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CAS No. : | 189367-54-2 | MDL No. : | MFCD03427215 |
Formula : | C25H32Br2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | OXFFIMLCSVJMHA-UHFFFAOYSA-N |
M.W : | 492.33 | Pubchem ID : | 3539647 |
Synonyms : |
|
Num. heavy atoms : | 27 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.52 |
Num. rotatable bonds : | 10 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 127.86 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -1.34 cm/s |
Log Po/w (iLOGP) : | 5.63 |
Log Po/w (XLOGP3) : | 11.22 |
Log Po/w (WLOGP) : | 9.42 |
Log Po/w (MLOGP) : | 7.68 |
Log Po/w (SILICOS-IT) : | 9.72 |
Consensus Log Po/w : | 8.74 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 1.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -9.63 |
Solubility : | 0.000000115 mg/ml ; 0.0000000002 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -11.19 |
Solubility : | 0.0000000032 mg/ml ; 0.0 mol/l |
Class : | Insoluble |
Log S (SILICOS-IT) : | -11.53 |
Solubility : | 0.0000000014 mg/ml ; 0.0 mol/l |
Class : | Insoluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 3.0 |
Synthetic accessibility : | 3.63 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302 | 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 |
---|---|---|
86% | Stage #1: With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water; dimethyl sulfoxide for 0.5 h; Stage #2: at 20℃; for 3 h; |
2,7-dibromo fluorene 1.5g, triethyl benzyl ammonium chloride 0.009g, 30mL dimethylSulfoxides discharge suspended in three flask, was added dropwise 1.5 mL of 50wtpercent aqueous sodium hydroxide,The reaction for half an hour, and then dropping 1.59g1- bromine hexane. The mixture was stirred at room temperature for 3 hours,Extracted with ether. The organic phase was washed with brine, dried over anhydrous magnesium sulfate. The solvent was distilled off, noRecrystallization from aqueous ethanol orange needle crystals of 2,7-dibromo-9,9-dihexylfluorene (fluorenyl Compound 2)1.96g, Yield: 86percent |
84.36% | With tetrabutylammomium bromide; sodium hydroxide In water; toluene at 80℃; for 24 h; Inert atmosphere | Dissolve hfluorene (5.00 g, 30.08 mmol) in 40 mL of chloroform solution.A solution of Br2 (3.08 mL) dissolved in 15 mL of chloroform was added dropwise to the above solution and stirred at 0°C for 10 hours in the dark.The reaction was stopped and the mixed solution was poured into an aqueous Na2S2O3 solution and extracted with dichloromethane (15 mL x 3).The combined organic layers were washed with deionized water (25 mL x 3) and saturated brine (20 mL), respectively.After that, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was recrystallized from an absolute ethanol solution to give 2,7-dibromo-fluorene (7.04 g, 72.2percent) as a white solid;Then, 2,7-dibromo-fluorene (6.40 g, 19.75 mmol) obtained from the previous reaction was dissolved with tetrabutylammonium bromide (0.10 g, 0.31 mmol) and 1-bromohexane (7.30 mL, 44.24 mmol). In 60mL of tolueneAnd 25mL of 50percent water by mass of NaOH solution, and argon is kept at 80°C and stirred under reflux for 24 hours.Stop the reaction and extract the solution with ethyl acetate (25mL x 3). Combine the organic layers with deionized water (25mL x 3)After washing with saturated brine (30 mL), the organic layer was dried over anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator.The crude product was separated on a chromatography column (petroleum ether:dichloromethane = 4:1) to give 2,7-dibromo-9,9-dihexyl-fluorene (8.20 g, 84.36percent) as a pale yellow solid;Finally, the resulting 2,7-dibromo-9,9-dihexyl-fluorene (1.00 g, 2.03 mmol) was reacted in the previous step.Dissolve in 30 mL of dichloromethane, add 5 mL of concentrated sulfuric acid, and cool to 0 °C.Ammonium cerium nitrate (3.34 g, 6.09 mmol) was added portionwise to the above mixed solution, and the reaction was stirred for 1 hour.Stop the reaction and add 30 mL of deionized water and extract with dichloromethane (15 mL × 3).The organic phase was washed with deionized water (15 mL x 3) and saturated brine (20 mL), respectively.The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by a chromatography column (petroleum ether: dichloromethane=2:1) to give an orange-yellow product.2,7-dibromo-9,9-dihexyl-1,6-dinitro-fluorene (0.62 g, 52.54percent), |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.2 %Turnov. | With N-Bromosuccinimide In water at 55℃; for 19 h; | A 250 ml flask equipped with a electric stirrer, nitrogen pad, thermowell, and heating mantle was wrapped in foil to minimize the introduction of light.It was loaded with 17.0 g (<=0.047 moles) crude 9,9-di-n-hexylfluorene from Example 1a, 21.1 g (0.119 moles) of N-bromosuccinimide (NBS), and 53.2 g of water.The system was heated to 55° C. for 19 hours where the conversion was determined to be 98.2percent (by area percent GC).Addition of 1.8 g (0.017 moles) NaHSO3 caused the color to change from red to yellow.The temperature was then increased to 65° C. The phases were separated.The top aqueous phase was extracted with 1*8 g of toluene.The combined organic phases were mixed with 32 g of acetonitrile and heated to reflux.It was then cooled to 10° C. and filtered. Air-Drying yielded 19.9 g of a yellow solid, an 84.3percent isolated yield (based on fluorene).Analyzing the filtrate gave a total accountability based on fluorene of about 92percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77.1 %Chromat. | With sodium hydroxide; Aliquat 336 In water; toluene at 55 - 75℃; for 33.5 h; | A mixture of 16.2 g (0.05 moles) dibromofluorene, 13.7 g (0.113 moles) chlorohexane, 0.9 g (0.002 moles) tricaprylmethylammonium chloride (commercially known as Aliquat 336) and 15 ml of toluene was heated to 55° C. under nitrogen. To this was shot added 60.1 g (0.76 moles) 50percent NaOH. No exotherm was detected. The system was heated at 55° C. for 3 hours, 65° C. for 19.5 hours, then 75° C. for 11 hours. At this point, a GC analysis indicated 98+percent conversion. The system was cooled to 60° C. The solids (NaCl) remained suspended in the top organic phase. The aqueous phase was separated and the organic phase was extracted with 1.x.18 ml water, keeping the system at about 60° C. This seemed to be enough water to dissolve all of the solids. The organic phase remained the top phase. The aqueous phase was separated and the organic phase extracted with 19 ml 3.5percent HCl. The organic phase now became the bottom phase and changed color from dark to green and then orange. The organic phase was separated off and product precipitated with of 30.6 g of acetonitrile. It was cooled to 10° C. and filtered. The cake was rinsed with 1.x.10 ml of acetonitrile and air-dried to 19.3 g of a pale yellow solid. By area percent GC it was 98.3percent 2,7-dibromo-9,9-di-n-hexylfluorene, a 77.1percent yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | In a three-neck round bottom flask 2,7-dibromofluorene (1 g, 3.11mmol), tert-BuONa (1.194 g, 12.44 mmol), KI (0.051 g, 0.311 mmol) andanhydrous THF (8 mL) were stirred for 1h under a nitrogen atmosphere.Then, bromohexane (1.30 g, 7.9 mmol) was added dropwise and thereaction mixture was stirred overnight at refilux. The reaction mixturewas cooled to rt, poured in water and extracted with diethyl ether. Theorganic layer was washed with water and dried over anhydrous Na2SO4and the solvent was evaporated under a reduced pressure. The cruderesidue was purified by column chromatography on silica gel (eluentpetroleum ether), to yield the pure product 1 as a white powder (96%yield). 1H NMR (400 MHz, CDCl3): 7.52 (d, J 7.7 Hz, 2 H), 7.47-7.44(m, 4H), 1.94-1.89 (m, 4H), 1.17-1.01 (m, 12H), 0.78 (t, 6H), 0.63-0.55(m, 4H). 13C NMR (100 MHz, CDCl3): 152.38, 138.86, 129.94, 125.97,121.25, 120.92, 55.49, 39.99, 31.26, 29.37, 23.44, 22.37, 13.79. GC-MSm/z 492.2 CG/MS (EI) calcd for C25H32Br2 m/z 492,09, found 492,10.Elemental analysis calcd for C25H32Br2: C, 60.99; H, 6.55; Br, 32.46.Found C, 60.85; H, 6.69. | |
89% | With potassium iodide; potassium hydroxide; In dimethyl sulfoxide; at 20℃; | 2,7-dibromo-9H-fluorene (15.2g, 45.4mmol, 1eq), bromo-n-hexane (45.4-136.2mmol, 1-3eq), potassium hydroxide (45.4-454mmol, 1-10eq), potassium iodide ( 4.5-45.4mmol, 0.1-1eq) was dissolved in DMSO (80110eq), the system was continuously stirred at 030 for 8-12 hours, then the reaction was followed by a dot plate. After the reaction, the liquid was filtered with suction and used for 300 The mixture was diluted with 500 eq ethyl acetate, the aqueous phase was separated and the aqueous phase was extracted again with 100-300 eq ethyl acetate. The combined organic phase was dried over anhydrous sodium sulfate and concentrated. The residual solid is purified by a silica gel column, and the eluent is petroleum ether and ethyl acetate, and the volume ratio is preferably 100:1 to obtain compound 1 in light green oily form with a yield of 89%. |
86% | 2,7-dibromo fluorene 1.5g, triethyl benzyl ammonium chloride 0.009g, 30mL dimethylSulfoxides discharge suspended in three flask, was added dropwise 1.5 mL of 50wt% aqueous sodium hydroxide,The reaction for half an hour, and then dropping 1.59g1- bromine hexane. The mixture was stirred at room temperature for 3 hours,Extracted with ether. The organic phase was washed with brine, dried over anhydrous magnesium sulfate. The solvent was distilled off, noRecrystallization from aqueous ethanol orange needle crystals of 2,7-dibromo-9,9-dihexylfluorene (fluorenyl Compound 2)1.96g, Yield: 86% |
84.36% | With tetrabutylammonium bromide; sodium hydroxide; In water monomer; toluene; at 80℃; for 24h;Inert atmosphere; | Dissolve hfluorene (5.00 g, 30.08 mmol) in 40 mL of chloroform solution.A solution of Br2 (3.08 mL) dissolved in 15 mL of chloroform was added dropwise to the above solution and stirred at 0C for 10 hours in the dark.The reaction was stopped and the mixed solution was poured into an aqueous Na2S2O3 solution and extracted with dichloromethane (15 mL x 3).The combined organic layers were washed with deionized water (25 mL x 3) and saturated brine (20 mL), respectively.After that, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was recrystallized from an absolute ethanol solution to give 2,7-dibromo-fluorene (7.04 g, 72.2%) as a white solid;Then, 2,7-dibromo-fluorene (6.40 g, 19.75 mmol) obtained from the previous reaction was dissolved with tetrabutylammonium bromide (0.10 g, 0.31 mmol) and 1-bromohexane (7.30 mL, 44.24 mmol). In 60mL of tolueneAnd 25mL of 50% water by mass of NaOH solution, and argon is kept at 80C and stirred under reflux for 24 hours.Stop the reaction and extract the solution with ethyl acetate (25mL x 3). Combine the organic layers with deionized water (25mL x 3)After washing with saturated brine (30 mL), the organic layer was dried over anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator.The crude product was separated on a chromatography column (petroleum ether:dichloromethane = 4:1) to give 2,7-dibromo-9,9-dihexyl-fluorene (8.20 g, 84.36%) as a pale yellow solid;Finally, the resulting 2,7-dibromo-9,9-dihexyl-fluorene (1.00 g, 2.03 mmol) was reacted in the previous step.Dissolve in 30 mL of dichloromethane, add 5 mL of concentrated sulfuric acid, and cool to 0 C.Ammonium cerium nitrate (3.34 g, 6.09 mmol) was added portionwise to the above mixed solution, and the reaction was stirred for 1 hour.Stop the reaction and add 30 mL of deionized water and extract with dichloromethane (15 mL × 3).The organic phase was washed with deionized water (15 mL x 3) and saturated brine (20 mL), respectively.The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by a chromatography column (petroleum ether: dichloromethane=2:1) to give an orange-yellow product.2,7-dibromo-9,9-dihexyl-1,6-dinitro-fluorene (0.62 g, 52.54%), |
With benzyl-triethyl-ammonium chloride; sodium hydroxide; In dimethyl sulfoxide; at 20℃; for 3h; | n three bottle was charged with 2,7-dibromo-fluorene (9.78,0.031111), benzyltriethylammonium chloride (0.078,0.3mmol), dimethyl sulfoxide 90mL and 45mL aqueous sodium hydroxide solution (mass fraction 50%). At room temperature with stirring to form a suspension. Solution of 1-bromo-n-hexane (12.5g, 65mmol), and continue stirring for 3 hours, and extracted with ether. It was washed with a saturated sodium chloride aqueous solution with diethyl ether, dried over anhydrous magnesium sulfate. The solvent was evaporated, the product using petroleum ether as the eluent was purified by column chromatography to give white crystals. | |
1. Add 7.2 mL (50 mmol) of 1-bromohexane and 0.33 g (1 mmol) of tetrabutylammonium bromide to a 50 mL round bottom flask.20mL of 50% KOH aqueous solution,After 30 minutes of deaeration, the reaction mixture was warmed to 75 C.1.62 g (5 mmol) of 2,7-dibromofluorene was added and refluxing was continued at 75 C for 15 minutes.The reaction mixture is subjected to extraction, drying and concentration, and then separated by column chromatography.Compound a-1 was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | n-Butyllithium in hexane (26.9 mL, 1.6 M, 0.043 mol) was added to a solution of 5 (20 g, 0.041 mol) in dry ether (150 mL) at -78 C under N2 atmosphere, and stirred for 1 h. Then chlorotrimethylsilane (6 mL, 0.0462 mol) was added slowly at -78 C and the reaction was allowed to slowly warm to room temperature and stirred overnight. The reaction mixture was quenched with saturated brine and the resulting solution was extracted by diethyl ether. The organic layer was washed with brine and H2O for three times and dried over MgSO4(S). After removing the solvent, the crude product was purified through chromatography on silica with hexane as eluent to give final purified product as a colorless oil (19.16 g, 97%). IR (KBr, cm-1): 3201 (C(sp2)-H stretching absorption), 2954, 2925, 2853 (C(sp3)-H stretching absorptions), 1609, 1482 (stretching absorptions of benzene rings), 1455 (CH2 bending absorption), 1376 (CH3 bending absorption), 1305 (Ar-N stretching absorption), 1246 (Si-C stretching absorption). 1H NMR (300 MHz, CDCl3, tentative assignment based on calculated values) δ: 7.85-7.84 (d, J=7.8 Hz, 1H, ArH on the fluorene unit), 7.77-7.73 (m, 2H, ArH on the fluorene unit), 7.63-7.61 (m, 2H, ArH on the fluorene unit), 7.54-7.52 (d, J=7.8 Hz, 1H, ArH on the fluorene unit), 2.13-2.12 (m, 4H, -CH2CH2CH2CH2CH2CH3), 1.20-1.19 (m, 12H, -CH2CH2CH2CH2CH2CH3), 0.91 (t, J=7.8 Hz, 6H, -CH2CH2CH2CH2CH2CH3), 0.64 (m, 4H, -CH2CH2CH2CH2CH2CH3), 0.46 (s, 9H, CH3 on the TMS unit); 13C NMR (75 MHz, CDCl3, tentative assignment based on calculated values) δ: 153.07 (aromatic carbon on the fluorene unit), 149.17 (aromatic carbon on the fluorene unit), 140.68 (aromatic carbon on the fluorene unit), 139.96 (aromatic carbon on the fluorene unit), 139.71 (aromatic carbon on the fluorene unit), 132.09 (aromatic carbon on the fluorene unit), 129.89 (aromatic carbon on the fluorene unit), 127.41 (aromatic carbon on the fluorene unit), 126.19 (aromatic carbon on the fluorene unit), 121.44 (aromatic carbon on the fluorene unit), 121.07 (aromatic carbon on the fluorene unit), 119.06 (aromatic carbon on the fluorene unit), 55.20 (sp3-carbon on the fluorene unit), 40.03 (carbon on the alkyl chain), 31.30 (carbon on the alkyl chain), 29.50 (carbon on the alkyl chain), 23.57 (carbon on the alkyl chain), 22.45 (carbon on the alkyl chain), 14.00 (carbon on the alkyl chain), -0.89 (carbon on the TMS unit); HRMS-FAB(m/z): [M+H]+ calcd for C28H41BrSi, 484.2161, found [(79Br)M+H]+=484.2150; [(81Br)M+H]+=486.2150. | |
88% | Under nitrogen protection,To a 300 ml two-necked bottle was added <strong>[189367-54-2]2,7-dibromo-9,9-dihexylfluorene</strong> (4.92 g, 10 mmol)With 120 ml of anhydrous tetrahydrofuran, the temperature was lowered to -78C.A solution of n-butyllithium in n-hexane (5.5 ml, 11 mmol) was slowly added dropwise.Continue stirring at -78C for half an hour.Trimethylsilyl chloride (1.63 g, 15 mmol) was then added.The temperature was slowly raised to room temperature for 8 hours.The reaction is quenched with a small amount of water and the product is extracted with dichloromethane.After the saturated sodium chloride solution was washed three times, the solvent of the organic phase was removed under reduced pressure.The crude product was purified by silica gel column chromatography (eluent was petroleum ether) to give 4.27 g of a yellow oily liquid in 88% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | General procedure: Anhydrous anaerobic reactor was assembled, under a continuing stirring and N2 protection, white 9.0mmol of2, 7- dibromo-9 , 9- dioctylfluorene were added into a three-necked flask, 150mL of refined tetrahydrofuran solvent wasadded by a syringe, 27.0 mmol of n-BuLi was added by a syringe under a temperature of -78C, the mixture was stirredfor 2 hours. Then, 30.6mmol of 2- isopropoxy-4, 4, 5, 5-tetramethyl-1, 3, 2- dioxaborolane was added by a syringe undera temperature of -78C, the temperature was raised to 20C, and the reaction was carried out for 14 hours.[0051] After the reaction was finished, a saturated aqueous NaCl solution was added, extracted with chloroform, driedby anhydrous sodium sulfate, suction filtered, and the filtrate was collected and solvent was rotary evaporated. The rawproduct was finally refined by a silica gel column chromatography using petroleum ether: ethyl acetate (v/v=15:1) aseluent to obtain powdered solid 2, 7- bis (4, 4, 5, 5-tetramethyl-1,3,2- the dioxaborolan- yl) -9, 9- dioctylfluorene in ayield of 65%. GC-MS (EI-m/z) : 642 (M+). The preparation process was similar to that of Step one in Example 1, and the differences were:[0061] In step S1, the temperature was -75C, and then was raised to 20C. The reaction time was 48 hours. Themole ratio of 2, 7-dibromo-9, 9-dioctylfluorene to n-BuLi was 1:2; the solvent is dichloromethane; the mole amount of2-isopropoxy-4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane was 3 times of that of 2, 7-dibromo-9, 9-dioctylfluorene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine; at 70℃; | A solution of ethynyltrimethylsilane (0.60 mE, 4.25 mmol) in triethylamine (8 mE) was slowly added to a solution of compound 3d (1 .0 g, 1.93 mmol), (PPh3)2PdC12 (0.068 g, 0.lOmmol), andcopperiodide (0.02 g, 0.lOmmol)intriethy- lamine (20 mE). The resulting mixture was heated at 70 C., overnight. The reaction was monitored by TLC using hexanes as the eluent. Work up: triethylamine was evaporated under reduced pressure and the residue was purified by column chromatography over silica gel, giving compound 7a as yellow solid in 95% yield (0.97 g, 1.8 mmol). |
91% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine; at 20 - 70℃; for 25h; | General procedure: To the mixture of corresponding dibromoaromatic compound (1.0 equiv), Pd(PPh3)2Cl2 (0.05 equiv), CuI (0.025 equiv) and the mixed solvent Et3N, trimethylsilylacetylene (4.0 equiv) was added at room temperature. After stirring one hour at room temperature, the reaction mixture was allowed to proceed at 70 C for 24 h. After cooling to room temperature, the reaction mixture was concentrated under vacuum to give the crude product, which was further purified by silica gel column chromatography with CH2Cl2/hexane as eluent to get the pure product as white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate; In N,N-dimethyl-formamide; at 155℃; for 12h; | Synthesis of Intermediate D (0141) A mixture of 17.06 g (100 mmol) of carbazole, 50.75 g (100.0 mmol) of 2.7-dibromo-9,9-dihexyl-9H-fluorene, 1.904 g (10 mmol) of CuI, 5.460 g (30.00 mmol) of 1,10-phenanthroline, 23.46 g (170.0 mmol) of K2CO3, and 100 ml of dimethylformamide (DMF) was stirred at 155 C. for 12 hours to obtain 40.50 g of Intermediate D with a yield of 70%. (0142) 1H-NMR (300 MHz, CDCl3): δ=8.235 (d, 2H), 7.933 (d, 1H), 7.690 (m, 4H), 7.487 (d, 4H), 7.387 (m, 2H), 2.063 (m, 4H), 1.558 (m, 12H), 1.203 (m, 10H) (0143) 13C-NMR (75 MHz, CDCl3): δ=153.2, 152.2, 141.0, 139.3, 136.8, 130.2, 126.3, 125.9, 123.4, 121.8, 121.5, 121.2, 120.9, 120.4, 119.9, 109.7, 55.7, 40.2, 31.5, 29.6, 23.8, 22.5, 14.0 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62.9% | With iodine; magnesium; In tetrahydrofuran; hexane; acetone; | Step 2 9,9-Di-n-hexylfluorene-2,7-diboronic acid The solution of <strong>[189367-54-2]2,7-dibromo-9,9-di-n-hexylfluorene</strong> in THF (50 mL) was added to a dry flask charged with magnesium turnings under an argon atmosphere. A few pieces of iodine were added to initiate the reaction. The formed Grignard reagent was added slowly to a solution of trimethyl borate in THF at -78 C. After the addition, the reaction mixture was allowed to warm up slowly and stirred continuously at room temperature for 72 h. The resulting mixture was poured into crushed ice containing 5% (w/w) sulphuric acid under stirring. The mixture was extracted with diethyl ether, washed with water and dried over MgSO4 overnight. The crude diboronic acid was purified by recrystallization from the mixture of hexane and acetone to afford 10.90 g of 9,9-di-n-hexylfluorene-2,7-diboronic acid as white crystalline powders (yield: 62.9%). M.P.: to 300 C. The structure was confirmed by FAB-MS, 1H NMR, 13C NMR, FT-IR, UV-Vis spectroscopy, and elemental analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | Compound 1 (2.45g, 5mmol, 1eq) was dissolved in redistilled THF (80110eq). After the system was continuously stirred at -20-80 for 13 hours, n-butyllithium (3.44mL, 1.6M solution in hexane, 5.6mmol, 0.8-3eq) was added dropwise within 7-30 minutes. Add DMF (0.53eq), stir in the cooling bath for 1-3 hours, and stir outside the bath for 1-3 hours. The reactants are then cooled to 5-20C. And quench the reaction with water. The mixture was diluted with 300-500 eq ethyl acetate, the aqueous phase was separated and extracted again with 100-300 eq ethyl acetate. The combined organic phase was dried over anhydrous sodium sulfate and concentrated. The residual solid is purified by a silica gel column, and the volume ratio of the eluent petroleum ether and ethyl acetate is preferably 25:1 to obtain the light green oily compound 2 with a yield of 52%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77.1%Chromat. | With sodium hydroxide; Aliquat 336; In water; toluene; at 55 - 75℃; for 33.5h; | A mixture of 16.2 g (0.05 moles) dibromofluorene, 13.7 g (0.113 moles) chlorohexane, 0.9 g (0.002 moles) tricaprylmethylammonium chloride (commercially known as Aliquat 336) and 15 ml of toluene was heated to 55 C. under nitrogen. To this was shot added 60.1 g (0.76 moles) 50% NaOH. No exotherm was detected. The system was heated at 55 C. for 3 hours, 65 C. for 19.5 hours, then 75 C. for 11 hours. At this point, a GC analysis indicated 98+% conversion. The system was cooled to 60 C. The solids (NaCl) remained suspended in the top organic phase. The aqueous phase was separated and the organic phase was extracted with 1×18 ml water, keeping the system at about 60 C. This seemed to be enough water to dissolve all of the solids. The organic phase remained the top phase. The aqueous phase was separated and the organic phase extracted with 19 ml 3.5% HCl. The organic phase now became the bottom phase and changed color from dark to green and then orange. The organic phase was separated off and product precipitated with of 30.6 g of acetonitrile. It was cooled to 10 C. and filtered. The cake was rinsed with 1×10 ml of acetonitrile and air-dried to 19.3 g of a pale yellow solid. By area % GC it was 98.3% 2,7-dibromo-9,9-di-n-hexylfluorene, a 77.1% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 24h;Reflux; Inert atmosphere; | Example 1 - Synthesis of compound A 1; To a mixture of 4-cyanophenylboronic acid (3.15 g, 21.4 mmol), 9,9-dihexyl-2,7- dibromofluorene (21.14g, 43.0 mmol), and tetrakis(triphenylphosphine)palladium (0.495 g, 0.428 mmol, 2% per C-Br bond), was added degassed K2CO3 aqueous solution (100 ml_) and degassed toluene (150 ml_). The solution was refluxed under N2 protection for 24 h. The resulting brown solution was extracted with CH2CI2 (100 ml_ * 4). The combined organic layers were dried over MgSO4 and evaporated under reduced pressure to remove the solvent. The residue was then purified with a silicon gel column using CH2CI2/hexane (1 :2) as the eluent to obtain the desired product as a light yellow solid (7.40 g, 67% yield). 1H NMR (400 MHz, CDCI3): δ (ppm) 7.75 - 7.77 (m, 5H), 7.56 -7.60 (m, 2H), 7.47 - 7.52 (m, 3H), 1.95 - 2.04 (m, 4H), 1.06 - 1.15 (m, 12H), 0.77 (t, 6H, J = 7.6 Hz), 0.62 - 0.66 (m, 4H). |
51% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; at 110℃; for 24h; | Synthesis of 4-(2-bromo-9,9-dihexyI-9H-fluoren-7-yI) benzonitrile: 4-(2-bromo-9,9-dihexyl-9H-fluoren-7-yl) benzonitrile was prepared through the following procedure. A mixture of 2,7-dibromo-9,9-dihexyl-9H- fluorene (0.985 g, 2 mmol), 4-cyanophenylboronic acid (0.146 g, 1 mmol), and tetrakis(triphenylρhosphine) palladium (11.6 mg, 0.01 mmol) were added to an air-free two-phase mixture of toluene (25 mL) and aqueous 2M Na2CO3 solution <n="24"/>(15 mL). The resulting mixture was vigourously stirred under argon atmosphere at 110C for 24 hours. The organic layer was separated and the aqueous phase was extracted with ether. The organic layers were washed with brine (2 x 50 mL), and dried with anhydrous MgSO4. The solvent was evaporated and the residue passed through a silica-gel column. 0.27 g of pure product were obtained by recrystallization in heptane with a yield of 51%. 1H NMR (400 MHz, CDCl3): δ(ppm) 7.766-7.751 (m, 5H), 7.605-7.583 (d, J= 8.8 Hz, IH), 7.583-7.564 (d, J= 7.6 Hz, IH)5 7.524 (s,lH), 7.495-7.476 (m, 2H). 2.013-1.964 (m, 4H), 1.140-1.053 (m,12H), 0.781-0.746 (t, J= 7.0 Hz, 6H), 0.658-0.624 (m, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72.3% | With (1R,2R)-1,2-diaminocyclohexane; potassium tert-butylate; In 1,4-dioxane; at 110℃; for 48h;Inert atmosphere; Darkness; | Reaction conditions two:Under N2 protection conditions, diphenylamine (169. lmg, lmmol),9,9-dihexyl-2,7-dibromocarboxylate (1.2 g, 2.5 mmol),Potassium tert-butoxide(202 · lmg, 1 · 8ππο1), pontic copper catalyst(11.4 mg, 0.06 mmol)And Η, Ν phase transfer catalyst(0.4mL) was dissolved in 80mL of anhydrous 1,4_ dioxane solution, the temperature was controlled at 110 C, the tin box paper dark, the reaction 48h; after the reaction was cooled to room temperature extraction and column purification The reaction product 2a (418.8 mg) was obtained in a yield of 72.3%. |
72.3% | With copper(l) iodide; (1R,2R)-1,2-diaminocyclohexane; potassium tert-butylate; In 1,4-dioxane; at 110℃; for 48h;Inert atmosphere; Darkness; | Diphenylamine (169.1 mg, 1 mmol), <strong>[189367-54-2]9,9-dihexyl-2,7-dibromofluorene</strong> (1.2 g, 2.5 mmol), potassium t-butoxide (202.1 mg, under N2 protection conditions). 1.8mmol), cuprous iodide catalyst (11.4mg, 0.06mmol) and phase transfer catalyst (0.4mL) dissolved in 80mL anhydrous 1,4-dioxane solution, temperature control 110 C conditions, tin foil paper In the dark, the reaction was carried out for 48 h; after the reaction was completed, it was cooled to room temperature, and purified by extraction and chromatography to give the product 2a (418.8 mg), yield 72.3%. |
Ca. 55% | With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; at 80℃; for 24h;Inert atmosphere; | To a mixture of compound 5 (30 g; 0.06 mol) and diphenylamine (11.34 g; 0.067 mol) in toluene (120 mL) was added of BINAP (1.14 g; 1.8 mmol), Pd2(dba)3 (0.56 g; 0.6 mmol), sodium tert-butoxide (8.2 g; 0.084 mol) and stirred at 80 C under Ar atmosphere for 24 h. After cooling to the room temperature, ∼100 mL of H2O was added to the reaction mixture. The above solution was then extracted with ethyl acetate and then dried over MgSO4(S). After removing the solvent, the crude product was purified through column chromatography on silica gel using hexane as the eluent to give the final purified product as pale-yellow oil with yield of ∼55% (19.44 g). IR (KBr, cm-1): 3063, 3033 (C(sp2)-H stretching absorptions), 2954, 2925, 2853 (C(sp3)-H stretching absorptions), 1608, 1482 (stretching absorptions of benzene rings), 1466 (CH2 bending absorption), 1375 (CH3 bending absorption), 1300 (Ar-N stretching absorption). 1H NMR (200 MHz, CDCl3, tentative assignment based on calculated values) δ: 7.54-7.50 (d, J=8.1 Hz, 1H, ArH on the fluorene unit), 7.50-7.44 (d, J=8.1 Hz, 1H, ArH on the fluorene unit), 7.45-7.40 (dd, J1=8.1 Hz, J2=3 Hz, 2H, ArH on the fluorene unit), 7.30-7.22 (m, 4H, ArH on the diphenylamino group), 7.14-7.11 (dd, J1=8.1 Hz, J2=3 Hz, 2H, ArH on the diphenylamino group), 7.10-7.07 (m, 4H, ArH on the diphenylamino group), 7.05-6.98 (m, 2H, ArH on the fluorene unit), 1.87-1.79 (m, 4H, -CH2CH2CH2CH2CH2CH3), 1.17-0.99 (m, 12H, -CH2CH2CH2CH2CH2CH3), 0.81 (t, J=7.04 Hz, 6H, -CH2CH2CH2CH2CH2CH3), 0.64 (m, 4H, -CH2CH2CH2CH2CH2CH3); 13C NMR (75 MHz, CDCl3, tentative assignment based on calculated values) δ: 152.79 (aromatic carbon on the fluorene unit), 151.67 (aromatic carbon on the fluorene unit), 147.82 (aromatic carbon on the diphenylamino group), 147.49 (aromatic carbon on the fluorene unit), 139.88 (aromatic carbon on the fluorene unit), 135.00 (aromatic carbon on the fluorene unit), 129.87 (aromatic carbon on the diphenylamino group), 129.13 (aromatic carbon on the fluorene unit), 125.89 (aromatic carbon on the fluorene unit), 123.41 (aromatic carbon on the fluorene unit), 122.85 (aromatic carbon on the fluorene unit), 120.41 (aromatic carbon on the fluorene unit), 122.58 (aromatic carbon on the diphenylamino group), 120.43 (aromatic carbon on the fluorene unit), 120.36 (aromatic carbon on the diphenylamino group), 120.14 (aromatic carbon on the fluorene unit), 119.01 (aromatic carbon on the fluorene unit), 55.26 (sp3-carbon on the fluorene unit), 40.10 (carbon on the alkyl chain), 31.44 (carbon on the alkyl chain), 29.51 (carbon on the alkyl chain), 23.66 (carbon on the alkyl chain), 22.50 (carbon on the alkyl chain), 14.03 (carbon on the alkyl chain); HRMS-FAB(m/z): [M+H]+ calcd for C37H42BrN, 579.2501, found [(79Br)M+H]+=579.2507; [(81Br)M+H]+=281.2483. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; | A synthesis was performed in the same manner as in the synthesis of Compound 1b, except that 2.00 g (4.06 mmol, 1 equivalent) of Compound 3a was used instead of using Compound 1a, and Pd(dppf)Cl2 was used instead of Pd(dba)2 and PCy3 as the catalyst. 1.79 g (yield 75%) of Compound 3b could be obtained. |
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃; for 8h;Inert atmosphere; | (3) Take 1.5 g of <strong>[189367-54-2]9,9-dihexyl-2,7-dibromofluorene</strong>, 1.7 g of divaleryl diboron, 0.89 g of potassium acetate,0.1 g of 1,1'-bis (diphenylphosphino) ferrocene palladium (II) dichloride in a round bottom flask,Add 30 ml of 1,4-dioxane, and pass in argon for 10 minutes while stirring.The reaction was performed at 80 degrees Celsius for 8 hours, and the obtained product was obtained by column chromatography; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol; In toluene; at 100℃; for 7h; | 2. Add 738.5 mg (1.5 mmol) of compound a-1 and 10 mL of toluene to a 25 mL round bottom flask.After removing oxygen for 30 minutes, 1.43 mL (4.5 mmol) was added in sequence.Tributylvinyltin, 2mg (0.0095mmol)2,6-di-tert-butylphenol and 47.4 mg (0.0675 mmol) of bis(triphenylphosphine)palladium chloride, the reaction mixture was refluxed at 100 C for 7 hours.After cooling to room temperature, 10 mL of a 10% KF aqueous solution was added and stirred overnight to remove the solid residue and then extracted.After drying and concentration, it was separated by column chromatography to give Compound b-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 45% | In N,N-dimethyl-formamide; at 110℃; for 12h; | To a mixture of compound 5 (8 g; 0.016 mol) in dry DMF (50 mL) was added CuCN (1.3 g; 14.6 mmol), and stirred at 110 C for 24 h. After cooling to the room temperature, ∼50 mL of NaOH(aq) was added to the reaction mixture. The above solution was then extracted with ethyl acetate and the organic layer was dried over MgSO4(S). After removing the solvent, the crude product was purified through column chromatography on silica gel using ethyl acetate/hexane (1:20) as the eluent to give the final purified product as orange powder with yield of ∼45% (3.21 g). Mp: 74.3-76.7. IR (KBr, cm-1): 3068, 3051 (C(sp2)-H stretching absorptions), 2947, 2922, 2853 (C(sp3)-H stretching absorptions), 2224 (CN stretching absorption), 1608, 1454 (stretching absorptions of benzene rings), 1463 (CH2 bending absorption), 1376 (CH3 bending absorption). 1H NMR (300 MHz, CDCl3, tentative assignment based on calculated values) δ: 7.75-7.72 (dd, J1=8.1 Hz, J2=0.6 Hz, 1H, ArH on the fluorene unit), 7.65-7.58 (m, 3H, ArH on the fluorene unit), 7.52-7.49 (m, 2H, ArH on the fluorene unit), 2.00-1.90 (t, J=8.4 Hz, 4H, -CH2CH2CH2CH2CH2CH3), 1.15-1.03 (m, 12H, -CH2CH2CH2CH2CH2CH3), 0.88-0.75 (t, J=8.4 Hz, 6H, -CH2CH2CH2CH2CH2CH3), 0.61-0.49 (m, 4H, -CH2CH2CH2CH2CH2CH3); 13C NMR (75 MHz, CDCl3, tentative assignment based on calculated values) δ: 153.46 (aromatic carbon on the fluorene unit), 150.99 (aromatic carbon on the fluorene unit), 144.51 (aromatic carbon on the fluorene unit), 138.08 (aromatic carbon on the fluorene unit), 131.40 (aromatic carbon on the fluorene unit), 130.51 (aromatic carbon on the fluorene unit), 126.44 (aromatic carbon on the fluorene unit), 126.38 (aromatic carbon on the fluorene unit), 123.17 (aromatic carbon on the fluorene unit), 122.09 (aromatic carbon on the fluorene unit), 120.29 (aromatic carbon on the fluorene unit), 119.59 (carbon on the cyano group), 110.34 (aromatic carbon on the fluorene unit), 55.75 (sp3-carbon on the fluorene unit), 39.95 (carbon on the alkyl chain), 31.36 (carbon on the alkyl chain), 29.42 (carbon on the alkyl chain), 23.60 (carbon on the alkyl chain), 22.46 (carbon on the alkyl chain), 13.90 (carbon on the alkyl chain); HRMS (m/z): [M+H]+ calcd for C26H32BrN, 437.1718, found [(79Br)M+H]+=438.1794; [(81Br)M+H]+=440.1794. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With potassium phosphate; copper(l) iodide; trans-1,2-Diaminocyclohexane; In toluene; for 24h;Inert atmosphere; Reflux; | A stirred mixture of <strong>[189367-54-2]2,7-dibromo-9,9-dihexylfluorene</strong> (1) (7.5 g, 23.18 mmol), 3,6-di-tert-butylcarbazole (2.16 g, 7.33 mmol), CuI (0.74 g, 3.86 mmol), K3PO4 (4.1 g, 19.3 mmol), and +/-trans-1,2-diaminocyclohexane in toluene (70 ml) was refluxed for 24 h under a N2 atmosphere. After cooling, the reaction mixture was extracted with dichloromethane (100 ml×3). The combined organic phase was washed with water (100 ml), brine solution (100 ml), dried over sodium sulfate (anhydrous), filtered and the solvent was removed in vacuum. Purification by column chromatography using silica gel eluting with hexane afforded viscous oil (3.69 g, 73%). FT-IR (KBr) 3028, 2954, 2926, 2853, 1617, 1560, 1489, 1474, 1364, 876, 811, and 614 cm-1; 1H NMR (300 MHz, CDCl3) δ 8.18 (2H, s), 7.86 (1H, d, J=7.7 Hz), 7.63 (1H, d, J=8.5 Hz), 7.56-7.47 (6H, m), 7.39 (2H, d, J=8.6 Hz), 2.04-1.98 (4H, m), 1.49 (18H, s), 1.19-1.11 (12H, m) and 0.81-0.77 (10H, m) ppm; 13C NMR (75 MHz, CDCl3) δ 153.24, 152.14, 142.91, 139.51, 137.35, 130.22, 126.29, 125.52, 123.62, 123.62, 121.42, 121.16, 120.87, 116.36, 109.19, 55.71, 40.36, 40.25, 32.06, 31.86, 29.96, 29.74, 29.27, 23.91, 22.64 and 14.10 ppm; HRMS-ESI calcd for C45H56BrN: m/z 689.3596 found 689.3371 [M+]. |
73% | With potassium phosphate; copper(l) iodide; trans-1,2-Diaminocyclohexane; In toluene; for 24h;Inert atmosphere; | 2-(3,6-di-tert-butylcarbazol-N-yl)-7-bromo-9,9-dihexylfluorene (1) A stirred mixture of <strong>[189367-54-2]2,7-dibromo-9,9-dihexylfluorene</strong> (7.5 g, 23.18 mmol), 3,6-di-tert-butylcarbazole (2.16 g, 7.33 mmol), CuI (0.74 g, 3.86 mmol), K3PO4 (4.1 g, 19.3 mmol) and ±trans-1,2-diaminocyclohexane in toluene (70 ml) was refluxed for 24 h under a N2 atmosphere. After cooling, the reaction mixture was extracted with dichloromethane (100 ml x 3). The combined organic phase was washed with water (100 ml), brine solution (100 ml), dried over sodium sulfate (anhydrous), filtered and the solvent was remove in vacuum. Purification by column chromatography using silica gel eluting with hexane afforded viscous oil (3.69 g, 73%). FT-IR (KBr) 3028, 2954, 2926, 2853, 1617, 1560, 1489, 1474, 1364, 876, 811, and 614 cm-1; 1H-NMR (300 MHz, CDCl3) d 8.18 (2H, s), 7.86 (1H, d, J = 7.7 Hz), 7.63 (1H, d, J = 8.5 Hz), 7.56-7.47 (6H, m), 7.39 (2H, d, J = 8.6 Hz), 2.04-1.98 (4H, m), 1.49 (18H, s), 1.19-1.11 (12H, m) and 0.81-0.77 (10H, m) ppm; 13C-NMR (75 MHz, CDCl3) d 153.24, 152.14, 142.91, 139.51, 137.35, 130.22, 126.29, 125.52, 123.62, 123.62, 121.42, 121.16, 120.87, 116.36, 109.19, 55.71, 40.36, 40.25, 32.06, 31.86, 29.96,29.74, 29.27, 23.91, 22.64 and 14.10 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With bis-triphenylphosphine-palladium(II) chloride; In toluene; at 100 - 110℃;Inert atmosphere; | General procedure: All monomers: 2-(2-(furan-2-yl)-9H-fluoren-7-yl)furan (FFF), 2,7-di (furan-2-yl)-9H-fluoren-9-one (FOF), and 2-(2-(furan-2-yl)-9,9-dihexyl-9H-fluoren-7-yl)furan (FHF), were synthesized by the Stille Coupling reactions of 2-(tributylstannyl)furan with corresponding 2,7-dibrominated fluorene and its derivatives in the presence of Pd as the catalyst (Scheme 1). 2-(Tributylstannyl) (2 equiv.), Pd(PPh3)2Cl2 (0.02 equiv.) and the corresponding 2,7-dibromofluorene derivatives were placed in a 100 mL two-necked flask equipped with reflux condenser under N2 atmosphere. Then, dry toluene was added as solvent and the reaction medium was heated till the reflux starts (100-110 C). When the reaction was completed, solvent was removed from the medium by distillation and the product was purified from the reaction side products with the help of column chromatography with hexane eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With 1,1'-bis-(diphenylphosphino)ferrocene; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 110℃; for 24h;Inert atmosphere; | General procedure: A mixture of bis(4-butylphenyl)amine (1.407 g, 5 mmol), 2,7-dibromo-9H-fluorene 1 (3.2401 g, 10mmol), sodium tert-butoxide (0.961 g, 10 mmol), dppf (0.0641 g, 0.12 mmol), Pd(dba)2 (0.0575 g, 0.1 mmol), and toluene (80 ml) was refluxed under nitrogen atmosphere for 24 h. After cooling to room temperature, water was added to quench the reaction. The product was extracted with dichloromethane (20 mL×3). The combined organic layers were dried over anhydrous MgSO4, and the solvent was removed under vacuum. The crude product was purified by column chromatography on silica (petroleum ether/ethyl acetate=100/1, v/v) to give a colorless oil 4 (1.2212 g, 2.33 mmol, 47%). 1H NMR (400MHz, CDCl3) δ 7.58-7.53 (m, 2H), 7.49 (d, J=8.0Hz, 1H), 7.43 (d, J=7.8Hz, 1H), 7.23 (s, 1H), 7.19 (s, 1H), 7.07-7.00 (m, 8H), 3.74 (s, 2H), 2.56 (t, J=7.6Hz, 4H), 1.61-1.56 (m, 4H), 1.40-1.34 (m, 4H), 0.94 (t, J=7.2Hz, 6H). 13C NMR (100MHz, CDCl3) δ 147.9, 145.6, 145.0, 144.2, 140.7, 137.5, 134.7, 129.8, 129.2, 128.1, 124.4, 122.4, 120.4, 119.7, 119.3, 36.7, 35.1, 33.8, 22.5, 14.1. HRMS (EI): calcd. for C33H34NBr, 523.1875 [M]+; found, 523.1870. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.8% | With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; for 24h;Reflux; Inert atmosphere; | In nitrogen atmosphere, a mixture ofbis(4-(hexyloxy)phenyl)amine (0.500 g, 1.35 mmol), Pd(OAc)2(6.70 mg, 0.0300 mmol), dppf (38.8 mg, 0.0700 mmol), <strong>[189367-54-2]9,9-dihexyl-2,7-dibromofluorene</strong> (2.00 g, 4.06 mmol), and sodium tert-butoxide(195 mg, 2.03 mmol) was dissolved in dry toluene (10 mL) and heatedto reflux for 24 h. After that, the reaction was cooled down to roomtemperature, quenched by distilled water and extracted with ethyl acetate. The organic layer was dried over anhydrous MgSO4 andremoved under reduced pressure. The crude product was purified bycolumn chromatography using CH2Cl2/hexane (1:6 b y volume) as theeluent to give 1 as an orange liquid (0.894 g, 84.8% yield). 1H NMR(300 MHz, CDCl3): δ (ppm)=7.43 (d, J=8.2 Hz, 1H), 7.40-7.37 (m,3H), 7.04 (d, J=8.9 Hz, 4H), 6.95 (d, J=1.9 Hz, 1H), 6.87 (dd,J=8.2 Hz, 1.9 Hz, 1H), 6.81 (d, J=8.9 Hz, 4H), 3.94 (t, J=6.5 Hz,4H), 1.83-1.74 (m, 8H), 1.50-1.42 (m, 4H), 1.37-1.30 (m, 8H),1.17-1.06 (m, 12H), 0.92 (t, J=6.9 Hz, 6H), 0.81 (t, J=7.0 Hz,6H), 0.66-0.63 (m, 4H). 13C NMR (75 MHz, CDCl3): δ (ppm)=155.38,152.90, 151.78, 148.84, 141.39, 140.49, 133.33, 129.96, 126.20,126.09, 120.69, 120.35, 120.24, 119.72, 116.26, 115.40, 68.50,55.43, 40.37, 31.84, 31.73, 29.81, 29.58, 25.99, 23.91, 22.81, 14.26.HRMS (FAB) m/z: [M]+ calcd for C49H66BrNO2, 779.4277; found,779.4268. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | at 110℃; for 16h;Inert atmosphere; | In the three-port flask 4 - (9H-carbazole-9-yl) aniline (5g, 19.36mmol), 2,7-dibromo -9,9-dihexylacrylamide-fluorenylmethylchloroformate (23.82g, 48 . 39mmol), then adding DPPF (214.61 mg, 3871 . 12umol), Pd2(dba)3(354.49 mg, 387 . 12umol), to the temperature rise under the protection of argon 110 C reaction 16 hours later, to room temperature. The reaction solution with ethyl acetate extraction, the product using petroleum ether: dichloromethane = 10:1 for elution chromatography method for purifying medicinal preparation column, yield: 78%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 16h;Inert atmosphere; | <strong>[189367-54-2]2,7-dibromo-9,9-dihexylfluorene</strong> (1.70g), 4- methoxycarbonyl phenyl boronic acid (CompoundWas 3,1.46g), anhydrous potassium carbonate (0.86 g of) was dissolved in 20mL tetrahydrofuran (THF)Under 9mL and water mixture, argon was added tetrakis (triphenylphosphine) palladium (108mg),At 80 reaction conditions 16h. The reaction solution was extracted with dichloromethane, and then washed with water and saturatedAnd washed with brine, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure, and then recrystallized ethanolCrystal have brown solid 4 (1.52g, 73% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | Tetra (dibenzylideneacetone) dipalladium (0) (0.103 g, 0.112 mol), 1,1'- bis (diphenylphosphino) ferrocene (0.096 g, 0.173 mmol) and 2,7-dibromo--9 , 9-dihexyl fluorene (5.42 g, 11 mmol) dissolved in toluene was then stirred for 15 bun dongan, sodium t-butoxide (1.08 g, 11.2 mmol) and 1,2,3,4-tetrahydroquinoline ( 1.0 g, 7.5 mmol) was allowed to 24 hours at 100 C. The reaction solution was extracted with ethylene acetate, The resulting organic layer was dried with MgSO4 and the solvent was removed. The resulting material hexane / ethylene acetate (10: 1) as a developing solvent to our column chromatography to give the result (2.04 g, 50%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine; at 90℃; for 24h;Inert atmosphere; | A mixture of <strong>[189367-54-2]2,7-dibromo-9,9-dihexyl-9H-fluorene</strong> (3a) (492 mg, 1.00 mmol), 2,3,4,5,6,-pentafluorostyrene (4Aa/4Ba) (524 mg, 2.7 mmol), P(o-tolyl)3 (12 mg, 0.04 mmol) and Pd(OAc)2 (4.5 mg, 0.02 mmol) in triethylamine (0.87 mL) was heated at 90 C. for 1 day under N2. The reaction mixture was cooled to room temperature and extracted with dichloromethane (3x1 5 mL), The organic layer was finally washed with water (3x30 mL). The organic phase was then dried over MgSO4 and evaporated under reduced pressure. The crude product was purified by column chromatography using hexane as the eluent to yield compound 2a as pale yellow solid (370 mg, 64%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | 2,7-Dibromo-9,9-dihexylfluorene (5.00 g, 1.0 eq, 10.2 mmol) was placed in a flask and deaerated with argon. Then anhydrous THF (70 mL) was added, and the mixture was cooled to -78 C. 9.7 mL (2.5M solution in hexanes, 2.4 ea, 24.4 mmol) n-butyllithium were then added dropwise; the resulting solution was stirred for 1 h at -78 C., and then progressively warmed to -50 C. After slow addition of pure chlorodiphenylphosphine (4.0 mL, 2.2 eq, 22.4 mmol), the mixture was left to stir overnight till room temperature. MeOH (20 mL) was added to quench the reaction, and the solution was evaporated to dryness. The solid was re-dissolved in DCM (50 mL), H2O2 (30 wt % aqueous solution, 15 mL) was added dropwise, and the mixture left under stirring. After 24 h, the organic phase was separated, washed subsequently with water and brine, dried over MgSO4, and evaporated to dryness. Purification by chromatography (silica, gradient elution from hexane EtOAc 1:1 v/v to neat EtOAc) provided the desired compound in 34% yield (2.51 g). The material was then further purified by vacuum sublimation. (0130) The pure sublimed compound was amorphous, with no detectable melting peak on the DSC curve, and decomposed at 485 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 100℃; for 24h;Inert atmosphere; | The reaction product 3a (0.94 g, 1.5 mmol), 9,9-dihexyl-2,7-dibromoethane (1.6 g, 3.2 mmol), Pd (PPh3) 4 (11.6mg, 0.01mmol) catalyst was dissolved in 45mL of toluene, and then added 15mL of K2C03 aqueous solution, the reaction temperature was controlled at 100 C 24h; After the reaction was cooled to room temperature extraction and purification by column chromatography to give the reaction product 2b (1.05 g), yield 76.5%. |
73.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 100℃; for 24h;Inert atmosphere; | The reaction product 3b (1.5 g, 1.5 mmol), <strong>[189367-54-2]9,9-dihexyl-2,7-dibromofluorene</strong> (1.6 g, 3.2 mmol), Pd(PPh3)4 (11.6 mg, 0.01) under N2. The catalyst is dissolved in 45 mL of toluene, then added to 15 mL of K2CO3 aqueous solution, and the reaction temperature is controlled at 100 C for 24 hours. After the reaction is completed, it is cooled to room temperature. The product is purified by extraction and column chromatography to obtain the reaction product 2c (1.37 g), yield 73.5. %. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 100℃; for 24h;Inert atmosphere; | Reaction Conditions Three: Under N2 protection, the reaction product 3b (1.5 g, 1.5 mmol), 9,9-dihexyl-2,7-Dibromoethane (1.6 g, 3.2 mmol), Pd (PPh3) 4 (11.6 mg, 0.01 mmol) was dissolved in 45 mL of toluene, And then adding 15mL of K2C03 aqueous solution, the reaction temperature was controlled at 100 C 24h; after the reaction was cooled to room temperature extraction and purification by column chromatography to give the reaction product 2c (1.37g), a yield of 73.5%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58.9% | With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In 1,4-dioxane; water; at 100℃; for 4.5h;Inert atmosphere; | To a reactor there were added acetamide (59.1 g, 1.00 mol), tris(dibenzylideneacetone)dipalladium(0) (3.66 g, 4 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (common name: Xantphos, 6.94 g, 12 mmol), cesium carbonate (391 g, 1.20 mol), 1,4-dioxane (800 ml) and ion-exchanged water (7.2 ml), and the mixture was bubbled with argon gas to replace the reactor interior with an argon gas atmosphere. After heating to 100 C., a solution of <strong>[189367-54-2]9,9-dihexyl-2,7-dibromofluorene</strong> (compound CM19a above, 98.5 g, 200 mmol) in 1,4-dioxane (300 ml) was slowly added over a period of about 0.5 hour, and the mixture was then stirred for 4 hours at the same temperature. The obtained reaction mixture was passed through a silica gel pad, and after concentrating the obtained filtrate it was slowly added to ion-exchanged water and stirred therewith, and the solid precipitated by stirring was filtered out, rinsed with ion-exchanged water and dried under reduced pressure to obtain 94.5 g of solid. The obtained solid was recrystallized using ethanol/ion-exchanged water and then further recrystallized twice with chloroform-hexane, active carbon was added while dissolved in ethanol, the mixture was heated to reflux, and then the active carbon was filtered out by Celite filtration. Next, a procedure of concentrating the filtrate and adding hexane to precipitate a solid was carried out for purification. The obtained solid was filtered and dried under reduced pressure to obtain the target compound CM19b (52.8 g) as a flesh-colored solid. Yield: 58.9%. The HPLC-area percent value of the obtained compound CM19b measured under analysis conditions 1 was 97.6%. 1H-NMR (300 MHz, THF-d8) δ (ppm)=9.05 (s, 2H), 7.69 (s, 2H), 7.51 (t, 4H), 2.06 (s, 6H), 1.95 (m, 4H), 1.10 (m, 12H), 0.78 (t, 6H), 0.66 (m, 4H). 13C-NMR (75 MHz, THF-d8) δ (ppm)=169.1, 152.9, 140.8, 138.3, 120.9, 119.6, 115.3, 56.9, 42.7, 33.7, 31.9, 25.8, 25.3, 24.6, 15.5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52.54% | With ammonium cerium (IV) nitrate; sulfuric acid; In dichloromethane; at 0℃; for 1h; | Dissolve hfluorene (5.00 g, 30.08 mmol) in 40 mL of chloroform solution.A solution of Br2 (3.08 mL) dissolved in 15 mL of chloroform was added dropwise to the above solution and stirred at 0C for 10 hours in the dark.The reaction was stopped and the mixed solution was poured into an aqueous Na2S2O3 solution and extracted with dichloromethane (15 mL x 3).The combined organic layers were washed with deionized water (25 mL x 3) and saturated brine (20 mL), respectively.After that, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was recrystallized from an absolute ethanol solution to give 2,7-dibromo-fluorene (7.04 g, 72.2%) as a white solid;Then, 2,7-dibromo-fluorene (6.40 g, 19.75 mmol) obtained from the previous reaction was dissolved with tetrabutylammonium bromide (0.10 g, 0.31 mmol) and 1-bromohexane (7.30 mL, 44.24 mmol). In 60mL of tolueneAnd 25mL of 50% water by mass of NaOH solution, and argon is kept at 80C and stirred under reflux for 24 hours.Stop the reaction and extract the solution with ethyl acetate (25mL x 3). Combine the organic layers with deionized water (25mL x 3)After washing with saturated brine (30 mL), the organic layer was dried over anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator.The crude product was separated on a chromatography column (petroleum ether:dichloromethane = 4:1) to give 2,7-dibromo-9,9-dihexyl-fluorene (8.20 g, 84.36%) as a pale yellow solid;Finally, the resulting 2,7-dibromo-9,9-dihexyl-fluorene (1.00 g, 2.03 mmol) was reacted in the previous step.Dissolve in 30 mL of dichloromethane, add 5 mL of concentrated sulfuric acid, and cool to 0 C.Ammonium cerium nitrate (3.34 g, 6.09 mmol) was added portionwise to the above mixed solution, and the reaction was stirred for 1 hour.Stop the reaction and add 30 mL of deionized water and extract with dichloromethane (15 mL × 3).The organic phase was washed with deionized water (15 mL x 3) and saturated brine (20 mL), respectively.The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by a chromatography column (petroleum ether: dichloromethane=2:1) to give an orange-yellow product.2,7-dibromo-9,9-dihexyl-1,6-dinitro-fluorene (0.62 g, 52.54%), |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 100℃; for 24h;Inert atmosphere; | The reaction product 3b (1.5 g, 1.5 mmol), <strong>[189367-54-2]9,9-dihexyl-2,7-dibromofluorene</strong> (1.6 g, 3.2 mmol), Pd(PPh3)4 (11.6 mg, 0.01) under N2. The catalyst is dissolved in 45 mL of toluene, then added to 15 mL of K2CO3 aqueous solution, and the reaction temperature is controlled at 100 C for 24 hours. After the reaction is completed, it is cooled to room temperature. The product is purified by extraction and column chromatography to obtain the reaction product 2c (1.37 g), yield 73.5. %. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64.6% | With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 12h; | 20ml of toluene was added to the flask, taking bis (4-(methylthio)phenyl)amine (Formula IV, 2.30 g, 8.8mmol), <strong>[189367-54-2]2,7-dibromo-9,9-dihexylfluorene</strong> (Formula III, 2 g, 4mmol), tris(dibenzylideneacetone)dipalladium (73.2mg, 0.08mmol), tri-tert-butylphosphonium tetrafluoroborate (34.8mg, 0.12mmol) and sodium tert-butoxide (1.152g, 12mmol) In the flask, stir in the oil bath for 12h. After the solution is cooled, add deionized water, extract three times with dichloromethane, combine the organic phases, and use saturated sodium chloride.The organic phase was washed twice with an aqueous solution. It was dried over anhydrous magnesium sulfate and purified on a neutral alumina chromatography column eluting with 20:1 (v/v) petroleum ether/ethyl acetate. The product obtained was dissolved in acetone and recrystallized from methanol to give product F1 as pale yellow solid (2.20 g, 64.6%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62.5% | To a 500 mL two-necked flask, 200 mL of a dehydrated THF solution of the above compound (2-a) 7.38 g (14.99 mmol) was placed under an argon atmosphere.Cooled from -65 C to -70 C,While stirring, 17 mL (45 mmol) of BuLi solution was added dropwise.Stir for 1.5 hours from -65 C to -70 C.Then, Bu3SnCl14.0g (43mmol) was added dropwise.Stir for 1 hour, then remove the cooling bath.Stir in a while. Add ethyl acetate,After quenching, the reaction mixture was concentrated to give a crude material.The obtained crude product was purified by column chromatography using silica gel adjusted to be basic.The above compound (2-b) was obtained (yield: 8.85 g, yield: 62.5%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 1-[2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)ethyl]-3-[2-hydroxy-(2,4-dichlorophenyl)ethyl]imidazolium bromide; potassium tert-butylate; potassium carbonate; palladium dichloride; In tetrahydrofuran; water; at 60 - 90℃; for 0.5h;Inert atmosphere; | General procedure: The appropriate amounts of PdCl2, Glu-IMSs, and t-BuOK were added to THF under N2 atmosphere. The mixture was stirred at 60 oC for 10 min, remove the solvent, then aryl halide (1.0 mmol), aryl boronic acid (1.5 mmol), K2CO3 (2.0 mmol) and water (3.0 mL) were added. The mixture was heated to appropriate temperature under N2 atmosphere. The conversion and yield was monitored by GC-MS analysis |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With 1-[2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)ethyl]-3-[2-hydroxy-(2,4-dichlorophenyl)ethyl]imidazolium bromide; potassium tert-butylate; potassium carbonate; palladium dichloride; In tetrahydrofuran; water; at 60 - 90℃; for 0.5h;Inert atmosphere; | General procedure: The appropriate amounts of PdCl2, Glu-IMSs, and t-BuOK were added to THF under N2 atmosphere. The mixture was stirred at 60 oC for 10 min, remove the solvent, then aryl halide (1.0 mmol), aryl boronic acid (1.5 mmol), K2CO3 (2.0 mmol) and water (3.0 mL) were added. The mixture was heated to appropriate temperature under N2 atmosphere. The conversion and yield was monitored by GC-MS analysis |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With 1-[2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)ethyl]-3-[2-hydroxy-(2,4-dichlorophenyl)ethyl]imidazolium bromide; potassium tert-butylate; potassium carbonate; palladium dichloride; In tetrahydrofuran; water; at 60 - 90℃; for 0.5h;Inert atmosphere; | General procedure: The appropriate amounts of PdCl2, Glu-IMSs, and t-BuOK were added to THF under N2 atmosphere. The mixture was stirred at 60 oC for 10 min, remove the solvent, then aryl halide (1.0 mmol), aryl boronic acid (1.5 mmol), K2CO3 (2.0 mmol) and water (3.0 mL) were added. The mixture was heated to appropriate temperature under N2 atmosphere. The conversion and yield was monitored by GC-MS analysis |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21%; 19%; 20% | With tris-(dibenzylideneacetone)dipalladium(0); tris(o-methoxyphenyl)phosphine; caesium carbonate; Trimethylacetic acid; In toluene; at 100℃; for 24h;Inert atmosphere; Green chemistry; | In a 25 mL Schlenk tube, based on a 2:1 molar ratio,200 mg of 2,5-diisooctyl-3,6-bisthiophenepyrrole [3,4-c]-pyrrole-1,4-dione (monomer 1),31.5 mg of 2,7-dibromo-9,9-dihexyl-9H-indole (monomer 2),Add 250mg of cesium carbonate in turn,11.7 mg of pivalic acid,5.2 mg of Pd2(dba)3 catalyst,4.0 mg P(o-MeOPh)3 ligand. UrgeChemical agent Pd2 (dba) 3,Ligand P(o-MeOPh)3,The moles of the promoter pivalic acid PivOH and the base Cs2CO3 were 1.5%, 3%, 30%, and 200%, respectively, of the monomer 1.In 6 mL of anhydrous toluene,Stir under inert atmosphere and heat to 100 C,Reaction for 24h.The obtained crude product was separated by silica gel column chromatography.Collecting different conjugate length oligomers,Rotary evaporator decompression steaming,The resulting solid product was vacuum dried,Five kinds of DA-type conjugated oligomers DPP-Fl-DPP, DPP-(Fl-DPP)2, DPP-(Fl-DPP)3, DPP-(Fl-DPP)4 and DPP-( Fl-DPP) 5.The yields of DPP-Fl-DPP, DPP-(Fl-DPP)2, DPP-(Fl-DPP)3, DPP-(Fl-DPP)4 and DPP-(Fl-DPP)5 were 20%, 21 respectively. %, 19%, 20%, and 12%, 1H NMR and mass spectrum of the above five oligomers can be seen in Figures 1 - 10, respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | With tris-(dibenzylideneacetone)dipalladium(0); P(p-CH3OC6H4)3; caesium carbonate; Trimethylacetic acid; In toluene; at 100℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: DPP (150 mg, 0.286 mmol, 1 equal), DBFL (93.87 mg, 0.191 mmol,2/3 equiv), PivOH (8.75 mg, 0.086mol), anhydrous Cs2CO3(186.26 mg, 0.572 mmol), Pd2 (dba)3 (3.92 mg, 1.5mol%), and tris(omethoxyphenyl)phosphine (3.02 mg, 3 mol%) were added into aSchlenk tube. The mixture in the Schlenk tube was evacuated andargon-filled three times. Then 5 ml toluene was added into the tube viaa syringe and the air in the reaction solution was removed by freezevacuum-thaw cycles three times. Next, the argon-filled reaction tubewas placed in an oil pot at 100 C for 24 h. Removal of the toluene byrotary evaporator afforded the crude product, which was purified bycolumn chromatography on silica gel using a mixture of CH2Cl2 andhexane as an eluent (The volume ratio CH2Cl2/hexane gradually increasedfrom 0.8 to 2) and successively gave oligomers Os1∼5, O1(45 mg, yield 23%), O2 (41 mg, yield 21%), O3 (39 mg, yield 20%), O4(28 mg, yield 14%), O5 (21 mg, yield 11%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
8% | With tris-(dibenzylideneacetone)dipalladium(0); P(p-CH3OC6H4)3; caesium carbonate; Trimethylacetic acid; In toluene; at 100℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: DPP (150 mg, 0.286 mmol) and DBFL (211.10 mg, 0.429 mmol, 1.5equiv.) were used as two reactants. Other additives and post-treatmentof the reaction are the same as those of Os1∼5. The crude productpurified by CC on silica gel using a mixture of CH2Cl2 and hexane as aneluent (gradually increased the ratio of CH2Cl2 to hexane between0.8-1, v/v) and successively gave oligomers O′s1∼7, O′1 (23 mg, yield8%), O′2 (31 mg, yield 11%), O′3 (37 mg, yield 13%), O′4 (40 mg, yield14%), O′5 (40 mg, yield 14%), O′6 (46 mg, yield 16%) and O′7 (55 mg,yield 19%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
11% | With tris-(dibenzylideneacetone)dipalladium(0); P(p-CH3OC6H4)3; caesium carbonate; Trimethylacetic acid; In toluene; at 100℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: DPP (150 mg, 0.286 mmol) and DBFL (211.10 mg, 0.429 mmol, 1.5equiv.) were used as two reactants. Other additives and post-treatmentof the reaction are the same as those of Os1∼5. The crude productpurified by CC on silica gel using a mixture of CH2Cl2 and hexane as aneluent (gradually increased the ratio of CH2Cl2 to hexane between0.8-1, v/v) and successively gave oligomers O′s1∼7, O′1 (23 mg, yield8%), O′2 (31 mg, yield 11%), O′3 (37 mg, yield 13%), O′4 (40 mg, yield14%), O′5 (40 mg, yield 14%), O′6 (46 mg, yield 16%) and O′7 (55 mg,yield 19%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
13% | With tris-(dibenzylideneacetone)dipalladium(0); P(p-CH3OC6H4)3; caesium carbonate; Trimethylacetic acid; In toluene; at 100℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: DPP (150 mg, 0.286 mmol) and DBFL (211.10 mg, 0.429 mmol, 1.5equiv.) were used as two reactants. Other additives and post-treatmentof the reaction are the same as those of Os1∼5. The crude productpurified by CC on silica gel using a mixture of CH2Cl2 and hexane as aneluent (gradually increased the ratio of CH2Cl2 to hexane between0.8-1, v/v) and successively gave oligomers O′s1∼7, O′1 (23 mg, yield8%), O′2 (31 mg, yield 11%), O′3 (37 mg, yield 13%), O′4 (40 mg, yield14%), O′5 (40 mg, yield 14%), O′6 (46 mg, yield 16%) and O′7 (55 mg,yield 19%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | With tris-(dibenzylideneacetone)dipalladium(0); P(p-CH3OC6H4)3; caesium carbonate; Trimethylacetic acid; In toluene; at 100℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: DPP (150 mg, 0.286 mmol, 1 equal), DBFL (93.87 mg, 0.191 mmol,2/3 equiv), PivOH (8.75 mg, 0.086mol), anhydrous Cs2CO3(186.26 mg, 0.572 mmol), Pd2 (dba)3 (3.92 mg, 1.5mol%), and tris(omethoxyphenyl)phosphine (3.02 mg, 3 mol%) were added into aSchlenk tube. The mixture in the Schlenk tube was evacuated andargon-filled three times. Then 5 ml toluene was added into the tube viaa syringe and the air in the reaction solution was removed by freezevacuum-thaw cycles three times. Next, the argon-filled reaction tubewas placed in an oil pot at 100 C for 24 h. Removal of the toluene byrotary evaporator afforded the crude product, which was purified bycolumn chromatography on silica gel using a mixture of CH2Cl2 andhexane as an eluent (The volume ratio CH2Cl2/hexane gradually increasedfrom 0.8 to 2) and successively gave oligomers Os1∼5, O1(45 mg, yield 23%), O2 (41 mg, yield 21%), O3 (39 mg, yield 20%), O4(28 mg, yield 14%), O5 (21 mg, yield 11%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | With tris-(dibenzylideneacetone)dipalladium(0); P(p-CH3OC6H4)3; caesium carbonate; Trimethylacetic acid; In toluene; at 100℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: DPP (150 mg, 0.286 mmol, 1 equal), DBFL (93.87 mg, 0.191 mmol,2/3 equiv), PivOH (8.75 mg, 0.086mol), anhydrous Cs2CO3(186.26 mg, 0.572 mmol), Pd2 (dba)3 (3.92 mg, 1.5mol%), and tris(omethoxyphenyl)phosphine (3.02 mg, 3 mol%) were added into aSchlenk tube. The mixture in the Schlenk tube was evacuated andargon-filled three times. Then 5 ml toluene was added into the tube viaa syringe and the air in the reaction solution was removed by freezevacuum-thaw cycles three times. Next, the argon-filled reaction tubewas placed in an oil pot at 100 C for 24 h. Removal of the toluene byrotary evaporator afforded the crude product, which was purified bycolumn chromatography on silica gel using a mixture of CH2Cl2 andhexane as an eluent (The volume ratio CH2Cl2/hexane gradually increasedfrom 0.8 to 2) and successively gave oligomers Os1∼5, O1(45 mg, yield 23%), O2 (41 mg, yield 21%), O3 (39 mg, yield 20%), O4(28 mg, yield 14%), O5 (21 mg, yield 11%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.55% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water;Inert atmosphere; Reflux; | 9,9-Dihexyl-2,7-dibromofluorene(492.3 mg, 1 mmol), 3-pyridineboronic acid (368.8 mg,3 mmol) Pd(PPh3)4 (92 mg, 0.08 mmol), and K2CO3(690 mg, 5 mmol) were added into a flask under N2 atmosphere,and then 25 mL of degassed THF/H2O (2:1) wasinjected. The solution was heated to reflux for 48 h. Afterextraction with CH2Cl2 (20 mL×3), the organic layer waswashed with water and dried over anhydrous MgSO4. Afterfiltration, rotary evaporation, and purification by columnchromatography, the product was recrystallized in dichloromethane/methanol to give a white solid (403.10 mg,yield 82.55%). 1H NMR (400 MHz, chloroform-d, ppm) δ8.93 (s, 2H), 8.61 (d, J=4.8 Hz, 2H), 7.96 (d, J=7.9 Hz, 2H),7.83 (d, J=7.8 Hz, 2H), 7.63-7.54 (m, 4H), 7.44-7.36 (m,2H), 2.10-2.01 (m, 4H), 1.18-1.02 (m, 12H), 0.89 (s, 4H),0.73 (dt, J=14.8, 7.6 Hz, 6H). 13C NMR (101 MHz, chloroform-d, ppm) δ 152.10, 148.48, 148.40, 140.60, 137.10,137.00, 134.43, 126.25, 123.61, 121.59, 120.56, 77.13,76.81, 55.53, 40.40, 31.48, 29.68, 23.87, 22.58, 14.00; MSfor C35H40N2: m/z 488; Anal. Calcd. (488.32). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 80℃;Inert atmosphere; | (5) Add 0.37 g of the product obtained in step (4) to a 100 ml round bottom flask, 0.53 g of 2,7-dibromo-9,9-alkylphosphonium, 52 mg of tetratriphenylphosphine palladium, 0.37 g of potassium carbonate, 20 ml of 1,4-dioxane and 4 ml of water, reaction at 80C overnight under Ar protection. 4-(7-bromo-9,9-dihexylfluorene)-7-(4-((R)-sec-butoxy)phenyl)benzothiadiazole; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃;Inert atmosphere; | (6) Add 2.5 g of 2,7-dibromo-9,9-alkylphosphonium to a 100 ml round bottom flask, 6.4 g of pinacol diborate, 3.4 g of potassium acetate, 0.2 g of 1,1'-bis(diphenylphosphino)ferrocene palladium(II)dichloride, 30ml of 1,4-dioxane, 80C overnight reaction under Ar protection, obtained after column chromatography 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxolane)-9,9-dihexylfluorene; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 85℃; for 7h;Inert atmosphere; | (2) Taking 1.5 g of the product obtained in step (1), and adding thereto 4.3 g of 9,9-dihexyl-2,7-dibromofluorene, 0.4 g of tetratriphenylphosphine palladium, 2.83 g of potassium carbonate,Then add 30 ml of 1,4-dioxane and 6 ml of water, and pass in argon to remove oxygen for 10 minutes under stirring.The reaction was performed at 85 degrees Celsius for 7 hours, and the obtained product was obtained by column chromatography; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | A microwave reactor vessel was charged with compound 1 (0.200 g,0.406 mmol), <strong>[101-70-2]bis(4-methoxyphenyl)amine</strong> (0.204 g, 0.90 mmol), tert-BuONa (0.128 g, 1.33 mmol) and anhydrous toluene (4 mL). The reactionmixture was degassed with argon at room temperature for 15 min,then Pd(dba)2 (5 mol %, 0.012 g, 0.02 mmol) and P(t-Bu)3 (1 M intoluene, 0.040 mmol) were added and the reaction mixture reacted at110 C in a microwave reactor for 50 min. Upon cooling, the solvent wasremoved under a reduced pressure and the crude product was dissolvedin CH2Cl2 and washed with water. The organic layer was dried overanhydrous Na2SO4 and the solvent evaporated under a reduced pressure.The crude product was purified by column chromatography on silica gel(petroleum ether/CH2Cl2 7/3), to yield the desired compound I as a greysolid (90% yield). 1H NMR (400 MHz, Acetone-d6) 7.50 (d, J 8.2 Hz,2H), 7.02 (d, J 9.0 Hz, 8H), 7.00 (d, J 2.0 Hz, 2H), 6.87 (d, J 9.0Hz, 8H), 6.83 (dd, J1 8.2, J2 2.0 Hz, 2H), 3.78 (s, 12H), 1.79-1.75(m, 4H), 1.20-1.07 (m, 12H), 0.83 (t, J 7.1 Hz, 6H), 0.75-0.66 (m,4H). 13C NMR (100 MHz, Acetone-d6) 155.50, 151.28, 147.26, 141.30,134.65, 125.44, 120.59, 119.18, 116.37, 114.37, 54.61, 54.44, 39.77,31.19, 23.50, 22.11, 13.26. LCMS (APCI) calcd for C53H60N2O4 [M H] 789.4, found 789.8. Elemental analysis calcd for C53H60N2O4: C,80.67; H, 7.66; N, 3.55; O, 8.11. Found C, 80.88; H, 7.59; N, 3.47. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | A microwave vessel was charged with compound 1 (200 mg, 0.205mmol), CuI (1.54 mg, 0.008 mmol), compound 5 (162 mg, 0.492 mmol)and a mixture 1:5 of TEA/DMF (8 mL). The mixture was degassed underargon at room temperature for 10 min, then Pd(PPh3)2Cl2 (6 mg, 0.008mmol) and PPh3 (42 mg, 0.16 mmol) were added. The reaction mixturewas heated in the microwave reactor at 100 C for 50 min, then cooled tort, diluted with diethyl ether and washed with water. The organic layerwas collected and dried over anhydrous Na2SO4. Removal of the solventunder a reduced pressure resulted in a crude residue, which was purifiedby column chromatography on silica gel (petroleum ether/CH2Cl2 6/4),to yield the desired compound III as a yellow solid (75% yield). 1H NMR(400 MHz, Acetone-d6) 7.82 (d, J 7.9 Hz, 2H), 7.58 (s, 2H), 7.50 (dd,J 7.9, J 1.4 Hz, 2H), 7.36 (d, J 8.9 Hz, 4H), 7.13 (d, J 9.0 Hz,8H), 6.95 (d, J 9.0 Hz, 8H), 6.89 (d, J 8.9 Hz, 4H), 3.81 (s, 12H),2.14-2.10 (m, 4H), 1.14-1.02 (m, 4H), 0.75 (t, J 6.8 Hz, 6H),0.64-0.56 (m, 4H). 13C NMR (100 MHz, Acetone-d6) 156.75, 150.88,149.03, 14.20, 139.63, 132.08, 130.22, 127.32, 125.29, 122.49, 119.90,117.97, 114.89, 113.21, 90.23, 88.55, 54.99, 54.67, 39.75, 31.20,29.20, 23.51, 22.12, 13.12. LCMS (APCI) calcd for C69H68N2O4[M2H] 990.5, found 990.1. Elemental analysis calcd for C69H68N2O4:C, 83.77; H, 6.93; N, 2.83; O, 6.47. Found C, 83.89; H, 7.11; N, 2.98. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4.52 g | Intermediate R0 (6.43 g, 18.3 mmol) was placed in a 500 mL round bottom flask, intermediate R1 (8.19 g, 38.4 mmol), Pd2(dba)3 (Tris(dibenzylideneacetone)dipalladium(0)) (0.5 g, 0.6 mmol) , DPPF (1,1'-Ferrocenediyl-bis(diphenylphosphine) (0.6 g, 1.2 mmol), toluene 100 mL was added, followed by stirring for 10 minutes.Sodium tert-butoxide (4.4 g, 46 mmol) was added and heated to 100C.After the reaction was completed, extraction was performed using dichloromethane and water, followed by distillation under reduced pressure, and the resulting brown solid was separated and purified by column chromatography to obtain compound H01 (4.52 g).The HOMO energy level of the synthesized compound H01 was -5.89 eV. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3.14 g | Intermediate R0 (5.00 g, 9.83 mmol) was placed in a 500 mL round bottom flask, intermediate R2 (117 g, 38.4 mmol), Pd2(dba)3 (0.5 g, 0.6 mmol), DPPF (0.6 g, 1.2 mmol), After adding 100 mL of toluene, it was stirred for 10 minutes.Sodium tert-butoxide (4.4 g, 46 mmol) was added and heated to 100C.When the reaction was completed, extraction was performed using dichloromethane and water, followed by distillation under reduced pressure, and the resulting brown solid was separated and purified by column chromatography to obtain compound H02 (3.14 g). The HOMO energy level of the synthesized compound H02 was -5.70 eV. |
Tags: 189367-54-2 synthesis path| 189367-54-2 SDS| 189367-54-2 COA| 189367-54-2 purity| 189367-54-2 application| 189367-54-2 NMR| 189367-54-2 COA| 189367-54-2 structure
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