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Structure of 12150-46-8 * Storage: {[proInfo.prStorage]}
* 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.
With tributylphosphine; iodine In tetrahydrofuran; acetonitrile at 20℃; for 0.166667 h; Inert atmosphere
EXAMPLE 4100 mg (0.171 mmol) of l,l'-Bis(diphenyloxyphosphino)ferrocene were treated with I2 4 mg (16 μιηο) and tributylphosphine 170 μ^ (0.68 mmol) in acetonitrile/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 μ). 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 under vacuum. The resulting residue was recrystallized from ethanol, the resulting crystals were filtered, washed and dried in vacuum, giving 89 mg (0.160 mmol, 94percent>) of Ι,Γ- Bis(diphenylphosphino)ferrocene (dppf).
With [AlH3(triethylamine)] In hexane at 20℃; for 0.166667 h; Inert atmosphere; Schlenk technique
General procedure: Triphenylphosphine oxide or sulfide (1 mmol), dry hexane (1 mL), and Ic (1 mmol) were added to a Schlenk tube under the atmosphere of nitrogen. The reaction was carried out at room temperature for 10 min and monitored by TLC. Upon completion of the process the reaction mixture was filtered by silica gel and washed several times with ethyl acetate. Ethyl acetate was evaporated and the residue purified by flash chromatography on silica gel with pure cyclohexane toafford the desired phosphine. The yield was determined by GC without additional purification.
Reference:
[1] Chemistry - A European Journal, 2017, vol. 23, # 58, p. 14434 - 14438
[2] ChemCatChem, 2017, vol. 9, # 24, p. 4460 - 4464
[3] Russian Journal of General Chemistry, 2015, vol. 85, # 5, p. 1156 - 1160[4] Zh. Obshch. Khim.,
3
[ 102-54-5 ]
[ 1079-66-9 ]
[ 12150-46-8 ]
Reference:
[1] Chemistry - A European Journal, 2012, vol. 18, # 39, p. 12267 - 12277
4
[ 591-51-5 ]
[ 1079-66-9 ]
[ 12150-46-8 ]
Reference:
[1] Journal of Organometallic Chemistry, 1980, vol. 185, # 1, p. C1 - C5
[2] Organometallics, 1982, vol. 1, p. 1275 - 1282
Reference:
[1] Journal of Organometallic Chemistry, 2004, vol. 689, # 11, p. 1978 - 1990
7
[ 12098-17-8 ]
[ 1079-66-9 ]
[ 12150-46-8 ]
Reference:
[1] Organometallics, 1986, vol. 5, p. 2537 - 2542
8
[ 201543-21-7 ]
[ 672-66-2 ]
[ 12150-46-8 ]
[ 717901-65-0 ]
Reference:
[1] Journal of Organometallic Chemistry, 2004, vol. 689, # 11, p. 1978 - 1990
9
[ 75-09-2 ]
[ 148-18-5 ]
[ 12150-46-8 ]
Reference:
[1] Journal of Organometallic Chemistry, 2004, vol. 689, # 11, p. 1978 - 1990
10
[ 33272-09-2 ]
[ 14311-22-9 ]
[ 12150-46-8 ]
Reference:
[1] Organometallics, 1992, vol. 11, p. 2543 - 2550
11
[ 105019-26-9 ]
[ 591-51-5 ]
[ 12150-46-8 ]
Reference:
[1] Organometallics, 1986, vol. 5, p. 2537 - 2542
12
[ 12150-46-8 ]
[ 72287-26-4 ]
Yield
Reaction Conditions
Operation in experiment
86%
for 8 h; Inert atmosphere; Schlenk technique; Reflux
To a dichloromethane solution (15 cm3) of dppf (189 mg, 0.34 mmol), a methanolic solution of Na2PdCl4 (100 mg, 0.34 mmol) was added with continuous stirring. The resulting reaction mixture was refluxed for 8 hours. The solvents were evaporated in vacuo and the residue was washed thoroughly with diethyl ether to remove excess phosphine. The residue was extracted with dichloromethane, filtered and passed through a Florisil column. The resulting solution on refrigeration at –5 oC afforded reddish orange crystals.(yield 214 mg, 86percent). Anal. Calcd. for C34H28P2FePdCl2: C, 55.81 ; H, 3.86 percent. Found: C, 55.86; H, 3.85 percent. 1H NMR (CDCl3) δ: 4.26 (br, 4H, C5H4), 4.71 (br, 4H, C5H4), 7.41-7.49 (m, Ph), 7.56-7.82 (m, Ph); 31P{1H}NMR (CDCl3) δ : 34.1 ppm.
The solution of dppf (1.6632g, 3mmol)in 15ml CH2Cl2 was added to a solution of PdCl2(0.5320g, 3mmol) that dissolved in 2 cm3 ethanoland 2 cm3 concentrate HCl. The mixture was reuxfor 3 hrs. And then the solvent was evaporate at roomtemperature to give red precipitate. A small portion ofthis complex was dissolve in CH2Cl2 and set to slowevaporation at room temperature after a few days, thered colored needle crystals were formed suitable forsingle-crystal diffraction analysis15. The melting pointis 253°C, yield is 2.086gm (95percent), formula: [Pd(k2-dppf)Cl2] and M.wt.is 816.58 gm/mole, as shown inFigure 1.
Reference:
[1] Oriental Journal of Chemistry, 2017, vol. 33, # 2, p. 584 - 592
With zinc(II) cyanide; tris-(dibenzylideneacetone)dipalladium(0) In DMF (N,N-dimethyl-formamide) at 120℃; for 2h;
25B
A degasssed mixture of ester EX-25A (10.35 g, 0.037 mol)), Pd(dba)3 (0.017 g, 0.018 mmol)), dppf (0.025 g, 0.045 mmol)) and Zn(CN)2 (2.6 g, 0.02 mol) in DMF (100 mL) was heated to 120 C. for 2 hours. The reaction mixture was poured into water and ethyl acetate. The organic layer was washed with water (2) and brine (1). The organic layer was collected, dried (MgSO4) and the solvent removed in vacuo to give 5.28 g methyl 2-cyano-5-methylbenzoate (EX-25B) as a brownish oil with m/z+1=176.
With sodium chloride; ammonium chloride In tetrahydrofuran
R.5 2-(4-cyano-2-nitrophenylmethyl)benzoic Acid Methyl Ester
REFERENCE EXAMPLE 5 2-(4-cyano-2-nitrophenylmethyl)benzoic Acid Methyl Ester Under atmosphere of argon, to a solution of zinc powder (1.89 g) in anhydrous THF (15 ml) was added dibromoethane (116 ul) and the mixture was stirred for five minutes at 60° C. To the reaction mixture was added a solution of 2-bromomethylbenzoic acid methyl ester (4.42 g) in anhydrous THF (15 ml) over a period of 30 minutes at 0° C. and the mixture was stirred for 2 hours at the temperature to give a 2-carbomethoxybenzylzinc (II) bromide (benzyl zinc) solution. Under atmosphere of argon, to a solution of 1-cyano-3-nitro-4-iodobenzene (2.00 g), bis(dibenzylideneacetone)palladium (42 mg) and 1,1'-bis (diphenylphosphino) ferrocene (41 mg) in anhydrous THF (10 ml) was added the above prepared benzyl zinc solution dropwise at room temperature and the mixture was stirred for 2 hours at 60° C. To the reaction mixture was added a saturated aqueous solution of ammonium chloride at 0° C. and was extracted with ethyl acetate. The organic layer was washed with water and a saturated aqueous solution of sodium chloride and was dried over magnesium sulfate and was concentrated. The residue was purified by column chromatography on silica gel (n-hexane:ethyl acetate=5:1) to give the title compound (809 mg) having the following physical data. TLC: Rf 0.61 (n-hexane:ethyl acetate=2:1); NMR(CDCl3): δ 8.25 (d, J=1.8 Hz, 1H), 8.05 (dd, J=7.8, 1.5 Hz, 1H), 7.66 (dd, J=8.0, 1.8 Hz, 1H), 7.54 (dt, J=7.8, 1.5 Hz, 1H), 7.42 (dt, J=7.8, 1.5 Hz, 1H), 7.23 (d, J=7.8 Hz, 1H), 7.10 (d, J=8.0 Hz, 1H), 4.69 (s, 2H), 3.76 (s, 3H)
With potassium carbonate In methanol; chloroform; N,N-dimethyl-formamide
1.A Step A
Step A 5-(2,4-diaminopyrimid-6-yl)pentanoic acid ethyl ester (2-2) Ethyl 4-pentenoate (4.93 gm, 38.4 mmol) was treated with 9-BBN (92.2 mL, 46.1 mmol; 0.5M in THE) at room temperature for 16 hours. To this solution was added Pd(OAc)2 (863 mg, 3.84 mmol), 6-chloro-2,4-diaminopyrimidine (2-1, 5.0 g, 34.6 mmol), K2CO3 (7.95 g, 57.6 mmol), 1,1'-bis(diphenylphosphino)-ferrocene (2.13 g, 3.84 mmol) and DMF (100 mL). The mixture was degassed with argon for 10 minutes then heated to 90° C. for 24 hours. The reaction mixture was cooled and stirred with ethanolamine (10 mL) for 1 hour. The volatiles were removed in vacuo and the black tarry residue was partitioned between water and EtOAc. After extraction with EtOAc (4*), the organic layers were washed with water (4*), then brine, dried (MgSO4) and concentrated. Purification by silica gel chromatography (5% MeOH in CHCl3) afforded the title compound 2-2 as an oil. 1H NMR (300 MHz, CDCl3): δ 5.72 (s, 1H), 4.97 (brs, 2H), 4.84 (brs, 2H), 4.12 (q, 2H), 2.43 (t, 2H), 2.32 (t, 2H), 1.67 (m, 4H), 1.25 (t, 3H) ppm.
With pyridine; potassium carbonate In tetrahydrofuran; N,N-dimethyl-formamide
22.B Step B
Step B 5-[2-(4-methoxybenzylamino)pyridin-6-yl]pentanoic acid ethyl ester (16-3) Ethyl 4-pentenoate (8.95 g, 69.8 mmol) was treated with 9-BBN (167 mL, 83.7 mmol; 0.5M in THF) at 0° C. then warmed to room temperature and stirred for 16 hours. To this solution was added Pd(OAc)2 (1.57 g, 6.98 mmol), pyridine 16-2 (18.4 g, 62.8 mmol), K2CO3 (14.4 g, 105 mmol), 1,1'-bis(diphenylphosphino)-ferrocene (3.87 g, 6.98 mmol) and DMF (200 mL). The mixture was degassed with argon for 10 minutes then heated to 80° C. for 24 hours. The reaction mixture was cooled and stirred with ethanolamine (20 mL) for 2 hours. The mixture was partitioned between water and EtOAc, extracted with EtOAc (3*), washed with water (3*), then brine, dried (MgSO4) and concentrated. Purification by silica gel chromatography (hexane:EtOAc 3:2) afforded the title compound 16-3 as an oil. 1H NMR (300 MHz, CDCl3) δ 7.32 (t, 1H), 7.28 (d, 2H), 6.88 (d, 2H), 6.45 (d, 1H), 6.19 (d, 1H), 4.89 (bt, 1H), 4.38 (d, 2H), 4.12 (q, 2H), 3.80 (s, 3H), 2.63 (t, 2H), 2.23 (t, 2H), 1.6 (m, 4H), 1.26 (t, 3H) ppm.
Palladium diammine dichloride and 1 mole equivalent of 1 ,2bis(diphenylphosphino)ferrocene (dppf) were suspended in acetonitrile at reflux for 4 hrs. A basic gas (believed to be ammonia) was evolved during the reaction. The product was filtered off at room temperature and dried. The product contained 7.29percent Fe and 14.44percent Pd by standard wet chemical analysis and was identified as Pd(dppf)CI2 by infra-red spectroscopy.
In dichloromethane; for 8h;Inert atmosphere; Schlenk technique; Reflux;
To a dichloromethane solution (15 cm3) of dppf (189 mg, 0.34 mmol), a methanolic solution of Na2PdCl4 (100 mg, 0.34 mmol) was added with continuous stirring. The resulting reaction mixture was refluxed for 8 hours. The solvents were evaporated in vacuo and the residue was washed thoroughly with diethyl ether to remove excess phosphine. The residue was extracted with dichloromethane, filtered and passed through a Florisil column. The resulting solution on refrigeration at ?5 oC afforded reddish orange crystals.(yield 214 mg, 86percent). Anal. Calcd. for C34H28P2FePdCl2 : C, 55.81 ; H, 3.86 percent. Found: C, 55.86; H, 3.85 percent. 1H NMR (CDCl3) delta: 4.26 (br, 4H, C5H4), 4.71 (br, 4H, C5H4), 7.41-7.49 (m, Ph), 7.56-7.82 (m, Ph); 31P{1H}NMR (CDCl3) delta : 34.1 ppm.
W(CO)4(1,1'-bis(diphenylphosphino)ferrocene)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
79%
With sodium tetrahydroborate; at 105℃; under 760.051 Torr; for 0.333333h;Microwave irradiation; Inert atmosphere; Green chemistry;
General procedure: The reactions were run in a CEM Corp. MARS microwave fitted with a fiber optic temperature probe and a port on top for a reflux condenser.1 mmol of Mo(CO)6 and dppe (0.425 g, 1.1 mmol) were combined with 20 mL of 1-propanol in a two-neck 100 mL RB flask. To this mixture was added NaBH4 (0.128 g, 3.3 mmol). The flaskwas placed in themicrowave and a reflux condenser attached through a hole in the top of the microwave. The mixture was sparged with nitrogen. The mixture was heated under nitrogen at 400 W for 1.5 min to reach reflux temperature. Once the reflux temperature was reached the microwave power was reduced and the temperature maintained for 18 min. The mixture was cooled to room temperature and 2-4 mL of water was added to the reaction to dissolve excess NaBH4 and promote product precipitation. The reaction was cooled -10 C for several hours. The light yellow complex was filtered in air and washed with 2×5 mL of petroleum ether/diethyl ether(1:1) mixture resulting in 580 mg of Mo(CO)4dppe after drying, a 95% yield.
In toluene; at 20℃; for 4h;Product distribution / selectivity;
A reaction flask was charged with 1 , l'-bis(diphenylphosphino)ferrocene (1.84 g, 3.32 mmol), bis(l,5-cyclooctadiene)nickel (0.75 g, 2.80 mmol) and oxygen-free toluene (10 mL) under a nitrogen atmosphere in a glovebox. After stirring for 4 h at room temperature, hexanes (40 mL) were added to the reaction mixture. The reaction mixture was allowed to stand overnight, and then the solvents were decanted off and the orange-yellow solid remaining was washed with hexanes. The solid was dried under vacuum to give the title compound as an orange-yellow solid (1.86 g, 78% yield). 31P NMR (benzene-^): δ 38.4 (s).
Cr(CO)4(1,1'-bis(diphenylphosphino)ferrocene)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
With sodium tetrahydroborate; In propan-1-ol; at 90℃; under 760.051 Torr; for 0.333333h;Microwave irradiation; Inert atmosphere; Green chemistry;
General procedure: The reactions were run in a CEM Corp. MARS microwave fitted with a fiber optic temperature probe and a port on top for a reflux condenser.1 mmol of Mo(CO)6 and dppe (0.425 g, 1.1 mmol) were combined with 20 mL of 1-propanol in a two-neck 100 mL RB flask. To this mixture was added NaBH4 (0.128 g, 3.3 mmol). The flaskwas placed in themicrowave and a reflux condenser attached through a hole in the top of the microwave. The mixture was sparged with nitrogen. The mixture was heated under nitrogen at 400 W for 1.5 min to reach reflux temperature. Once the reflux temperature was reached the microwave power was reduced and the temperature maintained for 18 min. The mixture was cooled to room temperature and 2-4 mL of water was added to the reaction to dissolve excess NaBH4 and promote product precipitation. The reaction was cooled -10 C for several hours. The light yellow complex was filtered in air and washed with 2×5 mL of petroleum ether/diethyl ether(1:1) mixture resulting in 580 mg of Mo(CO)4dppe after drying, a 95% yield.
(1,1′-bis(diphenylphosphino)ferrocene)Ni(I)Cl[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
32%
In benzene; at 20℃; for 16h;Glovebox; Inert atmosphere; Sealed tube;
In a glove box filled with nitrogen, Ni (cod) 2 (0.53mmol, 146.0mg), dppf (0.53mmol, 294.0mg) and benzene (10mL) were added to a 25mL sealed tube in sequence.After stirring at room temperature for 10 minutes, chlorobenzene (1 mL) was added to the system. After the system was allowed to react at room temperature for 16 hours, a yellow suspension was obtained. The yellow suspension was filtered with suction, washed with n-hexane, and dried in vacuo to obtain a yellow solid.At -30 C, recrystallize with n-hexane and tetrahydrofuran to obtain 109 mg of light yellow solid with a yield of 32%.
[Fe2(μ-toluene-3,4-benzenedithiolate)(CO)5(κ1-dppf)][ No CAS ]
C46H34Fe3O6P2S2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
1: 37%
2: 24%
Stage #1: trimethylamine-N-oxide; Fe2(CO)6[μ-SCCHCHC(CH3)CHCS] In acetonitrile at 20℃; for 0.25h; Inert atmosphere;
Stage #2: 1,1'-bis-(diphenylphosphino)ferrocene In acetonitrile for 1.5h; Inert atmosphere;
2.4 Synthesis
One portion of Me3NO.2H2O (0.051 g, 0.00046 mol) was added to a solution of 0.00046 mol of [Fe2{μ-L}(CO)6] 1 (L = μ-toluene-3,4-benzenedithiolate) inMeCN (30 mL) under argon. The mixture was stirredat room temperature for 15 min followed by the additionof the dppf ligand (0.128 g, 0.00023 mol). After1.5 h the volatiles were removed in vacuo. The resulting respective solid was purified by column chromatographyon silica gel with hexane/CH2Cl2 (1:4 v/v) as gradienteluent which gave 2 as a red-brown solid. Elutionwith CH2Cl2 gave 3 as a dark red-orange solid. Singlecrystals of 4 suitable for X-ray analysis were obtainedby slow evaporation of the CH2Cl2/hexane solution ofcomplex 3 at room temperature. The formation of complex4 could be due to the presence of N-methyl amineoxide as O-atom source in the reaction mixture. 2.4a [{Fe2(μ-toluene-3,4-benzenedithiolate)(CO)5}2(μ, κ2-dppf)], 2: Colour: red-brown. Yield: 24%(0.150 g). Anal. Calcd for C58H40Fe5O10P2S4: C, 50.98;H, 2.95. Found: C, 50.58; H, 3.00. IR (CH2Cl2, cm-1):2047, 1982, 1934. 1H NMR (400 MHz, CDCl3): δ 7.37(s, 10H, Ph); 7.13 (s, 10H, Ph); 6.45 (m, 2H); 6.12(s,2H); 6.01 (m, 2H); 3.94-4.46 (s, 8H, Cp); 1.81 (s, 6H,CH3) ppm. 31P NMR (161.8 MHz, CDCl3): δ 52.51(s, Fe - P) ppm.2.4b [Fe2(μ-toluene-3,4-benzenedithiolate)(CO)5(κ1-dppf)], 3: Colour: dark red-orange.Yield:37%(0.164 g).Anal. Calcd for C46H34Fe3O5P2S2: C, 57.53; H, 3.57.Found: C, 56.95; H, 3.70. IR (CH2Cl2, cm-1): 2048,1987, 1930. 1H NMR (400 MHz, CDCl3): δ 7.14-7.38(s, 20H, Ph); 6.47 (m, 1H); 6.13 (s, 1H); 6.03 (m, 1H);3.76-4.47 (s, 8H, Cp); 1.83, 1.82 (s, 3H, CH3) ppm. 31PNMR (161.8 MHz, CDCl3): δ 52.67, 52.53 (s, Fe - P);-16.68, -17.08 (s, P) ppm.2.4c [Fe2(μ-toluene-3,4-benzenedithiolate)(CO)5(κ1-dppfO)], 4: Colour: dark brown. Anal. Calcd forC46H34Fe3O6P2S2: C, 56.59; H, 3.51. Found: C, 56.90;H, 3.65. IR (CH2Cl2, cm-1): 2050, 1988, 1931. 31PNMR (161.8 MHz, CDCl3): δ 52.43 (s, Fe - P); 28.74(s, P = O) ppm.
The solution of dppf (1.6632g, 3mmol)in 15ml CH2Cl2 was added to a solution of PdCl2(0.5320g, 3mmol) that dissolved in 2 cm3 ethanoland 2 cm3 concentrate HCl. The mixture was reuxfor 3 hrs. And then the solvent was evaporate at roomtemperature to give red precipitate. A small portion ofthis complex was dissolve in CH2Cl2 and set to slowevaporation at room temperature after a few days, thered colored needle crystals were formed suitable forsingle-crystal diffraction analysis15. The melting pointis 253°C, yield is 2.086gm (95percent), formula: [Pd(k2-dppf)Cl2] and M.wt.is 816.58 gm/mole, as shown inFigure 1.
cis-[RuCl2(dipyrido[3,2-a:2′,3′-c]phenazine)(1,1‘-bis(diphenylphosphino)ferrocene)][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
General procedure: A degassed dichloromethane (25.0 mL) solution of [RuCl2(PPh3)3] (96 mg; 0.10 mmol) and dppf (60.0 mg; 0.11 mmol), in a Schlenk flask, was stirred for 30 min followed by the addition of 0.10 mmol of the polypyridyl ligand. After 30 min of stirring the resulting solution was concentrated until ca. 5 mL and addition of 10 mL of diethyl ether afforded a solid, which was collected by filtration, washed with diethyl ether and dried under vacuum.
Stage #1: 5-trifluoromethyl-3-(2′-pyridyl)-2H-1,2,4-triazole; tetrakis(acetonitrile)copper(I) perchlorate In dichloromethane at 20℃; for 0.5h; Inert atmosphere;
Stage #2: 1,1'-bis-(diphenylphosphino)ferrocene In dichloromethane at 20℃; for 1h; Inert atmosphere;
Stage #1: 5-trifluoromethyl-3-(2′-pyridyl)-2H-1,2,4-triazole; tetrakis(acetonitrile)copper(I) perchlorate In dichloromethane at 20℃; for 0.5h; Inert atmosphere;
Stage #2: 1,1'-bis-(diphenylphosphino)ferrocene In dichloromethane at 20℃; for 1h; Inert atmosphere;
Stage #3: With sodium hydroxide In dichloromethane at 20℃; for 2h; Inert atmosphere;