scholarly journals Conversion of triphenylphosphine oxide to organophosphorus via selective cleavage of C-P, O-P, and C-H bonds with sodium

2020 ◽  
Vol 3 (1) ◽  
Author(s):  
Jian-Qiu Zhang ◽  
Jingjing Ye ◽  
Tianzeng Huang ◽  
Hiroyuki Shinohara ◽  
Hiroyoshi Fujino ◽  
...  
Keyword(s):  
Organophosphorus Compounds ◽  
Triphenylphosphine Oxide ◽  
Starting Material ◽  
Phosphorus Compounds ◽  
Metallic Sodium ◽  
Chemical Waste ◽  
Paraffin Oil

AbstractFor over half a century, thousands of tons of triphenylphosphine oxide Ph3P(O) have been produced every year from the chemical industries as a useless chemical waste. Here we disclose efficient transformations of Ph3P(O) with cheap resource-abundant metallic sodium finely dispersed in paraffin oil. Ph3P(O) can be easily and selectively transformed to three reactive organophosphorus intermediates—sodium diphenylphosphinite, sodium 5H-benzo[b]phosphindol-5-olate and sodium benzo[b]phosphindol-5-ide—that efficiently give the corresponding functional organophosphorus compounds in good yields. These functional organophosphorus compounds are difficult to prepare but highly industrially useful compounds. This may allow Ph3P(O) to be used as a precious starting material for highly valuable phosphorus compounds.

Reaction of Trivalent Organophosphorus Compounds with Selenium

1978 ◽  
Vol 33 (9) ◽  
pp. 1040-1046 ◽  
Author(s):  
Maria Konieczny ◽  
George Sosnovsky
Keyword(s):  
Room Temperature ◽  
Organophosphorus Compounds ◽  
Phosphorus Compounds ◽  
Trivalent Phosphorus ◽  
Derivatives Of

Selenium derivatives of pentavalent organophosphorus compounds 9, 10, 11 (Ṙ = 2,2,6,6- tetramethyl-1-oxyl-4-piperidyl), 12 and 13 were prepared in 79-99%yields via the reaction of the corresponding trivalent phosphorus compounds 14, 15, 16, 17, 18 with blackselenium in benzene at room temperature in 20 hours.

Organophosphorverbindungen mit tertiären Alkylsubstituenten. III*: Synthese und Reaktionen Di-1-adamantylsubstituierter Phosphorverbindungen; Kristallstruktur von Di-1-Adamantylphosphinsäurechlorid / Organophosphorus Compounds with Tertiary Alkyl Substituents. Ill: Synthesis and Reactions of Di-1-adam antyl-Substituted Phosphorus Compounds; Crystal Structure of Di-1-adam antylphosphinic Chloride

1994 ◽  
Vol 49 (6) ◽  
pp. 801-811 ◽  
Author(s):  
Jens R. Goerlich ◽  
Axel Fischer ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Organophosphorus Compounds ◽  
Phosphorus Compounds ◽  
Secondary Phosphine ◽  
Phosphine Oxides ◽  
X Ray ◽  
Dry Air ◽  
Nmr Data ◽  
Standard Procedures ◽  
Hydrolysis Of ◽  
Tertiary Alkyl

The reaction of adamantane with PCl3/A1Cl3, followed by hydrolysis, gave (1-Ad)2P(:O)Cl 1, which was converted to (1-Ad)2P(:O)F 2 and (1-Ad)2P(:S)Cl 3 by standard procedures. The structure of 1 was confirmed by a single crystal X-ray structure determination; despite the bulky substituents the P-C bond lengths are normal (184.0(3), 185.0(3) pm). Whereas chlorine-fluorine exchange in 3 with AsF3 furnished (1-Ad)2P(:S)F 4, desulfuration of 3 with Ph3P to give (1-Ad)2PCl 5 failed. The secondary phosphine oxides R 1R2P(:O)H (R1, R2 = 1-Ad: 6; R1 = 1-Ad, R2 = tBu: 7; R1, R2 = tBu: 8) were synthesized by reaction of 1, 1-AdP(:O)Cl2 and tBuP(:0)Cl2 with tBuLi. 6 and 8 reacted readily with chloral to give the adducts R2P(:O)CH(OH)CCl3 (R = 1-Ad: 9; R = tBu: 10). Silylation of 6 with Me2NSiMe3 in the presence of dry air led to (1-Ad)2P(:O)OSiMe3 11, which was hydrolyzed to give (1-Ad)2P(:O)OH 12. (1-Ad)2POSiMe3 13 was obtained by the reaction of 6 with n-BuLi, followed by Me3SiCl. No reaction took place upon heating 6 with Mo(CO)6. (1-Ad)2PCl 5 was synthesized in low yield by the reaction of 6 with PCl3. The action of tetrachloro-obenzoquinone (TOB) upon 6 furnished (1-Ad)2P(:O)(o-OH)C6Cl4 15, whereas the tbutyl analogue of 15, 16, was synthesized by hydrolysis of the TOB-adduct of di-tbutylfluorophosphine. Analogous 1-adamantyl- and tbutyl-phosphorus compounds are compared with regard to their 31P NMR data

Organophosphorus compounds. VIII. Diphenylphosphinothioic acid derivatives as reagents for proteins

1969 ◽  
Vol 22 (11) ◽  
pp. 2359 ◽  
Author(s):  
RA Spence ◽  
JM Swan ◽  
SHB Wright
Keyword(s):  
Mass Spectra ◽  
Organophosphorus Compounds ◽  
Phosphorus Compounds ◽  
Radioactive Labelling ◽  
Condensing Agents ◽  
Derivatives Of ◽  
Model Reactions

Esters and other derivatives of diphenylphosphinothioic acids are examined as potential agents for the radioactive labelling of immunoglobulins and other proteins. Syntheses, model reactions with amines, and mass spectra of the organo-phosphorus compounds are discussed. The labelling of immunoglobulins by reaction with [32P]diphenylphosphinothioic chloride, with [32P]diphenylphosphinothioic isothiocyanate, and with [32P]diphenylphosphinodithioic acid in the presence of condensing agents such as dimethylcyanamide and carbodiimides is reported.

scholarly journals Syntheses and Reactions of Pyrroline, Piperidine Nitroxide Phosphonates

Molecules ◽  
2020 ◽  
Vol 25 (10) ◽  
pp. 2430
Author(s):  
Mostafa Isbera ◽  
Balázs Bognár ◽  
József Jekő ◽  
Cecilia Sár ◽  
Kálmán Hideg ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Antioxidant Capacity ◽  
Organic Compounds ◽  
Organophosphorus Compounds ◽  
Building Blocks ◽  
Phosphorus Compounds ◽  
Substitution Reactions ◽  
Carbon Bond ◽  
Bond Forming ◽  
Carbon Carbon Bond

Organophosphorus compounds occupy a significant position among the plethora of organic compounds, but a limited number of paramagnetic phosphorus compounds have been reported, including paramagnetic phosphonates. This paper describes the syntheses and further transformations of pyrroline and piperidine nitroxide phosphonates by well-established methods, such as the Pudovik, Arbuzov and Horner-Wadsworth-Emmons (HWE) reactions. The reaction of paramagnetic α-bromoketone produced a vinylphosphonate in the Perkow reaction. Paramagnetic α-hydroxyphosphonates could be subjected to oxidation, elimination and substitution reactions to produce various paramagnetic phosphonates. The synthesized paramagnetic phosphonates proved to be useful synthetic building blocks for carbon-carbon bond-forming reactions in the Horner-Wadsworth-Emmons olefination reactions. The unsaturated compounds achieved could be transformed into various substituted pyrroline nitroxides, proxyl nitroxides and paramagnetic polyaromatics. The Trolox® equivalent antioxidant capacity (TEAC) of new phosphonates was also screened, and tertiary α-hydroxyphosphonatate nitroxides exhibited remarkable antioxidant activity.

scholarly journals Synthesis and Characterization of New Thioxanthone Derivatives

2013 ◽  
Vol 10 (3) ◽  
pp. 724-735
Author(s):  
Baghdad Science Journal
Keyword(s):  
Sulfuric Acid ◽  
Benzoic Acid ◽  
Sodium Azide ◽  
Aromatic Amines ◽  
Chlorosulfonic Acid ◽  
Starting Material ◽  
Phosphorus Compounds ◽  
Synthesis And Characterization

This work comprises the synthesis of new thioxanthone derivatives containing C-substituted thioxanthone. To obtain these derivatives, the o-mercapto benzoic acid was chosen as the starting material, which was reacted with dry benzene in sulfuric acid (98 %) to produce the thioxanthone (1). The 2,7-(disulfonyl phosphine imine) thioxanthone (4-8) were prepared from reaction of compound (1) with chlorosulfonic acid gave 2,7-(disulfonyl chloride) thioxanthone (2). Treatment of (2) with sodium azide to produce 2,7-(disulfonyl azide) thioxanthone (3). Condensation of (3) with phosphorus compounds afforded compounds (4-8). The 2,7-(disulfonamide) thioxanthone (9-21) was obtained when compound (2) condensed with different aromatic amines, it gave the expected amides (9-21).

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