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CAS No. : | 13991-08-7 | MDL No. : | MFCD00014081 |
Formula : | C30H24P2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | NFRYVRNCDXULEX-UHFFFAOYSA-N |
M.W : | 446.46 | Pubchem ID : | 498379 |
Synonyms : |
|
Num. heavy atoms : | 32 |
Num. arom. heavy atoms : | 30 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 6 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 143.85 |
TPSA : | 27.18 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | Yes |
Log Kp (skin permeation) : | -3.85 cm/s |
Log Po/w (iLOGP) : | 4.47 |
Log Po/w (XLOGP3) : | 7.29 |
Log Po/w (WLOGP) : | 5.2 |
Log Po/w (MLOGP) : | 7.27 |
Log Po/w (SILICOS-IT) : | 8.92 |
Consensus Log Po/w : | 6.63 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -7.5 |
Solubility : | 0.0000142 mg/ml ; 0.0000000317 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -7.69 |
Solubility : | 0.00000918 mg/ml ; 0.0000000206 mol/l |
Class : | Poorly soluble |
Log S (SILICOS-IT) : | -12.56 |
Solubility : | 0.0000000001 mg/ml ; 0.0 mol/l |
Class : | Insoluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 5.36 |
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 |
---|---|---|
(i) nBuLi, (ii) /BRN= 512032/; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ammonia; sodium 1.) -70 deg C, 90 min; 2.) THF, 3h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | In dichloromethane at 20℃; for 12h; | |
55% | In dichloromethane (N2); drybox; C6H4(PPh2)2 in CH2Cl2 was added to soln. of Ga compd. in CH2Cl2; mixt. was stirred at room temp. for 12 h; solvent removed (vac.); pentane added; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With dihydrogen peroxide In chloroform at 20℃; for 1h; | |
99% | With dihydrogen peroxide In water at 20℃; for 0.5h; | |
82% | With dihydrogen peroxide In tetrahydrofuran at 20℃; for 2h; | Synthesis of the phosphine oxides General procedure: Synthesis of the phosphine oxidesThe phosphine oxides were synthesized by oxidation ofthe corresponding phosphines. Calculated amounts of H2O2(30%) were added slowly to the vigorously stirred THF solutionof the respective phosphine. Stirring was maintainedat room temperature for 2 h. After evaporation of THF, theresidue was treated with acetone-ethyl acetate to obtain therespective phosphine oxide product as a precipitate. The precipitatesthus obtained were filtered off and dried in a vacuum.All melting points were above 360 C with decomposition. OPPO: 1H NMR (250 MHz, CDCl3): d = 7:19 (m, 8H,Phen-H), 7.35 (m, 12H, Phen-H), 7.57 (t, 2H, Phen-H), 7.75(m, 2H, Phen-H). - MS (EI): m=z = 478. Yield 82%. |
With air; tin(IV) iodide In dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With 2,6-dimethylpyridine; tetraethylammonium hexafluorophosphate In 1,2-dichloro-ethane; acetonitrile for 6h; Electrochemical reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: chloro-diphenylphosphine With potassium In tetrahydrofuran Heating; Stage #2: ortho-difluorobenzene In tetrahydrofuran; toluene for 24h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | In ethanol N2 atmosphere; refluxing (4 d), cooling (room temp.); filtration, evapn., recrystn. (CH2Cl2/Et2O), filtration, washing (H2O, hexane and Et2O), drying; | |
40% | With aq. HBr In methanol N2 atmosphere; refluxing (4 d), cooling (room temp.); filtration, evapn., recrystn. (CH2Cl2/Et2O), filtration, washing (H2O, hexane and Et2O), drying; elem. anal.; | |
28% | In methanol N2 atmosphere; refluxing (4 d), cooling (room temp.); filtration, evapn., recrystn. (CH2Cl2/Et2O), filtration, washing (H2O, hexane and Et2O), drying; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | In dichloromethane Addn. of odppb at -78°C to soln. of Rh-complex under Ar, stirring (-78°C, 20 min), warming to 25°C, stirring (2 h).; Addn. of hexane, filtn., recrystn. (CH2Cl2), drying in a stream of air.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | In tetrahydrofuran under N2; soln. of complex treated with a slight excess of ligand, stirred for 24 h at room temp.; filtered, solvent removed (vac.), oily residue dissolved in CH2Cl2, chromy. (alumina, CH2Cl2/hexanes 1:3), collected, evapd. (vac.), recrystn. by dissolving in CH2Cl2, layered with 10-fold vol. of hexanes, cooled to -20°C for 24 h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Fe In ethanol; dichloromethane refluxing FeCl2*4H2O in ethanol with iron filings; filtration into a stirred soln. of ligand in ethanol/CH2Cl2; slowly reducing of solvent volume (vac., 0°C); filtration; washing (ethanol); drying in vac.; elem. anal.; | ||
In ethanol for 12h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | In tetrahydrofuran byproducts: AgI; stirred under N2 overnight; filtd., volatiles removed in vacuo, residue recrystd. from THF/pentane at -35°C; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In tetrahydrofuran byproducts: CF3SO3K; stirred under N2 at room temp. for 24 h; filtd., solvent removed in vacuo, residue recrystd. from toluene/pentaneat -35°C; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | In tetrahydrofuran byproducts: CF3SO3K; stirred under N2 at room temp. for 24 h; filtd., solvent removed in vacuo, residue recrystd. from toluene/pentaneat -35°C; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In tetrahydrofuran byproducts: CF3SO3K; stirred under N2 at room temp. for 24 h; filtd., solvent removed in vacuo, residue recrystd. from toluene/pentaneat -35°C; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | In tetrahydrofuran byproducts: CF3SO3K; stirred under N2 at room temp. for 24 h; filtd., solvent removed in vacuo, residue recrystd. from toluene/pentaneat -35°C; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | In tetrahydrofuran byproducts: CF3SO3K; stirred under N2 at room temp. for 24 h; filtd., solvent removed in vacuo, residue recrystd. from toluene/pentaneat -35°C; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | In tetrahydrofuran byproducts: CF3SO3K; stirred under N2 at room temp. for 24 h; filtd., solvent removed in vacuo, residue recrystd. from toluene/pentaneat -35°C; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With NaCl In ethanol under Ar, Schlenk techniques; mixt. of PdCl2 and NaCl in EtOH was stirred at room temp. for 1 h, filtered, addn. of the diphosphane to filtrate,stirred for 0.5 h; ppt. filtered off and recrystd. from CH2Cl2/EtOH; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: C2H5C(O)CH2C6H4-2-Me; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene-d6 byproducts: (CH3C6H4)CH2C(O)CH2CH3; at 90°C; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: t-BuOC(O)CH2C6H4-2-Me; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene-d6 byproducts: (CH3C6H4)CH2C(O)OC4H9; at 90°C; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: C6H5C(O)CH(CH3)C6H4-2-Me; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene-d6 byproducts: (CH3C6H4)CH(CH3)C(O)C6H5; at 90°C; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: 4-MeC6H4C(O)CH2C6H4-2-Me; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene-d6 byproducts: (CH3C6H4)CH2C(O)C6H4CH3; at 90°C; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: C6H5C(O)CH(CH3)C6H4-4-t-Bu; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene-d6 byproducts: (C4H9C6H4)CH(CH3)C(O)C6H5; at 90°C; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: 4-CH3C6H4C(O)CH2C6H4-4-t-Bu; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene-d6 byproducts: (C4H9C6H4)CH2C(O)C6H4CH3; at 90°C; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: 4-CF3C6H4C(O)CH2C6H4-2-Me; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene-d6 byproducts: (CH3C6H4)CH2C(O)C6H4CF3; at 90°C; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In methanol; acetonitrile phosphane added to suspn. of copper compd. in CH3CN (1:1), stirred for 2h at 50°C, pptd., methanolic soln. of thione (1 equiv.) added, r efluxed for 2 h to nearly complete dissolution of precipitate, soln. filtered; crystd. on storage at room temp., filtered off, dried (vac.), elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: 4-t-BuC6H4C(O)CH2C6H5; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: 4-t-BuC6H4C(O)CH2C6H4-4-Me; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: 4-t-BuC6H4C(O)CH2C6H4-4-Cl; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: 4-t-BuC6H4C(O)CH2C6H4-3-Cl; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene byproducts: 4-t-BuC6H4C(O)CH2C6H4-4-OMe; under N2; in NMR tube; react. of Pd complex and ligand (excess) in toluene at 90°C; monitored by UV-vis spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | In acetonitrile dppbz (1 mmol) added to suspn. of Cu compd. (1 mmol) in CH3CN; refluxed for 4 h, evapd. at room temp., crystd., filtered off, dried (vac.), elem. anal.; | |
75% | In acetonitrile for 4h; Inert atmosphere; Reflux; | |
58% | In toluene suspn. CuBr and ligand in toluene was stirred at room temp. for 5 h; ppt. was filtered, washed with toluene, MeCN, and MeOH, and dried in vacuo; |
18% | In toluene suspn. CuBr and ligand in toluene was stirred at room temp. for 5 h; ppt. was filtered, washed with toluene, MeCN, and MeOH, and dried in vacuo, sublimation with Ar stream under 330-360°C and 1E-3 Torr; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In methanol; acetonitrile dppbz (0.5 mmol) added to suspn. of Cu compd. (0.5 mmol) in CH3CN, stirred for 2 h at 50°C, pptd., methanolic. soln. of 2,4-dtucH2 (0.5 mmol) added; refluxed for 2 h, soln. filtered, evapd., crystd., filtered off, dried (vac.), elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In methanol; acetonitrile dppbz (0.5 mmol) added to suspn. of Cu compd. (0.5 mmol) in CH3CN, stirred for 2 h at 50°C, pptd., methanolic. soln. of 2,4-dtucH2 (0.5 mmol) added; refluxed for 2 h, soln. filtered, evapd., crystd., filtered off, dried (vac.), elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With pyridine In ethanol suspension of AgBr and the appropriate diphosphane in ethanol refluxed for 2 h until a white precipitate formed; soln. of pyridine-2-thione in ethanol treated with a small portion pyridine and added dropwise to the hot suspension; refluxed for 2 h; soln. filtered off; soln. kept at room temp.; slow evaporation of the solvent at room temp. gave microcrystalline solid, which filtered off and dried in vacuo; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In acetone suspension of AgBr and appropriate diphosphane in acetone refluxed for 2h; resulting mixture filtered off; clear soln. kept at room temp.; slow evaporation of the solvent at room temp. gave microcrystalline solid which was filtered off and dried in vacuo;, elem. anal.; | |
In dichloromethane at 40℃; for 10h; | 2 Experiment 2: The experimental multi-tooth phosphine coordination silver complex double emitting dye synthesis method according to the following steps:1 mmol of multidentate phosphine ligand, 1 mmol of AgBr, 5 ml of DCM were mixed and reacted at 40 ° C. for 10 hours. The mixture was spin-dried and purified by column chromatography with DCM and PE to obtain a multidentate phosphine coordination silver complex.Wherein the ratio of multidentate phosphine ligand to AgBr is 1: 1.The volume ratio of DCM to PE in the mixed solvent of DCM and PE is 1:20. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | In dichloromethane at 20℃; for 1h; Inert atmosphere; Schlenk technique; | |
In dichloromethane Cu complex and phosphorous ligand (1:2) reacted in CH2Cl2; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: diphenylphosphane With cesiumhydroxide monohydrate In N,N-dimethyl-formamide at 20℃; for 1h; Molecular sieve; Inert atmosphere; Stage #2: 2,3-dibromobenzene In N,N-dimethyl-formamide at 20℃; for 60h; Inert atmosphere; Molecular sieve; | 7 Comparative Catalyst Preparation Example 7Preparation of (phenyl)2P(1,2-phenyl)P(phenyl)2 ligand; A (phenyl)2P(1,2-phenyl)P(phenyl)2 ligand was prepared by reacting diphenylphosphine with 2 equivalents of dibromoalkyl in dimethylfluoromethylene (DMF) and cesium hydroxide atmospheres, as disclosed in the document “R. N. Salvatore et al, Tetrahedron Letters 44 (2003) 8373”. First, 360 mg (2.14 mmol) of a cesium hydroxide monohydrate was added to 16.6 ml of an anhydrous N,N-dimethylformamide suspension mixed with 1.0 g of activated molecular sieve powder having a particle size of 4 , and was then stirred in a nitrogen atmosphere. Subsequently, 0.38 ml (2.14 mmol) of diphenyl phosphine was added thereto, and was then stirred at room temperature for 1 hour to form a dark reddish orange solution. 0.16 ml (1.29 mmol) of 1,2-dibromobenzene was dropped into the solution, which thus became white. The solution was reacted for 60 hours at room temperature, and 60 ml of distilled water was added thereto, and the solution was extracted three times using 60 ml of DMC to form an organic layer. The organic layer was washed three times with distilled water, and was dried using anhydrous sodium sulfate, the solvent was removed therefrom in a vacuum, and then the organic layer, from which the solvent had been removed, was recrystallized in a benzene solvent, thereby obtaining air-sensitive white crystals (358 mg, yield 75%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49.6% | Chloro[l ,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I) (487.59 mg, 0.25 mmol) and silver triflate (64.2 mg, 0.25 mmol) were mixed under nitrogen in 25 mL flask and 10 mL of dry THF were added. Reaction mixture was stirred at RT for 30 minutes. Solution of 1 ,2-bis(diphenylphosphino)benzene (1 1 1.6 mg, 0.25 mmol) in dry THF (5 mL) was added. Reaction mixture was stirred at RT overnight. Resulting mixture was filtered through Celite and solvent was evaporated on rotovap. Recrystallization from CH2CI2 by vapor diffusion of Et20 gave 130 mg (49.6%) of white needle crystals. Structure confirmed by 1H-NMR spectrum of [(IPR)Cu(dppbz)]OTf (CDCb, 400MHz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: o-phenylenebis(diphenylphosphine); silver(I) chloride In acetonitrile at 20℃; for 6h; Inert atmosphere; Reflux; Stage #2: triphenylphosphine In dichloromethane at 40℃; for 0.166667h; Inert atmosphere; | 14 Under argon atmosphere, 25 mL of dry acetonitrile was added to silver(I) chloride (150 mg, 1.04 mmol) and 1,2-bis(diphenylphosphino)benzene (467 mg, 1.04 mmol), and the mixture was stirred at room temperature for one hour, followed by reflux for five hours. The reaction solution was allowed to reach room temperature, concentrated, and filtrated after being suspended in 7 mL of chloroform. The filtrated matter was subjected to thermal recrystallization from acetonitrile-chloroform and dried to obtain 258 mg of the colorless crystal complex. Under argon atmosphere, 3 mL of dry dichloromethane was added to the above obtained complex (80.0 mg, 0.0678 mmol) and triphenylphosphine (35.6 mg, 0.136 mmol), and the mixture was stirred at 40°C for 10 minutes. The reaction solution was concentrated, subjected to recrystallization by slow diffusion of chloroform-ether, and dried to provide 107 mg of the colorless crystal 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 (3). [Show Image] The NMR data of the obtained complex is provided below. 1H NMR (300 MHz, CDCl3) δ 7.48-7.17 (m, 31H), 7.06 (t, J = 7.0 Hz, 8H); 13C NMR (75 MHz, CDCl3) δ 134.9-134.8 (m), 134.5 (br), 134.4-134.1 (m), 130.1 (br), 129.7 (br), 129.8-129.7 (m), 129.0 (br), 128.9 (br), 128.8-128.7 (m); 31P NMR (122 MHz, CDCl3) δ 9.1 (br, W1/2 = 66 Hz), -14.8 (br, W1/2 = 390 Hz). The result of DART-MS measurement for the obtained complex is provided below. DART-MS (M/Z): found; 815.16. calcd; 815.13 (M-C1)+. Based on the DART-MS measurement of the obtained complex, it was confirmed that the obtained complex contained the following structure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: o-phenylenebis(diphenylphosphine); silver(I) iodide In acetonitrile for 7h; Reflux; Inert atmosphere; Stage #2: triphenylphosphine In dichloromethane at 20℃; for 0.5h; | 1 Under argon atmosphere, silver(I) iodide (235 mg, 1.00 mmol) and 50 mL of the solution of 1,2-bis(diphenylphosphino)benzene (447 mg, 1.00 mmol) in acetonitrile were mixed and the mixture was heated to reflux with stirring for seven hours. The reaction solution was allowed to reach room temperature and the precipitated colorless crystal was filtrated. The obtained filtrated matter was washed with acetonitrile and dried to obtain 531 mg of the complex. The mixture of this complex (49.7 mg) and triphenylphosphine (19.2 mg, 0.0730 mmol) was dissolved in 3 mL of dichloromethane, and the resulting solution was stirred for 30 minutes at room temperature. The reaction solution was concentrated, subjected to recrystallization by slow diffusion of chloroform-diethylether, and dried to provide 30.9 mg of the colorless solid complex. The result of elemental analysis for the obtained complex is shown in Table 2-1, and the composition ratio of the complex was obtained. The present complex corresponds to the above composition formula (3). [Show Image] The NMR data of the obtained complex is provided below. 1H NMR (300 MHz, CDCl3) δ 7.44-7.14 (m, 31H), 7.03 (t, J= 7.2 Hz, 8H); 13C NMR (75 MHz, CDCl3) δ 141.2 (t, J= 22.7 Hz), 134.5 (t, J= 3.0 Hz), 134.2-134.0 (m), 133.3 (d, J= 22.2 Hz), 132.2 (t, J= 10.9 Hz), 129.6 (s), 129.3 (s), 128.5 (d, J= 9.0 Hz), 128.2 (t, J= 4.5 Hz); 31P NMR (122 MHz, CDCl3) δ 3.7 (br, W1/2=159 Hz), -14.8 (br, W1/2 = 450 Hz). The result of DART-MS measurement of the obtained complex is provided below. DART-MS (M/Z): found; 815.16. calcd; 815.13 (M-I)+. Based on the DART-MS measurement of the obtained complex, it was confirmed that the obtained complex contained the following structure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: silver(I) bromide; o-phenylenebis(diphenylphosphine) In acetonitrile at 20℃; for 8h; Inert atmosphere; Reflux; Stage #2: triphenylphosphine In dichloromethane at 40℃; for 0.166667h; Inert atmosphere; | 13 Under argon atmosphere, 20 mL of dry acetonitrile was added to silver(I) bromide (170 mg , 0.904 mmol) and 1,2-bis(diphenylphosphino)benzene (404 mg, 0.904 mmol), and the mixture was stirred at room temperature for one hour and then heated to reflux for seven hours. The reaction solution was allowed to reach room temperature, concentrated, and filtrated after being suspended in 9 mL of chloroform. The filtrated matter was subjected to thermal recrystallization from acetonitrile-chloroform and dried to obtain 399 mg of the colorless crystal complex. Under argon atmosphere, 3 mL of dry dichloromethane was added to the above obtained complex (80.0 mg, 0.0631 mmol) and triphenylphosphine (33.1 mg, 0.126 mmol), and the mixture was stirred at 40°C for 10 minutes. The reaction solution was concentrated, subjected to recrystallization by slow diffusion of chloroform-ether, and dried to provide 108 mg of the 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 (3). The NMR data of the obtained complex is provided below. 1H NMR (300 MHz, CDCl3) δ 7.48-7.17 (m, 31H), 7.07-7.03 (m, 8H); 13C NMR (75 MHz, CDCl3) δ 134.8 (t, J = 2.4 Hz), 134.6-134.2 (m), 130.2-130.0 (m), 129.7 (br), 129.0 (br), 128.9 (br), 128.7-128.6 (m); 31P NMR (122 MHz, CDCl3) δ 8.1 (br, W1/2 = 87 Hz) , -14.8 (br, W1/2 = 340 Hz). The result of DART-MS measurement for the obtained complex is provided below. DART-MS (M/Z): found; 815.16. calcd; 815.13 (M-Br)+. Based on the DART-MS measurement of the obtained complex, it was confirmed that the obtained complex contained the following structure. |
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 |
---|---|---|
Stage #1: silver tetrafluoroborate; o-phenylenebis(diphenylphosphine) In dichloromethane at 20℃; for 0.5h; Inert atmosphere; Stage #2: 2,9-dichloro-[1,10]phenanthroline In dichloromethane for 2h; Reflux; | 20 Under argon atmosphere, 1,2-bis(diphenylphosphino)benzene (34.6 mg, 0.0776 mmol) was added to 5 mL of the solution of silver(I) tetrafluoroborate (15.1 mg, 0.0776 mmol) in dichloromethane, and the mixture was stirred at room temperature for 30 minutes. Then, 2,9-dichloro-1,10-phenanthroline (23.2 mg, 0.0931 mmol) was added to the reaction solution, which was heated to reflux with stirring for two hours. The reaction solution was filtrated, and the filtrate was concentrated, subjected to recrystallization by slow diffusion of dichloromethane-ether, and dried to provide 46.0 mg of the yellow solid complex. [Show Image] The NMR data of the obtained complex is provided below. 1H NMR (300 MHz, CDCl3) δ 8.80 (d, J = 8.1 Hz, 2H), 8.24 (s, 2H), 8.15 (d, J = 8.1 Hz, 2H), 7.62-7.51 (m, 4H), 7.39-7.29 (m, 20H); 31P NMR (122 MHz, CDCl3) δ -4.4 (d, J (31P-107Ag, 109Ag) = 325, 373 Hz). 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 |
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90% | In toluene at 20℃; for 0.166667h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
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98% | In toluene at 20℃; for 0.166667h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: benzene 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
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86% | In 1,1,2,2-tetrachloroethane at 110℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
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69% | In methanol at 90℃; for 48h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
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68.6% | In methanol at 90℃; for 48h; Inert atmosphere; | 19 Example 19 chloro[phenylene-1,2-bis(diphenylphosphane-κ2P,P,)](cis,cis-1,3,5-triaminocyclohexane-κ3N,N,,N")ruthenium(II) chloride hydrate [19][Cl] ([RuCl(dppben)(tach)]Cl) A solution of [8][CI] (50.0 mg, 0.109 mmol) in methanol (5 mL) with phenylene-1,2- bis(diphenylphosphane) was heated at 90 °C in sealed ampoule under argon for 48 hours. The deep orange solution was allowed to cool, over which a white precipitate formed. The unreacted phosphine precipitate was removed by filtration and diethyl ether (90 mL) added to the solution, forming a cream precipitate. The mixture was cooled to -20 °C for 2 hours, the product isolated by filtration, and dried in vacuo. Yield: 58.6 mg (68.6 %, 0.0748 mmol of rRuCl(K2-dppben)(K -cis-tach)]C1.2H20). NMR Spectroscopy b Cs mirror planelH NMR (CD3OD, 500.2 MHz, 295K) δ 8.07 (ddd, HP = 1 1.0 Hz, HH = 7.5 Hz, HH = 1.2 Hz, 4H, PPh2, Ar211), 7.52 (m, 6H: 2H, PPh2, Ar4a; 4H, PC6H4P, Br2 + Br3), 7.44 (t, VHH = 7.5 HZ, 4H, VPh2, Ar3a), 7.39 (dd, VHH = 7.4 Hz, VHH = 7.2 Hz, 4H, PPhz, Ar3b), 7.34 (td, VHH = 7.2 Hz, HH = 1.4 Hz, 4H, PPh2, Ar b), 7.34 (ddd, VHP = 10.0 Hz, VHH = 7.4 Hz, VHH = 1.4 Hz, 4H, fPh2, Ar4b), 4.93 (d, HH = 11 8 HZ, 2H, NH2, N2), 3.87 (d, HH = Π.8 Hz, 2H, NH2> N2), 3.56 (s, 2Η, CH, Cy2), 2.72 (s, 1Η, CH, Cy1), 2.30 (d, VHH = 15.4 Hz, 1H, CH2, Cy4), 2.14 (d, VHH = 15.4 Hz, 1H, CH2, Cy4), 1.86 (d, HH = 15.2 Hz, 2H, CH2, Cy3), 1.74 (d, VHH = 15.2 Hz, 2H, CH2, Cy3), 1.39 (s, 2H, NH2, N2); 3Ρ{} NMR (CD3OD 202.5 Hz, 295K) δ 72.9 (s, 2P, Ph2); "( {} NMR (CD3OD, 125.8 MHz, 2950K) δ 145.6 (vt, |VPC + VP C| = 82 Hz, PC6H4P, Br1), 139.9 (t, |VRC + VP>c| = 10 Hz, ?Ph2, Ar2a), 133.6 (m, PP/z2, ArIa + Arlb), 133.5 (t, |VPC + VP| = 17 Hz, PC^P, Br2), 133.0 (t, |VPC + VP.C| = 9 Hz, PPki, Ar215), 131.8 (s, PC6P, Br3; s, PP/*2, Ar a), 131.1 (s, P A2, Ar4b), 130.5 (t, |VPC + Vp-c| = 9 Hz, VPh2, Ar3 ), 129.5 (t, |VPC + VFC| = 9 Hz, Pi, Ar a), 44.7 (s, CH, Cy2), 44.4 (s, CH, Cy1), 35.6 (s, CH2, Cy4), 34.3 (s, CH2, Cy3). Mass Spectrometry ESI-MS-. m/z 712.1372 ([RuCl(K2-dppben)(K3-cw-tach)]+, Calc 712.1352, 100 %). Elemental Analysis H20 C / % H / % N / % Found 55.50 5.44 5.33 0 57.83 5.26 5.62 1 56.47 5.40 5.49 2 55.18 5.53 5.36 Table 0.11: CH Elemental analysis for [RuCl(K2-dppben)(K3-cis-tach)]Cl, C36H39N3P2Cl2Ru, calculated with varying water content.3 Integrations of the 1H NMR spectrum recorded in anhydrous CD2CI2 indicates at least 1 equivalent of water present. |