Lithium Aluminum Hydride Chemische Eigenschaften,Einsatz,Produktion Methoden
R-Sätze Betriebsanweisung:
R15:Reagiert mit Wasser unter Bildung hochentzündlicher Gase.
R34:Verursacht Verätzungen.
R14/15:Reagiert heftig mit Wasser unter Bildung hochentzündlicher Gase.
R11:Leichtentzündlich.
R36/37:Reizt die Augen und die Atmungsorgane.
R19:Kann explosionsfähige Peroxide bilden.
R40:Verdacht auf krebserzeugende Wirkung.
R10:Entzündlich.
R67:Dämpfe können Schläfrigkeit und Benommenheit verursachen.
R66:Wiederholter Kontakt kann zu spröder oder rissiger Haut führen.
R22:Gesundheitsschädlich beim Verschlucken.
R12:Hochentzündlich.
S-Sätze Betriebsanweisung:
S43:Zum Löschen . . . (vom Hersteller anzugeben) verwenden (wenn Wasser die Gefahr erhöht, anfügen: "Kein Wasser verwenden").
S7/8:Behälter trocken und dicht geschlossen halten.
S45:Bei Unfall oder Unwohlsein sofort Arzt zuziehen (wenn möglich, dieses Etikett vorzeigen).
S36/37/39:Bei der Arbeit geeignete Schutzkleidung,Schutzhandschuhe und Schutzbrille/Gesichtsschutz tragen.
S33:Maßnahmen gegen elektrostatische Aufladungen treffen.
S26:Bei Berührung mit den Augen sofort gründlich mit Wasser abspülen und Arzt konsultieren.
S16:Von Zündquellen fernhalten - Nicht rauchen.
S24/25:Berührung mit den Augen und der Haut vermeiden.
S27:Beschmutzte, getränkte Kleidung sofort ausziehen.
S29:Nicht in die Kanalisation gelangen lassen.
Aussehen Eigenschaften
LiAlH4; farbloses bis hellgraues, geruchloses Pulver (löslich in Ether, Chloroform, Benzol und Petrolether).
Gefahren für Mensch und Umwelt
Sehr heftige, u. U. explosionsartige Reaktion mit Wasser, Säuren, niederen Alkoholen und halogenierten Kohlenwasserstoffen. Eine große von Lithiumaluminiumhydrid ausgehende Gefahr ist die Verbrennung als Folge der Entzündung des Hydrids.
Die Einwirkung des Hydrids auf die feuchte Haut, bzw. Schleimhaut führt zur Bildung der entsprechenden Hydroxide und dadurch -je nach Menge- zu Reizungen oder Verätzungen. Durch den bei der Hydrolyse entstehenden Wasserstoff besteht die Gefahrder Bildung von Nebel und Aerosolen, dadurch können mitgerissene Hydrid-Partikel tief in die Atemwege eindringen. Augenkontakt durch Spritzer oder Patikel führt, wie bei Laugen, zu schweren Reizerscheinungen. Bei größeren Mengen können Magen-Darm-Reizungen, Herzrythmusstörungen, Störungen des ZNS, Krämpfe, Schock und Nierenschäden auftreten. ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ
Schwach wassergefährdender Stoff (WGK 1).
Schutzmaßnahmen und Verhaltensregeln
Trockene Schutzhandschuhe nur als kurzfristigen Staub- und Spritzschutz verwenden.
Verhalten im Gefahrfall
Verschüttetes LiAlH
4 sofort in ein trockenes Gefäß überführen und als Sondermüll entsorgen.
Zum Löschen Sand verwenden, notfalls auch NaCl.
Auf keinen Fall Wasser oder CO2 verwenden.
Erste Hilfe
Nach Hautkontakt: Zunächtst trocken abwischen, dann mit sehr viel Wasser spülen.
Nach Augenkontakt: Mindestens 10 Min. bei geöffnetem Lid mit Wasser spülen. Sofort zum Augenarzt.
Nach Einatmen: Frischluft. Sofort zum Arzt!
Nach Verschlucken: Viel Wasser trinken lassen. Kein Erbrechen auslösen. Sofort Arzt hinzuziehen.
Nach Kleidungskontakt: Verschmutzte Kleidung sofort entfernen, anhaftendes Hydrid trocken entfernen.
Ersthelfer: siehe gesonderten Anschlag
Sachgerechte Entsorgung
LiAlH
4 wird in Ether (z. B. Dioxan) aufgeschlämmt und unter Rühren tropfenweise in eine Essigester/Ether-Mischung getropft. Nach vollständiger Reaktion kann die Mischung als Sondermüll (halogenfreie Lösungsmittel) entsorgt werden.
Chemische Eigenschaften
Lithium aluminum hydride is a white to gray powder. A combustible solid. monoclinic crystals; grey in the presence of aluminum impurity; stable below 120°C in dry air; turns grey on standing; hygroscopic; density 0.917 g/cm3; melts at 190°C (decomposes); reacts with water and alcohols; soluble in diethylether and tetrahydrofuran (about 30 and 13 g/100g, respectively at 25°C; also soluble in dimethylcellosolve; sparingly soluble in dibutylether; slightly soluble in dioxane (1g/L) and practically insoluble in hydrocarbons; can be solubilized in benzene by crown ether.
Physikalische Eigenschaften
White crystalline powder when pure; monoclinic crystals; grey in the presence of aluminum impurity; stable below 120°C in dry air; turns grey on standing; hygroscopic; density 0.917 g/cm
3; melts at 190°C (decomposes); reacts with water and alcohols; soluble in diethylether and tetrahydrofuran (about 30 and 13 g/100g, respectively at 25°C; also soluble in dimethylcellosolve; sparingly soluble in dibutylether; slightly soluble in dioxane (1g/L) and practically insoluble in hydrocarbons; can be solubilized in benzene by crown ether.
Verwenden
Lithium aluminum hydride is among the most important industrial reducingagents. It is used extensively in organic syntheses and also in catalytichydrogenation. Reactant or reagent for:
1. The preparation of thermoplastic polyester polyamides from oleic acid
2. Lithium-polymer batteries
3. Hydrodefluorination of gem-difluoromethylene derivatives
4. Asymmetric aldol reactions
5. Synthesis of Li-Al-N-H composites with hydrogen absorption / desorption properties
6. LAH is a powerful reducing agent for many different reduction reactions such as that of ketones to alcohols
synthetische
Lithium aluminum hydride is prepared by reaction of lithium hydride with aluminum chloride in diethylether:
4LiH + AlCl3 →(C2H5)2O→LiAlH4+3LiCl
Application
Lithium aluminum hydride (LiAlH4) is an effective reducing agent that can be used in chemical synthesis to reduce esters, carboxylic acids, acyl chlorides, aldehydes, epoxides, and ketones into the corresponding alcohols. In addition, amide, nitro, nitrile, imine, oxime, and azide compounds are converted into amines.
LiAlH4 is a promising substance for hydrogen storage applications. Its properties include high gravimetric and volumetric hydrogen densities . It can also be used as a reducing agent in the preparation of reduced graphene oxide (rGO).
Allgemeine Beschreibung
A white powder that turns gray on standing. If spread out over a large flat combustible surface, friction can cause ignition. Used to make other chemicals, as a polymerization catalyst, as a hydrogen source, and as a propellant.
Air & Water Reaktionen
Reacts with water vigorously attaining incandescence and ignition of evolved hydrogen [Kelen, Cahiers, 1977, (86), 100]. Reactions with water or moist air (or heated air) are violent and may be explosive [Schmidt, D.L., et al. Inorg. Synth. 1973. p. 14, 51].
Reaktivität anzeigen
Lithium aluminium hydride is a powerful reducing agent. React violently on contact with many oxidizing agents. Ignites by friction, especially if powdered. Reacts vigorously with hydroxy compounds such as water, alcohols, carboxylic acids [Mellor 2 Supp. 2:142. 1961]. Caused a violent explosion when used to dry diethylene glycol dimethyl ether: Ignition may have been caused by heat from reaction with impurity water or perhaps decomposition of peroxides in the ether. About 75% of the ether had been removed when the explosion occurred [MCA Case History 1494. 1968]. Reduces carbon dioxide or sodium hydrogen carbonate to methane and ethane at elevated temperatures. These flammable or explosive gases can form when CO2 extinguishers are used to fight hydride fires. Forms explosive complexes with ether, dimethylamine and various tetrazoles. Tetrazoles include, 2-methyl, 2-ethyl, 5-ethyl, 2-methyl-5-vinyl, 5-amino-2-ethyl [US Pat. 3 396 170, 1968].
Hazard
Lithium aluminum hydride is a flammable substance. It ignites spontaneously on grinding and reacts violently with water and many organic substances. Diethyl ether, tetrahydrofuran or another suitable solvent should be used in its synthetic applications. Dry or powdered limestone is an appropriate fire extinguishing agent.
Health Hazard
Lithium aluminum hydride is highly corrosive to the skin, eyes, and mucous
membranes. Contact with moisture forms lithium hydroxide, which can cause severe
burns. Powdered LAH forms dusts that can pose an inhalation hazard. Ingestion of
this substance may cause aching muscles, nausea, vomiting, dizziness, and
unconsciousness and may be fatal. Ingestion can result in gas embolism due to the
formation of hydrogen.
No chronic effects of lithium aluminum hydride have been identified
Flammability and Explosibility
Lithium aluminum hydride is a highly flammable solid and may ignite in moist or
heated air. Exposure to water results in the release of hydrogen, which can be ignited
by the heat from the exothermic reaction. Lithium aluminum hydride should not be
used as a drying agent for solvents because fires can easily result (LAH decomposes
at about 125° C, a temperature easily reached at a flask's surface in a heating
mantle). The decomposition products of LAH can be quite explosive, and the
products of its reaction with carbon dioxide have been reported to be explosive. Use
dry chemical powder or sand to extinguish fires involving lithium aluminum
hydride. Never use water or carbon dioxide extinguishers on an LAH fire.
Sicherheitsprofil
Stable in dry air at
room temperature. It decomposes above
125' forming Al, H2, and lithium hydride.
Very powerful reducer. Can ignite if
pulverized even in a dry box. Reacts
violently with air, acids, alcohols, benzoyl
peroxide, boron trifluoride etherate, (2
chloromethyl furan + ethyl acetate),
diethylene glycol dimethyl ether, diethyl
ether, 1,2-dimethoxyethane, dimethyl ether,
methyl ethyl ether, (nitriles + H2O),
perfluorosuccinamide,
(perfluorosuccinamide + H20),
tetrahydrofuran, water. To fight fire, use dry
chemical, includmg special formulations of
dry chemicals as recommended by the
supplier of the lithium aluminum hydride.
Do not use water, fog, spray, or mist.
Incompatible with bis (2-methoxyethyl)ether, CO2, BF3, diethyl etherate,
dibenzoyl peroxide, 3,5
dbromocyclopentene, 172-dimethoxy
ethane, ethyl acetate, fluoro amides,
pyridine, tetrahydrofuran. Used as a
reducing agent in the preparation of
pharmaceuticals. See also ALUMINUM,
LITHIUM COMPOUNDS, and
HYDRIDES.
mögliche Exposition
This material is used as a catalyst and
as a specialty reducing agent in organic synthesis.
Lager
LAH should be handled in areas free of ignition sources
under an inert atmosphere. Safety glasses, impermeable gloves, and a fire-retardant
laboratory coat are required. A dry powder fire extinguisher or pail of sand (and
shovel) must be available in areas where LAH is to be handled or stored. Work with
large quantities of powdered LAH should be conducted in a fume hood under an
inert gas such as nitrogen or argon. Lithium aluminum hydride should be stored in
tightly sealed containers in a cool, dry area separate from combustible materials. Dry
LAH powder should never be exposed to water or moist air. Lithium aluminum
hydride can be a finely powdered reagent that produces a reactive dust on handling.
The older practice of grinding lithium aluminum hydride prior to use can cause
explosions and should not be employed.
Versand/Shipping
UN1410 Lithium aluminum hydride (dry),
Hazard Class: 4.3; Labels: 4.3-Dangerous when wet material. UN1411 Lithium aluminum hydride, ethereal, Hazard
Class: 4.3; Labels: 4.3-Dangerous when wet material, 3-
Flammable liquid.
läuterung methode
Extract it with Et2O, and, after filtering, the solvent is removed under vacuum. The residue is dried at 60o for 3hours, under high vacuum [Ruff J Am Chem Soc 83 1788 1961]. It is a strong reducing agent. It IGNITES in the presence of a small amount of water and reacts with it EXPLOSIVELY. [Becher in Handbook of Preparative Inorganic Chemistry (Ed. Brauer) Academic Press Vol I p 805 1963.]
Inkompatibilitäten
Combustible solid. Can ignite spontaneously in moist air or heat. Decomposes on heating @
125C forming aluminum, lithium hydride and flammable
hydrogen gas. A strong reducing agent; violent reaction
with oxidizers. Violent reaction with water, alcohols, acids,
dimethylether, ethers, tetrahydrofuran, benzoyl peroxide;
boron trifluoride etherate. Reduces carbon dioxide or
sodium hydrogen carbonate to methane and ethane at elevated temperatures. These flammable or explosive gases
can form when CO2 extinguishers are used to fight hydride
fires. Forms explosive complexes with ether, dimethylamine and various tetrazoles. Tetrazoles include, 2-methyl,
2-ethyl, 5-ethyl, 2-methyl-5-vinyl, 5-amino-2-ethyl .
Waste disposal
Small amounts of excess LAH can be destroyed by forming a suspension or solution in an inert solvent
such as diethyl ether or hexane, cooling in an ice bath, and slowly and carefully adding ethyl acetate
dropwise with stirring. This is followed by the addition of a saturated aqueous solution of ammonium
chloride.
Excess lithium aluminum hydride and the products of the treatment described above should be placed in an
appropriate container, clearly labeled, and handled according to your institution's waste disposal guidelines.
For more information on disposal procedures, see Chapter 7 .
Lithium Aluminum Hydride Upstream-Materialien And Downstream Produkte
Upstream-Materialien
Downstream Produkte
2-[4-(TRIFLUOROMETHYL)PHENYL]-1,3-THIAZOLE-4-CARBALDEHYDE
Toremifene
2-(2-FLUORO-PHENYL)-ETHANESULFONYL CHLORIDE
4-Tert-butylbenzylalkohol
1-(2-NAPHTHYL)METHANAMINE
4-MORPHOLINOBENZYLAMINE
3-FLUORO-N-METHYLANILINE
(R)-TERT-LEUCINOL
Tetrahydropyranyl-4-acetic acid
Flutoprazepam
3-[(N-(TERT-BUTYLOXYCARBONYL)AMINO)METHYL]PYRIDINE
3-(3,4-DIMETHOXY-PHENYL)-PROPYLAMINE
Picolamin
(S)-2-Amino-4-methylpentan-1-ol
2-Chloroisonicotinaldehyde
4-METHYL-2-[4-(TRIFLUOROMETHYL)PHENYL]-1,3-THIAZOLE-5-CARBALDEHYDE
2-NAPHTHALEN-1-YL-ETHYLAMINE
2-FLUOROPHENETHYL ALCOHOL
[6-(1-PYRROLIDINYL)-3-PYRIDINYL]METHANOL
L-Tryptophanol
3,5-Difluoropyridine
3-Methylbenzylamin
2,5-Dimethyl-piperazin (Gemischder cis- und trans-Isomeren)
3-(4-METHOXY-PHENYL)-PROPYLAMINE
2-(4-Methylthiazol-5-yl)ethanol
(1-phenylcyclopropyl)methanamine
(S)-2-(N，N-disubstitued aminomethy)indoline
4-HYDROXYMETHYL-NICOTINIC ACID
2,4-DIPHENYL-1,3-THIAZOLE-5-CARBALDEHYDE
trans-4-Aminocyclohexan-1-ol
(5-METHYL-1-PHENYL-1H-PYRAZOL-4-YL)METHANOL
4-(BOC-AMINOMETHYL)PYRIDINE
N-(2-Aminoethyl)piperidin
(4-AMINO-PYRIDIN-3-YL)-METHANOL
4,7,13,16,21-Pentaoxa-1,10-diazabicyclo[8.8.5]tricosan
2-o-Tolylethanol
2-(4-BIPHENYL)ETHYLAMINE
Vinylferrocen
α-(Aminomethyl)benzylalkohol
(1,5-DIMETHYL-1H-PYRAZOL-3-YL)METHANOL
