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CAS No. : | 4805-22-5 | MDL No. : | MFCD00219110 |
Formula : | C8H4Br2S2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | SXNCMLQAQIGJDO-UHFFFAOYSA-N |
M.W : | 324.06 | Pubchem ID : | 638908 |
Synonyms : |
|
Num. heavy atoms : | 12 |
Num. arom. heavy atoms : | 10 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 63.03 |
TPSA : | 56.48 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | Yes |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.71 cm/s |
Log Po/w (iLOGP) : | 2.79 |
Log Po/w (XLOGP3) : | 5.03 |
Log Po/w (WLOGP) : | 5.0 |
Log Po/w (MLOGP) : | 3.82 |
Log Po/w (SILICOS-IT) : | 6.22 |
Consensus Log Po/w : | 4.57 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -5.57 |
Solubility : | 0.000875 mg/ml ; 0.0000027 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -5.96 |
Solubility : | 0.000358 mg/ml ; 0.0000011 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -5.13 |
Solubility : | 0.00238 mg/ml ; 0.00000735 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.68 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280 | UN#: | N/A |
Hazard Statements: | H302+H312+H332 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With N-Bromosuccinimide; acetic acid In chloroform at 70℃; for 4 h; | A mixture of 2,2'-bithiophene (5.40 g, 32.4 mmol) and NBS (11.57 g, 64.8 mmol, 2 equiv) in a solvent mixture CHCl3/acetic acid 100percent (1:1 (v/v), 300 mL) was stirred at 70 °C for 4 h. The reaction media was diluted with CH2Cl2 (50 mL) and a saturated aqueous solution of Na2CO3 (100 mL). The organic phase was isolated and the aqueous phase extracted with CH2Cl2 (3 x 50 mL). The organic phases were assembled, dried with MgSO4, filtered and evaporated to give a pale yellow solid that was then washed with acetone giving the pure product 1a (10.42 g, 98percent). Recrystallization from THF afforded a highly pure product. 1H NMR (DMSO-d6, 600 MHz) δ (ppm): 7.23–7.22 (d, J = 3.9 Hz, 2H), 7.15–7.14 (d, J = 3.9 Hz, 2H). 13C NMR (DMSO-d6, 100 MHz) δ (ppm): 136.86, 131.60, 125.22, 110.84. MS(ESI+): m/z = 324.05. UV–visible (DMSO) λmax = 325 nm. IR(ATR): 3069 cm-1 (Ar–H)str; 1683 cm-1 (C=C conjugated)str; 1416 cm-1 (R1-C=C-R2 cis)str; 1293 cm-1 (C=C)bending. Elemental analysis: calculated: C 29.65; H 1.24; S 19.79; found: C 30.03; H 1.40; S 18.13. |
93% | With N-Bromosuccinimide In N,N-dimethyl-formamide for 8 h; | The compound 2, 2 '- bithiophene (1.66g, 10mmol) was dissolved in N,N-dimethylformamide (20 mL),N-Bromosuccinimide (0.31 g, 1.7 mmol) was dissolved in N, N-dimethylformamide (40 mL), and the latter was slowly added dropwise to the former. After the completion of the addition, the reaction was continued for 8 hours. After the completion of the reaction, a large amount of water was added. The petroleum ether was extracted, dried and filtered. The solvent was removed by rotary evaporation, and the crude product was recrystallized from ethanol as a white solid 19 (3.00 g, 93percent). |
90% | With N-Bromosuccinimide In N,N-dimethyl-formamideCooling with ice | To a solution of 2, 2'-bithiophene (12 mmol, 2 g) in anhydrousDMF (30 ml), NBS (24 mmol, 4.28 g) was added dropwisely (coolingwith ice-water during addition of NBS solution) and stirred for 3 h.The reaction mixture was then poured into 100 mL of ice water andthe beige solid was separated by vacuum filtration [1]. The crudewas purified with column chromatography (silica gel100e200 mesh), using hexane as eluent to yield yellow solid asproduct (3.6 g, yield 90percent). |
85% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; | N-Bromosuccinimide (NBS) (11.65 g, 65.450 mmol) was added in small portions to a solution of 2,2'-bithiophene 1 (5 g, 29.76 mmol) in DMF at 0 °C. After being stirred over night at room temperature, the reaction mixture was poured into water (200 mL) and extracted with CH2Cl2. The organic layer was thoroughly washed with water, aqueous sodium bicarbonate, brine and again with water, and then dried over Na2SO4. After removal of solvent, it was purified by column chromatography on silica gel using petroleum ether as eluant to afford 5,5'-dibromo-2,2'-bithiophene (2) (8.20 g, 85percent) as a white crystal solid. GC/MS: 324(M+). 1H NMR (400 MHz, CDCl3): δ(ppm) 6.97-6.96 (d, J = 4.0 Hz, 2H), 6.86-6.85 (d, J = 4.0 Hz, 2H). |
51% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃; for 12 h; | In dimethyl formamide, dissolved was 2- (thiophen-2- yl) thiophene (30 g, 0.18 mol) . Then, with the light shielded, N-bromosuccinimide (70.7 g, 0.4 mol) was diluted with dimethyl formamide, and the dilution was slowly added dropwise to the solution at 0 °C After 12 hours, the reaction was quenched, extracted with methylene chloride, and dried over magnesium sulfate. The solvent was removed, and the residue was purified via chromatography to obtain the desired compound, 2-bromo-5- (5-bromothiophen-2 -yl) thiophene (Compound 16) (29.8 g, yield: 51percent) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran; | All solvents were purified and dried by standard methods. 2,2′:5′,2″-Terthiophene (3T) was prepared by a Grignard coupling reaction between 2,5-dibromothiophene and 2-bromomagnesiothiophene in THF. The 2,2′:5′,2″:5″,2‴-quaterthiophene (4T) was also prepared by a Grignard coupling reaction between 2,5′-dibromo-2,2′-dithiophene and 2-bromomagnesiothiophene in THF. N-chlorosulfonylisocyanate (CSI), N,N-dimethylformamide (DMF) and 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) are commercially available. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With N-Bromosuccinimide; acetic acid; In chloroform; at 70℃; for 4h; | A mixture of 2,2'-bithiophene (5.40 g, 32.4 mmol) and NBS (11.57 g, 64.8 mmol, 2 equiv) in a solvent mixture CHCl3/acetic acid 100% (1:1 (v/v), 300 mL) was stirred at 70 C for 4 h. The reaction media was diluted with CH2Cl2 (50 mL) and a saturated aqueous solution of Na2CO3 (100 mL). The organic phase was isolated and the aqueous phase extracted with CH2Cl2 (3 x 50 mL). The organic phases were assembled, dried with MgSO4, filtered and evaporated to give a pale yellow solid that was then washed with acetone giving the pure product 1a (10.42 g, 98%). Recrystallization from THF afforded a highly pure product. 1H NMR (DMSO-d6, 600 MHz) δ (ppm): 7.23-7.22 (d, J = 3.9 Hz, 2H), 7.15-7.14 (d, J = 3.9 Hz, 2H). 13C NMR (DMSO-d6, 100 MHz) δ (ppm): 136.86, 131.60, 125.22, 110.84. MS(ESI+): m/z = 324.05. UV-visible (DMSO) λmax = 325 nm. IR(ATR): 3069 cm-1 (Ar-H)str; 1683 cm-1 (C=C conjugated)str; 1416 cm-1 (R1-C=C-R2 cis)str; 1293 cm-1 (C=C)bending. Elemental analysis: calculated: C 29.65; H 1.24; S 19.79; found: C 30.03; H 1.40; S 18.13. |
93% | With N-Bromosuccinimide; In N,N-dimethyl-formamide; for 8h; | The compound 2, 2 '- bithiophene (1.66g, 10mmol) was dissolved in N,N-dimethylformamide (20 mL),N-Bromosuccinimide (0.31 g, 1.7 mmol) was dissolved in N, N-dimethylformamide (40 mL), and the latter was slowly added dropwise to the former. After the completion of the addition, the reaction was continued for 8 hours. After the completion of the reaction, a large amount of water was added. The petroleum ether was extracted, dried and filtered. The solvent was removed by rotary evaporation, and the crude product was recrystallized from ethanol as a white solid 19 (3.00 g, 93%). |
93% | With N-Bromosuccinimide; In chloroform; acetic acid; for 6h;Reflux; Inert atmosphere; | Under a dry argon atmosphere, 2,2′-bithiophene (2T) (3.00 g, 0.0180 mol) and N-bromosuccinimide (6.75 g, 0.0379 mol) were dissolved in chloroform/acetic acid (49 mL, 4:3, v/v). The resulting reaction mixture was refluxed for 6 h. Then, the reaction mixture was poured into the stirred mixture of chloroform and water. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The crude product in the residue was purified by recrystallization from the mixed solvent of chloroform and methanol to afford Br2T as colorless crystals with the yield of 93% (5.46 g, 0.0168 mol). 1H NMR (CDCl3, 400 MHz, ppm): δ 6.96 (d, J=3.6 Hz, 2H, thienyl protons), 6.85 (d, J=4.1 Hz, 2H, thienyl protons). 13C NMR (CDCl3, 100 MHz, ppm): δ 137.8 (thienyl carbon), 130.7 (thienyl carbon), 124.2 (thienyl carbon), 111.6 (thienyl carbon). M.p.: 147 C. |
93% | With N-Bromosuccinimide; In N,N-dimethyl-formamide; for 2h;Reflux; | 2,2′-bithiophene (11.7 g, 70.1 mmol) is dissolved in 500 mL of N,N-dimethylmethanamide, and N-bromo succinimide (31 g, 175.2 mmol) is added in a dropwise fashion to bromide it. Then, the resultant is refluxed for 2 hours, water (1 L) is added thereto, and the produced precipitate is filtered and recovered. The recovered powder is dissolved in chloroform (700 mL), washed with water, and then dried with magnesium sulfate followed by evaporating the resultant. The resultant is washed with n-hexane and dried to obtain Compound 1 (A yield of 93%). (0221) 1H-NMR (300 MHz, CDCl3): δ 6.96 (d, J=3.6 Hz, 1H), 6.85 (d, J=3.6 Hz, 1H) |
90% | With N-Bromosuccinimide; In N,N-dimethyl-formamide;Cooling with ice; | To a solution of 2, 2'-bithiophene (12 mmol, 2 g) in anhydrousDMF (30 ml), NBS (24 mmol, 4.28 g) was added dropwisely (coolingwith ice-water during addition of NBS solution) and stirred for 3 h.The reaction mixture was then poured into 100 mL of ice water andthe beige solid was separated by vacuum filtration [1]. The crudewas purified with column chromatography (silica gel100e200 mesh), using hexane as eluent to yield yellow solid asproduct (3.6 g, yield 90%). |
85% | With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 20℃; | N-Bromosuccinimide (NBS) (11.65 g, 65.450 mmol) was added in small portions to a solution of 2,2'-bithiophene 1 (5 g, 29.76 mmol) in DMF at 0 C. After being stirred over night at room temperature, the reaction mixture was poured into water (200 mL) and extracted with CH2Cl2. The organic layer was thoroughly washed with water, aqueous sodium bicarbonate, brine and again with water, and then dried over Na2SO4. After removal of solvent, it was purified by column chromatography on silica gel using petroleum ether as eluant to afford 5,5'-dibromo-2,2'-bithiophene (2) (8.20 g, 85%) as a white crystal solid. GC/MS: 324(M+). 1H NMR (400 MHz, CDCl3): δ(ppm) 6.97-6.96 (d, J = 4.0 Hz, 2H), 6.86-6.85 (d, J = 4.0 Hz, 2H). |
85.69% | With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 20℃; for 3h; | 2,2-Bithiophene (5.00 g, 30.1 mmol) was dissolved in N,N-dimethylformamide (50 mL). With stirring, N-bromosuccinimide (12.3 g, 69.2 mmol) was added at 0C and the reaction mixture was stirred at rt for 3 h. The mixture was poured into methanol (150 mL) and filtered to obtain a white solid product. Yield: 8.35 g (85.69%). 1H NMR (400 MHz, CDCl3): δ (ppm) 6.96 (d, J = 3.9 Hz, 2H), 6.85 (d, J = 3.9 Hz, 2H). |
57% | With water; sodium bisulfate hydrate; sodium bromide; In acetonitrile; for 96h;Irradiation; | In a 25mL reaction tube, add dithiophene (23.6mg, 0.2mmol), sodium bromide (61.6mg, 0.6mmol), sodium bisulfate hydrate (55.2mg, 0.4mmol), water (72mg, 4mmol) and Acetonitrile (2mL), stirred under the irradiation of three 2-watt LED lamps for 96 hours, after the reaction was completed, extracted, dried, filtered, concentrated, and separated by column chromatography to obtain a white solid 2v (37mg, 57%); |
51% | With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0℃; for 12h; | In dimethyl formamide, dissolved was 2- (thiophen-2- yl) thiophene (30 g, 0.18 mol) . Then, with the light shielded, N-bromosuccinimide (70.7 g, 0.4 mol) was diluted with dimethyl formamide, and the dilution was slowly added dropwise to the solution at 0 C After 12 hours, the reaction was quenched, extracted with methylene chloride, and dried over magnesium sulfate. The solvent was removed, and the residue was purified via chromatography to obtain the desired compound, 2-bromo-5- (5-bromothiophen-2 -yl) thiophene (Compound 16) (29.8 g, yield: 51%) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | EXAMPLE 1 (i) Synthesis of Small Molecular Thiophene Compound (I) The preparation of precursor, 5,5'-bis(3-dodecyl-2-thienyl)-2,2'-dithiophene, (10), is illustrated in Scheme 1. A solution of <strong>[139100-06-4]2-bromo-3-dodecylthiophene</strong> (15.36 grams, 46.36 mmol) in 40 milliliters of anhydrous tetrahydrofuran (THF) was added slowly over a period of 20 minutes to a mechanically stirred suspension of magnesium turnings (1.69 grams, 69.50 mmol) in 5 milliliters of anhydrous THF in a 250 milliliter round-bottomed flask under an inert argon atmosphere. When reaction was initiated, the reaction mixture was stirred at 60 C. for 3 hours before cooling down to room temperature. The resultant mixture was then added via a cannula to a mixture of 5,5'-dibromo-2,2'-dithiophene (6.01 grams, 18.54 mmol) and [1,2-bis(diphenylphosphino)ethane]dichloronickel (II) (0.37 gram of (dppe)NiCl2, 0.70 mmol) in 80 milliliters of anhydrous THF in a 250 milliliter round-bottomed flask under an argon atmosphere, and then refluxed for 48 hours. Subsequently, the reaction mixture was cooled down to room temperature and washed with water. The crude product was extracted with ethyl acetate and dried with anhydrous sodium sulfate. A dark brown syrup, obtained after evaporation of the solvent, was purified by column chromotography on silica gel to yield crude 5,5'-bis(3-dodecyl-2-thienyl)-2,2'-dithiophene (10), which was recrystallized from a mixture of dichloromethane (10 ml), isopropanol (250 ml) and methanol (100 ml), yielding a yellow crystalline product in 66 percent yield, m.p. 58.9 C. The NMR spectrum of the above obtained compound was recorded at room temperature using a Bruker DPX 300 NMR spectrometer: 1H NMR (CDCl3): delta 7.18 (d, J=5.4 Hz, 2H), 7.13 (d, J=3.6 Hz, 2H), 7.02 (d, J=3.6 Hz, 2H), 6.94 (d, J=5.4 Hz, 2H), 2.78 (t, 4H), 1.65 (q, 1.65, 4H), 1.28 (bs, 36H), 0.88 (m, 6H). 13C NMR (CDCl3, ppm): delta 139.78, 136.73, 135.26, 130.26, 129.99, 126.43, 123.75, 123.71, 31.86, 30.59, 29.62, 29.61, 29.54, 29.46, 29.40, 29.30, 29.20, 22.63, 14.05. | |
66% | (i) Synthesis of Small Molecular Thiophene Compound (I) The preparation of precursor, 5,5'-bis(3-dodecyl-2-thienyl)-2,2'-dithiophene, (10), is illustrated in Scheme 1. A solution of <strong>[139100-06-4]2-bromo-3-dodecylthiophene</strong> (15.36 grams, 46.36 mmol) in 40 milliliters of anhydrous tetrahydrofuran (THF) was added slowly over a period of 20 minutes to a mechanically stirred suspension of magnesium turnings (1.69 grams, 69.50 mmol) in 5 milliliters of anhydrous THF in a 250 milliliter round-bottomed flask under an inert argon atmosphere. When reaction was initiated, the reaction mixture was stirred at 60 C. for 3 hours before cooling down to room temperature. The resultant mixture was then added via a cannula to a mixture of 5,5'-dibromo-2,2'-dithiophene (6.01 grams, 18.54 mmol) and [1,2-bis(diphenylphosphino)ethane]dichloronickel(II) (0.37 gram of (dppe) NiCl2, 0.70 mmol) in 80 milliliters of anhydrous THF in a 250 milliliter round-bottomed flask under an argon atmosphere, and then refluxed for 48 hours. Subsequently, the reaction mixture was cooled down to room temperature and washed with water. The crude product was extracted with ethyl acetate and dried with anhydrous sodium sulfate. A dark brown syrup, obtained after evaporation of the solvent, was purified by column chromotography on silica gel to yield crude 5,5'-bis(3-dodecyl-2-thienyl)-2,2'-dithiophene (10), which was recrystallized from a mixture of dichloromethane (10 ml), isopropanol (250 ml) and methanol (100 ml), yielding a yellow crystalline product in 66 percent yield, m.p. 58.9 C. The NMR spectrum of the above obtained compound was recorded at room temperature using a Bruker DPX 300 NMR spectrometer: 1H NMR (CDCl3): delta 7.18 (d, J=5.4 Hz, 2H), 7.13 (d, J=3.6 Hz, 2H), 7.02 (d, J=3.6 Hz, 2H), 6.94 (d, J=5.4 Hz, 2H), 2.78 (t, 4H), 1.65 (q, 1.65, 4H), 1.28 (bs, 36H), 0.88 (m, 6H). 13C NMR (CDCl3, ppm): delta 139.78, 136.73, 135.26, 130.26, 129.99, 126.43, 123.75, 123.71, 31.86, 30.59, 29.62, 29.61, 29.54, 29.46, 29.40, 29.30, 29.20, 22.63, 14.05. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | 5, 5'-diformyl-2, 2'-bithiophene (35): To a solution of 5,5'-dibromo- 2,2'-bithiophene (2.00 g, 6.17 mmol, Aldrich Co. ) in anhydrous THF (30 mL) was added dropwise n-butyllithium (5.43 mL, 13.6 mmol, 2.5 M in hexanes, Aldrich Co. ) AT-78C under argon. The mixture was stirred 30 min. AT-78C, warmed to room temperature and stirred for an additional 90 minutes. Anhydrous dimethylformamide (1.43 mL, 18.5 mmol, Aldrich Co. ) was added dropwise and the solution was stirred at room temperature for another 2 h. An aqueous HCI solution (1 M, 10 mL) was slowly added followed by the addition of acetone (50 mL). The resulting mixture was poured into 150 mL of hexanes at 0C and the brown precipitate was filtered, washed with hexanes and dried under vacuum for 24 h to provide 1.05 g of the title product as a orange-brown solid. M. P.: 213-214C (Yield : 76 %). 1H NMR (400 MHz, DMSO-d6, ppm): 9.89 (s, 2H); 8.00 (d, 2H, J = 4.0 Hz); 7.73 (d, 2H, J = 4.0 Hz). 13C NMR (100 MHz, DMSO-D6, ppm): 185.00 ; 144.14 ; 144.03 ; 139.60 ; 128. 57. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | 2.0 M lithium diisopropylamide (18.5 ml, 37.0 mmol) was slowly added to a solution of 5,5'-dibromo-2,2'-bithiophene (5.0 g, 15.4 mmol) dissolved in anhydrous THF (30 mL) at -78 C. After stirring for about 1 hour, trimethylsilyl chloride (46.2 mmol, 5.9 mL) was added slowly at -78 C and the mixture was stirred overnight at room temperature. The reaction was terminated by adding water and extracted with diethylether. The organic layer was extracted twice and the water was removed with MgSO4. The solvent of the extracted solution was removed and recrystallized from methanol to obtain 5.43 g (75%) of 5,5'-bis (trimethylsilyl) -4,4'-dibromo-2,2'-bithiophene (Compound 2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With tetrakis(triphenylphosphine) palladium(0); In N,N-dimethyl-formamide; at 125℃; for 2h;Inert atmosphere; | And, into the flask, 5,5'-dibromo-2,2'-bi-thiophene and 1.5g of tetrakis (triphenylphosphine) palladium and then put 0.27g nitrogen, N, N- dimethylformamide 20mL and a previously synthesized was added tributyl (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-5-yl) stannane 6.2g, the temperature was raised to 125C and was stirred for 2 hours .(function(){var src = document.getElementById('source');src.focus();src.select();src.style.boxSizing=src.style.WebkitBoxSizing=src.style.MozBoxSizing=src.style.MsBoxSizing='border-box';})();Type text or a website address or translate a document.Cancelgyoban hu, sil-onkkaji bangnaenghago, geogie nomalhegsein-eul gahayeo bun-aeghago, eod-eojin N,N-daimetilpom-amaideu cheung-eul iongyohwansuwa metan-ol-ui honhab-aeg jung-e jeoghahayeo jaechimjeon-eul haenghaessda.After stirring, the reaction mixture was allowed to cool to room temperature, and separated by adding to it in the normal hexane, it added dropwise to the thus obtained N, N- dimethylformamide in the layer of deionized water and a mixed solution of methanol was subjected to re-precipitation. And, recovering and drying the precipitate by filtration, to give the thiophene derivative oligo 3 (Unit: 1.4g, Yield: 66%). |
66% | With tetrakis(triphenylphosphine) palladium(0); In N,N-dimethyl-formamide; at 125℃; for 2h;Inert atmosphere; | Next, 1.5 g of 5,5'-dibromo-2,2'-dithiophene and 0.27 g of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) were placed in a separate flask to carry out nitrogen substitution.And adding 6.2 g of the above mixture containing tributyl (2,3-dihydrothieno[3,4-b][1,4]dioxin-5-ylstannane)20 mL of N,N-dimethylformamide, heated to 125 C,Stir for 2 hours.After completion of the stirring, the mixture was allowed to cool to room temperature, and n-hexane was added thereto to carry out liquid separation, and the obtained N,N-dimethylformamide layer was dropped into a mixed solution of ion-exchanged water and methanol to carry out reprecipitation.Then, the precipitate was recovered by filtration, and dried to obtain TP2 (yield: 1.4 g, yield: 66%). The measurement results of 1H-NMR are shown below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | An established procedure was used for the synthesis of2,2':5',2'':5'',2'''-Tetrathiophene 4. Mg turnings (0.40 g, 14.7 mmol)was added to a flame dried 100-mL two-necked flask containing 2-bromothiophene (2.1g, 12.7 mmol) in 20 mL anhydrous Ether atroom temperature under N2. The solution mixture was stirredvigorously and heated to reflux for 3 h. After cooling to roomtemperature the Grignard reagent of 2-bromothiophene(12.7 mmol) was added slowly to a solution of 5,5'-dibromo-2,2'-bithiophene (2.0g, 6.2 mmol) catalyzed with Ni(dppp)Cl2 (28 mg,0.052 mmol) in 20 mL anhydrous Ether and the solution wasrefluxing 14 h. After cooling to temperature, the reaction wasquenched with water and acidified with 6M HCl to pH 4-5. Thesolutionwas then extracted with CHCl3 (5 20 mL). The combinedorganic solvent was washed with brine, dried over Na2SO4 andevaporated to dryness [2]. The crude was purified with columnchromatography (silica gel 100-200 mesh), using hexane/DCM aseluent to yield bright yellow solid identified as tetrathiophene.Yield 1.98 g, 47%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tetraethylammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; for 5h;Heating / reflux; | Example 1 Compound (1) is prepared as follows : Step 1.1 : 2. 5'-Bis (4-hvdroxyphenYl) bithiophene.; To a solution of 5, 5'-dibromo-2, 2'-bithiophene (5.0 g, 15.43 mmol) in anhydrous THF (120 ml) is added tetrakis (triphenylphosphine) palladium (0.5 g, 0.43 mmol). This mixture is degassed with nitrogen for 20 min, followed by the addition of 4- (4, 4,5, 5-tetramethyl [1, 3,2] dioxoborolan-2-yl)-phenol (3.73 g, 16.95 mmol, Aldrich) and tetraethylamomnium hydroxide (20% solution in water, 50 ml). The mixture is heated at reflux for 5 h. After cooling, 1 M HCI solution (70 mt) is added and the precipitate is filtered off then washed with water (3 x 20 ml) and dried, to give a green solid (4.52 g, 84 %). NMR showed the expected signals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With tetra(n-butyl)ammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 100 - 140℃; for 0.283333h;Microwave irradiation; | Step 9.3; : A 20 ml microwave tube is charged with 5, 5'-dibromothiophene (0.20 g, 0.62 mmol), tetrakis (triphenylphosphine) palladium (0) (0.05 g, 0.04 mmol), 2-{4- [6-((3-ethyloxetan-3-yl) methoxy)-hexyl] phenyl}-4, 4,5, 5- tetramethyl-1, 3, 2-dioxaboro-nlane (0.75 g, 1.86 mmol), anhydrous THF (7 ml) and tetrabutylammonium hydroxide (20 % in water, 2 ml). The tube is sealed and heated and stirred in a microwave reactor (Emrys Creator) for 1 min at 100 C, 1 min at 120 C and 15 min at 140 C. After cooling, the mixture is poured into water (100 ml). The precipitate is filtrated off and washed with water and diethyl ether, to give a blue solid, which is purified by column chromatography on silica, eluting with petroleum ether/ethyl acetate (9: 1 to 4: 1), to give a yellow solid (0.23 g, 52%). 1H NMR (300 MHz, CDCl3) : 8 (ppm) 7.52 (d, J = 8. 3 Hz 4H, Ar-H), 7.19 (m, 6H, Ar-H), 7.14 (d, J = 3. 8 Hz, 2H, Ar-H), 4.45 (d, J = 5. 8 Hz, 4H, OCH2), 4.38 (d, J = 5. 8 Hz, 4H, OCH2), 3.52 (s, 4H, OCH2), 3.45 (t, J = 6.4 Hz, 4H, OCH2), 2.62 (t, J = 7.3 Hz 4H, ArCH2), 1.74 (q, J = 7.5 Hz, 4H, CH2), 1.60 (m, 8H, CH2), 1. 38 (m, 8H, CH2), 0.88 (t, J = 7.5 Hz, 6H, CH3) ; C NMR (75 MHz, CDCI3) : 8 (ppm) 143.2 (quat. ), 142.5 (quat. ), 136.3 (quat. ), 131.6 (quat. ), 129.0 (CH), 125.5 (CH), 124.3 (CH), 123.3 (CH), 78.7 (OCH2), 73.4 (OCH2), 71.6 (OCH2), 43.4 (quat. ), 35.6 (CH2), 31.4 (CH2), 29.5 (CH2), 29.1 (CH2), 26.8 (CH2), 26.1 (CH2), 8.3 (CH3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With 1,2-bis(diphenylphosphino)ethane nickel(II) chloride; In tetrahydrofuran; for 48h;Heating / reflux; | EXAMPLE 1; (i) Synthesis of Small Molecular Thiophene Compound (I); The preparation of precursor, 5,5'-bis(3-dodecyl-2-thienyl)-2,2'-dithiophene, (10), is illustrated in Scheme 1. A solution of 2-bromo-3-dodecylthiophene (15.36 grams, 46.36 mmol) in 40 milliliters of anhydrous tetrahydrofuran (THF) was added slowly over a period of 20 minutes to a mechanically stirred suspension of magnesium turnings (1.69 grams, 69.50 mmol) in 5 milliliters of anhydrous THF in a 250 milliliter round-bottomed flask under an inert argon atmosphere. When reaction was initiated, the reaction mixture was stirred at 60 C. for 3 hours before cooling down to room temperature. The resultant mixture was then added via a cannula to a mixture of 5,5'-dibromo-2,2'-dithiophene (6.01 grams, 18.54mmol) and [1,2-bis(diphenylphosphino)ethane]dichloronickel (II) (0.37 gram of (dppe)NiCl2, 0.70 mmol) in 80 milliliters of anhydrous THF in a 250 milliliter round-bottomed flask under an argon atmosphere, and then refluxed for 48 hours. Subsequently, the reaction mixture was cooled down to room temperature and washed with water. The crude product was extracted with ethyl acetate and dried with anhydrous sodium sulfate. A dark brown syrup, obtained after evaporation of the solvent, was purified by column chromotography on silica gel to yield crude 5,5'-bis(3-dodecyl-2-thienyl)-2,2'-dithiophene (10), which was recrystallized from a mixture of dichloromethane(10 ml), isopropanol(250 ml) and methanol (100 ml), yielding a yellow crystalline product in 66 percent yield, m.p. 58.9 C. The NMR spectrum of the above obtained compound was recorded at room temperature using a Bruker DPX 300 NMR spectrometer: 1H NMR (CDCl3): δ 7.18 (d, J=5.4 Hz, 2H), 7.13 (d, J=3.6 Hz, 2H), 7.02 (d, J=3.6 Hz, 2H), 6.94 (d, J=5.4 Hz, 2H), 2.78 (t, 4H), 1.65 (q, 1.65, 4H), 1.28 (bs, 36H), 0.88 (m, 6H). 13C NMR (CDCl3 ppm): δ 139.78, 136.73, 135.26, 130.26, 129.99, 126.43, 123.75, 123.71, 31.86, 30.59, 29.62, 29.61, 29.54, 29.46, 29.40, 29.30, 29.20, 22.63, 14.05. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; at 85℃; for 48h; | A mixture of 5,5'-dibromo-2,2'-bithiophene (6 g, 18.51 mmol) and naphthalene-2-ylboronic acid (2.22 g,12.95 mmol) were added to toluene (80 mL), 2 M K2CO3 (15 mL), and tetrakis(-triphenylphosphine) palladium(0) (0.17 g, 1.47 104 mol). After stirring for 48 h at 85 C, 2 N HCl (40 mL) were added. The crude product was extracted with dichloromethane and purified by column chromatography using hexane as the eluent. Yield: 2.5 g(53%); IR (KBr, cm1); 3031-3064 (aromatic CH), 1H NMR(300 MHz, CDCl3, ppm): d 8.04 (s, 1H), 7.88-7.86 (m, 3H),7.76-7.75 (d, J 1.8 Hz, 1H), 7.52-7.48 (m, 2H), 7.37-7.35 (d,J 3.9 Hz, 1H), 7.15-7.14 (d, J 3.6 Hz 1H), 7.02-6.98 (m, 2H). |
45% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; for 24h;Heating / reflux; | Synthesis of Compound 1195,5'-dibromo-2,2'-bothiophene (5.00 g, 15.4 mmol), naphthalene-2-boronic acid (1.86 g, 10.8 mmol) and potassium carbonate (30 mL, 2 M aqueous solution) were suspended in THF (50 mL). Tetrakis(triphenylphosphine)palladium (0.18 g, 0.16 mmol) was added to the suspension. The resulting mixture was stirred at reflux for about 24 hours and thereafter cooled to room temperature. Precipitate was filtered off with suction. The crude product was dissolved in THF, filtered, and washed with THF. The filtrate was concentrated in vacuo and recrystallized from ethyl acetate to give Compound 119 (2.60 g, 45%). |
45% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; for 24h;Heating / reflux; | 5,5'-dibromo-2, 2'-bothiophene (5.00 g, 15.4 mmol), naphthalene-2-boronic acid (1.86 g, 10.8 mmol) and potassium carbonate (30 mL, 2 M aqueous solution) were suspended in THF (50 mL). Tetrakis (triphenylphosphine) palladium (0.18 g, 0.16 mmol) was added to the suspension. The resulting mixture was stirred at reflux for about 24 hours and thereafter cooled to room temperature. Precipitate was filtered off with suction. The crude product was dissolved in THF, filtered, and washed with THF. The filtrate was concentrated in vacuo and recrystallized from ethyl acetate to give Compound 119 (2.60 g, 45%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 24h;Heating / reflux; | 5,5'-Dibromo-2,2'-dithiophene (5.00 g, 15.4 mmol), phenylboric acid (2.07 g, 17.0 mmol) and sodium carbonate (4.90 g, 46.3 mmol) were suspended in a mixture of toluene (30 mL) and water (15 mL). To the suspension, tetrakis(triphenylphosphine)palladium (0.50 g, 0.46 mmol) was added. The resulting mixture was stirred under reflux for about 24 hours. The refluxed mixture was cooled to room temperature and extracted using chloroform. The organic extract was dried over magnesium sulfate, and concentrated in vacuum. The residue was purified by column chromatography (n-hexane) to prepare a phenylthiophene compound B- 14-1 (2.8O g, yield 75%).[164] MS [M+H]+= 243 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.2% | With lithium diisopropyl amide; In tetrahydrofuran; at -70℃;Inert atmosphere; | a) A solution of 40 g of 1 in 200 ml of dry tetrahydrofuran (THF) is added rapidly to a solution of lithium diisopropylamide (LDA, prepared from 100 ml of 2.7 M solution of butyllithium in hexane and 28.8 g diisopropylamine in 200 ml of dry THF) at -70° C. under nitrogen atmosphere. After the colour of the mixture has become orange-brown, the mixture is allowed to warm to -20° C. and then 100 ml of water are added. The organic phase is separated, washed with brine, dried and evaporated. The residue is recrystallized from methanol to obtain 36.5 g of 4,4'-dibromo-2,2'-dithiophene as an off-white powder (yield: 91.2%). A solution of n-dodecyl magnesium bromide in ether (prepared from 9 g of magnesium turnings and 87.0 g n-dodecylbromide in 200 ml of diethylether) is slowly added to a solution of 40 g of 4,4'-dibromo-2,2'-dithiophene. 1 mol % NiCl 2(dppp) (dppp=Ph 2PCH 2Ch 2CH 2PPh 2) in 200 ml of diethylether is added in such a way, that the internal temperature does not exceed 20° C. Then the mixture is stirred at room temperature for 2 hours and 200 ml of water are added thereto. The organic phase is separated, washed with diluted hydrochloric acid and brine, dried and evaporated. The residue is suspended in methanol and 55.8 g of 4,4'-n-didodecyl-2,2-dithiophene is obtained as a beige powder by filtation (yield: 70%). 12.8 g of bromine are added dropwise to a solution of 10.1 g 4,4'-n-didodecyl-2,2-dithiophene in 100 ml chloroform and 40 ml acetic acid at 0° C. under nitrogen atmosphere. The mixture is heated at 60° C. for 16 hours. After cooling to room temperature the mixture is treated with 50 ml of a saturated solution of sodium sulfite. The organic phase is separated, washed with a saturated aqueous solution of sodium hydrogen carbonate and brine, dried and evaporated. The residue is suspended in methanol and 14.5 g of 2 is obtained as a beige powder by filtration (yield: 88.4%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | Tetrakis(triphenylphosphine)palladium(0) (0.05 g) was added to a solution 5,5'-dibromo-2,2'-bithiophene (0.10 g, 0.31 mmol) in dry THF (30 ml), with stirring, under nitrogen. After 20 min, 2-{5-[6-(tert- Butyldimethylsilanyloxy)-hexyl]-thieno[3,2-b]thiophen-2-yl@-4,4,5,5- tetramethyl-[1,3,2]dioxaborolane (0.44 g, 0.93 mmol ) and a solution of potassium carbonate (0.26 g, 1.88 mmol) in water (10 ml) was added. The resultant mixture was heated at reflux for 1.5 h. After cooling, water (100 ml) was added and the precipitate filtered off, washed with water and diethyl ether, to give a yellow solid, which was recrystallised with toluene to offer yellow crystals (0.19 g, 70 %). LC phases: K - 77C - Sx - 192C - SX1 - 227C - I. ¹H NMR (300 MHz, CDC13): 8 (ppm) 7.27 (s, 2H, Ar-H), 7.07 (m, 4H, Ar-H), 6.91 (s, 2H, Ar-H), 3.61 (t, J = 6.4 Hz, 4H, OCH2), 2.88 (t, J = 7.6 Hz, 4H, ArCH@), 1.37-1.79 (m, 16 H, CH2), 0.90 (s, 18 H, CH3), 0.05 (s, 12 H, CH3); ¹³C NMR (75 MHz, CDC13): 8 (ppm) 148.8 (quat.), 137.8 (quat.), 137.7 (quat.), 136.9 (quat.), 136.8 (quat.), 135.8 (quat.), 124.3 (CH), 124.1 (CH), 116.4 (CH), 116.0 (CH), 63.2 (OCH2), 32.8 (CH2), 31.5 (CH@), 31.2 (CH2), 28.9 (CH2), 26.0 (CH3) 25.6 (CH@), 18.4 (quat.), -5.2 (CH3) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37.6% | With triethylamine;bis(triphenylphosphine)palladium(II) dichloride; copper(I) iodide; In tetrahydrofuran; water; argon; | Synthesis of 5,5'-bis(5-octyl-2-thienylethynyl)-2,2'-bithiophene (8T-yne-TT-yne-T8) 2-Ethynyl-5-octylthiophene (11.8 g, 53.5 mmol) prepared above, 5,5'-dibromo-2,2'-bithiophene (8.46 g, 26.1 mmol), bis(triphenylphosphine)palladium(II) dichloride (917 mg, 1.31 mmol), copper(I) iodide (250 mg, 1.31 mmol), triethylamine (30 ml), and THF (100 ml) were placed in a 500-ml flask equipped with a reflux tube, and the mixture was refluxed in an argon gas stream over a period of about 6 hr. After the completion of the reaction, water (200 ml) was added to the reaction solution, and the organic layer was extracted with chloroform, was dried over sodium sulfate, and was applied to column chromatography (n-hexane) to give an objective compound 5,5'-bis(5-octyl-2-thienylethynyl)-2,2'-bithiophene (8T-yne-TT-yne-T8) as a light yellow powder (5.9 g, yield 37.6%). An NMR spectrum of the compound thus obtained was measured at room temperature with an NMR spectrometer (model JNM-LA400W, manufactured by Japan Electric Optical Laboratory). 1H-NMR (CDCl3, TMS/ppm): 0.88 (t, 6H, J=6.83 Hz), 1.30 (m, 20H), 1.66 (m, 4H), 2.79 (t, 4H, J=7.32 Hz), 6.68 (d, 2H, J=3.90 Hz), 7.06 (d, 2H, J=3.90 Hz), 7.10 (d, 2H, J=3.90 Hz), 7.13 (d, 2H, J=3.90 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16% | Synthesis of compound 4 (scheme 3)To a mixture of 2,5-dibromothiophene (0.50 g,1.54mmol) and metal Mg (0.089 g, 3.71 mmol) was added 20 mL of freshly distilled anhydrous THF. After being stirred for 3h at 50 0C, the solution was cooled down to ambient temperature. To another flask containing 9-fluorenone (0.61g, 3.39 mmol) in 10 mL anhydrous THF solution that was cooled to 0 0C, was added the clear solution of the resulting Grignard reagent via a double needle. The mixed solution was then stirred at this temperature for 30 min before being warmed up to ambient temperature by removing the ice bath. After being stirred for another hour, a saturated SnCl2 solution in 10% hydrochloric acid (40 mL) was added dropwise. The color of the solution immediately turned to deep blue. The solution was stirred at ambient temperature for two more hours, and the deep blue precipitate was collected by suction filtration and washed with THF, water, methanol and CH2Cl2 to afford compound 4 as dark blue solid (0.125 g, 16 % yield) . The solubility of compound 4 is very poor in any solvent, and NMR spectrum was not available. MS (MALDI ) : m/ z = 4 92 . 14 ( calcd . for C34H20S2 : 4 92 . 29 ) . HOMO : - 4 . 98 eV, LUMO : - 3 . 70 eV . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With sodium hydrogencarbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 100℃; for 14h;Inert atmosphere; | To a heat-dried stoppered test tube there were added 5,5'-dibromo-2,2'-bithiophene (242 mg, 0.75 mmol), 4-acetylphenylboronic acid (366 mg, 2.23 mmol), tetrakis(triphenylphosphine)palladium(0) (40 mg, 0.035 mmol), sodium hydrogencarbonate (438 mg, 5.21 mmol) and a dimethoxyethane (DME)/water mixed solvent (7 mL), and reaction was conducted at 100C with nitrogen exchange. After 14 hours, the reaction mixture was concentrated under reduced pressure to obtain a concentrate. The obtained concentrate was rinsed with methanol and ether and then subjected to sublimation purification in a vacuum, to obtain compound B represented by the following formula (22) (205 mg, 83% yield) as a light yellow solid. The reduction potential of compound B could not be measured because it was insoluble in monofluorobenzene. TLC Rf = 0.0(chloroform); 1H-NMR (400 MHz, CDCl3); δ7.96 (m, 2H), 7.68 (m, 2H), 7.36 (m, 2H), 7.23 (m, 2H), 2.60 (s, 3H); GC-MS (DI)m/z = 402 (M+) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium phosphate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In N,N-dimethyl-formamide; at 100℃; for 8h;Inert atmosphere; | To 170 ml of dimethylformamide were added 13.3 g of the compound (9-e) and 5.5 g of 5,5'-dibromo-2,2'-bithiophene (produced by Wako Pure Chemical Industries, Ltd.). Under a nitrogen atmosphere, 43.3 g of potassium phosphate (produced by Wako Pure Chemical Industries, Ltd.) and 690 mg of [bis(diphenylphosphino)ferrocene]dichloropalladium (produced by Aldrich Chemical Company, Inc.) were added and the resulting mixture was stirred at 100C for 8 hours. To the resulting solution were added 500 ml of water and 400 ml of hexane. Then, an organic layer was fractionated, washed with 500 ml of water, and then dried with magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: hexane/ethyl acetate) to obtain 3.91 g of compound (9-f) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium phosphate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In N,N-dimethyl-formamide; at 100℃; for 4h;Inert atmosphere; | To 200 ml of dimethylformamide (produced by Wako Pure Chemical Industries, Ltd.) were added 14.83 g of the compound (1-e) and 6.78 g of 5,5'-dibromo-2,2'-bithiophene (produced by Tokyo Chemical Industry Co., Ltd.). Under a nitrogen atmosphere, 26.6 g of potassium phosphate (produced by Wako Pure Chemical Industries, Ltd.) and 1.7 g of [bis(diphenylphosphino)ferrocene]dichloropalladium (produced by Aldrich Chemical Company, Inc.) were added and the resulting mixture was stirred at 100C for 4 hours. To the resulting solution were added 500 ml of water and 300 ml of ethyl acetate. Then, an organic layer was fractionated, washed with 500 ml of water, and then dried with magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: hexane) to obtain 4.53 g of compound (1-f) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | General procedure: Under a dry argon atmosphere, 1.57 mol/L n-butyllithium in hexane (0.52 mL, 0.816 mmol)) was added dropwise to 4TC (0.161 g 0.326 mmol) in dry ether (10 mL) at 0 C, and the resulting reaction mixture was stirred for 30 min. Chlorodimethylsilane (0.0927 g, 0.980 mmol) was added to this solution, and the reaction mixture was stirred for 24 h at room temperature and poured into water with stirring. The crude product was extracted with ethyl acetate. The combined organic layer was washed with water and brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The crude product in the residue was purified by silica gel column chromatography using hexane as eluent. The collected fraction with an Rf value of 0.13 was concentrated under reduced pressure and the residue was recrystallized from methanol to afford DMS4TC as yellow crystals with the yield of 62% (0.124 g, 0.203 mmol). | |
66% | In a 200 mL threeenecked flask was placed 5.0060 g(15.5 mmol) of 5,5’-dibromo-2,2’-bithiophene in 60 mL of diethylether. To this was added 13.0 mL (33.8 mmol) of a 2.6 M n-butyllithiumehexanesolution at -40 C. After the mixture was stirredfor 2 h at -40C, the resulting mixturewas slowly added to 3.0793 g(32.5 mmol) of chlorodimethylsilane at -40 C. After the mixturewas stirred for 1 h at -40 C, it was warmed to room temperatureand stirred over night. After the mixture was hydrolyzed withdilute hydrochloric acid. The organic layer was separated, washedwith water, and dried over anhydrous magnesium sulfate. After thesolvent was evaporated, compound 6 (2.9123 g, 66% yield) wasisolated by a silica gel column eluting with hexane: Calcd forC12H18Si2S2: C, 51.01; H, 6.42. Found: C, 51.30; H, 6.49. MS m/z 282(M); 1H NMR (δ CDCl3) 0.41 (d, 12H, Me2Si, J 4.0 Hz), 4.56 (sep,2H, HSi, J 4.0 Hz), 7.25 (d, 2H, thienyl ring protons, J 3.2 Hz), 7.19(d, 2H, thienyl ring protons, J 3.2 Hz); 13C NMR (δ CDCl3) 2.90(Me2Si), 125.26, 135.88, 142.86 (thienyl ring carbons); 29Si NMR (δ CDCl3) 22.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | To a solution of 2,2′-dibromobithiophene (1.0 g, 3.10 mmol) in ether (30 mL) was added a hexane solution of nBuLi (1.6 M, 2.13 mL, 3.41 mmol) dropwisely at -78 C. The mixture was stirred at the same temperature for 3 h. A solution of dimesitylboron fluoride (1.11 g, 3.72 mmol) in ether (20 mL) was added to the reaction mixture via syringe. The reaction mixture was gradually warmed to room temperature and stirred overnight. After addition of water (20 mL), the organic layer was separated and the aqueous layer was extracted with diethyl ether for three times. The combined organic layer was dried over MgSO4, filtered, and evaporated under reduced pressure. The mixture was purified by a silica gel column chromatography with hexane to afford L2-Br in 91% yield (1.40 g) as a bright yellow solid. L2-Br: Spectral data: 1H NMR (CDCl3): δ = 7.34-7.33 (d, J = 4.0 Hz, 1H, Ar), 7.22-7.21 (m, 1H, Ar), 7.00-6.95 (m, 2H, Ar), 6.84 (s, 4H, Ar), 2.31 (s, 6H, mesityl), 2.14 (s, 12H, mesityl). 13C NMR (CDCl3): δ = 148.57, 141.38, 140.79, 138.78, 138.63, 130.87, 128.18, 125.81, 124.89, 112.51 (Ar) 23.45, 21.21 (mesityl). FAB-MS: m/z = 492 (M+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; water; for 16h;Inert atmosphere; Reflux; | To a stirred solution of 5,5′-dibromo-2,2′-bithiophene (1 g, 3.09 mmol), 2 (2.35 g, 7.73 mmol) and tetrakis-(triphenylphosphine)palladium (535 mg, 0.46 mmol) in degassed DME (12 mL) at room temperature under argon was added a solution of sodium carbonate (983 mg, 9.27 mmol) in degassed water (4 mL). The mixture was heated at reflux for 16 h under argon, cooled, and then partitioned between water (50 mL) and dichloromethane (50 mL×3). The combined extracts were dried over Na2SO4 and evaporated in vacuum. Chromatography was performed with gradient elution using 5-10% of ether in pentane to eliminate the impurities, and then pure toluene to get the targeted product (1.61 g, 80%) as a yellow powder. 1H NMR (250 MHz, CDCl3) δ 11.81 (s, 2H), 9.92 (s, 2H), 7.73 (d, 2H, J=1.8 Hz), 7.58 (d, 2H, J=1.8 Hz), 7.15 (s, 4H), 1.45 (s, 18H). 13C NMR (90 MHz, CDCl3) δ 197.1, 161.0, 142.1, 139.2, 136.2, 131.7, 128.6, 125.6, 124.5, 123.3, 120.7, 35.1, 29.2. HRMS (ESI): calcd for C30H29O4S2 517.1513, found 517.1548. IR (KBr, ν (cm-1)) 3068, 2955, 2837, 2371, 1646, 1610, 1465, 1433, 1393, 1336, 1270, 1239, 1160, 1040, 808, 765, 747. Mp 215 C. |
Yield | Reaction Conditions | Operation 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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; copper(l) iodide; diisopropylamine; at 0 - 55℃; for 16.33h;Inert atmosphere; | Diisopropylamine (150 mL), CuI (0.31 g, 1.63 mmol), Pd(dppf)Cl2 (0.44 g, 0.54 mmol) and 5,5′-dibromo-2,2′-bithiophene (8.82 g, 27.2 mmol) were placed in flask and degassed with nitrogen at 0 C for 20 min. After cyclohexylacetylene (3 g, 27.7 mmol) was added, the mixture was heated at 55 C for 16 h. The mixture was poured into water, extracted with diethyl ether, and dried over MgSO4. The solvent was removed by rotary evaporation. The crude product was purified by column chromatography using n-hexane as the eluent. Yield: 4.5 g (34%). mp: 64 C, IR (KBr, cm-1); 3083 (aromtic C-H), 2970 (aliphatic C-H), 2217 (C≡C) 1H NMR (300 MHz, CDCl3, ppm): δ 7.00 (s, 1H), 6.97 (s, 1H), 6.94 (s, 1H), 6.89 (s, 1H), 2.63 (q, 1H), 1.82 (m, 5H), 1.46 (m, 5H). 13C NMR (75 MHz, CDCl3): δ138.4, 136.2, 131.6, 130.6, 123.8, 123.6, 123.5, 111.2, 100.0, 73.4, 32.4, 30.0, 25.8, 24.9. MS (m/z): [M+] = 349.9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine; In tetrahydrofuran; at 45℃; for 12h; | Intermediate 2 obtained in step 1 (1.89g, 4.4mmol), 5,5'- dibromo - (2,2'-bithiophene) (583mg, 1.8mmol), Pd (PPh3) 4 (42mg, 0.036mmol), CuI (14mg, a 0.072 mmol) and triethylamine (1.7 ml) were mixed in tetrahydrofuran (10 ml), was reacted for 12 hours while stirring at 45 C.. The resulting reaction solution by silica gel column chromatography to give a pale yellow liquid (1.56 g, 85% isolated yield) by (hexane: ethyl acetate = 15 1 mobile phase solvent). That it was the desired product was confirmed by 1H-NMR, 13C-NMR, and high resolution mass spectra (HRMS). 1H-NMR (400MHz, CDCl3): δ = 7.22 (dd, J = 0.8,5.1Hz, 2H), 7.17 (dd, J = 1.2,3.6Hz, 2H), 7.08 (d, J =4.0Hz, 4H), 7.02 (dd, J = 3.6,5.1Hz, 2H), 7.00 (d, J = 4.0Hz, 4H), 3.42-3.49 (m, 16H), 2.78 (s, 8H), 1.52-1.59 (m, 8H), 1.33-1.43 (m, 8H), 0.92 (t,J = 7.1Hz, 12H)13C-NMR (100MHz, CDCl3): δ = 144.2,144.1,137.2,136.1,136.05,136.03,135.9,127.9,125.09, 125.06,124.3,124.2,124.0,124.0,123.98,123.91,123.5,73.9,71.2,55.4,34.5,31.6,19.3,13.9HRMS (EI): 1082.2726 (calculated); 1082.2738 (measured value) |
Yield | Reaction Conditions | Operation in experiment |
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61% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 60℃; for 24h;Schlenk technique; Inert atmosphere; | Compound 3(2.00g, 6.17mmol), 5,5′-dibromo-2,2′-bithiophene (4.85g, 14.97mmol), and (PPh3)4Pd(0) (0.87g, 0.75mmol) were added to a 100mL Schlenk flask and subjected to three vacuum/nitrogen refill cycles. THF (60mL) and a nitrogen degassed aqueous solution of 2M K2CO3(25mL) were added and stirred for 10min under nitrogen. The mixture was heated at 60C for 24h and monitored via thin layer chromatography for reaction completion. THF was removed using a rotovap and the product was extracted with dichloromethane, successively washed with water, and dried over MgSO4. Removal of the solvent afforded the crude product. The crude product was subjected to a silica gel column using a hexane/dichloromethane mixture (8:1 by volume) as eluent. A yellow solid ofcompound 5was isolated in 61% yield (2.13g).1H NMR (CDCl3)δ(ppm): 0.86-0.89 (t, 3H, -CH3), 1.27-1.32 (q, 2H, -CH2-), 1.74-1.77 (t, 2H, -CH2-), 4.39-4.41 (t, 2H, -N-CH2-), 7.17-8.47 (11H, Ph-H and Th-H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.1% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate; In tetrahydrofuran; toluene; at 110℃; for 8h;Inert atmosphere; | In a 50-mL reaction container, 326.3 mg (1.01 mmol) of XX-4 (2, 5-dibromobithiophene) and 749.8 mg (3.57 mmol) of 2-isopropoxy-6-methoxyphenylboronic acid were mixed in a toluene/tetrahydrofuran (4 mL/4 mL) solvent mixture, and dissolved oxygen was removed by nitrogen. [0119] Subsequently, 5.9 mg (0.026 mmol) of Pd(OAc)2, 21.4 mg (0.052 mmol) of 2-dicyclohexylphosphino-2 ', 6'- dimethoxybiphenyl (S-Phos), and 1123.7 mg (4.88 mmol) of tripotassxum phosphate were added to the mixture under a nitrogen atmosphere, followed by heating to reflux at 110C for 8 hours. [0120] The reaction solution was cooled to room temperature, concentrated under reduced pressure, and subjected to silica gel chromatography (mobile phase: hexane/chloroform = 1/3) for isolation and purification to give compound B-l (418.8 mg, yield: 84.1%) as a white solid powder . [0121] As in Example 1, the structure of compound B-l was confirmed by NMR and MALDI-MS . Specifically, 494 as M+ of this compound was confirmed by MALDI-MS. The measurement results of NMR are shown below: 1NMR (CDCl3) σ (ppm) : 7.48 (d,2H), 7.18 (t,2H), 7.17 (d,2H), 6.65 (d,2H), 6.62 (d,2H), 4.58 (sept,2H), 3.87 (s,6H), 1.36 (s, 12H) . 13C-NMR (CDCl3) σ (ppm): 158.12, 156.14, 137.72, 133.35, 130.02, 128.42, 122.49, 114.24, 107.88, 104.54, 71.88, 56.27, 22.46. |
84.1% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate; In tetrahydrofuran; toluene; at 110℃; for 8h;Inert atmosphere; | <Synthesis Example 7: Synthesis of Exemplified Compound B-7>0149] In a 50-ml reaction vessel, XX-7 (2,5-dibromobithiophene) (326.3 mg, 1.01 mmol) and 2-isopropoxy-6-methoxyphenylboronic acid (749.8 mg, 3.57 mmol) were mixed in a toluene/tetrahydrofuran (4 ml/4 ml) mixed solvent. Dissolved oxygen was removed by nitrogen. [0150] Next, Pd(OAc)2 (5.9 mg, 0.026 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (S-Phos) (21.4 mg, 0.052 mmol), and tripotassium phosphate (1123.7 mg, 4.88 mmol) were added thereto in a nitrogen atmosphere. The mixture was then heated and refluxed at 110C to perform a reaction for 8 hours. [0151] The reaction solution was cooled to room temperature and then concentrated under reduced pressure. Separation and purification were performed by silica-gel chromatography (mobile phase: hexane/chloroform = 1/3) to give a white solid power B-7 (418.8 mg, yield: 84.1%). Measurement by MALDl-MS demonstrated that M+ of this compound was found to be 494.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.1% | With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In water; toluene; for 40.5h;Reflux; Irradiation; | A mixture of 2Br2T (0.32g, 1.00mmol), 4-(diphenylamino)phenylboronic acid (1.16g, 4.00mmol), cesium carbonate (1.30g, 4.00mmol), [Pd(PPh3)4] (0.06g, 0.05mmol), toluene (20mL), and water (5mL) was degassed for 0.5h and heated to reflux for 40h under argon atmosphere. The mixture was then allowed to cool to the room temperature and extracted with chloroform. The resulting organic layer was dried over anhydrous sodium sulfate and filtered. The filtrate was evaporated, and the residue was purified by column chromatography over silica gel using hexane and dichloromethane (1:1) as eluent to give 0.57g (88.1%) of 2TPA2T as a yellow solid. The yellow single crystals of 2TPA2T suitable for X-ray diffraction measurement were grown and isolated from DMF by slow evaporation in air at room temperature for 2 weeks. Melting point: >300C. Anal. Calcdfor [C44H32N2S2]: C, 80.95; H, 4.94; N, 4.29%. Found: C, 80.71; H, 5.12; N, 4.13%. Main FTIR absorptions (KBr pellets, cm-1): 3450 (b), 2361 (m), 1590 (s), 1490 (vs), 1327 (m), 1283 (s), 1183 (w), 1070 (w), 830 (w), 796 (w), 757 (m), 694 (m), 512 (w). 1H NMR (500MHz, CDCl3) δ: 7.46 (d, 4H, J=8.5Hz, ph), 7.28 (t, 8H, ph), 7.13 (d, 12H=8H+4H, J=7.5Hz, ph+thio), 7.07 (d, 4H, J=8.3Hz, ph), 7.04 (t, 4H, ph). 13C NMR (125MHz, CDCl3) δ: 147.5, 147.4, 142.9, 136.0, 129.3, 128.1, 126.4, 124.6, 124.3, 123.6, 123.2, 122.9. EI-TOF-MS (m/z): calcdfor [C44H32N2S2]+: 652.2 (100.0%), 653.2 (49.9%). Found: 652.0 (100.0%), 653.0 (11.6%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; for 24h;Reflux; | PREPARATION EXAMPLE II-14 Preparation of Compound B-14 (0118) (0119) 5,5′-Dibromo-2,2′-dithiophene (5.00 g, 15.4 mmol), phenylboric acid (2.07 g, 17.0 mmol) and sodium carbonate (4.90 g, 46.3 mmol) were suspended in a mixture of toluene (30 mL) and water (15 mL). To the suspension, tetrakis(triphenylphosphine)palladium (0.50 g, 0.46 mmol) was added. The resulting mixture was stirred under reflux for about 24 hours. The refluxed mixture was cooled to room temperature and extracted using chloroform. The organic extract was dried over magnesium sulfate, and concentrated in vacuum. The residue was purified by column chromatography (n-hexane) to prepare a phenylthiophene compound B-14-1 (2.80 g, yield 75%). MS [M+H]+=243 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With bis-triphenylphosphine-palladium(II) chloride; caesium carbonate; In water; N,N-dimethyl-formamide; at -5℃; for 6h; | The dimethyl formamide (DMF) 10 ml and H 2 O 1ml were mixed with 4 (N,Ndiphenylamino)phenyl bronic acid (4(N,NDiphenylamino)phenylboronic acid) 0.5 g (1.73 mmol), 5,5'dibromo2,2'bithiophene bromothiophene (5,5'dibromo2,2'bithiophene) 1.68 g (5.18 mmol), and the mixture of thecesium carbonate (cesium carbonate) 1.41 g (4.32mmol) and bis (triphenylphosphine) palladium (II)dicloride (bis(triphenylphosphine)palladium(II) dichloride) 0.121 g (0.173 mmol) and it was stirred in5for 6 hours. The solid compound which did notmelt in the dimethyl formamide (DMF) after the completion of reaction filtered and it removed and the dimethyl formamide solvent was evaporated. Next, after the solid mixture was mixed using thehydrochloride (HCl) 20 ml and dichloromethane 20ml for 10 minutes after the solvent disappeared the dichloromethane layer and aqueous solution liquid were separated. Next, the dichloromethane solution was dried using the Magnesium Sulfate Anhydrous (MgSO(sub)4(/sub)) and after it filtered the solvent was evaporated. Consequently, the product was refined using the dry column chromatography (dry column chromatography) (dichloromethane hexane: = 1:4) with the separation and product 4 (5bromothiophene2yl)N,Ndiphenylaniline (4(5Bromothiophene2yl)N,Ndiphenylaniline)(0.294 g, 34 %) of yellow were obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.3% | With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; potassium phosphate; tri-tert-butylphosphonium tetrafluoroborate; In water; toluene; at 80℃;Schlenk technique; Inert atmosphere; | In a Schienk flask, 5,5’- dibromo-2,2’-bithiophene 22 (1.0 g, 2.92 mmol) and 2-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)aniline 23 (1.6 g, 7.31 mmol) were charged under nitrogen. After adding 60 ml toluene, 20 ml aqueous solution of K3P04 (2.0 mol/l), the mixture was degassed for 30 mm. Pd2(dba)3CHCl3 (151.3 mg, 0.1462 mmol), (t-Bu)3PHBF4 (84.8 mg, 0.292 mmol) was added. The mixture was then heated to 80C, stirredovernight, poured into brine and extracted with dichioromethane for several times. The organic phase was dried over Mg2SO4 and the solvent was evaporated in vacuo. The product was purified by chromatography on silica gel to give product 24 (0.9 g, 88.3% yield) as golden brown flaky crystals. ‘H NMR (400 MHz, CDCI3, ppm): 4.06 (br, 4H), 6.78 (dd, .1 = 8.00, 0.93 Hz, 2H), 6.81 (dt, i = 7.49, 1.19Hz, 1H), 7.13 (d, J = 3.66 Hz, 2H),7.16 (ddd, J = 9.05, 7.46, 1.55 Hz, 2H), 7.19 (d, J3.67 Hz, 2H), 7.30 (dd, J = 7.62, 1.45 Hz, 2H). ‘3C NMR (400 MHz, CDCI3, ppm):116.3, 118.9, 119.8, 124.3, 126.8, 129.4, 130.9, 137.1, 140.4, 144.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; Trimethylacetic acid; In N,N-dimethyl acetamide; toluene; at 110℃; for 48h;Inert atmosphere; | General procedure: A mixture of aryl bromide (1 eq.), 2-thiophenecarbonitrile (3 eq.per site), K2CO3 (1.5 eq. per site), pivalic acid (0.15 eq. per site) andPd(PPh3)4 (4 mol % per site) in a solvent mixture of dry N,Ndimethylacetamide/toluene 50:50 (v/v %), C:0.23 M, was stirredunder argon atmosphere at 110 C during 48h. The reaction mixturewas then diluted with water, filtered on Celite and washed withdiethyl ether. The solidwas resolubilized in THF/diethyl ether 50:50(v/v %) and centrifuged (15 min, 4000 rpm, rt). The white solid waseliminated and the solution evaporated to give a product whichwas purified by successive recrystallizations in appropriate solvents:3, 4 and 6 in 1-butanol and 5 in toluene at room temperature.Yields: (3) 35%, yellow solid; (4) 45%, orange solid; (5) 72%, redsolid; (6) 93%, green solid. All amounts were calculated based oneach reactive site (-Br) of the starting precursor. |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; Trimethylacetic acid; In N,N-dimethyl acetamide; toluene; at 110℃; for 48h;Inert atmosphere;Catalytic behavior; | A mixture of 1a (745 mg, 2.30 mmol), 2-thiophenecarbonitrile (1.28 mL, 13.7 mmol, 6 equiv), K2CO3 (950 mg, 6.87 mmol, 3 equiv), pivalic acid (77.7 muL, 0.69 mmol, 0. 3 equiv) and Pd(PPh3)4 (212 mg, 0.18 mmol, 0.08 equiv) in a solvent mixture of anhydrous toluene/DMA (1:1 (v/v), 10 mL) was stirred under argon atmosphere at 110 C for 48 h. The reaction mixture was diluted with toluene (50 mL), filtered over celite and the solvent was evaporated in vacuo. The crude was purified by precipitation from toluene (3 times) giving 1f (629 mg, 72%) which was used without any further purification to the next step. 1H NMR at 40 C (DMSO-d6, 600 MHz) delta (ppm): 7.95-7.94 (d, J = 3.8 Hz, 2H), 7.57-7.56 (d, J = 3.8 Hz, 2H), 7.52-7.51 (d, J = 3.8 Hz, 2H), 7.47-7.46 (d, J = 3.8 Hz, 2H). 13C NMR at 40 C (DMSO-d6, 150 MHz) delta (ppm): 143.09, 140.11, 136.62, 133.42, 128.05, 126.25, 124.76, 113.93, 106.32. MS(ESI+): m/z = 379.8. UV-Visible (DMSO) lambdamax = 424 nm. IR(ATR): 3094 cm-1 (Ar-H)str, 2215 cm-1 (Ar-CN)str, 1446 cm-1 (C=C)bending, 852 cm-1 (R1CH=CR2R3)str. Elemental analysis: calculated: C 56.82; H 2.12; N 7.36; S 33.70; found: C 56.95; H 1.97; N 6.83; S 31.71. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | In toluene; at 100℃;Inert atmosphere; | EXAMPLE 4i Preparation of 4, 4′″-didodecyl-2,2′:5′, 2″:5″, 2′″-quaterthiophene (21) (0237) (0238) 5,5′-dibromo-2,2′-bithiophene and 4-dodecyl-3-(trimethylstannyl)thiophene (20) were degassed in a 100 ml 2-neck round bottom flask. 10 ml of anhydrous toluene was added to the reaction mixture and refluxed at 100 C. After cooling, the reaction mixture was extracted using DCM, washed with water, brine, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The crude mixture was purified using column chromatography using hexane as eluant to give the desired product 21 as an orange solid. Yield: 44% (0.4852 g). 1H-NMR (CD2Cl2, 400 MHz) δ 7.06 (s, 2H), 6.86 (s, 2H), 7.08-7.11 (m, 4H), 2.60 (t, 4H), 1.65 (m, 4H), 1.2-1.4 (m, 36H), 0.89 (t, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4.53 g | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate; In N,N-dimethyl-formamide; at 100℃; for 4h; | The compound (1-h)4. 53g dissolved in tetrahydrofuran (wako pure chemical industries (strain) made) 40 ml in, -80 C in cooling. N -1. 6M Phenylbicyclohexane soln. (wako pure chemical industries (strain) made) 6. 1 ml is added, is heated up to 5 C-, -80 C in cooling. 2-isopropoxydiphenyl -4, 4, 5, 5-tetramethyl -1, 3, 2-dioxaborolane (wako pure chemical industries (strain) made) 2. 3 ml is added, and heated to room temperature, the stirring 2 hours in a nitrogen atmosphere. A solution obtained by adding 150 ml and ethyl acetate 200 ml 1N aqueous ammonium chloride, fractionating the organic layer, after washing with 200 ml water, dried with magnesium sulfate. The resultant solution to column chromatography (filler: silica gel, eluent: dichlomethane/Phenylbicyclohexane) is purified by, compd. (1-i)2. 31g is obtained. |
Yield | Reaction Conditions | Operation in experiment |
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240 mg | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate; In 1,4-dioxane; toluene; at 100℃; for 6h;Inert atmosphere; | Synthesis Example 1: Synthesis of Exemplary Compound B-4 (0157) (0158) In a 50 mL reaction vessel, 300 mg (0.926 mmol) of XX-1 (5,5′-dibromo-2,2′-bithiophene) and 590 mg (3.24 mmol) of XX-2 were mixed with a toluene/1,4-dioxane (6 ml/6 ml) mixed solvent, and then dissolved oxygen was removed with nitrogen. Subsequently, 8.3 mg (0.037 mmol) of Pd(OAc)2 and 38 mg (0.093 mmol) of 2-dicyclohexyl phosphino-2′,6′-dimethoxy biphenyl (S-Phos), and 1.07 g (4.65 mmol) of tripotassium phosphate were added under a nitrogen atmosphere, heated and refluxed at 100 C., and then reacted for 6 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and then isolated and purified by silica gel chromatography (Mobile phase: Hexane/Chloroform=1/3), whereby B-4 of light yellow solid powder was obtained (240 mg). (0159) As a result of confirming the structure of the compound B-4 by measurement of mass-spectrum (MS) measurement and nuclear magnetic resonance spectrum (NMR) measurement, the molecular weight and the ratio of the NMR peak integrated values were well in agreement with the structure. Specifically, 438 which is M+ of this compound was confirmed by matrix assisted laser desorption ionization mass spectrum (MALDI-MS) measurement. The measurement results of the NMR spectrum are shown below. (0160) 1H-NMR (CDCl3) δ (ppm): 7.41 (d, 2H), 7.23 (t, 2H), 7.18 (d, 2H), 6.65 (d, 4H), 3.86 (s, 12H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 80℃; for 10h;Inert atmosphere; | General procedure: 4-Ethynyl-N,N-dihexadecylaniline (1.8 g, 3.2 mmol) obtained from previous work41 and 2-bromothiophene (421.0 mg, 2.6 mmol) were dissolved in the mixed solvent of 20 mL trimethylamine (TEA) and 20 mL tetrahydrofuran (THF). After the solution was flushed with bubbling Ar for 40 min, Pd(PPh3)2Cl2 (36.5 mg, 0.052 mmol) and CuI (19.86 mg, 0.104 mmol) were added. The reaction mixture was then stirred at 80 C for 10 h under an Ar atmosphere. The resulting mixture was concentrated, diluted with CH2Cl2, and filtered through a plug of silica gel. The solvent was removed in vacuo, and the product was purified by column chromatography (SiO2, petroleum ether/CH2Cl2 6:1) to give the monomer St1 (1.2 g, 71%) as a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
5.8% | With bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; toluene; at 90℃;Inert atmosphere; | A.The compound 5,5'-dibromo-2,2'-dithiophene (300 mg, 0.93 mmol)4-formylphenylboronic acid (305.4 mg, 2.04 mmol),Bis (triphenylphosphine) palladium dichloride Pd (PPh3) 2Cl2 (65 mg, 0.09 mmol)Was dissolved in 20 mL of a mixed solvent of toluene and tetrahydrofuran (Vtoluene: VTHF = 1: 1)The reaction was refluxed at 90 C under nitrogen,Thin layer chromatography to the reaction is complete.After the resulting solution was spin off the organic solvent,Extracted with ethyl acetate,Organic layer washed three times,Saturated NaCl solution once,Dried over anhydrous sodium sulfate,The solvent is evaporated under reduced pressure;The crude product was passed through a column of petroleum ether and ethyl acetate mixed solvent (20: 1)4,4 '- ([2,2'-bithiophene] -5,5'-diyl) benzaldehyde (yellow powder, 19.5 mg, yield 5.8%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | A 50 mL Schlenk tube was charged with 53.3 mg (2.19 mmol) of magnesium (scraped)6 mL of dehydrated THF was added.616 mg (2.22 mmol) of the compound (S7) was added dropwise over 5 minutes at room temperature,The mixture was stirred at 60 C. for 1 hour to prepare a Grignard reagent.After returning to normal temperature,To this solution, 38.0 mg (0.0519 mmol) of PdCl 2 (dppf)320 mg (0.988 mmol) of 5,5'-dibromo-2,2'-bithiophene was added and the mixture was stirred at 70 C. for 16 hours.After distilling off the reaction solution under reduced pressure,Add water,And extracted with chloroform.The organic layer was dried with sodium sulfate,Filter,The solvent was distilled off under reduced pressure.The obtained mixture was purified by silica gel chromatography (chloroform, Rf = 1.0)By recycling preparative preparative GPC (chloroform)(S8) as 407 mg of a yellow solid.The yield and physical properties of (S8) were as follows. (0.728 mmol, 78% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | 500mL three-necked flask was added magnesium tablets (10g) and 100mL ether under argon was added dropwise 2_ bromo-3-octylthiophene (35g) and 1,2-dibromoethane (5.65g) in 50mL of ether After the addition, reflux for three hours. After the reaction was completed, the reaction solution was added dropwise to the solution2,5-dibromo-bithiophene(15.87 g), Ni (dppp) 2 Cl2 (1.59 g) and 100 mL of diethyl etherThree bottles, after adding, reflux overnight. After completion of the reaction, dilute hydrochloric acid was added and the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate,The organic solvent was removed and the column was separated to give a light yellow liquid, Intermediate 4 (19.22 g, 71% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.4% | TT-Br (1.00 g, 3.08 mmol) was dissolved in distilled tetrahydrofuran (THF, 30 mL). With stirring, a solution of 1.6 M n-butyllithium in hexane (3.64 mL) was added dropwise at -78C, and the reaction mixture was stirred for 2 h. After stirring, 4-formylmorpholine (0.820 g, 7.09 mmol) was added dropwise to the reaction mixture, stirred for another 1 h, and warmed to rt. After stirring at rt for 2 h, the mixture was poured into methanol (150 mL) and filtered to give a yellow solid product. Yield: 0.470 g (69.4%). 1H NMR (400 MHz, CDCl3): δ (ppm) 9.92 (s, 2H), 7.73 (d, J = 4.0 Hz, 2H), 7.43 (d, J = 3.9 Hz, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 130℃; for 24h;Inert atmosphere; | 1-(5-Bromo-2,2':5',2"-trithiophene)-3,5-bis(2-thienyl)benzene (0.57 g, 1.0 mmol),2-(1,3,5-tris(2-thienyl)benzene)[4,4,5,5-tetramethyl-1,3,2-dioxaborane] (0.90 g, 2.0 mmol),K2CO3 (1.1g, 8mmol),4 ml of water, Pd(PPh3) 4 (10.0 mg, 0.007 mmol) was added sequentially under a nitrogen atmosphere.Add 6 ml of toluene, rapidly heat up to 130 C, and reflux the system for 24 h.The reaction was shut down, cooled to room temperature, extracted with deionized water and dichloromethane. The obtained organic phase was dried over anhydrous MgSO 4 and then purified by column chromatography. The stationary phase was 300 mesh silica gel and the mobile phase was dichloromethane. Petroleum ether (1:5),Finally, 0.97 g of an orange solid benzene-tetrathiophene-benzene derivative was obtained with a yield of 60%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With copper(l) iodide; diethylamine; In dichloromethane; at 20℃; for 4h;Schlenk technique; | General procedure: To a Schlenk flask containing [(PMe3)2(Br)Pd-Y-Pd(Br)(PMe3)2] (0.335 g, 0.40 mmol)were added CH2Cl2 (20 mL), CuI (15.2 mg, 0.080 mmol), Et2NH (0.124 mL, 1.20 mmol)and HCC-SiPh3 (0.340 g, 1.20 mmol) in that order. After stirring for 4 h at room temperature,the solvent was removed completely and the remaining solid was extractedwith CH2Cl2/H2O. The collected dichloromethane layer was dried over anhydrous CaCl2and evaporated under vacuum to give crude solid, which was washed with hexane(6 mLx 3) to remove side products. The remaining solid was recrystallized fromCH2Cl2/hexane to give a white powder of trans-[Pd(CC-SiPh3)2(PMe3)2] (16, 0.405 g,61%). The organic compound was identified as the bithiophene by GC-MS. Complex16: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | General procedure: PMe3 (1.96 mL, 19.0 mmol) was added to ice-cold diethyl ether (10 mL) solution ofPt(COD)Et2 [21] (3.13 g, 8.66 mmol). After the mixture was stirred for 1 h, the solventwas removed under reduced pressure to give crude solids, which were washed withhexane (3 mL 3) and then recrystallized from excess diethyl ether to afford whitecrystals of cis-PtEt2(PMe3)2 (2.70 g, 77%).To a Schlenk flask containing cis-[PtEt2(PMe3)2] (0.250 g, 0.62 mmol) at room temperaturewere added sequentially styrene (0.142 mL, 1.24 mmol) and toluene (3 mL).The mixture was heated at 80 C for 18 h to give a yellow solution. At room temperature,4,4'-dibromobenzil (0.114 g, 0.31 mmol) was added to the mixture, and then, theinitial pale yellow solution turned to a yellow solution. After stirring the reaction mixturefor 3 h, the solvent was removed completely under vacuum and, then, the resultingsolids were washed with diethyl ether (2 mL 3). The solids were filtered anddried to give pale crude solids, which were recrystallized from THF/(diethyl ether) togive pale yellow crystals of [(PMe3)2(Br)Pt-Y-Pt(Br)(PMe3)2] (YH2 = benzil), 7 (0.136 g,41%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | General procedure: PMe3 (1.96 mL, 19.0 mmol) was added to ice-cold diethyl ether (10 mL) solution ofPt(COD)Et2 [21] (3.13 g, 8.66 mmol). After the mixture was stirred for 1 h, the solventwas removed under reduced pressure to give crude solids, which were washed withhexane (3 mL 3) and then recrystallized from excess diethyl ether to afford whitecrystals of cis-PtEt2(PMe3)2 (2.70 g, 77%).To a Schlenk flask containing cis-[PtEt2(PMe3)2] (0.250 g, 0.62 mmol) at room temperaturewere added sequentially styrene (0.142 mL, 1.24 mmol) and toluene (3 mL).The mixture was heated at 80 C for 18 h to give a yellow solution. At room temperature,4,4'-dibromobenzil (0.114 g, 0.31 mmol) was added to the mixture, and then, theinitial pale yellow solution turned to a yellow solution. After stirring the reaction mixturefor 3 h, the solvent was removed completely under vacuum and, then, the resultingsolids were washed with diethyl ether (2 mL 3). The solids were filtered anddried to give pale crude solids, which were recrystallized from THF/(diethyl ether) togive pale yellow crystals of [(PMe3)2(Br)Pt-Y-Pt(Br)(PMe3)2] (YH2 = benzil), 7 (0.136 g,41%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.3% | 2,5-dibromo-bithiophene (20.3 g, 62.6 mmol) is put in 1.7 L of tetrahydrofuran to prepare a cold solution (-78 C.), n-butyllithium (2.5 M in hexane, 30 mL, 1.2 eq.) is added to the solution, and the reaction mixture is fervently stirred for 30 minutes. Subsequently, t-butyldimethylsilyl chloride (10.3 g, 68.9 mmol, 1.1 eq.) is added thereto. The obtained reaction mixture is stirred at -78 C. overnight, diluted with dichloromethane, and then washed with water and brine several times. Then, an organic layer therein is dried and evaporated with magnesium sulfate, and a yellow liquid therefrom is purified with a silica column chromatography to obtain 16.9 g of a while solid. (A yield of 75.3%) (0223) 1H-NMR (300 MHz, CDCl3): δ 7.17 (d, J =3.3 Hz, 1H), 7.12 (d, J=3.3 Hz, 1H), 6.96 (d, J=3.9 Hz, 1H), 6.85 (d, J=3.9 Hz, 1H) 0.94 (s, 9H), 0.29 (s, 6H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | With tetrafluoroboric acid diethyl ether; In 1,2-dichloro-ethane; | Add to the 250mL reaction bottle1b (50mg, 0.17mmol, 1equiv), Dibromodithiophene (56 mg, 0.17 mmol, 1 equiv),175 mL 1,2-dichloroethane (DCE), And start stirring, After stirring for a while to completely dissolve the reaction substrate, 0.85 mL of tetrafluoroboric acid diethyl ether was poured into the reaction solution. Quenched with water after 30s, Extracted with dichloromethane, Collect organic phase,Rotating off the solvent, And further separated and purified by circulating GPC. Get a brown powder,It is the organic nano macrocycle 2e (20%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With palladium diacetate; potassium carbonate; In ethanol; water; toluene; at 80℃; for 12h; | 5,5'-Dibromo-2,2'-bisthiophene (0.325 g, 1.0 mmol), (3,5-bis(trifluoromethyl)phenyl)boronic acid (0.774 g, 3.0 mmol),Palladium acetate (0.0058 g, 0.03 mmol) and potassium carbonate (0.415 g, 3.0 mmol) were mixed in a 100 mL reaction apparatus, and then a mixed liquid of 18 mL of toluene, 9 mL of ethanol, and 3 mL of water was added, and the mixture was reacted at 80 C for 12 hours.After completion of the reaction, the mixture was separated and evaporated with dichloromethane.The solvent was removed by a rotary evaporator to obtain a solid powder, which was then separated from the column using pure petroleum ether as a solvent and recrystallized from petroleum ether.An organic compound of 5-(3,5-bis(trifluoromethyl)phenyl)-2,2'-bisthiophene was obtained in a yield of 60%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In water; toluene; at 100℃; for 4h; | A stoichiometric amount Precursor D is reacted with the Secondary Precursor, 5,5 - dibromo-2,2'-bithiophene, resulting in compound 39. Here at least twice as much Precursor D is needed compared to the Secondary precursor. The reaction proceeds with a catalytic amount of PdCl2(dppf) in 1 :9 dilute toluene to water in presence of Potassium Carbonate. The two compounds are allowed to react for 4 hours at 100 degrees Celsius to produce the final product of compound 39. |
Tags: 4805-22-5 synthesis path| 4805-22-5 SDS| 4805-22-5 COA| 4805-22-5 purity| 4805-22-5 application| 4805-22-5 NMR| 4805-22-5 COA| 4805-22-5 structure
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