Azidotrimethylsilan Chemische Eigenschaften,Einsatz,Produktion Methoden
R-S?tze Betriebsanweisung:
R11:Leichtentzündlich.
R23/24/25:Giftig beim Einatmen, Verschlucken und Berührung mit der Haut.
R50/53:Sehr giftig für Wasserorganismen, kann in Gew?ssern l?ngerfristig sch?dliche Wirkungen haben.
R29:Entwickelt bei Berührung mit Wasser giftige Gase.
S-S?tze Betriebsanweisung:
S16:Von Zündquellen fernhalten - Nicht rauchen.
S36/37/39:Bei der Arbeit geeignete Schutzkleidung,Schutzhandschuhe und Schutzbrille/Gesichtsschutz tragen.
S45:Bei Unfall oder Unwohlsein sofort Arzt zuziehen (wenn m?glich, dieses Etikett vorzeigen).
S8:Beh?lter trocken halten.
S57:Zur Vermeidung einer Kontamination der Umwelt geeigneten Beh?lter verwenden.
S36/37:Bei der Arbeit geeignete Schutzhandschuhe und Schutzkleidung tragen.
S29:Nicht in die Kanalisation gelangen lassen.
Chemische Eigenschaften
clear colorless to slightly yellow liquid
Physikalische Eigenschaften
bp 95–96°C; n20
D 1.416; d 0.868 g cm?3; fp23°C;
IR νmax 2100 cm?1; 1H NMR (CDCl3) δ = 0.22.
Verwenden
Many applications of TMSA in organic synthesis have been reported but only representative examples are described herein.
Substitution Reactions.
Benzyl,allyl,and substituted alkyl halides are converted to the corresponding azides in 60–100% yields via reactions with TMSA under neutral conditions in a nonaqueous solvent (eq 1).By using tin(IV) chloride as a catalyst, secondary and tertiary cyclic and polycyclic halides are similarly transformed into the corresponding azides in 50–92% yields (eq 1).
synthetische
several methods for the synthesis of this
azide have been reported.The procedure involving aluminum
chloride is not recommended, since an explosive product is
formed.Azidotrimethylsilane is now commercially available,
and a representative synthetic procedure is as follows. A mixture
of sodium azide and chlorotrimethylsilane is refluxed in
di-n-butyl ether for 2 days and the azide is safely distilled directly
from the reaction vessel. Purer compound (99% content)
is obtained by redistillation of the product. Several improved
conditions have been reported for the preparation of this
azide.In these procedures, trimethylsilyl chloride is reacted
with sodium azide either neat or in a high boiling point solvent,
such as a mixture of silicone oil and polyethylene glycol.
Distillation of the crude product usually provides trimethylsilyl
azide (TMSA) in high purity (97.9%) and yield (97%).
l?uterung methode
Distil the azide through a Vigreux column (p 11) in a N2 atmosphere maintaining the oil bath temperature thermostat at 135-140o . Check the purity by 1H NMR [CHCl3, : single peak at 13cps from Me4Si]. Likely impurities are siloxane hydrolysis products. The azide is thermally stable even at 200o when it decomposes slowly without explosive violence. All the same, it is advisable to carry out the distillation behind a thick safety screen in a fumehood because unforseen EXPLOSIVE azides may be formed on long standing. [Birkofer & Wagner Org Synth Coll Vol VI 1030 1988.]
Azidotrimethylsilan Upstream-Materialien And Downstream Produkte
Upstream-Materialien
Downstream Produkte
