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CAS No. : | 119-91-5 | MDL No. : | MFCD00006740 |
Formula : | C18H12N2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | WPTCSQBWLUUYDV-UHFFFAOYSA-N |
M.W : | 256.30 | Pubchem ID : | 8412 |
Synonyms : |
|
Num. heavy atoms : | 20 |
Num. arom. heavy atoms : | 20 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 82.48 |
TPSA : | 25.78 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | Yes |
CYP3A4 inhibitor : | Yes |
Log Kp (skin permeation) : | -4.8 cm/s |
Log Po/w (iLOGP) : | 3.01 |
Log Po/w (XLOGP3) : | 4.31 |
Log Po/w (WLOGP) : | 4.45 |
Log Po/w (MLOGP) : | 3.16 |
Log Po/w (SILICOS-IT) : | 4.49 |
Consensus Log Po/w : | 3.88 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -4.82 |
Solubility : | 0.00389 mg/ml ; 0.0000152 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -4.57 |
Solubility : | 0.00698 mg/ml ; 0.0000272 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -7.52 |
Solubility : | 0.00000767 mg/ml ; 0.0000000299 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.98 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | 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 |
---|---|---|
91% | With 2,2,6,6-tetramethylpiperidinylmagnesium chloride; N,N,N,N,-tetramethylethylenediamine In toluene at 60℃; for 20h; Inert atmosphere; | |
91% | With 2,2,6,6-tetramethyl-piperidine; N,N,N,N,-tetramethylethylenediamine; butyl magnesium bromide In tetrahydrofuran at 0 - 60℃; for 20h; Inert atmosphere; | 1 Example 1 Under an argon atmosphere, to put a magnetic stir 5mL clean and dry round bottom flask nBuMgCl 1.5mmol a freshly prepared solution of tetrahydrofuran (0.8mmol / mL), at 0 slowly dropped to the reaction flask was added 1.5 mmol of 2,2,6,6-tetramethylpiperidine (TMPH), 15 minutes after the reaction, in tetrahydrofuran at 50 vacuum drained, refilled with argon the reaction, the reaction flask was cooled to 25 2mL of toluene was added to dissolve generated in situ TMP-MgCl, 1.2mmol added tetramethylethylenediamine, 10 minutes after complexation, at room temperature with 1mmol quinoline and reacted at 60 20h, TLC detection reaction, after completion of the reaction was cooled to room temperature, quenched with water and extracted with 4 × 15mL of dichloromethane, washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered to remove the sodium sulfate, after the solvent was evaporated to give the crude product under reduced pressure, petroleum ether / ethyl acetate as eluting machine, column chromatography pale yellow solid of 2,2'-quinoline 116.5mg product of the structural formula shown in Formula 8, the yield of 91% 2,2'-quinoline Characterization |
81% | Stage #1: quinoline With 3-chloro-benzenecarboperoxoic acid In 2-methyltetrahydrofuran at 40℃; for 6h; Inert atmosphere; Schlenk technique; Stage #2: With 2,2'-azobis(isobutyronitrile); potassium <i>tert</i>-butylate In 2-methyltetrahydrofuran at 40 - 65℃; for 0.333333h; Inert atmosphere; Schlenk technique; |
63% | Stage #1: quinoline With [{(MeCN-2,6-iPr2C6H3)2CH}Mg(2,2,6,6-tetramethylpiperidine)] In tetrahydrofuran at 70℃; Inert atmosphere; Stage #2: | |
59% | With palladium 10% on activated carbon; zinc at 100℃; Autoclave; | |
35% | With palladium diacetate; silver pivalate; Trimethylacetic acid at 140℃; for 18h; Schlenk technique; Sealed tube; Inert atmosphere; regioselective reaction; | |
34% | With 1,10-Phenanthroline; palladium diacetate; silver pivalate; Trimethylacetic acid at 140℃; for 18h; Inert atmosphere; | 9 Under a nitrogen atmosphere, palladium acetate (11.2 mg, 0.05mmol), 1, 10 - phenanthroline (49.6 mg, 0.25mmol), silver acetate (250 mg, 1.5mmol), (1 ml) was suspended in pyridine (51.1 mg, 0.5mmol) pivalic acid, stirred at 140 °C 26 hours. After the reaction mixture was cooled to room temperature, the insoluble matter was removed by filtration over celite, methylene chloride (10 ml) was washed. The filtrate was concentrated under reduced pressure, 1, 1, 2, 2 - tetrachloroethane (15.8 μl, 0.15mmol) was added as an internal standard substance was obtained residue,1H NMR (88%) yield was calculated based oxidizing agent. (Methylene chloride/hexane=5/95) to give a residue for a thin layer chromatography analysis, the subject compound (quantitative value NMR 89%, 80% isolated yield) was obtained as a white powder 93.1 mg.The same treatment as in Example 1-1 was carried out except that treatment was carried out under the conditions shown in Table 9 below.The results are shown in Table 9. |
With nickel at 325 - 335℃; | ||
Multi-step reaction with 3 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 6 h / 20 °C / Inert atmosphere 2: lithium tert-butoxide / toluene / 12 h / 90 °C / Inert atmosphere 3: phosphorus trichloride / 3 h / Inert atmosphere; Reflux | ||
Multi-step reaction with 3 steps 1: 3-chloro-benzenecarboperoxoic acid / 6 h / 25 °C 2: lithium tert-butoxide / toluene / 24 h / 90 °C 3: phosphorus trichloride / chloroform / 8 h / 70 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | With potassium hydroxide; palladium 10% on activated carbon; hydrazine hydrate In ethanol Reflux; | |
27% | Stage #1: With tri-n-butyllithium magnesate complex In tetrahydrofuran; diethyl ether; hexane at -30 - -10℃; Stage #2: 2-bromoquinoline With 1,1'-bis-(diphenylphosphino)ferrocene; bis(dibenzylideneacetone)-palladium(0) In tetrahydrofuran; diethyl ether; hexane at -10 - 20℃; for 19h; | |
With potassium hydroxide; Lindlar's catalyst; hydrazine hydrate |
Multi-step reaction with 2 steps 1: tetrahydrofuran / 2.5 h / -10 °C 2: 27 percent / bis(dibenzylideneacetone)palladium(O) (Pd(dba)2); 1,1'-bis(diphenylphosphino)ferrocene (dppf) / tetrahydrofuran / 18 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium hydroxide In water; N,N-dimethyl-formamide at 35℃; for 24h; Inert atmosphere; | |
91% | With bis(bipyridine)nickel(II) bromide; ethylene dibromide; sodium iodide In N,N-dimethyl-formamide at 20℃; for 2h; Electrochemical reaction; Inert atmosphere; | General procedure: DMF (40 mL), NaI (375 mg, 2.5 mmol), and 1,2-dibromoethane (100μL, 1.16 mmol) were added to an undivided electrochemical cell, fitted with an iron/nickel (64/36) anode, and surrounded by a nickel foam as the cathode (surface: 40 cm2, porosity: 500 μm, Goodfellow).The mixture was electrolyzed under argon at a constant current intensity of 0.2 A at r.t. for 15 min. The current was then stopped, then NiBr2bpy (187 mg, 0.5 mmol) and aryl or heteroaryl halide (5 mmol),were sequentially added. The solution was electrolyzed at 0.2 A untilthe starting aryl or heteroaryl halide had been totally consumed (2-5h). Sat. aq EDTA-Na2 solution (50 mL) was added, and the resultingsolution was extracted either with EtOAc (for aryl halides) or withCH2Cl2 (for heteroaryl halides) (3 × 50 mL). The combined organic layerswere washed with brine (50 mL), dried (MgSO4), filtered, and concentratedunder vacuum. The crude product was purified by flashchromatography (silica gel, 70-200 μm). |
84% | In tetrahydrofuran at 50℃; for 20h; |
83% | With triphenylphosphine; nickel dichloride; zinc In N,N-dimethyl-formamide at 50℃; for 4h; | |
83% | With triphenylphosphine; nickel dichloride; zinc In N,N-dimethyl-formamide at 50℃; for 4h; | |
72% | With nickel(II) chloride hexahydrate; iodine; acetic acid; lithium chloride; zinc In N,N-dimethyl-formamide at 50 - 60℃; for 6h; | |
70% | With nickel diacetate; triphenylphosphine; sodium t-butanolate In 1,2-dimethoxyethane at 45℃; for 3h; | |
62% | With tetrabutylammomium bromide; potassium carbonate; isopropyl alcohol In N,N-dimethyl-formamide at 115℃; for 22h; | |
43% | With sodium hydroxide In methanol; water | 10 Example 10 Example 10 5.00 g of 2-chloroquinoline and 1.80 g of sodium hydroxide are dissolved in a mixture of 20 ml of water and 16 ml of methanol. Following the addition of 1.5 g of palladium (10% by weight on activated carbon) as catalyst, the mixture is stirred for 24 h at 80-85° C. at 0.1 MPa. Then, following cooling, the catalyst and the precipitated product are filtered off. Extraction of the catalyst gives 1.7 g of 2,2'-biquinoline (43% yield). According to 1H NMR, the crude product has a purity of about 98%. CAS Registry Number: 119-91-5. 1H NMR (300 MHz, DMSO): d=8.81 (d, J=9 Hz, 2H); 8.58 (d, J=9 Hz, 2H); 8.20 (d broad, J=9 Hz, 2H); 8.08 (d broad, J=8 Hz, 2H); 7.86 (ddd, J 2, 7, 9 Hz, 2H), 7.86 (ddd, J=1, 7, 8 Hz, 2H). |
With [2,2]bipyridinyl; (2,2'-bipyridine)nickel(II) dibromide In various solvent(s) at 20℃; electrochemical reaction, magnesium anode, gold gauze cathode, -1,2 V; Yield given; | ||
Multi-step reaction with 3 steps 1: 92 percent / Et2NH; Cu2I2 / PdCl2(PPh3)2 / 0.5 h / 40 °C 2: 61 percent / NaOH / toluene / 1 h / Heating 3: 61 percent / Cu2I2; piperidine / PdCl2(PPh3)2 / 72 h / Heating | ||
With zinc In 1-methyl-pyrrolidin-2-one at 20 - 70℃; Inert atmosphere; | 25 To a glass reaction container equipped with a cooling apparatus, 15.3 mg of nickel bromide, 25.2 mg of 5,5'-bis(trimethylsilyl)-2,2'-bipyridine and 91.6 mg of zinc powder were added under an atmosphere of nitrogen at room temperature. To the obtained mixture, 114.5 mg of 2-chloroquinoline and 5 mL of N-methyl-2-pyrrolidone were added at room temperature. The obtained mixture was reacted at 70°C for 2 hours to obtain a reaction mixture containing 2,2'-biguinoline. The yield of 2,2'-biquinoline was 64.1 mg. | |
With manganese(ll) chloride; zinc In 1-methyl-pyrrolidin-2-one at 70℃; for 6h; Inert atmosphere; | 18 [Example 18] To a reaction container made of glass and equipped with a cooling apparatus, 8 mg of nickel bromide, 7 mg of 2,2'-bipyridine, 13 mg of manganese chloride and 92 mg of zinc powder were added in an atmosphere of nitrogen at room temperature. To the obtained mixture, 115 mg of 2-chloroquinoline and 5 mL of N-methyl-2-pyrrolidone were added at room temperature. The obtained mixture was stirred at 70°C for 6 hours to obtain a reaction mixture containing 2,2'-biquinoline was obtained. The yield of 2,2'-biquinoline was 85 mg. | |
Multi-step reaction with 3 steps 1: water / 8 h / 100 °C 2: tetrabutyl-ammonium chloride; sodium hypochlorite pentahydrate / water; dichloromethane / 0 - 20 °C 3: bis(1,5-cyclooctadiene)nickel (0); sodium t-butanolate; magnesium / toluene / 15 h / 150 °C / Schlenk technique; Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 2h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 72h; Ambient temperature; | |
68% | With dihydrogen peroxide In acetonitrile at 80℃; for 7h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With methylmagnesium bromide In tetrahydrofuran for 0.5h; Ambient temperature; var. Grignard reag.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With potassium carbonate In xylene at 130℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 65℃; for 3.16667h; Inert atmosphere; Schlenk technique; | |
70% | With N,N-Dimethyltrimethylsilylamine; tetramethylammonium fluoride In N,N-dimethyl-formamide at 120℃; for 48h; | |
39% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 25℃; for 24h; Inert atmosphere; |
Multi-step reaction with 2 steps 1: 47 percent / POCl3 / 3 h / Heating 2: 61 percent / Cu2I2; piperidine / PdCl2(PPh3)2 / 72 h / Heating | ||
Multi-step reaction with 4 steps 1: 47 percent / POCl3 / 3 h / Heating 2: 92 percent / Et2NH; Cu2I2 / PdCl2(PPh3)2 / 0.5 h / 40 °C 3: 61 percent / NaOH / toluene / 1 h / Heating 4: 61 percent / Cu2I2; piperidine / PdCl2(PPh3)2 / 72 h / Heating | ||
Multi-step reaction with 2 steps 1: N,N-Dimethyltrimethylsilylamine; tetramethylammonium fluoride / N,N-dimethyl-formamide / 48 h / 20 °C 2: N,N-Dimethyltrimethylsilylamine / N,N-dimethyl-formamide / 48 h / 120 °C | ||
Multi-step reaction with 2 steps 1: lithium tert-butoxide / toluene / 12 h / 90 °C / Inert atmosphere 2: phosphorus trichloride / 3 h / Inert atmosphere; Reflux | ||
Multi-step reaction with 2 steps 1: lithium tert-butoxide / toluene / 24 h / 90 °C 2: phosphorus trichloride / chloroform / 8 h / 70 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | In toluene at 20 - 25℃; for 12h; | Synthesis of (IMesH2)(C18H12N2)2(Cl)2Ru=CHPh Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and 2,2'-biquinoline (1.21 grams, 2 mol equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred for approximately 12 hours at about 20 C. to about 25 C. during which time a slight color change from dark purple to brown-purple was observed. The reaction mixture was transferred into 75 mL of cold (about 0 C.) pentane, and a brown-purple solid precipitated. The precipitate was filtered, washed with 420 mL of cold pentane, and dried under vacuum to afford (IMesH2)(C18H12N2)2(Cl)2Ru-CHPh 14 as a brown-purple powder (1.8 gram, 93% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; n-butyllithium; In tetrahydrofuran; hexane; water; ethyl acetate; | STR35 To a cooled solution of potassium ethyl malonate (20 g) (Compound 1) in water (12.5 mL) is added 12N HCl (10.1 mL) at a rate which allows the temperature to be maintained between 5-10 C. Once the addition is complete, the KCl formed is filtered and rinsed with ether (40 mL). The ethereal portion of the filtrate is separated and the aqueous portion is extracted with Et2 O (3*15 mL). The combined ether layers are dried (MgSO4) and the solvent removed in vacuo to give Compound 2. To a cooled (-30 C.) solution of 2,2-biquinoline (7.9 mg) and Compound 2 (8.2 g) in THF (95 mL), under N2, is added 2.5M n-BuLi in hexane until a pink color persists at -5 C. (approximately 50 mL). The mixture is cooled to -50 C. and a solution of 2,3,4,5-tetrafluorobenzoyl chloride (4.0 mL) (Compound 3) in THF (45 mL) is added dropwise so that the temperature is maintained at -50 C. After 30 minutes, the mixture is allowed to warm to ambient temperature and is quenched with 1M HCl (130 mL) at a rate which allows the temperature to be maintained at about 30 C. The organic layer is separated and the aqueous layer is extracted with Et2 O (4*40 mL). The combined organic layers are washed with 10% aqueous NaHCO3 (3*100 mL) and brine (3*100 mL). The organic portion is dried (MgSO4) and treated with activated charcoal. After removal of the solvents in vacuo, the residue obtained is subjected to column chromatography (silica, 5% EtOAc/hexane) to give a mixture of Compound 4 and its enol ether, which is used directly in the next step. To a solution of Compound 4 (3.5 g) in THF (70 mL) is added 1-methylpiperazine (5.88 mL). The reaction is heated at reflux, under N2, for 1 hour and the volatiles are removed in vacuo. The residue obtained is dissolved in EtOAc (40 mL), washed with water (4*35 mL), and dried (MgSO4). The solvent is removed in vacuo and the oil obtained is subjected to column chromatograpy (silica, 1:5:94 HOAc/MeOH/CH2 Cl2) to give a mixture of Compound 5 and its enol ether, which is used directly in the next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ammonium chloride; magnesium In tetrahydrofuran; isopropyl alcohol; toluene | 285 2,3-Dihydro-2-[1-[3-phenyl-3-(4-propylphenyl)propyl]-4-piperidinyl]-1H-isoindol-1-one, monohydrochloride STR169 EXAMPLE 285 2,3-Dihydro-2-[1-[3-phenyl-3-(4-propylphenyl)propyl]-4-piperidinyl]-1H-isoindol-1-one, monohydrochloride STR169 To a suspension of magnesium turnings (1.0 g, 41.2 mmol) in THF (8.2 mL) was added a solution of 1-bromo-4-propylbenzene (Aldrich) (1.64 g, 8.20 mmol) in THF (8.2 mL). The reaction was refluxed for 1.5 h, then cooled to RT. The Grignard solution was cannulated then titrated against 1.0M isopropanol in toluene using 2,2-biquinoline as an indicator to give title compound (0.35M, 70%) as a black solution. STR170 To a solution of Example 284 compound (500 mg, 1.37 mmol) in THF (8 mL) was added dropwise at 0° C. a solution of Part A compound (4.3 mL, 1.51 mmol). The reaction was stirred at 0° C. for 3 h then warmed to RT for 3 h. The reaction was quenched with saturated ammonium chloride solution (3 mL). Ethyl ether (200 mL) was added and the organic was washed with water (2*50 mL), brine (2*50 mL) and dried over MgSO4. Evaporation gave title compound (400 mg, 63%) as a crude oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With hydrogen In dichloromethane at 20℃; for 4h; | |
61.538 % de | With C26H29ClIrNO3; hydrogen In 2,2,2-trifluoroethanol at 20℃; for 3h; Overall yield = 97 %; Overall yield = 128.3 mg; | |
With C19H27N2O2RuS(1+)*CF3O3S(1-); hydrogen In isopropyl alcohol at 20℃; for 18h; Autoclave; | 29 In an autoclave, 0.001 mmol of chiral catalyst (specific selection see Table 2) and 0.1 mmol ofThe compound of formula (1-1) was dissolved in 1 mL of isopropanol. After replacing the atmosphere with nitrogen, 50 atm of hydrogen was charged and the reaction was stirred at 20 ° C for 18 h.The resulting reaction solution was subjected to silica gel column chromatography (eluent: dichloromethane) to remove the chiral catalyst.The reaction conversion ratio and trans / cis ratio (peak area ratio of nuclear magnetic characteristics) were measured by nuclear magnetic resonance using a reaction solution before purification, and the ee value, the trans / cis ratio and the ee value of the trans hydrogenated product were determined by high performance liquid chromatography Table 2 shows.The results of the identification of the resulting trans hydrogenation product (main product, chiral compound determined as (S, S) absolute configuration) and cis hydrogenation product (meso-compound meso-compound) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With triethylamine In ethanol dissolving equimolar amts. of Ru-compd. and biquinoline in N2-deaerated EtOH, addn. of Et3N, refluxing under N2 for 7h, colour changed from black to blue-green, cooling; evapn., suspn. in Et2O, vacuum filtration; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In acetonitrile Ar-atmosphere; stirring stoich. amts. at room temp. for 15 min; crystn. on concn.; elem. anal.; | |
In N,N-dimethyl-formamide soln. of Cu-compd. was mixed with 2 equiv. org. compd.; solvent was pumped off, recrystd. twice from ethanol, dried in vac.;; | ||
In dichloromethane at 25℃; for 8h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With 1,2-dimethoxyethane In dichloromethane byproducts: propene; (Schlenk, N2) a soln. of Mo-complex in CH2Cl2 was treated with 1 equiv of HBF4*(C2H5)2O, after 10 min, an excess of DME was added, the mixt. wasleft for 15 min, 2,2'-biquinoline was added, the mixt. was left for 2 h at room temp.; concd., hexane was added, filtered, recrystd. from CH2Cl2-hexane; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | In ethylene glycol (Ar); heating soln. of iridium compd. and diazafluorene deriv. in ethylene glycol at 150°C for 16 h, cooling o room temp., addn. of aq. soln. of NH4PF6; filtration, drying in oven at 80°C for 12 h, chromy. (silica gel,CH2Cl2/CH3CN (10:1)), NMR and HRMS; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: (η5-Ind)Mo(CO)2(η3-C3H5) With tetrafluoroboric acid diethyl ether complex In 1,2-dimethoxyethane; dichloromethane for 0.416667h; Stage #2: 2,2'-biquinoline In 1,2-dimethoxyethane; dichloromethane at 20℃; for 2h; | 1 A solution of (n5-Ind) Mo (CO) 2 (n3-C3Hs) (0.27g, 0.87 mmol) in CH2Cl2 was treated with HBF4. Et2O (1 eq. ). After 10 minutes dme was added in excess and the reaction was left for 15 minutes. 0.33 g (0.84 mmol) of 2, 2'-biquinoline were added and the reaction was left for 2 hours at room temperature. After concentration to about 5 ml and addition of Et2O, a deep blue complex precipitated. The mixture was filtered and the residue recrystallized from CH2Cl2/Et2O (= 90%). A drawing of the structure and physical data are given in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With bis-triphenylphosphine-palladium(II) chloride In N,N-dimethyl-formamide at 110℃; for 18h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74.6% | With LiCl In N,N-dimethyl-formamide Ru-complex, 2,2'-biquinoline and 8 equiv of LiCl were added to DMF, the mixt. was stirred at reflux for 2.5 h under N2, allowed to cool to room temp.; acetone was added, vac.-filtered, rinsed with water, washed with ether and air-dried; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: silver tetrafluoroborate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In dichloromethane at 20℃; for 0.25h; Inert atmosphere; Stage #2: 2,2'-biquinoline In dichloromethane for 1h; Reflux; | 24 Under argon atmosphere, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (66.0 mg, 0.114 mmol) was added to 4 mL of the solution of silver(I) tetrafluoroborate (22.2 mg, 0.114 mmol) in dichloromethane, and the mixture was stirred at room temperature for 15 minutes. Then, 2,2'-biquinoline (32.2 mg, 0.125 mmol) was added to the reaction solution, which was heated to reflux with stirring for one hour. The reaction solution was filtrated, and the filtrate was subjected to recrystallization by slow diffusion of dichloromethane-ether and dried to provide 103 mg of the complex of the yellow crystal. [Show Image] The NMR data of the obtained complex is provided below. 1H NMR (300 MHz, CDCl3) δ 8.79 (d, J = 8.7 Hz, 2H), 8.68 (d, J = 8.7 Hz, 2H), 7.92 (d, J = 8.2 Hz, 2H), 7.82 (d, J = 8.2 Hz, 2H), 7.73 (d, J = 6.8 Hz, 2H), 7.48 (t, J = 7.4 Hz, 2H), 7.28-7.23 (m, 6H), 7.13-7.06 (m, 10H), 7.02-6.96 (m, 8H), 6.54-6.50 (m, 2H), 1.85 (s, 6H); 31P NMR (122 MHz, CDCl3) δ -4.6 (d, J (31P-107Ag, 109Ag) = 361, 417Hz). The composition of the obtained complex was determined according to the same method as in Example 15. The present complex corresponds to the above composition formula (5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: silver tetrafluoroborate; 2,2'-bis(diphenylphosphino)biphenyl In dichloromethane at 20℃; for 1h; Inert atmosphere; Stage #2: 2,2'-biquinoline In dichloromethane at 20℃; for 1h; | 10 Under argon atmosphere, 2,2'-bis(diphenylphosphino)biphenyl (69.8 mg, 0.133 mmol) was added to 5 mL of the suspension of silver(I) tetrafluoroborate (26.0 mg, 0.133 mmol) in dry dichloromethane, and the mixture was stirred at room temperature for one hour. Then, 2,2'-biquinoline (34.2 mg, 0.133 mmol) was added to the reaction solution, which was stirred at room temperature for another one hour. The pale yellow reaction solution was filtrated, and the filtrate was concentrated, subjected to recrystallization by slow diffusion of chloroform-ether, and dried to provide 92.5 mg of the pale yellow solid complex. The result of elemental analysis for the obtained complex is shown in Table 2-2, and the composition ratio of the complex was obtained. The present complex corresponds to the above composition formula (5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: silver tetrafluoroborate; o-phenylenebis(diphenylphosphine) In dichloromethane at 20℃; for 1h; Inert atmosphere; Stage #2: 2,2'-biquinoline In dichloromethane at 20℃; for 1h; | 9 Under argon atmosphere, 1,2-bis(diphenylphosphino)benzene (91.7 mg, 0.205 mmol) was added to 5 mL of the suspension of silver(I) tetrafluoroborate (40.0 mg, 0.205 mmol) in dry dichloromethane, and the mixture was stirred at room temperature for one hour. Then, 2,2'-biquinoline (52.7 mg, 0.205 mmol) was added to the reaction solution, which was stirred at room temperature for another one hour. The pale yellow reaction solution was filtrated, and the filtrate was concentrated, subjected to recrystallization by slow diffusion of chloroform-ether, and dried to provide 171 mg of the pale yellow solid complex. The result of elemental analysis for the obtained complex is shown in Table 2-2, and the composition ratio of the complex was obtained. The present complex corresponds to the above composition formula (5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | Stage #1: gold(III) tetrachloride trihydrate With sodium hydrogencarbonate In water; acetonitrile Stage #2: 2,2'-biquinoline In water; acetonitrile at 120℃; for 0.333333h; Microwave irradiation; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With rhodium(III) acetylacetonate; 1,3-bis(mesityl)imidazolium chloride; sodium t-butanolate In toluene at 130℃; for 2h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With rhodium(III) acetylacetonate; 1,3-bis(mesityl)imidazolium chloride; sodium t-butanolate In toluene at 130℃; for 4h; High pressure; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | In chloroform at 40℃; for 2h; | 2.2 Synthesis of [CuI(bq)P(CH2N(CH2CH2)2O)3] (1bq) 1 (0.332 g, 1.0 mmol) and CuI (0.191 g, 1.0 mmol) were dissolved in 5 ml CHCl3. After a few minutes, bq (0.257 g, 1.0 mmol) in 10 ml CHCl3 was added. The mixture was stirred at 40 °C for 2 h. After this time, a burgundy solution was formed. Then the solvent was evaporated to dryness. A dark red solid was crystallized from CHCl3 to give microcrystals which are soluble in CHCl3, CH2Cl2, THF, DMSO, CH3CN and CO(CH3)2. Yield 52%. Anal. Calc. for C33H42CuIN5O3P: C, 50.94; H, 5.44; N, 9.00. Found: C, 50.78; H, 6.02; N, 8.91%. MS (CHCl3): 575.1 [Cu(bq)2]+ 100%, 319.0 [Cu(bq)]+ 13%, 650.2 [Cu(bq)1]+ 10%. NMR (298 K, CHCl3) 31P{1H}: -28 s∗; 1H: 8.21 s∗ (H3), 7.95-7.80 (H4 and H7), 7.65-7.55 (H5 and H6), 9.19 s∗ (H8), 2.78 s (H1-P), 2.40 s∗ (H2-P), 3.43 s∗ (H3-P); 13C{1H}:119.39 s (C1, C3), 137.63 s (C4), 128.01 s (C5), 127.53 s (C6), 130.22 s (C7), 130.93 s (C8), 146.42 s (C9), 128.61 s (C10), 55.18 s∗ (C1-P), 55.57 s (C2-P), 66.74 s (C3-P). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | In dichloromethane; acetonitrile at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With C21H21ClIrNO2 In tetrahydrofuran; 2,2,2-trifluoroethanol for 20h; Inert atmosphere; | |
79% | With tris(bipyridine)ruthenium(II) dichloride hexahydrate; chloropyridinecobaloxime(III); water at 30℃; for 48h; Schlenk technique; Inert atmosphere; Irradiation; | |
51% | With iron oxide surrounded by nitrogen doped graphene shell immobilized on carbon support In n-heptane at 100℃; for 12h; Autoclave; |
50% | With mesoporous Co3O4; air In dimethyl sulfoxide at 140℃; for 24h; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With lithium tetrafluoroborate In water; acetonitrile at 20℃; for 4h; Electrochemical reaction; Inert atmosphere; | |
71% | With N,N-Dimethyltrimethylsilylamine In N,N-dimethyl-formamide at 120℃; for 48h; | |
45% | With phosphorus trichloride for 3h; Inert atmosphere; Reflux; |
With phosphorus trichloride In chloroform at 70℃; for 8h; | 1.3 (3)Biclopidine oxynitride (21.9 mmol, 5.95 g) was dissolved in chloroform (50 mL)Added phosphorus trichloride (31.7 mmol, 2.74 mL) was heated to reflux (external temperature 70 ° C)Continue stirring reaction 8h,80mL water was added to quench the reaction, the organic layer was separated, the aqueous layer was extracted three times with methylene chloride,The combined organic layers were evaporated under reduced pressure to give a crude solid product,And further purified by column chromatography (eluent: methylene chloride / methanol mixture having a volume ratio of 200/1) to give a compound of the formula (1-1) in a yield of 95%The total yield was 36% (hereinafter, the yield of the compound represented by the formula (1) represents the three-step total yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With triethylamine In ethanol; water for 7h; Inert atmosphere; Reflux; Darkness; | |
With triethylamine; lithium chloride In ethylene glycol at 180℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Stage #1: 2,2'-biquinoline; C35H32IrN3O2 With trifluoroacetic acid In acetonitrile at 60℃; for 2h; Inert atmosphere; Stage #2: ammonium hexafluorophosphate; dichloromethane In water Inert atmosphere; Sonication; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In dichloromethane at 20℃; for 16h; | 4.5 Synthesis of [{η5-C5H4(C5F4N)}Mo(CO)2(phen)][BF4] (7) General procedure: [{η5-C5H4(C5F4N)}Mo(CO)2(NCMe)2][BF4] (6; 60 mg; 112 μmol) was dissolved in CH2Cl2 (10 mL) and treated with 1,10-phenanthroline (21 mg, 116 μmol). The solution was stirred for 16 h at room temperature. After that, the solvent was vacuum evaporated. The crude product was washed with ether, recrystallized from the mixture CH2Cl2/ether and vacuum dried. Yield: 64 mg (101 μmol, 90. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With potassium In tetrahydrofuran at 23℃; for 4h; Inert atmosphere; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With lithium chloride In N,N-dimethyl-formamide for 6h; Inert atmosphere; Reflux; | 12 [Ru(phen)2(CH3CN)2](PF6)2 Ru(phen)2Cl2 (0.055 g, 0.10 mmol) was dissolved in 20 mL of a mixture of CH3CN and H2O (50:50, v:v) and was refluxed for 4 hours. The solution was slowly cooled to room temperature and the solvent was evaporated to dryness by blowing with air. The remaining yellow solid was dissolved in 15 mL of H2O washed with 5 aliquots of 20 mL CH2Cl2 until the organic layer was clear. CH3CN (10 mL) was added to the aqueous layer and the mixture was refluxed for 1 hour. A saturated solution of NH4PF6 in water (5 mL) was added to the solution while hot, the mixture was allowed to cool slowly to room temperature, and was then placed in an ice bath. A yellow solid precipitated and the powder was collected by vacuum filtrations and washed with 20 mL of diethyl ether (0.053 mg, 62% yield). 1H NMR (400 MHz, (CD3)2CO) δ 10.05 (dd, 2H, 3J=5.3 Hz, 4J=1.2 Hz), 9.05 (dd, 2H, 3J=8.3 Hz, 4J=1.3 Hz), 8.64 (dd, 2H, 3J=7.1 Hz, 4J=1.4 Hz), 8.46 (d, 2H, 3J=9.1 Hz), 8.37 (m, 2H) 8.32 (d, 2H, 3J=9.0 Hz), 8.09 (dd, 2H, 3J=5.3 Hz, 4J=1.2 Hz) 2.45 (s, 6H). Elem. anal. calcd. for [Ru(phen)2(CH3CN)2](PF6)2: C, 40.3%; N, 10.1%; H, 2.66%. Found: C, 40.3%; N, 9.96%; H, 2.74%. Ru(biq)2C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis(tricyclohexylphosphine)nickel(II) dichloride; tetra-(n-butyl)ammonium iodide; zinc In 1,4-dioxane; methanol at 80℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | In acetone for 2h; | Synthesis of [Pt(p-MeC6H4)2(biq)], 1 To a solution of cis-[Pt(p-MeC6H4)2(SMe2)2] (0.040 g, 0.078 mmol) in acetone (6 mL) was added a solution of biquinoline (0.020 g, 0.078 mmol) in acetone (6 mL) and the mixture was stirred for 2 h. The solvent was evaporated and a red precipitate product separated and washed twice with n-hexane. Then, the precipitate was dried in vacuum. (Yield: 84%), red, m.p: 160 °C (decomp.), Anal. Calc. for [C32H26N2Pt] (1): (M.W: 633.654), C, 60.66; H, 4.14; N, 4.42%. Found: C, 60.09; H, 4.25; N, 4.17%; IR (KBr, y/cm1): (C]C) and (C]N) 1594sh, 1508sh, 1481s, 1431w, (CeH) 815sh, 800s, 746w, (MCl) 509w. 1H NMR (400 MHz, DMSO-d6, d/ppm): 2.17 (6H, s, C6H5CH3), 6.66 (4H, d, 3J(HoHm) 7.60 Hz, 7.23 (d, 4H, 3J(HmHo) 8.00 Hz, 7.29 (3J(PtHo) 17.21 Hz), 8.88 (d, 2H, 3J(H3H4) 8.40 Hz, H3 and H30 of biq), 8.63 (d, 2H, 3J(H4H3) 8.80 Hz, H4 and H40 of biq), 8.33 (dd, 2H, 3J(H8H7) 8.80 Hz, 3J(H8H6) 8.80 Hz, H8 and H80 of biq), 7.86 (d, 2H, 3J(H5H6) 8.00 Hz, H5 and H50 of biq), 7.51 (t, 2H, 3J(H6H5), 3J(H6H7) 16.0 Hz, H6 and H60 of biq). 7.61 (t, 2H, 3J(H7H6), 3J(H7H8) 16.81 Hz, H7 and H70 of biq). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With C46H49CoN3P4(2+)*2BF4(1-); hydrogen; potassium hydroxide In isopropyl alcohol; acetonitrile at 120℃; for 48h; Autoclave; Glovebox; chemoselective reaction; | |
79% | With hydrogen In toluene at 120℃; for 24h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With sodium hydroxide In ethanol; water at 35℃; for 3h; | 2 Synthesis of complex Tb(HDAP)3biq (1) The complex Tb(HDAP)3*biq was prepared by mixing ethanolic solutions of HDAP (0.58 g, 3 mmol) and biq (1 mmol) with an aqueous solution of Tb(NO3)3*5H2O (1 mmol) with constant stirring on magnetic stirrer. The pH of mixture was adjusted to 7-8 with 0.05 M NaOH solution. This resulted into formation of white precipitates. These precipitates were stirred for 3 h at 35 °C and then allowed to stand for 1 h. The precipitates were filtered, washed with water, ethanol, dried in air and then in vacuum desiccators to obtain complex Tb(HDAP)3*biq (1). White powder with 86% yield was obtained. The elemental analysis data of Tb(HDAP)3*biq (C48H45O12N2Tb) is found (calculated)% C, 57.56 (57.60); H, 4.54 (4.50); N, 2.78 (2.80). IR (KBr):cm-1 3008 (m), 2947 (m), 1616 (s), 1593 (s), 1534 (s), 1516 (s), 1496 (s), 1418 (m), 1384 (s), 1328 (m),1263 (m), 1220 (s), 1212 (m), 1159 (m), 1128 (s), 1057 (m), 1013 (w), 936 (m), 869 (m), 839 (m), 829 (s), 787 (m), 738 (s), 625 (m), 538 (w), 471 (w). 1H NMR (400 MHz, DMSO): δ 2.67 (bs, 9H, CH3), 3.52 (bs, 18H, OCH3), 6.31 (bs, 6H, Ar-H), 7.63 (d, 2H, biq), 7.84 (d, 2H, biq), 8.02 (d, 2H, biq), 8.21 (d, 2H, biq), 8.49 (d, 2H, biq), 8.83 (d, 2H, biq). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene at 70℃; | Synthesis of Compound 9 [CH{C(CH3)NDipp}2MgBu] (Dipp = 2,6-di-iso-propylphenyl) (1 mmol, 500 mg) was dissolved in toluene (c.a. 5 mL) followed by the addition of 1 eq. phenyl silane and then left to stir at 70 °C over 48 hrs. 1 eq. of biquinoline was then added causing an instant colour change from the pale yellow solution, of the hydride species, to a dark green solution. This was left to stir overnight at 70 °C before some solvent was removed to promote crystal growth for analysis. NMR spectrum contained large broad signals, making characterisation difficult. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With sodium hydroxide In ethanol; water at 50℃; for 4h; | General procedure: Similarly, the complexes C2-C5 were prepared with the same process as adopted in the synthesis of complex C1, but the mixture of DPBD (0.63 g, 3.2 mmol), biq (0.25 g, 1.0 mmol) and europium nitrate (0.42 g, 1.0 mmol) was used for complex C2, the mixture of DPBD (0.63 g, 3.2 mmol), phen (0.18 g, 1.0 mmol) and europium nitrate (0.42 g, 1.0 mmol) for complex C3, the mixture of DPBD(0.63 g, 3.2 mmol), neo (0.20 g, 1.0 mmol) and europium nitrate (0.42 g, 1.0 mmol) for complex C4 and the mixture of DPBD (0.63 g,3.2 mmol), bipy (0.15 g, 1.0 mmol) and europium nitrate (0.42 g,1.0 mmol) for complex C5 were used to synthesized the europium(III) ternary complexes. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | Stage #1: cis-dichloro(2,2′-bipyridine)ruthenium(II)chloride; 2,2'-biquinoline In ethylene glycol for 0.116667h; Reflux; Microwave irradiation; Inert atmosphere; Stage #2: potassium hexafluorophosphate In water; ethylene glycol at 20℃; Inert atmosphere; | Synthesis of the Hexafluorophosphate Salt of the RutheniumComplexes 2-6: General procedure: The ruthenium complex 2·(PF6)2 was synthesized by the following procedure. [Ru(bpy)2Cl2] (0.242 g, 0.5 mmol) and dmbpy (0.092 g, 0.5 mmol) were mixed in ethylene glycol (15 ml).After the suspended mixture was refluxed for 7 min in the microwave oven under purging nitrogen atmosphere. The reaction mixture was cooled to room temperature and then the saturated aqueous solution of KPF6 (20 ml)was added. An orange-red product began to precipitate and was collected in 60% yield. Complexes 2, 3,4, 5 and 6 were synthesized in the similar way. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran; hexane at 120℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With Ru(trifluoromethanesulfonate)(N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine)(η6-cymene); hydrogen In isopropyl alcohol at 20℃; for 24h; Inert atmosphere; Sealed tube; Glovebox; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
> 99 % ee | With (RuOTf((R,R)-N-Me-Tsdpen)(p-cymene)); hydrogen In isopropyl alcohol at 20℃; for 18h; Inert atmosphere; Autoclave; Glovebox; Overall yield = 90 %; stereoselective reaction; | |
> 99 % ee | With C32H37N2O2RuS(1+)*CF3O3S(1-); hydrogen In isopropyl alcohol at 20℃; for 18h; Autoclave; | 28 In an autoclave, 0.001 mmol of chiral catalyst (specific selection see Table 2) and 0.1 mmol ofThe compound of formula (1-1) was dissolved in 1 mL of isopropanol. After replacing the atmosphere with nitrogen, 50 atm of hydrogen was charged and the reaction was stirred at 20 ° C for 18 h.The resulting reaction solution was subjected to silica gel column chromatography (eluent: dichloromethane) to remove the chiral catalyst.The reaction conversion ratio and trans / cis ratio (peak area ratio of nuclear magnetic characteristics) were measured by nuclear magnetic resonance using a reaction solution before purification, and the ee value, the trans / cis ratio and the ee value of the trans hydrogenated product were determined by high performance liquid chromatography Table 2 shows.The results of the identification of the resulting trans hydrogenation product (main product, chiral compound determined as (S, S) absolute configuration) and cis hydrogenation product (meso-compound meso-compound) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In methanol; water | 4.3 Synthesis of complexes General procedure: All five Eu(III) complexes were synthesized adopting identical procedure only differing in addition of ancillary ligands in C2-C5 complexes. For C1, 3.2mmol of HOFHD in 15ml solution of methanol was mixed with 10ml solution of distilled water containing 1.0mmol of europium nitrate. The resulting mixture was stirred on magnetic stirrer set at temperature around 60°C. Also the pH of the mixture was adjusted to 6.5 with 0.05M NaOH solution. The off white precipitates formed were filtered, washed with water followed by methanol and then dried in hot air oven. Similarlly, the Gd(OFHD)3(H2O)2 (G1) was also prepared to estimate the lowest excited triplet state of OFHD ligand. To synthesize the C2-C5 complexes, the 1.0mmol of biq for C2, neo for C3, phen for C4 and bipy for C5 in 10 ml methanol was mixed with resulting mixture as prepared for C1. Then followed the aforementioned method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: tetrakis(actonitrile)copper(I) hexafluorophosphate; bis[2-(diphenylphosphino)phenyl] ether In dichloromethane at 20℃; for 3h; Stage #2: 2,2'-biquinoline In dichloromethane for 2h; | A1.1.1. [Cu(phen)(DPEphos)]BF4 (1) General procedure: A mixture of Tetrakis(acetonitrile)copper(I) tetrafluoroborate ([Cu(NCCH3)4]BF4, 3.11 g, 33.0 mmol) and Bis[(2-diphenylphosphino)phenyl]ether (O[C6H4P(C6H5)2]2, DPEphos, 5.33 g, 33.0 mmol) in 300 ml of CH2Cl2 was stirred at room temperature for 3 h. Upon addition of 1,10-Phenanthroline (C12H8N2, phen, 1.78 g, 33.0 mmol) the clear solution turned bright yellow, remained clear, and was stirred for an additional 2 h. Approximately 900 ml of diethyl ether ((CH3CH2)2O) was added to the solution to precipitate a bright yellow solid. The solution containing the newly precipitated solid was then left in the refrigerator for one day. It was vacuum filtered using a medium frit, washed with diethyl ether and dried under vacuum. A bright yellow powder was isolated (yield: 8.00 g, 93 %). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2,2'-biquinoline; C44H28Cl2F4Ir2N4 In ethylene glycol at 150℃; for 20h; Inert atmosphere; Glovebox; Schlenk technique; Stage #2: ammonium hexafluorophosphate In water; ethylene glycol at 20℃; Inert atmosphere; Glovebox; Schlenk technique; | Pg.2 7-8 Ionic Heteroleptic Iridium Complexes Metal complexes, especially light-emitting ionic iridium complexes, are synthesized as disclosed in J. D. Slinker et al., J. Am. Chem. Soc., 2004, 126, pages 2736-2767. The disclosure content of Slinker et al. in relation to the synthesis is hereby incorporated by reference. The required proportions of the ligands comprising the D1 and D2 rings (2.15 eq.) and the chlorine-bridged iridium dimers (i eq.) are transferred into a Schlenk vessel in an argon glovebox. Ethylene glycol is added, for example by means of a cannula, and the reaction mixture is boiled at 150° C. for 20 hours (under reflux and pressure-regulating conditions). This forms a clear solution. The solution can be cooled down to room temperature and introduced into another Schlenk vessel comprising distilled water. The excess of the aqueous solution of ammonium hexafluorophosphate (NH4PF6) is added to this aqueous solution, so as to result in an intermediate as precipitate of the desired heteroleptic iridium complex. The product is filtered and washed with water and diethyl ether and then dried under reduced pressure. The synthesized complex is purified by means of column chromatography. The product obtained is dried under reduced pressure. The synthesis, the operations and the purification are conducted under inert gas atmosphere. The following diagram shows the preparation of an ionic heteroleptic iridium complex: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 66% 2: 30% | With cobalt(II) tetrafluoroborate hexahydrate; tris(2-diphenylphosphinophenyl)phosphine; hydrogen In tetrahydrofuran at 100℃; for 40h; Autoclave; diastereoselective reaction; | |
1: 50.8% 2: 25.2% | With bis(1,5-cyclooctadiene)diiridium(I) dichloride; phenylsilane In methanol at 45℃; for 24h; Inert atmosphere; Sealed tube; | 23 Synthesize 1,2,3,4-tetrahydroquinoline with the following structural formula General procedure: Add 0.0067g (0.05mol) [Ir(cod)Cl]2 into a 25mL high-pressure reaction tube, use a double-row tube for three fillings, and then add 24μL (0.02mmol) quinoline and 0.1mL (0.8mmol) under a nitrogen stream. ) Phenylsilane, 2.5 mL of methanol, the tube was sealed, and the reaction was stirred at 45°C for 24 hours. The reaction was quenched by adding 10 mL of saturated aqueous ammonium chloride solution, extracted with ethyl acetate (10 mL each time, 3 times), and the extracts were combined. Add anhydrous sodium sulfate to dry, use a mixture of petroleum ether and ethyl acetate at a volume ratio of 10:1 as a developing solvent, and separate the products by column chromatography to obtain an oily product 1,2,3,4-tetrahydroquinoline The yield was 93.6%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With [(Cp*IrCl)2(4,4′,6,6′-tetrahydroxy-2,2′-bipyrimidine)][Cl]2; hydrogen In ethanol at 20℃; for 20h; Inert atmosphere; Schlenk technique; Autoclave; | |
53% | With palladium 10% on activated carbon; ammonium formate In ethanol at 80℃; for 12h; Schlenk technique; | 3. EXPERIMENTAL SECTION General procedure: The typical procedure for Pd/C catalyzed decarboxylation-transfer hydrogenation (DTH) of quinoline carboxylicacids and transfer hydrogenation (TH) of quinolines: A mixtureof quinoline 1 or 3 (0.50 mmol), Pd/C (10.0 mg, 10 wt%palladium on activated carbon paste and 50% moisture, 0.9mol% [Pd] based on starting material 1 or 3) in ethanol (3mL) was added into a Schlenk flask (25 mL) at room temperature.Then ammonium formate (126 mg, 2.0 mmol, 4.0equiv) was added and the mixture was stirred at 80 °C. Thereaction was monitored by thin layer chromatography (TLC).After the reaction was finished, the solvent was evaporatedunder reduced pressure and the residue was purified by columnchromatography (petroleum ether/ethyl acetate 20:1 to5:1) to provide 1,2,3,4-tetrahydroquinolines 2 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.1% | Stage #1: tetrakis-(benzo[h]quinoline(-1H))-μ-(dichloro)-diiridium(III); 2,2'-biquinoline With ethylene glycol at 150℃; for 24h; Schlenk technique; Inert atmosphere; Stage #2: ammonium hexafluorophosphate In water Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In dichloromethane at 20℃; Inert atmosphere; | |
In diethyl ether for 4h; Inert atmosphere; Schlenk technique; Darkness; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85 % ee | With (Cp*RhTsDPEN)+CF3SO3-; hydrogen In isopropyl alcohol at 20℃; for 18h; Autoclave; | 21 In an autoclave, 0.001 mmol of chiral catalyst (specific selection see Table 2) and 0.1 mmol ofThe compound of formula (1-1) was dissolved in 1 mL of isopropanol. After replacing the atmosphere with nitrogen, 50 atm of hydrogen was charged and the reaction was stirred at 20 ° C for 18 h.The resulting reaction solution was subjected to silica gel column chromatography (eluent: dichloromethane) to remove the chiral catalyst.The reaction conversion ratio and trans / cis ratio (peak area ratio of nuclear magnetic characteristics) were measured by nuclear magnetic resonance using a reaction solution before purification, and the ee value, the trans / cis ratio and the ee value of the trans hydrogenated product were determined by high performance liquid chromatography Table 2 shows.The results of the identification of the resulting trans hydrogenation product (main product, chiral compound determined as (S, S) absolute configuration) and cis hydrogenation product (meso-compound meso-compound) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; tetrabutylammonium tetrafluoroborate In water; acetonitrile at 20℃; for 4h; Electrochemical reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | Stage #1: tetrafluoroboric acid diethyl ether; (C5H4COOH)(η-allyl)(carbonyl)2Mo In dichloromethane; acetonitrile at 0 - 20℃; Inert atmosphere; Schlenk technique; Stage #2: 2,2'-biquinoline In acetone at 20℃; Inert atmosphere; Schlenk technique; | 14 4.14 Synthesis of [(η5-C5H4COOH)Mo(CO)2(bq)][BF4] (22) General procedure: [(η3-C3H5)(η5-C5H4COOH)Mo(CO)2] (3; 0.80g, 2.65mmol) was dissolved in CH2Cl2 (10ml), cooled at 0°C, treated with acetonitrile (1ml) and then with HBF4·Et2O (0.36ml, 2.65mmol). The reaction mixture was stirred at room temperature overnight and then volatiles were vacuum evaporated. The intermediate was washed with Et2O, recrystallized from a mixture CH2Cl2/Et2O dissolved in acetone (20ml) and treated with 1,10-phenanthroline (0.48g, 2.66mmol). The reaction mixture was stirred at room temperature overnight. The crude product was washed with Et2O, recrystallized from CH2Cl2/Et2O and vacuum dried. Yield: 1.15g (2.18mmol, 82%). 4.14 Synthesis of [(η5-C5H4COOH)Mo(CO)2(bq)][BF4] (22) The reaction was carried out as was described for compound 19, but with 2,2'-biquinoline (0.68 g, 2.65 mmol). Yield: 1.10 g (1.82 mmol, 69%). Red powder. Calcd for C26H17BF4MoN2O4: C, 51.69; H, 2.84; N, 4.64. Found: C, 51.36; H, 2.95; N, 4.35. 1H NMR (CD3CN, 400 MHz, δ ppm): 8.99 (d, 3J(1H,1H) = 8.7 Hz, 2H, H4,4', C18H12N2), 8.67 (d, 3J(1H,1H) = 8.7 Hz, 2H, H3,3', C18H12N2), 8.52 (d, 3J(1H,1H) = 8.7 Hz, 2H, H8,8', C18H12N2), 8.25 (d, 3J(1H,1H) = 8.3 Hz, 2H, H5,5', C18H12N2), 8.12 (ddd, 3J(1H,1H) = 8.7 Hz, 3J(1H,1H) = 7.0 Hz, 4J(1H,1H) = 1.3 Hz, 2H, H7,7', C18H12N2), 7.92 (ddd, 3J(1H,1H) = 8.3 Hz, 3J(1H,1H) = 7.0 Hz, 4J(1H,1H) = 1.0 Hz, 2H, H6,6', C18H12N2), 6.14 (t, 3J(1H,1H) = 4J(1H,1H) = 2.3 Hz, 2H, C5H4), 5.96 (t, 3J(1H,1H) = 4J(1H,1H) = 2.3 Hz, 2H, C5H4). FTIR (ATR, cm-1): 1975 vs [νa(C≡O)], 1895 vs [νs(C≡O)], 1723 s [ν(C=O)], 1030 vs-br [νa(BF)]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With sodium azide; diphenic acid In methanol; water at 140℃; for 3h; | 1 Example: Ζη(ΝO3) 2 · 6H20 (29.7 mg, 0.1 mmol), 2,2'-biquinoline (25.6 mg, 0.1 mmol), 2,2 -biphenyl diacid (24.0 mg, 0.1 mmol) and NaN3 (13.2 mg, 0.2 mmol), were added to a mixed solvent of 12 mL methanol and secondary deionized water (1:1 volume ratio), It was sealed in a 25 mL stainless steel container lined with tetrafluoroethylene, heated to 140 °C for 3 days, and then slowly cooled to room temperature. After filtration, the filter cake was washed with diethyl ether and dried in air to obtain colorless massive crystals, the calculated yield based on Zn(N03)2·6H20 was approximately 61%. This material was insoluble in water and other organic solvents. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | A Zn(NO3)2*6H2O dissolution (10.3 mg, 0.0346 mmol/2 ml ethanol:water 1:1) was added to another dissolution of <strong>[27148-03-4]thiosaccharine</strong> (12.3 mg, 0.062 mmol/2 ml ethanol:water 1:1). Finally, solid 2,2'-biquinoline was added (9.4 mg, 0.0367 mmol/2 ml ethanol:water1:1). A pale yellow powder was then obtained. Yield: 90%. Molar conductivity (mS M1) = 26.3. Analytical percent composition calculated for C32H20N4O4S4Zn: C = 53.520%; H = 2.807%; N = 7.801%. Found: C = 53.884%; H = 2.761%; N = 7.698%. Soluble in DMSO and DMF. Almost insoluble in water, ethanol, methanol, acetone, dichloromethane and chloroform. [DMSO, kmaxnm]: 339 1H NMR (300 MHz, DMSO) d 8.80 (dd, 1H), 8.58 (dd, 1H), 8.19(dd, 1H), 8.08 (dd, 1H), 7.89-7.95 (m, 1H), 7.85 (td, 1H), 7.53-7.73 (m, 4H). 13C NMR (75 MHz, DMSO) d 191.54 (C1), 155.21(C16), 147.16 (C8), 137.80 (C7), 137.36 (C14), 136.32 (C2), 132.16 (C4), 130.99 (C5), 130.18 (C10), 129.31 (C12), 128.16 (C13), 128.03(C11), 127.42 (C9), 125.10 (C3), 119.05 (C6), 118.87 (C15). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With sodium hydroxide In water at 50 - 60℃; for 2h; | Synthesis of Tb(III) Complexes General procedure: To an aqueous solution of terbium nitrate pentahydrate(1.0 mmol, 0.43 g) added an alcoholic solution of ligandHDPBD (3.2 mmol, 0.63 g) dropwise under vigorous stirringon magnetic stirrer. The pH of the resulting mixturewas adjusted to 6.5 with 0.05 M sodium hydroxide solution,resulting in the formation of white precipitates afterconstant stirring for two hours at a temperature of 50-60 °C. The precipitates were filtered out and dried inhot air oven to obtained C1 complex. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol at 120℃; for 16h; Autoclave; High pressure; | [Ni(biqu)Br2], 3 [Ni(biqu)Br2], 3. A mixture consisting of 0.109g of NiBr2 (0.5mmol) and 0.128g of biqu (0.5mmol) in 15cm3 of ethanol was placed into teflon-lined steel autoclave and heated to 120°C for 16h. Red crystals formed in the solution upon slow cooling of the mixture to the room temperature. Crystals were separated by filtration, rinsed with cold ethanol and dried in air. Anal. Calc. for C18H12Br2N2Ni (474.80g·mol-1): C, 45.53; H, 2.55; N, 5.90. Found: C, 45.25; H, 2.51; N, 5.86. IR bands ν/cm-1: 3086(w), 3055(w), 1965(w), 1934(w), 1822(w), 1586(m), 1508(s), 1434(m), 1380(m), 1366(w), 1341(w), 1302(w), 1214(m), 1145(s), 1106(m), 978(w), 957(w), 870(m), 829(s), 780(s), 746(s), 699(w), 659(w), 637(w), 526(w), 499(w), 487(s) (s=strong, m=medium, w=weak). UV/Vis (Nujol) νmax/103 cm-1 (relat. absorb.): 9.86 (0.282), 11.05 (0.246), 11.42 (0.247), 15.63 (0.225), 19.19 (0.481). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
24 %Spectr. | With bis(1,5-cyclooctadiene)nickel (0); magnesium; sodium t-butanolate In toluene at 150℃; for 15h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | In ethanol; acetonitrile at 69.84℃; for 0.666667h; | 2.2. Synthesis of (1) Cu(NO3)2.4H2O (103 mg, 0.4 mmol) and Na(dca) (71 mg,0.8 mmol) were dissolved in ethanol (60 ml) and stirred withheating to 343 K. To this hot solution, a solution of biq (205 mg, 0.8 mmol) in acetonitrile (75 ml) was added and stirring was continued for about 40 min. The resulting redsolution was filtered into a beaker and left undisturbed in thedark at room temperature. After 10 d, dark-green tabular crystals were obtained. The crystals were collected by filtration,washed with acetonitrile and dried in air [yield: 93 mg,26%, based on Cu(NO3)2.4H2O]. Elemental analysis (%)calculated for C44H24Cu2N16: C 58.47, H 2.68, N 24.79; found:C 58.36, H 2.71, N 24.86. IR (KBr, cm-1): 3631 (w), 3126 (w),3058 (w), 2347 (s), 2268 (s), 2210 (s), 2160 (s), 1618 (w), 1594(m), 1550 (w), 1509 (w), 1432 (w), 1381 (s), 1340 (m), 1290 (w),1214 (w), 1159 (w), 1102 (w), 971 (w), 914 (w), 819 (s), 781 (m),755 (m), 742 (m), 619 (w), 531 (w). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With sodium azide In water at 180℃; for 72h; Autoclave; | Zinc (NO3)2·6H2O (59.2 mg, 0.2 mmol), NaN 3 (26.0 mg, 0.4 mmol), 5-aminoPhthalic acid (18.1 mg, 0.1 mmol), 2,2'-biquinoline (25.63 mg, 0.1 mmol) in 15 mL of secondary deionized water for dissolutionThe agent was added to a 25 ml autoclave, heated to 180 ° C, and maintained at this temperature for 3 days. Allow yourself to cool to room temperature,Yellow block crystals were obtained, filtered, and the filter cake was washed with deionized water to obtain a single crystal of the target complex. Based on zinc (NO3) 2 · 6H2O calculationThe yield was about 51%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol at 60℃; for 5h; | Synthetic Procedure General procedure: The synthesis of complexes was carried out by single potsynthesis. An anhydrous methanolic solution (10 mL) of 4-fluoro-N-salicylideneaniline (0.6456, 3 mmol) was addeddropwise to a vigorously stirred solution of 2,2′-bipyridine(0.1561, 1 mmol) in 10 mL methanol. To this solution ofligands, a methanolic solution of EuCl3 (0.2583 g, 1 mmol)was added slowly with continuous stirring. The pH of thereaction mixture obtained was adjusted to 6.0-7.0. Afteradjusting the pH, the reaction mixture was refluxed at 60 °C.The refluxing was continued for 5 h. The light yellow solutionso obtained was evaporated at room temperature to give thesolid compound which was extracted with diethyl ether. Thecompound obtained after extraction is C1 (Scheme 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In tetrahydrofuran at 20℃; Glovebox; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
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93% | In benzene at 20℃; Inert atmosphere; Schlenk technique; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With lithium tetrafluoroborate In water; acetonitrile at 20℃; for 4h; Electrochemical reaction; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99 % ee | With Ru(trifluoromethanesulfonate)(N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine)(η6-cymene); hydrogen In isopropyl alcohol at 25℃; for 24h; Autoclave; Overall yield = 89percent; Overall yield = 184 mg; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.13 g | In dichloromethane at 20℃; for 0.25h; Darkness; | 4.7. General synthesis of heteroleptic Cu(I) photosensitizers The heteroleptic Cu(I) photosensitizers were prepared using a two-step, one-pot procedure.[11,27,47] Tetrakis(acetonitrile)copper(I)hexafluorophosphate, alkylated-Nixantphos, and biq were dissolved separately in minimal CH2Cl2 to afford colorless solutions. In the dark at room temperature, alkylated-Nixantphos was added dropwise to the rapidly stirring [CuI(CH3CN)4]PF6 solution to form [CuI(alkyl-Nixantphos)(CH3CN)2]PF6 in situ. After 15 min, the biq solution was added dropwise, immediately producing a dark orange-red solution. The solution was stirred for 15 min before added dropwise to 200 mL of rapidly stirring hexanes, followed by filtration to isolate an orange solid. The precipitate was dissolved in minimal CH2Cl2, reprecipitated in 200 mL of diethyl ether, and collected by vacuum filtration to produce an orange powder. 4.7.1. [CuI(Et-Nixantphos)(biq)]PF6 Starting materials: [Cu(CH3CN)4]PF6 (0.058 g, 0.159 mmol), Et-Nixantphos (0.100 g, 0.172 mmol), biq (0.036 g, 0.141 mmol). Orange powder; yield = 0.130 g (0.124 mmol, 82.1%). 1H NMR (500 MHz, 298 K, acetone-d6): δ (ppm) = 8.80 (d, J = 9.0 Hz, 2H), 8.68 (d,J = 9.0 Hz, 2H), 8.37 (d, J = 8.5 Hz, 2H), 8.12 (dd, J = 8.0, 1.0 Hz,2H), 7.67 (t, J = 7.5 Hz, 2H), 7.39 (t, J = 7.5 Hz, 2H), 7.37 (t,J = 7.0 Hz, 4H), 7.29 (dd, J = 8.0, 1.0 Hz, 2H), 7.16 (t, J = 7.5 Hz, 8H), 7.07-6.98 (m, 10H), 6.42-6.33 (m, 2H), 4.15 (q, J = 7.0 Hz, 2H), 1.56 (t, J = 7.0 Hz, 3H). 31P{1H} NMR (202 MHz, 298 K acetone-d6): δ(ppm) = - 15.22; -146.06 (PF6-). HR-ESI(+)-MS (CH3OH): [M -PF6]+ m/z = 898.2178 (calc. m/z = 898.2172). Elemental analysis calculated for C56H43N3OP3F6Cu·H2O: 63.31% C, 4.27% H, 3.96% N.Found: 63.36% C, 4.24% H, 4.05% N. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.138 g | In dichloromethane at 20℃; for 0.25h; Darkness; | 4.7. General synthesis of heteroleptic Cu(I) photosensitizers The heteroleptic Cu(I) photosensitizers were prepared using a two-step, one-pot procedure.[11,27,47] Tetrakis(acetonitrile)copper(I)hexafluorophosphate, alkylated-Nixantphos, and biq were dissolved separately in minimal CH2Cl2 to afford colorless solutions. In the dark at room temperature, alkylated-Nixantphos was added dropwise to the rapidly stirring [CuI(CH3CN)4]PF6 solution to form [CuI(alkyl-Nixantphos)(CH3CN)2]PF6 in situ. After 15 min, the biq solution was added dropwise, immediately producing a dark orange-red solution. The solution was stirred for 15 min before added dropwise to 200 mL of rapidly stirring hexanes, followed by filtration to isolate an orange solid. The precipitate was dissolved in minimal CH2Cl2, reprecipitated in 200 mL of diethyl ether, and collected by vacuum filtration to produce an orange powder. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.125 g | In dichloromethane at 20℃; for 0.25h; Darkness; | 4.7. General synthesis of heteroleptic Cu(I) photosensitizers The heteroleptic Cu(I) photosensitizers were prepared using a two-step, one-pot procedure.[11,27,47] Tetrakis(acetonitrile)copper(I)hexafluorophosphate, alkylated-Nixantphos, and biq were dissolved separately in minimal CH2Cl2 to afford colorless solutions. In the dark at room temperature, alkylated-Nixantphos was added dropwise to the rapidly stirring [CuI(CH3CN)4]PF6 solution to form [CuI(alkyl-Nixantphos)(CH3CN)2]PF6 in situ. After 15 min, the biq solution was added dropwise, immediately producing a dark orange-red solution. The solution was stirred for 15 min before added dropwise to 200 mL of rapidly stirring hexanes, followed by filtration to isolate an orange solid. The precipitate was dissolved in minimal CH2Cl2, reprecipitated in 200 mL of diethyl ether, and collected by vacuum filtration to produce an orange powder. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In water at 50℃; for 5h; | Preparation of complexes General procedure: For synthesizing complex C1, a hot aqueous solutionof Sm(NO3)3.6H2O (0.2225 g, 1 mmol) wasadded drop-wise to the hot ethanol solution of L(0.2822 g, 3 mmol). Then, the ethanol solution ofmphen (0.0971 g, 1 mmol) was mixed to theabove mixture. The aqueous 0.05M NaOH wasadded drop-wise to maintain neutral pH value.This solution was stirred for 3 h at 50 C andallowed to stand for 2 h, then filtered to get asolid product. The solid product was kept in adesiccator after washing with water and ethanol,to obtain anhydrous complex C1. The complexesC2 and C3 were synthesized in a similar fashionusing biq and bathocup, respectively. The preparatoryroute of complexes C1-C3 is given inFigure 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: tetrakis(acetonitrile)copper(I)tetrafluoroborate; o-phenylenebis(diphenylphosphine) In ethanol; acetonitrile at 20℃; for 0.5h; Stage #2: 2,2'-biquinoline In ethanol; acetonitrile at 20℃; | 4.2 Preparation of [Cu(dppb) (2,2′-biquinoline)]BF4 (1) At room temperature, a mixture of [Cu(CH3CN)4]BF4 (0.0138g, 0.05mmol) and dppb (0.0223g, 0.05mmol) in 4ml CH3CN/C2H5OH was stirred for 0.5h and then bbim (0.0128g, 0 0.05mmol) was added. The vapor diffusion of diethyl ether into the solution produced red block crystals. The complex was offered by filtration, washed with diethyl ether and dried in vacuo. Yield: 0.0134g (65%). IR (cm-1): 3433 (m), 1592(w), 1479 (m), 1433 (m), 1379 (w), 1086(s), 1050 (vs), 822(w), 780 (w), 742 (s), 696 (s), 520(s). 1H NMR (400MHz, DMSO, 25°C, TMS): δ=7.05-7.23 (m, 18H), 7.31(t, J=14.2Hz, 4H), 7.40(d, J=8.4Hz, 2H), 7.63(t, J=14.8Hz, 2H), 7.81-7.89 (m, 2H), 7.95(t, J=8.8Hz, 2H), 8.16(d, J=8.2Hz, 2H), 8.93(d, J=8.7Hz, 2H), 9.04(d, J=8.8Hz, 2H). 31P{1H}-NMR(DMSO, 25°C, TMS): -3.25ppm. Elemental analysis: calculated for C48H36BCuF4N2P2: C 67.58, H 4.25, N 3.28. Found C 67.26, H 4.62, N 3.25. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79.1% | Stage #1: Cd(2+)*2C7F5O2(1-)*4H2O; 2Eu(3+)*6C7F5O2(1-)*10H2O In acetonitrile at 70℃; for 0.333333h; Stage #2: 2,2'-biquinoline In acetonitrile at 70℃; | Synthesis of [Cd(Pfbz)2(Biquin)] (VIII) General procedure: A weighed sample of compound II (0.145 g, 0.083 mmol) was added to a solution of complex I (0.100 g, 0.166 mmol) in MeCN (5 mL). The reaction mixture was stirred at 70° for 20 min, and Biquin (0.043 mg, 0.166 mmol, Cd :L = 1 : 1) was added to the hot solution. Colorless crystals formed in5 days and suitable for XRD were decanted from themother liquor and washed with cold acetonitrile ( ≈5°C). The yield of complex VIII was 0.106 g (79.1%based on compound I). For |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.46 g | In dichloromethane for 2h; | 2.4.4. Synthesis of [Cu(bq)(P[C6H4-4-OMe]3)2]NO3 (Cu-OMe-2) A methanolic solution (20 mL) of Cu(NO3)2.2 1/2H2O (0.500 g, 2.15 mmol) was added slowly to tris(4-methoxyphenyl)phosphine (3.030 g, 8.60 mmol) in degassed methanol solution (30 mL). The reaction solution was stirred for 2 h and the volatiles was removed. Then, 2,2 -biquinoline (0.619 g, 0.24 mmol) and 20 mL DCM were added, and the reaction mixture was stirred for 2 h. The reaction mixture was reduced in volume under vacuum to about 10 mL and 50 mL diethylether was added, leading to an orange precipitate. The precipitate was collected by filtration and washed sev- eral times with petrol, yielding Cu-OMe-2 (0.460 g, 20%) as bright orange powder. HR ESI MS: calcd for [C39H3363 CuN 2 O 3 P] + [M- PR 3 ] + : 671.1625 found 671.1490. Anal. Calcd for C 60 H 54 CuN 3 O 9 P 2 : C, 66.32; H, 5.01; N, 3.87%; found: C, 66.04; H, 4.87; N, 3.52%. IR (solid, cm -1 ): 3352br, 1655s, 1571s, 1445 m, 1406 m, 1317s, 1267s, 1209 w, 1180 w, 1122 w, 1071 w, 893 m, 818 m, 740 m, 710 m, 696 m. 1 H NMR (CDCl 3 ) 8.94 (br, 2H, bq), 8.68 (br, 2H, bq), 7.88 (d, J HH = 7 Hz, 4H, bq), 7.47 (br, 2H, bq), 7.11 (br, 2H, bq), 6.95 (br, 12H, PR 3 ), 6.63 (br, 12H, PR 3 ), 3.74 (s, 18H, OCH 3 ). 31 P NMR (CDCl 3 ): -3.44 (s, P(C 6 H 4 -4-OMe) 3 ). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | In dichloromethane for 2h; Inert atmosphere; | 2.4. General procedure to synthesis [Cu(bq)(PR 3 ) 2 ]NO 3 { R = Ph (Cu-Ph-2); R = -C6H4-4-F (Cu-F-2); R = Cy (Cu-Cy-2)} General procedure: Cu(PR3)2 NO3 and one molar equivalent of 2,2 -biquinoline (bq) were stirred in 15 mL dichloromethane under nitrogen atmosphere. The reaction mixture turned immediately to orange and was left under stirring for further two hours. Petroleum ether (30 mL) was added to the reaction, the orange precipitation was collected by filtration, washed with diethylether and dried, affording the products as orange powders. The orange powders were re- dissolved in acetonitrile and precipitated by diethyl ether to remove the traces of the formed [Cu(bq)2]NO3. 2.4.1. Synthesis of [Cu(bq)(PPh 3 ) 2 ]NO 3 (Cu-Ph-2) Cu-Ph-1 (0.450 g, 0.69 mmol) and 2,2 -biquinoline (0.177 g, 0.69 mmol) reacted to yield yellow-orange powders of Cu-Ph-2 (0.599 g, 93%). HR ESI MS: calcd for [C 36 H 27 63 CuN 2 P] + [M-PR 3 ] + : 581.12024, found 581.11780.. Anal. Calcd for C 54 H 42 CuN 3 O 3 P 2 : C, 71.55; H, 4.67; N, 4.64%; found: C, 71.13; H, 4.87; N, 4.50%. IR (solid, cm -1 ): 3075 m, 3058 m, 1594 m, 1507 m, 1480 m, 1433s, 1334s, 1213 w, 1141 w, 1094s, 1027 w, 999 w, 828 s, 785 m, 743 s, 694 s. 1 H NMR (CDCl 3 ) δ 8.86 (br, 2H, bq), 8.65 (br, 2H, bq), 7.87 (d, J HH = 9 Hz, 4H, bq), 7.45 (br, 4H, bq), 7.30 (t, J HH = 9 Hz, 6H, PPh 3 ), 7.13 (br, 12H, PPh 3 ), 7.08 (br, 12H, PPh 3 ). 31 P NMR (CDCl 3 ): 0.22 (s, PPh 3 ). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | In dichloromethane for 2h; Inert atmosphere; | 2.4. General procedure to synthesis [Cu(bq)(PR 3 ) 2 ]NO 3 { R = Ph (Cu-Ph-2); R = -C6H4-4-F (Cu-F-2); R = Cy (Cu-Cy-2)} General procedure: Cu(PR3)2 NO3 and one molar equivalent of 2,2 -biquinoline (bq) were stirred in 15 mL dichloromethane under nitrogen atmosphere. The reaction mixture turned immediately to orange and was left under stirring for further two hours. Petroleum ether (30 mL) was added to the reaction, the orange precipitation was collected by filtration, washed with diethylether and dried, affording the products as orange powders. The orange powders were re- dissolved in acetonitrile and precipitated by diethyl ether to remove the traces of the formed [Cu(bq)2]NO3 . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
17% | In dichloromethane for 2h; Inert atmosphere; | 2.4. General procedure to synthesis [Cu(bq)(PR 3 ) 2 ]NO 3 { R = Ph (Cu-Ph-2); R = -C6H4-4-F (Cu-F-2); R = Cy (Cu-Cy-2)} General procedure: Cu(PR3)2 NO3 and one molar equivalent of 2,2 -biquinoline (bq) were stirred in 15 mL dichloromethane under nitrogen atmosphere. The reaction mixture turned immediately to orange and was left under stirring for further two hours. Petroleum ether (30 mL) was added to the reaction, the orange precipitation was collected by filtration, washed with diethylether and dried, affording the products as orange powders. The orange powders were re- dissolved in acetonitrile and precipitated by diethyl ether to remove the traces of the formed [Cu(bq)2]NO3 . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | In methanol; dichloromethane at 25℃; for 4h; Inert atmosphere; Schlenk technique; | Complex 3 μ-dichloro bridged Ir(III) dimer complex 2 (1.0 g, 0.29 mmol), 2,2'-Biquinoline (0.31 g, 0.60 mmol) were added into a mixture of degassed dichloromethane and methanol (30 mL, 1:1 v/v), the system was stirred at room temperature for 4 h under nitrogen atmosphere. Then the solvent was removed by a rotary evaporator. The crude product was purified by column chromatography using dichloromethane/methanol as eluent. Complex 3: orange-red powder (57% yield). 1H NMR (500 MHz, CDCl3, δ) 8.54 (d, J= 8.65 Hz, 2H), 8.15 (d, J= 8.65 Hz, 2H), 8.01 (d, J= 8.30 Hz, 2H), 7.92 (d, J= 8.10 Hz, 2H), 7.89 (s, 2H), 7.67 (s, 2H), 7.54 (t, J= 8.00 Hz, 4H), 7.48 (t, J= 7.50 Hz, 2H), 7.31 (d, J= 8.85 Hz, 2H), 7.13 (t, J= 7.20 Hz, 2H), 6.83 (t, J= 8.35 Hz, 2H), 6.53 (s, 2H), 2.96 (s, 6H). 13C NMR (125 MHz, CDCl3): 166.66, 159.63, 154.10, 150.55, 146.98, 146.54, 144.37, 141.78, 134.83, 133.70, 131.42, 131.33, 129.74, 129.12, 128.89, 127.97, 127.78, 126.43, 125.77, 124.87, 124.67 (q, 3J13C-19F= 5.05 Hz), 123.42 (q, 2J13C-19F= 31.3 Hz), 123.18 (q, 1J13C-19F= 270.9 Hz), 121.58, 117.48, 19.39. 31P NMR (202 MHz, CDCl3 δ): -144,25 (sep, J= 711.04 Hz). 19F NMR (470 MHz, CDCl3 δ): -61.92 (s), -72.97 (d, J= 709.70 Hz). MALDI-TOF-MS (m/z): calcd for C52H32Cl2F6IrN4, 1089.15; found, 1089.72. FT-IR: 1070 cm-1 (C-N stretching vibration), 1266/1257 cm-1 (C-C contraction vibration), 1386/1405 cm-1 (C-H stretching vibration), 1592 cm-1 (C=C contraction vibration), 2900/2981 cm-1 (Ar-H stretching vibrations). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With sodium hydroxide In lithium hydroxide monohydrate at 50℃; for 6h; | Preparation of Complexes General procedure: The solution of ancillary ligand (A, B, and C) (1 mmolin ethanol) was added to stirred solution of Sm3+salt (1 mmolin water) and L (3 mmol in ethanol). The pH was adjustednear 7 by N/20 NaOH solution and this resultant mixturewas continuously stirred for 6 h at about 50 °C tillpale yellow precipitates appear, which were filtered andwashed with water-ethanol (5 mL each). The precipitateswere kept in desiccator to acquire desired complex. Thepreparatory route of ternary Sm3+complexes C1-C3 isshown in Fig. 1. |
Tags: 119-91-5 synthesis path| 119-91-5 SDS| 119-91-5 COA| 119-91-5 purity| 119-91-5 application| 119-91-5 NMR| 119-91-5 COA| 119-91-5 structure
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H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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