with acetone. Thus, 25.3 g of light ashen solid product (compound 2) was obtained, with a yield of 86percent.
85% for 6 h; Reflux In a two-neck bottle (1000mL),Product 2 (5.00 g, 36.72 mmol),Hydrogen bromide (47percent, 80 mL) was added and stirred until dissolved.A mixed solution of liquid bromine (17.60 g, 110.16 mmol) and hydrogen bromide (47percent, 50 mL) was slowly added dropwise.Stir under reflux for 6 hours.Cooling and suction filtration, concentration,Purification to obtain a yellow powder of 4,7-dibromobenzo[c][1,2,5]thiadiazole,That is, product 3 (9.10 g, 85percent).
84% for 9 h; Reflux Compound 8 was obtained based on a procedure reported in the literature [51]. A total of 10.0 g (73.43 mmol) of 2,1,3-benzothiadiazole (7) and 150 mL of hydrobromic acid (48percent) were transferred to a 500 mL, two-neck, round-bottom flask. A reflux condenser was coupled to one input, and an additional funnel containing a solution of 35.2 g (220.3 mmol) of bromine in 100 mL of hydrobromic acid (48percent) was coupled to the other. Br2 was added dropwise over a period of three hours under reflux; then, another100 mL of hydrobromic acid (48percent) was added, and the reflux was maintained for a further 6 h. The reaction was accompanied by TLC using a mixture of toluene and ethyl acetate (5:1 v/v) as an eluent. A sodium-bisulfite-saturated solution was added at room temperature and stirred until the excess bromine had been complete consumed. The mixture was vacuum-filtered, and the obtained solid was washed with acetone and ethyl ether, and vacuum dried. A total of 18.2 g of a yellow solid (84percent) was obtained. Melting point:187-188 °C [51]. FTIR (KBr) vmax/cm-1: 3078, 3045, 1634. 1H NMR(CDCl3, δ ppm): 7.71 (s, 2H). NMR of 13C (CDCl3, δ ppm): 152.9,132.3,113.8.
83% for 10 h; Reflux 4,7-Dibromo-2,1,3-benzothiadiazole (2) As analogous to [1], 2,1,3-benzothiadiazole (1, 2 g, 14.69 mol) and 5 mL of HBr (48percent) wereplaced in a 100 mL two-necked round-bottomed flask. A solution of Br2 (1.5 mL, 29.4 mol)in HBr was added slowly through a dropping funnel at 0 °C. After completion of the addition,the mixture was stirred for 4 h at rt followed by reflux for 6 h. The formation of an orangesolid precipitate was observed. The mixture cooled to rt and a sufficient amount of saturatedsolution of NaHSO3 was added to remove excess bromine. The solid product was filtered offand thoroughly washed with DI water followed by diethyl ether. The product was purified byrecrystallization from ethanol. Yield 83percent
81% at 110℃; for 6 h; Then put the 2,1,3-benzothiadiazole (10g) To a round flask equipped with a condenser injecting hydrobromic acid (200mL), heated to 110 °C makes it. After the temperature of 110 °C slowly inject bromine (20mL), and reacted for 6 hours. If fy species when the reaction via the reaction H2O and then there is produced a solid, which after filtering through the semi-H2O, filtered the solid and re-crystallized through the MC and methanol, the 4,7-dibromobenzo [c] [1-white solid product, 2,5] thiadiazole to afford the (compound a-1). (Yield: 81percent).
80% Reflux The mixture of compound 1 (13.6g, 0.1mol) and HBr (40percent, 30mL) are heated to reflux under stirring. When Br2 (48.0g, 0.3mol) is dropwise added, the mixture is turned into suspension subsequently. After HBr (40percent, 15mL) is added, the mixture is stirred under refluxing for 6–8h. By the hot filtration, the residual is washed with distilled water and dried in vacuo. The light yellow solid is obtained in 80percent yield by recrystallizing from CHCl3. Mp=193–194°C. 1H NMR (400MHz, CDCl3) δ 7.74 (s, 2H). 13C NMR (101MHz, DMSO) δ 153 (s), 132 (s), 114 (s). IR (KBr, cm−1): 3078, 3046 (Ar−H), 1655 (C=N), 1587, 1477 (benzene ring). Anal. Calcd. For C6H2N2SBr2: C, 23.62; H, 0.832; N, 9.233. Found: C, 24.490; H, 0.680; N, 9.524.
79.6% for 2.5 h; Reflux Benzo [2,1,3] thiadiazole (8.16g, 60mmol), 40ml hydrobromic acid was added 500ml three-neck flask, was slowly added dropwise bromine (30.72g, 10ml, 192mmol) solution of hydrobromic acid is heated reflux for about 2.5h end.The reaction was cooled to room temperature, the reaction mixture was poured into ice water solution of sodium hydroxide, filtration to give a yellow solid (17.62g, yield 79.6percent).
77% With hydrogen bromide; bromine In water for 4 h; Reflux General Procedure I-DYA mixture of compound I-XVa (10.0 g, 73.4 mmol) in aq. HBr (48percent, 150 mL) was heated to reflux with stirring, while a solution containing Br2 (35.2 g, 220.3 mmol) in aq. HBr (48percent, 100 mL) was added dropwise very slowly. Towards the end of the addition, the mixture became a suspension. To facilitate stirring, aq. HBr (48percent, 50 mL) was added, and the reaction mixture was heated to reflux for 4 hours after completion of the Br2 addition. The mixture was filtered while hot and filtrate was washed with water. The crude product was dried and recrystallized from MeOH to give compound I-XVb as a white needles (16.5 g, yield 77percent).
72.56% for 4 h; Reflux 2,1,3-Benzothiadiazole (1 g, 73.7 mmol) was dissolved in 47percent hydrobromic acid (10 mL) in a 50 mL three-necked round bottomed flask. A solution of bromine (1.14 mL, 22.02 mmol) in 47percent hydrobromic acid (10 mL) was added dropwise into the solution. The mixture was refluxed and stirred for 4 h. Precipitates were isolated by filtration washed with water. The product was dried invacuo. Yield 1.57 g (72.56percent). 1H NMR (300 MHz, CDCl3): d 7.73 (s,2H) ppm. FT-IR (KBr, cm-1): 3077-3046 (C-H), 1870 (C=N), 1479(C=C), 586 (C-Br). Anal. Calcd for (C6H2Br2N2S): C, 24.5; H, 0.69; N,9.53; S, 10.9. Found: C, 24.3; H, 0.70; N, 9.21; S, 11.0.
72% With hydrogen bromide; bromine In water at 110℃; for 1 h; First, 20.0 g (146 mmol) of benzo [2,1,3] thiadiazole and 160 mL of hydrobromic acid (48percent aqueous solution) were placed in a 500 mL three-necked flask.The reaction solution was refluxed at 110 DEG C while dropwise adding 3 mL (446 mmol) of bromine.After completion of the dropwise addition, the mixture was further refluxed at 110 DEG C for 1 hour.After refluxing,The mixture was washed with water,The precipitate was collected by suction filtration. The obtained solid was recrystallized from methanol, and as a result,31.0 g of a light brown powdery solid of 4,7-dibromobenzo [2,1,3] thiadiazole was obtained (yield: 72percent).
29% With hydrogen bromide; bromine In water at 20℃; for 24.3333 h; Heating / reflux (2)
Synthesis of 4,7-dibromobenzothiadiazole
Into a 200 ml three-necked flask, 29.05 g (213 mmole) of benzothiadiazole was placed and dissolved into 42.9 ml of a 47percent aqueous solution of HBr.
To the obtained solution, 32.24 ml of bromine was added dropwise at the room temperature over 20 minutes, and then 21.3 ml of a 47percent aqueous solution of HBr was added.
The resultant mixture was heated under the refluxing condition for 24 hours.
After the resultant mixture was cooled to the room temperature, the solid component was dissolved into 1100 ml of dichloromethane.
To the obtained solution, 400 ml of a saturated aqueous solution of sodium thiosulfate was added, and the obtained mixture was treated by extraction sufficiently in a separation funnel.
The obtained dichloromethane layer was washed three times each with 150 ml of distilled water and dried with anhydrous sodium sulfate.
The dried dichloromethane solution was concentrated to 300 ml, and the recrystallization was conducted by leaving the solution standing at 4°C for 24 hours.
The formed needle crystals were separated by filtration, and 18.29 g (the yield: 29percent) of the object compound (4,7-dibromobenzothiadiazole) was obtained.

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YieldReaction ConditionsOperation in experiment
89% at 120℃; for 16 h; Step 1:
Synthesis of Intermediate V
A mixture of benzothiadiazole (5.00 G, 36.7 mmol), 48percent HBr (50 mL) and bromine (4.1 mL, 80 mmol) was stirred and heated at 120° C. under a reflux condenser for 16 hours.
The hot reaction mixture was poured slowly into a mixture of crushed ice (1 kG) and sodium bicarbonate (0.2 kG) in a 4 L beaker, stirred for 1 hour and extracted with 20percent THF in DCM (2*500 mL).
The extract was dried over magnesium sulfate, and the solvent was removed under reduced pressure.
The residue was triturated with hot ethanol (100 mL) and set aside at room temperature for 2 hours.
The crystals were filtered off and dried to give 4,7-dibromobenzothiadiazole (9.65 G, 89percent yield).
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YieldReaction ConditionsOperation in experiment
95%
Stage #1: at 90℃; for 5 h;
Stage #2: With sodium tetrahydroborate In ethanol at 20℃; for 20 h; Cooling with ice
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.
95% With sodium tetrahydroborate In ethanol at 0 - 20℃; for 3.16 h; 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).
91.1% With sodium tetrahydroborate In ethanol at 0 - 20℃; for 6 h; Inert atmosphere 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).
90% With sodium tetrahydroborate; ethanol In tetrahydrofuranReflux 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.
87% With sodium tetrahydroborate In ethanol at 0 - 20℃; for 20 h; Inert atmosphere 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.
84% With sodium tetrahydroborate In ethanol at 20℃; for 16 h; 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).
83% With sodium tetrahydroborate In ethanol at 0 - 20℃; 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.
83% With sodium tetrahydroborate In ethanol at 20℃; Inert atmosphere; Cooling 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.
82% With sodium tetrahydroborate In ethanol at 0 - 20℃; for 16 h; 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.
80% With sodium tetrahydroborate In ethanol at 0 - 20℃; for 20 h; Inert atmosphere 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 NaBH4 (1.7 g, 0.51 mol) was added to reaction mixture in portions. The reaction was stirred in the ice bath until gas evolution was stopped and then stirred for 20 h in room temperature. After the evaporation of ethanol, extraction was performed with water and diethyl ether. Extraction was carried out once again with brine to obtain faint yellow organic phase. Later, the organic phase was dried over MgSO4, evaporated under reduced pressure and a faint yellow solid, 3,6-dibromobenzene-1,2-diamine (3.5 g, yield 80percent) was obtained. The product is timesensitive, in couple of days, it may disintegrate. 1H NMR(400 MHz, CDCl3) δ (ppm): 6.78 (s, 2H), 3.82 (s, 4H). 13C NMR (100 MHz, CDCl3) δ (ppm): 133.5, 123.2, 109.5.
78% With sodium tetrahydroborate; cobalt(II) chloride hexahydrate In tetrahydrofuran; ethanol for 3 h; After 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).
77.1% With sodium tetrahydroborate In ethanol at 20℃; for 3 h; (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 NaBH4(11.0 G, 291.0 mmol), the reaction at room temperature 3 h. Adding water steaming and remove the anhydrous ethanol (100 ml) and methylene chloride (100 ml), the standing liquid, organic phase dried with anhydrous sodium sulfate, rotary evaporated to remove the dichloromethane shall sulphureum sheet-like crystal [compound IIIa] 2.53 g, yield 77.1percent.
71% With sodium tetrahydroborate In ethanol at 0 - 20℃; for 36 h; Synthesis 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.
63% With sodium tetrahydroborate In ethanol at 0 - 20℃; 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. 1H NMR (CDCl3, 500 MHz) δ (ppm): 6.80(s,2H), 3.60(s,4H). 13C NMR (CDCl3, 500 MHz) δ (ppm): 133.85, 123.08, 109.66. GC–MS: m/z = 263.
33% With sodium tetrahydroborate In ethanol at 0 - 20℃; for 20 h; 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). 1H NMR (300 MHz, CDCl3): d 7.27 (2H), 4.0 (4H) ppm. FT-IR (KBr, cm1): 3385 (NH2), 3079 (C-H), 1648 (N-H), 1452 (C=C),1240 (C=N). Anal. Calcd for (C6H6Br2N2): C, 27.1; H, 2.27; N, 10.53.Found: C, 27.5; H, 2.32; N, 10.4.
79.5% With sodium tetrahydroborate In ethanol; water EXAMPLE 28
Preparation of 2-Amino-3,6-dibromophenylamine
A mixture of 4,7-dibromo-2,1,3-benzothiadiazole (synthesised according to as described in K. Pilgram, J. Heterocycl. Chem., 7 (1970), 629) (16.0 g, 54.4 mmol) and NaBH4 (38.1 g, 1.0 mol) in 500 ml ethanol was stirred at room temperature for 30 hours.
The solvent was evaporated and the residue mixed with 500 ml water.
The obtained mixture was extracted into diethyl ether (5*150 ml).
The combined extracts were washed with brine (2*100 ml) and dried over anhydrous Na2SO4.
Evaporation of the solvent and drying under reduced pressure afforded 11.5 g (79.5percent) of the product.
2.37 g With sodium tetrahydroborate In ethanol at 5 - 20℃; for 48 h; Inert atmosphere 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 4 ((strain) made wako pure chemical industries) 13. 2g is added, and stirring at room temperature between 2. The solvent is then added to 500 ml distilled water, filtering a solid, washed with 1000 ml water. The obtained solid dissolved in diethyl ether 200 ml, 300 ml after washing with water, and dried with magnesium sulfate. By distilling, compd. (1-c) to 2. 37g obtained.
61 g With sodium tetrahydroborate; cobalt(II) chloride hexahydrate In tetrahydrofuran; ethanol at 67℃; for 13 h; Inert atmosphere 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.

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  • 10
  • [ 273-13-2 ]
  • [ 15155-41-6 ]
  • [ 69272-50-0 ]
YieldReaction ConditionsOperation in experiment
70% With acetic acid; zinc In water Method 2
Synthesis of 3,6-dibromo-1,2-phenylenediamine
4,7-dibromobenzo[1,2,5]thiadiazole (6.0 g, 20.3 mmol), prepared according to WO 00/55927 PCT/GB00/00911 by bromination of benzo[1,2,5]thiadiazole, was placed in a 200-mL flask under a nitrogen atmosphere.
Zinc dust (13.2 g, 203 mmol) and a mixture of acetic acid/water (35 mL/35 mL) were added.
The flask was loosely capped with an inverted 1-neck flask.
The reaction mixture was heated to 70° C. for 1 hr at which time reaction was complete as determined by TLC.
The mixture was then cooled to room temperature and filtered.
The solid was extracted with diethylether (3*100 mL).
The extract was washed with saturated aqueous sodium bicarbonate and dried over MgSO4.
The solution was filtered and evaporated to dryness using a rotary evaporator.
The solid was purified by chromatography on a silica gel column, using dichloromethane as eluent.
The appropriate fractions were combined and the solvent was removed under reducing pressure.
A light yellow product was obtained. Yield: 70percent.
Reference: [1] Patent: US2006/83945, 2006, A1,
  • 11
  • [ 15155-41-6 ]
  • [ 165617-59-4 ]
Reference: [1] Journal of the American Chemical Society, 2005, vol. 127, # 14, p. 5186 - 5195
[2] RSC Advances, 2014, vol. 4, # 85, p. 44902 - 44910
[3] Patent: JP2018/111679, 2018, A,
  • 12
  • [ 6165-68-0 ]
  • [ 15155-41-6 ]
  • [ 165190-76-1 ]
YieldReaction ConditionsOperation in experiment
95% With O4P(3-)*3K(1+)*5H2O; tri(1-adamantyl)phosphine; {2-[((acetyl-κO)amino)phenyl-κC](tri-1-adamantylphosphine)palladium}(p-toluenesulfonate) In tetrahydrofuran at 20℃; for 1 h; To a mixture of 4,7-dibromobenzo[cJ{1,2,5]thiadiazole (147 mg, 0.50 mmol, 1 equiv),thiophen-2-ylboronic acid (192 mg, 1.50 mmol, 3 equiv), and K3P045H20 (0.90 g, 3.0 mmol, 6 equiv) was added THF (900 jiL) then a THF stock solution of 3 and PAd3 (100 iL, 0.25 jtmol ofPd/PAds). The mixture was stirred at room temperature for 1 h. The reaction mixture was diluted with ethyl acetate then extracted with water. The combine organic layers were evaporated andthe crude product was purified by flash chromatography. After drying, 143 mg (95percent) of 40 was obtained as an orange solid. NMR spectroscopic data agreed with literature values.
84.3% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In toluene at 75℃; Inert atmosphere I) 4,7-dibromo-2,1,3-benzothiadiazole (2.01 g, 6.84 mmol), 2-thiopheneBoric acid (1.42 g, 11 mmol) was dissolved in 20 mL of toluene and 15 mL of 2M potassium carbonate solution was injected.(Tetraphenylphosphine) palladium (150 mg, 0.14 mmol) was added and heated to 75 ° C for 2-8 h. Natural cold to room temperature, dichloromethaneHexane extraction, drying, concentration and column chromatography to obtain red crystals of 4,7-dithiophene-2,1,3-benzothiadiazole 1.73 g, yield84.3percent.
80%
Stage #1: With potassium phosphate In 1,4-dioxane; water at 80℃; for 7 h;
Stage #2: With sodium cyanide In 1,3-dioxane; water
Preparation of bis-4,7-(thien-2-yl)-2,1,3-benzothiadiazole
13.5 g (11.7 mmol, 0.065 eq.) of Pd(PPh3)4 were added to a nitrogen-saturated mixture consisting of 52.92 g (180 mmol) of 1',4'-dibromo-2,1,3-benzothiadiazole, 60 g (468.9 mmol, 2.6 eq.) of thiophene-2-boronic acid, 149 g (702 mmol, 3.9 eq.) of K3PO4, 1 l of dioxane and 1 l of water and the suspension was heated at 80° C. for 7 hours. 0.8 g of NaCN was then added and the aqueous phase was separated off.
The organic phase washed twice with H2O and subsequently dried over Na2SO4.
The solvent was removed and the residue was recrystallized twice from CH2Cl2/MeOH to give dark red needles which according to HPLC had a purity of about 99percent.
The yield was 43 g (80percent).
1H NMR (CDCl3, 500 MHz): [ppm]=8.11 (dd, 3JHH=3.68 Hz, 2H), 7.89 (s, 2H), 7.46 (dd, 3JHH=5.2 Hz, 2H), 7.21 (dd, 3JHH=5.2 Hz, 2H).
Reference: [1] Journal of the American Chemical Society, 2016, vol. 138, # 20, p. 6392 - 6395
[2] Patent: WO2017/75581, 2017, A1, . Location in patent: Page/Page column 31
[3] Organic Letters, 2017, vol. 19, # 3, p. 654 - 657
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[5] Patent: CN106432178, 2017, A, . Location in patent: Paragraph 0051; 0052; 0053; 0055
[6] Chemical Communications, 2004, # 20, p. 2342 - 2343
[7] Patent: WO2004/2970, 2004, A1, . Location in patent: Page/Page column 22
[8] Patent: US2007/265473, 2007, A1, . Location in patent: Page/Page column 16
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[10] Journal of the American Chemical Society, 2012, vol. 134, # 46, p. 19035 - 19042
[11] Patent: US2004/229925, 2004, A1, . Location in patent: Page 3
[12] Inorganic Chemistry Communications, 2013, vol. 36, p. 130 - 132
[13] Patent: CN103601757, 2016, B, . Location in patent: Page/Page column 13
  • 13
  • [ 188290-36-0 ]
  • [ 15155-41-6 ]
  • [ 165190-76-1 ]
YieldReaction ConditionsOperation in experiment
80% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 130℃; for 4 h; EXAMPLE 1 Preparation of 4 , 7-di-2-thienyl-2 , 1 , 3-benzothiadiazole having formula (a) 4, 7-dibromo-2, 1, 3-benzothiadiazole (0.294 g, 1.0 mmoles), potassium acetate (0.295 g, 3.0 mmoles), N,N- dimethylacetamide (5 ml), thiophene (0.842 g, 10 mmoles) and palladium (II) acetate [Pd(OAc)2] (1.2 mg, 0.005 mmoles), were charged into a 10 ml Pyrex glass reactor equipped with a screw stopper. The reactor was placed in an oil bath preheated to 130°C and left under vigorous stirring, for 4 hours. After cooling to room temperature (25°C) , the reaction mixture was put into a saturated solution of sodium chloride (25 ml) and extracted with ethyl acetate (3 x 25 ml) . The organic phase obtained was dried on anhydrous sodium sulfate and evaporated. The residue obtained (brown solid) was purified by flash chromatography on silica gel using a mixture of n- heptane/ethyl acetate (1/1, vol/vol), as eluent, obtaining 240 mg of pure 4 , 7 -di-2-thienyl-2 , 1 , 3-benzo- thiadiazole as a red solid (yield 80percent) . Said , 7-di-2-thienyl-2 , 1 , 3-benzothiadiazole was characterized by means of 1H-NMR (400 MHz, CDC13) obtaining the following spectrum: δ = 8.07 (dd, J = 3.8, 1.2 Hz, 2H) , 7.80 (s, 2H) , 7.42 (dd, J • 5.1, 1.1 Hz, 2H) , 7.18 (dd, J = 5.1, 3.8 Hz, 2H) . Said 4 , 7-di-2-thienyl-2 , 1 , 3-benzothiadiazol'e was also characterized by means of MS mass analysis obtaining the following value: m/z: 301 (M+) .
80% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 130℃; for 4 h; 4,7-dibromo-2,1,3-benzothiadiazole (0.294 g, 1.0 mmoles), potassium acetate (0.295 g, 3.0 mmoles), N,N-dimethylacetamide (5 ml), thiophene (0.842 g, 10 mmoles) and palladium (II) acetate [Pd(OAc)2] (1.2 mg, 0.005 mmoles), were charged into a 10 ml Pyrex glass reactor equipped with a screw stopper.
The reactor was placed in an oil bath preheated to 130° C. and left under vigorous stirring, for 4 hours.
After cooling to room temperature (25° C.), the reaction mixture was put into a saturated solution of sodium chloride (25 ml) and extracted with ethyl acetate (3*ml).
The organic phase obtained was dried on anhydrous sodium sulfate and evaporated.
The residue obtained (brown solid) was purified by flash chromatography on silica gel using a mixture of n-heptane/ethyl acetate (1/1, vol/vol), as eluent, obtaining 240 mg of pure 4,7-di-2-thienyl-2,1,3-benzo-thiadiazole as a red solid (yield 80percent). Said 4,7-di-2-thienyl-2,1,3-benzothiadiazole was characterized by means of 1H-NMR (400 MHz, CDCl3) obtaining the following spectrum: δ=8.07 (dd, J=3.8, 1.2 Hz, 2H), 7.80 (s, 2H), 7.42 (dd, J=5.1, 1.1 Hz, 2H), 7.18 (dd, J=5.1, 3.8 Hz, 2H). Said 4,7-di-2-thienyl-2,1,3-benzothiadiazole was also characterized by means of MS mass analysis obtaining the following value: m/z: 301 (M+).
40% With palladium diacetate; potassium carbonate; Trimethylacetic acid In N,N-dimethyl-formamide at 80℃; for 4 h; Inert atmosphere 4,7-Dibromo-2,1,3-benzothiadiazole (0.2 g, 0.68 mmol) andthiophene (0.272 mL, 3.4 mmol) were dissolved in 40 mL dry DMF.The solution was purged with nitrogen for 10 min followed byaddition of pivalic acid (0.104 g, 1.02 mmol), K2CO3 (0.47 g,3.4 mmol) and catalyst Pd(OAc)2 (0.076 g, 0.34 mmol). The reactionwas conducted for 4 h at 80 °C under nitrogen atmosphere. Theproduct was extracted with ethyl acetate and the solvent wasevaporated to obtain crude product which was purified by silica gelcolumn chromatography using 3percent ethyl acetate/hexane as eluent toobtain M4, a bright orange colour solid (81.7 g, 40percent). Meltingpoint=128 °C. 1HNMR (300 MHz, CDCl3) δ: 8.13(d, 2H), 7.90(s, 2H),7.46(d, 2H), 7.23(m, 2H) [29].
Reference: [1] Patent: WO2013/21315, 2013, A1, . Location in patent: Page/Page column 26-27
[2] Patent: US2014/221663, 2014, A1, . Location in patent: Paragraph 0083; 0084; 0085; 0086; 0087
[3] Journal of Organic Chemistry, 2015, vol. 80, # 2, p. 980 - 987
[4] Organic Electronics: physics, materials, applications, 2017, vol. 40, p. 42 - 50
[5] Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, # 17, p. 3874 - 3881
[6] Dyes and Pigments, 2018, vol. 148, p. 167 - 179
  • 14
  • [ 15155-41-6 ]
  • [ 81745-84-8 ]
  • [ 165190-76-1 ]
YieldReaction ConditionsOperation in experiment
86%
Stage #1: at 20℃; for 1.58333 h;
Stage #2: With hydrogenchloride In tetrahydrofuran; water at 20℃; for 0.5 h;
The thien-2-yl-zinc chloride was prepared by adding n-butyllithium (2.5 M in hexane, 30 mL, 75.0 mmol) dropwise to a stirred solution of thiophene (6.5 g, 77.0 mmol) in THF (50 mL) at 0° C. under nitrogen over 15 minutes. Upon completion of addition, the solution was allowed to warm to room temperature with stirring. After stirring for 3 hours at room temperature, the mixture was cooled to 0° C. again and anhydrous zinc chloride (10.05 g, 75 mmol) was added in one portion. The resultant mixture was allowed to warm to room temperature and was stirred for an additional 1 hour. [0029] This resulting thien-2-yl-zinc chloride solution was added via a cannula to a stirred mixture of 4,7-dibromo-2,1,3-benzothiadiazole (10.28 g, 35 mmol), Pd(OAc)2 (39.2 mg, 0.175 mmol) and Ph3P (91.7 mg, 0.35 mmol) in THF (50 mL) at room temperature under nitrogen over 1 hour 15 minutes. The mixture was stirred for an additional 20 minutes at room temperature and quenched with aqueous HCl (3 N, 80 mL). After stirring for 30 minutes, the crude product was collected by filtration, rinsed with water (100 mL) and ethanol (50 mL) and dried. Crude product 9.47 g (98percent purity by GC area) was obtained, which was recrystallized from toluene/ethanol (40 mL/120 mL) to pure product (9.04 g, 86percent yield).
Reference: [1] Patent: US2004/229925, 2004, A1, . Location in patent: Page 3
  • 15
  • [ 15155-41-6 ]
  • [ 197024-83-2 ]
  • [ 165190-76-1 ]
YieldReaction ConditionsOperation in experiment
85% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In toluene at 85℃; for 48 h; Inert atmosphere 4,7-dibromobenzo[c][1,2,5]thiadiazole (1.32 g, 4.5 mmol), 2-(thiophen-2-yl)-1,3,2-dioxaborinane (1.68 g, 10 mmol) and 23.1 mg Pd(PPh3)4 (1percent mol) were added in the mixture of 30 mL toluene and 6 mL 2.0 M K2CO3, and then the mixture was stirred at 85°C under the N2 atmosphere for 48 h. The reaction was stopped by adding 20 mL water, and the product was extracted by CHCl3 three times. After dried over MgSO4, the solvent was removed by rotary evaporation. The product was preliminary purified by column chromatography using petroleum ether as the eluent to give the red solid. Yield: 85percent. 1H NMR (500 MHz, CDCl3, δ): 8.13 (d, J=3.6, 1.2Hz, 2H), 7.89 (s, 2H), 7.47 (d, J=5.1, 1.2Hz, 2H), 7.22 (t, J=5.1, 3.6, 1.2Hz, 2H).
Reference: [1] Dyes and Pigments, 2011, vol. 91, # 3, p. 356 - 363
[2] Polymer, 2013, vol. 54, # 22, p. 6191 - 6199
  • 16
  • [ 15155-41-6 ]
  • [ 37496-13-2 ]
  • [ 165190-76-1 ]
YieldReaction ConditionsOperation in experiment
90% With tris-(dibenzylideneacetone)dipalladium(0); tris-(o-tolyl)phosphine In toluene at 110℃; for 24 h; Inert atmosphere 4,7-Dithienyl-2,1,3-benzothiadiazole (3) As reported in [2], a solution of 4,7-dibromo-2,1,3-benzothiadiazole (2, 200 mg, 0.680 mmol)and 2-(tributylstannyl)thiophene (558.27 mg, 1.492 mmol) in 4 mL toluene was taken undernitrogen atmosphere. The reaction mixture was purged with N2 for 15 min andtris(dibenzylideneacetone)palladium(0) (12 mg, 0.014 mmol) and tri(o-tolyl)phosphine(21.2 mg, 0.05 mmol) were added. After flushing nitrogen for 15 min the mixture wasrefluxed 110 °C for 24 h under inert atmosphere. The resultant mixture was cooled andprecipitated from methanol. Yield 90percent
Reference: [1] Beilstein Journal of Organic Chemistry, 2017, vol. 13, p. 863 - 873
[2] Chemistry - A European Journal, 1998, vol. 4, # 7, p. 1235 - 1243
  • 17
  • [ 15155-41-6 ]
  • [ 54663-78-4 ]
  • [ 165190-76-1 ]
YieldReaction ConditionsOperation in experiment
99% at 145℃; for 0.583333 h; Inert atmosphere 1.00 g (3.4 mmoles) of 4 , 7-dibromo-2 , 1 , 3 -benzo- thiadiazole and 18 ml of a solution in anhydrous DMSO containing palladium (II) acetate and triphenylphosphine in concentrations of 9.44 x 10"5 M and 2.36 x 10"4 M, respectively, are charged under a nitrogen flow into a 3 -necked 50 ml flask, equipped with magnetic stirring, thermometer, cooler and drip funnel. The amount of palladium is therefore 1.7 x 10"6 moles, corresponding to 0.05 moles per 100 moles of 4 , 7-dibromo-2 , 1 , 3 -benzothiadiazole . The mixture is heated to 145°C and a solution of 2.54 g (6.8 mmoles) of tri-n-butyl (thien-2-yl) stannane in 7 ml of anhydrous DMSO, are added through the drip funnel over a time of 20 minutes. At the end of the addition, the reaction is continued for a further 15 minutes and then the advance degree is checked by gaschromatographic analysis which indicates that DTB has been formed with a yield of 99percent. The reaction mixture is then poured in water and ethyl acetate obtaining two phases : one prevalently organic and the other prevalently aqueous. The former is extracted three times with water to remove the DMSO; the aqueous phases are collected and extracted once or twice with ethyl acetate. The organic phases are collected , dried on anhydrous sodium sulfate (30 minutes under stirring) and filtered. The solvent is then removed in a rotating evaporator. Possible residual traces of DMSO can be removed by maintaining the residue under a nitrogen flow. The residue is recovered in the minimum volume of a 1:4 mixture of ethyl acetate and n-heptane and the resulting solution is filtered on a cake of Si02. The filtrate is brought to boiling point for a few minutes (causing a partial evaporation of the solvent) and then cooled to 0°C obtaining 1.01 g of orange crystals of DTB (99percent yield) .
76% at 70℃; Sonographic reaction 4,7-dibromo-2,1,3-benzothiadiazole of example 1.1 (2.026 g; 6.89 mmole) was placed in a tri-necked flask and the flask was subsequently filled with dried nitrogen, then anhydrous tetrahydrofuran (50 ml) and tributyl (2-thienyl) stannate of example 1.2 (6.7358 g; 20.7 mmole) were added. A catalyst solution was prepared by dispersing Pd(PPh3)Cl2 (107 ml, 0.15 mmole) in THF (5 ml) with an aid of sonification. The catalyst solution was then injected into the tri-necked flask, and the reaction was allowed to proceed by refluxing the mixture overnight at about 70°C. After the reaction was completed, the solvent was removed by reduced pressure evaporation, and the products were purified by column chromatography (moving phase: hexane/CH2Cl2 = 1/1). The concentrated solid was then re-crystallized with toluene/methanol, and an orange crystal was obtained. (1.5732 g; yield: 76percent) 1H NMR (ppm, CDCl3)7.20(dd, 1H), 7.44(d, 1H), 7.86(s, 1H), 8.10(d, 1H)
59% With tetrakis(triphenylphosphine) palladium(0) In toluene at 90℃; for 72 h; Inert atmosphere A solution with reaction mixture of 4,7-dibromobenzo[c]-1 ,2,5-thiadiazole (compound 11 , 2.00 g, 0.0068 mol), 2-(tributylstannyl)thiophene (5.59 g, 0.0150 mol) and toluene (30 ml) was bubbled through with nitrogen to deoxygenate the solvent. Under a nitrogen atmosphere Pd(PPh3)4 (0.50 g, 0.43 mmol) was added and heated at 90 °C with stirring for 3 days. The toluene was removed under reduced pressure and the crude product purified by gravity column chromatography (silica gel) using eluent 30percent CH2CI2 in hexanes followed by 2 χ recrystallisation from hexane to yield 12 as bright red crystals (1.21 g, 59percent). 1 H NMR (400 MHz, CDC ): δ (ppm) 7.20 (dd, 2H), 7.45 (dd, 2H), 7.88 (s, 2H), 8.12 (dd, 2H).
49% With bis-triphenylphosphine-palladium(II) chloride In tetrahydrofuranReflux; Inert atmosphere 4,7-Dibromo-2,1,3-benzothiadiazole (1 g, 3.4 mmol) is taken in dry THF (25 mL). Add to this 2-tributylstannylthiophene (2.37 mL, 7.48 mmol) and PdCl2 (PPh3)2 (0.11924 g, 0.17 mmol) and reflux for 10–12 h under nitrogen atmosphere. After cooling the reaction mixture, quench with water and extract in EtOAc. Purify using column chromatography on alumina using EtOAc / petroleum ether (1:20) as eluent and further recrystallize in petroleum ether.

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