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Chemical Structure| 273-13-2
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Product Details of [ 273-13-2 ]

CAS No. :273-13-2 MDL No. :MFCD00005809
Formula : C6H4N2S Boiling Point : -
Linear Structure Formula :- InChI Key :PDQRQJVPEFGVRK-UHFFFAOYSA-N
M.W : 136.17 Pubchem ID :67502
Synonyms :
Piazthiole

Calculated chemistry of [ 273-13-2 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 9
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 : 37.42
TPSA : 54.02 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.7 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.71
Log Po/w (XLOGP3) : 2.01
Log Po/w (WLOGP) : 1.69
Log Po/w (MLOGP) : 0.63
Log Po/w (SILICOS-IT) : 2.79
Consensus Log Po/w : 1.77

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -2.69
Solubility : 0.278 mg/ml ; 0.00204 mol/l
Class : Soluble
Log S (Ali) : -2.77
Solubility : 0.231 mg/ml ; 0.00169 mol/l
Class : Soluble
Log S (SILICOS-IT) : -2.57
Solubility : 0.37 mg/ml ; 0.00272 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.51

Safety of [ 273-13-2 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 273-13-2 ]

* 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 [ 273-13-2 ]
  • Downstream synthetic route of [ 273-13-2 ]

[ 273-13-2 ] Synthesis Path-Upstream   1~34

  • 1
  • [ 34357-13-6 ]
  • [ 273-77-8 ]
  • [ 273-13-2 ]
  • [ 395641-83-5 ]
Reference: [1] European Journal of Inorganic Chemistry, 2005, # 20, p. 4099 - 4108
  • 2
  • [ 95-54-5 ]
  • [ 273-13-2 ]
YieldReaction ConditionsOperation in experiment
97% With thionyl chloride; triethylamine In dichloromethane 2.7 Benzo[c][1, 2, 5]thiadiazole (1c) 1, 2-Diaminobenzene (3.250 g, 30.05 mmol) and triethylamine (18 mL, 130.0 mmol) were dissolved in CH2Cl2 (20 mL). A solution of SOCl2 (7.0 mL, 96.00 mmol) in CH2Cl2 (10 mL) was added dropwise. After removal of the solvent, the combined organic layer was concentrated under vacuum to give the product (3.956 g, 97percent) [34] Mp: 43 °C. 1H NMR (CDCl3, 400 MHz, TMS) δ: 8.04-8.00 (m, 2H), 7.62-7.57 (m, 2H).
93% With thionyl chloride; triethylamine In dichloromethane for 5 h; Reflux Example I-XVPreparation of Compounds 318 and 319General Procedure I-DXA 1000 mL of flask were charged with 1,2-phenylenediamine (10.0 g, 92.5 mmol), CH2Cl2 (300 mL) and triethylamine (37.4 g, 370 mmol). The solution was stirred until 1,2-phenylenediamine dissolved. Thionyl chloride (22.04 g, 184.9 mmol) was added dropwise very slowly, and then the mixture was heated to reflux for 5 hrs. The solvent was removed under reduced pressure, and water (700 mL) was added. Conc. HCl was added to achieve a final pH=1. The mixture was extracted with CH2Cl2 (200 mL.x.3), the combined organic layers were washed with brine, dried over anhydrous Na2SO4, and concentrated in vacuo to afford compound I-XVa as a dark red solid (11.7 g, yield 93percent).
90% With thionyl chloride; triethylamine In dichloromethane at 0 - 20℃; for 5.5 h; Reflux 2,1,3-benzothiadiazole (1) In a similar manner as described in [1], a mixture of o-phenylenediamine (2 g, 18.52 mmol)in 20 mL DCM and triethylamine (10.3 mL, 74.1 mol) were stirred at room temperature untiltotal dissolution of the diamine was observed. Thionyl chloride (2.69 mL, 37.3 mol) wasadded slowly to the reaction mixture via a syringe at 0 °C, the mixture stirred for 30 min atthe same temperature followed by reflux for 5 h. Afterwards, the reaction mixture wasconcentrated under reduced pressure and brought to pH 1 using conc.HCl. The organic layerwas extracted with DCM and then dried over anhydrous Na2SO4. The solvent was evaporatedusing a rotary evaporator under reduced pressure and the residue further purified by columnchromatography using hexane as the eluent. Yield Yield 90percent
88% With thionyl chloride; triethylamine In dichloromethane for 5 h; Reflux 10.0 g (92.5 mmol) of o-phenylenediamine and 300 ml of dichloromethane were mixed,37.4 g (370 mmol) of triethylamine was added, stirred and dissolved,13.6 ml (184.9 mmol) of thionyl chloride was added dropwise,The temperature was refluxed for 5 hours,L cooled to room temperature, concentrated under reduced pressure, add 700ml of water, add concentrated hydrochloric acid to adjust the pH for acid, filter, filter cake and then recrystallized from ethanol, 11g yellow solid, the yield of 88percent.
84% With thionyl chloride; triethylamine In dichloromethane for 20 h; Reflux In a two-neck bottle (1000mL),O-phenylenediamine (10.00 g, 92.46 mmol) was dissolved in dichloromethane (400 mL)And a mixed solvent of triethylamine (37.40 g, 370.00 mmol),Thionyl chloride (7.4 mL, 101.70 mmol) was slowly added dropwise.Heated back to reflux for 20 hours.Dichloromethane was removed, petroleum ether (600 mL) was added, filtered, and concentrated.Obtained an off-white powder of benzo[c][1,2,5]thiadiazole,That is, product 2 (10.6 g, 84percent).
82% at 0℃; for 24 h; Reflux 1,2-Diaminobenzene (10.8g, 0.1mol), thionyl chloride (53mL) are mixed together in a 100-mL flask under rapid stirring. After the mixture is cooled down to 0°C, pyridine (1mL) is added dropwise and refluxed for 24h. Then, the overdose of thionyl chloride is removed under reduced pressure. The residual is poured slowly into distilled water (250mL). The crude product is obtained by steam distillation. After extracting with CH2Cl2 (3×50mL) and drying with anhydrous MgSO4, the solvent is evaporated under reduced pressure. The refined product is obtained as white acerose crystal (82percent). Mp=43.7–44.0°C. 1H NMR (400MHz, CDCl3) δ 8.02 (q, J=6.8Hz, 2H), 7.60 (q, J=6.8Hz, 2H). 13C NMR (101MHz, CDCl3) δ 155 (s), 129 (s), 121 (s). IR (KBr, cm−1): 3088 (Ar−H), 1697 (C=N), 1608, 1519, 1478 (benzene ring). Anal. Calcd. for C6H4N2S: C, 52.44; H, 2.917; N, 20.66. Found: C, 52.92; H, 2.96; N, 20.57.
78.2% With pyridine; thionyl chloride In chloroform for 0.166667 h; Reflux o-phenylenediamine (8.85g, 81.84mmol), 30ml of pyridine and 45ml of chloroform was added to a 500ml three-necked flask, with a pressure-equalizing dropping funnel was slowly added dropwise a solution of 20ml chloroform and thionyl chloride was heated at reflux for 10min, the reaction was stopped, after cooling to room temperature, the reaction solution was poured into a large amount of ice water, CH2Cl2Extraction, drying over anhydrous MgSO4. After filtration spin dry, PE: EA = 10: 1 through the column as a white solid (8.71g, yield 78.2percent).
65% With thionyl chloride; triethylamine In dichloromethaneReflux To a 500 mL flask, o-phenylenediamine (10.00 g, 92.47 mmol), triethylamine (37.43 g,369.89 mmol) and 300 mL of anhydrous CH2Cl2 were added.Thionyl chloride was added dropwise slowly and the mixture was refluxed overnight.The solvent was removed via rotatory evaporator. Then 500 mL of water andconcentrated HCl was added to a final pH of 2. The resultant mixture was extractedwith CH2Cl2 (3 × 200 mL). The combined organic layer wasdried over anhydrous MgSO4, filtered and concentrated. The residuewas recrystallized in ethanol to obtain compound 4(8.20g, 65percent). 1H NMR (500 MHz, CDCl3):δ (ppm) 8.02 (dd, J = 6.8, 3.2 Hz, 2H),7.60 (dd, J = 6.8, 3.2 Hz, 2H).
77.5 g With thionyl chloride; triethylamine; sodium hydroxide In water; 1,2-dichloro-ethane at 68 - 75℃; for 2 h; Inert atmosphere To a thermometer,Mixing, reflux condenser,Exhaust gas absorption device (800ml saturated NaOH aqueous solution) of the three bottles pass N215min,100 g of 1,2-diamine, 374.1 g of triethylamine,Dichloroethane 1200ml, stirring, heating (75 ± 5 ) to complete dissolution,Stop heating(65 ± 3) began to slowly add SOCl2330.6g,Control the rate of dropping so that the system is in a weak return (68 ± 1) ° C state to drip finished,250min dripping finished; dripping after heating to reflux (72 ± 3) start timing reaction,2h start every 1h sampling tracking reaction,When the content of raw materials 1,2-diamine benzene LC 50percent to stop the reaction (see Figure 1, raw materials 1,2-diamine benzene LC = 0.8465percent, the main peak LC = 52.8365percent);The reaction solution was naturally cooled to room temperature (10 ° C)Add 500ml of water for 10min,Add dilute hydrochloric acid to adjust the PH value to 2 ~ 3, standing 30min,And the aqueous phase was added twice to 200 ml of dichloroethane,Combined organic phase,The organic phase was washed with 2000 ml of water to the neutral phase. The organic phase was dried with 50 g of anhydrous magnesium sulfate for 1 h,Filtered and rinsed with 100 ml of dichloroethane. The filtrate was passed through the column at room temperature (10 ° C)The combined column and eluent were concentrated under reduced pressure (-0.085 MPa, 35 ° C) to no liquid distillate,102 g of a brown solid was added; 51 ml of ethanol was added and heated to reflux (78 ° C) until complete dissolution,Natural cooling to room temperature (10 ), frozen crystallization 4h,Filtered, and rinsed with ethanol 20ml,Cake cake to constant weight (-0.085Mpa, 25 , 4h) to 77.5g brown crystal is high purity benzo [1,2,5] thiadiazole.

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  • 3
  • [ 14208-17-4 ]
  • [ 273-13-2 ]
YieldReaction ConditionsOperation in experiment
66% With pyridine; disulfur dichloride In acetonitrile at -25℃; for 5 h; Inert atmosphere; Reflux General procedure: S2Cl2 (0.64 mL, 8.00 mmol) was added dropwise to a stirred solution of the vic-glyoxime (2.0 mmol) and pyridine (0.80 mL, 10.0 mmol) in dry acetonitrile (10 mL) under argon at -25 °C. The mixture was stirred for 1 h at ambient temperature, refluxed for 4 h, filtered, and the solvent evaporated under reduced pressure. The residue was separated by column chromatography (silica gel Merck 60, hexane/CH2Cl2 mixtures).
Reference: [1] Tetrahedron, 2014, vol. 70, # 35, p. 5558 - 5568
[2] Journal of Organic Chemistry, 1970, vol. 35, p. 1165 - 1169
[3] Tetrahedron, 2014, vol. 70, # 35, p. 5558 - 5568
  • 4
  • [ 480-96-6 ]
  • [ 273-13-2 ]
Reference: [1] Bulletin des Societes Chimiques Belges, 1980, vol. 89, # 3, p. 247 - 254
  • 5
  • [ 4377-90-6 ]
  • [ 273-13-2 ]
Reference: [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1984, # 11, p. 2591 - 2593
  • 6
  • [ 95-54-5 ]
  • [ 25116-80-7 ]
  • [ 273-13-2 ]
  • [ 4377-90-6 ]
Reference: [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1984, # 11, p. 2591 - 2593
  • 7
  • [ 2958-89-6 ]
  • [ 273-13-2 ]
  • [ 5038-11-9 ]
  • [ 4377-90-6 ]
Reference: [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1984, # 11, p. 2591 - 2593
  • 8
  • [ 207670-82-4 ]
  • [ 273-13-2 ]
Reference: [1] European Journal of Inorganic Chemistry, 2001, # 8, p. 2123 - 2134
  • 9
  • [ 15995-56-9 ]
  • [ 273-13-2 ]
Reference: [1] Russian Journal of General Chemistry, 2001, vol. 71, # 7, p. 1050 - 1054
  • 10
  • [ 23431-06-3 ]
  • [ 273-13-2 ]
Reference: [1] Tetrahedron, 2014, vol. 70, # 35, p. 5558 - 5568
  • 11
  • [ 1753-97-5 ]
  • [ 273-13-2 ]
Reference: [1] Chemische Berichte, 1976, vol. 109, p. 2442 - 2455
  • 12
  • [ 14208-17-4 ]
  • [ 273-13-2 ]
  • [ 23431-06-3 ]
Reference: [1] Journal of Organic Chemistry, 1970, vol. 35, p. 1165 - 1169
[2] Zhurnal Obshchei Khimii, 1958, vol. 28, p. 2094; engl. Ausg. S. 2131
  • 13
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  • [ 17071-97-5 ]
  • [ 395641-83-5 ]
Reference: [1] European Journal of Inorganic Chemistry, 2005, # 20, p. 4099 - 4108
  • 14
  • [ 39145-59-0 ]
  • [ 273-13-2 ]
Reference: [1] Justus Liebigs Annalen der Chemie, 1893, vol. 274, p. 263
  • 15
  • [ 85786-50-1 ]
  • [ 273-13-2 ]
Reference: [1] Journal of General Chemistry USSR (English Translation), 1983, vol. 53, p. 530 - 537[2] Zhurnal Obshchei Khimii, 1983, vol. 53, p. 612 - 619
[3] Journal of General Chemistry USSR (English Translation), 1983, vol. 53, p. 530 - 537[4] Zhurnal Obshchei Khimii, 1983, vol. 53, p. 612 - 619
  • 16
  • [ 39145-59-0 ]
  • [ 222851-56-1 ]
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Reference: [1] Justus Liebigs Annalen der Chemie, 1893, vol. 274, p. 263
  • 17
  • [ 34357-13-6 ]
  • [ 273-77-8 ]
  • [ 273-13-2 ]
  • [ 395641-83-5 ]
Reference: [1] European Journal of Inorganic Chemistry, 2005, # 20, p. 4099 - 4108
  • 18
  • [ 13066-27-8 ]
  • [ 273-13-2 ]
Reference: [1] Journal of Organometallic Chemistry, 1989, vol. 377, p. 151 - 156
  • 19
  • [ 114811-56-2 ]
  • [ 273-13-2 ]
Reference: [1] Russian Journal of Physical Chemistry, 1980, vol. 54, # 5, p. 631 - 638[2] Zhurnal Fizicheskoi Khimii, 1980, vol. 54, # 5, p. 1097 - 1111
  • 20
  • [ 67-56-1 ]
  • [ 222851-56-1 ]
  • [ 95-54-5 ]
  • [ 273-13-2 ]
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  • 21
  • [ 64-17-5 ]
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  • [ 273-13-2 ]
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  • 22
  • [ 222851-56-1 ]
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  • [ 71-43-2 ]
  • [ 273-13-2 ]
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  • 23
  • [ 273-13-2 ]
  • [ 874-37-3 ]
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  • 24
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  • [ 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
49% With hydrogen bromide; bromine In water at 100℃; for 9 h; To a flask equipped with a reflux device, 25.0 g (183.7 mmol) of the compound (a), and 150 mL of 48percent hydrobromic acid were added. After heating to 100° C., 8.5 mL (165.4 mmol) of bromine was dropped, the resultant was stirred at 100° C. for nine hours, and then it was let cool. After a reaction was finished, 200 mL of dichloromethane was added, precipitated solid was dissolved, and further 100 mL of an aqueous sodium sulfate solution was added. An organic layer was collected, washed with a saturated aqueous sodium hydrogen carbonate solution, dried with anhydrous sodium sulfate, and then a solvent was removed under reduced pressure to obtain an unrefined compound (b). The compound (b) was suspended in 200 mL of hexane/ethyl acetate (4:1, volume ratio), remaining solids were filtered to thereby remove 4,7-dibromo-2,1,3-benzothiadiazole being a by-product. The filtrate was condensed again, suspended in 200 mL of hexane, and remaining solids were filtered, to thereby obtain 11.2 g of the compound (b). Further, the filtrate was condensed, and refinement was performed by a column chromatography method using hexane/ethyl acetate (97:3, volume ratio) as a developing solution, to thereby obtain 8.0 g of the compound (b). A sum total was 19.2 g (89.3 mmol), and a yield was 49percent.
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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.
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