Trimethylphosphin Chemische Eigenschaften,Einsatz,Produktion Methoden
R-S?tze Betriebsanweisung:
R11:Leichtentzündlich.
R36/37/38:Reizt die Augen, die Atmungsorgane und die Haut.
R67:D?mpfe k?nnen Schl?frigkeit und Benommenheit verursachen.
R65:Gesundheitssch?dlich: kann beim Verschlucken Lungensch?den verursachen.
R63:Kann das Kind im Mutterleib m?glicherweise sch?digen.
R48/20:Gesundheitssch?dlich: Gefahr ernster Gesundheitssch?den bei l?ngerer Exposition durch Einatmen.
R38:Reizt die Haut.
R17:Selbstentzündlich an der Luft. Spontaneously flammable in air.
S-S?tze Betriebsanweisung:
S9:Beh?lter an einem gut gelüfteten Ort aufbewahren.
S16:Von Zündquellen fernhalten - Nicht rauchen.
S26:Bei Berührung mit den Augen sofort gründlich mit Wasser abspülen und Arzt konsultieren.
S36/37/39:Bei der Arbeit geeignete Schutzkleidung,Schutzhandschuhe und Schutzbrille/Gesichtsschutz tragen.
S62:Bei Verschlucken kein Erbrechen herbeiführen. Sofort ?rztlichen Rat einholen und Verpackung oder dieses Etikett vorzeigen.
S36/37:Bei der Arbeit geeignete Schutzhandschuhe und Schutzkleidung tragen.
S7/9:Beh?lter dicht geschlossen an einem gut gelüfteten Ort aufbewahren.
S33:Ma?nahmen gegen elektrostatische Aufladungen treffen.
Chemische Eigenschaften
Clear colorless liquid
Verwenden
Trimethylphosphine (PMe
3) is an electron-rich phosphine ligand used as a reagent in Mitsunobu reaction.
It can be used:
- In transformation of azides into carbamates; aziridines to azidoalcohols; and ketoximes to ketones with 2,2′-dipyridyl diselenide.
- In Aza-Wittig reaction;, C-H bond activation of imines; cross-coupling reactions.
- In the preparation of (cyanomethylene) trimethylphosphorane (CMMP) which is used as a reagent in Mitsunobu type reaction.
- As a reagent in the synthesis of ruthenium trimethylphosphine complexes, which in turn are used as catalysts for hydrogenation of CO2 to formic acid.
Allgemeine Beschreibung
Trimethylphosphine is the reagent used in Mitsunobu reaction. It participates in the transformation of azides into carbamates, aziridines from azidoalcohols, iminophosphoranes and aza-Wittig reaction. Electron diffraction study of trimethylphosphine has been reported.
l?uterung methode
All operations should be carried out in an efficient fume cupboard because it is flammable, toxic and has a foul odor. Distil trimethylphosphine at atmospheric pressure in a stream of dry N2 (apparatus should be held together with springs to avoid loss of gas from increased pressure in the system) and the distillate run into a solution of AgI in aqueous KI whereby the silver complex [Me3PAgI]4 separates steadily. Filter off the complex, wash it with saturated aqueous KI solution, then H2O and dry it in a vacuum desiccator over P2O5. The dry complex is heated in a flask (in a stream of dry N2) in an oil bath at 140o, when pure Me3P distils off (bath temperature can be raised up to 260o). The vapour pressure of Me3P at 20o is 466mm and the b is 37.8o [Thomas & Eriks Inorg Synth IX 59 1967]. Alternatively, freshly distilled Me3P (6g) is shaken with a solution of AgI (13.2g, 1.1mol) in saturated aqueous KI solution (50mL) for 2hours. A white solid, not wetted with H2O, separates rapidly. It is collected, washed with the KI solution, H2O, and dried [Mann et al. J Chem Soc 1829 1937]. The silver complex is stable if kept dry in the dark, in which state it can be kept indefinitely. Me3P can be generated from the complex when required. Store it under N2 in a sealed container. It has been distilled in a vacuum line at -78o in vacuo and condensed at -96o [IR and NMR: Crosbie & Sheldrick J Inorg Nucl Chem 31 3684 1969]. The pK2 2 by NMR was 8.80 [Silver & Lutz J Am Chem Soc 83 786 1961, pK2 5 8.65: Henderson & Strueuli J Am Chem Soc 82 5791 1960].
Trimethylphosphin Upstream-Materialien And Downstream Produkte
Upstream-Materialien
Downstream Produkte