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CAS No. : | 1638-86-4 | MDL No. : | MFCD00009086 |
Formula : | C10H15O2P | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | RVDJLKVICMLVJQ-UHFFFAOYSA-N |
M.W : | 198.20 | Pubchem ID : | 74225 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-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 |
---|---|---|
89% | In diethyl ether for 1h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With silica gel In benzene | |
With water | ||
10.8 g | With hydrogenchloride; water In tetrahydrofuran at 20℃; for 0.333333h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.5% | With <i>N</i>,<i>N</i>-dimethyl-aniline In pentane for 0.5h; Ambient temperature; | |
87.5% | at 0 - 45℃; for 2.5h; Alkaline conditions; Sealed tube; | 2.2 (2) Synthesis of diethyl phenylphosphonate In the electric liquid seal stirring device, constant pressure dropping funnel,In a 250-ml four-necked flask with a thermometer and a bulb-type condenser tube (upper section equipped with a drying tube), 0.4 mol of absolute ethanol and 10 ml of basic ionic liquid were added. Add 0.1 mol of phenylphosphonium dichloride to the constant pressure dropping funnel with stirring, use the ice water bath and adjust the dropping speed of phenylphosphine dichloride, The reaction temperature was controlled at about 0C, and after completion of the dropwise addition, the mixture was stirred at about 45C for 2.5 hours. After the reaction is completed, the reaction solution is poured into a beaker, cooled and filtered to obtain a solid crude product of diethyl phenylphosphonate. The product was recrystallized from a mixture of petroleum ether and dichloromethane to obtain a pure product with a yield of 87.5%. |
86% | With pyridine In diethyl ether for 1h; Ambient temperature; |
75% | With amine | |
71% | Stage #1: Dichlorophenylphosphine With pyridine In hexane Inert atmosphere; Cooling with ice; Stage #2: ethanol In hexane at 0 - 26℃; for 17h; Inert atmosphere; | |
65% | at 20 - 25℃; | |
58% | With N,N-diethylaniline In diethyl ether at 5 - 20℃; | |
With <i>N</i>,<i>N</i>-dimethyl-aniline | ||
With <i>N</i>,<i>N</i>-dimethyl-aniline In diethyl ether Ambient temperature; | ||
With sodium ethanolate | ||
With pyridine | ||
With pyridine In hexane for 3h; Ambient temperature; | ||
70 g | In toluene | |
With triethylamine | ||
With pyridine In Petroleum ether | ||
In diethyl ether at -20℃; for 2h; Inert atmosphere; | ||
With pyridine In tetrahydrofuran at 20℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | at 26 - 80℃; for 21.5h; Inert atmosphere; | |
In benzene at 85℃; for 60h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With nickel dibromide In water at 160 - 180℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With nickel dibromide In water at 160 - 180℃; | |
57% | With nickel dibromide at 175℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With selenium In benzene for 24h; Ambient temperature; | |
51.6% | With selenium at 140℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In toluene at -50℃; 30 min at -50 deg C, then room temperature; | |
In toluene at -70℃; for 0.5h; to room t.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Yield given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | at 110℃; for 14h; Inert atmosphere; Schlenk technique; | |
at 140 - 170℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With ethyl iodide at 95℃; for 48h; | |
68% | With trimethylsilyl trifluoromethanesulfonate In chloroform at 60℃; for 72h; | |
42% | With trimethylsilyl bromide at 80℃; for 120h; |
With diiodomethane at 140 - 170℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With pyridine; water; iodine In tetrahydrofuran at -45 - 20℃; for 0.333333h; | |
With tris(1,10-phenanthroline)iron(III) tris(hexafluorophosphate); ethanol In acetonitrile at 25℃; | ||
With rhodamine 6G In water; acetonitrile at 25℃; Irradiation; |
With p-nitrostilbene dibromide In methanol; acetonitrile at 25℃; | ||
Multi-step reaction with 2 steps 1: 71 percent / cumene / standard deoxygenation route 2: 21 percent Spectr. / 0.17 h / 600 °C / 0 - 0.01 Torr / other time (80 min) | ||
Multi-step reaction with 2 steps 1: 91 percent / selenium / benzene / 24 h / Ambient temperature 2: 64 percent / di-n-hexyl sulphide / CHCl3; methanol / 1 h / Irradiation; other reagents | ||
With 3,6-bis(ethylamino)-9-[2-(methoxycarbonyl)phenyl]-xanthylium chloride In water; acetonitrile Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | at 20℃; for 2h; | |
58% | In diethyl ether at 20℃; Inert atmosphere; | 4.5.3. Preparation of ethyl bromodifluoromethylphenylphosphinate 16 Diethyl phenylphosphonite (11.6 g, 0.059 mol) and diethyl ether (125 ml) were combined in a 250 ml round bottom flask equipped with a water condensor topped by a glass tee leading to a source of dry nitrogen and a mineral oil bubbler. After cooling the flask in an ice bath, 1 (15 g, 0.07 mol) was added. The reaction mixture was stirred overnight at ambient temperature. The ether was removed by rotary evaporation at aspirator pressure and the residue distilled to give 16 in 58% yield (bp = 109-111 °C/ 0.6 mm Hg). 19F NMR (CDCl3) (ppm): ABX pattern δ (F1) = -62.5; δ (F2) = -62.1 (2JPF1 = 2JPF2 = 82 Hz; 2JF1F2 = 180 Hz); (31P NMR (CDCl3) (ppm): δ = 20.9 (t, 2JPF = 82 Hz); 13C NMR (CDCl3) (ppm): δ = 120.2 (td, 1JCF = 333 Hz, 1JCP = 150 Hz), d = 64. (2JCP = 7.4 Hz), d = 16.5 (3JCP = 5.9 Hz) and for the ring carbons, d = 123.5 (d, 1JCP = 146 Hz, a-carbon of ring), d = 128.9 (d, 1JCP = 13.2 Hz, m-ring carbons), d = 133.4 (d, 1JCP = 10.3 Hz, o-ring carbons), d = 134 (d, 1JCP = 2.9 Hz, p-ring carbon); 1H NMR (CDCl3) (ppm): δ = 1.45 (t, 3JHH = 7 Hz), d = 4.45 (qd, 3JHH = 7 Hz, 3JHP = 7.5 Hz), d = 7.5-8.0 (unresolved multiplet). GC-MS, m/z (relative intensity): 169 (57), 141 (100), 77 (64), 51 (34), 47 (15), 31 (22), 29 (34); no molecular ion observed: IR (P=O) 1252 cm-1: Anal. Calcd. for C8H10O2PCF2Br: C, 36.12%; H, 3.34%. Found C, 36.13%; H, 3.25%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | In toluene for 18h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | In tetrahydrofuran at 70℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With triethylamine In dichloromethane at 20℃; for 0.333333h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 48% 2: 37% | Stage #1: <3,5-bis(1,1,-dimethylethyl)-2-hydroxyphenyl>(4-methoxyphenyl)methanol With hydrogen bromide; phosphorus tribromide In toluene at -30 - 20℃; for 0.5h; Stage #2: diethyl phenylphosphonite In toluene at 25℃; for 6h; Stage #3: With sodium hydroxide In toluene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 78 percent / ethyl iodide / 48 h / 95 °C 2: oxalyl chloride / 0.67 h / 20 °C 3: triethylamine / diethyl ether / 24 h / 20 °C 4: bacterial phosphotriesterase G60A mutant / various solvent(s) / pH 9.0 | ||
Multi-step reaction with 4 steps 1: 78 percent / ethyl iodide / 48 h / 95 °C 2: oxalyl chloride / 0.67 h / 20 °C 3: triethylamine / diethyl ether / 24 h / 20 °C 4: bacterial phosphotriesterase I106G, F132G, S308A mutant / various solvent(s) / pH 9.0 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 78 percent / ethyl iodide / 48 h / 95 °C 2: oxalyl chloride / 0.67 h / 20 °C 3: triethylamine / diethyl ether / 24 h / 20 °C 4: bacterial phosphotriesterase I106G, F132G, S308A mutant / various solvent(s) / pH 9.0 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 78 percent / ethyl iodide / 48 h / 95 °C 2: oxalyl chloride / 0.67 h / 20 °C 3: triethylamine / diethyl ether / 24 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 78 percent / ethyl iodide / 48 h / 95 °C 2: oxalyl chloride / 0.67 h / 20 °C 3: triethylamine / diethyl ether / 24 h / 20 °C 4: bacterial phosphotriesterase G60A mutant / various solvent(s) / pH 9.0 | ||
Multi-step reaction with 4 steps 1: 78 percent / ethyl iodide / 48 h / 95 °C 2: oxalyl chloride / 0.67 h / 20 °C 3: triethylamine / diethyl ether / 24 h / 20 °C 4: bacterial phosphotriesterase I106G, F132G, S308A mutant / various solvent(s) / pH 9.0 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 78 percent / ethyl iodide / 48 h / 95 °C 2: oxalyl chloride / 0.67 h / 20 °C | ||
Multi-step reaction with 2 steps 1: benzene / 60 h / 85 °C 2: oxalyl chloride / benzene / 3 h / Ambient temperature | ||
Multi-step reaction with 2 steps 2: COCl2 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 76 percent |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 76 percent 5: 96 percent / 2.64 M n-butyllithium / hexane; tetrahydrofuran / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 1.80 M n-butyllithium / hexane; tetrahydrofuran / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 60.5 percent / 2.80 M n-butyllithium / diethyl ether / from -78 deg C to r.t. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 7 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 76 percent 5: 96 percent / 2.64 M n-butyllithium / hexane; tetrahydrofuran / -78 °C 6: potassium hydroxide / tetrahydrofuran; aq. ethanol / 106 h / Ambient temperature 7: sodium butylthiolate / dimethylformamide / 9 h / 80 °C | ||
Multi-step reaction with 5 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: potassium hydroxide / tetrahydrofuran; aq. ethanol / 106 h / Ambient temperature 5: sodium butylthiolate / dimethylformamide / 9 h / 80 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 92 percent / potassium hydroxide / methanol; tetrahydrofuran / 1 h / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 76 percent 5: 96 percent / 2.64 M n-butyllithium / hexane; tetrahydrofuran / -78 °C 6: potassium hydroxide / tetrahydrofuran; aq. ethanol / 106 h / Ambient temperature | ||
Multi-step reaction with 4 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: potassium hydroxide / tetrahydrofuran; aq. ethanol / 106 h / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 8 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 76 percent 5: 96 percent / 2.64 M n-butyllithium / hexane; tetrahydrofuran / -78 °C 6: potassium hydroxide / tetrahydrofuran; aq. ethanol / 106 h / Ambient temperature 7: sodium butylthiolate / dimethylformamide / 9 h / 80 °C 8: potassium hydroxide, / tetrahydrofuran; aq. ethanol / -78 °C | ||
Multi-step reaction with 6 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: potassium hydroxide / tetrahydrofuran; aq. ethanol / 106 h / Ambient temperature 5: sodium butylthiolate / dimethylformamide / 9 h / 80 °C 6: potassium hydroxide, / tetrahydrofuran; aq. ethanol / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 8 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 76 percent 5: 96 percent / 2.64 M n-butyllithium / hexane; tetrahydrofuran / -78 °C 6: potassium hydroxide / tetrahydrofuran; aq. ethanol / 106 h / Ambient temperature 7: sodium butylthiolate / dimethylformamide / 9 h / 80 °C 8: 1.) potassium hydroxide; 2.) lithium diisopropylamide / 1.) THF, aq. EtOH, -78 deg C; 2.) THF, 0 deg C, hexane | ||
Multi-step reaction with 6 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: potassium hydroxide / tetrahydrofuran; aq. ethanol / 106 h / Ambient temperature 5: sodium butylthiolate / dimethylformamide / 9 h / 80 °C 6: 1.) potassium hydroxide; 2.) lithium diisopropylamide / 1.) THF, aq. EtOH, -78 deg C; 2.) THF, 0 deg C, hexane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 60.5 percent / 2.80 M n-butyllithium / diethyl ether / from -78 deg C to r.t. 5: 3.7 percent / KH / tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 60.5 percent / 2.80 M n-butyllithium / diethyl ether / from -78 deg C to r.t. 5: 33.6 percent / KH / tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 1.80 M n-butyllithium / hexane; tetrahydrofuran / -78 °C 5: 22 percent / 1.80 M n-butyllithium / hexane; tetrahydrofuran / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: 25 °C 2: Fe, NH4Cl / H2O / Heating 4: 1.80 M n-butyllithium / hexane; tetrahydrofuran / -78 °C 5: 5 percent / 1.80 M n-butyllithium / hexane; tetrahydrofuran / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 2: concentrated aqueous HCl |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 2: COCl2 3: Et3N |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid; sodium hydrogencarbonate | 6 p-Tolylphenylphosphine oxide EXAMPLE 6 p-Tolylphenylphosphine oxide A solution of p-tolylmagnesium bromide [prepared from p-bromotoluene (29.1 g, 0.16 mol) and magnesium (4.38 g, 0.18 g-atom)] in ether (100 mL) was treated with a solution of ethyl phenylphosphonite (13,6 g, 0.08 mol) in ether (50 mL) with vigorous mechanical stirring. The mixture was heated at reflux for 1/2 hr., then 100 mL of 25% sulfuric acid was added cautiously. Three layers formed; the bottom (aqueous) layer was extracted with toluene. Addition of NaHCO3 to the combined upper layers produced a vigorous reaction and a single organic phase. The organic phase was washed with water and with saturated NaCl, dried and evaporated to give an oil (14 g). Kugelrohr distillation at 120°-160° C. (0.1 mmHg) followed by chromatography on silica gel (CHCl3), then 10% MeOH--CHCl3) gave 7.1 g of an oil. This was distilled in the Kugelrohr again (150° C., 0.1 mmHg) to give 6.2 g of product which appears to be pure by NMR and crystallized on standing. 1 H NMR (CDCl3) δ8.0-7.2 (m, 9H), 8.08 (d, J=480 Hz, 1H), 2.42 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dibenzoyl peroxide | 24 EXAMPLE 24 EXAMPLE 24 A mixture of 8.4 parts of diketene, 2.5 parts of benzoyl peroxide and 20.0 parts of ethyl phenylphosponite were added dropwise over 1 hr to 48.1 parts of vigorously stirred ethyl phenylphosphonite which was heated at 120° C. in an atmosphere of nitrogen. The excess phosphonite was removed by passing the reaction mixture down a wiped wall still at 80° C. at a pressure of 0.013 mb. The residue was distilled on a wiped wall still at a temperature of 110° C. and a pressure of 0.013 mb and the product, ethyl(2-oxo-4-oxetanylmethyl)phenylphosphinate, was obtained as a colourless oil which was shown by 31 P NMR to be a nearly equal mixture of diastereoisomers having chemical shifts at δ-37.5 and δ-37.7 and which had the following elemental analysis by weight. Calculated for C12 H15 O4 P C, 56.69; H, 5.95; P, 12.18: Found C, 56.15; H, 6.25; P, 12.06. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene | 9 EXAMPLE 9 EXAMPLE 9 Ethyl ethylphenylphosphinate: A mixture of diethyl phenyl phosphonite (4.5g, 22.70mmol), ethyl iodide (0.24mL, 3mmol) and benzene (100mL) is stirred and heated at 85°C for 24 hours. The reaction is 30% complete as indicated by tlc. Another portion of ethyl iodide (0.30mL, 3.75mmol) is added and the reaction is stirred for additional 36 hours at 85°C when it appears complete by tic. The volatiles are removed on a rotary evaporater to give ethyl ethylphenylphosphinate as an oil. Ethylphenylphosphinic chloride: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In (2)H8-toluene Irradiation (UV/VIS); continuous photolysis with a high-pressure mercury lamp, -70°C; | ||
In toluene Irradiation (UV/VIS); ambient temp., nitrogen-laser flash; observed by UV-spectroscopy; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In (2)H8-toluene Irradiation (UV/VIS); continuous photolysis with a high-pressure mercury lamp, -70°C; | ||
In toluene Irradiation (UV/VIS); ambient temp., nitrogen-laser flash; observed by UV-spectroscopy; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In (2)H8-toluene Irradiation (UV/VIS); continuous photolysis with a high-pressure mercury lamp, -70°C; | ||
In toluene Irradiation (UV/VIS); ambient temp., nitrogen-laser flash; observed by UV-spectroscopy; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In (2)H8-toluene Irradiation (UV/VIS); continuous photolysis with a high-pressure mercury lamp, -70°C; | ||
In toluene Irradiation (UV/VIS); ambient temp., nitrogen-laser flash; observed by UV-spectroscopy; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In (2)H8-toluene Irradiation (UV/VIS); continuous photolysis with a high-pressure mercury lamp, -70°C; | ||
In toluene Irradiation (UV/VIS); ambient temp., nitrogen-laser flash; observed by UV-spectroscopy; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With NaB(C6H5)4 In ethanol; benzene Ru(II) complex and a ligand in a mixt. of EtOH-C6H6 heating under reflux for 2 h under N2, soln. filtering, treating with NaB(C6H5)4 in EtOH, concg., standing overnight, ppt. filtering off, washing with EtOH and light petroleum, drying in vacuo; puirified by recrystallisation from CH2Cl2-EtOH; identified by elem. anal., IR and NMR spectra; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With carbon monoxide In hexane (N2), soln. of the P-compd. added dropwise to a suspn. of the Ir-complex in hexane over 1 h, treated with a stream of CO for 40 min; filtered, concd. in vacuo, cooled to -78°C, pptn. filtered off, washed 3 times with cold heptane, dried in vacuo, elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With carbon monoxide In hexane (N2), soln. of the P-compd. added dropwise to a suspn. of the Ir-complexin hexane over 1 h, treated with a stream of CO for 40 min; evapd. in vacuo, cooled to -78°C, filtered off, washed 3 times with cold heptane, dried in vacuo, elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene Irradiation (UV/VIS); a mixt. of (Co(PPh(OMe)2)4) with PPh(OEt)2 (molar ratio about 1:4) was irradiated (400 W, high-pressure Hg lamp, pyrex-filter, distance to the mixt. 75 mm) at 30°C for 4 h;; mixt. of products, detected by MS;; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In dichloromethane byproducts: PhCN; 3 equiv. of phosphite, stirring for 5 h at room temp.; evapn., trituration (EtOH), collection (filtration), crystn. (CH2Cl2:EtOH); elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With water In ethanol EtOH/H2O (85::15 v/v), 70°C, 20 h; chromy. in the dark; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | In ethanol EtOH (abs.), 70°C, 3 h; chromy. in the dark; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In not given inert atmosphere; 5 h (according to Brunet et al., Inorg. Synth. 1992, 29, 156); extn. with petroleum ether:C6H6=4:1, crystn. (to give oil); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With Zn In ethanol under Ar; PPh(OEt)2 (excess) added to suspn. of Os complex and Zn dust (excess) in EtOH; refluxed; filtered; filtrate evapd. to dryness; oil triturated with EtOH contg. NaBPh4 (excess); elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Stage #1: 4-dimethylaminocarbonyl-3-methyl-1-aminocarbonyl-1,2-diaza-1,3-butadiene; diethyl phenylphosphonite at 20℃; for 0.5h; Stage #2: In tetrahydrofuran at 20℃; for 1h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Stage #1: methyl 3-[(aminocarbonyl)diazenyl]pent-2-enoate; diethyl phenylphosphonite at 20℃; for 0.5h; Stage #2: In tetrahydrofuran at 20℃; for 2h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | Stage #1: ethyl 3-[(aminocarbonyl)diazenyl]but-2-enoate; diethyl phenylphosphonite at 20℃; for 0.5h; Stage #2: In tetrahydrofuran at 20℃; for 2h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: diethyl phenylphosphonite; 1-aminocarbonyl-3-methyl-4-methoxycarbonyl-1,2-diaza-1,3-diene at 20℃; for 0.5h; Stage #2: In tetrahydrofuran at 20℃; for 2h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In dichloromethane Ar or N2; excess ligand added to CH2Cl2 soln. of metal compd., mixt. stirred at room temp. for 3 h; evapd., triturated (n-hexane), ppt. filtered off, recrystd. (CH2Cl2/hexane); | |
In dichloromethane under Ar; phosphite (excess) added to soln. of Ru complex in CH2Cl2; stirred at room temp. for 3 h; solvent removed under reduced pressure; triturated with n-hexane; solid sepd.; filtered; crystd. from CH2Cl2-hexane; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In dichloromethane Ar or n2; excess ligand added to CH2Cl2 soln. of metal compd., mixt. stirred at room temp. for 3 h; evapd., triturated (n-hexane), ppt. filtered off, recrystd. (CH2Cl2/hexane); | |
In dichloromethane under Ar; phosphite (excess) added to soln. of Os complex in CH2Cl2; stirred at room temp. for 3 h; solvent removed under reduced pressure; triturated with n-hexane; solid sepd.; filtered; crystd. from CH2Cl2-hexane; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | In benzene at 30 - 40℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | Stage #1: bromobenzene With magnesium Inert atmosphere; Schlenk technique; Stage #2: triethyl phosphite In tetrahydrofuran at 0 - 65℃; for 2h; Inert atmosphere; Schlenk technique; | |
96 %Spectr. | Stage #1: bromobenzene With magnesium In tetrahydrofuran for 1h; Inert atmosphere; Reflux; Stage #2: triethyl phosphite In tetrahydrofuran for 5h; Inert atmosphere; Reflux; | |
Stage #1: bromobenzene With magnesium In tetrahydrofuran Inert atmosphere; Reflux; Stage #2: triethyl phosphite In tetrahydrofuran at 20℃; for 36h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With cesium fluoride; In acetonitrile; at 30℃; for 24h;Inert atmosphere; | To a stirred solution of CsF (70 mg, 0.46 mmol) in anhydrous acetonitrile (1 mL) was consecutively added o-trimethylsilyl phenyl inflate (25 mg, 0.08 mmol) and diethyl phenyl phosphonite (66 mg, 0.33 mmol). Reaction mixture was allowed to stir at room temperature (30 C) for 24 hrs. The reaction mixture was concentrated and directly loaded on silica gel column and purified by using solvent gradient of Pet. EthenEthyl Acetate (1 : 1) to yield a colourless liquid phosphinate (15.7 mg, 76%). Reaction Time: 24 h; Rf: 0.3 (1 : 1 EtOAc:Pet Ether); Thick oil; 15.7 mg, 76 %; NMR (400 MHz, CDC13) TMS) δ 7.87-7.77 (m, 4H), 7.55-7.48 (m, 2H), 7.47-7.39 (m, 4H), 4.1 1 (apparent quint, J = 7.1 Hz, 2H), 1.37 (t, J = 7.1 Hz, 3H); 13C NMR ( 100 MHz, CDC13, TMS) 5 132.0 (d, J = 2.1 Hz), 131.6 (d, J = 136.4 Hz), 131.5 (d, J = 10.1 Hz), 128.4 (d, J = 13.1 Hz ), 61.1 (d, J = 5.4 Hz), 16.4 (d, J = 6.2 Hz); 31 P NMR (162 MHz, CDC13) 8 31.3; HRMS-ESI (m/z) calcd (CMH,502P + H)+ : 247.0882 found: 247.0886; Known compound, Lit. C. Huang, X. Tang, H. Fu, Y. Jiang, Y. Zhao, J. Org. Chem. 2006, 71, 5020. |
76% | With cesium fluoride; In acetonitrile; at 30℃; for 24h; | To a stirred solution of CsF (70 mg, 0.46 mmol) in anhydrous acetonitrile (1 mL) was consecutively added o-trimethylsilyl phenyl triflate (25 mg, 0.08 mmol) and diethyl phenyl phosphonite (66 mg, 0.33 mmol). Reaction mixture was allowed to stir at room temperature (30 C.) for 24 hrs. The reaction mixture was concentrated and directly loaded on silica gel column and purified by using solvent gradient of Pet. Ether: Ethyl Acetate (1:1) to yield a colourless liquid phosphinate (15.7 mg, 76%). Reaction Time: 24 h; Rf: 0.3 (1:1 EtOAc:Pet Ether); Thick oil; 15.7 mg, 76%; 1H NMR (400 MHz, CDCl3, TMS) δ 7.87-7.77 (m, 4H), 7.55-7.48 (m, 2H), 7.47-7.39 (m, 4H), 4.11 (apparent quint, J=7.1 Hz, 2H), 1.37 (t, J=7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3, TMS) δ 132.0 (d, J=2.1 Hz), 131.6 (d, J=136.4 Hz), 131.5 (d, J=10.1 Hz), 128.4 (d, J=13.1 Hz), 61.1 (d, J=5.4 Hz), 16.4 (d, J=6.2 Hz); 31P NMR (162 MHz, CDCl3) δ 31.3; HRMS-ESI (m/z) calcd (C14H15O2P+H)+: 247.0882 found: 247.0886; Known compound, Lit. C. Huang, X. Tang, H. Fu, Y. Jiang, Y. Zhao, J. Org. Chem. 2006, 71, 5020 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With methyl-triphenylphosphonium iodide; N-ethyl-N,N-diisopropylamine In dichloromethane at 60℃; for 2h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With triphenylphosphonium tetrafluoroborate; N-ethyl-N,N-diisopropylamine In dichloromethane at 60℃; for 2h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With methyl-triphenylphosphonium iodide; triphenylphosphonium tetrafluoroborate; N-ethyl-N,N-diisopropylamine In dichloromethane at 60℃; for 2h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With pyridine; iodine; <SUP>18</SUP>O-labeled water In tetrahydrofuran at -45 - 20℃; for 0.333333h; | |
74% | With pyridine; iodine; <SUP>18</SUP>O-labeled water In tetrahydrofuran at -45 - 20℃; for 0.333333h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With pyridine; iodine; <SUP>17</SUP>O-water In tetrahydrofuran at -45 - 20℃; for 0.333333h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With cesium fluoride In acetonitrile at 20℃; for 32h; Inert atmosphere; | 12 Example 12: Ethyl (2,5-dimethylphenyl)(phenyl)phosphinate (11) 3,6-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (25 mg, 0.077 mmol), Cesium Fluoride (64 mg, 0.421 mmol), Diethyl phenylphosphonite (60 mg, 0.306 mmol), Acetonitrile (1 ml): Reaction Time: 32 h; Rf. 0.4 (1 : 1 EtOAc:Pet Ether); Thick oil; 13.0 mg, 62 %; NMR (400 MHz, CDC13, TMS) δ 7.81 -7.70 (m, 3H), 7.52-7.40 (m, 3H), 7.23 (d, J = 7.8 Hz, 1H), 7.12-7.05 (m, 1H), 4.11 (apparent quint, J = 7.0 Hz, 2H), 2.36 (s, 3H), 2.33 (s, 3H), 1.38 (t, J = 7.0 Hz, 3H); ,3C NMR (100 MHz, CDC13, TMS) 5 138.6 (d, J = 10.8 Hz), 135.0 (d, J = 12.3 Hz), 133.9 (d, J = 9.3 Hz), 132.5 (d, J = 124.1 Hz), 128.4 (d, J = 13.4 Hz ), 131.7, 131.5 (d, J = 7.7 Hz), 131.4, 131.3, 129.0 (d, J = 133.3 Hz), 128.4 (d, J = 13.1Hz), 60.7 (d, J= 5.4 Hz), 20.9, 20.7 (d, J = 3.9 Hz), 16.4 (d, J = 6.9 Hz); 3 IP NMR (162 MHz, CDC13,) δ 32.2; HRMS-ESI (m/z) calcd (β,6Η,9θ2Ρ + H)+ : 275.1 195 found: 275.1 193. |
62% | With cesium fluoride In acetonitrile at 20℃; for 32h; Inert atmosphere; | 12 Ethyl (2,5-dimethylphenyl)(phenyl)phosphinate (11) General procedure: To a flame dried two-neck round-bottom flask containing CsF (5.50 equiv.) was added o-silyl aryl triflate (II) (1.00 equiv.) in acetonitrile, followed by addition of phosphorous compound of formula (III) (4.00 equiv.) in acetonitrile under argon atmosphere. The reaction mixture was stirred at room temperature and the progress was monitored by TLC. After completion of the reaction, acetonitrile was removed on rotary evaporator and the crude product was dried under high vacuum and purified by flash silica gel column using a gradient of ethyl acetate-petroleum ether to afford corresponding aryl-phosphorous compounds of formula (I) in good to excellent yields. 3,6-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (25 mg, 0.077 mmol), Cesium Fluoride (64 mg, 0.421 mmol), Diethyl phenylphosphonite (60 mg, 0.306 mmol), Acetonitrile (1 ml): Reaction Time: 32 h; Rf 0.4 (1:1 EtOAc:Pet Ether); Thick oil; 13.0 mg, 62%; 1H NMR (400 MHz, CDCl3, TMS) δ 7.81-7.70 (m, 3H), 7.52-7.40 (m, 3H), 7.23 (d, J=7.8 Hz, 1H), 7.12-7.05 (m, 1H), 4.11 (apparent quint, J=7.0 Hz, 2H), 2.36 (s, 3H), 2.33 (s, 3H), 1.38 (t, J=7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3, TMS) δ 138.6 (d, J=10.8 Hz), 135.0 (d, J=12.3 Hz), 133.9 (d, J=9.3 Hz), 132.5 (d, J=124.1 Hz), 128.4 (d, J=13.4 Hz), 131.7, 131.5 (d, J=7.7 Hz), 131.4, 131.3, 129.0 (d, J=133.3 Hz), 128.4 (d, J=13.1 Hz), 60.7 (d, J=5.4 Hz), 20.9, 20.7 (d, J=3.9 Hz), 16.4 (d, J=6.9 Hz); 31P NMR (162 MHz, CDCl3,) δ 32.2; HRMS-ESI (m/z) calcd (C16H19O2P+H)+: 275.1195 found: 275.1193 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With water In dichloromethane at 20℃; for 48h; regioselective reaction; | |
50% | With water In dichloromethane for 48h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With caesium carbonate In toluene at 120℃; for 24h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With caesium carbonate In toluene at 120℃; for 24h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With copper(l) iodide; caesium carbonate In toluene for 24h; Reflux; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With copper(l) iodide; caesium carbonate In toluene for 24h; Reflux; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With copper(l) iodide; caesium carbonate In toluene for 24h; Reflux; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With copper(l) iodide; caesium carbonate In toluene for 24h; Reflux; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With copper(l) iodide; caesium carbonate In toluene for 24h; Reflux; Sealed tube; |