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Chemical Structure| 15754-51-5

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Product Details of [ 15754-51-5 ]

CAS No. :15754-51-5
Formula : C14H15O3P
M.W : 262.24
SMILES Code : COC1=CC=C(C=C1)P(=O)C1=CC=C(OC)C=C1
MDL No. :MFCD06754095
InChI Key :RREGWFNURZJKNB-UHFFFAOYSA-N
Pubchem ID :13583147

Safety of [ 15754-51-5 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319
Precautionary Statements:P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313

Application In Synthesis of [ 15754-51-5 ]

* 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.

  • Downstream synthetic route of [ 15754-51-5 ]

[ 15754-51-5 ] Synthesis Path-Downstream   1~35

  • 1
  • [ 104-92-7 ]
  • [ 15754-51-5 ]
YieldReaction ConditionsOperation in experiment
General procedure: A round-bottom flask fitted with a reflux condenser and an addition funnel was evacuated and back-filled with argon. The sequence was repeated three times. The flask was charged with Mg turnings (0.1 mol, 3.3 equiv) and then anhydrous THF (70 mL, 0.7 mL/mmol) and a few crystals of I2 were added. The mixture was refluxed until discoloration. A solution of halide (0.1 mol, 3.3 equiv) in THF (70 mL, 0.7 mL/mmol) was added dropwise at a rate that maintained gentle reflux. When the addition was complete, the mixture was additionally refluxed for 2-3 h. The reaction mixture was cooled to 0 C and a solution of diethyl phosphite (0.03 mol, 1 equiv) in THF (30 mL, 1 mL/mmol) was added dropwise over 30 min. The reaction mixture was stirred overnight, then cooled to 0 C and cautiously quenched with 1 M HCl to pH 4-5. The mixture was extracted twice with CH2Cl2 and the combined organic fractions were washed with water and dried over Na2SO4. After removal of the solvent under reduced pressure, the crude product was purified by column chromatography on silica gel (40-60 μm) using CH2Cl2-MeOH as eluent. Phosphine oxides derived from ethyl phenylphosphinate were obtained according to the above procedure, but with the following exceptions: 2.2 equivalents of both Mg turnings and halide instead of 3.3 equivalents, and ethyl phenylphosphinate instead of diethyl phosphite.45
General procedure: Magnesium chips (30mmol, 3.0 equiv.), catalytic amount of iodine (10 mol%) and 100mL anhydrous THF solution were added into a 250mL dry two-necked flask under nitrogen atmosphere. Afterwards, aryl bromide compound (5mmol, 0.5 equiv.) was added dropwise. After the initiation, aryl bromide compound (25mmol, 2.5 equiv.) was further added dropwise. The reaction mixture was refluxed for 30min before cooled to 0C. The solution of diethyl phosphite (10mmol, 1.0 equiv.) in 20mL THF was added dropwise to the reaction system at 0C, and the reaction mixture was kept stirring overnight. The reaction was then quenched with saturated NH4Cl, after which the resulting solution was filtered through Celite, washed with methyl tert-butyl ether (10 mL×3). The filtrate was extracted with methyl tert-butyl ether (50 mL×3), and the organic phase was collected, dried with anhydrous Na2SO4, recrystallized with DCM (dichloromethane) and PET (Petroleum ether) to obtain the target pure product.
References: [1]Advanced Synthesis and Catalysis,2018,vol. 360,p. 3999 - 4004.
[2]Journal of the American Chemical Society,2020,vol. 142,p. 7386 - 7392.
[3]Tetrahedron Asymmetry,2003,vol. 14,p. 2215 - 2224.
[4]Chemical Communications,2016,vol. 52,p. 6451 - 6454.
[5]Organic Letters,2019,vol. 21,p. 2597 - 2601.
[6]Molecules,2013,vol. 18,p. 2788 - 2802.
[7]Organic Letters,2019,vol. 21,p. 1526 - 1529.
[8]Helvetica Chimica Acta,1977,vol. 60,p. 2824 - 2829.
[9]Chemical Communications,2001,p. 1220 - 1221.
[10]Organic process research and development,2011,vol. 15,p. 1178 - 1184.
[11]Chemical Communications,2015,vol. 51,p. 10385 - 10388.
[12]Angewandte Chemie - International Edition,2017,vol. 56,p. 364 - 367.
    Angew. Chem.,2017,vol. 129,p. 370 - 373.
[13]Chemistry - A European Journal,2018,vol. 24,p. 3174 - 3177.
[14]Journal of Organic Chemistry,2019,vol. 84,p. 949 - 956.
[15]Synthesis,2019,vol. 51,p. 2379 - 2386.
[16]Advanced Synthesis and Catalysis,2020,vol. 362,p. 2268 - 2273.
[17]Chemical Communications,2021,vol. 57,p. 2069 - 2072.
[18]Angewandte Chemie - International Edition,2021,vol. 60,p. 14921 - 14930.
    Angew. Chem.,2021,vol. 133,p. 15048 - 15057.
[19]Chemistry - A European Journal,2021,vol. 27,p. 11285 - 11290.
[20]European Journal of Organic Chemistry,2021,vol. 2021,p. 3071 - 3078.
[21]Angewandte Chemie - International Edition,2021,vol. 60,p. 20424 - 20429.
    Angew. Chem.,2021,vol. 133,p. 20587 - 20592.
[22]Molecular catalysis,2022,vol. 517.
[23]Chemistry - An Asian Journal,2022,vol. 17.
[24]Chemical Communications,2022,vol. 58,p. 1135 - 1138.
  • 2
  • [ 15754-51-5 ]
  • (+/-)-2,2'-bis(trifluoromethanesulfonyloxy)-1,1-binaphthyl [ No CAS ]
  • [ 365240-78-4 ]
  • 3
  • [ 762-04-9 ]
  • [ 13139-86-1 ]
  • [ 15754-51-5 ]
YieldReaction ConditionsOperation in experiment
92% Symmetric secondary phosphine oxides were prepared by the method of Hays by adding 1 eq. of diethylphosphite to 3.3 eq. of the corresponding Grignard reagent at 0 C and warming to ambient temperature. A 100-mL round-bottom flask equipped with an addition funnel was evacuated/Ar filled, then charged with 33 mL of 1 M 4-methoxyphenylmagnesium bromide/THF (33 mmol, 3.3 eq.), and the solution cooled to 0 C under Ar. A solution of 1.38 g of diethylphosphite (10 mmol, 1.0 eq.) in 10 mL of THF was then added dropwise over 10 min. The mixture was aged 10 min at 0 C, then the bath was removed, and the mixture stirred 2 h at ambient temperature, then cooled again to 0 C. 25 mL 0.1 N HCl (deoxygenated water) was then added dropwise over 20 min, then 25 mL methyl tert-butyl ether (MTBE) was added, and the mixture agitated well for 5 min. The upper organic phase was decanted from the separator and saved. To the lower phase was then added 20 mL of 1 N HCl (deoxygenated water) again, and it was extracted with CH2Cl2 (2 9 30 mL). The organic phase was combined with the first organic phase, then filtered through a celite pad, washing the pad with CH2Cl2, dried magnesium sulfate (MgSO4), and the solvents removed in vacuo. The crude material was chromatographed on silica gel eluting with 2% MeOH/CH2Cl2, then recrystallized from hot ethyl acetate (EtOAc) to give 2.41 g of product (92%) as a colorless solid. Colorless solid; YIELD = 92%; 1H NMR (400 MHz, CDCl3) d: 8.01 (d, 1JHP = 473 Hz, 1H), 7.60 (dd, J = 13.8, 8.2 Hz, 4H), 6.97 (dd, J = 7.8, 2.4 Hz, 4H), 3.83 (s, 6H); 31P NMR (162 MHz, CDCl3) d: 21.0.
  • 4
  • [ 15754-51-5 ]
  • [ 13685-30-8 ]
YieldReaction ConditionsOperation in experiment
90% With acetyl chloride; In tetrahydrofuran; at 25℃; for 12h;Inert atmosphere; Sealed tube; General procedure: Choose other representative phosphine oxides, aromatic and aliphatic phosphine oxides, etc., which are easily reduced to the corresponding chlorophosphine compounds under similar reaction conditions and the yield is very high.In a sealed NMR tube filled with argon,Dissolve R1R2P (O) H (1.0 mmol) in 2.0 mL of THF, then add acetyl chloride (2.0 mmol, that is, the amount of acetyl chloride added is twice the equivalent of Ph2P (O) H).The mixture was heated at a certain temperature overnight. The chemical reaction formula is shown in formula (III).
87% With acetyl chloride; In tetrahydrofuran; at 25℃;Inert atmosphere; General procedure: To an 10mL oven-dried Schlenk tube under argon atmosphere were added R1R2P(O)H (1.0 mmol) and THF (2.0 mL), stirring the solution until all the solid was totally dissolved, and then MeC(O)Cl (2.0 mmol) was added to the solution and the mixture was stirred at room temperature or 50oC for overnight. After reaction, the excessive MeC(O)Cl, byproduct AcOH and solvent THF were removed under vacuum to afford pure R1R2PCl.
  • 5
  • [ 13139-86-1 ]
  • [ 15754-51-5 ]
YieldReaction ConditionsOperation in experiment
87% With diethyl phosphite; In tetrahydrofuran; at 0 - 20℃; for 2.25h;Inert atmosphere; A mixture of diethyl phosphonate (6.91 g, 50 mmol) and anhydrous THF (50 mL) was added slowly to the Grignard reagent (165 mL, 1.0 M in THF). When all the diethyl phosphonate had been added, the mixture was stirred for additional 15 minutes at low temperatures and two hours at room temperature. Subsequently 100 mL 0.1 N HCl were added drop wise over a period of 5 minutes at 0 C, followed by addition of 100 mL methyl tert-butyl ether (MTBE) and stirring for further 5 minutes. The upper organic phase was decanted from the formed gel. 120 mL CH2Cl2were added to the remaining gel and the mixture agitated well for additional 5 minutes. The resultant mixture was then filtered through a frit equipped with Celite. After washing the Celite with CH2Cl2(2 x 80 mL) the organic phases were combined, dried over Na2SO4and the solvent was removed in vacuo. The crude product was recrystallized from EtOAc/heptane (v/v = 1/1) to give the product as a white solid (11.4g, 43.5 mmol, 87% yield). bis(4-methoxyphenyl)phosphine oxide (1):White solid (11.4g, 43.5 mmol, 87% yield).The compound is known.[1]NMR Spectroscopy:1H NMR (400 MHz, CDCl3)δ 8.03 (d,J= 477.6 Hz, 1H), 7.60 (dd,J= 13.0, 8.6 Hz, 4H), 6.98 (d,J= 7.2 Hz, 4H), 3.84 (s, 6H)
  • 6
  • [ 15754-51-5 ]
  • (R)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1‘-spirobiindane [ No CAS ]
  • [ 528521-76-8 ]
  • 7
  • [ 15754-51-5 ]
  • [ 527750-97-6 ]
  • [ 527751-02-6 ]
  • 8
  • [ 15754-51-5 ]
  • [ 528521-80-4 ]
  • (R)-7-di(p-methoxyphenyl)phosphino-7'-di(p-methoxyphenyl)phosphinyl-1,1'-spirobiindane [ No CAS ]
  • 9
  • [ 15754-51-5 ]
  • bis(4-methoxyphenyl)phosphine-borane complex [ No CAS ]
  • 10
  • [ 15754-51-5 ]
  • [ 20434-06-4 ]
YieldReaction ConditionsOperation in experiment
With ethanol; (Dichloroiodo)benzene; In dichloromethane; at 20℃;Inert atmosphere; General procedure: Into a round bottom flask was added (dichloroiodo)benzene (2, 0.15 mmol, 1.02 equiv), DCM (0.25 mL, 0.6M), and to this was added excess ethanol (0.1 mL, 10 equiv), followed by the secondary phosphine oxide (0.15 mmol, 1.0 equiv,). The reaction mixture was stirred at room temperature for the indicated length of time, then concentrated in vacuo and purified by column chromatography.
  • 11
  • [ 15754-51-5 ]
  • [ 84127-04-8 ]
YieldReaction ConditionsOperation in experiment
90% General procedure: A 4-neck jacketed flask equipped with a bottom drain valve containing a 24/40 joint, mechanical stirrer, addition funnel, and an argon sparge line was evacuated/Ar filled, then charged with 15 mL of 1 M diisobutyl aluminium hydride (DIBALH)/ toluene (15.0 mmol, 3 eq.) through the addition funnel. THF (10 mL) was then used to wash the walls of the addition funnel into the flask. The addition funnel was then charged with a solution of secondary phosphine oxides (5.0 mmol, 1 eq.) in 20 mL of THF. This solution was then added dropwise over 10 min. THF (5 mL) was then used to wash the walls of the addition funnel into the flask. The resulting mixture was then stirred 2.0 h at ambient temperature, then 30 mL of MTBE was added dropwise via an addition funnel over 5 min. After 5 min, the sparge line was inserted beneath the solution surface and a slow argon flow was started and maintained throughout all subsequent operations. After sparging for 10 min, the mixture was cooled to an internal temperature of 5 C. The addition funnel was then charged with 20 mL of 2 N NaOH (deoxygenated water). This solution was then added dropwise via an addition funnel over 10 min. Washing of the organic phase with 15 mL of brine (deoxygenated water) was performed for 10 min. After 5 min, the agitation was stopped, and the lower aqueous phase was drained to waste through the bottom drain valve. Brine (30 mL 5% w/v, deoxygenated water) was then added dropwise via an addition funnel over 10 min, and the lower aqueous phase was again discarded to waste as described above. The resultant mixture was then filtered through 5 mg of MgSO4. The pad (MgSO4) was then washed with 25 mL of MTBE which was added to the reactor and degassed by Ar sparging for 10 min. This solution was then used as a wash of the solids. The organic phase was combined with the first organic phase and the solvents were removed in vacuo (kept under argon). The crude material was chromatographed on silica gel to give the product (kept under argon).
0.747 g (57%) With sodium hydroxide; trichlorosilane; In toluene; EXAMPLE 3 Bis-(4-methoxyphenyl)phosphine A solution-suspension of 1.4 g (5.34 mmol) of bis(4-methoxyphenyl)phosphine-oxide in 18 mL of toluene was treated under argon with 3.35 g (2.5 mL, 25 mmol) of trichlorosilane in one portion. This resulted in moderate heat and gas evolution and led to complete solution of the phosphine oxide. The mixture was heated at 90 for 5 h, whereupon the clear colorless solution was cooled to 0. With vigorous stirring, 8.0 mL of 2 N aqueous sodium hydroxide solution (16 mmol) was added slowly while cooling the mixture in an ice-bath to moderate the vigorous reaction. When all the sodium hydroxide had been added, the mixture was allowed to warm to room temperature and stirred vigorously until all solid dissolved (30-90 min), leaving two clear, colorless liquid phases. The layers were allowed to separate and the toluene layer was drawn off under argon via a cannula. The aqueous layer was extracted with 2*20 mL of toluene. The combined toluene extracts were dried (deoxygenated brine and sodium sulfate), filtered, and stripped of solvent on the rotary evaporator at 80/5 mm Hg to give 1.11 g (84.5%) of crude product. The thick oil was distilled by bulb to bulb distillation at 115-135/0.02 mm Hg for 1 h to give 0.747 g (57%) of bis-(4-methoxyphenyl)phosphine as a colorless thick oil which shortly crystallized to colorless, slightly greasy crystals.
  • 12
  • [ 15754-51-5 ]
  • (R)-(-)-1,1'-bi-2-naphthol triflate [ No CAS ]
  • (R)-2-[bis(4-methoxyphenyl)phosphinyl]-2'-[(trifluoromethanesulfonyl)oxy]-1,1'-binaphthyl [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With palladium diacetate; N-ethyl-N,N-diisopropylamine; 1,4-di(diphenylphosphino)-butane; In dimethyl sulfoxide; at 120℃; for 12h;Inert atmosphere; (R)-1,1'-Binaphthyl-2,2'-diyl-bis-trifluoromethanesulfonate 18 (0.60 g, 1 mmol) was added to a stirred solution of <strong>[15754-51-5]bis(4-methoxyphenyl)phosphine oxide</strong> (0.60 g, 3 mmol), palladium acetate (0.06 g, 0.3 mmol) and 1,4-bis(diphenylphosphino)butane (0.10 g, 0.3 mmol) under an atmosphere of argon. N,N-Diisopropylethylamine (0.70 g, 1.0 cm3, 6 mmol) was added dropwise and the reaction mixture heated to 120 C for 12 h. Upon cooling, the solution was diluted with ethyl acetate (50 cm3) and washed successively with water (3 * 20 cm3), 1 N HCl (20 cm3) and a 1M aqueous solution of NaHCO3 (20 cm3). The organic layer was dried over magnesium sulfate, filtered, and the solvent removed in vacuo to yield an orange oil. Purification of the crude material by flash column chromatography on silica gel using an eluent of 40% ethyl acetate: petroleum ether 40-60 C afforded the title compound as a white crystalline solid (700 mg, 87%); m.p. 81 C (lit [40]. 80-81 C); [α]25D +66.1 (c 0.7 in CHCl3, lit [40]. +66.2 c 0.7 in CHCl3); δH (400 MHz, CDCl3) 3.79 (3H, s, OCH3), 3.81 (3H, s, OCH3), 6.66-6.69 (2H, m, ArCH), 6.77-6.80 (2H, m, ArCH), 7.01 (1H, d, J 8.6, ArCH), 7.12 (1H, d, J 8.6, ArCH), 7.18-7.23 (1H, m, ArCH), 7.30-7.39 (6H, m, ArCH), 7.45 (1H, ddd, J 8.2, 6.9, 1.2, ArCH), 7.56-7.60 (1H, m, ArCH), 7.78 (1H, dd, J 11.4, 8.6, ArCH), 7.84 (1H, d, J 8.3, ArCH), 7.90 (1H, d, J 9.0, ArCH), 7.96 (1H, d, J 8.3, ArCH), 8.04 (1H, dd, J 8.8, 2.2, ArCH); δF (235 MHz, CDCl3) -75.0; δP (101 MHz, CDCl3) 27.9. All data is in accordance with the literature.
  • 13
  • [ 866397-22-0 ]
  • [ 15754-51-5 ]
  • (R)-1-(di(p-methoxyphenyl)phosphinyl)-1'-(trifluoromethanesulfonyloxy)-9,9'-spirobifluorene [ No CAS ]
  • 14
  • [ 2769-71-3 ]
  • [ 15754-51-5 ]
  • [1-[Bis-(4-methoxy-phenyl)-phosphinoyl]-meth-(E)-ylidene]-(2,6-dimethyl-phenyl)-amine [ No CAS ]
  • 15
  • [ 2769-71-3 ]
  • [ 15754-51-5 ]
  • {bis-[bis-(4-methoxy-phenyl)-phosphinoyl]-methyl}-(2,6-dimethyl-phenyl)-amine [ No CAS ]
  • 16
  • [ 835652-12-5 ]
  • [ 15754-51-5 ]
  • [ 835652-16-9 ]
  • 17
  • Diethyl phosphonate [ No CAS ]
  • [ 15754-51-5 ]
YieldReaction ConditionsOperation in experiment
54.1% Reference Example 3 bis(4-methoxyphenyl)phosphine oxide Under an argon atmosphere, a solution of magnesium (6.5 g, 1.0 equivalent) and a small amount of iodine in THF (65 ML) was stirred at room temperature for 1 hr. 4-Bromoanisole (50 g, 0.27 MoL) was added at 42C, and the mixture was stirred at 5C for 1 hr.. Then, diethyl phosphite (18.4 g, 0.50 equivalent) was added at 15 to 20C, and the mixture was stirred at 5C for 1 hr.. water (60 ML) was added at 3C, and toluene (120 ML) and 6M-HCl (60 ML) were added.. The mixture was stirred at room temperature for 30 min.. The reaction mixture was partitioned, and the aqueous layer was extracted 3 times with toluene (60 ML).. The combined organic layer was dried over anhydrous magnesium sulfate, filtered by gravity, and the filtrate was concentrated under reduced pressure.. The residue was recrystallized from diisopropyl ether to give the title compound (18.9 g, white crystals).. yield 54.1%. melting point: 126.0C.1H-NMR (300 MHz, CDCl3, TMS) δ: 3.85 (s, 6H), 6.99 (d, 2H, J = 8.79 Hz), 7.00 (d, 2H, J = 8.73 Hz), 7.61 (dd, 4H, J = 8.73 Hz, 13.13 Hz), 8.02 (d, 1H, J = 477.2 Hz).31P-NMR (121 MHz, CDCl3, 85%H3PO4) δ: 21.21 (dquint, J = 474.1 Hz, 13.0 Hz).
30.0% Reference Example 4 Di-p-methoxyphenylphosphine oxide In a stream of nitrogen, a solution of magnesium (19.45 g, 4.00 equivalents), a slight amount of iodine and 1,2-dibromoethane in tetrahydrofuran (140 mL) was stirred at room temperature for 30 minutes. After addition of a solution of 1-boromo-4-methoxybenzene (151.47 g, 4.00 equivalents) in tetrahydrofuran (650 mL) at 25 to 30C, the mixture was stirred at 40C for 1 hour. Then, a solution of diethyl phosphite (27.71 g, 0.20 mol) in tetrahydrofuran (60 mL) was added thereto at 25 to 30C. Further 6M-HCl (110 mL) was added thereto at 0 to 5C, followed by further addition of water (110 mL) and toluene (110 mL). The reaction mixture was separated into layers and the organic layer obtained was successively washed with water (110 mL), an aqueous 5% NaHCO3 solution (110 mL) and an aqueous 5% NaCl solution (110 mL). The organic layer was dried over magnesium sulfate (25 g) and concentrated under reduced pressure. The residue was recrystallized from n-hexane and dried (in reduced pressure at 40C) to obtain the titled compound (15.71 g, white powder). The yield was 30.0%. 1H-NMR (300 MHz, CDCl3, TMS) δ: 3.85 (s, 6H), 6.98 (d, 2H, J = 2.1 Hz), 7.01 (d, 2H, J = 2.1 Hz), 7.57 (s, 1 H), 7.60 (s, 1 H), 7.62 (s, 1 H), 7.65 (s, 1 H), 8.03 (d, 1 H, JH-P = 477 Hz). 13C-NMR (75 MHz, CDCl3, CDCl3) δ: 55.31, 114.29, 114.28, 122.27, 123.70, 132.51, 132.68, 162.87. 31P-NMR (121 MHz, CDCl3, 85% H3PO4) δ: 21.19 (dq, JH-P = 477 Hz, JH-CCP = 13 Hz).
  • 18
  • [ 15754-51-5 ]
  • bis(4-methoxyphenyl)phosphine-borane complex [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With borane-THF; In tetrahydrofuran; toluene; at 25℃; Example 5 Di(p-methoxyphenyl)phosphine-borane complex Under an argon atmosphere, 80 mL of toluene was added to <strong>[15754-51-5]di(p-methoxyphenyl)phosphine oxide</strong> synthesised in Reference Example 4 (13.11 g, 0.17 mmol) at a room temperature (25C) to obtain a solution. Then, to the solution was added 1.02 mol/L of a borane-tetrahydrofuran complex (165 mL, 3.30 equivalents) was added over 2 hours. After addition of silica gel (20 g), the reaction mixture was filtered and concentrated under reduced pressure. The resulting residue was recrystallized from n-hexane and dried (under reduced pressure at 40C) to obtain the titled compound (11.1 g, white powder). The yield was 85%. 1H-NMR (300 MHz, CDCl3, TMS) δ: 0.26-1.65 (m, 3 H), 3.83 (s, 6H), 6.26 (dm, 1 H, JH-P = 378 Hz), 6.94 (s, 1 H), 6.95 (s, 1 H), 6.96 (s, 1 H), 6.97 (s, 1 H), 7.55 (s, 1 H), 7.57 (s, 1 H), 7.58 (s, 1 H), 7.61 (s, 1 H). 13C-NMR (75 MHz, CDCl3, CDCl3) δ: 55.30, 114.59, 114.74, 116.84, 117.67, 134.43, 134.57, 162.23. 31P-NMR (121 MHz, CDCl3, 85% H3PO4) δ: -4.5-(-3.2) (m), - 1.6-0.4 (m).
41.3% With sodium tetrahydroborate; lithium aluminium tetrahydride; cerium(III) chloride; In tetrahydrofuran; at 5 - 20℃; for 3h; Example 3 bis(4-methoxyphenyl)phosphine-borane complex Under an argon atmosphere, a solution of cerium chloride (7.03 g, 3.0 equivalents) in THF (20 ML) was stirred at room temperature (25C) for 30 min.. sodium borohydride (1.08 g, 3.1 equivalents) was added, and the mixture was stirred at room temperature for 1 hr.. Then <strong>[15754-51-5]bis(4-methoxyphenyl)phosphine oxide</strong> (2.5 g, 9.1 MmoL) synthesised in Reference Example 3 and lithium aluminum hydride (0.43 g, 1.2 equivalents) were successively added at 5C and the mixture was stirred at room temperature for 3 hrs.. water (20 ML) was added at 3C, and then toluene (50 ML) and 6M-HCl (10 ML) were added.. The mixture was stirred at room temperature for 30 min.. The reaction mixture was partitioned, and the aqueous layer was extracted 3 times with toluene (20 ML).. The combined organic layer was washed successively with 5% aqueous NaHCO3 solution (20 ML) and 5% aqueous NaCl solution (20 ML).. Then the organic layer was dried over anhydrous magnesium sulfate, filtered by gravity, and the filtrate was concentrated under reduced pressure.. The residue was purified by column chromatography (silica gel 30 g, n-hexane/ethyl acetate=5/12/1).. The residue was recrystallized from heptane to give the title compound (0.98 g, white crystals).. yield 41.3%. melting point: 65.8C.1H-NMR (300 MHz, CDCl3, TMS) δ: 0.43-1.57 (m, 3H), 3.82 (s, 6H), 6.24 (dq, 1H, J = 377.9Hz, 6.78Hz), 6.95 (dd, 4H, J = 8.71 Hz, 1. 72 Hz), 7.53-7.60 (m, 4H).31P-NMR (121 MHz, CDCl3, 85%H3PO4) δ: -4.53- -2.73 (m), -1.26-0.40 (m), -4.15 (m).
  • 19
  • [ 956833-12-8 ]
  • [ 15754-51-5 ]
  • [ 1228338-60-0 ]
  • 20
  • [ 15754-51-5 ]
  • methyl (R)-2'-(((trifluoromethyl)sulfonyl)oxy)-[1,1'-binaphthalene]-2-carboxylate [ No CAS ]
  • C36H29O5P [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% With palladium diacetate; N-ethyl-N,N-diisopropylamine; 1,4-di(diphenylphosphino)-butane; In dimethyl sulfoxide; at 120℃; for 24h; General procedure: To a solution of (aR)-14 (115 mg, 0.25 mmol), diarylphosphine oxide (0.50 mmol), palladium diacetate (5.6 mg, 0.025 mmol), and 1,4-bis(diphenylphosphino)butane (10.7 mg, 0.025 mmol), in 1.5 mL of DMSO was added diisopropylethylamine (0.21 mL, 1.2 mmol), and the mixture was stirred at 120 C for 24 h. After being cooled to room temperature, the reaction mixture was diluted with EtOAc, washed with H2O, and dried over MgSO4. Removal of the solvent followed by column chromatography on silica gel (elution with n-hexane/EtOAc=1/2) gave compound (aR)-2.
  • 21
  • [ 15754-51-5 ]
  • [ 98-80-6 ]
  • [ 799-55-3 ]
  • 23
  • [ 15754-51-5 ]
  • bBis(4-methoxyphenyl)phosphinic fluoride [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With sodium fluoride; trifluoroacetic anhydride; In dimethyl sulfoxide; acetonitrile; at 100℃; for 11h;Inert atmosphere; Take bis(4-methoxyphenyl) phosphorous oxide (78.6mg, 0.3mmol) and sodium fluoride (25.2mg, 0.6mmol) into a 10mL reaction tube, and use a double-row tube to replace the air in the reaction tube with nitrogen , Replace three times, and then sequentially add 2mL acetonitrile, trifluoroacetic anhydride (157.5mg, 0.75mmol), DMSO (47.9mg, 0.6mmol), and place the reaction in an oil bath at 100C for 11 hours. After the reaction, the reaction solution was concentrated, and the mixture of petroleum ether and ethyl acetate with a volume ratio of 3:1 was used as the eluent, and the product bis(4-methoxyphenyl)phosphoryl fluoride was obtained by column chromatography. The yield was Is 83%.
  • 24
  • [ 1452757-48-0 ]
  • [ 15754-51-5 ]
  • bis(4-methoxyphenyl)(morpholino)phosphine oxide [ No CAS ]
  • 25
  • [ 15754-51-5 ]
  • [ 88284-48-4 ]
  • [ 799-55-3 ]
YieldReaction ConditionsOperation in experiment
95% With caesium carbonate; cesium fluoride; In 1,2-dimethoxyethane; at 100℃; for 12h;Sealed tube; General procedure: In a typical reaction, to an oven-dried 25 mL heavy walled sealtube fitted with Teflon plug valve was added CsF (0.90 mmol),Cs2CO3 (0.60 mmol), o-(trimethylsilyl)aryl triflate (0.30 mmol) anddiarylphosphine oxide (0.32 mmol). DME (3 mL) was added viaa syringe. The tube was sealed with Teflon plug valve and then thereaction mixture was stirred at 100 C for 12 h. The reaction wasallowed to cool to room temperature. Then reaction mixture wasdiluted with 5 mL water. The aqueous layer was extracted withethyl acetate (35 mL). The combined organic layers were driedover Na2SO4, filtered and concentrated. The product was isolatedthrough preparative thin-layer chromatography.
  • 26
  • [ 95-16-9 ]
  • [ 15754-51-5 ]
  • benzo[d]thiazol-2-ylbis(4-methoxyphenyl)phosphine oxide [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With tert-butylammonium hexafluorophosphate(V); In N,N-dimethyl-formamide; at 20℃; for 10h;Electrochemical reaction; Green chemistry; General procedure: To an undivided cell equipped with a stirring bar, a mixture of substrates 1a (0.5mmol, 68mg), 2a (1.5mmol, 303mg), tetrabutylammonium hexafluorophosphate (n-Bu4NPF6) (0.3mmol, 115mg), and N,N-Dimethylformamide (DMF) (5.0mL) were added. The cell was equipped with glassy carbon electrode (GC) as the anode and copper foam electrode (CF) as the cathode. The reaction mixture was stirred and electrolyzed at a constant current of 14mA at room temperature for 10h. Upon completion, the solvent was removed by extraction and under reduced pressure to afford the crude product, which was further purified by flash column chromatography (petroleum ether / ethyl acetate=3/1) to afford the desired products.
  • 27
  • [ 1195-32-0 ]
  • [ 15754-51-5 ]
  • (2-hydroxy-2-(p-tolyl)propyl)bis(4-methoxyphenyl)phosphine oxide [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With oxygen; In tetrahydrofuran; at 65℃; for 12h;Green chemistry; General procedure: α-methylsytrene (65 μL, 0.5 mmol) was added to a dried 25 mL round-bottom flask with diphenylphosphine oxide (253 mg, 1.25 mmol) in THF (2 mL) under dioxygen. The reaction mixture was stirred at 65 C for 12 h. After the reaction, the solution was concentrated in vacuum. The resulting mixture purified by flash chromatography on silica gel (petroleum ether/ethylacetate 1:1) to afford the product (2-hydroxy-2-phenylpropyl) diphenylphosphine oxide (3aa) in 86% yield.
  • 28
  • [ 15754-51-5 ]
  • [ 98-83-9 ]
  • (2-hydroxy-2-phenylpropyl)bis(4-methoxyphenyl)phosphine oxide [ No CAS ]
YieldReaction ConditionsOperation in experiment
56% With oxygen; In tetrahydrofuran; at 65℃; for 12h;Green chemistry; General procedure: α-methylsytrene (65 μL, 0.5 mmol) was added to a dried 25 mL round-bottom flask with diphenylphosphine oxide (253 mg, 1.25 mmol) in THF (2 mL) under dioxygen. The reaction mixture was stirred at 65 C for 12 h. After the reaction, the solution was concentrated in vacuum. The resulting mixture purified by flash chromatography on silica gel (petroleum ether/ethylacetate 1:1) to afford the product (2-hydroxy-2-phenylpropyl) diphenylphosphine oxide (3aa) in 86% yield.
  • 29
  • [ 15754-51-5 ]
  • [ 536-74-3 ]
  • 1,2-bis(bis(4-methoxyphenyl)phosphinyl)-2-phenylethane [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% General procedure: In a Schlenk flask wereplaced diphenylphosphine oxide (0.2 mmol), and tBuOLi of THF solution (5 mol%, 0.01 mmol) in THF (0.15mL) under nitrogen. The mixture was stirred at ambient temperature for 1 h. Etynylbenzene(0.1 mmol) was added to the solution under nitrogen and the mixture was heatedat 70 C for 4 h.
76% With lithium tert-butoxide; In tetrahydrofuran; at 70℃;Inert atmosphere; Schlenk technique; The reaction was carried out using various phosphorus compounds by the following procedure.In a nitrogen atmosphere, 0.1 mmol of a phosphorus compound was charged in a glass Schlenk and dissolved with 0.15 mL of THF. Next, 0.2 mmol of phenylacetylene and 5 mol% of t-BuOLi solution were added, and the mixture was heated and stirred at 70 C. The reaction solution was allowed to cool to room temperature, quenched with methanol, and the solvent was distilled off. Thereafter, the product was isolated and purified using GPC to obtain the desired product. The results are shown in Table 2. The reaction proceeded even when the substituent on phosphorus was changed to a cycloalkyl group or an alkyl group
  • 30
  • [ 15754-51-5 ]
  • [ 536-74-3 ]
  • 2-(bis(4-methoxyphenyl)phosphoryl)-1-phenylethan-1-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
50% With oxygen; copper(l) cyanide; In dimethyl sulfoxide; at 55℃; for 24h; General procedure: An oven-dried flask with the mixture of CuCN (0.025 mmol), alkynes 1 (0.5 mmol), H-phosphine oxides 2 (1.0 mmol) and DMSO (1.0 ml) was charged with O2. The reaction mixture was stirred at 55 C for 24 hours. After completion of the reaction, water (10 ml) was added and extracted with EtOAc (5.0 ml×3). The combined organic layers were dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. The resulting mixture purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired products 3
  • 31
  • [ 15754-51-5 ]
  • [ 536-74-3 ]
  • 2-oxo-2-phenylethyl bis(4-methoxyphenyl)phosphinate [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With [bis(acetoxy)iodo]benzene; water; In acetonitrile; at 60℃; for 24h; General procedure: 2.1. General procedure for the synthesis of a-hydroxyketonephosphates 3 To a solution of diarylphosphine oxides 2 (0.5 mmol) inacetonitrile (3.0 mL) were added PhI(OAc)2 (1.25 mmol), H2O(2.0 mmol) and alkynes 1 (0.75 mmol). The reaction mixture wasthen stirred for 24 h at 60 8C in air. After the reaction, thesolvents were removed under vacuum. The residue was puriedby ash chromatography on silica gel using a mixture ofpetroleum ether and ethyl acetate (1:1) as eluent to give thedesired product 3.
  • 32
  • 4-methyl-N'-(1-ferrocenylethylidene)benzenesulfonohydrazide [ No CAS ]
  • [ 15754-51-5 ]
  • bis(4-methoxyphenyl)(1-ferrocenylethyl)phosphine oxide [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With copper(l) iodide; potassium carbonate; In 1,4-dioxane; for 12h;Inert atmosphere; General procedure: 0.30 mmol H-phosphorus oxide or H-phosphonate, 0.25mmol N-Tosylhydrazone, 0.025mmol of CuI and 0.75mmol K2CO3 were charged into 25mL oven-dried flasks, and back filled with Argon three times. 3mL freshly distilled 1,4-dioxane was then injected into the flask, which were heated up to reflux for 12 h. The solvent was eliminated under vacuum pump and ammonia water and dichloromethane was added and the layers were separated. The aqueous phase was extracted three times with dichloromethane. The combined organic phase was dried over Na2SO4. The concentrated residue was purified by column chromatography over silica gel using petroleum ether/ethyl acetate (1:3) as eluent to get the product.
81% With copper(l) iodide; potassium carbonate; In 1,4-dioxane; for 12h;Reflux; P-toluenesulfonyl hydrazone, bis (4-methoxyphenyl) phosphine oxide,Cuprous iodide, potassium carbonate and 1,4-dioxane,Heat to reflux for 12h.After pumping solvent to cool to room temperature,Ammonia and methylene chloride were added, the organic phase was separated,Washed with water, dried over anhydrous sodium sulfate.The petroleum ether: ethyl acetate volume ratio of 1: 1 as eluant column chromatography purification can be obtainedBis (4-methoxyphenyl) - (1-ferrocenylethyl) phosphine oxide.Its structure is shown below:The compound was a yellow solid in 81% yield.
  • 33
  • [ 32629-33-7 ]
  • [ 15754-51-5 ]
  • 1,1'-bis(1-(bis(4-methoxyphenyl)phosphino)ethyl)ferrocene [ No CAS ]
YieldReaction ConditionsOperation in experiment
66% With copper(l) iodide; potassium carbonate; In 1,4-dioxane; for 18h;Inert atmosphere; Reflux; General procedure: 0.36 mmol H-phosphorus oxide or ethyl phenylphosphinate, 0.15mmol 1,1′-ferrocenyl diketone-derived N-tosylhydrazone, 0.03 mmol of CuI and 0.90 mmol K2CO3 were charged into 25 mL oven-dried flask, and back filled with argon three times. 5mL freshly-distilled 1,4-dioxane was then injected into the flask, then heated to reflux for 18 h. The crude reaction mixture was allowed to reach room temperature, the solvent was eliminated under vacuum. Ammonia water and dichloromethane was added and the layers were separated. The aqueous phase was extracted three times with dichloromethane. The combined organic phase was dried over Na2SO4. The concentrated residue was purified by column chromatography over silica gel using petroleum ether/dichloromethane/NEt3 (1:2:0.1) as eluent to get the product 5.
66% With copper(l) iodide; potassium carbonate; In 1,4-dioxane; for 18h;Reflux; P-toluenesulfonyl hydrazone, bis (4-methoxyphenyl) phosphine oxide,Copper iodide, potassium carbonate and 1,4-dioxane are heatedReflux 18h. After pumping solvent to cool to room temperature,Ammonia and methylene chloride were added, the organic phase was separated,Washed with water, dried over anhydrous sodium sulfate.To petroleum ether: dichloromethane: triethylamine volume ratio of 1: 2: 0.1 eluant column chromatography to obtain1,1'-bis (1- (bis (4-methoxyphenyl) phosphino) ethyl) ferrocene.Its structure is shown below:The compound was a yellow solid in 66% yield.
  • 34
  • [ 15754-51-5 ]
  • N-(1-methylindol-2-ylidene-3-diazo)-4-methylbenzene-1-sulfonamide [ No CAS ]
  • C38H45N2O5PS [ No CAS ]
  • 35
  • N-(1-methylindol-2-ylidene-3-diazo)-4-methylbenzene-1-sulfonamide [ No CAS ]
  • [ 15754-51-5 ]
  • C30H29N2O5PS [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With tetrakis(actonitrile)copper(I) hexafluorophosphate; In chloroform; for 2h; Weigh bis (4-methoxyphenyl) phosphine oxide (0.2 mmol)And tetrafluoroacetonitrile hexafluorophosphate (3.72 mg, 0.01 mmol) in a round bottom flask,Adding 0.8 mL of trichloromethane,Placed in 5050 oil bath;A solution of N- (1-methylindol-2-ylidene-3-diazo) -4-methylbenzenesulfonamide (0.2 mmol)Dissolved in 0.8mL trichloromethane,And through the peristaltic pump 1 hour into the reaction system,After completion of the injection, stirring was continued for 1 hour,The product was then isolated by column chromatography (petroleum ether: ethyl acetate = 3: 1). Yield 88%.
 

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