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CAS No. : | 612-71-5 | MDL No. : | MFCD00003060 |
Formula : | C24H18 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | SXWIAEOZZQADEY-UHFFFAOYSA-N |
M.W : | 306.40 | Pubchem ID : | 11930 |
Synonyms : |
|
Num. heavy atoms : | 24 |
Num. arom. heavy atoms : | 24 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 102.75 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -3.34 cm/s |
Log Po/w (iLOGP) : | 3.56 |
Log Po/w (XLOGP3) : | 6.8 |
Log Po/w (WLOGP) : | 6.69 |
Log Po/w (MLOGP) : | 7.19 |
Log Po/w (SILICOS-IT) : | 6.68 |
Consensus Log Po/w : | 6.18 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 1.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -6.57 |
Solubility : | 0.0000833 mg/ml ; 0.000000272 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -6.61 |
Solubility : | 0.0000756 mg/ml ; 0.000000247 mol/l |
Class : | Poorly soluble |
Log S (SILICOS-IT) : | -9.93 |
Solubility : | 0.0000000357 mg/ml ; 0.0000000001 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.94 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P233-P260-P261-P264-P271-P280-P302+P352-P304-P304+P340-P305+P351+P338-P312-P321-P332+P313-P337+P313-P340-P362-P403-P403+P233-P405-P501 | UN#: | N/A |
Hazard Statements: | 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 |
---|---|---|
13.3% | With iodine; sodium hydrogencarbonate; sodium thiosulfate; acetic acid In toluene | Example 1 (Preparation of 1,3,5-tris(4-iodophenyl)benzene) 116 g of 1,3,5-triphenylbenzene, 19 mL of concentrated sulfuric acid as a catalyst, and 1520 mL of 80percent acetic acid as a reaction solvent were placed in a 2 L capacity flask, and the mixture was heated to a temperature of 70°C with stirring. Then, 143 g of iodine and 69.3g of orthoperiodic acid were added 1/10 at a time over about 2 hours and a half into a flask, followed by reacting for 6 hours with stirring, to obtain a reaction product containing white precipitates. Toluene was added to the reaction mixture to dissolve the precipitates therein, and the toluene layer was separated from the water layer. The toluene layer was washed with an aqueous solution of sodium hydrogencarbonate and then with an aqueous solution of sodium thiosulfate. The organic layer was then concentrated and subjected to silica gel chromatography and the reaction product was separated, which was recrystallized from ethanol/toluene/, thereby providing 34.6g of desired 1,3,5-tris(4-iodophenyl)benzene as white needle crystals. The yield was 13.3percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With toluene-4-sulfonic acid In neat (no solvent) at 80℃; for 12h; | |
85% | With toluene-4-sulfonic acid In 1,2-dichloro-ethane at 80℃; for 12h; | Examples of specific preparation methods 1 mmol of β-methylchromone and 0.1 mmol of p-toluenesulfonic acid were added to it 0.2 mL dichloroethane solvent, Stir at 80 ° C for 12 hours. After the reaction, To the reaction system was added 2 mL of dichloromethane and 3 mL of saturated aqueous sodium bicarbonate solution, Then followed by extraction, Dried over anhydrous sodium sulfate, filter, Vacuum desolventizing, Column chromatography and other operations,1,3,5-triphenylbenzene was obtained.T he yield is 85% White solid, |
65% | With iron(III) trifluoromethanesulfonate In 1,2-dichloro-ethane at 90℃; for 12h; |
bei der Destillation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With nickel kieselguhr; methyl cyclohexane at 200℃; Hydrogenation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With samarium(III) chloride; acetyl chloride In pentane for 2h; Ambient temperature; | |
With acetyl chloride | ||
Multi-step reaction with 2 steps 1: iodine 2: hydrogen chloride / 180 - 190 °C |
Multi-step reaction with 3 steps 1: iodine 2: Sieden |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.8% | With chloro-trimethyl-silane In butan-1-ol; benzene at 40℃; for 20h; Inert atmosphere; regioselective reaction; | |
93% | With (1,2-dimethoxyethane)dichloronickel(II); tetrahydroxydiboron In acetonitrile at 100℃; for 12h; Inert atmosphere; Schlenk technique; Sealed tube; regioselective reaction; | |
93% | With (1,2-dimethoxyethane)dichloronickel(II); tetrahydroxydiboron In acetonitrile at 100℃; for 12h; Schlenk technique; Inert atmosphere; | 1-4 Example 1: Synthesis of 1,3,5-trisubstituted benzene compound (2a): (MeCN is used as a solvent for the synthesis of trisubstituted aryl compound 2a). Take the magneton into a 25mL Schlenk bottle, add NiCl2·DME (22.0mg, 0.1mmol, 0.1equiv), B2(OH)4 (26.9mg, 0.3mmol, 0.3equiv) in the reaction flask, and use it on the double-row tube Replace with argon three times, then add MeCN (5.0 mL), add phenyl acetylene (1a, 110.0 μL, 1.0 mmol, 1.0 equiv) dropwise with a micro-syringe, then move the reaction tube into an oil bath and react at 100°C for 12 hours. After the reaction was completed, the reaction solution was transferred to a round bottom flask, and the acetonitrile solvent was removed by rotary evaporation. Then, 5 mL of water was added and extracted with 10 mL of ethyl acetate. The aqueous phase was extracted three times with ethyl acetate (5 mL x 3), and the organic phases were combined. , The organic phase was washed with 10mL water, saturated sodium chloride aqueous solution (10mL x 2), then dried with anhydrous NaSO4, filtered, the filtered organic phase was rotary evaporated, and the concentrated liquid after rotary evaporation was transferred to the silica gel column. 94.5 mg (white solid) of pure product was obtained by column chromatography (PE). Yield: 93% |
91% | With indium(III) chloride; 2-Iodophenol In chlorobenzene for 24h; Reflux; regioselective reaction; | |
90% | In toluene for 0.0833333h; | |
90% | With carbon dioxide; copper dichloride; palladium dichloride In water at 20℃; for 24h; | |
87% | With toluene-4-sulfonic acid In neat (no solvent) at 60 - 140℃; for 14h; Green chemistry; regioselective reaction; | |
86% | With Cr2[μ-HC(N-2,6-iPr2C6H3)2]2 In diethyl ether at 20℃; for 3h; | |
76% | With trifluorormethanesulfonic acid; silver trifluoromethanesulfonate In water; toluene at 40℃; for 8h; Green chemistry; | General procedure for eq1and eq2 General procedure: (1) A test tube (15 mL) was chargedwith alkynes 2 (0.05mmol), AgOTf(0.025 mmol, 5 mol %), HOTf (0.05 mmol, 10 mol%), H2O(0.2 mL), and toluene (3 mL) were added. The mixture was stirred at 40 oC in air for 8 hours, the reaction was cooleddown to room temperature. The solvent was removed under reducedpressure, and the products were isolated by column chromatography onsilica gel (hexane/AcOEt = 20:1). |
40% | With (acetonitrile)[2-di-tert-butyl(2′,4′,4′,6'-triisopropylbiphenyl)phosphine]gold(I) hexafluoroantimonate In 1,2-dichloro-ethane at 50℃; for 16h; Inert atmosphere; | |
20% | In dichloromethane | |
20% | With {NbCl2(dimethyl selenide)}2(μ-Cl)2(μ-dimethyl selenide) In dichloromethane at 20℃; for 1h; Schlenk technique; Inert atmosphere; regioselective reaction; | 4.3 Catalytic cyclotrimerization of phenylacetylene with complexes General procedure: Phenylacetylene in 200-fold equivalent was added to each complexes 1a-2g (50mg) in any solvent (20mL), and the mixture was stirred at any temperature. The solution caused the formation of a precipitate. We calculate the completion of the reaction determined by the comparison of literature data [15]. The solution was removed by filtration and the resultant filtrate was concentrated to dryness. The crude product was washed with hexane and dried under reduced pressure. The results are collected in Tables2-4, respectively. |
at 0℃; ΔS; ΔH; ΔG; various temperatures.; | ||
With water; methylamine at 260℃; | ||
With triphenyl phosphite; dicobalt octacarbonyl; carbon monoxide; bicyclo[2.2.1]hepta-2,5-diene In 1,2-dimethoxyethane at 120℃; for 24h; Yield given; | ||
Multi-step reaction with 2 steps 1: Einleiten von HBr 2: anhydrous ethanol / 55 °C | ||
With [(pentamethylcyclopentadienyl)Co(indenyl)]; zinc In toluene at 80℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With trichloro(trifluoromethanesulfonato)titanium(IV) at 90 - 100℃; for 10h; | |
98% | With zirconocene bis(perfluorooctanesulfonate) In toluene at 110℃; for 3h; chemoselective reaction; | |
98% | With [Cp2Zr(OSO2C8F17)2]*3H2O*THF In toluene at 110℃; for 3h; |
97% | With nano-silica sulfuric acid In neat (no solvent) at 90℃; for 0.25h; Microwave irradiation; | |
95% | With solid phase supported H3PW12O40 at 90℃; for 0.3h; Microwave irradiation; Neat (no solvent); | |
95% | With tris(hydrogensulfato)boron In neat liquid at 100℃; for 5h; Green chemistry; | |
95% | With 4-n-butyl-4-(3-sulfopropyl)thiomorpholinium 1,1-dioxide trifluoromethanesulfonate at 100℃; for 3h; Green chemistry; | |
95% | With nanoclinoptilolite modified with hexadecyltrimethylammonium bromide In neat (no solvent) at 100℃; for 2h; Green chemistry; | |
94% | With para-dodecylbenzenesulfonic acid In neat (no solvent) at 130℃; for 3h; Green chemistry; | 3 General procedure for the synthesis of 1,3,5-triarylbenzenes General procedure: A mixture of acetophenone (3 mmol) and DBSA (0.6 mmol) was heated at 130 °C in a preheated oil bath for 3-8 hours. After completion of the reaction as indicated by thin layer chromatography (TLC), the reaction mixture was cooled to room temperature and diluted with equal volumes of saturated solution of NaHCO3 and brine (5 mL + 5 mL). The resulting solution was extracted with ethyl acetate (10 mL × 3) and the organic layers were combined, dried over anhydrous Na2SO4 and evaporated under reduced pressure to dryness. The crude product obtained was purified by silica gel (60-120 mesh size) column chromatography using 1-2% ethyl acetate in heptane as the eluent to afford the desired products in pure form. |
94% | With Wells-Dawson heteropoly acid H6P2W18O62 immobilized on Nanoclinoptilolite In neat (no solvent) at 100℃; for 3h; Green chemistry; | |
94% | With sulfated tungstate In neat (no solvent) at 130℃; for 10h; | 3. General experimental procedure for the synthesis of 1,3,5-triarylbenzenes General procedure: In round bottom flask equipped with condenser a mixture of aryl alkyl ketones (3mmol) and sulfated tungstate (20 wt. %) were stirred at 130 C, the progress of the reaction was monitored by TLC. After disapperance of the aryl alkyl ketones and the reaction was continued for additional time of 2 h. The reaction mixture was cooled, diluted with 30 mL of ethyl acetate and filtered to recover the catalyst. The filtrate was washed with 10 mL of water, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel ( 60-120) with (PE:EA=9:1) as eluent to get pure 1,3,5-arylenzenes. |
91% | With Montmorillonite K 10; anhydrous tin tetrachloride; toluene-4-sulfonic acid for 0.1h; microwave irradiation; | |
91% | With toluene-4-sulfonic acid In lithium hydroxide monohydrate at 130℃; for 10h; Neat (no solvent); chemoselective reaction; | |
91% | With toluene-4-sulfonic acid In neat (no solvent) at 130℃; for 12h; | |
90% | With magnetic MIL-101 SO3H nanocatalyst In toluene at 100℃; for 3h; | |
90% | With 18-crown-6 ether; potassium hydroxide In 1,4-dioxane at 130℃; for 12h; | 1 mmol of acetophenone, 1 mmol of potassium hydroxide,1 mmol of 18-crown-6 and 0.5 ml of 1,4-dioxane were mixed together,The reaction was stirred at 130 ° C for 12 hours. After the end of the reaction,Washed, concentrated, purified by column chromatography,1,3,5-triphenylbenzene was obtained. The yield was 90%, white solid |
88% | With toluene-4-sulfonic acid In neat (no solvent) at 60 - 140℃; for 14h; Green chemistry; regioselective reaction; | |
87% | With 12-molybdophosphoric acid In ethanol for 5h; Reflux; | |
87% | With Ethane-1,2-diamine; trifluoroacetic acid In nitromethane for 48h; Reflux; | 2. General Procedure for triple condensation reaction of aryl methyl ketones catalyzed by amine and trifluoroacetic acid. General procedure: To a solution of aryl methyl ketone (1, 1.5mmol) in dry nitromethane (1.5mL) was added trifluoroacetic acid (0.045 mL, 0.6mmol) and ethylenediamine (0.020 mL, 0.3mmol). The mixture was stirred at reflux and detected by TLC. After completion of the reaction, the reaction mixture was cooled to room temperature, quenched with saturated NH4Cl, extracted with Ethyl acetate. Combined organic layers were washed with brine, dried over Na2SO4, and concentrated. The residue was purified by silica gel column chromatography to give product 2. |
87% | With thionyl chloride; ethanol for 1.5h; Reflux; | |
86% | With silicium tetrachloride In ethanol for 6h; Ambient temperature; | |
86% | With silicium tetrachloride In ethanol for 6h; | |
86% | With silicium tetrachloride In ethanol at 20℃; | |
86% | With p-toluene sulfinic acid; anhydrous tin tetrachloride In pentan-1-ol for 3h; microwave irradiation; | |
85% | With thionyl chloride; ethanol for 1h; Heating; | |
85% | In ethanol for 1h; Heating; | |
85% | With H5PW10V2O40 supported on γ-Al2O3 nanoparticles In neat (no solvent) at 90℃; for 2.5h; Green chemistry; | |
83% | With silicium tetrachloride In ethanol at 20℃; for 20h; Inert atmosphere; | |
83% | With copper(II) bis(trifluoromethanesulfonate) In toluene at 100℃; for 14h; | |
82% | With trifluorormethanesulfonic acid; oxygen In neat (no solvent) at 120℃; for 12h; Green chemistry; chemoselective reaction; | |
80% | With bismuth(III) trifluoromethanesulfonate tetrahydrate In toluene for 5h; Reflux; | |
80% | With anhydrous zinc chloride In neat (no solvent) at 140℃; for 24h; Schlenk technique; Inert atmosphere; | |
78% | With iodine; 1,2-diamino-benzene In chlorobenzene at 120℃; for 12h; Sealed tube; chemoselective reaction; | General Procedure for synthesis of 4 General procedure: Acetophenone 1 (1mmol), 2-amino aniline 2a (108mg, 1mmol), I2 (13mg, 5mol%), PhCl (3 mL) were added to a reaction tube. The reaction mixture was stirred in a sealed tube at 120 °C for 12 h. The reaction was monitored by TLC. Once the reaction was completed, the reaction mixture was treated with H2O (15.0 mL) and EtOAc (8.0 mL). The organic phase was then separated, and the aqueous phase was extracted with EtOAc (3 x 8 mL). The combined organic phase was dried over Na2SO4, then the solvent was removed under a reduced pressure and the remaining residue was purified by column chromatography. |
73% | With toluene-4-sulfonic acid; sulphur at 120℃; for 16h; Sealed tube; Inert atmosphere; | |
65% | With titanium(IV) tetrachloride In toluene Heating; | |
63% | With silicium tetrachloride In ethanol at 0 - 40℃; for 20h; Inert atmosphere; | |
62% | With hydrogenchloride In benzene at 20℃; for 1h; | |
60% | With orthoformic acid triethyl ester | |
60% | With Amberlyst 15 In toluene at 110 - 120℃; for 10h; | |
39% | With copper chloride (II) at 140℃; for 4h; | |
36% | With iron(III) trifluoromethanesulfonate In 1,2-dichloro-ethane at 90℃; for 12h; Sealed tube; | |
32% | With silicium tetrachloride In ethanol Heating; | |
23% | With anhydrous silver tetrafluoroborate In 1,2-dichloro-ethane at 70 - 80℃; for 72h; | |
16% | With N-benzyl-N-isopropylpropan-2-amine; iodine; titanium(IV) tetrachloride In 1,2-dichloro-ethane at 25℃; for 6h; | |
at 500℃; Leiten ueber Silicagel; | ||
at 300℃; | ||
With formamide; anhydrous zinc chloride at 170 - 180℃; | ||
With potassium pyrosulfate; sulfuric acid at 80℃; | ||
With hydrogenchloride at 100℃; unter Druck; | ||
With mesoporous silica at 500℃; | ||
With beryllium(II) chloride; benzene at 120℃; | ||
With iodine | ||
With iodine; aniline | ||
With fired clay at 270 - 300℃; unter Druck; | ||
With diethyl ether; ethyl iodide; aluminium | ||
With aluminum(III) oxide at 200 - 300℃; | ||
With potassium pyrosulfate; sulfuric acid at 45℃; | ||
With hydrogenchloride | ||
With Benzenamine hydrochloride; aniline at 170 - 175℃; | ||
With titanium(III) trichloride 1.) r.t., 5 d; 2.) 30 min; Yield given. Multistep reaction; | ||
Multi-step reaction with 2 steps 1: alcohol 2: acetyl chloride | ||
720.1 mg | With CF3O3S(1-)*C48H36N4(2-)*Rh(3+) at 200℃; for 24h; Inert atmosphere; Darkness; Neat (no solvent); | |
With thionyl chloride In ethanol | ||
Multi-step reaction with 2 steps 1: 4-chloro-phenol; sulfuric acid / 30 - 50 °C 2: toluene-4-sulfonic acid / neat (no solvent) / 12 h / 80 °C | ||
With iodine at 180 - 190℃; | ||
With orthoformic acid triethyl ester; trifluoroacetic acid In neat (no solvent) at 100℃; for 1h; | ||
With thionyl chloride; ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With (DMSC)TiCl2; sodium In benzene-d6 at 80℃; for 0.5h; | |
90% | With Mo-complexes In acetone at 0℃; for 36h; | |
1: 90% 2: 10% | With [Rh(5,5′-bis[di(3,5-di-tert-butyl-4-methoxyphenyl)phosphino]-4,4′-bi-1,3-benzodioxole)(MeOH)2](BF4) at 25℃; for 0.75h; Inert atmosphere; Schlenk technique; |
1: 72% 2: 28% | With C45H59CoFeN4Si2 In toluene at 100℃; for 48h; Inert atmosphere; | |
1: 24% 2: 71% | In water at 380℃; for 2h; | |
1: 70% 2: 22% | With Ni2(N,N’-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis(1-(pyridin-2-yl)methanimine))(diphenylacetylene) In benzene-d6 at 50℃; for 24h; Inert atmosphere; Glovebox; | |
1: 7.2% 2: 64.8% | In benzene for 1h; Heating; | |
1: 51% 2: 30% | In methanol; water at 75℃; for 19h; | |
1: 48% 2: 49% | With [U(N[SiMe3]2)3] In benzene-d6 at 75℃; for 72h; Sealed tube; regioselective reaction; | |
1: 42% 2: 42% | With [{Ni(μ-[(2,4-Me2C6H3)NC(Me)]2)}3] In hexane at 100℃; for 5h; Sealed tube; Inert atmosphere; | |
1: 29% 2: 35% | In diethylamine for 24h; Heating; | |
In benzene at 60℃; for 1h; other halides of Nb and Ta, various solvents and temperatures; | ||
With Ti(η6-toluene){(μ-Br)2(AlBr2)}2 In toluene at 80℃; for 15h; further temperature; | ||
With uranium for 0.166667h; Yield given. Yields of byproduct given; | ||
In tetrachloromethane at 60℃; for 1h; Yield given. Yields of byproduct given; | ||
With (8-hydroxyquinoline)Rh(CO)AsPh3 In ethanol at 60 - 70℃; for 6h; Yield given. Yields of byproduct given; | ||
With hexachlorodisilane at 200℃; for 15h; Yield given. Yields of byproduct given; | ||
In benzene at 80℃; for 3h; | ||
In benzene at 60℃; for 1h; Yield given. Yields of byproduct given; | ||
With Mo-complexes In toluene at 0℃; | ||
With titanium; zirconium In tetrahydrofuran at 25℃; for 3h; other alkynes; var. solvents and time; other metals as catalysts; | ||
With zirconium In tetrahydrofuran at 25℃; for 3h; Yield given; Yields of byproduct given. Title compound not separated from byproducts; | ||
With indium; molybdenum(V) chloride In 1,2-dimethoxyethane at 80℃; for 1h; | ||
With molybdenum(V) chloride; aluminium In 1,2-dimethoxyethane at 50℃; for 3h; | ||
With troppPh; cobalt(II) bromide; zinc at 90℃; | ||
In tetrahydrofuran at 20℃; for 46h; Title compound not separated from byproducts; | ||
In chloroform at 62℃; for 16h; | ||
With dicarbonylcyclopentadienylcobalt; supercritical CO2 at 90℃; for 24h; Irradiation; | ||
With [2,3-[C5(CH3)5]Rh}2B3H7] In tetrahydrofuran at 22℃; for 24h; Title compound not separated from byproducts; | ||
1: 94 % Chromat. 2: 6 % Chromat. | With [Mo(CO)3(1-methyl imidazole)3] In toluene at 60℃; for 8h; | |
In ethanol at 25℃; for 7h; Title compound not separated from byproducts; | ||
With tantalum thiochloride In toluene at 20℃; for 2h; Title compound not separated from byproducts; | ||
1: 99 % Chromat. 2: 1 % Chromat. | With HIr(1,5-cyclooctadiene)(bis(diphenylphosphino)methane) In tetrahydrofuran at 60℃; for 0.25h; Title compound not separated from byproducts; | |
With bis(cyclopentadienyl)titanium dichloride; C14H10Mg(THF)3 In benzene-d6 at 75℃; for 2h; | ||
In various solvent(s) at 155℃; for 20h; | ||
With hexacarbonyl molybdenum; 2-fluorophenol In chlorobenzene Heating; Title compound not separated from byproducts; | ||
In toluene at 25℃; for 20h; Title compound not separated from byproducts; | ||
In dichloromethane at 30℃; for 16h; | ||
With magnesium; zinc(II) iodide; zinc In dichloromethane at 20℃; for 3h; | ||
With sodium In toluene at 20℃; for 20h; | ||
With N,N'-dicyclohexylethylenediimine; zinc(II) iodide; zinc In acetonitrile at 20℃; for 0.25h; | ||
With titanium(IV) isopropylate; chloro-trimethyl-silane; magnesium In tetrahydrofuran at 20℃; for 12h; | ||
In various solvent(s) at 100℃; | ||
With rhodium(III) chloride; N-ethyl-N,N-diisopropylamine In toluene for 12h; Heating; | ||
With tetrachlorosilane; dysprosium(II) iodide In 1,2-dimethoxyethane at 70℃; for 72h; | ||
With silver trifluoromethanesulfonate; 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; zinc In tetrahydrofuran at 20℃; for 0.5h; Title compound not separated from byproducts.; | ||
With rhodium(III) chloride; N-ethyl-N,N-diisopropylamine In toluene for 12h; Heating; | ||
With [1,2-bis(4-methoxyphenylthio)ethane]cobalt dibromide; zinc(II) iodide; zinc In dichloromethane at 25℃; for 0.0833333h; Inert atmosphere; regioselective reaction; | ||
With μ1-carbonyl-η5-cyclopentadienyl-η2-dimethylfumaratecobalt In N,N-dimethyl-formamide at 200℃; for 0.166667h; Microwave irradiation; | ||
With [μN,κP,κC,κN-{2-(i-Pr2PO),6-(CH2NBn)-(C6H3)}Ni]2 In benzene-d6 at 50℃; Inert atmosphere; | ||
With dichloro(2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine)iron(II); zinc(II) iodide; zinc In acetonitrile at 50℃; for 8h; regioselective reaction; | ||
With arachno-[(η5-C5Me5RuCO)2B2H6] In toluene at 75℃; for 36h; Inert atmosphere; | ||
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2 In tetrahydrofuran at 65℃; for 2h; regioselective reaction; | ||
With bis(piperidine)molybdenum tetracarbonyl; tin(IV) chloride In dichloromethane at 20℃; for 24h; Inert atmosphere; stereoselective reaction; | 2.4 Reaction of alkynes in the presence of 2 and SnCl4 General procedure: A dichloromethane solution (15 cm3) of 2 (0.02 g, 0.053 mmol), SnCl4 (0.012 cm3, 0.11 mmol), and an alkyne: PhC≡CH, tBuC≡CH, nBuC≡CH (ca. 0.2-0.3 cm3), in a 1:2:50 molar ratio, was stirred at room temperature for 24 h. All volatile components were then evaporated under reduced pressure at room temperature, and the residue was analyzed by the GC-MS method and NMR spectroscopy, which revealed a ca. 100% conversion of the alkyne and the formation of cyclotrimers as the major products (see Table 1 and Section 2.7.). | |
With cobalt(II) chloride hexahydrate; phthalic acid dimethyl ester; 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; zinc at 50℃; Overall yield = 99 %; | ||
With nido-[(η5-C5Me5Rh)2B6H10] In toluene at 75℃; for 40h; Inert atmosphere; Overall yield = 68 %Spectr.; | General procedure for catalytic process General procedure: Catalytic data for the alkyne cyclotrimerization was shown in Tables 1 and 2. All the alkynes were purchased from Sigma Aldrich and used as received. In a typical reaction, 1 (0.02 g) was dissolved in toluene (15 ml) and alkynes were added to that solution. The resulting reaction mixture was stirred at a temperature range 50-80 °C for 24-60 h (see Tables 1 and 2). The solvent was evaporated in vacuo; residue was extracted into hexane and passed through Celite. After removal of solvent from the filtrate, the residue was subjected to chromatographic work using silica gel TLC plates. Elution with hexane:CH2Cl2 yielded the corresponding benzene derivatives. Note that the formation of cyclotrimerized products and the ratios of the isomers were confirmed by 1H, and 13C NMR and mass spectrometry. The yield of the cyclotrimerized products was determined by 1H NMR spectroscopy employing a reference compound of known weight. | |
With (p-cymene)ruthenium(II) chloride In toluene at 80℃; for 1h; Inert atmosphere; Schlenk technique; Overall yield = 65 %Chromat.; | 2.3. General procedure for the in situ switching between cyclotrimerization and enyne metathesis reactions General procedure: A reactor was charged with [RuCl2(p-cymene)]2 (0.033 mmol, 0.020 g) and phenylacetylene (0.66 mmol, 72 μl) in 3 ml toluene and heated at 80 °C. After 10 min, 2.0 mol equivalent of IPr (0.066 mmol, 0.026 g) was added to the reaction medium and stirred at 80 °C under an ethylene atmosphere (1 atm). Aliquots taken periodically from the reaction mixture were analyzed by GC-MS. | |
With (Me2S)Cl2Ta(μ-Me2S)(μ-Cl)2TaCl2(SMe2) In toluene at 60℃; for 4h; Schlenk technique; Inert atmosphere; Overall yield = 50 %; regioselective reaction; | 4.3 Catalytic cyclotrimerization of phenylacetylene with complexes General procedure: Phenylacetylene in 200-fold equivalent was added to each complexes 1a-2g (50mg) in any solvent (20mL), and the mixture was stirred at any temperature. The solution caused the formation of a precipitate. We calculate the completion of the reaction determined by the comparison of literature data [15]. The solution was removed by filtration and the resultant filtrate was concentrated to dryness. The crude product was washed with hexane and dried under reduced pressure. The results are collected in Tables2-4, respectively. | |
With Nb2(μ-Cl)2(μ-SMe2)Cl4(SMe2)2 In toluene at 70℃; for 4h; Schlenk technique; Inert atmosphere; Overall yield = 54 %; regioselective reaction; | 4.3 Catalytic cyclotrimerization of phenylacetylene with complexes General procedure: Phenylacetylene in 200-fold equivalent was added to each complexes 1a-2g (50mg) in any solvent (20mL), and the mixture was stirred at any temperature. The solution caused the formation of a precipitate. We calculate the completion of the reaction determined by the comparison of literature data [15]. The solution was removed by filtration and the resultant filtrate was concentrated to dryness. The crude product was washed with hexane and dried under reduced pressure. The results are collected in Tables2-4, respectively. | |
With nickel(II) chloride hexahydrate; 2-(1-methyl-2-benzimidazole)-6-(1-(2,6-dimethylphenyl)iminoethyl)pyridine; zinc(II) iodide; zinc In acetonitrile at 20℃; for 1h; Schlenk technique; Overall yield = 94%; | ||
With CpCo(S<SUB>2</SUB>C<SUB>2</SUB>B<SUB>10</SUB>H<SUB>8</SUB>)(CH=CHCO<SUB>2</SUB>Me)<SUB>2</SUB> In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere; Overall yield = 73 %; | General procedures for the alkyne cyclotrimerization General procedure: The corresponding alkyne, the catalyst 1 and toluene (10 mL) were introduced in a schlenk tube and the reaction mixture was stirred at 70 °C or 110 °C for the indicated time (see Table 1 and Scheme 4). The reaction was monitored by regular sampling and analysis by gas chromatography. The resulting arenes were isolated by TLC and confirmed by NMR and mass spectroscopy. | |
With [{Rh(μ-Cl)(1,3-bis-(2,6-diisopropylphenyl)imidazol-2-carbene)(η2-cyclooctene)}2]; triethylamine In benzene-d6 at 40℃; for 16h; Schlenk technique; chemoselective reaction; | ||
With N-[3-(trimethoxysilyl)propyl]-N.N.N-trimethylammonium chloride; tetraethoxy orthosilicate; cetyltrimethylammonim bromide; sodium 4-dodecylbenzenesulfonate In methanol; propan-1-ol; water at 60℃; for 1h; | General procedure for the cyclotrimerization of alkynes General procedure: The above microemulsion of the substrate, together with immobilized rhodium catalyst (15mg RhCl3), were placed in either an autoclave or in a pressure vessel and heated with stirring to the desired temperature for the required length of time. The reaction vessel was cooled to room temperature and the mixture was filtered. The filtrate was treated with NaCl (2g), which caused the mixture to separate into two phases. The sol-gel material, as well as the aqueous layer, were extracted with CH2Cl2 (2× 10ml) to ensure complete removal of the products. The combined organic solutions were dried (MgSO4), concentrated and analyzed both by GC and 1H NMR and compared with authentic samples. The heterogenized catalyst was dried at 80°C and 0.1Torr for 5h in order to be ready for use in the next run. | |
With C8H6B2O8Re2(1-) In hexane at 30℃; for 3h; Overall yield = 70 %; regioselective reaction; | ||
With [i‑Prnaphthyridine−diimine]Ni2(C6H6) In 1,3,5-trimethyl-benzene; benzene at 60℃; for 0.666667h; Inert atmosphere; Sealed tube; Overall yield = > 99 %Chromat.; | ||
With mer-[Rh(κ3-P,O,P-(4,5-bis(diphenylphosphino)-9,9-dimethylxanthene))(η2-PhCCPh)][BArF4] In (2)H8-toluene at 24.84℃; for 20h; Inert atmosphere; | ||
With naphthalene; C61H60NiP4Si In Cyclooctan for 0.25h; | ||
With iron(II) bis(trimethylsilyl)amide In toluene at 20℃; for 3h; Glovebox; Inert atmosphere; Sealed tube; Overall yield = 90 %; regioselective reaction; | ||
With C21H47ClNNiP2(1+)*Cl(1-); zinc In toluene at 40℃; for 5h; Inert atmosphere; Schlenk technique; Overall yield = 25 %; regioselective reaction; | 4.2.10 General procedure for cycloaddition reaction of alkyne General procedure: To a 50mL Schlenk flask acetylene derivatives (1mmol), Ni(II) complex (2.5mol%), Zn (5mol%) and 3mL acetonitrile were added. The reaction mixture was heated at 40°C using an oil bath. After completion of the reaction, the crude reaction mixture was dried under vacuo and dissolved in diethyl ether and filtered through silica gel. The volatiles were removed under vacuo and column chromatography was performed to isolate the final product. | |
With C21H47ClNNiP2(1+)*Cl(1-); zinc In acetonitrile at 40℃; for 3h; Inert atmosphere; Schlenk technique; Overall yield = 95 %; regioselective reaction; | 4.2.10 General procedure for cycloaddition reaction of alkyne General procedure: To a 50mL Schlenk flask acetylene derivatives (1mmol), Ni(II) complex (2.5mol%), Zn (5mol%) and 3mL acetonitrile were added. The reaction mixture was heated at 40°C using an oil bath. After completion of the reaction, the crude reaction mixture was dried under vacuo and dissolved in diethyl ether and filtered through silica gel. The volatiles were removed under vacuo and column chromatography was performed to isolate the final product. | |
With C30H42Br2N2Ni; zinc In acetonitrile at 50℃; for 9h; Schlenk technique; Inert atmosphere; Overall yield = 88 %; regioselective reaction; | ||
With palladium-gold alloy nanoparticles supported on TiO2 catalyst In toluene at 100℃; Schlenk technique; Inert atmosphere; Overall yield = 74 %; | ||
With C36H114Mn6N6Si12 In hexane at 20℃; for 72h; Overall yield = 47 %; Overall yield = 19 mg; | ||
With {6-(η5-C5Me5)-nido-6-RhB9H13} In 5,5-dimethyl-1,3-cyclohexadiene for 2h; Reflux; Inert atmosphere; Overall yield = 74 %Spectr.; | General procedures for alkynes in the presence of catalytic amount (1 mol %) of 1 General procedure: Compound 1 (3.0mg, 0.0086mmol) and alkyne (0.86mmol) dissolved in 10mL of dry xylene was refluxed under nitrogen for 2h. All volatile components were then evaporated under reduced pressure at room temperature and the residue was analyzed by GCMS and NMR spectroscopy. The solvent was evaporated under vacuum and the residue was extracted into hexane and passed through Celite. After removal of the hexane, the filtrate was subjected to chromatographic silica gel TLC plate with hexane:CH2Cl2 (3:1) as eluent to give the substituted benzenes. The characterization of the products was completed by 1H, 13C NMR spectroscopy, mass spectrometry and by a comparison with literature data [49,50]. The yield of substituted benzenes was determined by 1H NMR spectroscopy employing a reference known weight compound using a literature method [30]. | |
With C24H28CoNO5 In tetrahydrofuran-d8; water-d2 at 60℃; for 72h; Inert atmosphere; regioselective reaction; | ||
With dicobalt octacarbonyl In toluene at 180℃; Sealed tube; Overall yield = 80 %; | ||
With chloro-trimethyl-silane; cyclopentadienyl titanium(IV) trichloride; magnesium In tetrahydrofuran at 40℃; for 12h; Inert atmosphere; Overall yield = 74 %; | ||
With C15H23Cl2FeN3; ethylmagnesium bromide In tetrahydrofuran at 20℃; for 5h; Inert atmosphere; Glovebox; Sealed tube; Overall yield = 76 %; Overall yield = 39 mg; regioselective reaction; | 4.9 General procedure for catalytic cyclotrimerization of alkynes General procedure: To a stirred solution of catalyst 1 in THF (1mL), alkyne (0.5mmol) and then EtMgBr (11mol%, 1M in THF) was charged in PTFE screw-capped reaction vial equipped with a stirrer bar inside the glovebox. Then, the reaction mixture was brought outside and stirred at room temperature. Progress of the reaction was monitored by GC, which indicated the completion of the reaction in specified time. The reaction mixture was quenched by exposing it to the open atmosphere. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography to provide cyclotrimerized product. | |
With C9H18O2Ti In tetrahydrofuran at 0 - 100℃; for 0.5h; Microwave irradiation; Inert atmosphere; Overall yield = 64 %; Overall yield = 197 mg; regioselective reaction; | ||
1: 23 %Chromat. 2: 8 %Chromat. | Stage #1: phenylacetylene With lithium triethylborohydride; cobalt(II) bromide In tetrahydrofuran Inert atmosphere; Glovebox; Stage #2: With hydrogen In tetrahydrofuran at 20℃; for 24h; | |
With Au-Pd/TiO2 In toluene at 75℃; for 3h; Inert atmosphere; Overall yield = 58 %; | 12; 4; 13-19 Example 12, Comparative Example 4 General procedure: The catalysts obtained in Examples 1 to 4 and the catalysts of Comparative Examples 1 to 3 and the catalyst of (Pd: Pt = 1: 3) composed of Pd and Pt as comparison objects and the catalyst of Pt and Au (Pt : Au = 1: 3), benzene compounds were produced. As shown in the following chemical formula, 1.5 mmol of Compound 1 was dissolved in 1 ml of toluene, each catalyst was added so that the total solution became 1 mol%, and the reaction was carried out at 75 ° C. under an argon atmosphere for 3 hours , Thereby obtaining the benzene compound represented by the compounds 2 and 3. The yield of each catalyst is shown in FIG. 3. The yield and reaction rate (conv.) Were measured by gas chromatography ("GC-2014" manufactured by Shimadzu Corporation), respectively. As is clear from the results shown in FIG. 3, it is understood that the catalyst of the present invention exhibits excellent catalytic activity. On the other hand, when the ratio of Pd and Au is outside the range of the present invention, it is found that there is no catalytic activity or is extremely low. | |
With C56H92Mn4N4Si8 In toluene at 70℃; for 24h; Overall yield = 41 %; | ||
With (1,2-dimethoxyethane)dichloronickel(II); tetrahydroxydiboron In acetonitrile at 100℃; for 12h; Inert atmosphere; Schlenk technique; Sealed tube; Overall yield = 66 percentSpectr.; regioselective reaction; | ||
With C27H40Cl2FeN4; sodium triethylborohydride In toluene at 20℃; for 16h; Overall yield = 73 percent; regioselective reaction; | ||
1: 42 %Spectr. 2: 20 %Spectr. | With chloro(η4-cycloocta-1,5-diene)[1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-2-ylidene]rhodium(I) In methanol; N,N-dimethyl acetamide at 70℃; for 24h; Schlenk technique; Inert atmosphere; | |
85.714 % de | With (1,2-dimethoxyethane)dichloronickel(II); tetrahydroxydiboron In acetonitrile at 80℃; for 12h; Schlenk technique; Inert atmosphere; Overall yield = 89 percent; | |
With bis(1,3-dimesityl-1H-imidazol-2(3H)-ylidene)nickel(0) In benzene-d6 at 60℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 50.6% 2: 35.5% 3: 7.5% 4: 4% | With cobaltocene In toluene at 110℃; for 7h; | |
1: 4% 2: 35.5% 3: 7.5% 4: 50.6% | With cobaltocene In toluene at 110℃; for 7h; | |
1: 28.6% 2: 1.4% 3: 37.6% 4: 15.4% | With cobaltocene In toluene at 110℃; for 7h; |
In hexane at 20℃; for 72h; Yield given. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 30% 2: 25% 3: 8% | In ethanol; water for 5h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With phenol In toluene Yield given. Further byproducts given. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In hexane at 20℃; for 72h; Yield given. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
29% | With dicobalt octacarbonyl at 120℃; for 32h; Further byproducts given. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | In N,N-dimethyl-formamide at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 70 % Turnov. 2: 28 % Turnov. 3: 2 % Turnov. | In tetrahydrofuran at 65℃; for 24h; | |
1: 26 % Turnov. 2: 13 % Turnov. | In tetrahydrofuran-d8 at 65℃; for 67h; | |
1: 76 % Turnov. 2: 18 % Turnov. 3: 4 % Turnov. 4: 2 % Turnov. | In tetrahydrofuran-d8 at 65℃; for 78h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 115℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene at 90℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 60% 2: 21.5% | In diethylamine for 6h; Heating; other catalysts, other solvent, various reaction time; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With cobaltocene In toluene at -78℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 300℃; optically inactive 1,3,4-triphenyl-4-<i>trans</i>-styryl-cyclohexene; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 61% 2: 27% | Stage #1: 1,3,5-trichlorobenzene With trimethylstannylsodium In ammonia for 1.75h; Irradiation; Stage #2: iodobenzene In N,N-dimethyl-formamide at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | In tetrahydrofuran Heating; | |
97% | In tetrahydrofuran for 6h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With bis(1,5-cyclooctadiene)nickel (0); tricyclopentylphosphine In methanol; acetic acid methyl ester at 50℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran at 79.85℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ethylaluminum dichloride In tetrahydrofuran at 25℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | In methanol at 25℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | In tetrahydrofuran at 25℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With {2,6-bis[(di-1-piperidinylphosphino)amino]phenyl}palladium(II) chloride; potassium carbonate In 1,4-dioxane; water; butan-1-ol at 100℃; for 1h; | |
97% | With sodium carbonate In water; N,N-dimethyl-formamide at 60℃; for 12h; | |
96% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); tri-tert-butyl phosphine In 1,1,1,2,3,3,3-Heptafluoropropane; ethanol; 1,1,1,3,3-pentafluorobutane at 20℃; for 24h; Inert atmosphere; |
96.6% | With tetrabutylammomium bromide; potassium carbonate In 1,4-dioxane; water at 80℃; for 24h; | 2.1.1 Synthesis of Biphenyl (9) General procedure: A round bottom flask was charged with iodobenzene (0.2 g,0.980 mmol), catalyst B-2 (0.061 g, 0.000098 mmol Pd, 0.01 mol %), phenyl boronic acid (0.143 g, 1.176 mmol),dry potassium carbonate (0.270 g, 1.960 mmol), TBAB(0.063 g, 0.196 mmol) and dioxane-water (1:1; 10 mL) assolvent. This mixture was heated to 80 C and continued for24 h. The reaction mixture was filtered to remove the catalystand was quenched with water and extracted with ethylacetate (3 9 25 mL). The combined organic phase waswashed with water and dried over anhydrous sodium sulfate.Solvent was removed in vacuum and the crude product waspurified by column chromatography on silica gel to affordbiphenyl (0.148 g, 98.7 %) as white solid (m.p. 66-67 C, lit[73] 68-70 C). |
95% | With [Pd(N-(3-chloro-2-quinoxalinyl)-N'-(2,6-diisopropylphenyl)imidazolium)(PPh3)Cl2]; potassium carbonate In water at 70℃; for 3h; | |
94% | With potassium carbonate In water; N,N-dimethyl-formamide at 70℃; for 0.133333h; Microwave irradiation; | |
94% | With C42H54Cl2N6Pd; triphenylphosphine; sodium hydroxide In 1,4-dioxane at 105 - 110℃; for 3.5h; Inert atmosphere; | |
93% | With C20H18I2N4Pd; potassium <i>tert</i>-butylate In ethanol at 30℃; for 6h; | General procedure for Suzuki-Miyaura coupling General procedure: A mixture of aryl halide (100 mg scale, 1.0 eq), phenylboronic acid (1.2 eq),t-BuOK (1.5 eq), complex 5 (1 mol%with respect to substrate) in EtOH (5 mL) was stirred at room temperature (30 oC)until the starting aryl halide disappeared (checked by TLC). The reactionmixture was diluted with ice cold water (10 mL) and extracted with ethylacetate. Removal of solvent under vacuumgave the crude product which was purified either by chromatography on silicagel or by simply washing with hexane. The products and their spectral data arereported in literature and they were characterized by 1H and 13CNMR spectroscopic data in the present study. |
92% | With potassium phosphate; dichloro{bis[1-(dicyclohexylphosphanyl)(II) In toluene at 80℃; for 0.25h; Air; | |
92% | With bis[1-((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)-3-methyl-4-phenyl-1,2,3-triazol-5-ylidene]palladium(II) iodide; potassium <i>tert</i>-butylate In ethanol at 20℃; for 8h; Inert atmosphere; | General procedure for the Suzuki reaction General procedure: Bromo compound (0.5 mmol, 1eq), boronic acid ( 0.6mmol, 1.2 eq )was dissolved in absolute ethanol (10 mL) in a 25 mL two neck flask . The contents of the flask were degassed with nitrogen. Potassium t-butoxide (0.75 mmol, 1.5 eq) was added followed by (0.5 mol %) of the complex, [Bis[1-((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)-3-methyl-4-phenyl-1,2,3-triazol-5-ylidene]palladium (II) iodide (11)]. The contents of the flask were stirred at room temperature under nitrogen atmosphere. The reaction was monitored by thin layer chromatography. After completion of the reaction (disappearance of the bromo compound) solvent was evaporated and the residue was dissolved in water (20 mL) and extracted with dichloromethane (3 x 20 mL). The dichloromethane layer was washed with saturated sodium chloride solution (20 mL) and water (20 mL). The organic layer was evaporated; the compound was purified by column chromatography using hexane as solvent. |
92% | With potassium carbonate In ethanol; water at 20℃; for 0.333333h; Green chemistry; | |
91% | With sodium acetate In water; N,N-dimethyl-formamide at 80℃; for 1.5h; | |
91% | With sodium carbonate In water; N,N-dimethyl-formamide at 90℃; for 2h; | |
90% | With potassium fluoride; palladium diacetate for 0.116667h; microwave irradiation; | |
90% | With potassium phosphate; C19H24Cl2NPPd In ethanol; water at 20℃; for 24h; Schlenk technique; Inert atmosphere; | General procedure for the Suzuki-Miyaura cross-coupling reactions General procedure: In a Schlenk-flask equipped with a septum and a magnetic stirring bar, phenylboronic acid (73 mg, 0.6 mmol), the corresponding base (1 mmol) and catalyst 1a-e (0.002 mmol) were dissolved in a deoxygenated ethanol/water 1:1 mixture (4 mL) under an argon atmosphere. In the next step the aryl-halogenide (0.5 mmol) (or its solution) was added through the septum and the reaction mixture was stirred thoroughly at room temperature. After being stirred, the solvent was evaporated and the product was purified by column chromatography (silica, eluent: hexane/ethyl-acetate). The products were analysed by 1H-NMR and GC-MS techniques and the data were compared with the literature results. |
89% | With 1-((dimethylamino)(phenyl)methyl)naphthalen-2-ol; tetrabutylammomium bromide; palladium diacetate; potassium carbonate In 1,4-dioxane; water at 95℃; for 15h; | |
87% | With potassium carbonate In 1-methyl-pyrrolidin-2-one at 100℃; for 3.5h; | |
80% | With bis(1,5-cyclooctadiene)nickel (0); potassium phosphate; tricyclohexylphosphine In tetrahydrofuran for 20h; Inert atmosphere; | |
72% | With potassium carbonate In ethanol; water at 65℃; for 24h; | |
71% | With tetrabutylammomium bromide; potassium carbonate In 1,4-dioxane for 12h; Inert atmosphere; | |
68.1% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran at 74℃; for 8h; Inert atmosphere; Reflux; | |
8% | With potassium carbonate In toluene at 120℃; for 2h; | 2.3. Catalytic test General procedure: For the Suzuki-Miyaura coupling reactions, SG-1, 1,3,5-tribromobenzene or 2-bromopyridine(1.0 mmol), phenylboronic acid (1.5 mmol), potassium carbonate (276 mg, 2.0 mmol), and SG-1 (5 mg, 1.2 mol%) were added to a pressure flask with dry toluene (4 mL). Then the reaction mixturewas stirred at 120°C at ambient atmosphere. After 2 h, the mixturewas centrifuged, and the solid was washed with dichloromethane (3 5 mL). The combined organic phase was washed with water (3 15 mL) to remove potassium carbonate. The organic phasewas then evaporated under reduce pressure to leave the crude products which were further puried by column chromatography over silica gel to obtain the desired products. |
With potassium carbonate In methanol at 20℃; for 24h; | ||
With palladium; potassium hydroxide In ethanol at 30℃; for 16h; Inert atmosphere; | Suzuki reaction crosscoupling. 1,3,5-Tribromobenzene(0.16 g, 0.52 mmol), phenylboronic acid (0.28 g, 2.33 mmol),and potassium hydroxide (0.13 g, 2.33 mmol) were added toa colloid solution of palladium obtained as above (9 mL). The reaction mixture was stirred for 16 h at 30 °C. The componentsof the reaction were extracted with toluene and analyzed without isolation of the reaction products. | |
With tri(tert-butyl)(decyl)phosphonium tetrafluoroborate; potassium hydroxide In ethanol at 30℃; for 16h; Inert atmosphere; Schlenk technique; | 2.4. General procedure for the Suzuki cross-coupling reaction 0.18 g (0.57 mmol) 1,3,5-tribromobenzene, 0.32 g (2.6 mmol) phenylboronic acid, and 0.15 g (2.6 mmol) potassium hydroxide were added to a fresh suspension of PdNPs (see 2.3). The re- action mixture was stirred for 16 hours at 30 ° . Organic com- pounds were extracted with 10 ml toluene and analyzed by GC- MS without product isolation. The conversion was calculated by using the correction factor which was obtained by GC-MS anal- ysis of an equimolar mixture of 1,3,5-tribromobenzene and 1,3,5- triphenylbenzene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 78% 2: 19% 3: 1% | With triethylsilane In tetrahydrofuran at 65℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 31% 2: 64% | With zinc(II) iodide; zinc In dichloromethane at 20℃; | |
1: 47% 2: 23% | With N,N'-dicyclohexylethylenediimine; zinc(II) iodide; zinc In tetrahydrofuran at 20℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 60 % Chromat. 2: 6 % Chromat. 3: 9 % Chromat. | With 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate at 150℃; for 72h; | |
72 %Chromat. | With vanadyl(IV) phthalocyanine at 160 - 180℃; for 48h; Inert atmosphere; neat (no solvent); | |
20 %Chromat. | With ruthenium porphyrin-Merrifield resin adduct at 160 - 180℃; for 48h; Neat (no solvent); Inert atmosphere; |
51 %Chromat. | With Ru(CO)((C6H5)3C20H8N4C6H4CH2OH) at 160 - 180℃; Neat (no solvent); Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With 1-[2-(diphenylphosphino)phenyl]ethanol; bis(acetylacetonate)nickel(II) In diethyl ether at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With sodium hydroxide at 60℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With aluminum (III) chloride In carbon disulfide at 0 - 50℃; for 21h; Inert atmosphere; Cooling with ice; | |
64% | With aluminum (III) chloride In dichloromethane at 20℃; for 2h; Cooling with ice; Inert atmosphere; | |
11 g | With aluminium trichloride In dichloromethane at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
13.3% | With iodine; sodium hydrogencarbonate; sodium thiosulfate; acetic acid In toluene | 1 (Preparation of 1,3,5-tris(4-iodophenyl)benzene) Example 1 (Preparation of 1,3,5-tris(4-iodophenyl)benzene) 116 g of 1,3,5-triphenylbenzene, 19 mL of concentrated sulfuric acid as a catalyst, and 1520 mL of 80% acetic acid as a reaction solvent were placed in a 2 L capacity flask, and the mixture was heated to a temperature of 70°C with stirring. Then, 143 g of iodine and 69.3g of orthoperiodic acid were added 1/10 at a time over about 2 hours and a half into a flask, followed by reacting for 6 hours with stirring, to obtain a reaction product containing white precipitates. Toluene was added to the reaction mixture to dissolve the precipitates therein, and the toluene layer was separated from the water layer. The toluene layer was washed with an aqueous solution of sodium hydrogencarbonate and then with an aqueous solution of sodium thiosulfate. The organic layer was then concentrated and subjected to silica gel chromatography and the reaction product was separated, which was recrystallized from ethanol/toluene/, thereby providing 34.6g of desired 1,3,5-tris(4-iodophenyl)benzene as white needle crystals. The yield was 13.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene under N2 in Schlenk tube, stirred overnight at 55-60°C, soln. pumped to dryness, redissolved in hexane/ether (3:1); sepn. by chromy. on silica gel, hexane eluent; two triphenylbenzene isomers and CoW(CO)4(PhC2H)2(C5H4Me) complexes spectroscopically (IR, NMR, MAS) identified; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene under N2, Schlenk tube stirred at 55-60°C for 1 d, soln. pumped to dryness, dissolved in hexane/ether/dichloromethane (2:1:1); sepn. by chromy. on silica gel, hexane/ether (1:1) eluent; two triphenylbenzene isomers and Co2W2(CO)8(PhC2H)(C5H4Me) complexes spectroscopically (IR, NMR, MAS) identified; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tetrabutylammomium bromide; potassium carbonate In water at 120℃; for 0.333333h; Microwave irradiation; solid phase reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With 2-bromo-1,3,5-triphenylbenzene; calcium at -78 - -60℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 13% 2: 3% | Stage #1: dicobalt octacarbonyl; N,N,N'-trimethyl-N'-allylthiourea; phenylacetylene With 1,1,3,3-tetramethyl-2-thiourea In toluene for 0.0833333h; Inert atmosphere; Stage #2: carbon monoxide In toluene at 110℃; for 24h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With iron(III) chloride; bis(trimethylsilyl)amide yttrium(III) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | Stage #1: phenylacetylene With palladium dichloride zirconia vibration ball mill; neat (no solvent); Stage #2: at 20℃; for 2h; neat (no solvent); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With palladium diacetate; triphenylphosphine In tetrahydrofuran at 110℃; for 6h; Inert atmosphere; | 4.3. General procedure for the synthesis of 1,3-diynes, 1,3-enynes and tri-substituted benzenes General procedure: A solution of terminal alkyne (1.0 mmol), Pd(AcO)2 (4 mg, 0.02 mmol), PPh3 (21 mg, 0.08 mmol), and Et3N (202 mg, 2.0 mmol) in THF (10 mL) was heated at reflux, under magnetic stirring for 6 h. The solution was cooled to room temperature and the solvent was removed under reduced pressure to give a crude material. The crude mixture was then purified by chromatography on silica gel (petroleum ether/Et2O 95:5) to afford, as shown in Table 1 and Table 2, 1,4-dialkyl- and 1,4-diaryl-1,3-butadiynes 2a-c together with dimerization products 3a-d and 4a-d, asymmetrical and symmetrical cyclotrimerisation products 5a-d and 6a-d. | |
1: 36 %Spectr. 2: 13 %Spectr. 3: 9 %Spectr. 4: 8 %Spectr. | With [Rh(η4-1,5-cyclooctadiene)(1,3-bis-(2,6-diisopropylphenyl)imidazolin-2-carbene)(NCCH3)][PF6] In methanol; N,N-dimethyl acetamide at 70℃; for 24h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With toluene-4-sulfonic acid In neat (no solvent) at 60 - 140℃; for 13h; Green chemistry; regioselective reaction; | |
15% | With indium(III) chloride; 2-Iodophenol In chlorobenzene for 72h; Reflux; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; tricyclohexylphosphine In toluene at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluorormethanesulfonic acid In 1,2-dichloro-ethane for 4.5h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluorormethanesulfonic acid In 1,2-dichloro-ethane for 4h; Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluorormethanesulfonic acid In 1,2-dichloro-ethane at 140℃; for 0.5h; Inert atmosphere; Microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With potassium phosphate; palladium bis(dibenzylideneacetone)palladium(0); catacxium A; In toluene; at 110℃; for 24h;Inert atmosphere; Sealed tube; | General procedure: An oven-dried and argon-flushed pressure tube was charged with <strong>[108-70-3]1,3,5-trichlorobenzene</strong>, 1,2,4-trichlorobenzene or 1,2,3-trichlorobenzene (0.25 mmol), Pd2(dba)2 (1.25 mol%), cataCXium A (5.0 mol%), boronic acid (1.5 mmol) and K3PO4 (1.5 mmol) followed by anhydrous toluene (4.0 mL). The tube was sealed with a Teflon valve and the reaction mixture was stirred at 110 C for 24 h. The cooled reaction mixture was diluted with water and extracted with DCM. The combined organic layers were dried (Na2SO4), filtered and the filtrate was concentrated in vacuo. The residue was purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With bis(tricyclohexylphosphine)nickel(II) dichloride In toluene at 130℃; for 24h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With (p-cymene)ruthenium(II) chloride; ethene; tricyclohexylphosphine In toluene at 80℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90 %Chromat. | Stage #1: phenylacetylene With (p-cymene)ruthenium(II) chloride In toluene at 80℃; for 0.0833333h; Inert atmosphere; Schlenk technique; Stage #2: With ethene; 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene In toluene at 80℃; for 2h; | 2.3. General procedure for the in situ switching between cyclotrimerization and enyne metathesis reactions General procedure: A reactor was charged with [RuCl2(p-cymene)]2 (0.033 mmol, 0.020 g) and phenylacetylene (0.66 mmol, 72 μl) in 3 ml toluene and heated at 80 °C. After 10 min, 2.0 mol equivalent of IPr (0.066 mmol, 0.026 g) was added to the reaction medium and stirred at 80 °C under an ethylene atmosphere (1 atm). Aliquots taken periodically from the reaction mixture were analyzed by GC-MS. |
27 %Chromat. | Stage #1: phenylacetylene With (p-cymene)ruthenium(II) chloride In toluene at 80℃; for 1h; Inert atmosphere; Schlenk technique; Stage #2: With ethene; 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene In toluene at 80℃; for 4h; | 2.3. General procedure for the in situ switching between cyclotrimerization and enyne metathesis reactions General procedure: A reactor was charged with [RuCl2(p-cymene)]2 (0.033 mmol, 0.020 g) and phenylacetylene (0.66 mmol, 72 μl) in 3 ml toluene and heated at 80 °C. After 10 min, 2.0 mol equivalent of IPr (0.066 mmol, 0.026 g) was added to the reaction medium and stirred at 80 °C under an ethylene atmosphere (1 atm). Aliquots taken periodically from the reaction mixture were analyzed by GC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With [{Rh(μ-Cl)(1,3-bis-(2,6-diisopropylphenyl)imidazol-2-carbene)(η2-cyclooctene)}2]; acetonitrile In benzene-d6 at 40℃; for 8h; Schlenk technique; chemoselective reaction; | ||
1: 55 %Spectr. 2: 25 %Spectr. 3: 15 %Spectr. | With di[(N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)(cyclooctene)chlororhodium(I)] In methanol; N,N-dimethyl acetamide at 70℃; for 24h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In neat (no solvent) at 150℃; for 0.5h; Microwave irradiation; regioselective reaction; | m-Terphenyl Derivatives 11a-g from Sultones 2a-g; General Procedure 2, Microwave Preparation General procedure: Sultone 2 (0.30 mmol) was placed into a microwave test tube and DMAD (5; 340 mg, 2.4 mmol) was added. The resulting suspension was placed in a microwave apparatus and exposed to the radiation (100 W, 20 min) with 5 min starting time and external cooling with N2 gas. The resulting red-brown highly viscous crude product mixture was purified by flash chromatography with pentane-EtOAc (5:1 for products 11a-e, 3:1 for products 11f, 11g) under TLC control. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 84% 2: 11% | With iron(III) trifluoromethanesulfonate In 1,2-dichloro-ethane at 90℃; for 12h; Sealed tube; | |
1: 46% 2: 52% | With iron(III) trifluoromethanesulfonate In 1,2-dichloro-ethane at 110℃; for 12h; Sealed tube; | |
With sulfuric acid at 65 - 70℃; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate In 1,4-dioxane; water at 95℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With toluene-4-sulfonic acid In neat (no solvent) at 80℃; for 12h; | |
69% | With iron(III) trifluoromethanesulfonate In 1,2-dichloro-ethane at 90℃; for 12h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 85% 2: 10% | With (R)-1-{(S)-2-(dicyclohexylphosphino)ferrocenyl}ethyldicyclohexylphosphine; dicobalt octacarbonyl In toluene at 120℃; for 12h; Autoclave; Inert atmosphere; Schlenk technique; | 2.7 Catalytic Pauson-Khand reactions effected by [Co2(CO)8] or [Co4(CO)12] in conjunction with chiral auxiliary diphosphine ligands In a typical experiment, the autoclave was loaded with either 6 mol% [Co2(CO)8], or 3.5 mol% [Co4(CO)12], 8 mol% of the relevant chiral diphosphine (Josiphos or Walphos) as auxiliary chiral ligand/promoter, and the substrates norbornene and phenyl acetylene. Toluene (5 ml) was added and the autoclave was purged several times before being pressurized with 10 bar of CO. The reaction mixture was stirred at 120 °C for 12 h, after which the reaction was allowed to cool down to room temperature. The autoclave was depressurized carefully before it was opened at room temperature. The reaction mixture was transferred into a round bottom flask and the solvent was removed in vacuo. Ensuing work-up as described above gave 1,3,5-triphenyl benzene (6) and 4-phenyltricyclo[5.2.1.0]dec-en-3-one (7) in varying yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With calcined hydrotalcite In toluene at 150℃; for 3h; Sealed tube; | 5.4 Example 4 Self-condensation of 2-butanone Example 4 Self-condensation of 2-butanone [0201] This Example demonstrates the formation of cyclic ketones from 2-butanone (also known as methyl ethyl ketone) using hydrotalcite as the catalyst. 94% Yield [0202] The reaction involving 2-butanone of this Example was performed according to the procedure set forth in Example 1 above. The reaction after 2 hours was observed to produce a mixture of C12 trimers formed by cyclization, Michael addition. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triiron dodecarbonyl In diethyl ether at 120℃; for 12h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In 1,4-dioxane at 20℃; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With 2-phenyl-6,7-dihydro-5H-pyrrolo[2,1-c][1,2,4]triazol-2-ium tetrafluoroborate; caesium carbonate In 1,4-dioxane at 20℃; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 65% 2: 10% 3: 20% 4: 4% | With [(bis(diisopropylphosphino)ethane)Ni(H)]2 In toluene at 50℃; for 69h; | 4.2.1. General procedure for the catalytic production of aepyrones General procedure: [(dippe)Ni(m-H)]2 (1) (0.031 mmol) and the correspondingalkyne (0.311 mmol) and toluene (10 mL) were charged in a100-mL Parr reactor. On reacting 1 with all acetylenes, a colorchange from wine red to brown was observed with a lightbubbling; the reactor was immediately closed and then pressurizedout of the dry box with CO2 (150 psi). Afterward, thereaction vessel was heated up to 50 C for 69 h. After this time,the reactor was cooled down to room temperature and ventedinto a hood; the reaction mixture was directly analyzed by GCMS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With sodium t-butanolate at 60℃; for 5h; | 1 Preparation of 1,3,5-triphenylbenzene will1,2 mmol of chalcone, 1.5 mmol of t-butoxide and 2.0 mL of dimethylsulfoxide were added to 10 mL of the reaction tube,Placed in an oil bath at 60 ° C,Open toairIn the reaction 5h.The reaction was stopped and allowed to cool to room temperature. The reaction solution was extracted with ethyl acetateDiluted with water three times, the organic phase with anhydrous Na2SO4 drying, filtration, column chromatography to get 28.2mg headThe yield of the product was 77%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C21H47ClNNiP2(1+)*Cl(1-); zinc In tetrahydrofuran at 40℃; for 12h; Inert atmosphere; Schlenk technique; Overall yield = 40 %; regioselective reaction; | 4.2.10 General procedure for cycloaddition reaction of alkyne General procedure: To a 50mL Schlenk flask acetylene derivatives (1mmol), Ni(II) complex (2.5mol%), Zn (5mol%) and 3mL acetonitrile were added. The reaction mixture was heated at 40°C using an oil bath. After completion of the reaction, the crude reaction mixture was dried under vacuo and dissolved in diethyl ether and filtered through silica gel. The volatiles were removed under vacuo and column chromatography was performed to isolate the final product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With tetrabutyl ammonium fluoride; palladium diacetate; XPhos; In tetrahydrofuran; toluene; at 100℃; for 3h;Schlenk technique; | General procedure: Palladium(II) acetate (0.025 mmol, 5.6 mg), XPhos (0.0375 mmol, 17.9 mg), and phenylsilatrane (2a, 0.75 mmol, 188.5 mg) were added to a Schlenk flask. The flask was then purged with nitrogen. 4-Chloroanisole (1a) (0.50mmol, 71.3 mg), toluene (1.5 mL), and TBAF (0.75 mmol, 0.75 mL in ca. 1.0 M THF solution) were subsequently added. The mixture was stirred at 100 C for 3 h, then quenched by addition of water, and extracted with EtOAc. The organic layer was washed with brine, dried over anhydrous Na2SO4, filtered,and concentrated in vacuo. The crude product was purified by flash column chromatography on silica gel (hexane) to provide 3a (75.2 mg, 0.408 mmol) in 82% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | Stage #1: 1,3,5-triphenylbenzene; 4-Fluorobenzenesulfonyl chloride at 100℃; for 0.0833333h; Inert atmosphere; Stage #2: With iron(III) chloride In nitrobenzene at 100℃; for 3h; | 1.1 (1) Preparation of intemrediate 1-1 Add 1,3,5-triphenylbenzene (1.6g, 4.9mmol) and 4-fluorobenzenesulfonyl chloride (6.7g, 34mmol) into the two-neck flask, connect the condenser and connect to the double-row tube,Connect argon protection. Heat the flask in a 100°C oil bath for 5 minutes, then add nitrobenzene (5mL), and then slowly add anhydrous ferric chloride (0.56g, 3.5mmol),Heat and stir at 100 degrees for 3 hours. The reaction solution was poured into 50 mL of hydrochloric acid methanol solution (volume concentration 5%) and stirred vigorously, filtered, washed with 3% hydrochloric acid aqueous solution and deionized water, and vacuum dried to obtain a brown crude product solid.Dissolve the crude product solid in acetic acid, add activated carbon and heat to reflux,The receptor intermediate 1-1 was obtained by recrystallization, and 2.56 g of off-white solid was obtained after vacuum drying, with a yield of 67%. |
62% | With iron(III) chloride In nitrobenzene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; 2C18H42NSi2(1-)*Ba(2+) In benzene at 120℃; for 24h; Autoclave; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | Stage #1: 1,3,5-triphenylbenzene; 4-fluorobenzoyl chloride at 100℃; for 0.0833333h; Inert atmosphere; Stage #2: With iron(III) chloride In nitrobenzene at 100℃; for 3h; | 4.1 (1) Preparation of intemrediate 1-1 General procedure: Add 1,3,5-triphenylbenzene (1.6g, 4.9mmol) and 4-fluorobenzenesulfonyl chloride (6.7g, 34mmol) into the two-neck flask, connect the condenser and connect to the double-row tube,Connect argon protection. Heat the flask in a 100°C oil bath for 5 minutes, then add nitrobenzene (5mL), and then slowly add anhydrous ferric chloride (0.56g, 3.5mmol),Heat and stir at 100 degrees for 3 hours. The reaction solution was poured into 50 mL of hydrochloric acid methanol solution (volume concentration 5%) and stirred vigorously, filtered, washed with 3% hydrochloric acid aqueous solution and deionized water, and vacuum dried to obtain a brown crude product solid.Dissolve the crude product solid in acetic acid, add activated carbon and heat to reflux,The receptor intermediate 1-1 was obtained by recrystallization, and 2.56 g of off-white solid was obtained after vacuum drying, with a yield of 67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With SIPr-PdCl<SUB>2</SUB>-Py; sodium t-butanolate In tetrahydrofuran at 70℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23 %Spectr. | With potassium phosphate; palladium diacetate; DavePhos In toluene at 90℃; Schlenk technique; | Cross-coupling reactions (general procedure) General procedure: A 10 mL Schlenk fl ask equipped witha stirring bar was charged with Pd(OAc)2 (7 mg, 0.03 mmol),ligand L1-L5 (0.06 mmol), C6Cl6 (1) (142 mg, 0.5 mmol),PhB(OH)2 (66 mg, 0.55 mmol), and K3PO4 (339 mg, 1.6 mmol)and then capped with a rubber septum. Air was removed by repeatedevacuation and fi lling with argon. Toluene (1 mL) was injectedunder argon. The mixture was stirred at 90 C for 7-8 h.A heterogeneous aliquot taken from the reaction mixture was dilutedwith benzene, fi ltered through a short layer of silica, and thefi ltrate was analyzed by GC-MS. Exhaustive phenylation of hexachlorobenzenewas attempted using the following amounts of thereagents: C6Cl6 (1) (71 mg, 0.25 mmol), PhB(OH)2 (261 mg,2.15 mmol), and K3PO4 (636 mg, 3.00 mmol). |
Tags: 612-71-5 synthesis path| 612-71-5 SDS| 612-71-5 COA| 612-71-5 purity| 612-71-5 application| 612-71-5 NMR| 612-71-5 COA| 612-71-5 structure
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P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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