Structure of 4805-22-5
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CAS No. : | 4805-22-5 |
Formula : | C8H4Br2S2 |
M.W : | 324.06 |
SMILES Code : | BrC1=CC=C(S1)C2=CC=C(S2)Br |
MDL No. : | MFCD00219110 |
InChI Key : | SXNCMLQAQIGJDO-UHFFFAOYSA-N |
Pubchem ID : | 638908 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302+H312+H332 |
Precautionary Statements: | P280 |
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 ? Topological Polar Surface Area: Calculated from |
56.48 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
2.79 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
5.03 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
5.0 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
3.82 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
6.22 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
4.57 |
Log S (ESOL):? ESOL: Topological method implemented from |
-5.57 |
Solubility | 0.000875 mg/ml ; 0.0000027 mol/l |
Class? Solubility class: Log S scale |
Moderately soluble |
Log S (Ali)? Ali: Topological method implemented from |
-5.96 |
Solubility | 0.000358 mg/ml ; 0.0000011 mol/l |
Class? Solubility class: Log S scale |
Moderately soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-5.13 |
Solubility | 0.00238 mg/ml ; 0.00000735 mol/l |
Class? Solubility class: Log S scale |
Moderately soluble |
GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
High |
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg |
Yes |
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) |
Yes |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
Yes |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
Yes |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
Yes |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
No |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
No |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-4.71 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
0.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
0.0 |
Muegge? Muegge (Bayer) filter: implemented from |
1.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
0.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<1.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
2.68 |
* 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 |
---|---|---|
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 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, 18.54 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): 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. | |
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 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, 18.54 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): 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 |
---|---|---|
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 |
---|---|---|
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; at 85℃; for 48h; | A mixture of 5,5'-dibromo-2,2'-bithiophene (5 g, 15.42 mmol) and phenylboronic acid (5 g, 12.34 mmol) were added to a mixturetoluene (50 mL), 2 M K2CO3 (10 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) was added. The crude product was extracted with dichloromethane and purified by column chromatography using hexane as the eluent. Yield: 2.3 g(60%); IR (KBr, cm1); 3031e3064 (aromatic CH), 1H NMR (300 MHz,CDCl3, ppm): d 7.62-7.59 (m, J 5.2 Hz, 2H), 7.40-7.38 (t,J 3.9 Hz, 2H), 7.31-7.28 (m, 1H), 7.24-7.23 (d, J 3 Hz, 1H),7.10-7.09(d, J 3 Hz, 1H), 7.01-6.95 (dd, J 9 Hz, 2H). |
57% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 24h;Heating / reflux; | Synthesis of Compound 1175,5'-dibromo-2,2'-bothiophene (5.00 g, 15.4 mmol), phenylboronic 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). Tetrakis(triphenylphosphine)palladium (0.50 g, 0.46 mmol) was added to the suspension. The resulting mixture was stirred at reflux for about 24 hours. The refluxed mixture was cooled to room temperature and was extracted with chloroform. The organic extract was dried over MgSO4 and concentrated in vacuo. Purification by column chromatography (n-hexane) afforded Compound 117 (2.80 g, 57%). |
57% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 24h;Heating / reflux; | 5, 5'-dibromo-2, 2'-bothiophene (5.00 g, 15.4 mmol), phenylboronic 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). Tetrakis (triphenylphosphine) palladium (0.50 g, 0.46 mmol) was added to the suspension. The resulting mixture was stirred at reflux for about 24 hours. The refluxed mixture was cooled to room temperature and was extracted with chloroform. The organic extract was dried over MgSO4 and concentrated in vacuo. Purification by column chromatography (n-hexane) afforded Compound 117 (2.80 g, 57%). |
56.6% | 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), phenyl boronic 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, was added tetrakis(triphenylphosphine)palladium (0.50 g, 0.46 mmol). The mixture was stirred under reflux for about 24 hours. The refluxed mixture was cooled to room temperature, and extracted by chloroform. The organic extract was dried over magnesium sulfate, and concentrated in vacuo. The resultant was purified by column chromatography (n-hexane) to prepare a compound 1-1 (2.80 g, yield 56.6 %).[191] MS: [M+H]+ = 321 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60%Chromat. | With 1,10-phenanthroline-5,6-dione; oxygen; palladium diacetate; manganese (II) acetate tetrahydrate; p-benzoquinone; In dimethyl sulfoxide; at 100℃; under 760.051 Torr; for 16.0833h;Sealed tube; | To a 13×100 mm borosilicate glass heavy wall test tube was added phd (3.5 mg, 0.017 mmol) and Mn(OAc)2.4H2O (4.0 mg, 0.017 mmol). A stock solution of Pd(OAc)2 (148 mg, 0.660 mmol, 66.0 mM) in 10.0 mL DMSO was created. A stock solution of BQ (44.6 mg, 0.413 mmol, 82.6 mM) in 5.0 mL DMSO was created. To the test tube was added 250 μL (0.017 mmol) of the Pd(OAc)2 stock solution and 200 μL (0.017 mmol) of the BQ stock solution. Then, 2-bromothiophene (53 μL, 0.55 mmol) was added to the test tube. The test tube with reaction mixture was placed on an orbital mixing block with heating element. The mixing block was sealed, purged with O2 for five minutes, cooling water was turned on, and then the block was heated to 100 C. under 1 atm O2 with shaking for 16 hours. After 16 hours, the shaking was stopped, the block was depressurized, and the reaction test tube was removed and allowed to cool. An aliquot of a stock solution of phenanthrene in THF was added to the reaction mixture, and the DMSO/THF mixture was filtered through Celite. The test tube was washed with more THF, which was filtered through the Celite, and then the Celite was washed once more with THF. The filtrate was diluted with additional THF, and then it was shaken so that everything was evenly mixed. The reaction mixture was assayed by HPLC against a calibration curve of 5,5′-dibromo-2,2′-bithiophene and phenanthrene using a reverse phase column (elutent: 100% acetonitrile, 2 mL/minute). The HPLC yield of 5,5′-dibromo-2,2′-bithiophene was determined to be 60%. |