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Product Details of [ 110046-60-1 ]

CAS No. :110046-60-1 MDL No. :MFCD01321134
Formula : C9H5BrOS2 Boiling Point : -
Linear Structure Formula :- InChI Key :NTHMTYNJFSUBMF-UHFFFAOYSA-N
M.W : 273.17 Pubchem ID :11065610
Synonyms :

Safety of [ 110046-60-1 ]

Signal Word:Danger Class:6.1
Precautionary Statements:P261-P301+P310-P305+P351+P338 UN#:2811
Hazard Statements:H301-H315-H319-H335 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 110046-60-1 ]

* 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.

  • Downstream synthetic route of [ 110046-60-1 ]

[ 110046-60-1 ] Synthesis Path-Downstream   1~54

  • 1
  • [ 110046-60-1 ]
  • [ 110046-61-2 ]
YieldReaction ConditionsOperation in experiment
97% With sodium tetrahydroborate In methanol; dichloromethane for 0.5h; Cooling with ice;
91% With sodium tetrahydroborate In 1,4-dioxane; methanol at 0℃; for 1h;
  • 2
  • [ 110046-60-1 ]
  • [ 74-99-7 ]
  • [ 102054-37-5 ]
YieldReaction ConditionsOperation in experiment
83% With sodium hydroxide; copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); N-benzyl-N,N,N-triethylammonium chloride In benzene at 5℃; for 3h;
With copper(l) iodide; N-benzyl-N,N,N-triethylammonium chloride In benzene at 0℃;
  • 3
  • [ 3779-27-9 ]
  • [ 110046-60-1 ]
YieldReaction ConditionsOperation in experiment
95% With N-Bromosuccinimide; In dichloromethane; acetic acid; at 0 - 20℃; for 18h;Inert atmosphere; Darkness; N-Bromosuccinimide (2.74 g, 15.4 mmol) was added dropwise under argon to a stirred solution of [2,2']bithiophenyl-5-carboxaldehyde (3.00 g, 154 mmol) in a 1/1 mixture of CHCl3 (15 mL) and acetic acid (15 mL) kept in the dark at 0 C. The solution was left to warm to room temperature and stirred overnight. The reaction mixture was then extracted with ethyl acetate (500 mL) and the organic phase was washed with a saturated NaHCO3 solution in water followed by water, then dried over anhydrous Na2SO4, and concentratedunder vacuum to give (a) (4.00 g, 95%) as a yellow solid.
86.3% With bromine; acetic acid; In chloroform; at 20℃; for 2h; To a stirring solution of 2,2'-bithiophene-5-carbaldehyde (1.94 g, 10.00 mmol) in CHCl3 (20 mL) at 0 C, was added bromine (1.60 g, 10.00 mmol) dissolved in CHCl3 (20 mL). The mixture was stirred at room temperature for 2 h. The organic layer was washed with saturated NaHCO3 aqueous solution, and dried with anhydrous Na2SO4. Evaporation of the solvent under reduced pressure gave 4 as a yellow solid (yield 86.3%). 1H NMR (400 MHz, CDCl3) delta 9.79 (s, 1H), 7.59 (d, J = 4.0 Hz, 1H), 7.11 (d, J = 3.9 Hz, 1H), 7.03 (d, J = 3.8 Hz, 1H), 6.96 (d, J = 3.8 Hz, 1H). MS(ESI): m/z calcd for C9H5BrOS2 271.90; found 272.9 [M + H]+.
86% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0 - 20℃; N-bromosuccinimide (1.78 g, 10.0 mmol) was portion wise added to a solution of 4 (1.94 g, 10.0 mmol) in DMF (60 mL) kept at 0 C. The system was then allowed to reach room temperature and to react overnight. The reaction mixture was poured into water (500 mL) and the resulting precipitate was filtered, washed with water and purified by flash chromatography (SiO2, CH2Cl2) to give 6 in 86% yield as a pale yellow solid. 1H NMR (700 MHz, CDCl3): delta 9.89 (s, 1H), 7.68 (d, J = 4.0 Hz, 1H), 7.20 (d, J = 4.0 Hz, 1H), 7.13 (d, J = 3.9 Hz, 1H), 7.06 (d, J = 3.9 Hz, 1H) ppm. 13C{1H} NMR (176 MHz, CDCl3): delta 182.4, 145.8, 142.1, 137.5, 137.1, 131.2, 126.2, 124.4, 114.2 ppm.
81% With N-Bromosuccinimide; In N,N-dimethyl-formamide;Darkness; A solution of 0.8 g of 2,2'-bithiophene-5-acetaldehyde (4. lmmol) in 1 to 2 mL of DMF was placed in a 25 mL flask and 4. l mmol (0.73 g) of N-bromide Diimide dissolved in 2 ~ 3mL DMF solution, drop out, covered with a glass stopper, wrapped with aluminum foil in the dark, stirring overnight; after the end of the reaction, the reaction solution into the amount of ice water, with 10mL ether The organic phases were combined several times, washed once with l0 mL of water, dried over anhydrous sodium sulfate and spin dried to give the crude product which was purified by column chromatographyMethod Separation and purification, eluent: ethyl acetate: petroleum ether = 1:20 to give a dark yellow powder in 81% yield.
75% With bromine; sodium hydrogencarbonate; In chloroform; for 5h;Reflux; Compound 2 (5'-bromo-2,2'-bithiophene-5-carbaldehyde) was obtained as follows: To a solution of 5-formyl-2,2'-bithiophene (18 g, 92.8 mmol) and sodium bicarbonate(8.4 g, 97.4 mmol, 1.05 eq) in dry chloroform (160 mL) was added dropwise a solution of bromine (15.57 g, 97.4 mmol, 1.05 eq) in dry chloroform (84 mL) over a period of 1 h. The reaction mixture was refluxed for 4 h, cooled to room temperature and poured into cold water. A large volume of CHCI3 was added and the organic phase washed with a saturated aqueous solution of NaHC03. Upon drying on Mg2S04 and evaporation of solvent, the crude product was recrystallized twice in toluene and rinsed with pentane. The pure product was obtained as a yellow solid (19 g, 75 %): no melting point, decomposition at 145 <.1H NMR (CDCI3, ppm): delta= 9.87 (s, 1H, CHO), 7.66 (d, J=3.9 Hz, 1H, 4'-H), 7.18 (d, J=4.0 Hz, 1H, 3'-H), 7.11 (d, J= 3.9 Hz, 4-H), 7.04 (d, J=4.0 Hz, 1H, 3- H). 13C NMR (CDCI3, ppm): delta= 181.68 (1C, CHO), 145.77 (1C, CS), 141.92 (1C, CS), 137.36 (1C, CS), 137.23 (1C, CH), 131.16 (1C, CH), 126.17 (1C, CH), 124.34 (1C, CH), 114.12 (1C, CBr).
61.8% With N-Bromosuccinimide; In dichloromethane; at 25℃;Inert atmosphere; EXAMPLE 5 Synthesis of Compound (5) The synthesis of Compound (5) was carried out in accordance with Scheme 5 indicated hereunder: reflux Compound (5) Scheme 5 For this purpose, a mixture of 2 , 2 ' -dithiophene-5- carbaldehyde (3960 mg, 20.4 mmoles) and N- bromosuccinimide (NBS) (3630 mg, 20.4 mmoles), in dichloromethane (CH2C12) (80 ml) , was put under stirring, for 1 night, under a stream of argon, at room temperature (25C) . Sodium thiosulfate (100 ml of an aqueous solution 1 M) was then added, the organic phase was separated from the aqueous phase by extracting twice with dichloromethane (100 ml x 2). The organic phase thus obtained was then anhydrified on sodium sulfate (Na2S04) and concentrated under vacuum obtaining a reaction raw product. The reaction raw product thus obtained was purified by means of column chromatography [silica gel, gradients from n-heptane 100% to n- heptane/ethyl acetate = 8:2 (v/v) as eluent] obtaining 3430 mg (61.8% in moles) of Compound (5) . Said Compound (5) was characterized by means of XH- NMR (400 MHz, CDC13) obtaining the following spectrum: delta = 9.87 ppm (s, 1H, -CHO) ; 7.70-7.65 ppm (d, 1H, Br-Th- CH-CH-CHO) ; 7.20-7.18 ppm (d, 1H, Br-Th-CH-CH-CHO) , 7.13-7.10 ppm (d, 1H, CHO-Th-CH-CH-Br) ; 7.07-7.04 ppm (d, 1H, CHO-Th-CH-CH-Br) . Said Compound (5) was also characterized by means of IR (KBr) spectrum showing the following bands: v = 1652 cm-1 (aldehyde C . = 0 stretching) , 460 cm"1 (deformation C - Br of the thiophene) .
With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0℃; 5-Formyl-2,2'-bithiophene (5.00 g) was dissolved in DMF (6 mL) and cooled to 0 C.N-bromosuccinimide (4.80 g) was added thereto.After completion of the reaction,Add water,And separated and washed.The organic phase was dried over anhydrous sodium sulfate,The solvent was distilled off to obtain a crude product.This was washed with THF and ethyl acetate,The product (5-bromo-5'-formyl-2,2'-bithiophene, 6.00 g) was obtained.

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[13]Dyes and Pigments,2013,vol. 98,p. 221 - 231
[14]Patent: CN104387790,2016,B .Location in patent: Paragraph 0036-0038; 0044-0045
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[16]RSC Advances,2014,vol. 4,p. 24377 - 24383
[17]Journal of Polymer Science, Part A: Polymer Chemistry,2015,vol. 53,p. 2878 - 2889
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[19]New Journal of Chemistry,2011,vol. 35,p. 127 - 136
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[22]ChemPlusChem,2012,vol. 77,p. 832 - 843
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[26]Patent: JP2015/86268,2015,A .Location in patent: Paragraph 0176-0178
  • 4
  • [ 1449-46-3 ]
  • [ 110046-60-1 ]
  • (E)-5-bromo-5'-styryl-2,2'-bithiophene [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With sodium methylate In tetrahydrofuran Reflux; 4.6. General procedure for the synthesis of SBTPs (4-9, 11-33) General procedure: To a stirring solution of 5'-substituted-2,2'-bithiophene-5-carbaldehyde (1.00 mmol) and 4-substituted-benzyl halide (1.00 mmol) in THF (50 mL), was added CH3ONa (1.00 mmol). The mixture was then refluxed for 2-6 h. After cooling, water (20 mL) was added to the reaction mixture. The resulting mixture was extracted by dichloromethane (3 times) and the organic layer was washed with brine and dried over anhydrous MgSO4. The organic solvent was removed in vacuum and the residue was purified by column chromatography.
63% With lithium methanolate In methanol; N,N-dimethyl-formamide at 20℃; for 1h;
  • 5
  • [ 110046-60-1 ]
  • [ 142-84-7 ]
  • [ 1043448-20-9 ]
YieldReaction ConditionsOperation in experiment
9.7% With copper(l) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 120℃; for 18h;
9.7% With copper(l) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 100℃; for 18h; 5 5'-Dipropylamino-2,2'-bithiophene-5-carboxaldehyde. 5'-Bromo-2,2'-bithiophene-5-carboxaldehyde (546 mg, 2.0 mmol), dipropylamine (405 mg, 4.0 mmol), CuI (76 mg, 0.40 mmol), K2CO3 (829 mg, 6.0 mmol), (L)-Proline (92 mg, 0.80 mmol) and 5 mL DMSO were stirred at 100° C. in a pressure vessel for 18 h. Solution turned brown during the reaction. After cooling down, 10 mL H2O and 20 mL EtOAc were added to the reaction mixture. The organic compounds were extracted with EtOAc, concentrated under vacuum, and then purified by column chromatography (SiO2, 1:1 Hexane/CH2Cl2 to CH2Cl2) to give 56.7 mg red solid (9.7%). The product shows strong green fluorescence when dissolved in CH2Cl2. Rf (silica gel, CH2Cl2)=0.21; 1H NMR (400 MHz, CDCl3): δ 0.95 (t, J=7.2 Hz, 6 H, 2 CH3), 1.68 (m, 4 H, 2 CH2), 3.24 (t, J=7.6 Hz, 4 H, 2 CH2), 5.75 (d, J=4.0 Hz, 1 H, ArH), 6.91 (d, J=4.0 Hz, 1 H, ArH), 7.11 (d, J=4.0 Hz, 1 H, ArH), 7.56 (d, J=4.0 Hz, 1 H, ArH), 9.74 (s, 1 H, CHO); MS (EI): m/z=293 [M]+.
  • 6
  • [ 110046-60-1 ]
  • [ 111-92-2 ]
  • [ 1043448-21-0 ]
YieldReaction ConditionsOperation in experiment
6.5% With potassium phosphate; copper(l) iodide; copper In various solvent(s) at 80℃; for 87h;
6.5% With copper(l) iodide; 2-(N,N-dimethylamino)ethanol; potassium phosphate monohydrate; copper In water at 80℃; for 87h; 6 5'-Dibutylamino-2,2'-bithiophene-5-carboxaldehyde. 5'-Bromo-2,2'-bithiophene-5-carboxaldehyde (104 mg, 0.38 mmol), dibutylamine (1.0 g, 7.7 mmol), CuI (13.9 mg, 0.073 mmol), Cu (4.7 mg, 0.074 mmol), K3PO4.H2O (155.4 mg, 0.73 mmol) and 1 mL N,N-dimethylethanolamine were stirred at 80° C. in a pressure vessel for 87 h. After cooling down, the reaction mixture was filtered through a short column of silica gel and eluted with more EtOAc. The eluent was concentrated under vacuum and was purified by column chromatography (SiO2, 1:2 CH2Cl2/Hex to CH2Cl2) to furnish 8.0 mg red solid (6.5%). The product shows strong green fluorescence when dissolved in CH2Cl2. Rf (silica gel, CH2Cl2)=0.31; 1H NMR (400 MHz, CDCl3): δ 0.96 (t, J=7.2 Hz, 6 H, 2 CH3), 1.36 (m, 4 H, 2 CH2), 1.63 (m, 4 H, 2 CH2), 3.26 (t, J=7.6 Hz, 4 H, 2 CH2), 5.75 (d, J=4.4 Hz, 1 H, ArH), 6.91 (d, J=4.4 Hz, 1 H, ArH), 7.11 (d, J=4.0 Hz, 1 H, ArH), 7.56 (d, J=4.0 Hz, 1 H, ArH), 9.73 (s, 1 H, CHO); MS (EI): m/z=321 [M]+.
  • 7
  • [ 110046-60-1 ]
  • [ 124-40-3 ]
  • [ 150239-77-3 ]
YieldReaction ConditionsOperation in experiment
86% With potassium phosphate; copper(l) iodide; copper In water at 80℃; for 87h;
86% With copper(l) iodide; 2-(N,N-dimethylamino)ethanol; potassium phosphate monohydrate; copper In water 3 5'-Dimethylamino-2,2'-bithiophene-5-carboxaldehyde. 5'-Bromo-2,2'-bithiophene-5-carboxaldehyde (100 mg, 0.37 mmol), dimethylamine (40% solution in H2O, 1 g, 8.9 mmol), CuI (13.9 mg, 0.073 mmol), Cu (4.7 mg, 0.074 mmol), K3PO4.H2O (155.4 mg, 0.73 mmol) and 1 mL N,N-dimethylethanolamine were stirred at 80° C. in a pressure vessel for 87 h. Solution turned red during the reaction. After cooling down, the reaction mixture was filtered through a short column of silica gel and eluted with more EtOAc. The eluent was concentrated under vacuum and was purified by column chromatography (SiO2, CH2Cl2) to furnish 74.8 mg red solid (86%). The product shows strong green fluorescence when dissolved in CH2Cl2. Rf (silica gel, CH2Cl2)=0.36; 1H NMR (400 MHz, CDCl3): δ 3.00 (s, 6 H, 2 CH3), 5.81 (d, J=4.0 Hz, 1 H, ArH), 6.95 (d, J=4.0 Hz, 1 H, ArH), 7.13 (d, J=4.0 Hz, 1 H, ArH), 7.57 (d, J=4.0 Hz, 1 H, ArH), 9.75 (s, 1 H, CHO); MS (EI): m/z=265 [M]+.
37% With potassium phosphate; copper(l) iodide; copper In N,N-dimethyl-formamide at 80℃; for 87h; High pressure; 1.A.4 4) Synthesis of 5- (dimethylamino) _2,2'-dithiophene-5'-carbaldehyde: 100 mg of 5'-bromo-2,2'-bis-thiophene-5-carbaldehyde (0.37 mmol)18 dimethylamine (40% aqueous solution, 8.9 mmol)13.9 mg of copper iodide (0.103 mmol),4.7 mg of copper powder (0.074 mmol),155.4 mg of potassium phosphate (0.73 mmol) and lmL Of DMF was added to the high pressure reaction vessel,The mixture was reacted at 80 ° C for 87 hours,The color of the solution becomes red during the reaction; after the reaction is finished, it is cooled to room temperature,Filter with a short silica gel column,Rinsed with ethyl acetate; spin-dried to give the crude product,By column chromatography separation and purification,Eluent: Dichloromethane (product dissolved in methylene chloride showed strong green fluorescence) to give an orange-red solid in 37% yield.
37% With copper(l) iodide; copper In water; N,N-dimethyl-formamide at 80℃; for 87h; 1.1 (1) Synthesis of 5- (dimethylamino) -2,2'-bithiophene-5'-carboxaldehyde: 100 mg of 5'-bromo-2,2'-bithiophene-5-carbaldehyde (0.37 mmol), 1 g of dimethylamine (40% in water,8.9 mmol), 13.9 mg cupric iodide (0.073 mmol), 4.7 mg copper powder (0.074 mmol), 155.4 mg potassium phosphate(0.73 mmol) and 1 mL of DMF were charged into a high-pressure reaction vessel, and the mixture was reacted at 80 ° C for 87 hours. During the reaction,Liquid color turns red; after the reaction was cooled to room temperature, filtered through a short silica gel column, rinsed with ethyl acetate; spin dried to give the crude product,Separation and purification by column chromatography, eluent: dichloromethane (the product dissolved in methylene chloride showed a strong green fluorescence)An orange solid was obtained in 37% yield.

  • 8
  • [ 110046-60-1 ]
  • [ 109-89-7 ]
  • [ 600173-79-3 ]
YieldReaction ConditionsOperation in experiment
12% With copper(l) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 120℃; for 15h;
12% With copper(l) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 120℃; for 15h; 4 5'-Diethylamino-2,2'-bithiophene-5-carboxaldehyde. 5'-Bromo-2,2'-bithiophene-5-carboxaldehyde (546 mg, 2.0 mmol), diethylamine (293 mg, 4.0 mmol), CuI (76 mg, 0.40 mmol), K2CO3 (829 mg, 6.0 mmol), (L)-Proline (92 mg, 0.80 mmol) and 5 mL DMSO were stirred at 120° C. in a pressure vessel for 15 h. Solution turned black during the reaction. After cooling down, 10 mL H2O and 20 mL EtOAc were added to the reaction mixture. The organic compounds were extracted with EtOAc, concentrated under vacuum, and then purified by column chromatography (SiO2, CH2Cl2) to give 64.5 mg red solid (12%). The product shows strong green fluorescence when dissolved in CH2Cl2. Rf (silica gel, CH2Cl2)=0.20;1H NMR (400 MHz, CDCl3): δ 1.23 (t, J=7.2 Hz, 6 H, 2 CH3), 3.35 (q, J=7.2 Hz, 4 H, 2 CH2), 5.78 (d, J=4.0 Hz, 1 H, ArH), 6.92 (d, J=4.0 Hz, 1 H, ArH), 7.12 (d, J=4.0 Hz, 1 H, ArH), 7.56 (d, J=4.0 Hz, 1 H, ArH), 9.74 (s, 1 H, CHO).
  • 10
  • [ 1255708-16-7 ]
  • [ 110046-60-1 ]
  • [ 1255708-19-0 ]
YieldReaction ConditionsOperation in experiment
In N,N-dimethyl-formamide at -78 - 20℃; for 16h; Reflux; 5 Next, 1.45 g of Br-Dithiphene-aldehyde and 4g of TMSn-CPDT-TPA([4-(4,4-Dioctyl-6-trimethylatannanyl-4H-cyclopenta[2,1-b;3,4-b']dithiophen-2-yl)-phenyl]-diphenyl-amine) were added into a reaction bottle and dissolved in 50 ml of DMF (dimethylformamide). The mixture was cooled to -78° C. and heated to room temperature and filled and exhausted with Ar (four times). Next, 0.14 g of Pd(PPh3)4 (dissolved in 20 ml of DMF) was added into the bottle and heated to reflux for 16 hr. After cooling to room temperature, saturated NH4Cl was added to quench the reaction. The result was extracted using CH2Cl2. An organic phase was separated and dried by MgSO4. After filtrating, the filtrate was concentrated to remove the organic solvent. After purification by column chromatography with n-hexane as the extraction solvent, F-C2-aldehyde(5'-[6-(4-diphenylamino-phenyl)-4,4-Dioctyl-4H-cyclopenta-[2,1-b;3,4-b']dithiophen-2-yl]-2,2'-bithiophenyl-5-carbaldehyde) was obtained as a red solid.
  • 11
  • [ 1265622-23-8 ]
  • [ 110046-60-1 ]
  • [ 1265622-25-0 ]
YieldReaction ConditionsOperation in experiment
69.5% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; toluene for 36h; Inert atmosphere; Reflux; 4.2.7. 5',5-(4-(Heptadecan-9-yl)-4H-dithieno[3,2-b:2',3'-d]pyrrole-2,6-diyl)di-2',2-bithiophene-5-carbaldehyde (8b) General procedure: Mixture of compounds 6 (0.3 g, 0.46 mmol), 7a (0.197 g, 1.03 mmol), and K2CO3 (0.161 g, 1.16 mmol) were dissolved in 20 mL of toluene/ethanol (3:1) and degassed for 10 min, which was followed by the addition of 20 mg Pd(PPh3)4 as a catalyst. The resulting mixture was stirred under reflux for 36 h. The solvent was removed under vacuum and extracted with dichloromethane and washed with water followed by a little brine. The organic phase was dried with anhydrous MgSO4, and the solvent was removed by rotary evaporator. Afterward, the crude compound was purified by column chromatography (silica) using a mixture of hexane and dichloromethane (1:1) as an eluent. The obtained product was recrystallized from ethanol to yield an orange color solid (210 mg, 70%).
  • 12
  • [ 110046-60-1 ]
  • [ 254755-24-3 ]
  • [ 1265622-26-1 ]
YieldReaction ConditionsOperation in experiment
78.2% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; toluene for 36h; Inert atmosphere; Reflux; 4.2.8. 5',5-(9,9-Dihexyl-9H-fluorene-2,7-diyl)di-2,2'-bithiophene-5'-carbaldehyde (10a) General procedure: Mixture of compounds 6 (0.3 g, 0.46 mmol), 7a (0.197 g, 1.03 mmol), and K2CO3 (0.161 g, 1.16 mmol) were dissolved in 20 mL of toluene/ethanol (3:1) and degassed for 10 min, which was followed by the addition of 20 mg Pd(PPh3)4 as a catalyst. The resulting mixture was stirred under reflux for 36 h. The solvent was removed under vacuum and extracted with dichloromethane and washed with water followed by a little brine. The organic phase was dried with anhydrous MgSO4, and the solvent was removed by rotary evaporator. Afterward, the crude compound was purified by column chromatography (silica) using a mixture of hexane and dichloromethane (1:1) as an eluent. The obtained product was recrystallized from ethanol to yield an orange color solid (210 mg, 70%).
  • 13
  • [ 1530-38-7 ]
  • [ 110046-60-1 ]
  • [ 1207108-00-6 ]
YieldReaction ConditionsOperation in experiment
86% With sodium methylate In tetrahydrofuran Reflux; 4.6. General procedure for the synthesis of SBTPs (4-9, 11-33) General procedure: To a stirring solution of 5'-substituted-2,2'-bithiophene-5-carbaldehyde (1.00 mmol) and 4-substituted-benzyl halide (1.00 mmol) in THF (50 mL), was added CH3ONa (1.00 mmol). The mixture was then refluxed for 2-6 h. After cooling, water (20 mL) was added to the reaction mixture. The resulting mixture was extracted by dichloromethane (3 times) and the organic layer was washed with brine and dried over anhydrous MgSO4. The organic solvent was removed in vacuum and the residue was purified by column chromatography.
  • 14
  • [ 1530-42-3 ]
  • [ 110046-60-1 ]
  • [ 1207107-98-9 ]
YieldReaction ConditionsOperation in experiment
45% With sodium methylate In tetrahydrofuran Reflux; 4.6. General procedure for the synthesis of SBTPs (4-9, 11-33) General procedure: To a stirring solution of 5'-substituted-2,2'-bithiophene-5-carbaldehyde (1.00 mmol) and 4-substituted-benzyl halide (1.00 mmol) in THF (50 mL), was added CH3ONa (1.00 mmol). The mixture was then refluxed for 2-6 h. After cooling, water (20 mL) was added to the reaction mixture. The resulting mixture was extracted by dichloromethane (3 times) and the organic layer was washed with brine and dried over anhydrous MgSO4. The organic solvent was removed in vacuum and the residue was purified by column chromatography.
  • 15
  • (4-fluorobenzyl)(triphenyl)phosphonium bromide [ No CAS ]
  • [ 110046-60-1 ]
  • [ 1312948-79-0 ]
YieldReaction ConditionsOperation in experiment
81% With sodium methylate In tetrahydrofuran Reflux; 4.6. General procedure for the synthesis of SBTPs (4-9, 11-33) General procedure: To a stirring solution of 5'-substituted-2,2'-bithiophene-5-carbaldehyde (1.00 mmol) and 4-substituted-benzyl halide (1.00 mmol) in THF (50 mL), was added CH3ONa (1.00 mmol). The mixture was then refluxed for 2-6 h. After cooling, water (20 mL) was added to the reaction mixture. The resulting mixture was extracted by dichloromethane (3 times) and the organic layer was washed with brine and dried over anhydrous MgSO4. The organic solvent was removed in vacuum and the residue was purified by column chromatography.
  • 16
  • [ 61130-13-0 ]
  • [ 110046-60-1 ]
  • [ 1312948-84-7 ]
YieldReaction ConditionsOperation in experiment
79% With sodium methylate In tetrahydrofuran Reflux; 4.6. General procedure for the synthesis of SBTPs (4-9, 11-33) General procedure: To a stirring solution of 5'-substituted-2,2'-bithiophene-5-carbaldehyde (1.00 mmol) and 4-substituted-benzyl halide (1.00 mmol) in THF (50 mL), was added CH3ONa (1.00 mmol). The mixture was then refluxed for 2-6 h. After cooling, water (20 mL) was added to the reaction mixture. The resulting mixture was extracted by dichloromethane (3 times) and the organic layer was washed with brine and dried over anhydrous MgSO4. The organic solvent was removed in vacuum and the residue was purified by column chromatography.
  • 17
  • [ 1530-37-6 ]
  • [ 110046-60-1 ]
  • [ 1207107-99-0 ]
YieldReaction ConditionsOperation in experiment
79% With sodium methylate In tetrahydrofuran Reflux; 4.6. General procedure for the synthesis of SBTPs (4-9, 11-33) General procedure: To a stirring solution of 5'-substituted-2,2'-bithiophene-5-carbaldehyde (1.00 mmol) and 4-substituted-benzyl halide (1.00 mmol) in THF (50 mL), was added CH3ONa (1.00 mmol). The mixture was then refluxed for 2-6 h. After cooling, water (20 mL) was added to the reaction mixture. The resulting mixture was extracted by dichloromethane (3 times) and the organic layer was washed with brine and dried over anhydrous MgSO4. The organic solvent was removed in vacuum and the residue was purified by column chromatography.
  • 18
  • [ 51044-13-4 ]
  • [ 110046-60-1 ]
  • [ 1312948-82-5 ]
YieldReaction ConditionsOperation in experiment
86% With sodium methylate In tetrahydrofuran Reflux; 4.6. General procedure for the synthesis of SBTPs (4-9, 11-33) General procedure: To a stirring solution of 5'-substituted-2,2'-bithiophene-5-carbaldehyde (1.00 mmol) and 4-substituted-benzyl halide (1.00 mmol) in THF (50 mL), was added CH3ONa (1.00 mmol). The mixture was then refluxed for 2-6 h. After cooling, water (20 mL) was added to the reaction mixture. The resulting mixture was extracted by dichloromethane (3 times) and the organic layer was washed with brine and dried over anhydrous MgSO4. The organic solvent was removed in vacuum and the residue was purified by column chromatography.
  • 19
  • [ 1530-39-8 ]
  • [ 110046-60-1 ]
  • [ 1207107-97-8 ]
YieldReaction ConditionsOperation in experiment
60% With sodium methylate; In tetrahydrofuran;Reflux; General procedure: To a stirring solution of 5'-substituted-2,2'-bithiophene-5-carbaldehyde (1.00 mmol) and 4-substituted-benzyl halide (1.00 mmol) in THF (50 mL), was added CH3ONa (1.00 mmol). The mixture was then refluxed for 2-6 h. After cooling, water (20 mL) was added to the reaction mixture. The resulting mixture was extracted by dichloromethane (3 times) and the organic layer was washed with brine and dried over anhydrous MgSO4. The organic solvent was removed in vacuum and the residue was purified by column chromatography.
  • 20
  • [ 65413-33-4 ]
  • [ 110046-60-1 ]
  • [ 1207108-01-7 ]
YieldReaction ConditionsOperation in experiment
85% With sodium methylate In tetrahydrofuran Reflux; 4.6. General procedure for the synthesis of SBTPs (4-9, 11-33) General procedure: To a stirring solution of 5'-substituted-2,2'-bithiophene-5-carbaldehyde (1.00 mmol) and 4-substituted-benzyl halide (1.00 mmol) in THF (50 mL), was added CH3ONa (1.00 mmol). The mixture was then refluxed for 2-6 h. After cooling, water (20 mL) was added to the reaction mixture. The resulting mixture was extracted by dichloromethane (3 times) and the organic layer was washed with brine and dried over anhydrous MgSO4. The organic solvent was removed in vacuum and the residue was purified by column chromatography.
  • 21
  • [ 123-75-1 ]
  • [ 110046-60-1 ]
  • [ 146823-45-2 ]
YieldReaction ConditionsOperation in experiment
4.6% With copper(l) iodide; 2-(N,N-dimethylamino)ethanol; potassium phosphate monohydrate; copper In water at 80℃; for 208h; 7 5'-Pyrrolidino-2,2'-bithiophene-5-carboxaldehyde. 5'-Bromo-2,2'-bithiophene-5-carboxaldehyde (100 mg, 0.37 mmol), pyrrolidine (1.0 g, 14 mmol), CuI (26 mg, 0.136 mmol), Cu (7 mg, 0.111 mmol), K3PO4.H2O (155.4 mg, 0.73 mmol) and 1 mL N,N-dimethylethanolamine were stirred at 80° C. in a pressure vessel for 208 h. After cooling down, the reaction mixture was filtered through a short column of silica gel and eluted with more EtOAc. The eluent was concentrated under vacuum and was purified by column chromatography (SiO2, 1:1 CH2Cl2/Hex) to furnish 4.4 mg red solid (4.6%). The product shows strong green fluorescence when dissolved in CH2Cl2. Rf (silica gel, CH2Cl2)=0.16; 1H NMR (400 MHz, CDCl3): δ2.07 (m, 4 H, 2 CH2), 3.33 (t, J=6.6 Hz, 4 H, 2 NCH2), 5.70 (d, J=4.4 Hz, 1 H, ArH), 6.92 (d, J=4.0 Hz, 1 H, ArH), 7.15 (d, J=4.0 Hz, 1 H, ArH), 7.57 (d, J=4.0 Hz, 1 H, ArH), 9.74 (s, 1 H, CHO).
  • 22
  • [ 110046-60-1 ]
  • [ 126-30-7 ]
  • [ 1372699-62-1 ]
YieldReaction ConditionsOperation in experiment
87% With toluene-4-sulfonic acid In benzene for 2.5h; Dean-Stark; Reflux;
In toluene for 6h; Reflux; 1 Example 1 : 2-(5'-bromo-2, ioxane (3); A solution of 5'-bromo-2,2'-bithiophene-5-carbaldehyde 2 (20 g, 73.2 mmol, 1 eq), p-toluenesulfonic acid (0.31 g, 1 .6 mmol, 0.052 eq) and 2,2-dimethyl-1 ,3-propanediol (1 15 g, 1 .1 mol, 15 eq) in toluene (700 mL) was refluxed during 6 h using a dean-stark apparatus and then cooled down to room temperature. The organic phase was washed one time with an aqueous solution of NaHC03 and three times with water, and then dried over MgS04 and condensed under vacuum. The crude product was recrystallized in ethanol, cooled at 0°C and filtered. This process was repeated two or three times, until no impurity remained on TLC. The product was obtained as pure white needles (24.5 g, 93%): mp=105-106 °C.1H NMR (CDCI3, ppm): 6=7.02 (dd, 1H, J1= 3.6 Hz, J2=0.63 Hz, 3'-H), 6.98 (dd, 2H, J1= 5.5 Hz, J2=3.8 Hz, 3-H,4'-H), 6.90 (1H, d, J= 3.8 Hz, 3'-H), 5.67 (s, 1H, CH), 3.79-3.95 (m, 4H, 2xCH2), 1.57 (s, 3H, CH3), 1.11 (S, 3H, CH3).13C NMR (CDCI3, ppm): δ= 140.57 (1C, CS), 138.67 (1C, CS), 136.54 (1C, CS), 130.55 (1C, CH), 125.69 (1C, CH), 123.87 (1C, CH), 123.32 (1C, CSBr), 111.01 (1C, CH), 97.96 (C, HC02), 77.48 (2C, OCH2C), 30.23 (1C, CCH3CH3), 22.98 (1C, CH3), 21.84 (1C, CH3).
With toluene-4-sulfonic acid In benzene for 5h; Inert atmosphere; Reflux; Schlenk technique;
  • 23
  • [ 1372699-75-6 ]
  • [ 110046-60-1 ]
  • [ 1372700-01-0 ]
YieldReaction ConditionsOperation in experiment
28.3% In N,N-dimethyl-formamide at 60℃; for 20h; 8 Example 8: 5""-(5,5-diethyl-1 ,3-dioxan-2-yl)-2,2,:5',2":5",2",:5"',2""-quinquethiophene-5-carbaldehyde (12); To a deoxygenated solution of 5'-bromo-2,2'-bithiophene-5-carbaldehyde 2 (0.581 mmol, 156 mg) and tributyl[5"-(5,5-diethyl-1 ,3-dioxan-2-yl)-2,2':5',2"-terthien-5-yl]stannane 8 (0.639 mmol, 434 mg) in DMF (5 ml) was added Pd(PPh3)4 (3.1 x10~3 mmol, 3.68 mg). The mixture was heated at 60 °C until the starting material was consumed according to TLC analysis (-20 h). The reaction mixture was cooled to room temperature and added to water. The orange suspension formed was filtered and washed with water, diethyl ether and pentane. The product was then recrystallized in toluene, filtered and washed with pentane to afford orange crystals (95.8 mg, 28.3 %). Anal, calcd for C19H1803S3: C, 59.76; H, 4.50; O, 8.24; S, 27.51 . Found: C, 55.52; H, 4.26; O, 8.82, S, 25.16. Mass spectrum (ESI-MS): 583 [M+H]+.
  • 24
  • [ 4805-22-5 ]
  • [ 33513-42-7 ]
  • [ 110046-60-1 ]
YieldReaction ConditionsOperation in experiment
76% Under nitrogen, 250 mL of SchlenkThe flask was charged with compound 19 (3.24 g, 10 mmol) and anhydrous tetrahydrofuran(1.4 mL, 2.4 M) was slowly added dropwise to the solution at -78 C, and the reaction was continued at -78 C with stirring Hour, then anhydrous N, N-dimethylformamide (0.88 g, 12. Ommol) was added and the reaction was continued for 1 hour at the temperature maintained. The system was allowed to stir at room temperature overnight. The reaction mixture was quenched with dilute hydrochloric acid and extracted with petroleum ether. The combined organic phases were washed with brine and water, dried over anhydrous sodium sulfate, filtered and the organic solvent was removed by rotary evaporation. The crude product was subjected to silica gel column chromatography using petroleum ether: chloroform (V: V = 5: 1) as eluant to give pale yellow solid 20 (3.02 g, 76% yield).
60% Compound 2 (5.0 g, 15.43 mmol) was dissolved in 200 ml THF in a well-dried flask under the protection of N2 flow. n-BuLi (6.8 ml, 16.98 mmol, 2.5 M in hexane) was added dropwise by syringe under -78 C. After addition, the reaction mixture was stirred at -78 C for 2 h and DMF (1.43 ml, 18.52 mmol) was added dropwise, then the mixture was warmed to room temperature. After stirring for 12 h, the mixture was poured into water and extracted with dichloromethane. The organic layer was washed with brine and dried over Na2SO4. After solvent removal, the residue was purified by column chromatography on silica gel using petroleum/CH2Cl2 5:1 as eluant to afford Compound 3 (2.53 g, 60%) as a yellow solid. GC/MS: 273 (M+). 1H NMR (400 MHz, CDCl3): δ(ppm) 9.87 (s, 1H), 7.67-7.66 (d, J = 4.0 Hz, 1H), 7.19-7.18 (d, J = 3.8 Hz, 1H), 7.11-7.10 (d, J = 3.8 Hz, 1H), 7.04-7.03 (d, J = 4.0 Hz, 1H).
  • 25
  • [ 110046-60-1 ]
  • [ 73183-34-3 ]
  • [ 1421238-78-9 ]
YieldReaction ConditionsOperation in experiment
68% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 90℃; Inert atmosphere;
48% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 90℃; for 24h; Inert atmosphere;
40% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 90℃; for 18h; Inert atmosphere; 4.1.3. 5'-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-yl) [2,2']bithiophenyl-5-carboxaldehyde (b). 5'-Bromo-[2,2']bithiophenyl-5-carboxaldehyde (1.88 g, 6.9 mmol) and bis(pinacolato)diboron (1.92 g, 7.5 mmol, 1.1 equiv) were dissolved under argon in anhydrous dioxane (40 mL) in a 100 mL round bottom flask, in which KOAc (1.69 g, 17.2 mmol) and Pd(dppf)Cl2 (252 mg, 0.3 mmol) were added. The reaction mixture was stirred at 90 °C overnight. After cooling, the mixture was filtered through a pad of Celite, then concentrated under pressure. Crude product was precipitated by addition of diethyl ether then collected by filtration yielding a brown solid. Purification was achieved by sublimation (100 °C, 2.5 mbar), affording analytically pure product (b) (820 mg, 40%) as a yellow powder.
  • 26
  • [ 1422273-19-5 ]
  • [ 110046-60-1 ]
  • [ 1422273-21-9 ]
YieldReaction ConditionsOperation in experiment
64.5% With tetrakis(triphenylphosphine) palladium(0) In toluene at 90℃; for 24h; 2.4 4.1.2.4 5-(5-6-[3,4,5-Tris(dodecyloxy)phenyl]dithieno[3,2-b:2',3'-a]thiophylthiophen-2-yl)thiophene-2-carbaldehyde (8) A 250-mL two-neck flask containing 5 (1.1 mmol, 0.85 g), 6 (0.77 mmol, 0.21 g), and Pd(PPh3)4 (0.03 mmol, 0.026 g), in toluene (15 mL) was heated at 90 °C for 24 h. The mixture was the partitioned between CH2Cl2 and water. The organic phase was dried (MgSO4) and concentrated under reduced pressure. The residue was purified through column chromatography (SiO2; CH2Cl2/hexane, 1:1) to give a red-orange solid (0.5 g, 64.5%).
  • 27
  • [ 190334-75-9 ]
  • [ 110046-60-1 ]
  • 5',5''',5'''''-((1E,1'E,1"E)-(nitrilotris(benzene-4,1-diyl))tris(ethene-2,1-diyl))tris(([2,2'-bithiophene]-5-carbaldehyde)) [ No CAS ]
YieldReaction ConditionsOperation in experiment
With tetrabutylammomium bromide; sodium acetate; palladium diacetate In N,N-dimethyl-formamide at 115℃; for 48h; Inert atmosphere; 4.3 2.4.3 5',,-((1E,1'E,1"E)-(nitrilotris(benzene-4,1-diyl))tris(ethene-2,1-diyl))tris(([2,2'-bithiophene]-5-carbaldehyde)) (5) A mixture of Compound 4 (896 mg, 2.78 mmol), Pd(OAc)2 (37.3 mg, 0.166 mmol), NaOAc (6.82 g, 83.2 mmol), Compound 3 (2.5 g, 9.16 mmol) and n-Bu4NBr (428.7 mg, 1.33 mmol) was dissolved in degassed DMF (40 mL). The solution was kept under a nitrogen atmosphere at 115 °C for 2 days. The mixture was poured into water. The precipitate was filtered, washed with water and dissolved in dichloromethane, and dried over Na2SO4. After evaporation of the solvent, the residue was used in the next reaction without any purification.
  • 28
  • [ 478706-06-8 ]
  • [ 110046-60-1 ]
  • [ 1431471-26-9 ]
YieldReaction ConditionsOperation in experiment
64% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene Inert atmosphere; Reflux; 3.5 4.3.5. 5',5'-(9-octyl-9H-carbazole-3,6-diyl)di-2,20-bithiophene-5-carbaldehyde (6) A mixture of 5 (0.74 g, 2.72 mmol), 2 (0.72 g, 1.35 mmol) and Pd(PPh3)4 (23 mg, 0.02 mmol) in toluene (16 mL) and a 2.0 M K2CO3 aqueous solution (8 mL) was refluxed overnight. After cooling the mixture down to room temperature, CH2Cl2 (40 mL) was added and the obtained mixture was washed with water (3 x 40 mL). After solvent removal, the crude product was purified by flash chromatography (SiO2, CH2Cl2) to afford 6 (0.57 g, 64%) as an orange solid. 1H NMR (700 MHz, CDCl3): δ 9.90 (s, 2H), 8.39 (s, 2H), 7.78 (d, J = 8.8 Hz, 2H), 7.72 (d, J = 3.9 Hz, 2H), 7.46 (d, J = 8.8 Hz, 2H), 7.41 (d, J = 3.6 Hz, 2H), 7.36 (d, J = 3.6 Hz, 2H), 7.31 (d, J = 3.9 Hz, 2H), 4.36 (t, J = 7.0 Hz, 2H), 1.95-1.90 (m, 2H), 1.44-1.39 (m, 2H), 1.38-1.33 (m, 2H), 1.32-1.23 (m, 6H), 0.88 (t, J = 7.0 Hz, 3H) ppm. 13C{1H} NMR (176 MHz, CDCl3): δ 182.4, 147.6, 141.3, 140.9, 137.4, 134.0, 127.3, 125.2, 124.5, 123.6, 123.3, 123.2, 118.0, 109.6, 43.5, 31.8, 29.3, 29.1, 29.0, 27.3, 22.6, 14.0 ppm. Elemental analysis for C38H33NO2S4: calcd. C, 68.74; H, 5.01; N, 2.11; found C, 68.71; H, 4.95, N, 2.00.
  • 29
  • [ 110046-60-1 ]
  • [ 258865-48-4 ]
  • [ 1446101-17-2 ]
YieldReaction ConditionsOperation in experiment
67.4% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; N,N-dimethyl-formamide for 4h; Reflux; Inert atmosphere; 6 Synthesis of Compound (6) EXAMPLE 6 Synthesis of Compound (6) The synthesis of Compound (6) was carried out in accordance with Scheme 6 indicated hereunder: For this purpose, a mixture of 9, 9-dioctylfluorene- 2, 7-diboronic acid (1450 mg, 3.04 mmoles) , Compound (5) (1500 mg, 5.52 mmoles) and palladium (tetrakis ) - triphenylphosphine [Pd(Ph3P)4] (176 mg, 0.152 mmoles), in N, -dimethylformamide (N, -DMF) (140 ml) and sodium carbonate (Na2C03) (10 ml of an aqueous solution 2 M) , was heated to reflux temperature for 4 hours, under a stream of argon. The reaction mixture was left to cool to room temperature (25°C) , 100 ml of distilled water were added and the whole mixture was then filtered, obtaining a solid which was recovered. The solid thus obtained was partially dissolved in ethyl acetate (100 ml), subsequently filtered and the liquid phase obtained was concentrated under vacuum obtaining a reaction raw product. The reaction raw product thus obtained was purified by means of column chromatography [silica gel, gradients from n-heptane 100% to n-heptane/ethyl acetate = 8:2 (v/v) as eluent] obtaining 1060 mg (67.4% in moles) of Compound (6). Said Compound (6) was characterized by means of 1H- NMR (400 MHz, CDC13) obtaining the following spectrum: δ = 9.90 ppm (s, 1H, -CHO) ; 7.75-7.72 ppm (d, 2H, Hm-CH- Th) ; 7.72-7.70 ppm (d, 2H, Th-CH-CH-CHO) ; 7.66-7.62 ppm (q, 2H, Hm-CH-Th) ; 7.59-7.57 ppm (d, 2H, Ho-Th) ; 7.41- 7.39 ppm (d, 2H, CH-CH-Th-CHO) ; 7.38-7.36 ppm (d, 2H, CH-CH-Th-CHO); 2.10-2.03 ppm (m, 4H, C- (CH2) 2- (CH2) 12- CH3), 1.22-1.04 ppm (m, 24H, C- (CH2) 2- (C) 12-CH3) ; 0.84- 0.76 ppm (t, 6H, C- (CH2) 2- (CH2) 12-CH3_) . Said Compound (6) was also characterized by means of IR ( Br) spectrum showing the following bands: v = 1662 cm-1 (aldehyde C-0 stretching) ; 1515 cm"1 (ring mode of the thiophenes), 795 cm-1 (deformation conjugated dithienyls) .
  • 30
  • [ 1375927-64-2 ]
  • [ 110046-60-1 ]
  • [ 1375927-67-5 ]
YieldReaction ConditionsOperation in experiment
27% Stage #1: C22H20BrNS With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran; hexane at -78 - 20℃; for 1.5h; Stage #3: 5'-bromo-2,2'-bithiophene-5-carboxaldehyde With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran; hexane at 20℃; for 3h; 2 Next, 2 g of the compound B1 was dissolved in 40 ml of dried tetrahydrofuran, and to the resulting solution, 4.6 ml of a 1.6 mol/L hexane solution of n-butyllithium was dropwise added in argon atmosphere at -78° C. The resulting solution was stirred for 30 minutes, and then 0.731 g of zinc chloride was added to the solution and stirred at -78° C. for 30 minutes and at room temperature for 1 hour. To the resulting mixture, 0.666 g of 5-bromo-2,2′-bithiophene-5′-carooxyaldehyde and 0.169 g of tetrakis(triphenylphosphine)palladium were added and stirred at room temperature for 3 hours. To the reaction mixture, 200 ml of ethyl acetate was added, and washed with a 3% by mass aqueous solution of sodium carbonate and an aqueous solution of NaCl in this order. Next, the reaction mixture was dried with magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was separated and purified with silica gel column (developing solvent: a hexane/ethyl acetate (volume mixing ratio: 2/1) mixed solvent) to yield 0.348 g (yield: 27%) of the compound B2
  • 31
  • [ 625-82-1 ]
  • [ 110046-60-1 ]
  • C21H21BrN2S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 48h; Inert atmosphere; 2.1.1 General procedure for synthesis of BODIPYs 1-11 General procedure: In an oven dried flask, 2,4-dimethylpyrrole (0.9990g, 10.5mmol) and the corresponding aryl aldehyde (5.0mmol) were dissolved in dry dichloromethane (DCM, 300mL). Boron trifluoride diethyl etherate (BF3·OEt2, 0.15mL) was added drop-wise and the mixture was stirred at room temperature under nitrogen atmosphere for 48h (until TLC revealed disappearance of the aldehyde). 2,3-Dichloro-5,6-dicyano-p-benzoquinone (DDQ, 1.1578g, 5.1mmol) in DCM (5mL) was added to the solution and stirred for 1h. Triethylamine (3.8216g, 37.5mmol) was then added to the mixture and stirred for 30min followed by the introduction of BF3·OEt2 (6.17mL, 50mmol) in DCM (10mL) and stirred for 3h. The mixture was poured into water and the organic layer was washed twice with saturated sodium chloride. The organic layer was passed through a bed of anhydrous Na2SO4 and the solvent was evaporated under reduced pressure. The resulting residue was passed through a silica plug using dichloromethane as eluent. The solvent was again removed under vacuum and the crude product was purified by silica gel flash chromatography using 30% dichloromethane in petroleum ether.
  • 32
  • [ 110046-60-1 ]
  • [ 17573-94-3 ]
  • [ 1564286-89-0 ]
YieldReaction ConditionsOperation in experiment
77% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran for 16h; Inert atmosphere; Reflux; 2.2.1. General procedure for the synthesis of aldehydes 4-5 throughSonogashira coupling General procedure: Aldehydes 2 [47] or 3 [48] (0.81 mmol) were coupled with 4-ethynyl-N,N-dimethylaniline 1 (0.114 g, 0.78 mmol), in a mixtureof THF (10 mL), trimethylamine (6 mL), Pd(PPh3)2Cl2 (0.023 g,0.02 mmol) and copper iodide (0.002 g, 0.01 mmol), at reflux undernitrogen. The reaction was monitored by TLC, which determinedthe reaction time (16 h). After cooling, 10 mL of water were addedand the reaction mixture was extracted with dichloromethane(3 x 20 mL). The combined organic layers were dried over anhydrousMgSO4, filtered, and the solvent evaporated under reducedpressure. The crude products were purified by column chromatography(silica gel, mixtures of chloroform and light petroleum ofincreasing polarity) to give the pure compounds 4-5.
40% Stage #1: 5'-bromo-2,2'-bithiophene-5-carboxaldehyde With copper(l) iodide; palladium 10% on activated carbon; potassium carbonate; triphenylphosphine In 1,2-dimethoxyethane; water at 20℃; for 0.583333h; Inert atmosphere; Stage #2: 4-ethynyl-N,N-dimethylaniline In 1,2-dimethoxyethane; water Inert atmosphere; Reflux; 2.4.2 Compound 5 5-Bromo-2,2′-bithiophene-5′-carboxaldehyde 2 (0.50 g, 1.83 mmol), 10% Pd/C (0.06 g, 0.06 mmol), CuI (0.10 g, 0.55 mmol), Ph3P (0.40g, 1.50mmol) and K2CO3 (0.40 g, 2.90 mmol) were dissolved at room temperature in a 1:1 mixture of water (15 mL) and DME (15 mL). The mixture was degassed with N2 for 5 min and stirred for 30 min under N2. Then 4-ethynyl-N,N-dimethylaniline 3 (0.40 g, 2.75 mmol) was added to the mixture. The reaction mixture was heated under reflux overnight. The mixture was then cooled and DCM (80 mL) was added and the organic layers were separated, dried over MgSO4 and filtered. Then the solvent was evaporated under reduced pressure and the residue was then purified by column chromatography (SiO2; DCM/petroleum ether, 9:1) to give 5 as an orange solid (0.37 g, 40%); mp. 200-203°C; 1H NMR (400 MHz, CDCl3) δ 9.86 (s, 1H), 7.66 (d, J=4.0Hz, 1H), 7.39 (d, J=8.9Hz, 2H), 7.23 (d, J=3.4Hz, 1H), 7.22 (d, J=3.4Hz, 1H), 7.13 (d, J=4.0Hz, 1H), 6.66 (d, J=8.9Hz, 2H), 3.01 (s, 6H) ppm; 13C NMR (100 MHz, CDCl3) δ 182.4 (C-H), 150.4 (C-C), 146.6 (C-C), 141.6 (C-C), 137.3 (C-H), 135.8 (C-C), 132.7 (2×C-H), 131.8 (C-H), 126.3(C-C), 126.0 (C-H), 124.2 (C-H), 111.7 (2×C-H), 108.8 (C-C), 97.3 (C≡C), 80.2 (C≡C), 40.1 (2×CH3-N) ppm; IR (film) υ 2787, 2185, 1654, 1228cm-1; HRMS m/z (EI+) calculated for C19H15NOS2 337.0595 found 337.0591.
  • 33
  • 4′-(hexyloxy)-N-(4′-(hexyloxy)-[1,1′-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)[1,1′-biphenyl]-4-amine [ No CAS ]
  • [ 110046-60-1 ]
  • 5'-(4-(bis(4'-(hexyloxy)biphenyl-4-yl)amino)phenyl)-2,2'-bithiophene-5-carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,2-dimethoxyethane Reflux; 4.4.1. Synthesis of 5'-(4-(bis(4'-(hexyloxy)biphenyl-4-yl)amino)phenyl)-2,2'-bithiophene-5-carbaldehyde (7). To a 100 mL two-neck-round-bottom flask, 25 mL 1, 2-dimethoxyethane, compound of 5 (361.7 mg, 0.5 mmol), 5-(5-bromothiophen-2-yl)thiophene-2-carbaldehyde (54.4 mg, 0.2 mmol), Pd(PPh3)4 (23.1 mg,0.02 mmol), K2CO3 (276 mg, 2 mmol, 2 M), were added. The crude product was extracted into ethyl acetate, washed with water and dried over anhydrous sodium sulfate. The solvent was evaporated and the remaining crude product was purified by column chromatography (using an eluent gradient of petroleum ether/ethylacetate (15:1)) to give desired aldehydes 7 (yellow solid, 85% yield).
  • 34
  • [ 1352642-37-5 ]
  • [ 110046-60-1 ]
  • 5',5'''-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis-(([2,2-bithiophene]-5-carbaldehyde)) [ No CAS ]
YieldReaction ConditionsOperation in experiment
42% With tris-(dibenzylideneacetone)dipalladium(0); tris-(o-tolyl)phosphine In toluene at 100℃; for 3h; Inert atmosphere; 5,5-(4,8-Bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b]dithiophene-2,6-diyl)-bis-(([2,2-bithiophene]-5-carbaldehyde)) BDT(TTA)2. A mixture of Br-TTA (1.5 g,5.49 mmol) and (4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b]dithiophene-2,6-diyl)bis(trimethylstannane) (BDT) (2.48 g, 2.74 mmol), tri(o-tolyl)phosphine (0.067 g,0.22 mmol)), and tris(dibenzylideneacetone)dipalladium(0) (0.050 g, 0.055 mmol) in toluene (300 mL) was stirred under reflux at 100 °C for 3 hr. The reaction mixture was extracted with dichloromethane, washed with water, dried over Na2SO4, and the solvent was removed in vacuo. Recrystallization of the crude product from dichloromethane and n-hexane to afford a orange neddle-like solid (yield = 42%). 1H NMR (300 Mz, CDCl3, δ,ppm) : 9.84 (s, 2H), 7.6 5 (d, 4H, J = 4.2 Hz), 7.31 (d, 2H, J = 3.6 Hz), 7.27 (s, 1H), 7.21(m, 4H), 6.95 (d, 2H, J = 3.6 Hz), 2.91(d, 4H, J = 6.6 Hz), 1.75-1.71 (m, 2H), 1.50-1.37(m, 16H), 1.01-0.92 (m, 12H).
  • 35
  • [ 110046-60-1 ]
  • [ 201802-67-7 ]
  • [ 762269-61-4 ]
YieldReaction ConditionsOperation in experiment
88% With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In ethylene glycol dimethyl ether; ethanol; lithium hydroxide monohydrate at 80℃; for 12h; Inert atmosphere;
67% With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; potassium carbonate In methanol; toluene Inert atmosphere; Reflux; 2.1 The 4-(diphenylamino) phenylboronic acid (1.3equiv, 688mg, 2.38mmol), 5-bromo-2,2'-bithiophene-5'-formaldehyde (1equiv, 500mg, 1.83mmol), [1, 1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.1equiv, 133.93mg, 0.183mmol) and K2CO3 (5equiv, 1.26g, 9.15mmol) are placed in the reaction flask, and toluene/methanol is added (50ml/50mL), heated to reflux for 12 hours under the protection of nitrogen, and cooled to room temperature after the reaction. The solvent was distilled off under reduced pressure, dichloromethane was added, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and separated by silica gel column chromatography to obtain compound III-b as an orange solid product with a yield 67%.
56% With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In tetrahydrofuran; lithium hydroxide monohydrate for 24h; Reflux; Inert atmosphere; 1-2 Preparation steps for (Z)-4-(1-cyano-2-(5'-(4-(diphenylamino)phenyl)-[2,2'-bisthiophene]-5-yl)vinyl)-1-methylpyridine hexafluorophosphate (IIa): Place 2.0 mmol 5-bromo-2,2'-bithiophene-5'-carbaldehyde, 2.4 mmol 4-boronic acid triphenylamine, 0.04 mmol tetrakis(triphenylphosphine)palladium, 20 mmol potassium carbonate in 70 mL tetrahydrofuran/water (volume ratio 6/1) in the solvent, heated to reflux for 24 hours under a nitrogen atmosphere, the reaction was completed, the tetrahydrofuran was removed by rotary evaporation under reduced pressure, extracted with dichloromethane, the organic phase was rotary evaporated under reduced pressure to obtain a solid, and the solid was distilled with dichloromethane/n-hexane. After passing through a silica gel column, an orange precursor compound (I) was obtained in a yield of 56%.
52% With tetrakis-(triphenylphosphine)-palladium; sodium hydroxide In monoethylene glycol diethyl ether; lithium hydroxide monohydrate at 100℃; for 2h; Inert atmosphere; 5-[4-(Diphenylamino)phenyl]-2-thiophenecaroxbaldehyde (1b) General procedure: To a 1,2-diethoxyethane solution (30 ml) of 5-bromothiophene-2-carboaldehyde 0.5 g (2.62mmol) was added 4-(diphenylamino)phenylboronic acid 0.91 g (3.14 mmol),tetrakis(triphenylphosphine)paladium 61 mg (0.052 mmol) and an aqueous solution of 1M-NaOH 18ml under N2, and the mixture was stirred at 100 °C for 2 h. The reaction mixture was extractedwith ethyl acetate. The extracts were washed with water and brine, and dried over anhydrousmagnesium sulfate. After the removal of the solvent, the product mixture was recrystrized from amixture of ethyl acetate and hexane to give 1b (0.54 g, 61%).

  • 36
  • [ 110046-60-1 ]
  • [ 13361-34-7 ]
  • C20H22BrNO2S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With triethylamine; In chloroform; at 20℃; for 12h; Take compound 20 (1.66g, 6.1mmol) and isooctyl cyanoacetate (5.99g, 30.5mmol) in anhydrous chloroform (50mL), was added a small amount of triethylamine (0.1mL), and then for 12 hours at room temperature, the reaction after washing with water, dried, filtered and the solvent was removed by rotary evaporation with petroleum ether to silica gel column chromatography eluent, to give an orange-yellow solid 21 (2.32g, 84%).
  • 37
  • [ 624744-67-8 ]
  • [ 110046-60-1 ]
  • C43H26OS2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% To a 250 ml 2-neck round bottom flask was added compound 10 (4 g, 7.1875 mmol), 5-bromo-2,2'-bithiophene-5 '-Carboxaldehyde, 2.94 g, 10.7813 mmol) were placed in 150 ml of toluene and stirred.The temperature was raised to ~ 50 C and Pd (0) (0.37 mg, 3 mol%) was added.Stir for a few minutes.And 2M aq. K2CO3 was added thereto, and the temperature was increased to 90 DEG C and stirred.After the reaction, the solution was reacted at 90 DEG C for 12 hours.This solution was poured into water, extracted twice with chloroform,Washed twice with water, and the residue was removed with magnesium sulfate (MgSO4).The solvent was distilled off under reduced pressure, and a fine powder was obtained through a silica column (eluent; hexane / EA = 10: 5) (yield: 71%).
  • 38
  • [ 419536-33-7 ]
  • [ 110046-60-1 ]
  • 2-{5'-[4-(9H-carbazol-9-yl)phenyl]-2,2'-bithiophen-5-yl}-2-carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; benzene for 24h; Reflux; Inert atmosphere; Synthesis of compounds 5, 6 (General method). General procedure: Amixture of bromo-substituted aldehyde 3, 4 (0.02 mol),4-(9-carbazol-9-yl)phenylboronic acid (2) (5.74 g, 0.02 mol),Pd(PPh3)4 catalyst (3% by weight of bromo-substitutedaldehyde), PhH (20 ml), and 2 M aqueous Na2CO3 (10 ml)was heated under reflux under argon for 24 h. Uponcompletion of the reaction (monitoring by TLC), themixture was cooled to room temperature and the organicphase was separated. The aqueous phase was extractedwith CH2Cl2, the organic phases were combined andconcentrated. The residue was purified by columnchromatography (eluent CH2Cl2).
75% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; benzene for 24h; Inert atmosphere; Reflux; Synthesis of compounds 5, 6 (General method) General procedure: Amixture of bromo-substituted aldehyde 3, 4 (0.02 mol),4-(9-carbazol-9-yl)phenylboronic acid (2) (5.74 g, 0.02 mol),Pd(PPh3)4 catalyst (3% by weight of bromo-substitutedaldehyde), PhH (20 ml), and 2 M aqueous Na2CO3 (10 ml)was heated under reflux under argon for 24 h. Uponcompletion of the reaction (monitoring by TLC), themixture was cooled to room temperature and the organicphase was separated. The aqueous phase was extractedwith CH2Cl2, the organic phases were combined andconcentrated. The residue was purified by columnchromatography (eluent CH2Cl2)
  • 39
  • [ 6973-60-0 ]
  • [ 110046-60-1 ]
  • 5-(5-(1-methyl-1H-pyrrol-2-yl)thiophen-2-yl)thiophene-2-carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
39% With bis(tri-t-butylphosphine)palladium(0); tetrabutyl-ammonium chloride; caesium carbonate In N,N-dimethyl-formamide at 140℃; regioselective reaction; 4.2.3. Method C: decarboxylative coupling. General procedure: General procedure for the synthesis of pyrroles 5a-d through decarboxylative cross-coupling reaction: The following reagents were added to an open flask: heteroaromatic halides 2a-d (1 equiv), 1-methyl-2-pyrrolecarboxylic acid 3 (2 equiv), n-Bu4NCl.H2O (1 equiv), Cs2CO3 (1.5 equiv) and catalyst Pd[P(t-Bu)3]2 (0.05 equiv). Anhydrous DMF (4 ml) was then added and the mixture was stirred for 1-4 h in an oil bath at 140 °C. The reaction mixture was then diluted with ethyl acetate (50 ml), and the organic layer was washed with saturated KHSO4 solution (2×10 ml) and with brine (1×20 ml). The organic layer was dried over MgSO4 and filtered, and the solvent removed to give the crude mixtures. The crude products were purified through a silica gel chromatography column using petroleum ether (40-60 °C) and mixtures of petroleum ether (40-60 °C) and dichloromethane. The elution began with petroleum ether (40-60 °C) and continue with mixtures of petroleum ether (40-60 °C)-dichloromethane of increasing polarity until (50:50) to yield the pure coupled products 5a-d. In all chromatography purifications the fractions containing the pure compounds 5a and 5c were eluted using a mixture of petroleum ether (40-60 °C)-dichloromethane (70:30). On the other hand, more polar derivatives 5b and 5d were eluted using a mixture of petroleum ether (40-60 °C)-dichloromethane (50:50).
  • 40
  • [ 850567-47-4 ]
  • [ 110046-60-1 ]
  • 5-(5-(1-methyl-1H-pyrrol-2-yl)thiophen-2-yl)thiophene-2-carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
15% With tetrakis(triphenylphosphine) palladium(0); water; sodium carbonate In 1,2-dimethoxyethane at 80℃; for 24h; Inert atmosphere; 4.2.1. Method A: Suzuki coupling. General procedure for the synthesis of pyrroles 5 through Suzuki cross coupling reaction General procedure: Bromo-thiophene derivatives 2a-d (1 equiv) were coupled to 1-methyl-1H-pyrrole-2-boronic acid (1.2 equiv) in a mixture of DME (10 ml), aqueous 2 M Na2CO3 (1 ml) and Pd(PPh3)4 (3 mol %) at 80 °C under nitrogen. The reaction was monitored by TLC, which determined the reaction time (24 h). After cooling, the mixture was extracted with dichloromethane (3×20 ml) and a saturated solution of NaCl was added (20 ml) and the phases were separated. The organic phase was washed with water (3×10 ml) and with a solution of NaOH (10%) (1×10 ml). The organic phase obtained was dried with MgSO4, filtered, and the solvent removed to give a crude mixture. The crude products were purified through a silica gel chromatography column using petroleum ether (40-60 °C) and mixtures of petroleum ether (40-60 °C) and dichloromethane. The elution began with petroleum ether (40-60 °C) and continue with mixtures of petroleum ether (40-60 °C)-dichloromethane of increasing polarity until (50:50) to yield the pure coupled products 5a-d.
  • 41
  • C30H43NS2Sn [ No CAS ]
  • [ 110046-60-1 ]
  • 5''-(8-butyl-8H-thieno[2,3-b]indol-2-yl)-[2,2':5',2''-terthiophene]-5-carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
23% With tetrakis(triphenylphosphine) palladium(0) In 1,2-dimethoxyethane at 95℃; for 8h; Inert atmosphere; General procedure for the synthesis of thieno[2,3-b]indole-based thienaldehydes (2b-d). General procedure: 1.6 M Solution of n-butyllithium in hexane (2.5 mL, 4 mmol) was added to the solution of thieno[2,3-b]indole 1b, 1c or 1e (2 mmol) in dry glyme (15 mL) at 0 °C under an argon atmosphere. It was stirred at 0 °C for 1 h and then tributyltin chloride (1.08 mL, 4 mmol) was added dropwise at -40 °C. The mixture was stirred at room temperature overnight. The appropriate bromo-containing 2-thienaldehyde (2.2 mmol) and Pd(Ph3P)4 (0.18 g, 0.16 mmol) were added to the reaction mixture that was then heated at 95 °C for 8 h. Then the mixture was stirred with 10% KF (100 mL) for 5 h and extracted with EtOAc (100 mL). Organic layer was separated and the solvent was removed under reduced pressure. The residue was purified by column chromatography (silica gel, CH2Cl2) affording red powders of aldehydes 2b-d.
Stage #1: C30H43NS2Sn; 5'-bromo-2,2'-bithiophene-5-carboxaldehyde With tetrakis(triphenylphosphine) palladium(0) In 1,2-dimethoxyethane at 95℃; for 8h; Stage #2: With potassium fluoride In 1,2-dimethoxyethane for 5h; General procedure for the synthesis of thieno[2,3-b]indole-based thienaldehydes (2b-d). General procedure: 1.6 M Solution of n-butyllithium in hexane (2.5 mL, 4 mmol) was added to the solution of thieno[2,3-b]indole 1b, 1c or 1e (2 mmol) in dry glyme (15 mL) at 0 °C under an argon atmosphere. It was stirred at 0 °C for 1 h and then tributyltin chloride (1.08 mL, 4 mmol) was added dropwise at -40 °C. The mixture was stirred at room temperature overnight. The appropriate bromo-containing 2-thienaldehyde (2.2 mmol) and Pd(Ph3P)4 (0.18 g, 0.16 mmol) were added to the reaction mixture that was then heated at 95 °C for 8 h. Then the mixture was stirred with 10% KF (100 mL) for 5 h and extracted with EtOAc (100 mL). Organic layer was separated and the solvent was removed under reduced pressure. The residue was purified by column chromatography (silica gel, CH2Cl2) affording red powders of aldehydes 2b-d.
  • 42
  • [ 863992-56-7 ]
  • [ 110046-60-1 ]
  • C32H18O2S4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 78℃;Inert atmosphere; General procedure: The optimized procedure is based on similar reports.S8,S9 To a solution of <strong>[863992-56-7]9,10-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anthracene</strong> (1) (0.930 mmol), brominated aromatic aldehyde (2.800 mmol) and Pd(PPh3)4 ( 0.140 mmol) in THF (30 mL), was added drop-wise an aqueous solution of K2CO3 (2.6 mL, 2M) at room temperature under argon atmosphere. After refluxing at 78 C for 12 hours, the reaction mixture was cooled to room temperature. The solvent was evaporated under reduced pressure. The solid residue was dissolved in DCM and washed with water. The organic layers were dried over MgSO4 and concentrated. Further purification was carried out by silica column chromatography.
  • 43
  • [ 18512-55-5 ]
  • [ 110046-60-1 ]
  • 5',5'''-(anthracene-9,10-diylbis(ethyne-2,1-diyl))bis(([2,2'-bithiophene]-5-carbaldehyde)) [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran Inert atmosphere; 2.3.General procedure for the synthesis of 9,10-bis(ethnylarylaldehyde)anthracene (6-8). General procedure: 9,10-bis(ethynyl)anthracene (5) was freshly prepared prior to subsequent coupling reaction using a previously published procedure.S4 Diterminal alkyne (5) was coupled with the brominated aromatic aldehydes under Sonogashira coupling conditions. THF (30mL), brominated aromatic aldehydes (3.049 mmol), CuI (0.148 mmol) and Pd(PPh3)2Cl2 (0.152 mmol)were placed in a flask, degassed and backfilled with argon. To this solution was subsequently added a solution of 9,10-bis(ethynyl)anthracene (1.016 mmol) in THF (10 mL). Then 12 mL of TEA was added and the reaction mixture was refluxed for 12 hours. After removal of the solvent, the residue was dissolved in dichloromethane, washed with water and dried over MgSO4. After solvent removal, the residue was purified by column chromatography.
  • 44
  • [ 18512-55-5 ]
  • [ 110046-60-1 ]
  • C42H18N4S4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: triethylamine; bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide / tetrahydrofuran / Inert atmosphere 2: triethylamine / chloroform / Reflux
  • 45
  • [ 71597-85-8 ]
  • [ 110046-60-1 ]
  • 5'-(4-hydroxyphenyl)-[2,2'-bithiophene]-5-carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,2-dimethoxyethane; ethanol for 3.5h; Inert atmosphere; 5'-(4-hydroxyphenyl)-[2,2'-bithiophene]-5-carbaldehyde (5) In a 25 mL two-necked flask, a mixture of 4 (191 mg, 2.0 mmol), (4-hydroxyphenyl)boronic acid(126 mg, 0.91 mmol) and PdCl2(PPh3)2 (49 mg, 0.07 mmol) were dissolved in 3 mL of DME. Then, 1.5mL of EtOH were added followed by addition of 2.5 mL of Na2CO3 (2M). The reaction mixture wasflushed with nitrogen and refluxed for 3.5 h, then the solution was cooled at room temperature. Afterelimination of the volatiles under vacuum, the aqueous phase was extracted with ethyl acetate, dried byanhydrous Na2SO4 and concentrated under reduced pressure. The crude product was recrystallized fromCH2Cl2 to afford 183 mg (91%) of the compound 5 as a dark yellow solid. 1H NMR (400 MHz, DMSO-d6)δ: 10.01 (s, 1H), 9.87 (s, 1H), 8.00 (d, J = 4.0 Hz, 1H), 7.56 (d, J = 3.9 Hz, 1H), 7.52 (d, J = 6.9 Hz, 2H),7.51 (d, J = 2.2 Hz, 1H), 7.38 (d, J = 3.9 Hz, 1H), 6.86 (d, J = 8.6 Hz, 2H) . 13C NMR (100 MHz,DMSO-d6) δ: 183.7, 158.37, 146.1, 145.8, 140.7, 139.3, 132.5, 128.2, 127.0, 124.6, 123.7, 123.3, 116.1.HR-EI-MS(m/z): M+ calcd. for C15H10O2S2: 286.0122, found: 286.0123.
  • 46
  • 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-d:4,5-d']bis(thiazole) [ No CAS ]
  • [ 110046-60-1 ]
  • C50H48N2O2S8 [ No CAS ]
YieldReaction ConditionsOperation in experiment
0.37 g Stage #1: 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-d:4,5-d']bis(thiazole) With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: With trimethyltin(IV)chloride In tetrahydrofuran; hexane at 20℃; for 4h; Stage #3: 5'-bromo-2,2'-bithiophene-5-carboxaldehyde With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran at 100℃; for 10h; Synthesis of Compound a18-2 A tetrahydrofuran (30 mE) solution of compound al-li (0.6 g) was cooled down to -78° C., and 1.5 mE of nl3uEi (1.6 M hexane solution) was added dropwise to the resultant solution. The solution afier addition was stirred for 1 hout Continuously, Me3SnCl (0.5 g) was added to the resultant stirred solution, and the resultant mixture was lefi to cool down to room temperature. The resultant cooled down mixture was stirred for 4 hours. Water and ethyl acetate were added to the resultant stirred mixture to concentrate an organic layet The resultant concentrate and 0.7 g of compound a18-1 were mixed in THF (30 mE), and Pd(PPh3)4 (250 mg) was added to the resultant mixture. The mixture after addition was heated to 100° C., and was stirred for 10 hours. The resultant stirred mixture was lefi to cool down to room temperature, and water and chloroform were added to the resultant cooled down mixture. The mixture afier addition was subjected to liquid separation to concentrate an organic layer, and the organic layer was purified with column chromatography, thereby obtaining 0.37 g of compound a18-2. A structure of the compound al 8-2 was confirmed with mass spectrometry (MS). MS-ESI mlz=965.2 (M+H7
  • 47
  • [ 110046-60-1 ]
  • [ 13361-34-7 ]
  • C46H48N2O6S5 [ No CAS ]
  • 48
  • [ 162607-17-2 ]
  • (E)-1-(5-bromothiophen-2-yl)-N-(4-methylpyridin-2-yl)methanimine [ No CAS ]
  • [ 110046-60-1 ]
YieldReaction ConditionsOperation in experiment
45% General procedure: The catalyst Pd(PPh3)4 (5 mol%) was added in the Schiff bases (0.712 mmol, 1 eq), under an inert nitrogen atmosphere. The reaction mixture was stirred for 30 min after addition of a 1,4-dioxane solvent (8 mL). Then, aryl/het-aryl boronic acids (0.783 mmol, 1.1 eq), K3PO4 (1.43 mmol, 2 eq) and H2O (2 mL) were added [26,27] and stirring of mixture was done for 20-25 h at 90 C. The mixture was diluted with ethyl acetate at room temperature. The separated organic layer was dried with magnesium sulphate (MgSO4) and the solvent was removed under a vacuum. The crude product was purified by column chromatography using ethyl-acetate and n-hexane. For characterization of synthesized products, different spectroscopic techniques were used.
  • 49
  • C33H28BNO2 [ No CAS ]
  • [ 110046-60-1 ]
  • C40H27NOS2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
46% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 10h; Inert atmosphere; Reflux; 2.S2 S2: Take 0.273 g of the compound represented by formula (VI), 0.023 g of tetratriphenylphosphine palladium and 0.284 g of potassium carbonate in a mixed solution of 10 mL of tetrahydrofuran and 4 ml of water.Then add the solution containing the boric acid ester compound represented by formula (IV) obtained in step S1, and react under reflux under a protective atmosphere of N2 for 10 hours;After the reaction was completed, 10 mL of water was added to the reaction solution for dilution, and extraction was performed three times (15 mL × 3) with dichloromethane.The organic layers were combined, washed successively with saturated brine, dried over anhydrous sodium sulfate, and the solvent was spin-dried.Then separated by column chromatography (eluent is a mixed solution of CH2Cl2 and PE with a volume ratio of 1: 4) to obtain a compound having a structure represented by formula (II-2) as an orange-red solid 0.24 g (yield 46%), mp140 ~ 142 °C
  • 50
  • [ 952431-30-0 ]
  • [ 110046-60-1 ]
  • 5'-(4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)-[2,2'-bithiophene]-5-carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); potassium carbonate In tetrahydrofuran; water at 70℃; Microwave irradiation;
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); potassium carbonate at 70℃; for 2h; Microwave irradiation; Sealed tube;
  • 51
  • [ 201802-29-1 ]
  • [ 110046-60-1 ]
  • [ 1219091-31-2 ]
YieldReaction ConditionsOperation in experiment
67% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In methanol; toluene Inert atmosphere; Reflux; 4.1 4,4'-Dimethoxy-4"-boronic acid triphenylamine (1.3equiv, 3.32g, 9.52mmol), 5-bromo-2,2'-bithiophene-5'-carbaldehyde (1equiv, 2g, 7.32 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.025equiv, 133.93mg, 0.183mmol) and K2CO3 (1.25equiv, 1.26g, 9.15mmol) are placed in the reaction To the bottle, add toluene/methanol (50ml/50mL), heat and reflux for 12 hours under the protection of nitrogen. After the reaction, cool to room temperature. Distill under reduced pressure to remove the solvent, add dichloromethane, and wash with water and saturated brine successively. It was dried with sodium sulfate, filtered, concentrated under reduced pressure, and separated by silica gel column chromatography to obtain compound III-d as a red solid product with a yield of 67%
  • 52
  • C13H10O4 [ No CAS ]
  • [ 110046-60-1 ]
  • 5’-((6,7-dimethoxi-2-oxo-2H-chromen-3-yl)ethynyl)-[2,2’-bithiophene]-5-carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
46.3% With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); diisopropylamine; triphenylphosphine In 1,4-dioxane at 45℃; Sealed tube; Inert atmosphere; 3.1 General method for the synthesis of coupled aldehydes (4 - 7) General procedure: To a sealed tube, PPh3 (0.06 eq), CuI (0.12 eq), Pd(PPh3)4 (0.15), aldehyde (1 eq.) and 5 mL of dry dioxane were added under a N2 atmosphere. After a few minutes ethynylcoumarin (3) (1 eq.) and dry (i-Pr)2NH (2 eq.) were added and the solution wasstirred at 45°C overnight under a N2 atmosphere. Once the reaction was confirmed tobe complete by TLC (hexane/AcOEt (7:3 v/v)), the solution was cooled to roomtemperature, the solvent was removed under reduced pressure and the solid residuedried in vacuo before being purified by flash chromatography with DCM/MeOH(99.8:0.02 v/v and 99.5:0.05 v/v) as eluent, affording a bright yellow solid in all cases.
  • 53
  • 5,7-dimethoxy-3-ethynylcoumarin [ No CAS ]
  • [ 110046-60-1 ]
  • 5’-((5,7-dimethoxi-2-oxo-2H-chromen-3-yl)ethynyl)-[2,2’-bithiophene]-5-carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
14.1% With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); diisopropylamine; triphenylphosphine In 1,4-dioxane at 45℃; Sealed tube; Inert atmosphere; 3.1 General method for the synthesis of coupled aldehydes (4 - 7) General procedure: To a sealed tube, PPh3 (0.06 eq), CuI (0.12 eq), Pd(PPh3)4 (0.15), aldehyde (1 eq.) and 5 mL of dry dioxane were added under a N2 atmosphere. After a few minutes ethynylcoumarin (3) (1 eq.) and dry (i-Pr)2NH (2 eq.) were added and the solution wasstirred at 45°C overnight under a N2 atmosphere. Once the reaction was confirmed tobe complete by TLC (hexane/AcOEt (7:3 v/v)), the solution was cooled to roomtemperature, the solvent was removed under reduced pressure and the solid residuedried in vacuo before being purified by flash chromatography with DCM/MeOH(99.8:0.02 v/v and 99.5:0.05 v/v) as eluent, affording a bright yellow solid in all cases.
  • 54
  • C50H50S6 [ No CAS ]
  • [ 110046-60-1 ]
  • C68H58O2S10 [ No CAS ]
YieldReaction ConditionsOperation in experiment
75.1% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 130℃; for 20h; Inert atmosphere; Synthesis of Intermediate 8-4: Intermediate 8-2 (0.1 mol), compound 8-3 (0.25 mol), KOAc (0.3 mol), Pd(OAc) 2 (0.03 mmol) were dissolved in 1L DMAC, N2 The reaction was stirred at 130°C for 20 hours under the atmosphere. After the reaction was completed, the solvent was removed, and the silica gel chromatography was used for separation and purification. The mobile phase was petroleum ether/dichloromethane (15/1, v/v) to obtain Intermediate 8-4 (92.08g, yield 75.1%)
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