* 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.
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
[4] Organic and Biomolecular Chemistry, 2011, vol. 9, # 17, p. 6111 - 6119
[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
[9] Journal of Materials Chemistry, 2006, vol. 16, # 8, p. 736 - 740
[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
2
[ 188290-36-0 ]
[ 15155-41-6 ]
[ 165190-76-1 ]
Yield
Reaction Conditions
Operation 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
3
[ 15155-41-6 ]
[ 81745-84-8 ]
[ 165190-76-1 ]
Yield
Reaction Conditions
Operation 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).
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
5
[ 15155-41-6 ]
[ 37496-13-2 ]
[ 165190-76-1 ]
Yield
Reaction Conditions
Operation 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
6
[ 15155-41-6 ]
[ 54663-78-4 ]
[ 165190-76-1 ]
Yield
Reaction Conditions
Operation 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.
Reference：
[1] Patent: WO2012/7834, 2012, A1, . Location in patent: Page/Page column 11; 17-18
[2] European Journal of Organic Chemistry, 2012, # 11, p. 2142 - 2151
[3] Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, # 21, p. 4618 - 4625
[4] Journal of the American Chemical Society, 2011, vol. 133, # 44, p. 17777 - 17785
[5] Journal of Materials Chemistry, 2002, vol. 12, # 10, p. 2887 - 2892
[6] Journal of Materials Chemistry, 2005, vol. 15, # 25, p. 2499 - 2507
[7] Journal of Materials Chemistry, 2008, vol. 18, # 43, p. 5223 - 5229
[8] European Journal of Organic Chemistry, 2013, # 22, p. 4761 - 4769
[9] Chemical Communications, 2014, vol. 50, # 67, p. 9497 - 9500
[10] New Journal of Chemistry, 2011, vol. 35, # 2, p. 385 - 393
[11] Dyes and Pigments, 2018, vol. 148, p. 154 - 166
[12] Patent: EP2333017, 2011, A1, . Location in patent: Page/Page column 9
[13] Journal of Materials Chemistry A, 2014, vol. 2, # 1, p. 155 - 171
[14] Journal of Materials Chemistry C, 2017, vol. 5, # 27, p. 6891 - 6898
[15] Angewandte Chemie - International Edition, 2016, vol. 55, # 33, p. 9783 - 9787[16] Angew. Chem., 2016, vol. 128, p. 9935 - 9940,6
[17] Catalysis Science and Technology, 2018, vol. 8, # 14, p. 3539 - 3547
[18] Macromolecules, 2013, vol. 46, # 6, p. 2078 - 2091
[19] Patent: WO2015/159098, 2015, A1, . Location in patent: Page/Page column 46
[20] Synthetic Communications, 2016, vol. 46, # 12, p. 1052 - 1061
[21] RSC Advances, 2016, vol. 6, # 53, p. 47676 - 47686
[22] Journal of the American Chemical Society, 1995, vol. 117, # 25, p. 6791 - 6792
[23] Synlett, 2001, # 5, p. 634 - 636
[24] Journal of Materials Chemistry, 2009, vol. 19, # 41, p. 7730 - 7737
[25] Polymer, 2010, vol. 51, # 2, p. 390 - 396
[26] Chemical Communications, 2011, vol. 47, # 31, p. 8847 - 8849
[27] Macromolecules, 2010, vol. 43, # 6, p. 2873 - 2879
[28] Organic Electronics: physics, materials, applications, 2010, vol. 11, # 12, p. 1877 - 1885
[29] Journal of Polymer Science, Part A: Polymer Chemistry, 2012, vol. 50, # 16, p. 3415 - 3424
[30] Macromolecules, 2012, vol. 45, # 4, p. 1847 - 1857
[31] Dyes and Pigments, 2012, vol. 95, # 2, p. 229 - 235
[32] Chemistry of Materials, 2012, vol. 24, # 21, p. 4123 - 4133
[33] RSC Advances, 2014, vol. 4, # 67, p. 35318 - 35331
[34] New Journal of Chemistry, 2015, vol. 39, # 12, p. 9591 - 9595
[35] RSC Advances, 2017, vol. 7, # 33, p. 20440 - 20450
Reference：
[1] Patent: EP2333017, 2011, A1,
[2] Organic Electronics: physics, materials, applications, 2010, vol. 11, # 12, p. 1877 - 1885
[3] Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, # 15, p. 3355 - 3365
[4] Dyes and Pigments, 2012, vol. 95, # 2, p. 229 - 235
[5] Macromolecules, 2013, vol. 46, # 6, p. 2078 - 2091
[6] RSC Advances, 2014, vol. 4, # 67, p. 35318 - 35331
[7] RSC Advances, 2016, vol. 6, # 53, p. 47676 - 47686
[8] Synthetic Communications, 2016, vol. 46, # 12, p. 1052 - 1061
[9] RSC Advances, 2017, vol. 7, # 33, p. 20440 - 20450
[10] Patent: CN103601757, 2016, B,
[11] Beilstein Journal of Organic Chemistry, 2017, vol. 13, p. 863 - 873
10
[ 1003-09-4 ]
[ 15155-41-6 ]
[ 165190-76-1 ]
Reference：
[1] Journal of Materials Chemistry, 2008, vol. 18, # 23, p. 2709 - 2715
11
[ 15155-41-6 ]
[ 1380314-82-8 ]
[ 165190-76-1 ]
Reference：
[1] Journal of Photochemistry and Photobiology A: Chemistry, 2012, vol. 231, # 1, p. 51 - 59
12
[ 95-54-5 ]
[ 165190-76-1 ]
Reference：
[1] Dyes and Pigments, 2012, vol. 95, # 2, p. 229 - 235
[2] RSC Advances, 2014, vol. 4, # 67, p. 35318 - 35331
[3] Synthetic Communications, 2016, vol. 46, # 12, p. 1052 - 1061
[4] Beilstein Journal of Organic Chemistry, 2017, vol. 13, p. 863 - 873
13
[ 188290-36-0 ]
[ 165190-76-1 ]
Reference：
[1] Chemical Communications, 2018, vol. 54, # 53, p. 7322 - 7325
14
[ 15155-41-6 ]
[ 193978-23-3 ]
[ 165190-76-1 ]
Reference：
[1] Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, # 15, p. 3355 - 3365
[2] Tetrahedron, 2013, vol. 69, # 44, p. 9175 - 9182
15
[ 165190-76-1 ]
[ 288071-87-4 ]
Yield
Reaction Conditions
Operation in experiment
95%
With N-Bromosuccinimide In chloroform at 0℃; Darkness
M4 (0.07 g, 0.233 mmol) was dissolved in 3.3 mLdry CHCl3 followed by addition of NBS (0.87 g, 0.489 mmol) at 0 °C.The reaction was conducted in dark by covering the flask withaluminium foil. The product was extracted with CHCl3 and thesolvent was evaporated to obtain crude product which was purifiedby silica gel column chromatography using 5percent ethyl acetate/hexaneas eluent to obtain M5 as bright orange solid (0.101 g, 95percent). Meltingpoint = 258 °C. 1HNMR (300 MHz, CDCl3) d: 7.85(s, 2H), 7.80(d, 2H),7.13(d, 2H) [29] (see Scheme 5).
85%
With N-Bromosuccinimide In chloroform at 20℃; for 0.25 h;
Preparation of bis-4,7-(2'-bromo-5'-thienyl)-2,1,3-benzothiadiazole (N2S-1)-T2-Br2 9.51 g (54 mmol) of N-bromosuccinimide were added to a solution of 7.72 g (25.7 mmol) of bis-4,7-(thien-2-yl)-2,1,3-benzothiadiazoline in 770 ml of chloroform over a period of 15 minutes at RT in a protective gas atmosphere and with exclusion of light. The mixture was stirred for 6 hours, and 80 ml of saturated Na2CO3 solution were subsequently added, the organic phase was separated off and dried over Na2SO4. After removal of the solvent, the residue was recrystallized from DMF/EtOH. Dying at 50° C. under reduced pressure gave the product in the form of yellow-orange crystals which according to HPLC had a purity of about 99.6percent. The yield was 10 g (85percent). 1H NMR (DMSO-d6, 500 MHz): [ppm]=8.17 (s, 2H), 7.95 (d, 3JHH=4.2 Hz, 2H), 7.40 (d, 3JHH=4.2 Hz, 2H).
84.8%
With N-Bromosuccinimide In 1,2-dichloro-benzene at 55 - 150℃; for 3 h;
A 5-liter reactor equipped with agitator, condenser and thermometer, were charged with o-dichlorobenzene (3L), 4,7-bis(thien-2-yl)-2,1,3-benzothiadiazole (150.0 g, 0.5 mol) and NBS (170.0 g, 0.95 mol). The mixture was heated slowly to 55° C. After stirring at 55° C. for 3 hours, the resulting slurry was heated to 150° C. to dissolve the solids. When all solids disappeared, the mixture was allowed to cool to room temperature. Stirring was stopped and the supernatant liquid was drawn off by vacuum (aspirator) using a glass fritted sparge tube (removing as much liquid as possible). The remaining wet cake was slurried/stirred with water (2.x.2, 500 mL) and ethanol (500 mL), and each time the supernatant liquid was drawn off by vacuum as described above. The wet cake was dried by passing a nitrogen stream over the solids, followed by pulling vacuum on the vessel. The crude product which had 98.4percent purity by GC area, was recrystallized from o-dichlorobenzene as follows: 1,200 mL of o-dichlorobenzene was added to the reactor. The mixture was heated with stirring to 150° C. until all solids were dissolved, then allowed to cool to room temperature. The liquid was drawn off in vacuo using a glass fritted sparge tube, the reactor was recharged with 1,200 mL of o-dichlorobenzene and the above recrystallization process repeated. The wet cake was washed with o-dichlorobenzene (100 mL) and ethanol (400 mL) and dried at 50° C./2-3mmHg overnight. Pure product (194.2 g) was obtained in 84.8percent yield, which was of 99.7percent of purity as measured by GC area. M.p.247-248° C., 1H NMR spectroscopic analysis:(300 MHz/DMSO-d6) 8.16 (s, 2H), 7.97(m, 2H), 7.39 (m, 2H).
76%
With N-Bromosuccinimide; acetic acid In chloroform at 20℃; for 36 h;
4,7-Di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (4.0 g,13.3 mmol) was dissolved in CHCl3 (100 mL) and a catalyticamount of acetic acid. Then, N-bromosuccinimide(NBS) (5.5 g, 30.6 mmol) was added portion wise, andthe mixture was stirred for 36 h at room temperature withlight protection. The precipitate was filtered through aBüchner funnel, and then washed with copious amountsof MeOH, water, and acetone. The product was collectedas a red solid (4.6 g, 76percent). 1H NMR (400 MHz, CDCl3: 7.80 (dd, 4 H), 7.13 (d, 2 H). 13C NMR (400 MHz,CDCl3: 154.2, 140.8, 131.1, 129.6, 129.1, 128.0,111.6.
60%
With N-Bromosuccinimide; acetic acid In chloroform at 0 - 20℃; for 24 h; Inert atmosphere
4,7-Bis(5-bromothiophen-2-yl)benzo(1,2,5)thiadiazole (M1) Compound 3 (100 mg, 0.332 mmol) and 1.5 mL acetic acid and 3 mL of CHCl3 were stirredat 0 °C under nitrogen purging for 10 min. NBS (130 mg, 0.732 mmol) was added in portionsat the same temperature and the reaction mixture stirred for 24 h at rt under inert atmosphere.Then it was poured into water and extracted with dichloromethane. The organic phase wasdried over anhydrous sodium sulfate and concentrated in a rotary evaporator under reducedpressure. Further purification of the monomer M1 was carried out by columnchromatography with hexane as the eluent. Yield: 60percent
Reference：
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16
[ 165190-76-1 ]
[ 1093862-55-5 ]
[ 288071-87-4 ]
Reference：
[1] Journal of Photochemistry and Photobiology A: Chemistry, 2012, vol. 231, # 1, p. 51 - 59
17
[ 1066-45-1 ]
[ 165190-76-1 ]
[ 1025451-57-3 ]
Yield
Reaction Conditions
Operation in experiment
89%
Stage #1: With 2,2,6,6-tetramethyl-piperidine; n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2 h; Stage #2: at -78 - 20℃; for 12 h;
To a solution of 2,2,6,6-tetramethylpiperidine (4.22 g, 29.9 mmol) in THF (85 mL), n-butyllithium hexane solution (1.6 M, 18.69 mL, 29.9 mmol) was added at a temperature of 78 °C. Afterstirring for 1 h at 78 °C, the reaction mixture was warmed up to room temperature, and then cooled again to 78 °C, followed with the dropwise addition of a solution of 4,7-di(2-thiophene)-2,1,3-benzothiadiazol (3.45 g, 11.5 mmol) in THF (35 mL). After stirringat 78 °C for 2 h, Me3SnCl hexane solution (1.0 M, 29.9 mL, 29.9 mmol) was added and the reaction mixture was warmed up to room temperature. After stirred for 12 h, the reaction was quenched with deionized water and extracted with diethyl ether. The organic phase was washed with deionized water several times, dried over MgSO4, and evaporated to dryness. The residue was subjected to recrystallization from acetone, affording 4,7-Di(2-trimethylstannylthiophen-5-yl)-2,1,3-benzothiadiazole (6.38 g) as orange crystals with a yield of 89percent.
75%
Stage #1: With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 1 h; Stage #2: at 20℃;
A solution of compound 1 (0.77 g, 2.56 mmol) in anhydrousTHF (40 mL) was added dropwise at −78 °C to 2.0M lithiumdiisopropylamine (LDA, 3.20 mL, 6.4 mmol). After stirring for 1 h at−78 °C, trimethyltin chloride (7.69 mL, 7.68 mmol, 1M in hexanes)was added dropwise to the reaction mixture. Subsequently, the reactionflask was warmed to room temperature and stirred overnight. The reactionmixture was quenched with distilled water and extracted withdiethyl ether. The organic layer was washed twice with brine and driedover MgSO4. After drying the extracts, the obtained residue was purifiedby recrystallization from ethanol to yield red crystals. Yield: 75percent(1.2 g). 1H NMR (300 MHz, CDCl3, ppm): δ 8.18 (d, J=3.3 Hz, 2H),7.87 (s, 2H), 7.30 (d, J=3.6 Hz, 2H), 0.43 (s, 18H).
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palladium diacetate; triphenylphosphine; In dimethyl sulfoxide; at 145℃; for 0.583333h;Inert atmosphere;Product distribution / selectivity;
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 145C 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 99%. 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 0C obtaining 1.01 g of orange crystals of DTB (99% yield) .
99%
With tetrakis(triphenylphosphine) palladium(0); In N,N-dimethyl-formamide; toluene; at 100℃; for 2h;
4,7-dibromobenzo [c] [1,2,5] thiadiazole (0.3 g, 1.02 mmol) in a reaction flask, 2-(Tributylstannyl)thiophene (0.81 mL, 2.56 mmol)And Tetrakis (triphenylphosphine) palladium (0) (47.2 mg, 0.0408 mmol) was added,It was dissolved in anhydrous DMF (4 mL) and anhydrous toluene (4 mL).The reaction mixture was stirred at reflux at 100 C.After 2 hours, the reaction mixture was extracted three times with dichloromethane and water.Dry the organic layer with anhydrous MgSO 4, After evaporating the solvent,Purification by recrystallization from methanol gave a red solid. (0.30 g, yield 99%).
86%
With tetrakis(triphenylphosphine) palladium(0); In toluene; at 100 - 110℃; for 24h;Inert atmosphere;
In a 100 ml three-necked flask, 4,7-dibromo-2,1,3-benzothiadiazole (1.0 g, 3.4 mmol) was added.And tributylstannyl thiophene (2.8g, 7.5mmol),Add 60mL of anhydrous toluene to dissolve;Under nitrogen protection,Add tetratriphenylphosphine palladium (120mg),Heated at 100 C-110 C for 24 hours under reflux;Then, 20 mL of deionized water was added to quench the reaction,And extracted the organic layer (3 x 80 mL) with dichloromethane,The combined organic layers were washed with saturated brine (3 × 150 mL) and dried over anhydrous magnesium sulfate.Remove the solvent,The obtained crude product was separated by column chromatography to obtain an orange-yellow solid (0.86 g),The yield was 86%.
76%
bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; 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 70C. 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: 76%) 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 72h;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 30% CH2CI2 in hexanes followed by 2 chi recrystallisation from hexane to yield 12 as bright red crystals (1.21 g, 59%). 1 H NMR (400 MHz, CDC ): delta (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 tetrahydrofuran;Reflux; 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.
With O4P(3-)*3K(1+)*5H2O; tris(1-adamantyl)phosphine; {2-[((acetyl-kappaO)amino)phenyl-kappaC](tri-1-adamantylphosphine)palladium}(p-toluenesulfonate); In tetrahydrofuran; at 20℃; for 1h;
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 (95%) 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, yield84.3%.
80%
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 99%. The yield was 43 g (80%). 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).
With sodium carbonate;palladium diacetate; triphenylphosphine; In tetrahydrofuran; water; at 20℃; for 5.16667h;Heating / reflux;
To a 1-liter reactor equipped with condenser, agitator, thermometer, and N2 inlet and outlet, was added Pd(OAc)2 (224 mg, 1.0 mmol), Ph3P (524 mg, 2.0 mmol), and THF (100 mL) under nitrogen. The mixture was stirred at room temperature until all solids were dissolved (10 minutes) at which time 4,7-dibromo-2,1,3-benzothiadiazole (58.8 g, 0.2 mmol), 2-thiopheneboronic acid (64.0 g, 0.50 mol), THF (300 mL), and Na2CO3 (2 M, 250 mL) were added to the reactor. The mixture was heated to reflux with stirring for 5 hours, after which the mixture was allowed to cool to room temperature, then poured into water (400 mL) to precipitate the product. The crude product was collected by filtration and rinsed with water (500 mL) and ethanol (100 mL). After air drying, the crude product was recrystallized with toluene/ethanol to yield 54.5 g of 99.5% pure product. M.p. 121-122 C. 1H NMR spectroscopic analysis: (300 MHZ/DMSO-d6) 8.25 (m, 2H), 8.10 (s,2 H), 7.77 (d, J=5.0, 2H), 7.28 (m,J=5.02 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 (98% purity by GC area) was obtained, which was recrystallized from toluene/ethanol (40 mL/120 mL) to pure product (9.04 g, 86% yield).
With N-iodo-succinimide; acetic acid; In tetrahydrofuran; at 0 - 20℃; for 2h;
Compound 1 (0.25g, 8.22mmol) was dissolved in THF (10ml) and acetic acid (10ml), and the resulting solution was cooled to 0C. NIS (0.39g, 1.75mmol) in THF (5ml) was added slowly. The reaction mixture was stirred at room temperature for 2h followed by the addition of CH2Cl2 (20ml). The organic phase was washed with NaHCO3 solution (50ml), water (50ml), brine solution (50ml), dried over anhydrous Na2SO4, filtered and the solvent was removed to dryness. The product was obtained by silica gel chromatography eluting with a mixture of CH2Cl2 and hexane (1:4) as orange solids (0.42g, 92%); 1H NMR (300MHz, CDCl3) delta 7.79 (2H, s), 7.27 (2H, d, J=3.9Hz), 7.35 (2H, d, J=3.9Hz) ppm; 13C NMR (75MHz, CDCl3) delta 145.05, 137.78, 128.48, 125.28ppm; MALDI-TOF (m/z) calcd for C14H6I2N2S3: 551.7782; found 551.2311 (M+).
With N-Bromosuccinimide; acetic acid; In dichloromethane; at 20℃;Cooling with ice;
/V-Bromosuccinimide (recrystallised from water, 0.59 g, 3.3 mmol) was slowly added to a solution of compound 12 (1.00 g, 3.3 mmol) in dry DCM (40 ml) and acetic acid (20 ml) in an ice-water bath with stirring. The resulting reaction mixture was stirred overnight at room temperature. The reaction mixture was added to DCM (500 ml) and a saturated aqueous NaHCC>3 solution (100 ml) was added. The organic layer was washed with water (2 x 200 ml), dried (MgS04), filtered and concentrated under reduced pressure. The crude product was purified by gravity column chromatography (silica gel) using 20% CH2CI2 in hexanes to yield 13 as a red powder (0.75 g, 60%). 1 H NMR (400 MHz, CDC ): delta (ppm) 7.16 (d, 1 H), 7.22 (dd, 1 H), 7.47 (dd, 1 H), 7.79-7.82 (m, 2H), 7.87 (d, 1 H), 8.13 (dd, 1 H).
Take DMF (0.39 mL, 5 mmol) in a round-bottom flask under a nitrogen atmosphere and cool it to 0 C. To this solution add POCl 3 (0.47 mL, 5 mmol) dropwise and stir it for 15 min at room temperature. After this add compound 4 (0.150 g, 0.5 mmol in 20 mL of DCM) and reflux the reaction mixture for 17 h. After cooling add sodium acetate (50 mL) and stir the reaction mixture for 2 h at room temperature. Extract the compound with DCM and purify by column chromatography on silica gel using EtOAc / petroleum ether (2:10) as eluent.
1.4 The synthesis of 5-7-(thiophen-2-yl)-2,1,3-benzothiadiazole-4-yl)thiophen-2-carbaldehyde 4,7-di(thiophen-2-yl)-2,1,3-benzothiadiazole of example 1.3 (1.9998 g; 6.66 mmole) was placed into a flask with a rounded bottom, which was pre-filled with dried nitrogen, 1,2-dichloroethane (30 ml) was then added to dissolve 4,7-di(thiophen-2-yl)-2,1,3-benzothiadiazole of example 1.3 therein. POCl3 (0.71 ml, 7.62 mmole) and anhydrous DMF (0.56 ml, 7.21 mmole) were subsequently added under an ice bath, the mixture was stirred for 10 minutes before removing the ice bath. After the temperature of the mixture returned to room temperature, it was then placed in an oil bath and continuously refluxed at 85Cfor overnight, a saturated solution of sodium acetate (150 ml) was then added and stirred for at least 6 hours before extracting with dichloromethane (70 ml each time) for at least 3 times. The organic layers were pooled together and dried with anhydrous MgSO4. The dried organic layer was filtered, and the solvent was removed by a cyclone condenser. The obtained product was then purified by column chromatography (moving phase: hexane/CH2Cl2 = 4/1). An orange solid was obtained. (1.725 g; yield: 78.8%) 1H NMR (ppm, CDCl3) 7.21, (dd, 1H), 7.49(d, 1H), 7.82(d, 1H), 7.88(d, 1H), 7.97(d, 1H), 8.15(dd, 1H), 8.17(d, 1H)
3,6-di(thiophen-2-yl)benzene-1,2-diamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With iron; acetic acid; at 140℃; for 0.5h;
M2 (300 mg, 1.0 mmol) and Fe powder (1.3 g, 20 mmol) were put into the two-neck bottle, and the 50 mL ice acetate was added. The mixture was refluxed for 30 min. When the color of the liquid was changed from orange to white, the reaction was stopped. The product does not need to be purified and used as the starting material to synthesize M6.
With acetic acid; zinc; at 80℃; for 12h;
General procedure: A mixture of the appropriate thiophene-attached benzothiadiazoles (1 or 2, 2.5 mmol) and zinc powder (20 equiv., 50 mmol) in acetic acid (60 mL) was stirred at 80 C for 12 h. Upon completion of the reaction, the mixture was filtered to remove zinc powder and the filtrate was carefully collected. After addition of alpha-diketone (benzil or 4,4'-difluorobenzil, 2.5 mmol) to the filtrate, the solution was heated to reflux overnight. The solution was cooled to room temperature, and the mixture was poured into water and extracted with chloroform. The organic layers were separated, dried over magnesium sulfate, and filtered. Solvents were removed under reduced pressure, and the crude residue was further purified bycolumn chromatography with chloroform/ethanol (1/4, v/v).
With potassium acetate; palladium diacetate; In N,N-dimethyl acetamide; at 130℃; for 4h;
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 130C and left under vigorous stirring, for 4 hours. After cooling to room temperature (25C) , 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 80%) . Said , 7-di-2-thienyl-2 , 1 , 3-benzothiadiazole was characterized by means of 1H-NMR (400 MHz, CDC13) obtaining the following spectrum: delta = 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 4h;
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 80%). Said 4,7-di-2-thienyl-2,1,3-benzothiadiazole was characterized by means of 1H-NMR (400 MHz, CDCl3) obtaining the following spectrum: delta=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 4h;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 3% ethyl acetate/hexane as eluent toobtain M4, a bright orange colour solid (81.7 g, 40%). Meltingpoint=128 C. 1HNMR (300 MHz, CDCl3) delta: 8.13(d, 2H), 7.90(s, 2H),7.46(d, 2H), 7.23(m, 2H) [29].
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; at 85℃; for 48h;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 (1% mol) were added in the mixture of 30 mL toluene and 6 mL 2.0 M K2CO3, and then the mixture was stirred at 85C 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: 85%. 1H NMR (500 MHz, CDCl3, delta): 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).
4,7-bis[5-{2-(2-tetrahydropyranyloxymethyl)phenyldimethylsilyl}]-2-thienyl-benzo[1,2,5]thiadiazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; tert-butylethylene; 4,4'-di-tert-butyl-2,2'-bipyridine; In di-isopropyl ether; at 80℃; for 86h;Inert atmosphere; Sealed tube;
General procedure: 3-Bromothiophene (81 mg, 0.49 mmol), 1b (378 mg, 1.5 mmol) and 2-norbornene (143 mg, 1.5 mmol) wereadded sequentially to a solution of [Ir(OMe)(cod)]2 (17 mg, 26 mumol), 3,4,7,8-Me4-phen (12 mg, 50 mumol)in (i-Pr)2O (0.25 mL) prepared in a 3 mL-vial in a dry box. The vial was closed with a screw PTFE septumcap and the resultant mixture was heated at 80 C for 5 h. The resultant mixture was filtered through Celite,and the filtrate was evaporated and dried in vacuo. The desired product 7b were obtained in 88% yield (281mg, 0.43 mmol) by preparative TLC.
5-((5-(7-(5-(4-(bis(4-(2-ethyl-hexyloxy)phenyl)amino)phenyl)thiophen-2-yl)benzo[2,1,3]thiadiazol-4-yl)-thiophen-2-yl)ethynyl)thiophene-2-carbaldehyde[ No CAS ]
2-cyano-3-(5-((5-(7-(5-(4-(bis(4-(2-ethyl-hexyloxy)phenyl)amino)phenyl)thiophen-2-yl)benzo[2,1,3]thiadiazol-4-yl)-thiophen-2-yl)ethynyl)thiophen-2-yl)acrylic acid[ No CAS ]
With palladium diacetate; potassium carbonate; In N,N-dimethyl acetamide; at 100 - 130℃;Inert atmosphere;
In a 100 mL Schlenk tube, trimethylacetic acid (33 mg, 0.32 mmol), potassium carbonate (400 mg, 2.9 mmol), 4,7-dithiophene-2,1,3-benzothiadiazole (340 mg, 1.13 mmol ), 9,9-bis (3,3'-dipropionate tert-butyl) -2-bromofluorene (1 g, 2 mmol) was dissolved in 35 ml of anhydrous N, N-dimethylacetamide, Three times, under the protection of nitrogen, adding palladium acetate (60mg, 0.27mmol), heated to 100-130 , the reaction 6-12h.Dichloromethane, extracted, dried, concentrated and chromatographed to give 1.6 g of red crystal TBBT-1 in 70% yield..
Di-thien-BTZ (70.00mg, 0.235mmol, 1 eq) and di-Br-EH-carbazole (822.00mg, 1.88mmol, 8 eq) were dissolved in 10mL of DMAc, in a round bottom flask equipped with a stirring bar and a reflux condenser, under inert atmosphere, followed by the addition of CH3COOK (78mg, 0.7mmol, 3 eq) and Pd(OAc)2 (1.00mg, 3.50 mumol, 0.015 eq). The mixture was refluxed for 24hr, cooled at RT and a solution of perfluorophenyl boronic acid (104.60mg, 0.49mmol, 2.1 eq) in 0.6mL of DMAc was then added for another 24hr under reflux. After cooling at RT, the mixture was poured into 50mL of MeOH, stirred for 2hr, filtered and consecutively washed with boiling petroleum ether, MeOH, H2O and again with MeOH, before drying under vacuum at 45C for 18h. Yield 58%.
General procedure: Di-thien-BTZ (70.00mg, 0.235mmol, 1 eq) and di-Br-EH-carbazole (822.00mg, 1.88mmol, 8 eq) were dissolved in 10mL of DMAc, in a round bottom flask equipped with a stirring bar and a reflux condenser, under inert atmosphere, followed by the addition of CH3COOK (78mg, 0.7mmol, 3 eq) and Pd(OAc)2 (1.00mg, 3.50 mumol, 0.015 eq). The mixture was refluxed for 24hr, cooled at RT and a solution of perfluorophenyl boronic acid (104.60mg, 0.49mmol, 2.1 eq) in 0.6mL of DMAc was then added for another 24hr under reflux. After cooling at RT, the mixture was poured into 50mL of MeOH, stirred for 2hr, filtered and consecutively washed with boiling petroleum ether, MeOH, H2O and again with MeOH, before drying under vacuum at 45°C for 18h. Yield 58percent.
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