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CAS No. : | 161265-03-8 | MDL No. : | MFCD00233866 |
Formula : | C39H32OP2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | CXNIUSPIQKWYAI-UHFFFAOYSA-N |
M.W : | 578.62 | Pubchem ID : | 636044 |
Synonyms : |
|
Num. heavy atoms : | 42 |
Num. arom. heavy atoms : | 36 |
Fraction Csp3 : | 0.08 |
Num. rotatable bonds : | 6 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 182.88 |
TPSA : | 36.41 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -2.94 cm/s |
Log Po/w (iLOGP) : | 5.48 |
Log Po/w (XLOGP3) : | 9.7 |
Log Po/w (WLOGP) : | 7.63 |
Log Po/w (MLOGP) : | 7.77 |
Log Po/w (SILICOS-IT) : | 11.07 |
Consensus Log Po/w : | 8.33 |
Lipinski : | 2.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 1.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.17 |
Log S (ESOL) : | -9.78 |
Solubility : | 0.0000000968 mg/ml ; 0.0000000002 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -10.38 |
Solubility : | 0.000000024 mg/ml ; 0.0 mol/l |
Class : | Insoluble |
Log S (SILICOS-IT) : | -15.7 |
Solubility : | 0.0 mg/ml ; 1.98e-16 mol/l |
Class : | Insoluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 5.68 |
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 |
---|---|---|
88% | Stage #1: With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In tert-butyl methyl ether; cyclohexane at 6 - 10℃; Stage #2: at 20℃; for 14 h; Stage #3: at 10 - 20℃; for 5.16667 h; |
Example 2A Preparation of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, Xantphos To a 5L round bottom flask (RBF) are added MTBE (2.5 L), 9,9-dimethylxanthene (131.4 g, 0.60 mole) and TMEDA (155 g, 1.32 mole). After degassing the solution, s-BuLi (1.11 L, 1.3 M in cyclohexane, 1.44 mole) is cannulated into a dropping funnel and then slowly added over 60 min while maintaining the batch temperature at 6-10° C. The mixture is then aged for 14 h at room temperature. Ph2PCl is added slowly via a dropping funnel while maintain the mildly exothermic reaction at 10-20° C. ~60percent of the Ph2PCl (175 mL, 0.93 mole) is added in 0.5 hour. The mixture is aged for 10 minutes before addition of the remaining Ph2PCl (120 mL, 0.63 mole). After aged for 5 h at room temperature, the reaction is quenched with MeOH (9.9 mL, 0.24 mole). The product is filtered and the slightly yellow solid is washed consecutively with MTBE (250 mL), MeOH (2*250 mL), water (2*300 mL), MeOH (2*250 mL) and MTBE (250 mL) and dried to give an off-white solid as product (304.2 g, 88percent yield). |
77% | Stage #1: With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In tert-butyl methyl ether; cyclohexane at 10 - 20℃; for 16 h; Stage #2: at 20℃; for 5.75 h; |
Example 2 Preparation of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, Xantphos To a 1L round bottom flask (RBF) are added MTBE (500 mL), 9,9-dimethylxanthene (26.65 g) and TMEDA (30.6 g). After degassing the solution, s-BuLi (155 g, 1.3 M in cyclohexane) is cannulated into a dropping funnel and then slowly added over 30 min while maintaining the batch temperature at 10-20° C. The mixture is then aged for 16 h at room temperature. Ph2PCl is added slowly via a dropping funnel while maintain the mildly exothermic reaction at 10-20° C. ~60percent of the Ph2PCl (30 mL) is added in 0.5 hour. The mixture is aged for 15 minutes before addition of the remaining Ph2PCl. After aged for 5.5 h at room temperature, the reaction is quenched with MeOH (2.0 mL). The product is filtered and the slightly yellow solid is washed consecutively with MeOH (200 mL), water (200 mL), MeOH (200 mL) and MTBE (200 mL) and dried to give an off-white solid as product (54.8 g, 77percent yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Example 2A Preparation of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, Xantphos To a 5L round bottom flask (RBF) are added MTBE (2.5 L), <strong>[19814-75-6]9,9-dimethylxanthene</strong> (131.4 g, 0.60 mole) and TMEDA (155 g, 1.32 mole). After degassing the solution, s-BuLi (1.11 L, 1.3 M in cyclohexane, 1.44 mole) is cannulated into a dropping funnel and then slowly added over 60 min while maintaining the batch temperature at 6-10 C. The mixture is then aged for 14 h at room temperature. Ph2PCl is added slowly via a dropping funnel while maintain the mildly exothermic reaction at 10-20 C. ~60% of the Ph2PCl (175 mL, 0.93 mole) is added in 0.5 hour. The mixture is aged for 10 minutes before addition of the remaining Ph2PCl (120 mL, 0.63 mole). After aged for 5 h at room temperature, the reaction is quenched with MeOH (9.9 mL, 0.24 mole). The product is filtered and the slightly yellow solid is washed consecutively with MTBE (250 mL), MeOH (2*250 mL), water (2*300 mL), MeOH (2*250 mL) and MTBE (250 mL) and dried to give an off-white solid as product (304.2 g, 88% yield). | |
84% | Add <strong>[19814-75-6]9,9-dimethylxanthene</strong> (0.02mol) and tetramethylethylenediamine (TMEDA) (42mmol),Dilute in hexane (50 mL) and at -78 C,A solution of n-BuLi (42 mmol) in hexane (added in about 5 min) was added dropwise, and the reaction was carried out for 1 h.Then it was raised to room temperature (about 25 C), and the reaction was stirred for 16h;Then 15 mL of a solution of diphenylphosphine chloride (42 mmol) in n-hexane was added dropwise to the reaction system of step (1) in an ice-water bath, and the reaction was continued at room temperature (about 25 C). The reaction was stirred for 16 h under reduced pressure; the solvent was removed by rotary evaporation to obtain a pale yellow viscous oil, which was washed with acetone and dried under vacuum to obtain 9.7 g of a white powder, which is the compound represented by formula (3-1): the yield was 84% , | |
77% | Example 2 Preparation of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, Xantphos To a 1L round bottom flask (RBF) are added MTBE (500 mL), <strong>[19814-75-6]9,9-dimethylxanthene</strong> (26.65 g) and TMEDA (30.6 g). After degassing the solution, s-BuLi (155 g, 1.3 M in cyclohexane) is cannulated into a dropping funnel and then slowly added over 30 min while maintaining the batch temperature at 10-20 C. The mixture is then aged for 16 h at room temperature. Ph2PCl is added slowly via a dropping funnel while maintain the mildly exothermic reaction at 10-20 C. ~60% of the Ph2PCl (30 mL) is added in 0.5 hour. The mixture is aged for 15 minutes before addition of the remaining Ph2PCl. After aged for 5.5 h at room temperature, the reaction is quenched with MeOH (2.0 mL). The product is filtered and the slightly yellow solid is washed consecutively with MeOH (200 mL), water (200 mL), MeOH (200 mL) and MTBE (200 mL) and dried to give an off-white solid as product (54.8 g, 77% yield). |
Comparative Diphosphine 1 B: 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, known as XANTPHOS At room temperature under argon, a solution of sec-BuLi (22 cm3, 1.3 mol dm-3, 0.029 mol, 3 eq) in hexane is added dropwise to a stirred solution of <strong>[19814-75-6]9,9-dimethylxanthene</strong> (2 g, 9.5*10-3 mol, 1 eq) and TMEDA (3.41 g, 0.029 mol, 3 eq) in dry degassed diethyl ether and stirred for 16 hours. A solution of chlorodiphenylphosphine (5.2 cm3, 0.029 mol, 3 eq) in hexane is then added dropwise, and the reaction mixture stirred for a further 16 hours. The solvent is removed under reduced pressure, and the resulting oil dissolved in CH2Cl2, washed with water and dried with MgSO4. The solvent is removed under reduced pressure, and the resulting yellow oil is recrystallized from ethanol to yield 9,9-dimethyl-4,6-bis(diphenylphosphino)xanthene. | ||
To a 1L RBF are added MTBE (500 mL), <strong>[19814-75-6]9,9-dimethylxanthene</strong> (26.65 g) and TMEDA (30.6 g). After degassing the solution, s-BuLi (155 g, 1.3 M in cyclohexane) is cannulated into a dropping funnel and then slowly added over 30 min while maintaining the-batch temperature at 10-20 C. The mixture is then aged for 16 h at room temperature. Ph2PCl is added slowly-via a dropping funnel while maintain the mildly exothermic reaction at 10-20 C. [0232] Approximately 60% of the Ph2PCl (30 mL) is added in 0.5 hour. The mixture is aged for 15 minutes before addition of the remaining Ph2PCl. After aged for 5.5 h at room temperature, the reaction is quenched with MeOH (2.0 mL). The product is filtered and the slightly yellow solid is washed consecutively with MeOH (200 mL), water (200 mL), MeOH (200 mL) and MTBE (200 mL) and dried to give an off-white solid as product. | ||
To a 1 L RBF are added MTBE (500 mL), <strong>[19814-75-6]9,9-dimethylxanthene</strong> (26.65 g) and TMEDA (30.6 g). After degassing the solution, s-BuLi (155 g, 1.3 M in cyclohexane) is cannulated into a dropping funnel and then slowly added over 30 min while maintaining the batch temperature at 10-20 C. The mixture is then aged for 16 h at room temperature. Ph2PCl is added slowly via a dropping funnel while maintain the mildly exothermic reaction at 10-20 C. [0257] Approximately 60% of the Ph2PCl (30 mL) is added in 0.5 hour. The mixture is aged for 15 minutes before addition of the remaining Ph2PCl. After aged for 5.5 h at room temperature, the reaction is quenched with MeOH (2.0 mL). The product is filtered and the slightly yellow solid is washed consecutively with MeOH (200 mL), water (200 mL), MeOH (200 mL) and MTBE (200 mL) and dried to give an off-white solid as product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
To a 1L RBF are added MTBE (500 mL), <strong>[19814-75-6]9,9-dimethylxanthene</strong> (26.65 g) and TMEDA (30.6 g). After degassing the solution, s-BuLi (155 g, 1.3 M in cyclohexane) is cannulated into a dropping funnel and then slowly added over 30 min while maintaining the batch temperature at 10-20 C. The mixture is then aged for 16 h at room temperature. Ph2PCl is added slowly via a dropping funnel while maintain the mildly exothermic reaction at 10-20 C. [0225] Approximately 60% of the Ph2PCl (30mL) is added in 0.5 hour. The mixture is aged for 15 minutes before addition of the remaining Ph2PCl. After aged for 5.5 h at room temperature, the reaction is quenched with MeOH (2.0 mL). The product is filtered and the slightly yellow solid is washed consecutively with MeOH (200 mL), water (2000 mL), MeOH (200 mL) and MTBE (200 mL) and dried to give an off-white solid as product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With caesium carbonate;palladium diacetate; In 1,4-dioxane; | Part A. [1-(4-Bromo-phenyl)-2-oxo-azepan-3-yl]-carbamic acid tert-butyl ester 3-t-butoxycarbonylamino-2-oxoazepane (4.4 mmol), p-bromoiodobenzene (1 eq), 4,5-bis (diphenyl-phosphino)-9, 9-dimethylxanthene (0.15 eq), cesium carbonate (1.5 eq), and palladium acetate (0.1 eq) were placed in a round bottom flask and it was evacuated and flushed 3 times with nitrogen. To this solution, 45 mL of dioxane was added and the resulting solution was evacuated and flushed 3 more times with nitrogen gas. The mixture was allowed to stir at 75 C. overnight. The mixture turned from black to bright yellow suspension. The mixture was cooled and diluted with dichloromethane and then was filtered through a pad of Celite. The filtrate was removed under reduced pressure and the residue was purified by flash column chromatography eluding with 50% EtOAc/Hex to give the desired product as an off-white foam (68%). Mass spectrum, ESI (M+H) 383.2, 385.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With caesium carbonate;palladium diacetate; In 1,4-dioxane; | Part A. 1-Benzyl-4-(4-bromo-phenyl)-[1,4]diazepan-5-one: Commercially available <strong>[55186-89-5]1-benzyl-(1,4)-diazepan-5-one</strong> (14.7 mmol), p-bromoiodobenzene (1 eq), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.15 eq), cesium carbonate (1.5 eq), and palladium acetate (0.1 eq) were placed in a round bottom flask and it was evacuated and flushed 3* with nitrogen. To this mixture was then added 200 mL of dioxane and the resulting solution was again evacuated and flushed 3* times with nitrogen gas. The mixture was allowed to stir at 75 C. overnight during which time the mixture turned from brown to bright yellow suspension. The mixture was cooled and diluted with dichloromethane and then was filtered through a pad of celite. The filtrate was removed under reduced pressure and the residue was purified by flash column chromatography eluding with 50% EtOAc/Hex to give compound 1 as an off-white solid (63%). Mass spectrum, ESI (M+H) 359.3, 361.3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With caesium carbonate; aniline; In 1,4-dioxane; toluene; | A. 2-(4-nitrophenyl)-6-(phenylamino)-2-hydroisoguinolin-1-one To a dry RBF under argon was added 6-bromo-2-(4-nitrophenyl)-2-hydroisoquinolin-1-one (66 mg, 0.191 mmol) (prepared as outlined in Example 1125), cesium carbonate (106 mg, 0.325 mmol), tris(dibenzylideneacetone) dipalladium(0) (3.5 mg, 0.076 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphino) xanthene (12 mg, 0.0207 mmol) and neat aniline (0.026 mL, 0.285 mmol). To this flask was added dry dioxane (0.5 mL) and dry toluene (0.5 mL). The reaction was stirred at 80 C. for 5 hr, concentrated and chromatographed on silica gel to give pure 2-(4-nitrophenyl)-6-(phenylamino)-2-hydroisoquinolin-1-one (55 mg, 81%). ES-MS (M+H)+=358. |
81% | With caesium carbonate; aniline; In 1,4-dioxane; toluene; | A. 2-(4-nitrophenyl)-6-(phenylamino)-2-hydroisoguinolin-1-one To a dry RBF under argon was added 6-bromo-2-(4-nitrophenyl)-2-hydroisoquinolin-1-one (66 mg, 0.191 mmol) (prepared as outlined in Example 1125), cesium carbonate (106 mg, 0.325 mmol), tris(dibenzylideneacetone) dipalladium(0) (3.5 mg, 0.076 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphino) xanthene (12 mg, 0.0207 mmol) and neat aniline (0.026 mL, 0.285 mmol). To this flask was added dry dioxane (0.5 mL) and dry toluene (0.5 mL). The reaction was stirred at 80 C. for 5 hr, concentrated and chromatographed on silica gel to give pure 2-(4-nitrophenyl)-6-(phenylamino)-2-hydroisoquinolin-1-one (55 mg, 81%). ES-MS (M+H)+=358. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; at 20℃; for 6h;Darkness; | To the solution of Xantphos (0.1 mmol) in dry DCM(0.2M), DMSAuCl (0.2 mmol) was added.The mixture was stirring at room temperature for 6h in dark. After the reaction is finished, the mixture was filtrated through a celite plug. The solvent was removed under reduced pressure andthe resulting solid was recrystallized by DCM and Hexanes to provide cat-1 as white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | Step I: 6-Chloro-2,4,8,19,23-pentaazatetracyclo[15.3.1.1(3,7).1(10,14)]tricosa-1(21),3(23),4,6,10(22),11,13,17,19-nonaen-13-amine Into a reaction flask were added N-{4-amino-3-[2-(5-aminopyridin-3-yl)ethyl]benzyl}-2,5-dichloropyrimidin-4-amine trihydrochloride (0.29 g, 0.74 mmol), 1,4-dioxane (5 mL), and triethylamine (0.31 mL, 2.2 mmol). The mixture was stirred at rt under N2 for 5 minutes, followed by an addition of palladium acetate (5 mg, 0.02 mmol), (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (12.9 mg, 0.02 mmol), and cesium carbonate (500 mg, 2.0 mmol). The reaction mixture was degassed with N2 bubbling. The tube was then sealed and heated at 160 C. for 2 hours. After concentration, the crude product was purified by silica gel column chromatography to give the desired product as a white powder (100 mg, 42%). LCMS for C18H18ClN6 (M+H)+: m/z=353.0. 1H NMR (400 MHz, DMSO-d6): delta 9.65 (s, 1H), 8.44 (d, J=1.6 Hz, 2H), 8.16 (d, J=2.3 Hz, 1H), 8.01 (s, 1H), 7.11 (m, 2H), 7.03 (m, 2H), 6.69 (s, 1H), 4.14 (d, J=5.8 Hz, 2H), 2.88 (m, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With dihydrogen peroxide; In dichloromethane; at 0℃; for 2h; | Compound 1 (1.0 g, 1.7 mmol) (purchased from Tokyo Chemical Industries, Co., Ltd.) was melted in CH2C12, and H2O2 (30 %, 4.0 mL) was dropped therein while cooling the mixture at 0 C. This mixture was stirred for 2 hours. A reaction solution was separated by use of CH2C12 and an organic layer was dried with magnesium sulfate. Thereafter, magnesium sulfate was removed by filtration and the solvent was distilled off. An obtained solid was washed with hexane and filtered, which yielded a compound 2 (white powder, 1.06 g, 100 %). IR (ATR) 1190 (st, P=O), 1100-1229 (st, C-O-C) cm-1 1H NMR (300 MHz, CDC13/TMS) 67.58-7.60 (d, J = 6 Hz, 2H), 7.30-7.47 (m, 20H), 6.94-7.00 (t, J = 6Hz, 2H), 6.78-6.85 (m, 2H), 1.69 (s, 6H) ppm. 31P NMR (200 MHz, CDC13, 25 C) delta33.55 (1P), 30.32 (1P) ppm FAB-Mass (m/z) = 611 [M+H]+. |
93.4% | With dihydrogen peroxide; In tetrahydrofuran; for 6h;Inert atmosphere; | To a THF (25 mL) solution of the (9,9-dimethyl-9H-xanthene-4,5-diyl) bis(diphenylphosphane) (1.157 g, 2.00 mmol) wasslowly added three drops (0.15 mL) of H2O2 and the formed solutionwas stirred for 6 h. The solvent was removed under a reduced pressureand the resultant raw product was dissolved in dichloromethane forcrystallization. Finally, a light yellow solid was collected by filtration,washed with cold methanol and dried in vacuum (1.140 g, 93.4%yield). 1H NMR (400 MHz, CDCl3, ppm): 7.92-7.49 (m, 4H), 7.51-7.19 (m,16H), 7.05 (d, 4H, J=47.5 Hz,), 6.78 (d, 2H, J=13.9 Hz), 1.70 (s,6H). 31P NMR (162 MHz, CDCl3, ppm): 29.71 (s). IR (KBr, cm-1): 1437,1101, 720 (upsilonP-Ph), 1274 (upsilonP=O), 1192 (upsilonC-P) |
77% | With dihydrogen peroxide; In tetrahydrofuran; at 20℃; for 2h; | 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 XANTPO: 1H NMR (250 MHz, CDCl3): d = 7:59 - 7:62(d, 2H, Phen-H), 7.24 - 7.48 (m, 20H, Phen-H), 6.94 - 7.20(t, 2H, Phen-H), 6.74 - 6.84 (m, 2H, Phen-H), 1.70 (s, 6H,2Me). - MS (EI): m=z = 610. Yield 77%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
To 1 mL of the solution of silver(I) tetrafluoroborate (1.17 mg, 0.00601 mmol) in dichloromethane was added 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (3.48 mg, 0.00601 mmol), and the mixture was stirred at room temperature for 15 minutes. Then, f23 (2.03 mg, 0.00601 mmol) was added to the reaction solution, which was stirred at 40C for five minutes. The reaction solution was subjected to recrystallization by slow diffusion of dichloromethane-ether and dried to provide 5.40 mg of the complex of the pale yellow crystal. [Show Image] The NMR data of the obtained complex is provided below. 1H NMR (300 MHz, CDCl3) delta 8.50 (brd, 2H), 8.13 (brs, 2H), 7.84 (brd, 2H), 7.62 (brd, 2H), 7.26-7.04 (m, 22H), 6.78 (br, 2H), 1.71 (s, 6H); 31P NMR (122 MHz, CDCl3); 31P NMR (122 MHz, CDCl3) delta -4.9 (d, J (31P-107Ag, 109Ag) = 392, 451 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 |
---|---|---|
95% | With tributylphosphine; iodine; In tetrahydrofuran; acetonitrile; at 20℃; for 0.166667h;Inert atmosphere; | EXAMPLE 3100 mg (0.164 mmol) of 9,9-Dimethyl-4,6-bis(diphenyloxyphosphino)xanthene were treated with 4 mg I2 (16 muiotaetaomicron) and tributylphosphine 162 muEpsilon (0.65 mmol) in acetoni- trile/THF (1 : 1 v/v) 1 mL. The mixture was stirred at room temperature for 10 minutes under nitrogen atmosphere before it was quenched with H20 (100 mu). The reaction mixture was diluted with ethyl acetate (lOmL) and was washed with portions of sat. NaHC03 (3x5 mL). The organic fraction was dried with Na2S04, filtered and the solvent evaporated un- der vacuum. The resulting residue was recrystallized from 1-propanol, the resulting crystals were filtered, washed and dried in vacuum, giving 90 mg (0.156 mmol, 95%) of 9,9- Dimethyl-4,6-bis(diphenyloxyphosphino)xanthene (Xanthphos). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With caesium carbonate;palladium diacetate; In toluene; | a) Methyl 2-(4'-bromobiphenyl-4-ylamino)benzoate 200 g (641.0 mmol) of 4,4'-dibromobenzene and 41.4 ml (320.5 mmol) of methyl anthranilate are dissolved in 1500 ml of toluene, and the solution is degassed by passing in an inert gas. 229.7 g (705.1 mmol) of Cs2CO3, 3.59 g (16.02 mmol) of Pd(OAc)2 and 6.29 g (32.05 mmol) of xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene), all degassed, are subsequently added. The reaction mixture is subsequently stirred at 82 C. for 6 h and filtered through aluminium oxide (basic activity grade 1). The product is purified by column chromatography on silica gel with heptane/toluene (1:49), giving 79.2 g (65%) of the product as a pale-yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | The compound B3 was synthesized in accordance with the method described in Tetrahedron Letters 41, 6809-6813 (2000).Silver(I) tetrafluoroborate (6.10 mg, 0.0313 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (18.1 mg, 0.0313 mmol) were stirred in dehydrated methylene chloride (2 mL) under an argon atmosphere at room temperature for 5 minutes. The compound B3 (31.0 mg, 0.0360 mmol) was added to the reaction solution, and the homogeneous reaction solution was stirred under heating at 40 C. for 5 minutes. Vapor of diethyl ether was diffused gradually in the reaction solution to perform recrystallization. The obtained crystal was dried under vacuum at 50 C. for 5 hours to obtain the metal complex C3 (35.0 mg, yield: 68%).1H NMR (300 MHz, CDCl3): delta 8.78 (s, 2H), 8.67 (s, 2H), 8.27 (s, 2H), 7.89 (s, 2H), 7.69 (d, J=8.4 Hz, 8H), 7.58-7.56 (m, 12H), 7.26-7.19 (m, 8H), 7.12-7.08 (m, 16H), 6.99-6.94 (m, 2H), 6.61 (br, 2H), 1.42 (s, 36H).31P NMR (122 MHz, CDCl3): delta-4.8 (d, J(31P-107Ag, 109Ag)=375, 433 Hz).Elemental Analysis Found(%) C: 75.54, H: 5.77, N: 1.61,Calcd for C3(%) C: 75.69, H: 5.92, N: 1.71The metal complex C3 emitted green light under ultraviolet excitation (365 nm), the emission peak wavelength was 553 nm, and the excitation lifetime was 1.8 mus.The metal complex C3 was easily dissolved in chloroform at room temperature.When the metal complex C3 was left to stand in air at 100 C. for 7 hours, change in emission intensity was hardly observed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | General procedure: A suspension of 0.5 mmol of copper(I) halide (49.5 mg for CuCl, 72 mg for CuBr, 95 mg for CuI) in 50 mL of dry acetonitrile was stirred to give a clear solution which was then treated with solid 4,5-bis(diphenylphosphano)-9,9-dimethyl-xanthene (289.3 mg, 0.5 mmol) added in small portions. After stirring for two hours at 50 C, a solution of N-methylbenzothiazole-2-thione (90 mg, 0.5 mmol) dissolved in a small amount (~20 mL) of methanol was added and the new reaction mixture was stirred for additional two hours at 50 C. Slow evaporation of the clear solution at ambient afforded a pale yellow microcrystalline solid, which was filtered off and dried in vacuo. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | General procedure: A suspension of 0.5 mmol of copper(I) halide (49.5 mg for CuCl, 72 mg for CuBr, 95 mg for CuI) in 50 mL of dry acetonitrile was stirred to give a clear solution which was then treated with solid 4,5-bis(diphenylphosphano)-9,9-dimethyl-xanthene (289.3 mg, 0.5 mmol) added in small portions. After stirring for two hours at 50 C, a solution of N-methylbenzothiazole-2-thione (90 mg, 0.5 mmol) dissolved in a small amount (~20 mL) of methanol was added and the new reaction mixture was stirred for additional two hours at 50 C. Slow evaporation of the clear solution at ambient afforded a pale yellow microcrystalline solid, which was filtered off and dried in vacuo. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.2% | With tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; hexane; ethyl acetate; | Step 10: N-(6-((4R,6S)-2-benzamido-4-(difluoromethyl)-6-(trifluoromethyl)-5,6-dihydro-4H-1,3-oxazin-4-yl)-5-fluoropyridin-2-yl)-5-chloropicolinamide (11u) A round-bottomed flask was charged with Pd2(dba)3 (2.91 mg, 3.17 mumol), (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (7.35 mg, 0.013 mmol), N-((4R,6S)-4-(6-bromo-3-fluoropyridin-2-yl)-4-(difluoromethyl)-6-(trifluoromethyl)-5,6-dihydro-4H-1,3-oxazin-2-yl)benzamide (21 mg, 0.042 mmol), 5-chloropicolinamide (9.61 mg, 0.061 mmol), and cesium carbonate (34.5 mg, 0.106 mmol). The flask was evacuated under vacuum and then flushed with nitrogen. Dioxane (0.5 mL) was then added and the reaction was stirred in a 90 C. oil bath for 10 h. The reaction mixture was cooled to RT, filtered through celite and washed with EtOAc. The filtrate was concentrated and the residue was purified by chromatography through a Redi-Sep pre-packed silica gel column (12 g), eluting with a gradient of 0% to 30% EtOAc in hexane, to provide N-(6-((4R,6S)-2-benzamido-4-(difluoromethyl)-6-(trifluoromethyl)-5,6-dihydro-4H-1,3-oxazin-4-yl)-5-fluoropyridin-2-yl)-5-chloropicolinamide (17 mg, 0.030 mmol, 70.2% yield) as white solid. MS m/z=572, 574 M+, Calculated for C24H16ClF6N5O3: 571.86. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | In benzene; at 50℃; for 5h; | To [Ir(H)(CO)(PPh3)3] (0.22 g, 0.22 mmol) in benzene (20 mL), xantphos (0.1 g, 0.17mmol) was added. The resulting yellow solution was left to stir at 50 C for 5 h. Thereafter, the solvent was reduced to half its volume, after which a yellow precipitate was formed, and the excess solvent was removed via a cannula. The yellow solid was first washed with methanol, then hexane and dried under vacuum. Complex 3 was recrystallized from dichloromethane/hexane (1/1) to afford 79% (143 mg) of a yellow powder. Melting point in air: 463-465 K (decomposed) and DSC 523 K (under N2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In chloroform; for 3h;Inert atmosphere; Reflux; | A dried three-necked round bottom flask equipped with a condenser had RuCl2(PPh3)3 (1) (1.156 g, 1.2 mmol), xantphos (0.7630 g, 1.32 mmol) and dry CHCl3 (50 mL) added under argon atmosphere. The reaction mixture was refluxed for 3h with stirring. After the reaction mixture was cooled to room temperature, the solvent was removed to ca. 5 mL under reduced pressure, and Et2O (15 mL) was then added slowly. The resulting mixture was kept until a large enough amount of crystalline solid was formed. The resulting crystalline solid was filtered, washed three times with 5 mL of benzene, and dried in vacuo to give RuCl2(xantphos)PPh32a (95%). M.p.=215-217C (dec). 1H NMR (CDCl3, 300MHz) delta (ppm)=1.71 (6H, m, C(CH3)2), 6.75-6.81 (6H, m, ArH), 7.04-7.30 (33H, ArH), 7.47-7.50 (2H, m, ArH). 31P{1H} NMR (CDCl3, 121.4MHz) delta (ppm)=34.2 (2P, d, Jpp=30.6Hz, xantphos-P), 55.9 (1P, t, Jpp=30.6Hz, PPh3-P). FAB-MS (M++PPh3) 1012 (m/z). HRMS (M+-PPh3) calcd: 1012.1260, found: 1012.1273. Crystallographic data of 2a: (C57H47Cl2OP3Ru), M=1012.82, monoclinic, a=10.3028(14) , b=24.773(3) , c=18.654(3) , beta=102.880(3), V=4641.4(12) 3, space group P21/n (No. 14), Z=4, 46,546 reflections collected, 10,572 unique (Rint=0.0449), R1 (I>2sigma(I))=0.0756, wR2 (I>2sigma(I))=0.1401 (all data). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.1% | In dichloromethane; at 20℃; for 5h;Inert atmosphere; Schlenk technique; | General procedure: [Cu(CH3CN)4]ClO4 (32.6 mg, 0.100 mmol) was added to a dichloromethane (DCM) solution (about 10 mL) of BrphenBr (33.6 mg, 0.100 mmol) and BINAP (63.5 mg, 98%, 0.100 mmol) under a stream of dry argon using Schlenk techniques at room temperature. After stirring for 5 h at room temperature, n-hexane was carefully dropped over the DCM solution, and orange-yellow crystals were obtained a few days later in 52.5% yield (67.9 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.1% | at 20℃; for 5h;Inert atmosphere; Schlenk technique; | General procedure: [Cu(CH3CN)4]ClO4 (32.6 mg, 0.100 mmol) was added to a dichloromethane (DCM) solution (about 10 mL) of BrphenBr (33.6 mg, 0.100 mmol) and BINAP (63.5 mg, 98%, 0.100 mmol) under a stream of dry argon using Schlenk techniques at room temperature. After stirring for 5 h at room temperature, n-hexane was carefully dropped over the DCM solution, and orange-yellow crystals were obtained a few days later in 52.5% yield (67.9 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9.3 mg | With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; In 1,4-dioxane; at 140℃; for 0.5h;Microwave irradiation; | 0386-3 A mixture of 2-chloro-7-(3-ethyl-1-(3-(pyrrolidin-1-yl)propyl)-1H-pyrazol-4-yl)-1,5-naphthyridine (161 mg), 5-isopropylpyridazine-3-amine (9.6 mg), tris(dibenzylideneacetone)dipalladium(0) (4.2 mg), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (5.4 mg), cesium carbonate (38 mg), and 1,4-dioxane (1 mL) was stirred at 140 C. for 30 minutes using a microwave reaction apparatus. The reaction mixture was cooled to room temperature, the insolubles were filtered off using celite, and the obtained solution was purified by silica gel column chromatography (methanol-ethyl acetate, NH silica), thereby obtaining 7-(3-ethyl-1-(3-(pyrrolidin-1-yl)propyl)-1H-pyrazol-4-yl)-N-(5-isopropylpyridazin-3-yl)-1,5-naphthyridine-2-amine (9.3 mg). 1H-NMR(CDCl3/CD3OD=4/1) delta: 8.95 (1H, brs), 8.78 (1H, d, J=2.1 Hz), 8.71 (1H, m), 8.22 (1H, d, J=8.7H z), 8.09 (1H, d, J=2.1 Hz), 7.77 (1H, s), 7.50 (1H, d, J=8.7 Hz), 4.22 (2H, t, J=7.5 Hz), 3.10-2.98 (1H, m), 2.89 (2H, q, J=7.2 Hz), 2.65-2.48 (6H, m), 2.21-2.07 (2H, m), 1.88-1.80 (4H, m), 1.41 (6H, d, J=7.5 Hz), 1.31 (3H, t, J=7.2 Hz). MS m/z (M+H): 471. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47.4% | To a solution of HPDPH (35.5mg, 0.16mmol) in THF (6mL) was added NaH (60%, 6.51mg, 0.16mmol) to form a yellow solution. After stirring for 10min, CuCl (15.87mg, 0.16mmol) and XANTPhos (92.85mg, 0.16mmol) were added. The yellow resulting solution was stirred overnight and filtered. The filtrate was layered with hexane to give yellow crystals which were suitable for an X-ray diffraction study. Isolated yield: 65.8mg (47.4%). 1H NMR (CDCl3, delta, ppm): 8.56-8.55 (d, J=2Hz, 2H), 7.94-7.93 (d, J=2Hz, 2H), 7.74-7.72 (d, J=4Hz, 2H), 7.54-7.52 (m, 2H), 7.14-7.07 (m, 20H), 7.03-7.01 (t, J=4Hz, 2H), 6.69-6.67 (d, J=4Hz, 2H), 6.61-6.57 (m, 2H), 6.50-6.44 (m, 2H), 1.79 (s, 6H); 31P NMR (CDCl3, delta, ppm): -16.06 (s, XANTPhos). IR (KBr, cm-1): 3049(w), 2964(w), 1596(s), 1508(m), 1428(s), 1402(s), 1324(s), 1223(s), 1149(w), 1098(w), 848(w), 748(s), 694(s), 508(s). Anal. Calc. for: C53H42CuN3OP2: C, 73.81; H, 4.91; N, 4.87. Found: C, 73.83; H, 4.92; N, 4.80%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30.5% | General procedure: To a solution of HPDPH (35.5mg, 0.16mmol) in THF (6mL) was added NaH (60%, 6.51mg, 0.16mmol) to form a yellow solution. After stirring for 10min, CuCl (15.87mg, 0.16mmol) and XANTPhos (92.85mg, 0.16mmol) were added. The yellow resulting solution was stirred overnight and filtered. The filtrate was layered with hexane to give yellow crystals which were suitable for an X-ray diffraction study. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | In acetonitrile; at 20℃; for 3h;Schlenk technique; Inert atmosphere; | A 50 mL Schlenk flask was loaded with ligand (L2) (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) (xantphos) (1 mmol, 0.57 g) and [Cu(CH3CN)4]ClO4 (1 mmol, 0.32 g), and acetonitrile. The reaction mixture was stirred for 3 h at room temperature. Then filtered through the pad of celite, the filtrate was concentrated under reduced pressure and diethyl ether was added to yield complex 2 as a white solid. Yield: 91%. Complex 2 was further purified by crystallization (DCM/diethyl ether) to yield analytically pure compound. 1H NMR (400 MHz, CDCl3) d 7.51 (d, J 6.8 Hz, 2H, AreH), 7.30e7.05 (m, 22H, AreH), 6.54 (d, J 3.6 Hz, 2H, AreH), 2.06 (s, 6H, CH3CN), 1.60 (s, 6H, eCH(CH3)2). 31P NMR (162 MHz, CDCl3) d 14.65. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | In toluene; at 20℃; for 1h;Glovebox; | 16.7mg mesityl -Cu and 3ml of THF were added to 17.8mg (0.09mmol) of 7-PyIn and 53.0mg (0.09 mmol) of xantphos in a glove box. It forms ayellow solution. It was filtered, dried in vacuum, dissolved in dichloromethaneand coated with a layer of hexane. It forms orange crystals. Under UV (356nm),these emit light in a strong orange and the solution emits strong orange in thesame way. Yield: 79%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In toluene; at 20℃; for 1h;Glovebox; | 35.0mg mesityl -Cu and 3ml toluene were added to 38.2mg (0.19mmol) of 7-TpIn and 110.9mg of xantphos (0.19 mmol) in a glove box. yellow /orange solution, yellow solid content were formed. The solid content was filteredoff, and the solution was dried in vacuum, dissolved in dichloromethane, and itwas coated with a layer of hexane. crystals of orange color were formed. underUV (356nm), they emit strong white color, and the solution emits a strong bluecolor. Yield: 92%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | In toluene; at 20℃; for 1h;Glovebox; | 35.6mg mesityl -Cu and 3ml of toluene were added to 37.8mg(0.20 mmol) of 8-PyQ and 112.6mg (0.20 mmol) of xantphos in a glove box. Itforms a Red solution. This was filtered, the solvent was allowed to slowlyevaporate.it forms red crystals. under UV (356nm), they emit a strong red, andthe solution in the same way emits a strong red. Yield: 74%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | In toluene; at 20℃; for 1h;Glovebox; | 61.0mg mesityl -Cu and 3ml of toluene were added to 100.0mg(0.33 mmol) of 7-BTpCa and 193.0mg (0.33 mmol) of xantphos in a glove box. itforms a yellow suspension. This was filtered, concentrated in vacuum, dissolvedin DCM and was coated with a layer of hexane. It forms yellow crystals. underUV (356nm), these emit a strong green, and the solution in the same way emits astrong green. Yield: 86%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In toluene; at 20℃; for 1h;Glovebox; | 27.7mg mesityl -Cu and 3ml of toluene were added to 37.8mg (0.15mmol) of 7-BTpIn and 87.7mg (0.15 mmol) of xantphos in a glove box. It forms ayellow solution. This was filtered, coated with a layer of hexane. It formsyellow crystals. Under UV (356nm), these emit strong blue and the solutionemits strong blue in the same way. Yield: 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.5% | The above synthesis reaction is performed according to the following procedure, it was synthesized silver complex of Comparative Example 1.Under an argon atmosphere, silver tetrafluoroborate (the I) (27.5 mg, 0.141 mmol) in dichloromethane 8mL solution of 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (81.7 mg, 0 .141mmol), and the mixture was stirred for 15 minutes at room temperature.To the reaction mixture 2,9-dichloro-1,10-phenanthroline (44.0 mg, 0.177 mmol) was added and reflux heated for 1 hour.The reaction mixture was filtered and the filtrate was concentrated, chloroform - and recrystallized by slow diffusion with ether to give dried complex of pale yellow solid 135 mg (93.5% yield). | |
93.5% | Under an argon atmosphere, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (81.7 mg, 0 (0.7 mmol)) was added to a solution of silver (I) tetrafluoroborate (27.5 mg, 0.141 mmol) in 8 mL of dichloromethane .141 mmol), and the mixture was stirred at room temperature for 15 minutes. 2,9-Dichloro-1,10-phenanthroline (44.0 mg, 0.177 mmol) was added to the reaction solution, and the mixture was heated under reflux for 1 hour. The reaction solution was filtered, the filtrate was concentrated, recrystallized by slow diffusion with chloroform-ether, and dried to obtain 135 mg (yield 93.5%) of a pale yellow solid complex. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | General procedure: A solution of [Cu(CH3CN)4](ClO4) (35.3mg, 0.108mmol) and 1,2-bis(diphenylphosphino)ethane (dppe) (43.2mg, 0.108mmol) in CH2Cl2 (10mL) was stirred for 30min at room temperature. A solution of Hbmp (22.6mg, 0.108mmol) in CH2Cl2 (5mL) was added, and this mixture was stirred for another 2h to give a light-yellow solution. The solvent was evaporated to dryness at reduced pressure. The residue was dissolved in a mixture of acetone/dichloromethane (1:5 v/v), and slow diffusion of petroleum ether into the above solution gave light-yellow crystals of 2 (69.4mg, 0.090mmol, 83%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | A solution of [Cu(MeCN)4][PF6] (112 mg, 0.30 mmol) and xantphos (174 mg, 0.30 mmol) in CH2Cl2 (40 mL) was stirred for 2 h, after which 1 (58 mg, 0.15 mmol) was added. The dark red solution was stirred for 2 h, and then filtered. After removal of solvent from the filtrate, [Cu2(1)(xantphos)2][PF6] was isolated as a red powder (285 mg, 0.15 mmol, 97%). 1H NMR (500 MHz, CD2Cl2, 295 K) delta/ppm 7.93 (broad, see text), 7.63 (dd, J = 7.8, 1.2 Hz, 4H, HC5), 7.26 (overlapping m, 12H, HD4+C4), 7.17 (t, J = 7.5 Hz, 16H, HD3), 7.09 (m, 16H, HD2), 6.97 (broad, see text), 6.84 (m, 4H, HC3), 6.72 (broad, see text), 1.61 (s, 12H, Hxantphos-Me). 13C{1H} NMR (126 MHz, CD2Cl2) delta/ppm 154.6 (CC1), 153.2 (CA2/B2), 152.2 (CA2/B2), 150.1 (CB6), 137.4 (br, CB4), 134.2 (CC6), 133.3 (t, JPC = 8.2 Hz, CD2), 131.2 (m, CD1), 130.9 (CD4), 129.5 (t, JPC = 4.8 Hz, CD3), 128.1 (CC5), 126.4 (br, CB3/B5), 126.2 (br, CB3/B5), 125.6 (CC4), 119.5 (m, CC2), 36.2 (Cxantphos-bridge), 28.2 (Cxantphos-Me). 31P{1H} NMR (202 MHz, CD2Cl2) delta/ppm -13.8 (FWHM = 45 Hz, xantphos), -144.6 (septet, JPF = 711 Hz, [PF6]-). UV-Vis (CH2Cl2, 2.5 * 10-5 mol dm-3): lambda/nm (epsilon/dm3 mol-1 cm-1) 275 (58 180), 333 (18 460), 485 (5390). ESI MS: m/z 1029.7 [Cu(1)(xantphos)]+ (Calc. 1029.3), 641.4 [Cu(xantphos)]+ (Calc. 641.1), 611.4 [(xantphos)O2 + H]+ (Calc. 611.2). Found C, 60.22; H, 4.11; N, 4.28; C102H80Cu2F12N6O2P6.H2O requires C, 61.85; H, 4.17; N, 4.24%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.6% | A CH2Cl2 (40 mL) solution of [Cu(MeCN)4][PF6] (112 mg, 0.30 mmol) and xantphos (174 mg, 0.30 mmol) was stirred for 2 h. Then 2 (47 mg, 0.15 mmol) was added. The red solution was stirred for 2 h, then was filtered and the filtrate evaporated to dryness. [Cu2(2)(xantphos)2][PF6]2 was isolated as a dark red powder (265 mg, 0.140 mmol, 93.6%). 1H NMR (500 MHz, CD2Cl2, 295 K) delta/ppm 8.90 (br), 8.83 (br), 8.29 (br), 8.25 (br), 7.70 (d, J = 7.7 Hz), 7.65 (dd, J = 7.8, 1.4 Hz), 7.41 (br), 7.33-7.21 (br), 7.21 (t, J = 7.7 Hz), 7.05 (br), 6.99 (br), 6.87 (br), 6.09 (br), 5.82 (br). 13C{1H} NMR (126 MHz, CD2Cl2, 295 K, see text) delta/ppm 155.1 (t, JPC = 6.4 Hz, CC1), 150.0, 140.6, 134.4 (CC6), 133.2 (t, JPC = 7.6 Hz), 131.0, 129.8, 129.3, 128.5 (CC5), 125.8 (CC4), 119.5 (m, CC2), 36.4 (Cxantphos-bridge), 31.1 (Cxantphos-Me), 26.2 (Cxantphos-Me), see text discussion. 31P{1H} NMR (202 MHz, CD2Cl2) delta/ppm -12.2 (br, FWHM = 100 Hz, xantphos), -144.4 (septet, JPF = 711 Hz, [PF6]-). UV-Vis (CH2Cl2, 2.5 * 10-5 mol dm-3): lambda/nm (epsilon/dm3 mol-1 cm-1) 279 (71,920), 486 (6200). ESI MS: m/z 953.6 [Cu(1)(xantphos)]+ (Calc. 953.2), 611.4 [(xantphos)O2 + H]+ (Calc. 611.2). Found C, 61.02; H, 4.42; N, 4.77; C96H76Cu2F12N6O2P6 requires C, 61.12; H, 4.06; N, 4.45%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72.1% | With sodium hydroxide; In methanol; dichloromethane; at 20℃; for 4h;Inert atmosphere; Schlenk technique; | [Cu(CH3CN)4]ClO4 (32.6 mg, 0.100 mmol) was added to a mixture of L1 (19.5 mg, 0.0500 mmol) and xantphos (59.0 mg, 98%,0.100 mmol) in DCM (about 12 mL) under a stream of dry argon by using Schlenk techniques and a vacuum-line system at room temperature, then methanol suspension (1.00 mL) containing NaOH (20.0 mg, 0.500 mmol) was added. An orange-red solution was obtained quickly and then stirred for 4 h at room temperature. Layering n-hexane dropwise onto the DCM solution carefully produced the product as yellow prism crystals a few days later in 72.1% yield (63.9 mg). Anal. Calcd for C97H74BrClCu2N4O7P4 (1a)(1773.92): C 65.76, H 4.21, N 3.16. Found: C 65.57, H 4.30, N3.21. ESI-MS (m/z): 2065.28 [Cu2(L1-H)2(xantphos)2] +H+ (calcd2065.26); 1673.29 [Cu2(L1-H)(xantphos)2]+ (calcd 1673.25);1033.17 [Cu(L1)(xantphos)]+ (calcd 1033.13). 1H NMR (400 MHz,CD2Cl2, d, ppm): 8.56-6.18 (m, 62H), 1.89-1.58 (m, 12H). 31PNMR (400 MHz, CD2Cl2, d, ppm): 19.7, 18.2, 17.6, 16.0,15.6, 13.2, 11.9. Characteristic IR spectrum (KBr, cm1):1094s (ClO4). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63.9% | With sodium hydroxide; In methanol; at 20℃; for 4h;Inert atmosphere; Schlenk technique; | [Cu(CH3CN)4]ClO4 (29.3 mg, 0.0900 mmol) was added to a dichloromethane (DCM) solution (about 12 mL) of L1 (11.7 mg,0.0300 mmol), xantphos (53.1 mg, 98%, 0.0900 mmol) under a stream of dry argon by using Schlenk techniques at room temperature and a vacuum-line system. Then methanol suspension (1.00 mL) containing NaOH (20.0 mg, 0.500 mmol) was added. An orange-yellow solution was obtained quickly and then stirred for 4 h at room temperature. Layering n-hexane dropwise onto the DCM solution carefully produced the product as red crystals a few weeks later in 63.9% yield (46.3 mg). Anal. Calcd forC136H105BrClCu3N4O8P6 (1b) (2415.19): C 67.71, H 4.39, N 2.32.Found: C 67.62, H 4.32, N 2.39. ESI-MS (m/z): 2315.371[Cu3(L1-2H)(xantphos)3]+ (calcd 2315.364); 1673.27 [Cu2(L1-H) (xantphos)2]+ (calcd 1673.25); 1033.17 [Cu(L1)(xantphos)]+ (calcd1033.13). 1H NMR (400 MHz, CD2Cl2, d, ppm): 8.98-7.79 (m, 5H),7.73-5.79 (m, 82H), 1.94-1.53 (m, 18H). 31P NMR (400 MHz,CD2Cl2, d, ppm): 20.2, 18.2, 16.0, 15.6, 11.8. Characteristic IR spectrum (KBr, cm1): 1095s (ClO4). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.3% | With sodium hydroxide; In methanol; dichloromethane; at 20℃; for 4h;Inert atmosphere; Schlenk technique; | General procedure: [Cu(CH3CN)4]ClO4 (32.6 mg, 0.100 mmol) was added to a mixture of L1 (19.5 mg, 0.0500 mmol) and xantphos (59.0 mg, 98%,0.100 mmol) in DCM (about 12 mL) under a stream of dry argon by using Schlenk techniques and a vacuum-line system at room temperature, then methanol suspension (1.00 mL) containing NaOH (20.0 mg, 0.500 mmol) was added. An orange-red solution was obtained quickly and then stirred for 4 h at room temperature. Layering n-hexane dropwise onto the DCM solution carefully produced the product as yellow prism crystals a few days later in 72.1% yield (63.9 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.6% | With sodium hydroxide; In methanol; dichloromethane; at 20℃; for 4h;Inert atmosphere; Schlenk technique; | General procedure: [Cu(CH3CN)4]ClO4 (29.3 mg, 0.0900 mmol) was added to a dichloromethane (DCM) solution (about 12 mL) of L1 (11.7 mg,0.0300 mmol), xantphos (53.1 mg, 98%, 0.0900 mmol) under a stream of dry argon by using Schlenk techniques at room temperature and a vacuum-line system. Then methanol suspension (1.00 mL) containing NaOH (20.0 mg, 0.500 mmol) was added. An orange-yellow solution was obtained quickly and then stirred for 4 h at room temperature. Layering n-hexane dropwise onto the DCM solution carefully produced the product as red crystals a few weeks later in 63.9% yield (46.3 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54.2% | With sodium hydroxide; In methanol; dichloromethane; at 20℃; for 4h;Inert atmosphere; Schlenk technique; | General procedure: [Cu(CH3CN)4]ClO4 (32.6 mg, 0.100 mmol) was added to a mixture of L1 (19.5 mg, 0.0500 mmol) and xantphos (59.0 mg, 98%,0.100 mmol) in DCM (about 12 mL) under a stream of dry argon by using Schlenk techniques and a vacuum-line system at room temperature, then methanol suspension (1.00 mL) containing NaOH (20.0 mg, 0.500 mmol) was added. An orange-red solution was obtained quickly and then stirred for 4 h at room temperature. Layering n-hexane dropwise onto the DCM solution carefully produced the product as yellow prism crystals a few days later in 72.1% yield (63.9 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42.5% | With sodium hydroxide; In methanol; dichloromethane; at 20℃; for 4h;Inert atmosphere; Schlenk technique; | General procedure: [Cu(CH3CN)4]ClO4 (29.3 mg, 0.0900 mmol) was added to a dichloromethane (DCM) solution (about 12 mL) of L1 (11.7 mg,0.0300 mmol), xantphos (53.1 mg, 98%, 0.0900 mmol) under a stream of dry argon by using Schlenk techniques at room temperature and a vacuum-line system. Then methanol suspension (1.00 mL) containing NaOH (20.0 mg, 0.500 mmol) was added. An orange-yellow solution was obtained quickly and then stirred for 4 h at room temperature. Layering n-hexane dropwise onto the DCM solution carefully produced the product as red crystals a few weeks later in 63.9% yield (46.3 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In dichloromethane; for 1h;Inert atmosphere; Schlenk technique; | Similar procedure described for 5b was used in the synthesis of 6b by using xantphos instead of dppbz. Yield: 85%. 31P-NMR(121.42 MHz, 298 K, acetone-d6): 20.9 ppm (d, 1J(Rh-P) = 137 Hz). 1H-NMR (300 MHz, 298 K, acetone-d6):8.94 (br, 8H, Ha-pyr), 8.08 (m, 8H, Hb-pyr), 7.92-6.83 (m,112H, Ph ? HArom,Xanthene), 2.30 (m, 24H, (CH3)2,Xanthene).Maldi/TOF m/z: 1599.2 (M - 2Cl- - CO, calc.: 1599.1),1586.2 (M - 2Cl- - 2CO, calc.: 1586.10), 1572.2(M - 2Cl- - 3CO, calc.: 1572.1), 1557.2 (M - 2Cl-- 4CO, calc.: 1557.1), 1543.3 (M - 2Cl- - 4CO - 2CH3, calc.: 1543.2), 1525.2 (M - 2Cl- - 4CO - 4 CH3,calc.: 1525.2), 1510.2 (M - 2 Cl- - 4 CO - 6 CH3, calc.:1510.2), 1373.9 (M - xantphos -2 Cl-? CH2Cl2 ?H2O, calc.: 1373.8), 1353.1 (M - xantphos - 2 Cl- ?MeOH ?2 H2O, calc.: 1353.1), 1322.0 (M - xantphos- 2Cl-, calc.: 1322.0). IR (KBr, cm-1): 2099, 2012 s,1986 m, 1966 w, m(C:O); 1612 m, m(C=N).Synthesis of [Rh(CO)2(dppm)](OTf) (1c) Solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In dichloromethane; for 0.25h;Inert atmosphere; Schlenk technique; | Similar procedure described for 1c was used in the synthesis of 6c by using xantphos instead of dppm to obtain a pale yellow solid.Yield: 90%. 31P-NMR (121.42 MHz, 298 K, CDCl3):36.7 ppm (d, 1J(Rh-P) = 123 Hz). 1H-NMR (300 MHz,298 K, CDCl3): 7.83-7.42 (m, 26H, Ph), 1.74 (s, 6H, CH3).ESI-MS(?): 710.1 (M?-CO, calc.: 710.1). IR (KBr, cm-1)1974, m(C:O); 1101, 1029 (OTf-). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In dichloromethane; at 20℃; for 1h;Inert atmosphere; Schlenk technique; | Similar proceduredescribed for 2a was used in the synthesis of 5a using dppbz instead of dppe to obtain a pale yellow solid. Yield:70%. 31P-NMR (121.42 MHz, 298 K, CDCl3): 62.3 ppm(d, 1J(Rh-P) = 134 Hz). 1H-NMR (300 MHz, 298 K,CDCl3): 7.59-6.83 (m, Ph ? P - C6H4 - P). ESI-MS(?)m/z: 995.0 ([M-3 Ph]?, calc.: 994.9). IR (KBr, cm-1):1973 versus, m(C:O). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | General procedure: Under a N2 atmosphere, [(CH3CN)4Cu]BF4 (1.0 equiv) and theorganic phosphine ligand (2.0 equiv for PPh3 and TPA-PPP; 1.0equiv for DPEPHOS and XANTPHOS) were mixed in CH2Cl2. Afterstirring for 2 h at room temperature, the corresponding 2,2'-bipyrimidine-based ligand (0.5 equiv) was added. The reaction wasallowed to proceed at room temperature for 4 h. The solvent wasremoved under reduced pressure. The colored residue was dissolvedin CH2Cl2 (2 mL) and precipitated in diethyl ether. Theprecipitation was collected by filtration and washed with diethylether three times. The title Cu(I) complexes were obtained ascolored solids in high yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | In methanol; dichloromethane; at 20℃; for 5h;Inert atmosphere; | To a solution of L1 (30 mg, 0.067 mmol) in degassed,dry DCM (5 mL) and MeOH (5 mL), was added[CuI(MeCN)4]BF4 (25 mg, 0.080 mmol) and Xantphos(42 mg, 0.074 mmol). Then the mixture was degassed byvacuum and charged with N2 (three times). The mixturewas stirred at room temperature for 5 h under nitrogen atmosphere.The resulting solution was concentrated andEt2O was added to precipitate the product 1 (42 mg, yield:53%) as a red solid. 1H NMR (400 MHz, CDCl3) delta 8.50(d, J = 4.4 Hz, 2H), 8.15 (d, J = 8.0 Hz, 2H), 7.85 (dd, J1= 4.8 Hz, J2 = 8.0 Hz, 2H), 7.69 (d, J = 7.6 Hz, 2H),7.11?7.25 (m, 8H), 7.04?7.08 (m, 8H), 6.86?6.91 (m,8H), 2.49 (s, 6H), 1.78 (s, 6H). FT-IR (KBr, cm-1):3056(w), 2922(w), 1578(w), 1405(s), 1228(m), 1058(s),746(m), 696(m). MS (EI): m/z 1089.1 (M-BF4). Anal.Calcd for C57H44BCuF4N2OP2S6 (%): C 58.14, H 3.77, N2.38; Found: C 57.87, H 3.53, N 2.42. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With tris-(dibenzylideneacetone)dipalladium(0); In Petroleum ether; | Step 3: tert-Butyl 4-(1-oxo-3H-isobenzofuran-5-yl)piperazine-1-carboxylate To a solution of 5-bromo-3H-isobenzofuran-1-one (45 g, 211.24 mmol, 1.00 eq) and tert-butyl piperazine-1-carboxylate (39.34 g, 211.24 mmol, 1.00 eq) in dioxane (500 mL) was added tris(dibenzylideneacetone)dipalladium(0) (19.34 g, 21.12 mmol, 0.10 eq), 4,5-bis (diphenylphosphino)-9,9-dimethylxanthene (12.22 g, 21.12 mmol, 0.10 eq) and potassium phosphate (89.68 g, 422.48 mmol, 2.00 eq). The mixture was heated to 100 C. for 16 hr under nitrogen protection. The mixture was filtered through a pad of celite and filtrate was concentrated in vacuum. The residue was triturated in ethyl acetate: petroleum ether (500 mL, v/v=1:2). Tert-Butyl 4-(1-oxo-3H-isobenzofuran-5-yl)piperazine-1-carboxylate (50 g, 122.5 mmol, 58% yield, 78% purity) was obtained as yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Under inert gas protection, xylene (10 mL) was added to a 50 mL Schlenk reaction tube.Cuprous bromide (0.036 g, 0.25 mmol), 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (0.36 g, 0.625 mmol), stirred at room temperature for 3 h,Add 3,4,7,8-tetramethyl-1,10-phenanthroline (0.11 g, 0.5 mmol) at room temperature for 5 h.Activated zinc powder (3.0 g, 48 mmol) was added, and dibromomethane (8.1 g, 48 mmol) was added dropwise at -15C.The mixture was heated to reflux for 16 h until the zinc powder was completely reacted and cooled to room temperature to give a milky white suspension. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Into a 50 mL Schlenk reaction tube, add water-free THF (5 mL) under inert gas protection. Copper tetrafluorophosphate hexafluorophosphate (0.075 g, 0.2 mmol), 4,5-bisdiphenylphosphine-9,9 dimethyl xanthene (0.29 g, 0.5 mmol),Stir at 40C for 3 h, then add 4,7-dibromophenyl-1,10-phenanthroline (0.29 g, 0.6 mmol) and stir at 40C for 9 h. Without treatment, reduce to 25 C, add activated zinc powder (5g, 80mmol), Dibromomethane (23.12g, 136mmol) was added dropwise at about 15C and the mixture was heated at reflux for 10h.Cool to room temperature and stir until the zinc powder reaction is complete to give a milky white suspension. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Under inert gas protection, 1,4-dioxane (10 mL) was added to a 50 mL Schlenk reaction tube. Copper tetrafluorophosphate hexafluorophosphate (0.075g, 0.2mmol),4,5-bisdiphenylphosphine-9,9-dimethylxanthine (0.23 g, 0.4 mmol), stirred at 35C for 2.5 h, Then 2,9-dibromo-4,7-diphenyl-1,10-phenanthroline (0.25 g, 0.52 mmol) was added for reaction at 25C for 6 h. After the reaction was completed, activated zinc powder (2.5 g, 40 mmol) was added. Dibromomethane (13.6g, 80mmol) was added dropwise at about 0C, and heated to 65C for 15h. After the zinc powder was reacted, it was cooled to room temperature to give a milky white suspension. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57.6% | In dichloromethane; at 20℃; for 2h;Inert atmosphere; Schlenk technique; | General procedure: [Cu(CH3CN)4]ClO4 (16.3mg, 0.050mmol) was added to a mixture of pipH (7.4mg, 0.025mmol) and POP (26.9mg, 0.050mmol) in DCM under a stream of dry argon by using Schlenk techniques and a vacuum-line system at room temperature. A lemon-yellow solution was obtained quickly and then stirred for 2h at room temperature. After filtration through the absorbent cotton, layering n-hexane dropwise onto the dichloromethane filtrate carefully produced the target product as yellow crystals a few days later. The sample was obtained in an 84.4% yield (35.8mg) after being dried using infrared dry technique. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50.2% | With sodium hydroxide; In methanol; dichloromethane; at 20℃; for 2h;Inert atmosphere; Schlenk technique; | General procedure: [Cu(CH3CN)4]ClO4 (16.3mg, 0.050mmol) was added to a mixture of pipH (7.4mg, 0.025mmol) and POP (26.9mg, 0.050mmol) in DCM under a stream of dry argon by using Schlenk techniques and a vacuum-line system at room temperature. Then the NaOH (10.0mg, 0.250mmol) suspension in about 1.00mL methanol was added. A yellow solution was obtained quickly and then stirred for 2h at room temperature. Layering n-hexane onto the DCM filtrate carefully gave the product as yellow crystals a few weeks later. The sample was obtained in 80.1% yield (32.0mg) after being dried using infrared dry technique. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In dichloromethane; | Preparation of a large number of phosphorescent complex materials [Cu (Xantphos) (3-RhoBeta0) 2] (PF6) crystal samples: weight 0. 037g (0.1mmol) of Cu (CH3CN) 4PF6, 0 · 058g (0.1mmol) of Xantphos, 0 · 039g (0 · 2mmol) of 3-RhoBeta0; after dissolving with 5 ml of dichloromethane respectively mixed well, stir well enough to fully react, obtained an orange-yellow clear solution; the above solution was evaporated under reduced pressure at room temperature to remove all solvents, finally obtained a yellow crystal product, yield is 90% (calculated as Cu). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54.6% | In dichloromethane; at 20℃; for 2h;Inert atmosphere; Schlenk technique; | General procedure: [Cu(CH3CN)4]ClO4 (16.3 mg, 0.050 mmol) was added to a mixtureof ppipH (19.3 mg, 0.050 mmol) and POP (27.9 mg, 98%,0.050 mmol) in DCM under a stream of dry argon with a vacuum-line system and Schlenk techniques and the mixture was stirredfor 2 h at room temperature. After filtration, layering n-hexanecarefully onto the DCM filtrate produced orange-yellow crystals afew days later as 1aCH2Cl2. The orange-yellow product wasobtained in a 55.4% yield (32.4 mg) after being dried under aninfrared lamp. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41.2% | With sodium hydroxide; In methanol; dichloromethane; at 20℃; for 4h;Inert atmosphere; Schlenk technique; | General procedure: [Cu(CH3CN)4]ClO4 (16.3 mg, 0.050 mmol) was added to a mixtureof ppipH (19.3 mg, 0.050 mmol) and POP (27.9 mg, 98%,0.050 mmol) in DCM under a stream of dry argon using a vacuum-line system and Schlenk techniques at room temperature.Then the NaOH (20.0 mg, 0.50 mmol) suspension in about1.00 mL methanol was added to the stirred mixture, and then themixture was stirred for 4 h at room temperature. Layering n-hexanecarefully onto the DCM filtrate gave the product as yellow longprism crystals a few weeks later as 1bCH2Cl2. The yellow productwas obtained in a 62.7% yield (33.6 mg) after being dried under aninfrared lamp. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In methanol; dichloromethane; at 20℃; for 6h; | A mixture of 0.0630 g [Cu(CH3CN)4]BF4 (0.2 mmol), 0.0464 gdpq (0.2 mmol) and 0.1157 g xantphos (0.2 mmol) were dissolved in the mixed solvents of 5 mL CH3OH and 5 mL CH2Cl2, stirred atroom temperature for 6 h. The filtrate was evaporated slowly at room temperature for around 4 days to yield yellow crystalline products. Yield: 80%. Anal. Calc. for C55H49BCuF4N4O3.50P2: C,63.87; H, 4.78; N, 5.42. Found: C, 65.11; H, 4.16; N, 5.76%. 1HNMR (600 MHz, DMSO, 298 K): delta, ppm: 6.92-7.86 (m, xantphosaromaticring), 8.00-9.52 (m, dpq-heteroaromatic ring); 31P NMR(600 MHz, DMSO, 298 K): delta, ppm: 12.92 (s, xantphos). IR for 1(KBr pellets, cm-1): 2972(m), 1579(w), 1435(m), 1403(m), 1386(m), 1226(m), 1122(w), 1057(vs), 749(vs), 696(vs), 514(m), 440(w). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In dichloromethane; at 20℃; for 6h; | General procedure: A mixture of 0.0630 g [Cu(CH3CN)4]BF4 (0.2 mmol), 0.0464 gdpq (0.2 mmol) and 0.1157 g xantphos (0.2 mmol) were dissolved in the mixed solvents of 5 mL CH3OH and 5 mL CH2Cl2, stirred atroom temperature for 6 h. The filtrate was evaporated slowly at room temperature for around 4 days to yield yellow crystalline products. Yield: 80%. Anal. Calc. for C55H49BCuF4N4O3.50P2: C,63.87; H, 4.78; N, 5.42. Found: C, 65.11; H, 4.16; N, 5.76. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | Dap (10.7 mg, 98percent, 0.050 mmol), xantphos (59.0 mg, 98percent,0.100 mmol) and [Cu(CH3CN)4]ClO4 (32.6 mg, 0.100 mmol) wasadded to a DCM solution (about 12 mL) of dap (10.7 mg, 98percent,0.050 mmol) which had been stirred for 0.5 h in air, and the resultingmixture was further stirred in air for 1 h. After filtrationthrough absorbent cotton, layering n-hexane onto the DCM solutionin air produced 1b as black-blue block crystals and the product1c as orange-yellow crystals in 32percent yield (29.8 mg). The two kindsof crystals were separated by hand. Anal. Calc. for the weatheredproduct C102H82Cl2Cu2N8O10P4 (1c): C, 64.48; H, 4.35; N, 5.90.Found: C, 63.97; H, 4.31; N, 5.83percent. ESI-MS (m/z): 1802.31[Cu2(l-ttpd)2(xantphos)2]ClO4}+ (calcd. 1802.29); 1060.25[Cu(ttpd)(xantphos)]+ (calcd. 1060.29); 851.2059 [Cu2(l-ttpd)2(xantphos)2]2+ (calcd. 851.2054); 641.123 [Cu(xantphos)]+ (calcd.641.122). Characteristic IR spectrum (KBr, cm-1): 3444m (NH2and NH), 3371m (NH2 and NH), 3352m (NH2 and NH), 2966m(CH3), 2922w (CH3); 1101vs (ClO4). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | at 20℃; for 1h;Inert atmosphere; Schlenk technique; | [Cu(CH3CN)4]ClO4 (32.6 mg, 0.100 mmol) was added to adichloromethane (DCM) solution (about 12 mL) of dap (21.4 mg,98percent, 0.100 mmol) and xantphos (59.0 mg, 98percent, 0.100 mmol) undera stream of dry argon by using Schlenk techniques at room temperatureand a vacuum-line system, then orange-red solutionwas obtained quickly and stirred for 1 h at room temperature.The above process can also be carried out in air with the existenceof oxygen. After filtration through absorbent cotton, layeringn-hexane onto the filtrate in air produced the product as orangeredcrystals in 35?44percent yield (39.1?49.3 mg). Anal. Calc. forC52H44Cl3CuN4O5P2 (1aCH2Cl2): C, 60.34; H, 4.29; N, 5.42. Found:C, 60.01; H, 4.34; N, 5.45percent. ESI-MS (m/z): 851.214[Cu(dap)(xantphos)]+ (calcd 851.212); 641.123 [Cu(xantphos)]+(calcd 641.122). 1H NMR (400 MHz, DMSO-d6, delta, ppm): 8.681 (d,2H, J = 8.4 Hz), 8.209 (d, 2H, J = 4.4 Hz), 7.852 (dd, 2H, J = 7.6 Hz,J0 = 1.2 Hz), 7.650 (dd, 2H, J = 8.4 Hz, J0 = 4.4 Hz), 7.252 (t, 6H,J = 7.6 Hz), 7.102 (t, 8H, J = 7.6 Hz), 6.888?6.844 (m, 8H), 6.476?6.438 (m, 2H), 5.758 (s, 2H, CH2Cl2), 5.638 (s, 4H, NH2), 1.745 (s,6H, CH3). 31P{1H} NMR (400 MHz, DMSO-d6, delta, ppm): 13.097.Characteristic IR spectrum (KBr, cm-1): 3444m (NH2), 3372m(NH2), 2969m (CH3), 2925w (CH3), 1101vs (ClO4). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With air; at 20℃; for 1h;Inert atmosphere; Schlenk technique; | [Cu(CH3CN)4]ClO4 (32.6 mg, 0.100 mmol) was added to a DCMsolution (about 12 mL) of dap (10.7 mg, 98percent, 0.0500 mmol) andxantphos (59.0 mg, 98percent, 0.100 mmol) under a stream of dry argonby using Schlenk techniques at room temperature and a vacuumlinesystem, then orange-red solution was obtained quickly andstirred for 1 h at room temperature. The above process can alsobe carried out in air with the existence of oxygen. After filtrationthrough absorbent cotton, layering n-hexane onto the DCM solutionin air produced the product as bluish violet to black-blue blockcrystals in 76percent yield (63.0 mg). Anal. Calc. for C90H72Cl2Cu2N4O10P4(1b): C, 63.97; H, 4.30; N, 3.32. Found: C, 64.25; H, 4.35; N, 3.26percent.ESI-MS (m/z): 1589.25 [Cu2(l-pdi)(xantphos)2]ClO4}+ (calcd1589.27); 849.1963 [Cu(pdi)(xantphos)]+ (calcd 849.1968);745.153 [Cu2(l-pdi)(xantphos)2]2+ (calcd 745.159); 641.1222[Cu(xantphos)]+ (calcd 641.1224). 1H NMR (400 MHz, DMSO-d6,delta, ppm): 13.190 (s, 2H, CNH), 9.030 (d, 2H, J = 8.0 Hz), 8.452 (d,2H, J = 4.8 Hz), 7.888 (dd, 2H, J = 8.0 Hz, J0 = 1.2 and 0.8 Hz),7.846?7.814 (m, 4H), 7.340?7.149 (m, 36H), 6.983?6.938 (m, 8H),6.729?6.694 (m, 2H), 6.650?6.615 (m, 2H), 1.732 (s, 6H, CH3),1.653 (s, 6H, CH3). 31P{1H} NMR (400 MHz, DMSO-d6, delta, ppm):5.980, 12.816. Characteristic IR spectrum (KBr, cm-1): 3258m(NH), 2961m (CH3), 2923w (CH3), 2858w (CH3); 1097s (ClO4). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With trifluorormethanesulfonic acid; In toluene; at 200℃; for 16h;Inert atmosphere; | Under argon protection, bis(2-diphenylphosphinophenyl)ether (Compound 2) 538 g, toluene solvent was added to the reaction vessel.700 mL, 8.8 mL of trifluoromethanesulfonic acid, 150 mL of acetone, the reaction system was heated to 200 C, and after 16 h of reaction, it was reduced toAt room temperature, after extraction, drying and recrystallization, the desired product 4,5-bisdiphenylphosphino-9,9-dimethyloxaxan (Compound 1) is obtained.549 g (yield 95%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | (1) 9,9-Dimethyloxaindole (0.02 mol) and tetramethylethylenediamine (TMEDA) (42 mmol) were diluted in hexane (50 mL), and added dropwise at -78 C. -BuLi (42 mmol) in hexane (added in about 5 min), reacted for 1 h, then raised to room temperature (about 25 C), and continued to stir the reaction for 16 h;(2) Then, 15 mL of a solution of diphenylphosphonium chloride (42 mmol) in n-hexane was added dropwise to the reaction system of the step (1) in an ice water bath (added in about 5 minutes), and then continued at room temperature (about 25 C). The reaction was stirred for 16 h; the solvent was removed by rotary evaporation to afford a pale yellow viscous oil, washed with acetone and dried in vacuo., getting 9.7g of white powder,That is, the compound represented by the formula (3-1): the yield is 84% |
Tags: 161265-03-8 synthesis path| 161265-03-8 SDS| 161265-03-8 COA| 161265-03-8 purity| 161265-03-8 application| 161265-03-8 NMR| 161265-03-8 COA| 161265-03-8 structure
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P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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