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CAS No. : | 90-90-4 | MDL No. : | MFCD00000103 |
Formula : | C13H9BrO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | KEOLYBMGRQYQTN-UHFFFAOYSA-N |
M.W : | 261.11 | Pubchem ID : | 7030 |
Synonyms : |
|
Num. heavy atoms : | 15 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 64.02 |
TPSA : | 17.07 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | Yes |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.97 cm/s |
Log Po/w (iLOGP) : | 2.52 |
Log Po/w (XLOGP3) : | 4.12 |
Log Po/w (WLOGP) : | 3.68 |
Log Po/w (MLOGP) : | 3.66 |
Log Po/w (SILICOS-IT) : | 4.08 |
Consensus Log Po/w : | 3.61 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -4.51 |
Solubility : | 0.00799 mg/ml ; 0.0000306 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -4.18 |
Solubility : | 0.0171 mg/ml ; 0.0000653 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -5.72 |
Solubility : | 0.0005 mg/ml ; 0.00000191 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.49 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | 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 |
---|---|---|
89% | Stage #1: With n-butyllithium In tetrahydrofuran for 1.33333 h; Inert atmosphere; Cooling with ice Stage #2: at 20℃; for 12 h; |
16.7 mL (0.1 mol) of diphenylmethane and 300 ml of tetrahydrofuran (THF) were added to a solution of500ml three-necked flask, magnetic stirring and argon, ice salt bath 40min, to the three bottles by adding 54.5mL (0.12mol) n-butyl lithium solution, continue ice salt bath 40min, add 13.0555g4-bromobenzophenone(Bis (4-bromophenyl) methanone, 0.05),After the reaction was carried out at room temperature for 12 h, 250 ml of saturated ammonium chloride (NH4Cl) solution was added to the three-necked flask. After stirring for 10 min, the reaction solution was poured into a separatory funnel, the supernatant was taken and the water in the solution was adsorbed with 300 g of anhydrous sodium sulfate. And then heated to 110 ° C. After adding 5 g of p-toluenesulfonic acid, the mixture was refluxed for 12 hours. After the reaction was stopped, the reaction solution was dried and dried. The reaction mixture was heated to 110 ° C, The product was spin dried to dry the powder and the powder was dried in vacuo at 60 ° C for 24 h to give the white intermediate Si-Br in 89percent yield. |
73.03% | Stage #1: With n-butyllithium In tetrahydrofuran at 0℃; for 1 h; Inert atmosphere Stage #2: at 20℃; for 6 h; Stage #3: With toluene-4-sulfonic acid In tolueneReflux |
1, under the conditions of a temperature of 0 ° C, the 100ml three-necked flask was evacuated and filled with N2 three times,12 mmol of diphenylmethane and 50 ml of dehydrated tetrahydrofuran were evacuated, and 10 mmol of n-butyllithium was gradually introduced into the flask. While maintaining the atmosphere of nitrogen at 0 ° C, n-butyllithium was subjected to dehydrogenation for 1 hour. To the solution was added 9.5 mmolBromobenzophenone, the reaction was allowed to return to room temperature and stirred for 6 hours. The reaction was quenched by the addition of saturated aqueous ammonium chloride. The organic phase was extracted with CH 2 Cl 2, washed three times with saturated brine and dried over anhydrous Na 2 SO 4. The organic solvent , The residue,Toluenesulfonic acid and 60 ml of toluene were added to a 100 ml two-necked flask, and the mixture was refluxed for 6-8 hours. The mixture was cooled to room temperature and the organic layer was washed with 10percent aqueous NaHCO 3 solution Three times, the combined organic phases were dried over anhydrous Na2SO4 and the solvent toluene was evaporated under reduced pressure. The residue was purified by column chromatography to give a white solid Product 1-1. Yield: 73.03percent. 1-1 |
66% | Stage #1: With n-butyllithium In tetrahydrofuran at 0℃; for 0.5 h; Stage #2: at 20℃; for 6 h; Stage #3: With toluene-4-sulfonic acid In toluene at 110℃; |
In a 250 mL three-necked flask,Diphenylmethane (10.0 g, 59.5 mmol) was dissolved in 150 mL of re-distilled tetrahydrofuran,At 0 slowly added dropwise n-BuLi (25mL, 2.5M),After reaction for 30 min, 4-bromobenzoylbenzene (5.2 g, 20.0 mmol) was slowly added dropwise.Then, the temperature was raised to room temperature for 6 h, quenched with ammonium chloride,The reaction was extracted with CH2Cl2 (3 x 20 mL) and the extract was washed with water (3 x 20 mL)Dried over anhydrous MgSO4 and the solvent was removed under reduced pressure to give an alcohol.The above alcohol solution was dissolved with toluene,P-toluenesulfonic acid (1.7 g, 0.01 mol) was added,The reaction was carried out at 110 ° C for 3-4 h with a water distilling apparatus.The reaction was extracted with sodium bicarbonate. The extract was washed with water (3 x 20 mL) and dried over anhydrous MgSO4. The solvent was removed under reduced pressure and the column was separated (PE) to give 5.3 g of product (yield: 66percent) as a white solid. |
64% | Stage #1: With n-butyllithium In tetrahydrofuran; cyclohexane at 0℃; for 0.5 h; Inert atmosphere Stage #2: at 20℃; for 10 h; Stage #3: With toluene-4-sulfonic acid In toluene for 5 h; Reflux |
1. Add 10.09 g (0.06 mol) of diphenylmethane to a 500 mL three-necked flask.And 250 mL of dry tetrahydrofuran, vacuum replacement, cooling to 0 ° C,Maintain mixing,Slowly add to the mixture with a syringe under nitrogen protection24.0 mL of 2.5 mol/L (0.06 mol) n-butyllithium in cyclohexane solution,Stirring was continued for 30 min after the addition, and then 40 mL of a dry tetrahydrofuran solution containing 15.14 g (0.058 mol) of 4-bromobenzophenone was added dropwise.After stirring at room temperature for 10 h, the reaction mixture was quenched with aqueous ammonium chloride, and extracted with dichloromethane (300 mL×3×),Rinse alternately with saturated aqueous sodium chloride solution and deionized water (300 mL × 3 times).Dry with anhydrous magnesium sulfate, filter, and distill off the solvent.The intermediate 2-(4-bromophenyl)-1,1,2-triphenylethanol was obtained.The obtained intermediate was dissolved in 300 mL of toluene with 1.0 g of anhydrous p-toluenesulfonic acid.After refluxing for 5 h, toluene was distilled off, and the obtained solid was dissolved in 300 mL of dichloromethane.Then alternately wash with saturated aqueous sodium chloride solution and deionized water (300mL×3 times).Drying anhydrous magnesium sulfate, filtering, and distilling off the solvent to obtain a crude product;Taking cyclohexane/dichloromethane (v/v=5:1) as the eluent,The crude product was separated by silica gel column chromatography.15.27g of white solid 1-(4-bromophenyl)-1,2,2-triphenylethylene,The yield was 64percent. |
37% | Stage #1: With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 0.5 h; Inert atmosphere Stage #2: at 0 - 20℃; for 6 h; Stage #3: With toluene-4-sulfonic acid In toluene for 16 h; Reflux |
Step 1, synthesis of bromotetraphenylethene (TPE-Br) The benzylbenzene (2.0g, 11.9mmol) was dissolved in 20mL of anhydrous tetrahydrofuran, was stirred at 0°C under nitrogen atmosphere, 1.6M n-hexane solution of n-butyllithium (7.4mL, 11.9mmol) was slowly added, reacted for 30 minutes; and then 4-bromo-benzophenone (3.1g, 11.9mmol) was added, slowly warmed to room temperature and the reaction mixture was stirred for 6 hours, followed by addition of a small amount of water to the reaction solution for the reaction to stop, the reaction solution was extracted twice with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate and was filtered. The solvent was distilled off under reduced pressure. The resulting solid was dissolved in 80mL of toluene, p-toluenesulfonic acid monohydrate (500mg, 2.6mmol, catalyst) was added, and refluxed for 16 hours, the reaction was cooled to room temperature and extracted twice with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate and was filtered. The solvent was distilled off under reduced pressure. The crude product with hexane as a mobile phase and the silica gel as the stationary phase was pass through column chromatography, obtaining a white solid 1.8g, 37percent yield; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sodium isopropylate; acetonitrile; In isopropyl alcohol; at 80℃; for 2h;Catalytic behavior; | General procedure: The hydrogenation of ketones was carried out by taking15mg of Feimine-mont-K10 catalyst (19.9mol%),1mmol of ketone, 5mL sodium iso-propoxide (Na-i-OPr),5mL acetonitrile and i-PrOH (5mL) in a round bottomedflask and stirring at 80C for required time (Table5). Theprogress of the reaction was monitored from time to timeby thin layer chromatography (TLC) using 5% ethylacetate-hexane as the eluent. After completion of the reaction(monitored by GC-MS), the catalyst was separatedby filtration. The filtrate was diluted with water (10mL)and then extracted with ethyl acetate (10mL) followedby washing with brine and dehydrated using anhydrousNa2SO4.The resulting residue was purified by silica gelcolumn chromatography using ethylacetate-hexane (5:95)as the eluent to get the pure products. In order to recyclethe catalyst, it was separated from the reaction mixture bycentrifugation and then washed several times with waterand ethyl acetate after each cycle. After drying at 110Cin an oven for overnight, the recovered catalyst was subjectedto subsequent runs under same reaction conditions. |
55%Spectr. | With C22H25Cl2N3ORuS2; potassium hydroxide; In isopropyl alcohol; at 82℃; for 14h;Catalytic behavior; | General procedure: Catalyst (0.1mol %) and KOH (1mmol) were dissolved in 2-propanol (4mL). To this solution, substrate (1mmol) was added and the mixture was refluxed (82C). The progress of the reaction was monitored by GC at regular intervals. After the completion of the reaction, the reaction mixture was cooled to room temperature and filtered through silica gel or alumina bed, and eluted using 50% ethyl acetate-hexane mixture. The eluted solution was reduced and analyzed by GC and/or GCMS. |
Step 2; (4-bromophenyl )(phenyl)methanol;To a solution of (4-bromophenyl)(phenyl)methanone (200 g, 0.766 mole) in THF 30 (600 mL) and methanol (400 mL) was added in portions pulverized sodium borohydride (29 g, 0.766 mole) while maintaining the internal temperature between 3C and 10C. After stirring for an additional 15 minutes, acetone (125 mL) was added and the mixture stirred for a subsequent 10 minutes. The solution was concentrated and the residue partitioned between water (250 mL) and ethyl acetate (1.0 L). The organic layer was separated, dried (Na2SO4), filtered and concentrated. The residue was pumped on by high vacuum for 18 hours to give the title compound as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With magnesium sulphate; vanadyl(IV) sulphate pentahydrate; oxygen; 4,4'-di-tert-butyl-2,2'-bipyridine; In water; at 90℃; under 750.075 Torr; for 96h; | General procedure: VOSO4·5H2O (126.5 mg, 0.5 mmol), 4,4?-di-tert-butyl-2,2?-bipyridyl (268.4 mg, 1 mmol), and p-nitrobenzhydrol (229.3 mg, 0.05 mmol) were placed in a 100 mL round-bottomed flask, and then water (50 mL) was added. Next, the mixture was stirred, and then anhydrous MgSO4 (18.06 g, 150 mmol) was slowly added into the mixture (cooling by ice water). After that, substrate (10 mmol) was added into the mixture at room temperature, and the mixture was stirred at 90 C for the appropriate time under open-air atmosphere. After the reaction, the mixture was extracted with ethyl acetate and dried over anhydrous MgSO4. The extracts were concentrated in vacuo. Purification of the products was carried out by silica gel column chromatography using hexane and diethyl ether as eluent to afford the analytically pure ketones. In Table 7 (entries 3, 7, and 8), crude products were purified by recrystallization with ethyl acetate in refrigerator, afforded analytically pure ketones. The product was identified by comparison with the commercially available sample using 1H NMR spectroscopy. |
87% | With tert.-butylhydroperoxide; In water; at 100℃; for 2.5h; | General procedure: Hydrocarbon or secondary alcohol (1 mmol), CoGO/Fe3O4/Ldopa(0.05 g, 1.84 mol% Co) and 70% t-BuOOH (0.25 mL, 1.5 mmol)were dispersed in deionized water (5 mL) and stirred at 100 C till thecompletion of reaction (Table 5). Afterwards, catalyst was removedfrom the reaction mixture via external magnet and the reaction mixturewas diluted with EtOAc (3×5 mL) and filtered. The organic fractionwas washed with brine solution (3×25 mL) and dried using anhydrousNa2SO4. Finally, the product was obtained either by the removal of thesolvent under reduced pressure or by passing through column of silicagel. The removed catalyst was washed with EtOH (3×5 mL), deionizedwater (3×10 mL) and dried under vacuum. |
84% | With 1-butyl-3-methylimidazolium hydrogen sulfate; sodium bromate; In water; at 60℃; for 1h;Green chemistry; | General procedure: In a typical experiment, a mixture of 1,2-diols/a-hydroxyketones/alcohols (1 mmol), sodium bromate (3 mmol),and bmim[HSO4]:H2O 3:1 (v/v) along with a stir bar was placed in a RB flask fitted with a condenser. The reaction mixture was stirred magnetically in an oil-bath maintained at 60 C for an appropriate time as mentioned in Tables 3,4, and 5, respectively. After completion of the reaction, as monitored by TLC using petroleum ether:ethyl acetate(80:20, v/v) as eluent, the reaction mixture was cooled to room temperature and worked up as mentioned above. The product obtained was identified by m.p (wherever applicable), IR and NMR spectra. |
84% | With indium(III) triflate; chloroamine-T; In acetonitrile; for 4h;Reflux; Inert atmosphere; | General procedure: The starting 1-(paratolyl)ethanol (1 mmol), chloramine-T (1 mmol), and In(OTf)3(0.3 mmol) were dissolved in CH3CN (10 mL) in a 100 mLflask equipped with a magnetic stirrer and a reflux condenser.The reaction mixture was heated at reflux for 3 h under anArgon atmosphere and was monitored for completion by TLC.After the reaction mixture was cooled to room temperature,the solvent was removed via rotary evaporation. The residueof the reaction mixture was separated through flash columnchromatography on silica gel. The obtained product was confirmed by spectroscopy. |
80% | With urea hydrogen peroxide adduct; lanthanum(lll) triflate; at 70℃; for 0.666667h;Ionic liquid; Green chemistry; | General procedure: A mixture of secondary alcohol (4) (1.0 mmol), UHP (2.0-3.0 mmol), 10 mol% (CF3SO3)3La and[bmim]BF4 (5 mmol) was placed in a 50 mL RB flask fitted with a calcium chloride guard tube.The reaction mixture was stirred magnetically in an oil-bath maintained at 70C for anappropriate time as mentioned in Table 2. The progress of the reaction was monitored by TLCusing petroleum ether:ethyl acetate (70:30). After completion of the reaction, the reactionmixture was cooled to room temperature and washed with diethyl ether (3×10 mL). Thecombined ethereal layer was washed with water (2×10 mL) and dried over anhyd. Na2SO4. Theethereal extract was concentrated on a rotary evaporator to give corresponding ketone. |
With tert.-butylhydroperoxide; cerium chromite; In dimethyl sulfoxide; at 90℃; for 5h;Sonication; | To a clean dry 10 mL round-bottomed flask containing 1 mmol of alcohol, 70% TBHP (3 mmol) was added. This was followed by the addition of 10 mol% of CeCrO3 catalyst. The mixture was sonicated for 5 min and then stirred at 90 C. The progress of the reaction was monitored by gas chromatograph. After an appropriate time, the reaction mass was cooled and the catalyst was separated by filtration. The yields of the products were based on GC analysis. The products were identified by GC-MS analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With trans-chloro(1-naphthyl)bis-(triphenylphosphine)nickel(II); tricyclohexylphosphine tetrafluoroborate; potassium carbonate In water monomer; toluene at 20℃; for 24h; Inert atmosphere; | |
99% | With potassium carbonate In water monomer; N,N-dimethyl-formamide at 100℃; for 6h; | |
98% | With potassium carbonate In xylene at 130℃; for 72h; |
98% | With potassium carbonate; cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane In xylene at 130℃; for 72h; | |
98% | With sodium hydroxide In water monomer at 80℃; for 0.333333h; Inert atmosphere; Green chemistry; | 6. General procedure for Suzuki-Miyaura reaction General procedure: 5 mL distilled water was taken in a 25 mL round bottom flask, equipped with a magnetic bar and a water condenser, and deoxygenated with nitrogen gas for 5 min. Aryl halide (1 mmol), arylboronic acid (1.2 mmol), NaOH (1.2 mmol) and Pd-γ-Fe2O3 (20 mg) were added to it and allowed to stir at 80 °C under nitrogen atmosphere. The progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was recovered using an external magnet. The reaction mixture was extracted with EtOAc (3 x 10 mL) and the combined organic layer was washed with water, brine solution and dried over anhydrous Na2SO4. The crude product was concentrated in a rotary evaporator and purified by column chromatography. The purified compounds were characterized by 1H and 13C NMR. |
98% | With palladium nanoparticles-supported custard apple peels-ash catalyst In ethanol; water monomer at 20℃; for 0.166667h; Green chemistry; | 2.4 General Experimental Procedure forSuzuki-Miyaura Coupling Reaction General procedure: All the Suzuki-Miyaura coupling reactions were carriedout under air atmosphere in dried glassware. In a 25 mLround bottom flask equipped with a magnetic stirrer, arylbromides (1.0 mmol), arylboronic acids (1.2 mmol), Pd/CAP-ash (5 wt%) and water:ethanol (3 mL) were placed.The resulting reaction mixtures were stirred at room temperaturefor appropriate time. The progress of reactionswas monitored by TLC. After completion of reactions,the reaction mixtures were extracted with ethyl acetate(2 × 10 mL). The organic layers were washed with brine(2 × 10 mL). The combined organic layer was collected,dried over Na2SO4and concentrated in vacuo. The residuewas purified by silica gel column chromatography usingn-hexane:EtOAc (9:1 v/v) to give the corresponding biarylcompound. The desired products were characterized bycomparing 1H, 13C NMR spectral data with authenticsamples. |
98% | With palladium diacetate; potassium carbonate; dicyclohexyl(2’,4’,6’-triisopropyl-[ 1,1’-bi-phenyl]-2-yl)phosphane In ethanol at 60℃; for 5h; Inert atmosphere; Green chemistry; | Suzuki coupling Under an argon atmosphere, two parallel oven-dried Schlenk tubes were each charged with 4-bromobenzophenone (0.5 mmol), phenylboronic acid (0.55 mmol), Pd(OAc)2 (0.005 mmol), XPhos (0.01 mmol), K2CO3 (1 mmol), EtOH/H2O (3.6 mL/0.4 mL) was added by syringe. The reaction was stirred at 60 C for 5 h and monitored by TLC. After the reaction was completed, the reaction was worked-up using the following methods: LLE-based workup: The reaction mixture was quenched with water (15 mL) and extracted with EtOAc (3 x 20 mL); the combined organic layers were dried over Na2SO4 and filtered, the excess solvent in the filtrate was removed under reduced pressure. The residue was subjected to silica gel chromatography to afford the desired product 122.9 mg (95%). Fast2Flash-based workup: The reaction mixture was worked-up and purified according to the direct method to afford the desired product 126.3 mg (98%). Eluent: PE/EA=20/1 1H NMR (600 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 2H), 7.84 (d, J = 7.7 Hz, 2H), 7.71 (d, J = 8.2 Hz, 2H), 7.65 (d, J = 7.3 Hz, 2H), 7.60 (t, J = 7.4 Hz, 1H), 7.50 (dt, J = 12.5, 7.7 Hz, 4H), 7.41 (t, J = 7.4 Hz, 1H). Its spectroscopic data is consistent with the literature report. |
97% | With potassium carbonate In water monomer; N,N-dimethyl-formamide at 80℃; for 0.333333h; Schlenk technique; | 19. General procedure for the Suzuki-Miyaura reaction: General procedure: An oven-dried Schlenk flask, equipped with a magnetic stir bar, septum, and a condenser was charged with aryl halide (1.0 mmol), arylboronic acid (1.2 mmol), K2CO3 (2 mmol), 4 (0.143 g, 1 mol %), and 5 mL of solvent. The flask was immersed in an oil bath and stirred at 80 °C. Upon complete consumption of starting materials as determined by TLC analysis, the reaction mass was filtered and the solid washed with water (2Χ5 mL), and extracted with diethyl ether (3Χ5 mL). The combined organic layers were collected, dried over anhydrous Na2SO4, and concentrated in vacuum to afford product which was purified by silica gel column chromatography (n-hexane/EtOAc = 9:1) |
97% | With Cs2CO3 In water monomer; N,N-dimethyl-formamide at 80℃; for 2h; | Suzuki-Miyaura Reaction; General Procedure: General procedure: Arylhalide 19 or 22 (1.0 mmol), phenylboronic acid (20; 1.2mmol, 0.146 g), 18 (0.015 mmol, 0.002 g), Cs2CO3 (1.5mmol, 0.489 g), DMF (2.5 mL), and H2O (2.5 mL) wereplaced in a 25 mL round-bottomed flask equipped with amagnetic stirrer. The flask was immersed in an oil bathregulated at 80 or 100 °C for the reaction time indicated inTable 1 or Table 2. After the reaction mixture was cooled tor.t., Et2O (8 mL) and H2O (8 mL) were added to the flask.The resulting mixture was vigorously stirred for 5 min, andthen filtered. The solid 18 collected on the filter was washedwith H2O (10 mL) and Et2O (10 mL) and then dried. Thefiltrate was transferred to a separation funnel and the organicphase was separated and washed with H2O (5 × 25 mL) andbrine (10 mL), and then dried over MgSO4. The solvent wasremoved under reduced pressure and the resulting residuewas analyzed by 1H and 13C NMR spectroscopy. When arylchlorides were used as substrates, the crude products werepurified by silica gel column chromatography. |
97% | With C56H52N12O12Pd4S4; potassium carbonate In ethanol; water monomer at 62℃; for 2h; | |
96% | With Pd/SiO2; potassium hydroxide In water monomer for 0.116667h; Microwave irradiation; Green chemistry; | |
95% | With potassium fluoride; [(ferrocenyl)(phenyl)methyl]diphenylphosphane; palladium diacetate In tetrahydrofuran at 20℃; for 48h; | |
95% | With C34H32Cl2FeP2Pd In ethanol at 80℃; for 2h; Schlenk technique; | General procedure for the Suzuki-Miyaura reaction General procedure: An oven-dried Schlenk flask, equipped with a magneticstir bar, a septum and a condenser was charged with arylhalide (1.0 mmol), arylboronic acid (1.2 mmol), the gelentrappedbase (1 g, 2 mmol), Pd(dppf)Cl2 (0.0085 g,1 mol%) and 5 mL of 95% ethanol. The flask was immersedand stirred in an oil bath at 80 8C. Upon completeconsumption of starting materials as determined by TLCanalysis, the gel was separated by filtration and water(10 mL) was added. The filtrate was extracted with diethylether (3 5 mL). The combined organic layer was collected,dried over anhydrous Na2SO4 and concentratedunder vacuum to afford the product, which was purified bysilica gel column chromatography (n-hexane:ethyl acetate9:1) |
95% | With potassium carbonate In ethanol at 80℃; for 2.5h; Schlenk technique; | |
95% | With potassium carbonate In water monomer at 60℃; for 0.583333h; Schlenk technique; Green chemistry; | |
94% | With tripotassium phosphate tribasic; 1,2,3,4,5-pentaphenyl-1′-(di-tert-butylphosphino)ferrocene; Palladium(0) bis(dibenzylideneacetone) In toluene at 100℃; for 1h; | |
94% | With {2-[1-(benzyloxyimino)ethyl]benzothiazole-k2N,N'}dichloropalladium(II); tetrabutylammonium bromide; potassium hydroxide In water monomer at 160℃; for 0.1h; Microwave irradiation; | |
94% | With potassium carbonate In ethanol at 80℃; for 2h; Schlenk technique; | |
94% | With potassium carbonate In ethanol at 80℃; for 2h; Schlenk technique; | 4.4 Typical experimental procedure for the Suzuki-Miyaura reaction General procedure: In a typical procedure 50mL Schlenk tube containing magnetic stirring bar and equipped with reflux condenser was charged aryl bromide (1.0mmol), arylboronic acid (1.2mmol), K2CO3 (2.0mmol), and 0.009g catalyst (0.02mol%) in ethanol (5mL). The reaction mixture was vigorously stirred at 80°C. After completion of the reaction as monitored by TLC, the catalyst was separated out by filtration, followed by washing with water and diethyl ether. The filtrate was extracted with diethyl ether (3×10mL). The combined organic layers were collected, dried over anhydrous Na2SO4 and concentrated in vacuum to afford crude product, which was purified by silica gel column chromatography (n-hexane:EtOAc=9:1). |
93% | With C56H44N2OP2Pd(2+)*2ClO4(1-); potassium carbonate In water monomer at 20℃; for 20h; | |
93% | Stage #1: (4-bromophenyl)(phenyl)methanone; phenylboronic acid With sodium 2,5-dimethylbenzene sulfonate In water monomer at 28℃; for 0.0833333h; Stage #2: With palladium 10% on activated carbon; potassium carbonate In water monomer at 28℃; for 2h; | |
93% | With 2Na(1+)*C26H18N2O8PdS2(2-); potassium carbonate In water monomer at 20℃; for 10h; | General procedure: The Suzuki reaction was performed in a 50 mL round-bottomed flask, aryl halide (0.5 mmol), arylboronic acid (0.65 mmol), K2CO3 (1 mmol), Complex 1 (0.2-1 mol%) and water (4 mL) were charged and stirred for the required time at room temperature for aryl bromides or at 100 °C for aryl chlorides. After completion, the mixture was cooled down to room temperature, diluted with water (10 mL) and extracted with diethyl ether (3 × 15 mL). The organic layer was washed with brine (3 × 15 mL), dried over anhydrous Na2SO4. The crude products were chromatographed on silica gel (ethyl acetate/hexane). |
92% | With dichloro[N-hydroxy-1-(1-methyl-1H-benzimidazol-2-yl-κN3)ethanamine-κN]palladium; tetrabutylammonium bromide; potassium hydroxide In water monomer at 160℃; for 0.0666667h; Microwave irradiation; | |
92% | With potassium carbonate In ethanol at 20℃; for 3h; Schlenk technique; | General procedure for the Suzuki coupling reaction General procedure: Aryl halide (1.0 mmol), arylboronic acid (1.2 mmol), K2CO3 (2.0 mmol), Pd(at)Al2O3-agarose (100 mg) and EtOH (5 mL) were added to a Schlenk flask. The mixture was stirred at room temperature under air. Upon complete consumption of starting materials as determined by TLC analysis, the solid was filtered and washed with acetone (3 × 5 mL). The combined organic solvents were concentrated in vacuum to afford product which was purified by silica gel column chromatography (petroleum ether/EtOAc = 10:1). |
92% | With tetrabutylammonium bromide; potassium carbonate In water monomer at 100℃; for 0.666667h; Green chemistry; | 2.6. General procedure for the Pd(0)-EDA/SC-2 catalyzed Suzukireaction General procedure: To a mixture of aryl halide (1 mmol), aryl/heteroaryl boronicacid (1.2 mmol), TBAB (0.25 mmol), K2CO3(0.25 mmol) and Pd(0)-EDA/SC-2 (0.2 g, 2.5 mol% Pd), double distilled water (5 mL) wasadded and the reaction mixture was stirred in a microwave syn-thesizer at 100C for an appropriate time (monitored by TLC)(Scheme 2). After completion, the reaction mixture was cooledto room temperature and filtered. The catalyst was washed withEtOAc (3 × 5 mL) followed by double distilled water (3 × 10 mL). Itwas dried at 100C for 1 h and could be used in subsequent reac-tions. The organic layer was washed with water and dried overanhydrous Na2SO4. Finally, the product was obtained after removalof the solvent under reduced pressure followed by crystallizationfrom a suitable solvent or passing through column of silica gel(EtOAc-pet. ether). |
92% | With [PdCl2(2-(pyridine-2-ylmethyl)sulfanylbenzoic acid)]; tetrabutylammonium bromide; potassium carbonate In water monomer at 110℃; for 8h; | |
91% | With potassium carbonate In water monomer; isopropanol at 60℃; for 4h; | |
91% | Stage #1: (4-bromophenyl)(phenyl)methanone With N2,N6-dibenzylpyridine-2,6-dicarboxamidopalladium(II)triphenylphosphine; potassium carbonate In ethanol; water monomer for 0.0833333h; Stage #2: phenylboronic acid In ethanol; water monomer at 82℃; for 16h; | 2.3 Suzuki-Miyaura cross-coupling reaction General procedure: A mixture of aryl halide (1mmol), catalyst (0.005mmol) and K2CO3 (2mmol) was stirred in EtOH-H2O (4:1) (5mL) for 5min. Phenylboronic acid (1.5mmol) was added to the above mixture and stirring was continued for required time at 82°C. Then, reaction mixture was diluted with ethyl acetate and water, and the catalyst was separated by centrifugation. The centrifugate was dried over anhydrous sodium sulphate, filtered and evaporated. Then the product was analyzed by GC/GCMS. |
90% | With potassium carbonate In ethanol at 80℃; for 1h; Green chemistry; | |
89% | With chloro[4-tert-butyl-benzaldehyde 4-(β-d-glucopyranosyl)thiosemicarbazone]palladium(II) dimer; potassium carbonate In N,N-dimethyl-formamide at 100℃; for 24h; | 2.4. General experimental procedure for the Suzuki-Miyaura coupling General procedure: Aryl bromide (1.0 mmol), phenylboronic acid (183 mg,1.5 mmol), K2CO3 (276 mg, 2.0 mmol), complex 2 in DMF(0.25 mM, 2 mL, 0.5 lmol) and dodecane (70 lL, 0.3 mmol) asinternal standard were stirred at 100 C in air for 24 h, and thenallowed to cool to room temperature. After addition of water(5 mL) and extraction with dichloromethane (2 10 mL), theorganic phase was washed with brine (10 mL), dried overNa2SO4, filtered, passed through Celite and analyzed by GC andGC-MS. After evaporation of the volatiles, isolation of the purebiaryl was achieved by column chromatography on silica gel usinghexane/AcOEt as eluent. All biaryls are known compounds andwere characterized by 1H NMR spectra. |
89% | With dicyclohexyl({2’,6’-dimethoxy-[1,1‘-biphenyl]-2-yl})phosphane; palladium diacetate; potassium carbonate In 1,4-dioxane; water monomer at 100℃; Schlenk technique; | |
88% | With (1-(2,6-diisopropylphenyl)-2,3-dihydro-1H-imidazol-2-yl)(methyl(λ1-oxidaneyl)diphenyl-λ5-phosphaneyl)palladium(II) chloride; Cs2CO3 In methanol; dichloromethane; toluene at 100℃; Glovebox; | |
87% | With C40H56Cl2FeN2O4P2; anhydrous sodium carbonate In water monomer; propan-2-one at 20℃; for 4h; | |
87% | With PdCl(2-HO-C6H4-CH(Ph)-NH-(CH2)3-SeC6H5); potassium carbonate In water monomer; N,N-dimethyl-formamide for 5h; Heating; Aerobic conditions; | |
87% | With palladium diacetate; potassium carbonate | |
85% | With potassium carbonate In ethanol; water monomer at 20℃; for 2h; | |
85% | With palladium; potassium carbonate In ethanol; water monomer at 50℃; for 1h; | |
83% | With potassium carbonate In water monomer at 20℃; for 6h; | Suzuki-Miyaura cross-coupling reaction General procedure: For Suzuki-Miyaura reaction, appropriate amount of the catalyst, PdNP-NMe2SiO2, was added to a mixture of aryl halide (0.5 mmol), arylboronic acid (0.65 mmol), K2CO3 (1.5 mmol) in 6 mL solvent. The reaction was then stirred under desired temperature for the required time. The initial progress of the reaction was monitored by TLC using aluminum coated TLC plates (Merck) under UV light and the product formation was determined using GC-MS. After completion, the catalyst was collected by filtration and washed with isopropanol-water. The filtrate was diluted with water and extracted with ether and then dried over Na2SO4. After evaporation of the solvent under reduced pressure, the residue was chromatographed (silica gel, ethyl acetate-hexane, 1:9) to obtain the desired product. |
81% | With sodium phosphate tribasic dodecahydrate In ethanol; water monomer at 20℃; for 22.5h; Green chemistry; | |
80% | With palladium diacetate; triphenylphosphine-3,3',3''-trisulfonic acid trisodium salt; isopropylamine In water monomer; acetonitrile at 80℃; for 1h; | |
78% | With tripotassium phosphate tribasic; C35H43ClN7Ni(1+)*BF4(1-) In acetonitrile at 80℃; for 8h; | |
75% | With potassium carbonate In ethanol; water monomer at 20℃; for 8h; Green chemistry; | 2.8 General Procedure for Suzuki-Miyaura Cross-Coupling Reaction General procedure: A mixture of aryl halide (0.27 mmol), phenylboronicacid (1 mmol), NHC-PdGO heterogeneous catalyst(0.01g) and potassium carbonate (1.1mmol) was stirred inEtOH:H2O (1:1) solvent system at room temperature for designated hours. The progress of the reaction was monitoredby TLC. After reaction completion, the mixture was cooledto room temperature and NHC-PdGO heterogeneous catalystwas separated through centrifugation. To the filtrate,dichloromethane and water were added. Dichloromethanelayer was separated from the water layer using a separatoryfunnel and dried with magnesium sulphate. The drieddichloromethane was concentrated in vacuum and obtainedcrude product was purified from column chromatographyover silica gel using hexane and ethyl acetate as eluting solventto get the corresponding products in good to excellentyields. All the coupled products were known molecules andwere confirmed by comparing the 1H NMR spectral datawith those of authentic samples. |
74% | With potassium carbonate In water monomer at 100℃; for 4.25h; | 2.3. General procedure for the CoGO/Fe3O4/L-dopa catalyzed Suzukicross-coupling General procedure: A mixture of aryl halide (1 mmol), phenyl boronic acid (1.2 mmol),K2CO3 (1.2 eq.) and CoGO/Fe3O4/L-dopa (0.05 g, 1.84 mol% Co) in double distilled water (5 mL) was stirred in a round bottom flask (50 mL) at 100 °C till the completion of reaction (monitored by TLC) (Table 3). After that, the reaction mixture was cooled to room temperature.The catalyst was removed via external magnet and washed with EtOAc (3×5 mL) followed by deionized water (3×10 mL). It was dried under vacuum for 2 h. The organic fraction was washed with brine solution and dried over anhydrous Na2SO4. Finally, the product was obtained either by the exclusion of the solvent under reduced pressure or by passing through column of silica gel using EtOAc-pet.ether as eluting solvent. |
72% | With potassium carbonate In ethanol; water monomer at 20℃; for 2h; Green chemistry; | 2.4 General procedure for Suzuki-Miyaura cross-coupling reaction General procedure: In a 10 mL glass vial equipped with a cap containing 5 mL of ethanol:water (1:1) mixture, aryl halide (1 equiv), phenylboronic acid (1.1 equiv), K2CO3 (2.5 equiv) were added followed by dipping of the dip catalyst into the reaction mixture which was then stirred magnetically at room temperature for required time. The progress of the reaction was monitored by thin layer chromatography (TLC). After reaction completion, the dip catalyst was simply removed from the reaction mass and washed with ethanol (1 x 5 mL) and water (1 x 5 mL) and was reused without purifying further. The product was extracted using dichloromethane (2 x 10 mL) and the combined organic layer was subjected to water wash (2 x 10 mL) followed by drying of the organic layer over Na2SO4. The dried organic layer was concentrated in vacuo, and the product was purified by column chromatography using n-hexane and ethyl acetate as eluents to afford the corresponding products in good to excellent yields. All the coupled products were known molecules and were confirmed by comparing with our previous standards (Kandathil et al., 2017; Vishal et al., 2017). |
70% | With Ni0.90Pd0.10; potassium carbonate In ethanol; water monomer at 50℃; for 24h; | |
67% | With potassium carbonate In ethanol; water monomer at 100℃; for 15h; Green chemistry; | |
61% | With potassium carbonate In ethanol; water monomer at 20℃; for 12h; Green chemistry; | 2.3.5. General procedure for Suzuki-Miyaura cross-coupling reactionscatalyzed by MNPs(at)SB-Pd nanomagnetic catalyst General procedure: An oven-dried flask was charged with aryl halide (0.27 mmol),phenylboronic acid (0.036 g, 0.30 mmol), MNPsSB-Pd nanomagneticcatalyst (0.05 mol% Pd) and K2CO3 (0.082 g, 0.60 mmol).EtOH:H2O (1:1, 10 mL) was added and the reaction mixture wasstirred at room temperature for designated time. The progress ofthe reaction was monitored using TLC. Then the reaction mixturewas allowed to cool to room temperature and quenched by addingdichloromethane (20 mL) and the MNPsSB-Pd nanomagnetic catalystwas separated using a permanent magnet. Dichloromethanelayer was separated from water layer through separatory funneland dried with anhydrous MgSO4. The dried dichloromethane layerwas concentrated in vacuum and purified through column chromatographyusing hexane and ethyl acetate as eluting solvent toget the corresponding products in excellent yields. |
With potassium carbonate In toluene at 110℃; for 15h; Yield given; | ||
99 % Chromat. | With potassium fluoride; [(μ-PPh2CH2PPh2)Co2((CO)4][μ,η-PhCCP(cy)2] In toluene at 40℃; for 16h; | |
With Merrifield resin-supported salen-type palladium(II); N-ethyl-N,N-diisopropylamine In water monomer; N,N-dimethyl-formamide at 100℃; | ||
With potassium carbonate In methanol; toluene for 16h; Reflux; | ||
95.6 %Chromat. | With potassium carbonate In water monomer; N,N-dimethyl-formamide at 50℃; for 3h; | |
With potassium carbonate In ethanol; water monomer at 70℃; for 1h; Green chemistry; | The general procedure for the PdIRA-900 catalyzed Suzuki coupling reaction was as follows. A 25 mL three necked flask was charged with PdIRA-900 (50 mg). The solvent (5 mL) and phenylboronic acid (1.1 mmol) were added followed by bromobenzene (1.0 mmol) and K2CO3 (2.2 mmol). The flask was stirred and maintained at 70 °C in a water bath for an appropriate time. The reaction products were analyzed by GC-MS. | |
With C55H66N2O2; palladium diacetate; potassium carbonate In methanol; dichloromethane at 30℃; for 0.5h; | ||
88 %Chromat. | With C39H39ClN2NiP; Cs2CO3 In toluene at 80℃; Inert atmosphere; Schlenk technique; Glovebox; | |
80 %Chromat. | With palladium dibromo{N,N-bis(diphenylphosphanyl)tert-butylamine}; Cs2CO3 In N,N-dimethyl-formamide at 80℃; for 1h; Inert atmosphere; Schlenk technique; | 4.5 General experimental procedure for the Suzuki-Miyaura coupling General procedure: Aryl bromide (1.0mmol), phenylboronic acid (183mg, 1.5mmol), Cs2CO3 (652mg, 2.0mmol), palladium(II) complex [Pd(P,P)Br2] in DMF (0.5mM, 2mL, 1.0μmol) and dodecane (70μL, 0.3mmol) as internal standard were stirred over a preheating oil bath at 80°C under argon for 1h. After cooling to room temperature, addition of water (5mL) and extraction with dichloromethane (2×10mL), the organic layer was washed with brine (10mL), dried over Na2SO4, filtered, passed through celite and analyzed by GC. GC retention times were compared with those of authentic samples. After evaporation of the any volatile residue, isolation of the pure biaryl was achieved by column chromatography on silica gel using a mixture of hexane/AcOEt as eluent. All biaryls are known compounds [25c], and were characterized by 1H and 13C NMR spectra. |
86 %Chromat. | With potassium carbonate In ethanol; water monomer at 70℃; for 1h; | |
With potassium carbonate In ethanol at 50℃; Sonication; | ||
With C42H26Cl2N2PdS2; potassium carbonate at 90℃; for 8h; | ||
With tripotassium phosphate tribasic In toluene | 74 4-phenylbenzophenone (Table 10, Entry 2) Example 74 4-phenylbenzophenone (Table 10, Entry 2) According to the general procedure described above, 4-Bromobenzophenone (131 mg, 0.50 mmol) reacted with phenylboronic acid (92 mg, 0.75 mmol) using 0.0005 mol % of Pd(dba)2, 0.002 mol % of Ph5FcP(t-Bu)2, and K3PO4 (318 mg, 1.50 mmol) in toluene solvent at 100° C. for 1 hr to title compound (121 mg, 94%) as a solid: 1H-NMR (400 MHz, CDCl3): δ 7.92 (d, 2H, J=8.4 Hz), 7.87 (d, 2H, J=7.2 Hz), 7.73 (d, 2H, J=8.4 Hz), 7.18 (d, 2H, J=6.8 Hz), 7.63 (m, 1H), 7.51 (m, 3H), 7.43 (m, 2H). 13C{1H}-NMR (100 MHz, CDCl3): δ 196.30, 145.16, 139.89, 137.68, 136.15, 132.34, 130.69, 129.96, 128.92, 128.26, 128.14, 127.25, 126.91. GC/MS(EI): m/z 181 (M-77+). Anal. Calcd for C19H14O: C, 88.34; H, 5.46. Found: C, 88.26; H, 5.62. | |
With C25H22Cl2NPPd; potassium carbonate In water monomer; N,N-dimethyl-formamide at 105℃; for 10h; | 2.5.1. Suzuki coupling (i.e., C-C coupling) reaction General procedure: A 100 mL round bottom flask (equipped with a refluxing con- denser) was charged with aryl halide (1.0 mmol), phenylboronic acid (1.1 mmol, 0.133 g), K 2 CO 3 (2.0 mmol, 0.276 g), Pd(II) complex (0.01 or 0.001 mol%) and aqueous DMF (5.0 mL). The reaction mix- ture was refluxed at 105 °C for 10 h and the progress of catalytic reaction was monitored using thin layer chromatography (TLC). Af- ter completion of ten hours, the resultant mixture was cooled to room temperature and water was added to it. Thereafter, the ex- traction of cross-coupled product was carried out using diethyl ether. The organic layer was dried over anhydrous Na 2 SO 4 and the solvent was evaporated using rotary evaporator to obtain the prod- uct. The % conversion was estimated using 1 H NMR and GC stud- ies. Thereafter, the product was subjected to silica gel column chro- matography for purification using ethyl acetate and n -hexane mix- ture as an eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bismuth(lll) trifluoromethanesulfonate; In neat (no solvent); at 140℃; for 0.666667h;Sealed tube; Microwave irradiation; | General procedure: A 10-mL pressurized glass tube with Teflon-coated septum equipped with amagnetic stirrer was charged with substrate (1 mmol), benzoyl chloride (1 mmol),and metal triflate (0.1 equiv). The tube was sealed and placed into a CEM microwaveat the temperature for the appropriate time. The reaction mixture was allowed tocool to the room temperature in the MW oven. After cooling, water (15 mL) wasadded to the mixture and the product was extracted by ethyl acetate or dichloromethane,which gave similar results (315mL). The organic layer was decanted;washed with water, aqueous NaHCO3, and brine; and dried with MgSO4. Thesolvent was then removed on a rotary evaporator and subjected to flash chromatographyon silica gel (mixture of hexane and ethyl acetate solvent to elute theproduct). The fractions containing product were concentrated and dried undervacuum to yield pure product. All products are known compounds; the purity and identityof all products were confirmed by GC-MS and 1H and 13C NMR spectroscopy. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium phosphate; triphenylphosphine In N,N-dimethyl-formamide at 90℃; for 1h; | |
84 % Chromat. | With tetrakis(triphenylphosphine) palladium(0); cesium fluoride In 1,2-dimethoxyethane at 100℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With palladium diacetate; potassium carbonate In methanol for 0.75h; Heating; | |
92% | With potassium carbonate In methanol for 0.75h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With acetic acid microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: (4-bromophenyl)(phenyl)methanone; sodium cyanide With potassium iodide; N,N`-dimethylethylenediamine In toluene at 110℃; for 24h; Stage #2: With ammonia In water; ethyl acetate; toluene at 25℃; for 0.166667h; | 26 Example 26; [4-BENZOYLBENZONITRILE] An oven dried screw cap test tube was charged with [NACN] (91 mg, 1.857 mmol), dried KI (51 mg, 0.307 mmol, 20 mol%), Cul [(30] mg, 0.157 mmol, 10 mol%), (4- bromophenyl) -phenyl-methanone (404 mg, 1.548 mmol), evacuated and backfilled with argon three times. N, N'-dimethylethylenediamine (165 [PL,] 1.550 mmol) and anhydrous toluene (1 mL) were added under argon. The tube was sealed and the reaction mixture was stirred magnetically at [110 °C] for 24 h. The resulting suspension was cooled to room temperature, 2 mL of ethyl acetate, 1 mL of ammonium hydroxide (30%) and 1 mL of water were added. The mixture was stirred at [25 °C] for 10 min then the organic layer was washed with 1 mL of water and dried over [MGS04.] The GC analysis showed complete conversion of starting material with formation of title product (confirmed by GC-MS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran; water; | Example 2 Synthesis of 9,10-bis[2-(4-bromophenyl)-2-phenylethenyl]anthracene Under an inert atmosphere, 4-bromobenzophenone (3.917 g, 15 mmol), and 9,10-bis-(diethylphosphonomethyl) anthracene (2.942 g, 6.15 mmol) were dissolved in tetrahydrofuran (40 g). At room temperature, tetrahydrofuran (16.38 g) solution of tert-butoxy potassium (2.070 g, 18.45 mmol) was added dropwise for 5 minutes, and successively stirred for 3.5 hours. The reaction mixture was charged into water (100 ml) and neutralized with 5% sulfuric acid. After neutralization, the crystal was filtrated and the dissolved in tetrahydrofuran (300 ml). Then, the solvent was partly distilled off under reduced pressure, and cooled to deposit crystal. The crystal was filtrated and dried to give the desired product. (Yield: 1.10 g, 26%) MS Spectrum: M+ 693.1 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With n-butyllithium; sodium chloride; In tetrahydrofuran; diethyl ether; hexane; acetone; | A. Preparation of alpha-(p-bromophenyl)-alpha-phenyl-1-(toluene-p-sulphonyl)imidazole-2-methanol. To a solution of 33.3 g. (0.15 mol) of 1-(toluene-p-sulphonyl)imidazole (H. A. Staab and K. Wendel, Ber. 93, (1960) 2902) in 300 ml. of anhydrous tetrahydrofuran and 150 ml. of anhydrous diethyl ether at a temperature of -40 to -50 C. under a nitrogen atmosphere were added drop-wise 91 ml. of a 20% solution of butyllithium in n-hexane (0.20 mol.) dissolved in 150 ml. of anhydrous diethyl ether. Upon completion of the addition, the mixture was kept at a temperature of -40 to -50 C. for one hour. Next and under identical conditions as to temperature 44.4 g. (0.17 mol) of 4-bromobenzophenone in 200 ml. of anhydrous tetrahydrofuran and 100 ml. of anhydrous diethyl ether were added drop-wise and the mixture was kept under the same conditions for another 3.5 hours. Cooling was stopped and the mixture was allowed to reach ambient temperature in 1/2 hour. It was then poured out into about 250 ml. of a sodium chloride solution. The aqueous layer was separated and discarded, the organic solvents layer was washed with 100 ml. of a sodium chloride solution, dried and concentrated. The residual oil was brought to crystallisation by addition of a very small amount of diethyl ether. Purification was brought about by crystallisation from warm ethanol to which some acetone was added. Melting point of the product was 138-140 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With caesium carbonate; triphenylphosphine In N,N-dimethyl acetamide at 90℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With titanium tetrachloride; zinc In tetrahydrofuran; toluene at 0 - 90℃; for 2.16667h; | 9.1 Step 1. 1-Bromo-4-[phenyl(3,3,5,5 tetramethylcyclohexylidene)methyl]benzene (16)A stirred suspension of Zn dust (3.76 g, 57.5 mmol), 3,3,5,5-tetramethyl cyclohexanone (2.95 g, 19.2 mmol), 4-bromobenzophenone (5.00 g, 19.15 mmol) and anhydrous THF (100 mL) under N2 was cooled to -10° C. and a 1 M solution of TiCl4 in toluene (30 mL) added, dropwise, over 10 min. The temperature was maintained below 0° C. during the addition. After addition was complete the reaction was allowed to warm to RT and then heated at 90° C. for 2 h. The reaction was cooled to -10° C. and concentrated HCl (15 mL) added dropwise followed by water (15 mL). After stirring 30 min, EtOAc (100 mL) was added and the pale yellow 2-phase mixture washed with water (2×75 mL) and brine (1×75 mL) then dried (MgSO4) and concentrated to 8.26 g of a pale yellow oil. The crude oil is purified by column chromatography on 250 g silica gel with 2% EtOAc/hexanes to afford 4.17 g (58%) of the title compound (16) as a white solid. 1H-NMR indicated that the product (16) was contaminated with 8% of an impurity consistent with the pinacol intermediate formed during the McMurry reaction. 1H NMR (400 MHz, DMSO-d6): δ7.46 (d, J=8.3 Hz, 2H), 7.28 (t, J=7.5 Hz, 2H), 7.04-7.19 (m, 5H), 1.87 (s, 4H), 1.24 (s, 2H), 0.87 (s, 6H), 0.86 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | With diethylzinc; palladium diacetate; tert-butyl XPhos In hexanes; N,N-dimethyl acetamide at 40℃; Automated synthesizer; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.0 g of <strong>[902518-11-0]9-(2-bromophenyl)-9H-carbazole</strong> as the intermediate of preparation example 8 was dissolved in 10 mL of purified tetrahydrofuran, and the resulting solution was cooled to -78 degree C, and 1.613 mL of butyllithium was slowly added dropwise. The mixture was stirred at the same temperature for 30 min, and 1.05 g of 4-bromobenzophenone was added. The mixture was stirred at the same temperature for 40 minutes, and then further stirred at room temperature for an additional 3 hours. The reaction was terminated with aqueous ammonium chloride, and the reaction mixture was extracted with ethyl ether. The organic layer was dewatered using anhydrous magnesium sulfate, and the organic solvent was then removed. The resulting solid was then dispersed in ethanol, stirred for one day, filtered and vacuum dried, thus obtaining an intermediate material. The solid thus obtained was dispersed in 10 ml of acetic acid, and 10 drops of concentrated sulfuric acid were added, after which the mixture was refluxed for 4 hours. The resulting solid was filtered, washed with ethanol, and vacuum dried, yielding 8-(4-bromophenyl)-8-phenyl-8H-indolo-[3,2,1-de]acridine compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With 2-(2-methoxyphenyl)-1-methyl-3-(diphenylphosphino)-1H-indole; potassium <i>tert</i>-butylate; triethylamine; bis(dibenzylideneacetone)-palladium(0) In dichloromethane; water; acetonitrile at 50℃; for 24h; Inert atmosphere; | 2. General procedures for palladium-catalyzed cyanation of aryl bromides General procedure: An oven-dried Schlenk tube with the presence of magnetic stir bar which is Teflon-coated was charged with Pd(dba)2 (11.5 mg, 0.02 mmol, 2 mol%) and ligand L4 (8.4 mg, 0.02 mmol, 2 mol%). The flask was evacuated and backfilled with nitrogen (3 cycles). Pre-complexation of palladium and ligand was initiated by injecting freshly distilled dry dichloromethane (2.0 mL) and Et3N (0.1 mL) into the tube. The solution was stirred and warmed with hair drier till the solvent condensed on the tube wall. The solvent was removed under vacuum. Aryl bromide (1.0 mmol), KOt-Bu (0.25 mmol), and potassium hexacyanoferrate(II) trihydrate (0.23 mmol) were charged successively to the tube followed by another 3 evacuation-nitrogen refill cycles. Water (1.0 mL) and acetonitrile (1.0 mL) were used as a solvent mixture. The tube was immersed into a preheated 50 °C oil bath for 24 hours. The reaction was quenched by cooling to ambient temperature and added with EtOAc and water. The organic supernatant was analyzed by GC. The organic layer was separated and the remained aqua medium was further extracted with EtOAc (10 mL × 3). The combined organic phases were concentrated under reduced pressure. The crude product was purified by flash column chromatography on silica gel (230-400 mesh). The pure fractions were collected, dried under vacuum, and followed by proton (1H) and carbon (13C) NMR characterization |
87% | With potassium phosphate tribasic trihydrate; C38H28O4P2Pd In N,N-dimethyl-formamide at 130℃; for 12h; | |
80% | With sodium carbonate In N,N-dimethyl-formamide at 120℃; for 7h; | 2.5 General Procedure for Cyanation of Aryl Halides General procedure: In a 25mL round bottom flask containing 6mL of DMF, arylhalide (1 equiv), K4Fe(CN)6·3H2O (0.17 equiv), Na2CO3(1.5 equiv) and Pd NPs (0.5mol%) were added and stirredmagnetically at 120°C for required time. The reaction masswas cooled to room temperature after reaction completion(as monitored by TLC), followed by the recovery of PdNPs by centrifugation at 6000rpm for 15min. The productwas then extracted using dichloromethane (2 × 20mL)and subjected to water wash (2 × 20mL) followed by dryingof the organic layer over Na2SO4.The dried organic layerwas concentrated in vacuo, and the product was purified bycolumn chromatography using n-hexane and ethyl acetateas eluents to afford the corresponding products in good toexcellent yields. All the aryl nitrile products were knownmolecules and were confirmed by comparing the meltingpoint, 1H NMR and ATR-IR data with authentic samples(see Supporting Information for details). |
47% | With potassium phosphate; 2-pyridinecarboxaldehyde N-methyl-N-phenylhydrazone; palladium(II) trifluoroacetate In N,N-dimethyl-formamide at 110℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With dichlorobis(dibenzyl diisopropylphosphoramidite)palladium(II); sodium fluoride In N,N-dimethyl-formamide at 130℃; for 16h; | Typical Procedure for the Synthesis of Aromatic nitriles General procedure: TThe complex [(PhCH2O)2P(CH3)2CHNCH(CH3)2]2PdCl2} (PdCl2L2) was prepared according to the literatureprocedure[19]. A mixture of aryl bromide (1.0 mmol),K4[Fe(CN)6] (0.22 mmol), NaF (2.0 mmol), DMF (4 ml) andcatalyst PdCl2L2 (3 %) was stirred at 130 0C under air. Thereaction mixture was stirred for 16 h, and then quenchedwith water. The mixture was diluted with ethyl acetate. Theorganic layer was separated and the aqueous layer was extractedwith ethyl acetate (3 10 ml). The combined organicphase was dried with MgSO4, filtered, solvent was removedon a rotary evaporator, and the product was isolated by thinlayer chromatography. The purified products were identifiedby 1H NMR, 13C NMR spectroscopy and melting points bycomparison with those reported in the literatures [9, 11]. |
91% | With dichloro[bis{1-(dicyclohexylphosphanyl)piperidine}]palladium; sodium carbonate In 1-methyl-pyrrolidin-2-one at 140℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With pyridine; titanium tetrachloride; zinc; In tetrahydrofuran; at 0 - 70℃;Inert atmosphere; | The 24.2g (372mmol) of zinc powder was suspended in 250mL of tetrahydrofuran(THF) was added 1L three-neck flask, a magnetic stirred and purged with argon. Thesystem was reduced to 0 added dropwise 21mL (186mmol) of titanium tetrachloride wasadded dropwise at room temperature to complete the reaction system was returned after 30min, was heated in an oil bath and then raised to 70 C , the reaction 3h. After again lowered to 70 C, was added dropwise to 7.4g (93mmol) of pyridine, 200mL Afterdropping was dissolved tetrahydrofuran (THF) of 4,4'-dimethoxy-benzophenone 9g(37.2mmol) and 4-bromo benzophenone 12.6g (48.4mmol), after the completion of thedropwise addition heated at 70 C for 8 hours under an oil bath overnight. After completion of the reaction, the system was again cooled to 0 C, was added200mL quenched with saturated sodium bicarbonate solution, diatomaceous earth, thefilter cake was washed with 200mL ethyl acetate and the filtrate was partitioned, theorganic phase by rotary evaporation, mixed with silica gel kind, by column to give 9.9 g of product, 57% yield |
46% | With titanium tetrachloride; zinc; In tetrahydrofuran; at -10℃; for 12.5h;Inert atmosphere; Reflux; | 4, 4'-dimethoxybenzophenone (20 mmol, 4.84 g) , 4-bromobenzophenone (24 mmol, 6.26 g) and zinc dust (80 mmol, 5.2 g) were added to a 500 mL round-bottom flask. Then the flask was evacuated under vacuum and flushed with dry nitrogen three times. After addition of 250 mL of anhydrous THF, the mixture was cooled to -10 and TiCl4(7.7 mL, 70 mmol) was added dropwise and stirred for 30 minutes. The mixture was heated to reflux and stirred for 12 hours. After cooling to room temperature, the reaction was quenched by 1 M HCl solution, and the mixture was extracted with dichloromethane three times. The organic phase was combined, dried with MgSO4, and the solvent was evaporated under reduced pressure. The crude product was purified on a silica gel column chromatography using dichloromethane/hexane (v/v 1: 5) as the eluent to give 4, 4'- (2- (4-bromophenyl) -2-phenylethene-1, 1-diyl) bis (methoxybenzene) as a white solid (46%yield) . |
40% | With titanium tetrachloride; zinc; In tetrahydrofuran; for 5h;Reflux; Inert atmosphere; | To a suspension of powder zinc (2.15 g, 33 mmol) in dry THF (40 mL) was added titanium(IV)chloride (1.81 mL, 16.5 mmol) dropwise under argon at 0 C. The mixture was allowed to reflux for 4 h and then cooled to room temperature. A solution of (4-bromophenyl)phenylmethanone (980 mg, 4.12 mmol) and 4, 4′-dimethoxybenzophenone (1.0 g, 4.12 mmol) in THF (70 mL) was added to this suspension at once. Reaction mixture was heated to reflux for 5 h. The mixture was cooled to room temperature, quenched with 10% aqueous K2CO3 solution (100 mL). The dispersed insoluble material was removed by vacuum filtration using a Celite pad. The organic layer was separated, and the aqueous layer was extracted with CH2Cl2 (3×50 mL), the combined organic fractions were washed with water (20 mL) and dried over Na2SO4. The solvent was removed under reduced pressure to afford the crude product, which was purified by column chromatography (silica gel/ethyl acetate: petroleum ether 1:5) afforded 4 (776 mg, 40%) as a light yellow solid. Mp 120-121 ºC; IR (KBr, cm-1): 3032, 2942, 2834, 1610; 1H NMR (300 MHz, CDCl3): δ 7.21 (d, 2H, J = 8.4 Hz), 7.13-7.05 (m, 4H), 7.04-6.97 (m, 2H), 6.96-6.84 (m, 5H), 6.65 (d, 2H, J = 8.4 Hz), 6.62 (d, 2H, J = 8.4 Hz), 3.75 (s, 3H), 3.72 (s, 3H); MS (EI): m/z 471, 473 (M+, M++2, 100, 95%). |
37% | With titanium tetrachloride; zinc; In tetrahydrofuran; at -78℃; for 16h;Inert atmosphere; Reflux; | 1. Add 4,4'-dimethoxybenzophenone (1.96g, 8.1mmol), 4-bromobenzoylbenzene (2.74g, 10.5mmol) and zinc powder ( 3.05g, 47mmol), 40mL of dry tetrahydrofuran was added under the protection of argon. The mixture was cooled to -78C, and 2.5 mL of titanium tetrachloride was added dropwise with stirring. After the addition, the system was gradually raised to room temperature and heated to reflux for 16 hours. After the reaction is over, cool to room temperature, slowly add 50 mL of saturated aqueous sodium bicarbonate solution dropwise in an ice bath, extract the reaction solution with ethyl acetate, combine the organic phases, wash with water, wash with saturated brine, dry with anhydrous sodium sulfate, filter, and depressurize Concentrated to obtain a yellow crude product, column chromatography was separated to obtain a light yellow solid, that is, intermediate 1, with a yield of 37%. |
29% | With titanium tetrachloride; zinc; In tetrahydrofuran; at 0℃; for 4.5h;Reflux; | A mixture of zinc powder (1.56 g, 24 mmol), 4-bromobenzophenone (313 mg, 1.2 mmol) of 4,4'-dimethoxybenzophenone (242 mg, 1.0 mmol) Was added to anhydrous tetrahydrofuran and the suspension was cooled to 0 & lt; 0 & gt; C with stirring.The titanium tetrachloride (2.276 g, 12 mmol) was then slowly added dropwise with a syringe and the mixture was stirred for 30 min at 0 C and the mixture was refluxed for 4 h.After cooling, stir into the sodium carbonate solution until no bubbles are generated.The organic phase was dried over anhydrous sodium sulfate, concentrated and chromatographed to give compound 2 in a yield of 29%. |
25% | With titanium tetrachloride; zinc; In tetrahydrofuran; at 78℃; for 12h;Inert atmosphere; | General procedure: Michler's ketone (1 g, 3.726mmol), 4,4′-Dibromobenzophenone (1.2 g, 3.726mmol), and zinc powder (2.9 g, 44.71mmol) were mixed in freshly distilled cold tetrahydrofuran (THF, 20mL, 0C), and titanium tetrachloride (TiCl4, 2.8mL) was added dropwise under an argon atmosphere with the rapid stirring of over 10min. The mixture was then slowly warmed up to 78C with stirring, and the reaction was allowed to further proceed for 12h under reflux. After the reaction, the mixture was cooled to room temperature, and deionized water (DI H2O, 25mL) was added to quench the reaction. The resulting solution was filtered through a pad of celite to remove the remaining zinc powder. The filtrated solution was washed with ethyl acetate (EtOAc) and DI H2O. The collected organic extract was washed with brine and dried over anhydrous sodium sulfate (Na2SO4). The resulting residue was concentrated in vacuo and was purified by flash column chromatography (n-hex/EtOAc=9:1, v/v, TLC: Rf 0.5). TPE-N2-Br2 was collected with a 29% yield (bright yellow solid). |
With titanium tetrachloride; zinc; In tetrahydrofuran; at 75 - 85℃; for 9.5h;Sealed tube; Inert atmosphere; | 1) 4-bromobenzophenone (3.0 g, 11.5 mmol),4,4-dimethoxybenzophenone (2.78 g, 11.5 mmol) and zinc powder (5.97 g, 92 mmol) were dissolved in freshly distilled tetrahydrofuran (150 mL) and connected to a condensing unit. The reaction system was sealed, the air in the reaction system was purged with nitrogen, and the ice water bath was kept at a low temperature. Then titanium tetrachloride (8.72 g, 46 mmol) was added to the above system and stirred for 0.5 hour, and the reaction system was heated to 75-85 C to maintain Reflux for 9 hours, Then, it was cooled to room temperature, water was added, the reaction mixture was extracted with dichloromethane, the operation was repeated three times, and the obtained organic mixed solution was dried over anhydrous sodium sulfate.Taking petroleum ether/dichloromethane (5:1 by volume) as eluent,The crude product was purified by silica gel column to obtain MeO-TPE-indo; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | 16.7 mL (0.1 mol) of diphenylmethane and 300 ml of tetrahydrofuran (THF) were added to a solution of500ml three-necked flask, magnetic stirring and argon, ice salt bath 40min, to the three bottles by adding 54.5mL (0.12mol) n-butyl lithium solution, continue ice salt bath 40min, add 13.0555g4-bromobenzophenone(Bis (4-bromophenyl) methanone, 0.05),After the reaction was carried out at room temperature for 12 h, 250 ml of saturated ammonium chloride (NH4Cl) solution was added to the three-necked flask. After stirring for 10 min, the reaction solution was poured into a separatory funnel, the supernatant was taken and the water in the solution was adsorbed with 300 g of anhydrous sodium sulfate. And then heated to 110 C. After adding 5 g of p-toluenesulfonic acid, the mixture was refluxed for 12 hours. After the reaction was stopped, the reaction solution was dried and dried. The reaction mixture was heated to 110 C, The product was spin dried to dry the powder and the powder was dried in vacuo at 60 C for 24 h to give the white intermediate Si-Br in 89% yield. | |
73.03% | 1, under the conditions of a temperature of 0 C, the 100ml three-necked flask was evacuated and filled with N2 three times,12 mmol of diphenylmethane and 50 ml of dehydrated tetrahydrofuran were evacuated, and 10 mmol of n-butyllithium was gradually introduced into the flask. While maintaining the atmosphere of nitrogen at 0 C, n-butyllithium was subjected to dehydrogenation for 1 hour. To the solution was added 9.5 mmolBromobenzophenone, the reaction was allowed to return to room temperature and stirred for 6 hours. The reaction was quenched by the addition of saturated aqueous ammonium chloride. The organic phase was extracted with CH 2 Cl 2, washed three times with saturated brine and dried over anhydrous Na 2 SO 4. The organic solvent , The residue,Toluenesulfonic acid and 60 ml of toluene were added to a 100 ml two-necked flask, and the mixture was refluxed for 6-8 hours. The mixture was cooled to room temperature and the organic layer was washed with 10% aqueous NaHCO 3 solution Three times, the combined organic phases were dried over anhydrous Na2SO4 and the solvent toluene was evaporated under reduced pressure. The residue was purified by column chromatography to give a white solid Product 1-1. Yield: 73.03%. 1-1 | |
66% | In a 250 mL three-necked flask,Diphenylmethane (10.0 g, 59.5 mmol) was dissolved in 150 mL of re-distilled tetrahydrofuran,At 0 slowly added dropwise n-BuLi (25mL, 2.5M),After reaction for 30 min, 4-bromobenzoylbenzene (5.2 g, 20.0 mmol) was slowly added dropwise.Then, the temperature was raised to room temperature for 6 h, quenched with ammonium chloride,The reaction was extracted with CH2Cl2 (3 x 20 mL) and the extract was washed with water (3 x 20 mL)Dried over anhydrous MgSO4 and the solvent was removed under reduced pressure to give an alcohol.The above alcohol solution was dissolved with toluene,P-toluenesulfonic acid (1.7 g, 0.01 mol) was added,The reaction was carried out at 110 C for 3-4 h with a water distilling apparatus.The reaction was extracted with sodium bicarbonate. The extract was washed with water (3 x 20 mL) and dried over anhydrous MgSO4. The solvent was removed under reduced pressure and the column was separated (PE) to give 5.3 g of product (yield: 66%) as a white solid. |
64% | 1. Add 10.09 g (0.06 mol) of diphenylmethane to a 500 mL three-necked flask.And 250 mL of dry tetrahydrofuran, vacuum replacement, cooling to 0 C,Maintain mixing,Slowly add to the mixture with a syringe under nitrogen protection24.0 mL of 2.5 mol/L (0.06 mol) n-butyllithium in cyclohexane solution,Stirring was continued for 30 min after the addition, and then 40 mL of a dry tetrahydrofuran solution containing 15.14 g (0.058 mol) of 4-bromobenzophenone was added dropwise.After stirring at room temperature for 10 h, the reaction mixture was quenched with aqueous ammonium chloride, and extracted with dichloromethane (300 mL×3×),Rinse alternately with saturated aqueous sodium chloride solution and deionized water (300 mL × 3 times).Dry with anhydrous magnesium sulfate, filter, and distill off the solvent.The intermediate 2-(4-bromophenyl)-1,1,2-triphenylethanol was obtained.The obtained intermediate was dissolved in 300 mL of toluene with 1.0 g of anhydrous p-toluenesulfonic acid.After refluxing for 5 h, toluene was distilled off, and the obtained solid was dissolved in 300 mL of dichloromethane.Then alternately wash with saturated aqueous sodium chloride solution and deionized water (300mL×3 times).Drying anhydrous magnesium sulfate, filtering, and distilling off the solvent to obtain a crude product;Taking cyclohexane/dichloromethane (v/v=5:1) as the eluent,The crude product was separated by silica gel column chromatography.15.27g of white solid 1-(4-bromophenyl)-1,2,2-triphenylethylene,The yield was 64%. | |
37% | Step 1, synthesis of bromotetraphenylethene (TPE-Br) The benzylbenzene (2.0g, 11.9mmol) was dissolved in 20mL of anhydrous tetrahydrofuran, was stirred at 0C under nitrogen atmosphere, 1.6M n-hexane solution of n-butyllithium (7.4mL, 11.9mmol) was slowly added, reacted for 30 minutes; and then 4-bromo-benzophenone (3.1g, 11.9mmol) was added, slowly warmed to room temperature and the reaction mixture was stirred for 6 hours, followed by addition of a small amount of water to the reaction solution for the reaction to stop, the reaction solution was extracted twice with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate and was filtered. The solvent was distilled off under reduced pressure. The resulting solid was dissolved in 80mL of toluene, p-toluenesulfonic acid monohydrate (500mg, 2.6mmol, catalyst) was added, and refluxed for 16 hours, the reaction was cooled to room temperature and extracted twice with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate and was filtered. The solvent was distilled off under reduced pressure. The crude product with hexane as a mobile phase and the silica gel as the stationary phase was pass through column chromatography, obtaining a white solid 1.8g, 37% yield; | |
10 g of diphenylmethane was placed in a two-neck reaction flask, nitrogen was distilled off three times, and 50 mL of tetrahydrofuran was added under a nitrogen atmosphere.25 mL of 2.5 M n-butyllithium was slowly injected under ice bath at 0 C. After one hour of activation, a solution of 12.2 g of 4-bromobenzophenone in 20 mL of tetrahydrofuran was added thereto, and the mixture was reacted at room temperature for 8 hours.The reaction was quenched with saturated ammonium chloride solution, extracted with dichloromethane. The organic phase was collected and concentrated in vacuo. The obtained solid was washed with n-hexane and methanol to remove excess diphenylmethane, and the remaining solid residue was poured into a reaction flask, and 30 mL of toluene was added. With 20 mg of p-toluenesulfonic acid, refluxed overnight to obtain a crude product using n-hexane over silica gel column.The white solid product 2-(4-bromophenyl)-1,1,2-triphenylethylene was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: phenylmagnesium bromide With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Stage #2: (4-bromophenyl)(phenyl)methanone With cobalt(II) chloride; tricyclohexylphosphine In tetrahydrofuran at 20℃; for 4h; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: phenyllithium With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Stage #2: (4-bromophenyl)(phenyl)methanone With tributylphosphine; cobalt(II) chloride In tetrahydrofuran at 20℃; for 4h; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With pyridine; titanium tetrachloride; zinc In tetrahydrofuran Inert atmosphere; Reflux; | |
42% | With titanium tetrachloride; zinc In tetrahydrofuran at -78℃; Inert atmosphere; Reflux; | |
42% | With titanium tetrachloride; zinc In tetrahydrofuran at 78℃; for 12h; Inert atmosphere; | [TPE-N2-Br2] General procedure: Michler's ketone (1 g, 3.726mmol), 4,4′-Dibromobenzophenone (1.2 g, 3.726mmol), and zinc powder (2.9 g, 44.71mmol) were mixed in freshly distilled cold tetrahydrofuran (THF, 20mL, 0°C), and titanium tetrachloride (TiCl4, 2.8mL) was added dropwise under an argon atmosphere with the rapid stirring of over 10min. The mixture was then slowly warmed up to 78°C with stirring, and the reaction was allowed to further proceed for 12h under reflux. After the reaction, the mixture was cooled to room temperature, and deionized water (DI H2O, 25mL) was added to quench the reaction. The resulting solution was filtered through a pad of celite to remove the remaining zinc powder. The filtrated solution was washed with ethyl acetate (EtOAc) and DI H2O. The collected organic extract was washed with brine and dried over anhydrous sodium sulfate (Na2SO4). The resulting residue was concentrated in vacuo and was purified by flash column chromatography (n-hex/EtOAc=9:1, v/v, TLC: Rf 0.5). TPE-N2-Br2 was collected with a 29% yield (bright yellow solid). |
31% | Stage #1: (4-bromophenyl)(phenyl)methanone; bis(p-dimethylaminophenyl)methanone With zinc In tetrahydrofuran at -70℃; Inert atmosphere; Cooling with acetone-dry ice; Stage #2: With titanium tetrachloride In tetrahydrofuran at -78 - 20℃; for 8h; Inert atmosphere; Cooling with acetone-dry ice; | |
With titanium tetrachloride; zinc In tetrahydrofuran | ||
With pyridine; titanium tetrachloride; zinc In tetrahydrofuran Inert atmosphere; Reflux; | 2.3. Synthesis Under N2 atmosphere, a three-necked flask equipped with a magnetic stirrer was charged with zinc powder (4.2 g, 65 mmol)and 40 mL THF. The mixture was cooled to -5-0 °C, and TiCl4 (3.6 mL, 32.4 mmol) was slowly added by a syringe with the temperature kept under 10 °C. The suspending mixture was warmed to room temperature and stirred for 0.5 h, then heated at reflux for 2.5 h. The mixture was again cooled to -5-0 °C, charged with pyridine (0.24 mL, 3 mmol) and stirred for 10 min. The solution of two carbonyl compounds (in 6:6 mmol to 6:7.2 mmol mole ratios, in 15 mL THF) was added slowly. After addition, the reaction mixture was heated at reflux until the carbonyl compounds were consumed (monitored by TLC). The reaction was quenched with10% Na2CO3 aqueous solution and taken up with CH2Cl2. The organic layer was collected and concentrated. The crude material was purified by flash chromatography to give the desired products.The 1-(4-bromophenyl)-1,2,2-triphenylethylene was solved inTHF, the added n-BuLi at -78 °C for 2 h, followed by addition of dimethylformamide, the crude material was kept at room temperaturefor 2 h. The mixture was quenched by water and purified by flash chromatography, gave the expected aldehyde. Knoevenagel reaction was taking place between the aldehyde and the cyano derivative under alkaline conditions. The mixture was purified by flash chromatography, gave the target molecular. | |
With titanium tetrachloride In tetrahydrofuran Inert atmosphere; | ||
With titanium chloride; zinc In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sodium hydroxide In ethylene glycol at 100℃; for 3h; | 2.6 General Procedure for Hiyama Cross-Coupling Reaction General procedure: In a 25mL round bottom flask containing 5mL of ethyleneglycol, aryl halide (1 equiv), trimethoxyphenylsilane (1.5equiv), NaOH (3 equiv) and Pd NPs (0.2mol%) were takenand stirred at 100°C for required time. The reaction masswas cooled to room temperature after reaction completion(as monitored by TLC), followed by the recovery of Pd NPsby centrifugation at 6000rpm for 30min. The product wasthen extracted using dichloromethane (2 × 20mL) and subjectedto water wash (1 × 20mL) and brine wash (1 × 20mL)followed by drying of the organic layer over Na2SO4.Thedried organic layer was concentrated in vacuo, and the productwas purified by column chromatography using n-hexaneand ethyl acetate as eluents to aford the corresponding productsin good to excellent yields. All the coupled productswere known molecules and were confirmed by comparingthe melting point, 1H NMR and LC-MS data with authenticsamples (see Supporting Information for details). |
84% | With N-methyliminodiacetic acid; sodium fluoride; potassium hydroxide; palladium dichloride In water; isopropyl alcohol at 80℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 90℃; for 2h; | General procedure: The molecular structure and synthetic route of 1-3 compounds are outlined in Scheme 1. General procedure for the Suzuki cross-coupling reaction: the corresponding hetero aryl bromide (1.0mol), 10-(naphthalen-2-yl)anthracene-9-ylboronic acid (1.2mol) and Pd(PPh3)4 (0.04mol) were mixed in a solution of aqueous 2.0M Na2CO3 (10.0mol), ethanol and toluene. The mixture was refluxed at 90C for 2h. After the reaction had finished, the reaction mixture was extracted with toluene and washed with water. The organic layer was dried with anhydrous MgSO4 and filtered with charcoal. The solution was then evaporated. The crude product was purified by column chromatography with silica gel and subsequent recrystallization from THF/MeOH and then hot hexane filter. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With sodium periodate; tetraethylammonium iodide In water; acetonitrile at 105℃; for 12h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With oxygen; copper diacetate; potassium carbonate; aniline; In dimethyl sulfoxide; at 120℃;Schlenk technique; Sealed tube; | General procedure: An oven-dried Schlenk tube was charged with a magnetic stir-bar, 1,2-diarylalkynes 1 (0.5mmol), aniline (0.6mmol), K2CO3 (0.5mmol), Cu(OAc)2 (0.075mmol), DMSO (3mL), The tube was sealed, and oxygen was purged through syringe. Reaction was stirred at 120C for 16-18h. After the reaction was finished, the reaction mixture was diluted in 30mL ethyl acetate, filtered on Celite pad. The organic portion was washed with a saturated solution of brine (8mL), saturated NH4Cl (8mL), a saturated solution of brine (8mL), dried (Na2SO4) and concentrated in vacuum, and the resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate) to afford the desired products 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With copper(l) iodide; tris(triphenylphosphine)rhodium(l) chloride; potassium carbonate; In 5,5-dimethyl-1,3-cyclohexadiene; at 120℃; for 2h; | General procedure: A reaction vessel was charged with a mixture of a benzoic anhydride (or an aryl carboxylic anhydride) (0.30 mmol), potassium aryltrifluoroborate (or potassium phenyltrifluoroborate) (0.60 mmol), K2CO3 (0.60 mmol), CuI (0.30 mmol), RhCl(PPh3)3 (0.003 mmol, 1.0 mol %) and xylene (1.5 mL). The mixture was heated to 120 C and stirred for 2 h. After the completion of the reaction, the mixture was quenched with 5 mL of water, and then extracted with ethyl acetate (3×10 mL). The combined organic layers were dried over magnesium sulfate. After removal of the solvent in vacuo, the product was isolated by column chromatography. Ethyl acetate/petroleum ether was used for elution and the yield was calculated based on the amount of aryl benzoic anhydride (the purified products were identified by NMR spectra). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate; nickel dibromide; In N,N-dimethyl-formamide; at 100℃; for 2.5h; | General procedure: 4-Iodotoluene (1.0 mmol, 0.21 g) was added to a flask equipped with Ph3SnCl (0.4 mmol, 0.15 g), NiBr2 (16.0 mol%, 0.034 g), K2CO3 (3.0 mmol, 0.29 g), and Cr(CO)6 (1.0 mmol, 0.22 g) in DMF (3.0 mL) and the resulting mixture was heated in an oil bath at 100 C and stirred for 2.7 h. Progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature, then H2O (10 mL) was added and the mixture was transferred to a separatory funnel. The aqueous phase was further washed with EtOAc (3×10 mL) and the combined organic phases were dried over anhydrous Na2SO4 and then filtered. Column chromatography of the obtained residue on silica gel (n-hexane/EtOAc=20:1) gave the desired ketone in 89% yield (0.11 g) (Table4, entry 2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium carbonate; nickel dibromide; In N,N-dimethyl-formamide; at 100℃; for 2.5h; | General procedure: 4-Iodotoluene (1.0 mmol, 0.21 g) was added to a flask equipped with Ph3SnCl (0.4 mmol, 0.15 g), NiBr2 (16.0 mol%, 0.034 g), K2CO3 (3.0 mmol, 0.29 g), and Cr(CO)6 (1.0 mmol, 0.22 g) in DMF (3.0 mL) and the resulting mixture was heated in an oil bath at 100 C and stirred for 2.7h. Progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature, then H2O (10 mL) was added and the mixture was transferred to a separatory funnel. The aqueous phase was further washed with EtOAc (3×10 mL) and the combined organic phases were dried over anhydrous Na2SO4 and then filtered. Column chromatography of the obtained residue on silica gel (n-hexane/EtOAc=20:1) gave the desired ketone in 89% yield (0.11 g) (Table4, entry 2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.3 g | With titanium tetrachloride; zinc; In tetrahydrofuran; at 80℃;Inert atmosphere; | In a 250 mL flask equipped with a stirrer zinc powder (2.54 g, 40 mmol) and anhydrous THF (150 mL) were added. TiCl4 (5 mL, 50 mmol) was added slowly into the above mixture at -78C under an atmosphere of nitrogen. After returning to room temperature, the mixture was heated to reflux for 4 h. Subsequently, 4-bromobenzophenone (2.59 g, 10 mmol) and <strong>[90-93-7]4,4'-bis(diethylamino)benzophenone</strong>(3.24 g, 10 mmol) were added after the reaction mixture was cooled to room temperature. Then the resulting mixture was heated to 80C and refluxed overnight. The reaction was quenched with 10% K2CO3 aqueous solution and extracted with CH2Cl2. The combined organic layers were washed with water for three times and dried over anhydrous magnesium sulfate. After filtration and solvent evaporation, the crude product was purified by silica-gel column chromatography using dichloromethane/petroleum ether as eluent to yield a light yellow powder (1.3 g). 1H NMR (600 MHz, CDCl3) delta (ppm): 7(m, 7H), 6.82 (d, 6H), 6.41 (d, 4H), 3.27 (m, 8H), 1.045 (d, 12H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 110℃; for 24h;Inert atmosphere; Reflux; | M 8 synthetic: under the protection of the argon, will be 4-polybromide benzophenoneoxime (10mmol, 2 . 77g), M 1 (20mmol, 3 . 02g) input 250 ml in the reaction bottle of the three-port, by adding 100 ml of toluene to dissolve them. After dissolving, butyl sodium alcoholate joins uncle sequentially (4.8g, 50mmol), three extra butyl phosphine (0.5 ml, 1M/L) and palladium acetate (112 mg, 0 . 5mmol), system is greenish black. After finishing the feeding, heating to 110 C, reflux, reaction 24h. After the reaction, water washing after methylene chloride extraction, column separation to obtain the yellow solid 2.74g, yield 83% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With (PAd2-DalPhos)NiCl(o-tol); sodium t-butanolate In toluene at 90℃; for 18h; Inert atmosphere; Glovebox; Sealed tube; | |
80 %Chromat. | With bis(1,5-cyclooctadiene)nickel (0); CyPAd-DalPhos; sodium 2,2,2-trifluoroacetate; 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 110℃; for 18h; Inert atmosphere; Sealed tube; Glovebox; | N-Arylation of Amides with Aryl Electrophiles (Figures 3 and4); General Procedure General procedure: In a N2-filled glovebox, a screw-capped vial containing a magneticstirrer bar was charged with Ni(COD)2 (5 mol%), CyPAd-DalPhos (5 mol%), the appropriate aryl (pseudo)halide (0.45mmol, 1.0 equiv, 0.12 M), DBU (2.0 equiv), NaTFA (2.0 equiv),and the appropriate amide (1.1 equiv), followed by the additionof toluene (3.75 mL). The vial was sealed with a cap containing aPTFE septum, removed from the glovebox, and placed in a temperature-controlled aluminum heating block set to 100 °C for 18h, with magnetic stirring. The vial was then removed from theheating block and left to cool to rt. The crude reaction mixturewas filtered through a short plug of Celite and silica gel (3:1v/v), eluting with EtOAc. The volatile materials were evaporatedin vacuo, and the crude product was purified by flash-columnchromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9%; 90% | With nickel(II) bromide dimethoxyethane; zinc; 1,2-bis-[(2,6-diisopropylphenyl)imino]acenaphthene; In tetrahydrofuran; at 70℃; for 24h; | General procedure: Activated zinc (75 mg, 1.15 mmol), NiBr2(DME) (15.4 mg, 0.05 mmol), and ligand L12 (0.05 mmol) were placed into a 8-mL glass vial using an atmosphere controlled glove box. Then, 0.2 M solution of benzaldehyde (5 mL, 1 mmol) in THF and aryl halide (1.15 mmol) were added to this mixture. The reaction mixture was magnetically stirred at 70 C, the target product was isolated from the reaction mixture by column chromatography on silica gel 60 A (40-63 um). |
44%; 10% | With nickel(II) bromide dimethoxyethane; N,N'-di-tert-pentyl-1,4-diaza-1,3-butadiene; lithium chloride; zinc; In tetrahydrofuran; at 70℃; for 24h; | General procedure: Activated zinc (75 mg, 1.15 mmol), LiCl (21.3 mg, 0.05 mmol), NiBr2(DME) (15.4 mg, 0.05 mmol), and ligand L4 (0.05 mmol) were placed into a 8-mL glass vial using an atmosphere controlled glove box. Then, 0.2 M solution of benzaldehyde (5 mL, 1 mmol) in THF and aryl halide (1.15 mmol) were added to this mixture. The reaction mixture was magnetically stirred at 70 C, the target product was isolated from the reaction mixture by column chromatography on silica gel 60 A (40-60 mesh). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tris-(dibenzylideneacetone)dipalladium(0); tributylphosphine; sodium t-butanolate; In toluene; for 24h;Inert atmosphere; Reflux; | 250ml of four bottles, in the atmosphere of nitrogen,0.01 mol of 4-bromobenzophenone was added,0.015 mol of intermediate B, 0.02 mol of sodium tert-butoxide,5 x 10-5 mol Pd2 (dba) 3,5 x 10-5 mol tri-tert-butylphosphine,150ml toluene, heated to reflux for 24 hours, sampling point plate,The reaction was complete; natural cooling, filtration, the filtrate was steamed and passed through a silica gel column to give the target product with 99.4% purity and 80% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With caesium carbonate; In dimethyl sulfoxide; at 25℃; for 1.0h;Inert atmosphere; UV-irradiation; | A 25 mL storage flask was charged with a stir bar, flame dried under vacuum and back filled with nitrogen three times. The flask was then charged with Cs2CO3 (97.7 mg, 0.3 mmol, 1.5 eq.), (4-bromophenyl)(phenyl)methanone (52.2 mg, 0.2 mmol, 1.00 eq.), p-Toluenethiol (37.3 mg, 0.3 mmol, 1.5 eq.) and 1.5 mL DMSO. The reaction mixture was evacuated and purged with inert gas (N2) three times. The reaction mixture was then placed into an LED-lined beaker and stirred with an air gas tube for cooling. After stirred for 1 hour, the reaction mixture was washed with water, extracted with EtOA and concentrated in vacuum. The product was isolated by flash chromatography (1:6 EtOAc:hexanes) as white solid (X=Br, 55 mg, 90%). Physical State: white solid; Rf=0.4 (silica gel, 1:5 EtOAc:hexanes); 1H NMR (300 MHz, CDCl3) delta 7.77-7.74 (m, 2H), 7.70-7.66 (m, 2H), 7.60-7.54 (m, 1H), 7.50-7.42 (m, 4H), 7.25-7.17 (m, 4H), 2.40 (s, 3H); 13C NMR (75 MHz, CDCl3) delta 195.7, 145.3, 139.3, 137.7, 134.5, 134.4, 132.2, 130.7, 130.5, 129.8, 128.2, 128.0, 126.5, 21.3; HRMS (ESI-TOF): m/z calcd. for C20H16OS ([M+H]+) 305.1000, found 305.0998. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83.5% | Synthesis of BP - DPAC. The 4 - bromo benzophenone (0.055 g, 0 . 21 mmol), 9, 10 - dihydro - 9, 9 - diphenyl acridine (0.077 g, 0 . 23 mmol), tri-tert-butylphosphonium tetrafluoroboronate(0.02 g), sodium tertiary butyl alcohol (0.2 g) adding 100 ml three-neck bottle in, vacuum replace the nitrogen three times, after the added into the dry toluene 15 ml. Stir at room temperature 15 min, adding Pd2(dba)3 (0.02 G), 120 C under stirring 18 h. Ling actually to the room temperature, over-elution column (for eluting DCM), turns on lathe does, [...] powder sample, carrying out column chromatography separation. For methanol reprecipitation, to obtain white solid 0.09 g (Y=83.5%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 90℃;Inert atmosphere; | General procedure: Under a nitrogen atmosphere, 100 ml of toluene, 1 g of intermediate 10 (2.99 mmol), 1.40 g of dimethyl acridine (2.5 equ) were added to a three-necked flask, and 0.90 g of sodium t-butylate was added thereto with stirring, followed by addition of 59.8. Mg palladium acetate, tri-tert-butylphosphine, reacted at 90 C overnight. The temperature was lowered, and the organic phase was extracted with dichloromethane, dried and passed through a column. The product was obtained in 1.50 g, yield 68%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With [2,2]bipyridinyl; [NiCl(bpy)(IPr)]; sodium t-butanolate In tetrahydrofuran at 80℃; for 48h; Glovebox; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With [2,2]bipyridinyl; [NiCl(bpy)(IPr)]; sodium t-butanolate In tetrahydrofuran at 80℃; for 48h; Glovebox; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: N-(4-methoxyphenyl)phenylamine With N,N,N,N,N,N-hexamethylphosphoric triamide; potassium <i>tert</i>-butylate at 60℃; for 2h; Inert atmosphere; Stage #2: (4-bromophenyl)(phenyl)methanone at 120℃; for 6h; Inert atmosphere; | 5 Example 5: Preparation of a compound of formula (VIII) 3.98 g (20 mmol) of 4-methoxyphenylaniline and 2.47 g (22 mmol) of potassium t-butoxide were placed in a 250 mL two-necked flask, protected with nitrogen, and 15 mL of HMPA was added thereto, and the mixture was stirred at 60 ° C for 2 h. 5.72 g (22 mmol) of 4-bromobenzophenone was added in portions and reacted at 120 ° C for 6 h. The mixture was extracted with saturated brine and EtOAc. The organic solvent was distilled off under reduced pressure to give a crude material. Purified by column chromatography,Ethyl acetate / petroleum ether was used as an eluent to give an orange powder, yield 86%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | To a solution of 2-bromotriphenylamine (1.62 g, 5.00 mmol) inanhydrous tetrahydrofuran (40 mL) was added 5.50 mmol solution of nbutyllithiumin hexane at -78 C under a nitrogen atmosphere. Afterstirring for 1 h, 4-bromobenzophenone (1.44 g, 5.50 mmol) was addedand the mixture was stirred at -78 C for 1 h, with the temperaturegradually rising to room temperature overnight. Then water was addedto the mixture to quench the reaction. The mixture was extracted withdichloromethane and water, and the organic layer was dried over anhydroussodium sulfate, filtered and evaporated. The resulting crudeintermediate was dissolved in 25 mL acetate acid and 2.5 mL hydrochloricacid. The solution was refluxed for 4 h and then cooled to roomtemperature and filtered. The mixture was purified by silica gel columnchromatography using petroleum ether as eluent. The 9-(4-bromophenyl)-9,10-diphenyl-9,10-dihydropyridine (BDPDHR) was collectedas a white powder (1.63 g, 67% yield) and dried at 40 C overnight in avacuum oven before use. M.p.: 233.5-234.1 C. 1H NMR (400 MHz,DMSO-d6, ppm): 7.64 (dd, J=8.3, 6.9 Hz, 2H), 7.59-7.49 (m, 3H), 7.31(dq, J=12.8, 7.0 Hz, 3H), 7.08 (dtd, J=8.5, 3.7, 1.5 Hz, 4H), 6.95-6.81 (m, 6H), 6.76 (dd, J=7.8, 1.5 Hz, 2H), 6.33 (dd, J=8.3, 1.2 Hz,2H); 13C NMR (126 MHz, Chloroform-d) delta 145.98, 145.71, 142.12,140.50, 132.13, 131.22, 130.73, 130.59, 130.37, 129.83, 128.81,128.33, 127.77, 127.07, 126.50, 120.25, 114.11, 56.43. FT-IR (KBrpellet) nu: 3060, 3031, 1591, 1487, 1470, 1453, 818, 750 cm-1; MALDITOF-MS m/z: calc. for C31H22BrN [M-H] +: 487.1; found 487.1; Anal.calcd (%) for C31H22BrN: C, 76.23; H, 4.54; N, 2.87. Found: C, 76.65; H,4.45; N, 7.91 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With potassium carbonate In acetonitrile at 50℃; for 12h; | 5.0 Exact experimental procedure for the synthesis of 4-methyl-1,1'-biphenyl (3c) General procedure: The acetonitrile (3 mL) were added in to the oven dried 25mL R.B.F containing compound 1a (54.07mg, 0.5 mmol), followed by addition of K2CO3 (152.02 mg, 2.2 equiv), catalyst (2.39 mg, 2 mol% 44.48w/v), compound 2c (0.55 mmol, 119.91 mg, 1.1 equiv). The reaction mixture was stirred at 50 °C for 16 h, after complete conversion of starting material (indicated by TLC), the solvent was evaporated by rotary evaporator and crude compound was purified by column chromatography (eluent: 2% EA/Hexane) to get the compound 4-methyl-1,1'-biphenyl (3c, 73.08 mg, 87%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With palladium nanoparticles-supported custard apple peels-ash catalyst In ethanol; water at 20℃; for 0.25h; Green chemistry; | 2.4 General Experimental Procedure forSuzuki-Miyaura Coupling Reaction General procedure: All the Suzuki-Miyaura coupling reactions were carriedout under air atmosphere in dried glassware. In a 25 mLround bottom flask equipped with a magnetic stirrer, arylbromides (1.0 mmol), arylboronic acids (1.2 mmol), Pd/CAP-ash (5 wt%) and water:ethanol (3 mL) were placed.The resulting reaction mixtures were stirred at room temperaturefor appropriate time. The progress of reactionswas monitored by TLC. After completion of reactions,the reaction mixtures were extracted with ethyl acetate(2 × 10 mL). The organic layers were washed with brine(2 × 10 mL). The combined organic layer was collected,dried over Na2SO4and concentrated in vacuo. The residuewas purified by silica gel column chromatography usingn-hexane:EtOAc (9:1 v/v) to give the corresponding biarylcompound. The desired products were characterized bycomparing 1H, 13C NMR spectral data with authenticsamples. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
29.96% | With copper(I) oxide; potassium carbonate; N,N`-dimethylethylenediamine; In N,N-dimethyl-formamide; at 150℃; for 1h;Microwave irradiation; | General procedure: The 1-01 (180 mg, 0.67mmol), 3-01 (126 mg, 0.61mmol), Cu 2O (54 mg, 0.73mmol), K 2CO 3 (185 mg, 1.34mmol) and N 1, N 2-dimethylethane-1,2-diamine (118 mg, 1.34mmol) were mixed in DMF (5mL). The reaction mixture was reacted in microwave at 150C for 1h. The reaction mixture was diluted by water, and the aqueous was extracted by EA for several times. The organic layers were combined, washed with water, brine in turn, dried over Na 2SO 4. Filtrated and evaporated to remove solvent to give crude product, which was purified by silica gel chromatography (PE to PE: EA=2: 1) to give 147 mg 3-02 as light pink powder in a yield of 61.8%. Mass (m/z) : 396.27 [M+H] +. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In N,N-dimethyl-formamide at 100℃; for 24h; |
Tags: 90-90-4 synthesis path| 90-90-4 SDS| 90-90-4 COA| 90-90-4 purity| 90-90-4 application| 90-90-4 NMR| 90-90-4 COA| 90-90-4 structure
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