Reduction of nitro compounds

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The reduction of nitro compounds are chemical reactions of wide interest in organic
chemistry. The conversion can be effected by many reagents. The nitro group was one
of the first functional groups to be reduced. Alkyl and aryl nitro compounds behave
differently. Most useful is the reduction of aryl nitro compounds.

Contents

 1Aromatic nitro compounds

o 1.1Reduction to anilines
o 1.2Reduction to hydroxylamines
o 1.3Reduction to hydrazino compounds
o 1.4Reduction to azo compounds
 2Aliphatic nitro compounds
o 2.1Reduction to hydrocarbons
o 2.2Reduction to amines
o 2.3Reduction to hydroxylamines
o 2.4Reduction to oximes
 3References

Aromatic nitro compounds[edit]

Reduction to anilines[edit]

The reduction of nitroaromatics is conducted on an industrial scale. [1] Many methods

exist, such as:

 Catalytic hydrogenation using: Raney

nickel[2] or palladium-on-carbon,[3][4][5] platinum(IV)
oxide, or Urushibara nickel.[6]
 Iron in acidic media.[7][8][9]
 Sodium hydrosulfite[10]
 Sodium sulfide (or hydrogen sulfide and base).
Illustrated by the selective reduction of dinitrophenol
to the nitroaminophenol.[11]
  Tin(II) chloride[12]
 Titanium(III) chloride
 Samarium[13]
 Hydroiodic acid[14]
Metal hydrides are typically not used to reduce aryl nitro compounds to anilines
because they tend to produce azo compounds. (See below)
Reduction to hydroxylamines[edit]
Several methods have been described for the production of aryl hydroxylamines from
aryl nitro compounds:

 Raney nickel and hydrazine at 0-10 °C[15]

 Electrolytic reduction[16]
 Zinc metal in aqueous ammonium chloride[17]
 Catalytic Rhodium on carbon with excess hydrazine
monohydrate at room temperature [18]
Reduction to hydrazino compounds[edit]
See also: Hydrazine
Treatment of nitroarenes with excess zinc metal results in the formation of N,N'-
diarylhydrazine.[19]
Reduction to azo compounds[edit]

Treatment of aromatic nitro compounds with metal hydrides gives good yields of azo
compounds. For example, one could use:

 Lithium aluminium hydride[20]

 Zinc metal with sodium hydroxide.[19] (Excess zinc will
reduce the azo group to a hydrazino compound.)

Aliphatic nitro compounds[edit]

Reduction to hydrocarbons[edit]

Hydrodenitration (replacement of a nitro group with hydrogen) is difficult to achieve but

can be effected by catalytic hydrogenation over platinum on silica gel at high
temperatures.[21] The reaction can also be effected through radical reaction with tributyltin
hydride and a radical initiator, AIBN as an example.[22]
Reduction to amines[edit]

Aliphatic nitro compounds can be reduced to aliphatic amines by several reagents:

 Catalytic hydrogenation using platinum(IV)

oxide (PtO2)[23] or Raney nickel[24]
 Iron metal in refluxing acetic acid[25]
 Samarium diiodide[26]
 Raney nickel, platinum on carbon, or zinc dust
and formic acid or ammonium formate[6]
α,β-Unsaturated nitro compounds can be reduced to saturated amines by:

 Catalytic hydrogenation over palladium-on-carbon

 Iron metal
 Lithium aluminium hydride[27] (Note: Hydroxylamines
and oximes are typical impurities.)
 Lithium borohydride or sodium
borohydride and trimethylsilyl chloride[28]
 Red-Al[29]
Reduction to hydroxylamines[edit]
Aliphatic nitro compounds can be reduced to aliphatic hydroxylamines using diborane.[30]

The reaction can also be carried out with zinc dust

and ammonium chloride:[31][32][33]
R-NO2 + 4 NH4Cl + 2 Zn → R-NH-OH + 2 ZnCl2 + 4
NH3 + H2O
Reduction to oximes[edit]
Nitro compounds are typically reduced to oximes using
metal salts, such as stannous chloride[34] or chromium(II)
chloride.[35] Additionally, catalytic hydrogenation using a
controlled amount of hydrogen can generate oximes. [36]

References[edit]
1. ^ Gerald Booth (2007). "Nitro Compounds,
Aromatic".  Ullmann's Encyclopedia of Industrial
Chemistry. Weinheim: Wiley-
VCH.  doi:10.1002/14356007.a17_411.
2. ^ Allen, C. F. H.; VanAllan, J. (1955). "2-Amino-p-
cymene".  Organic Syntheses.; Collective Volume,  3,
p. 63
3. ^ Bavin, P. M. G. (1973). "2-
Aminofluorene".  Organic Syntheses.; Collective
Volume, 5, p.  30
4. ^ Smith, Michael B.; March, Jerry (2007). March's
Advanced Organic Chemistry (6th  ed.). John Wiley
& Sons. p. 1816.  ISBN  978-0-471-72091-1.
5. ^ Ram, Siya; Ehrenkaufer, Richard E. (1984). "A
general procedure for mild and rapid reduction of
aliphatic and aromatic nitro compounds using
ammonium formate as a catalytic hydrogen transfer
agent".  Tetrahedron Lett. 25 (32): 3415–
3418.  doi:10.1016/S0040-4039(01)91034-2. hd
l:2027.42/25034.
6. ^ Jump up to:a b Adams, J. P. (2002). "Nitro and related
groups". Journal of the Chemical Society, Perkin
Transactions 1  (23): 2586–
2597.  doi:10.1039/b009711j.
7. ^ Fox, B. A.; Threlfall, T. L. (1964). "2,3-
Diaminopyridine". Organic Syntheses.  44:
34.  doi:10.15227/orgsyn.044.0034.
8. ^ Mahood, S. A.;
Schaffner\doi=10.15227/orgsyn.011.0032, P. V. L.
(1931). "2,4-Diaminotoluene". Organic
Syntheses.  11: 32.  doi:10.15227/orgsyn.011.0032.
9. ^ "O-Aminobenzaldehyde, Redox-Neutral Aminal
Formation and Synthesis of
Deoxyvasicinone". Organic Syntheses.  89: 274.
2012.  doi:10.15227/orgsyn.089.0274.
10. ^ Redemann, C. T.; Redemann, C. E. (1955). "5-
Amino-2,3-dihydro-1,4-phthalazinedione". Organic
Syntheses.; Collective Volume, 3, p.  69
11. ^ Hartman, W. W.; Silloway, H. L. (1945). "2-Amino-
4-nitrophenol".  Organic Syntheses. 25:
5. doi:10.15227/orgsyn.025.0005.
12. ^ Faul, Margaret M.; Thiel, Oliver R. (2005). "Tin(II)
Chloride".  Encyclopedia of Reagents for Organic
Synthesis. doi:10.1002/047084289X.rt112.pub2. IS
BN  9780470842898.
13. ^ Basu, M. K. (2000). "Ultrasound-promoted highly
efficient reduction of aromatic nitro compounds to
the aromatic amines by samarium/ammonium
chloride".  Tetrahedron Lett. 41 (30): 5603–
5606.  doi:10.1016/S0040-4039(00)00917-5.
14. ^ Kumar, J. S. Dileep; Ho, ManKit M.; Toyokuni,
Tatsushi (2001). "Simple and chemoselective
reduction of aromatic nitro compounds to aromatic
amines: reduction with hydriodic acid
revisited".  Tetrahedron Letters. 42 (33): 5601–
5603.  doi:10.1016/s0040-4039(01)01083-8.
15. ^ Ayyangar, N. R.; Brahme, K. C.; Kalkote, U. R.;
Srinivasan, K. V. (1984). "Facile Transfer-Reduction
of Nitroarenes to N Arylhydroxylamines with
Hydrazine in the Presence of Raney
Nickel".  Synthesis.  1984  (11): 938. doi:10.1055/s-
1984-31027.
16. ^ Harman, R. E. (1963). "Chloro-p-
benzoquinone".  Organic Syntheses.; Collective
Volume, 4, p.  148
17. ^ Kamm, O. (1941).  "β-
Phenylhydroxylamine".  Organic
Syntheses.; Collective Volume, 1, p.  445
18. ^ Ichikawa, S.; Zhu, S.; Buchwald, S. (2018).  "A
Modified System for the Synthesis of
Enantioenriched N-Arylamines through Copper-
Catalyzed Hydroamination". Angewandte Chemie
International Edition. 57 (28): 8714–
8718.  doi:10.1002/anie.201803026.  hdl:1721.1/1257
26.  PMC 6033674. PMID 29847002.
19. ^ Jump up to:a b Bigelow, H. E.; Robinson, D. B.
(1955).  "Azobenzene". Organic
Syntheses.; Collective Volume, 3, p.  103
20. ^ R. F. Nystrom & W. G. Brown (1948). "Reduction
of Organic Compounds by Lithium Aluminum
Hydride. III. Halides, Quinones, Miscellaneous
Nitrogen Compounds".  J. Am. Chem. Soc. 70 (11):
3738–3740.  doi:10.1021/ja01191a057.  PMID  18102
934.
21. ^ M. J. Guttieri & W. F. Maier (1984). "Selective
cleavage of carbon-nitrogen bonds with platinum".  J.
Org. Chem.  49  (16): 2875–
2880.  doi:10.1021/jo00190a006.
22. ^ T. V. (Babu) RajanBabu, Philip C. Bulman Page,
Benjamin R. Buckley, "Tri-n-butylstannane"
Encyclopedia of Reagents for Organic Synthesis
2004, John Wiley & Sons.
doi:10.1002/047084289X.rt181.pub2
23. ^ A. T. Nielsen (1962). "The Isomeric
Dinitrocyclohexanes. II. Stereochemistry".  J. Org.
Chem.  27  (6): 1998–
2001.  doi:10.1021/jo01053a019.
24. ^ Dauben, Jr., H. J.; Ringold, H. J.; Wade, R. H.;
Pearson, D. L.; Anderson, Jr., A. G.
 (1963).  "Cycloheptanone".  Organic
Syntheses.; Collective Volume, 4, p.  221
25. ^ Senkus, M. (1948). "Ind. Eng. Chem". 40: 506.
26. ^ A. S. Kende & J. S. Mendoza (1991). "Controlled
reduction of nitroalkanes to alkyl hydroxylamines or
amines by samarium diiodide". Tetrahedron
Letters.  32  (14): 1699–1702. doi:10.1016/S0040-
4039(00)74307-3.
27. ^ A. Burger, M. L. Stein and J. B. Clements (1957).
"Some Pyridylnitroalkenes, Nitroalkanols, and
Alkylamines".  J. Org. Chem.  22  (2): 143–
144.  doi:10.1021/jo01353a010.
28. ^ Giannis, A.; Sandhoff, K. (1989).
"LiBH4(NaBH4)/Me3SiCl, an Unusually Strong and
Versatile Reducing Agent".  Angewandte Chemie
International Edition in English. 28 (2): 218–
220.  doi:10.1002/anie.198902181.
29. ^ Butterick, John R.; Unrau, A. M. (1974).
"Reduction of β-nitrostyrene with sodium bis-(2-
methoxyethoxy)-aluminium dihydride. A convenient
route to substituted phenylisopropylamines".  J.
Chem. Soc., Chem. Commun. (8): 307–
308.  doi:10.1039/c39740000307.
30. ^ H. Feuer, R. S. Bartlett, B. F. Vincent and R. S.
Anderson (1965). "Diborane Reduction of Nitro
Salts. A New Synthesis of N-Monosubstituted
Hydroxylamines".  J. Org. Chem.  30  (9): 2880–
2882.  doi:10.1021/jo01020a002.
31. ^ Smith, P.W.G.; Tatchell, A.R. (1965), "Aliphatic
Nitro Compounds and Amines", Fundamental
Aliphatic Chemistry, Elsevier, pp. 245–
266,  doi:10.1016/b978-0-08-010746-2.50016-8,  ISB
N 978-0-08-010746-2, retrieved  2021-01-27
32. ^ Kelly, Sean M.; Lipshutz, Bruce H. (2014-01-
03).  "Chemoselective Reductions of Nitroaromatics
in Water at Room Temperature".  Organic
Letters.  16  (1): 98–
101.  doi:10.1021/ol403079x.  ISSN  1523-7060. PM
C 4013784. PMID 24341483.
33. ^ Ung, Stéphane; Falguières, Annie; Guy, Alain;
Ferroud, Clotilde (August 2005).  "Ultrasonically
activated reduction of substituted nitrobenzenes to
corresponding N-arylhydroxylamines".  Tetrahedron
Letters.  46  (35): 5913–
5917.  doi:10.1016/j.tetlet.2005.06.126.
34. ^ Braun, V. J.; Sobecki, W. (1911). "Über primäre
Dinitro-, Nitronitrit- und Dialdoxim-Verbindungen der
Fettreihe".  Ber.  44  (3): 2526–
2534.  doi:10.1002/cber.19110440377.
35. ^ J. R. Hanson & E. Premuzic (1967). "Applications
of chromous chloride--II  : The reduction of some
steroidal nitro-compounds". Tetrahedron.  23  (10):
4105–4110.  doi:10.1016/S0040-4020(01)97921-9.
36. ^ C. Grundmann (1950). "Über die partielle
Reduktion von Nitro-cyclohexan". Angewandte
 Chemie.  62  (23–24): 558–
560.  doi:10.1002/ange.19500622304.

Categories: 
 Organic redox reactions
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Lithium aluminium hydride

From Wikipedia, the free encyclopedia
Jump to navigationJump to search

Names

Preferred IUPAC name

Lithium tetrahydridoaluminate(III)

Systematic IUPAC name

Lithium alumanuide

Other names

Lithium aluminium hydride

Lithal

Lithium alanate

Lithium aluminohydride

Lithium tetrahydridoaluminate

Identifiers

CAS Number  16853-85-3 

 14128-54-2 (2H4) 

3D model (JSmol)  Interactive image

Abbreviations LAH

ChEBI  CHEBI:30142 

ChemSpider  26150 

ECHA InfoCard 100.037.146 

EC Number  240-877-9

Gmelin Reference 13167

PubChem CID  28112

 11062293 (2H4)

 11094533 (3H4)

RTECS number  BD0100000

UNII  77UJC875H4 

CompTox  DTXSID70893441 
Dashboard (EPA)

show
InChI

show

SMILES

Properties

Chemical formula LiAlH4

Molar mass 37.95 g/mol

Appearance white crystals (pure samples)

grey powder (commercial material)

hygroscopic

Odor odorless

Density 0.917 g/cm3, solid

Melting point 150 °C (302 °F; 423 K) (decomposes)

Solubility in water Reacts

Solubility in tetrahyd 112.332 g/L

rofuran

Solubility in diethyl 39.5 g/100 mL

ether

Structure

Crystal structure monoclinic

Space group P21/c

Thermochemistry

Heat capacity (C) 86.4 J/mol K

Std molar 87.9 J/mol K

entropy (So298)

Std enthalpy of -117 kJ/mol

formation (ΔfH⦵298)

Gibbs free -48.4 kJ/mol

energy (ΔfG˚)

Hazards[2]

Safety data Lithium aluminium hydride

 sheet (SDS)

GHS labelling:

Pictograms

Signal word Danger

Hazard statements H260, H314

Precautionary P223, P231+P232, P280, P305+P351+P338, P37
statements
0+P378, P422[1]

NFPA [3]

704 (fire diamond)

3
2
2
W

Flash point 125 °C (257 °F; 398 K)

Related compounds

Related hydride aluminium hydride

sodium borohydride

sodium hydride

Sodium aluminium hydride

Except where otherwise noted, data are given for materials in

their standard state (at 25 °C [77 °F], 100 kPa).

 verify (what is   ?)

Infobox references

Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic

compound with the chemical formula LiAlH4. It is a grey solid. It was discovered by
Finholt, Bond and Schlesinger in 1947.[4] This compound is used as a reducing
agent in organic synthesis, especially for the reduction of esters, carboxylic acids,
and amides. The solid is dangerously reactive toward water, releasing
gaseous hydrogen (H2). Some related derivatives have been discussed for hydrogen
storage.
 Contents

 1Properties, structure, preparation

o 1.1Structure
o 1.2Preparation
o 1.3Solubility data
o 1.4Thermodynamic data
o 1.5Thermal decomposition
 2Applications
o 2.1Use in organic chemistry
o 2.2Inorganic chemistry
o 2.3Hydrogen storage
o 2.4Other tetrahydridoaluminiumates
 3See also
 4References
 5Further reading
 6External links

Properties, structure, preparation[edit]

SEM image of LAH powder

LAH is a colourless solid but commercial samples are usually gray due to
contamination.[5] This material can be purified by recrystallization from diethyl ether.
Large-scale purifications employ a Soxhlet extractor. Commonly, the impure gray
material is used in synthesis, since the impurities are innocuous and can be easily
separated from the organic products. The pure powdered material is pyrophoric, but not
its large crystals.[6] Some commercial materials contain mineral oil to inhibit reactions
with atmospheric moisture, but more commonly it is packed in moisture-proof plastic
sacks.[7]
LAH violently reacts with water, including atmospheric moisture, to liberate dihydrogen
gas. The reaction proceeds according to the following idealized equation: [5]
LiAlH4 + 4 H2O → LiOH + Al(OH)3 + 4 H2
This reaction provides a useful method to generate
hydrogen in the laboratory. Aged, air-exposed samples
often appear white because they have absorbed enough
moisture to generate a mixture of the white
compounds lithium hydroxide and aluminium hydroxide.[8]
Structure[edit]

The crystal structure of LAH; Li atoms are purple and AlH 4 tetrahedra are
tan.

LAH crystallizes in the monoclinic space group P21/c.

The unit cell has the dimensions: a = 4.82, b = 7.81,
and c = 7.92 Å, α = γ = 90° and β = 112°. In the structure,
Li+ centers are surrounded by five AlH−
4 tetrahedra. The Li  centers are bonded to
+

one hydrogen atom from each of the surrounding

tetrahedra creating a bipyramid arrangement. At high
pressures (>2.2 GPa) a phase transition may occur to give
β-LAH.[9]

X-ray powder diffraction pattern of as-received LiAlH4. The asterisk

designates an impurity, possibly LiCl.

Preparation[edit]
LiAlH4 was first prepared from the reaction between lithium
hydride (LiH) and aluminium chloride:[4][5]
4 LiH + AlCl3 → LiAlH4 + 3 LiCl
In addition to this method, the industrial synthesis
entails the initial preparation of sodium aluminium
hydride from the elements under high pressure and
temperature:[10]
 Na + Al + 2 H2 → NaAlH4
LiAlH4 is then prepared by a salt metathesis
reaction according to:
NaAlH4 + LiCl → LiAlH4 + NaCl
which proceeds in a high yield. LiCl is removed
by filtration from an ethereal solution of LAH,
with subsequent precipitation of LiAlH 4 to yield a
product containing around 1% w/w LiCl.[10]
An alternative preparation starts from LiH, and
metallic Al instead of AlCl3. Catalyzed by a small
quantity of TiCl3 (0.2%), the reaction proceeds
well using dimethylether as solvent. This method
avoids the cogeneration of salt.[11]
Solubility data[edit]
Solubility of LiAlH4 (mol/L)[12]

Temperature (°C)
Solvent
0 25 50 75 100

Diethyl ether – 5.92 – – –

THF – 2.96 – – –

Monoglyme 1.29 1.80 2.57 3.09 3.34

Diglyme 0.26 1.29 1.54 2.06 2.06

Triglyme 0.56 0.77 1.29 1.80 2.06

Tetraglyme 0.77 1.54 2.06 2.06 1.54

Dioxane – 0.03 – – –
 Dibutyl
– 0.56 – – –
ether

LAH is soluble in many ethereal solutions.

However, it may spontaneously decompose due
to the presence of catalytic impurities, though, it
appears to be more stable
in tetrahydrofuran (THF). Thus, THF is preferred
over, e.g., diethyl ether, despite the lower
solubility.[12]
Thermodynamic data[edit]
The table summarizes thermodynamic data for
LAH and reactions involving LAH,[13][14] in the form
of standard enthalpy, entropy, and Gibbs free
energy change, respectively.

Thermodynamic data for reactions involving LiAlH4

ΔH° ΔS° ΔG°

Reaction (kJ/mol (J/(mol·K) (kJ/mol Comment
) ) )

Li (s) + Al (s) + 2 H2(g) →

−116.3 −240.1 −44.7 Standard formation from the elements.
LiAlH4 (s)

Using ΔH°f(LiH) = −90.579865,

LiH (s) + Al (s) + 3⁄2 H2 (g)
−95.6 −180.2 237.6 ΔS°f(LiH) = −679.9, and ΔG°f(LiH) =
→ LiAlH4 (s)
−67.31235744.

Heat of fusion. Value might be

LiAlH4 (s) → LiAlH4 (l) 22 – –
unreliable.

LiAlH4 (l) → 1⁄3 Li3AlH6 (s) ΔS° calculated from reported values of

3.46 104.5 −27.68
+ 2⁄3 Al (s) + H2 (g) ΔH° and ΔG°.

Thermal decomposition[edit]
LAH is metastable at room temperature. During
prolonged storage it slowly decomposes to
 Li3AlH6 and LiH.[15] This process can be
accelerated by the presence
of catalytic elements, such
as titanium, iron or vanadium.

Differential scanning calorimetry of as-received LiAlH4.

When heated LAH decomposes in a three-

step reaction mechanism:[15][16][17]
3 LiAlH4 → Li3AlH6 + 2  
 
(R
Al + 3 H2 1)
 

2 Li3AlH6 → 6 LiH + 2  
 
(R
Al + 3 H2 2)
 

2 LiH + 2 Al → 2  
 
(R
LiAl + H2 3)
 

R1 is usually initiated by

the melting of LAH in the temperature
range 150–170 °C,[18][19][20] immediately
followed by decomposition into solid
Li3AlH6, although R1 is known to
proceed below the melting point of
LiAlH4 as well.[21] At about 200 °C,
Li3AlH6 decomposes into LiH (R2)[15][17]
[20]
 and Al which subsequently convert
into LiAl above 400 °C (R3).
[17]
 Reaction R1 is effectively
irreversible. R3 is reversible with an
equilibrium pressure of about 0.25
bar at 500 °C. R1 and R2 can occur
at room temperature with suitable
catalysts.[22]

Applications[edit]
Use in organic chemistry[edit]
Lithium aluminium hydride (LiAlH4) is
widely used in organic chemistry as
a reducing agent.[5] It is more powerful
than the related reagent sodium
borohydride owing to the weaker Al-H
bond compared to the B-H bond.
[23]
 Often as a solution in diethyl
ether and followed by an acid workup,
it will convert esters, carboxylic
acids, acyl chlorides, aldehydes,
and ketones into the
corresponding alcohols (see: carbony
l reduction). Similarly, it
converts amide,[24][25] nitro, nitrile, imin
e, oxime,[26] and organic azides into
the amines (see: amide reduction). It
reduces quaternary ammonium
cations into the corresponding tertiary
amines. Reactivity can be tuned by
replacing hydride groups by alkoxy
groups. Due to its pyrophoric nature,
instability, toxicity, low shelf life and
handling problems associated with its
reactivity, it has been replaced in the
last decade, both at the small-
industrial scale and for large-scale
reductions by the more convenient
related reagent sodium bis (2-
methoxyethoxy)aluminium hydride,
which exhibits similar reactivity but
with higher safety, easier handling
and better economics.[27]
LAH is most commonly used for the
reduction of esters[28][29] and carboxylic
acids[30] to primary alcohols; prior to
the advent of LiAlH4 this was a difficult
conversion involving sodium metal in
boiling ethanol (the Bouveault-Blanc
reduction). Aldehydes and ketones[31] 
can also be reduced to alcohols by
LAH, but this is usually done using
milder reagents such as NaBH4; α, β-
unsaturated ketones are reduced to
allylic alcohols.[32] When epoxides are
reduced using LAH, the reagent
attacks the less hindered end of the
epoxide, usually producing a
secondary or tertiary
alcohol. Epoxycyclohexanes are
reduced to give axial alcohols
preferentially.[33]
Partial reduction of acid chlorides to
give the corresponding aldehyde
product cannot proceed via LAH,
since the latter reduces all the way to
the primary alcohol. Instead, the
milder lithium aluminium tri(t-
butoxy)hydride, which reacts
significantly faster with the acid
chloride than with the aldehyde, must
be used. For example,
when isovaleric acid is treated
with thionyl chloride to give
isovaleroyl chloride, it can then be
reduced via lithium aluminium tri(t-
butoxy)hydride to give
isovaleraldehyde in 65% yield.[34]

Lithium aluminium hydride also

reduces alkyl halides to alkanes.[35]
[36]
 Alkyl iodides react the fastest,
followed by alkyl bromides and then
 alkyl chlorides. Primary halides are
the most reactive followed by
secondary halides. Tertiary halides
react only in certain cases.[37]
Lithium aluminium hydride does not
reduce
simple alkenes or arenes. Alkynes ar
e reduced only if an alcohol group is
nearby.[38] It was observed that the
LiAlH4 reduces the double bond in the
N-allylamides.[39]
Inorganic chemistry[edit]
LAH is widely used to prepare main
group and transition metal
hydrides from the corresponding
metal halides. For example, sodium
hydride (NaH) can be prepared
from sodium chloride (NaCl) through
the following reaction:[13]
LiAlH4 + 4 NaCl → 4 NaH + LiCl + AlCl3
LAH also reacts with many
inorganic ligands to form
coordinated alumina complexes
associated with lithium ions.[13]
LiAlH4 + 4NH3 → Li[Al(NH2)4] + 4H2
Hydrogen storage[edit]

Volumetric and gravimetric

hydrogen storage densities of
different hydrogen storage
methods. Metal hydrides are
 represented with squares and
complex hydrides with triangles
(including LiAlH4). Reported values
for hydrides are excluding tank
weight. DOE FreedomCAR targets
are including tank weight.

LiAlH4 contains 10.6 wt%

hydrogen, thereby making
LAH a potential hydrogen
storage medium for future fuel
cell-powered vehicles. The
high hydrogen content, as well
as the discovery of reversible
hydrogen storage in Ti-doped
NaAlH4,[40] have sparked
renewed research into
LiAlH4 during the last decade.
A substantial research effort
has been devoted to
accelerating the
decomposition kinetics by
catalytic doping and by ball
milling.[41] In order to take
advantage of the total
hydrogen capacity, the
intermediate
compound LiH must be
dehydrogenated as well. Due
to its high thermodynamic
stability this requires
temperatures in excess of
400 °C, which is not
considered feasible for
transportation purposes.
Accepting LiH + Al as the final
product, the hydrogen storage
capacity is reduced to 7.96 wt
%. Another problem related to
hydrogen storage is the
recycling back to LiAlH4 which,
owing to its relatively low
stability, requires an extremely
high hydrogen pressure in
excess of 10000 bar.[41] Cycling
only reaction R2 — that is,
 using Li3AlH6 as starting
material — would store 5.6 wt
% hydrogen in a single step
(vs. two steps for
NaAlH4 which stores about the
same amount of hydrogen).
However, attempts at this
process have not been
successful so far.[citation needed]
Other
tetrahydridoaluminium
ates[edit]
A variety of salts analogous to
LAH are known. NaH can be
used to efficiently
produce sodium aluminium
hydride (NaAlH4)
by metathesis in THF:
LiAlH4 + NaH → NaAlH4 + LiH
Potassium aluminium
hydride (KAlH4) can be
produced similarly
in diglyme as a solvent:[42]
LiAlH4 + KH → KAlH4 + LiH
The reverse, i.e.,
production of LAH from
either sodium
aluminium hydride or
potassium aluminium
hydride can be
achieved by reaction
with LiCl or lithium
hydride in diethyl
ether or THF:[42]
NaAlH4 + LiCl → LiAlH4 + NaCl
KAlH4 + LiCl → LiAlH4 + KCl
"Magnesium
alanate"
(Mg(AlH4)2)
arises similarly
using MgBr2:[43]
2 LiAlH4 + MgBr2 → Mg(AlH4)2 + 2 LiBr
 Red-Al (or
SMEAH,
NaAlH2(OC2
H4OCH3)2) is
synthesized
by reacting
sodium
aluminum
tetrahydride
(NaAlH4)
and 2-
methoxyeth
anol:[44]

See
also[edit]
Wikimedia Commons has
media related to lithium
aluminium hydride.

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6. 
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53
,
31
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,
pp 
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55
at
p 
47
2.
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hi
u
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ni
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m
hy
dri
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mp
up
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b
 
Fi
n
h
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A.
E.
;
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o
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C.
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c
hl
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all
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p
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or
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a
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m
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of
th
e
A
m
er
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a
n
C
h
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m
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al
S
o
ci
et
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6
9 
(5
):
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1
9
9
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1
2
0
3. 
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oi
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1
0
2
1/
ja
0
1
1
9
7
a
0
6
1.
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mp
up
to:a
 
  
b c

d
 
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er
ra
n
s,
G
.
C.
;
H
ar
t
m
a
n
n-
P
et
er
s
e
n,
P.
(2
0
0
7)
. "
Li
th
iu
m
Al
u
m
ini
u
m
H
y
dr
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e"
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a
s
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E
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cl
 o
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of
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ci
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e
w
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a
B
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ks
.
p. 
1
4
3. 
IS
B
N 
9
7
8-
1-
8
6
9
2
8-
3
8
4-
1.
6. ^ 
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e
e
s
e,
R.
;
Br
ä
n
dl
e,
M
.;
T
o
u
b
e,
T.
P.
(2
0
0
6)
. 
Pr
a
cti
c
al
O
rg
a
ni
c
S
y
nt
h
e
si
s:
A
St
u
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e
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s
G
ui
d
e.
J
o
h
n
W
ile
 y
a
n
d
S
o
n
s.
p. 
1
3
4. 
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B
N 
0-
4
7
0-
0
2
9
6
6-
8.
7. ^ 
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n
dr
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a
s
e
n,
A.
;
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e
g
g
e,
T.
;
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d
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s
e
n,
A.
S.
(2
0
0
5)
. "
D
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dr
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e
n
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n
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of
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s-
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c
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d
a
n
d
B
all
-
M
ill
e
d
Li
Al
H4
"  (
P
D
F)
. 
J
o
ur
n
al
of
S
oli
d
St
at
e
C
h
e
m
ist
ry
. 
1
7
8 
(1
2)
:
3
6
7
2
–
3
6
7
8. 
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b
c
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2
0
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J
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1
7
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3
6
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7.
8. ^ 
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1
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Li3
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12. ^ 
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in
of
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A
c
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2
 0 
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2
5
0
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1
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3
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1
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13. ^ 
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mp
up
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b c

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. 
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b
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ra
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ll.
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4
9
2. 
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B
N 
9
7
8-
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7-
0
4
9
4
3
9-
8.
14. ^ 
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m
it
h,
M
.
B.
;
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a
ss
,
G
.
E.
(1
9
6
3)
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s
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of
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u
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H
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dr
id
e"
. 
J
 o
ur
n
al
of
C
h
e
m
ic
al
&
E
n
gi
n
e
er
in
g
D
at
a. 
8 
(3
):
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4
2
–
3
4
6. 
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0.
1
0
2
1/
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6
0
0
1
8
a
0
2
0.
15. ^ 
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mp
up
to:a
 
  
b c

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;
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a
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v,
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P.
;
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v,
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;
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lin
a,
T.
A.
;
Si
z
ar
e
v
a;
A.
S.
(1
9
9
4)
. 
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u
ss
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n
J
o
ur
n
al
of
C
 o
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di
n
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n
C
h
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m
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. 
2
0:
2
7
9. 
Mi
ss
in
g
or
e
m
pt
y 
|
t
i
t
l
e
= 
(h
el
p)
16. ^ 
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lts
,
J.
A.
;
A
s
h
b
y,
E.
C.
(1
9
7
2)
.
"T
h
er
m
al
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o
m
p
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e
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n
or
g
a
ni
c
C
h
e
m
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. 
1
1 
(6
):
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2
3
0
–
1
2
3
6. 
d
oi
 :1
0.
1
0
2
1/
ic
5
0
1
1
2
a
0
1
5.
17. ^ 
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mp
up
to:a
 
  
b c

Bl
a
n
c
h
ar
d,
D.
;
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in
ks
,
H.
;
H
a
u
b
a
ck
,
B.
;
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or
b
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P.
(2
0
0
4)
.
"
D
e
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or
pt
io
n
of
Li
Al
H4 
wi
th
Ti
-
a
n
d
V-
B
a
s
e
d
A
d
di
tiv
e
s"
. 
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at
er
ial
s
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e
n
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a
n
d
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n
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n
e
er
in
g
B. 
1
0
8 
(1
–
2)
:
 5
4
–
5
9. 
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oi
:1
0.
1
0
1
6/
j.
m
s
e
b.
2
0
0
3.
1
0.
1
1
4.
18. ^ 
C
h
e
n,
J.
;
K
ur
iy
a
m
a,
N.
;
X
u,
Q
.;
T
a
k
e
s
hi
ta
,
H.
T.
;
S
a
k
ai
,
T.
(2
0
0
1)
.
"
R
e
v
er
si
bl
e
H
y
dr
o
g
e
n
St
or
a
g
e
vi
a
Ti
ta
ni
u
m
-
C
at
al
yz
e
d
Li
Al
H4 
a
n
d
Li3
Al
H6
". 
T
h
e
J
o
ur
 n
al
of
P
h
ys
ic
al
C
h
e
m
ist
ry
B. 
1
0
5 
(4
5)
:
1
1
2
1
4
–
1
1
2
2
0. 
d
oi
:1
0.
1
0
2
1/
jp
0
1
2
1
2
7
w.
19. ^ 
B
al
e
m
a,
V.
;
P
e
c
h
ar
sk
y,
V.
K.
;
D
e
n
ni
s,
K.
W
.
(2
0
0
0)
. "
S
oli
d
St
at
e
P
h
a
s
e
Tr
a
n
sf
or
m
at
io
n
s
in
Li
Al
H4 
d
ur
in
g
Hi
g
h-
E
n
er
g
y
B
all
-
M
illi
n
g"
. 
J
o
ur
n
al
of
Al
lo
ys
a
n
d
C
o
m
p
o
u
n
d
s. 
3
1
3 
(1
–
2)
:
6
9
–
7
4. 
d
oi
:1
0.
1
0
1
6/
S
0
9
2
5-
8
3
8
8(
0
0)
0
 1
2
0
1-
9.
20. ^ 
Ju
mp
up
to:a
 
b
 
A
n
dr
e
a
s
e
n,
A.
(2
0
0
6)
.
"E
ff
e
ct
of
Ti
-
D
o
pi
n
g
o
n
th
e
D
e
h
y
dr
o
g
e
n
at
io
n
Ki
n
et
ic
P
ar
a
m
et
er
s
of
Li
th
iu
m
Al
u
m
in
u
m
H
y
dr
id
e"
. 
J
o
ur
n
al
of
Al
lo
ys
a
n
d
C
o
m
p
o
u
n
d
s. 
4
1
9 
(1
–
2)
:
4
0
–
4
4. 
d
oi
:1
0.
 1
0
1
6/
j.j
all
c
o
m
.2
0
0
5.
0
9.
0
6
7.
21. ^ 
A
n
dr
e
a
s
e
n,
A.
;
P
e
d
er
s
e
n,
A.
S.
;
V
e
g
g
e,
T.
(2
0
0
5)
.
"
D
e
h
y
dr
o
g
e
n
at
io
n
Ki
n
et
ic
s
of
a
s-
R
e
c
ei
v
e
d
a
n
d
B
all
-
M
ill
e
d
Li
Al
H4
". 
J
o
ur
n
al
of
S
oli
d
St
at
e
C
h
e
m
ist
ry
. 
1
7
8 
(1
2)
:
3
 6
7
2
–
3
6
7
8. 
Bi
b
c
o
d
e:
2
0
0
5
J
S
S
C
h.
1
7
8.
3
6
7
2
A. 
d
oi
:1
0.
1
0
1
6/
j.j
ss
c.
2
0
0
5.
0
9.
0
2
7.
22. ^ 
B
al
e
m
a,
V.
;
W
ie
n
c
h,
J.
W
.;
D
e
n
ni
s,
K.
W
.;
Pr
u
sk
i,
M
.;
P
e
c
h
ar
sk
y,
V.
K.
(2
0
0
1)
. "
Ti
ta
ni
u
m
C
at
al
yz
e
d
S
oli
d-
St
at
e
Tr
a
n
sf
or
m
at
io
n
s
in
Li
Al
H4 
D
ur
in
g
Hi
g
h-
E
n
er
g
y
B
all
-
M
illi
n
g"
. 
J
o
ur
n
al
of
Al
lo
ys
a
n
d
C
o
m
p
o
u
n
d
s. 
3
2
9 
(1
–
2)
:
1
0
8
 –
1
1
4. 
d
oi
:1
0.
1
0
1
6/
S
0
9
2
5-
8
3
8
8(
0
1)
0
1
5
7
0-
5.
23. ^ 
Br
o
w
n,
H.
C.
(1
9
5
1)
.
"
R
e
d
u
cti
o
n
s
b
y
Li
th
iu
m
Al
u
m
in
u
m
H
y
dr
id
e"
. 
O
rg
a
ni
c
R
e
a
cti
o
n
s. 
6:
4
6
9. 
d
oi
:1
0.
1
0
0
2/
0
4
7
1
2
6
4
1
8
0.
or
0
0
6.
1
0. 
IS
B
N 
0
4
7
1
2
6
4
 1
8
0.
24. ^ 
S
e
e
b
a
c
h,
D.
;
K
ali
n
o
w
sk
i,
H.
-
O
.;
L
a
n
g
er
,
W
.;
C
ra
ss
,
G
.;
W
ilk
a,
E.
-
M
.
(1
9
9
1)
. "
C
hi
ra
l
M
e
di
a
fo
r
A
sy
m
m
et
ri
c
S
ol
v
e
nt
In
d
u
cti
o
n
s.
(S
,S
)-(
+
)-
1,
4-
bi
s(
Di
m
et
h
yl
a
m
in
o)
-
2,
3-
Di
m
et
h
o
xy
b
ut
a
n
e
fr
o
m
(
R,
R
)-(
 +
)-
Di
et
h
yl
T
ar
tr
at
e"
. 
O
rg
a
ni
c
S
y
nt
h
e
s
e
s.; 
C
oll
e
cti
v
e
V
ol
u
m
e, 
7,
p. 
4
1
25. ^ 
P
ar
k,
C.
H.
;
Si
m
m
o
n
s,
H.
E.
(1
9
7
4)
. "
M
a
cr
o
cy
cli
c
Di
i
m
in
e
s:
1,
1
0-
Di
a
z
a
cy
cl
o
o
ct
a
d
e
c
a
n
e"
. 
O
rg
a
ni
c
S
y
nt
h
e
s
e
s. 
5
4:
8
8.; 
C
oll
e
cti
v
e
V
ol
 u
m
e, 
6,
p. 
3
8
2
26. ^ 
C
h
e
n,
Y.
K.
;
J
e
o
n,
S.
-
J.
;
W
al
s
h,
P.
J.
;
N
u
g
e
nt
,
W
.
A.
(2
0
0
5)
. "
(2
S)
-
(−
)-
3-
e
x
o-
(
M
or
p
h
 oli
n
o)
Is
o
b
or
n
e
ol
". 
O
rg
a
ni
c
S
y
nt
h
e
s
e
s. 
8
2:
8
7.
27. ^ 
"
R
e
d-
Al
,
S
o
di
u
m
bi
s(
2-
m
et
h
o
xy
et
h
o
xy
)a
lu
m
in
u
m
h
 y
dr
id
e"
.
O
rg
a
ni
c
C
h
e
m
ist
ry
P
or
ta
l.
28. ^ 
R
e
et
z,
M
.
T.
;
D
re
w
e
s,
M
.
W
.;
S
c
h
wi
ck
ar
di
,
R.
(1
9
9
9)
. "
Pr
e
p
ar
at
io
n
of
E
n
a
nt
io
m
er
ic
all
y
P
ur
e
α-
N,
N
-
Di
b
e
n
zy
la
m
in
o
Al
d
e
h
y
d
e
s:
S-
2-
(
N,
N
-
Di
b
e
n
zy
la
m
in
o)
-
3-
P
h
e
n
yl
pr
o
 p
a
n
al
". 
O
rg
a
ni
c
S
y
nt
h
e
s
e
s. 
7
6:
1
1
0.; 
C
oll
e
cti
v
e
V
ol
u
m
e, 
1
0,
p. 
2
5
6
29. ^ 
Oi
,
R.
;
S
h
ar
pl
e
ss
,
K.
B.
(1
9
9
6)
. "
3-
[(
1
S)
-
1,
2-
Di
h
y
dr
o
xy
et
h
yl]
-
1,
5-
Di
h
y
dr
o-
3
H
-
2,
4-
B
e
n
z
o
di
o
x
e
pi
n
e"
. 
O
rg
a
ni
c
S
y
nt
h
e
s
e
s. 
7
3:
1.; 
C
 oll
e
cti
v
e
V
ol
u
m
e, 
9,
p. 
2
5
1
30. ^ 
K
o
p
p
e
n
h
o
ef
er
,
B.
;
S
c
h
ur
ig
,
V.
(1
9
8
8)
. "
(
R
)-
Al
ky
lo
xi
ra
n
e
s
of
Hi
g
h
E
n
a
nt
io
m
er
ic
P
ur
ity
fr
o
m
(S
)-
2-
C
hl
or
o
al
k
a
n
oi
c
A
ci
d
s
vi
a
(S
)-
2-
C
hl
or
o-
1-
Al
k
a
n
ol
s:
(
R
)-
M
et
h
yl
o
xi
ra
n
e"
. 
O
rg
 a
ni
c
S
y
nt
h
e
s
e
s. 
6
6:
1
6
0.; 
C
oll
e
cti
v
e
V
ol
u
m
e, 
8,
p. 
4
3
4
31. ^ 
B
ar
ni
er
,
J.
P.
;
C
h
a
m
pi
o
n,
J.
;
C
o
ni
a,
J.
M
.
(1
9
8
1)
. "
C
yc
lo
pr
o
p
a
n
e
c
ar
b
o
x
al
d
e
h
y
d
e"
. 
O
rg
a
ni
c
S
y
nt
h
e
s
e
s. 
6
0:
2
5.; 
C
oll
e
cti
v
e
V
ol
u
m
e, 
7,
p. 
1
2
9
32. ^ 
El
p
hi
m
of
f-
F
el
ki
n,
I.;
S
ar
d
a,
P.
(1
9
7
7)
. "
R
e
d
u
cti
v
e
Cl
e
a
v
a
g
e
of
Al
lyl
ic
Al
c
o
h
ol
s,
Et
h
er
s,
or
A
c
et
at
e
s
to
Ol
 ef
in
s:
3-
M
et
h
yl
cy
cl
o
h
e
x
e
n
e"
. 
O
rg
a
ni
c
S
y
nt
h
e
s
e
s. 
5
6:
1
0
1.; 
C
oll
e
cti
v
e
V
ol
u
m
e, 
6,
p. 
7
6
9
33. ^ 
Ri
ck
b
or
n,
B.
;
Q
u
ar
tu
cc
i,
J.
(1
9
6
4)
.
"S
te
re
o
c
h
e
m
ist
ry
a
n
d
M
e
c
h
a
ni
s
m
of
Li
th
iu
m
Al
u
m
in
u
m
H
y
dr
id
e
a
n
d
M
ix
e
d
H
y
dr
id
e
R
e
d
u
cti
o
n
of
4-
t-
B
ut
yl
cy
cl
o
h
e
x
e
n
e
O
xi
d
e"
. 
T
h
e
J
o
ur
n
al
of
O
rg
a
ni
c
C
h
e
m
ist
ry
. 
2
9 
(1
1)
:
3
1
8
 5
–
3
1
8
8. 
d
oi
:1
0.
1
0
2
1/
jo
0
1
0
3
4
a
0
1
5.
34. ^ 
W
a
d
e,
L.
G
.
Jr
.
(2
0
0
6)
. 
O
rg
a
ni
c
C
h
e
m
ist
ry 
(6
th 
e
d.
).
P
e
ar
s
 o
n
Pr
e
nt
ic
e
H
all
. I
S
B
N 
0-
1
3-
1
4
7
8
7
1-
0.
35. ^ 
J
o
h
n
s
o
n,
J.
E.
;
Bl
iz
z
ar
d,
R.
H.
;
C
ar
h
ar
t,
H.
W
.
(1
9
4
8)
.
"
H
y
dr
o
g
e
n
ol
ys
is
of
Al
ky
l
H
ali
d
e
s
b
y
Li
th
iu
m
Al
u
m
in
u
m
H
y
dr
id
e"
. 
J
o
ur
n
al
of
th
e
A
m
er
ic
a
n
C
h
e
m
ic
al
S
o
ci
et
y. 
 7
0 
(1
1)
:
3
6
6
4
–
3
6
6
5. 
d
oi
:1
0.
1
0
2
1/
ja
0
1
1
9
1
a
0
3
5. 
P
M
ID 
1
8
1
2
1
8
8
3.
36. ^ 
Kr
is
h
n
a
m
ur
th
y,
S.
;
Br
o
w
n,
H.
C.
(1
9
8
2)
.
"S
el
e
cti
v
e
R
e
d
u
cti
o
n
s.
2
8.
T
h
e
F
a
st
R
e
a
cti
o
n
of
Li
th
iu
m
Al
u
m
in
u
m
H
y
dr
id
e
wi
th
Al
ky
l
H
ali
d
e
s
in
T
H
F.
A
R
e
a
p
pr
ai
s
al
of
th
e
S
c
o
p
e
of
th
e
R
e
a
cti
o
n"
. 
T
h
e
J
o
ur
n
al
of
O
rg
a
ni
c
C
h
e
m
ist
ry
. 
4
7 
(2
):
2
 7
6
–
2
8
0. 
d
oi
:1
0.
1
0
2
1/
jo
0
0
3
4
1
a
0
1
8.
37. ^ 
C
ar
ru
th
er
s,
W
.
(2
0
0
4)
. 
S
o
m
e
M
o
d
er
n
M
et
h
o
d
s
of
O
rg
a
ni
c
 S
y
nt
h
e
si
s.
C
a
m
br
id
g
e
U
ni
v
er
sit
y
Pr
e
ss
.
p. 
4
7
0. 
IS
B
N 
0-
5
2
1-
3
1
1
1
7-
9.
38. ^ 
W
e
n
d
er
,
P.
A.
;
H
ol
t,
D.
A.
;
Si
e
b
ur
th
,
S.
M
c
N.
(1
9
8
6)
. "
2-
Al
k
e
n
yl
C
ar
bi
n
ol
s
fr
o
m
2-
H
al
o
K
et
o
n
e
s:
2-
E-
Pr
o
p
e
n
yl
cy
cl
o
h
e
x
a
n
ol
". 
O
rg
a
 ni
c
S
y
nt
h
e
s
e
s. 
6
4:
1
0.; 
C
oll
e
cti
v
e
V
ol
u
m
e, 
7,
p. 
4
5
6
39. ^ 
T
hi
e
d
e
m
a
n
n,
B.
;
S
c
h
m
itz
,
C.
M
.;
St
a
u
bi
tz
,
A.
(2
0
1
4)
.
"
R
e
d
u
cti
o
n
of
N
-
all
yl
a
m
id
e
s
b
y
Li
Al
H4
:
U
n
e
x
p
e
ct
e
d
At
ta
ck
of
th
e
D
o
u
bl
e
B
o
n
d
W
it
h
M
e
c
h
a
ni
sti
c
St
u
di
e
s
of
Pr
o
d
u
ct
a
n
d
B
y
pr
o
d
u
ct
F
or
m
at
io
n"
. 
T
h
e
J
o
ur
n
al
of
O
rg
a
ni
c
C
h
e
m
ist
ry
. 
7
9 
(2
1)
:
1
 0
2
8
4
–
9
5. 
d
oi
:1
0.
1
0
2
1/
jo
5
0
1
9
0
7
v. 
P
M
ID 
2
5
3
4
7
3
8
3.
40. ^ 
B
o
g
d
a
n
o
vi
c,
B.
;
S
c
h
wi
ck
ar
di
,
M
.
(1
9
9
7)
.
"T
i-
D
o
p
e
d
Al
k
ali
M
et
al
Al
u
m
ini
u
m
H
y
dr
id
e
s
a
s
P
ot
e
nt
ial
N
o
v
el
R
e
v
er
si
bl
e
H
y
dr
o
g
e
n
St
or
a
g
e
M
at
er
ial
s"
. 
J
o
ur
n
al
of
Al
lo
ys
a
n
d
C
o
m
p
o
u
n
d
s.
2
5
3
–
2
5
4:
1
–
9. 
d
oi
:1
0.
1
0
1
6/
S
0
9
2
5-
8
3
8
8(
9
6)
0
3
0
4
 9-
6.
41. ^ 
Ju
mp
up
to:a
 
b
 
V
ar
in
,
R.
A.
;
C
z
uj
k
o,
T.
;
W
ro
n
sk
i,
Z.
S.
(2
0
0
9)
. 
N
a
n
o
m
at
er
ial
s
fo
r
S
oli
d
St
at
e
H
y
dr
o
g
e
n
St
 or
a
g
e 
(5
th 
e
d.
).
S
pr
in
g
er
.
p. 
3
3
8. 
IS
B
N 
9
7
8-
0-
3
8
7-
7
7
7
1
1-
5.
42. ^ 
Ju
mp
up
to:a
 
b
 
S
a
nt
h
a
n
a
m
,
R.
;
M
c
G
ra
d
y,
G
.
S.
(2
0
0
8)
.
"S
y
nt
h
e
si
s
of
Al
k
ali
M
et
al
H
e
x
a
h
y
dr
o
al
u
m
in
at
e
C
o
m
pl
e
x
e
s
U
si
n
g
Di
m
et
h
yl
Et
h
er
a
s
a
R
e
a
cti
o
n
M
e
di
u
m
". 
In
or
g
a
ni
c
a
C
hi
m
ic
a
A
ct
a. 
3
6
1 
(2
):
4
7
3
–
4
7
8. 
d
oi
:1
0.
1
0
1
6/
j.i
c
a.
2
0
0
7.
0
4.
0
4
4.
43. ^ 
W
ib
er
g,
E.
;
W
ib
er
g,
N.
;
H
oll
e
m
a
n,
A.
F.
(2
0
0
1)
. I
n
or
g
a
ni
c
C
h
e
m
ist
ry
.
A
c
a
d
e
m
ic
Pr
e
ss
.
p. 
1
0
5
6. 
IS
B
N 
0-
 1
2-
3
5
2
6
5
1-
5.
44. ^ 
C
a
s
e
n
sk
y,
B.
;
M
a
c
h
a
c
e
k,
J.
;
A
br
a
h
a
m
,
K.
(1
9
7
1)
.
"T
h
e
c
h
e
m
ist
ry
of
s
o
di
u
m
al
k
o
xy
al
u
m
ini
u
m
h
y
dr
id
e
s.
I.
S
y
nt
h
e
si
s
of
s
o
di
u
m
bi
s(
2-
m
et
h
o
xy
et
h
o
xy
)a
lu
m
ini
u
m
h
y
dr
id
e"
. 
C
oll
e
cti
o
n
of
C
z
e
c
h
o
sl
o
v
a
k
C
h
e
m
ic
al
C
o
m
m
u
ni
c
at
io
n
s. 
3
6 
(7
):
2
6
4
8
–
2
6
5
7. 
d
oi
:1
0.
1
1
3
5/
cc
cc
1
9
7
1
2
6
4
8.
Further
reading[
edit]

 W
ib
er
g,
E
.;
A
m
b
er
g
er
,
E
.
(1
9
7
1)
. 
H
y
dr
id
e
s
of
th
e
El
e
m
e
nt
s
of
M
ai
n
G
ro
 u
p
s
I-
I
V
.
El
s
e
vi
er
. 
I
S
B
N 
0-
4
4
4-
4
0
8
0
7-
X
.
 H
aj
o
s,
A
.
(1
9
7
9)
. 
C
o
m
pl
e
x
H
y
dr
id
e
s
a
n
d
R
el
at
e
d
R
e
d
u
ci
n
g
A
g
e
nt
s
in
O
rg
a
ni
c
S
y
nt
h
e
si
s.
El
s
e
vi
er
. 
I
S
 B
N 
0-
4
4
4-
9
9
7
9
1-
1.
 Li
d
e,
D
.
R
.,
e
d.
(1
9
9
7)
. 
H
a
n
d
b
o
o
k
of
C
h
e
m
is
tr
y
a
n
d
P
 h
y
si
c
s.
C
R
C
P
re
s
s. 
I
S
B
N 
0-
8
4
9
3-
0
4
7
8-
4.
 C
ar
e
y,
F.
A
.
(2
0
0
2)
. 
O
rg
a
ni
c
C
h
e
m
is
tr
y
w
it
h
O
nl
in
e
L
e
ar
ni
n
g
C
e
nt
er
a
n
d
L
e
ar
ni
n
g
b
y
M
o
d
el
C
D
-
R
O
M
.
M
c
G
 ra
w
-
H
ill
. 
I
S
B
N 
0-
0
7-
2
5
2
1
7
0-
8.
 A
n
dr
e
a
s
e
n,
A
.
(2
0
0
5)
. 
"
C
h
a
pt
er
5:
C
o
m
pl
e
x
H
y
dr
id
e
s" 
(P
D
F)
. 
H
y
dr
o
g
e
n
S
to
ra
g
e
M
at
er
ia
ls
w
it
h
F
o
c
u
s
o
n
M
ai
n
G
ro
u
p
I-
II
El
e
m
e
nt
s.
R
is
ø
N
at
io
n
al
L
a
b
or
at
or
y. 
I
S
B
N 
8
7-
5
5
0-
3
4
9
8-
5.
A
rc
hi
v
e
d
fr
o
m 
th
 e
or
ig
in
al 
(P
D
F) 
o
n
2
0
1
2-
0
8-
1
9.

Externa
l
links[edit]
Look up lithium
aluminium hydride in
Wiktionary, the free
dictionary.

 "
U
s
a
g
e
of
Li
Al
H
4".

O
rg
a
ni
c
S
 y
nt
h
e
s
e
s.
 "
Li
th
iu
m
T
et
ra
h
y
dr
id
o
al
u
m
in
at
e
-
C
o
m
p
o
u
n
d
S
u
m
m
ar
y
(
C
I
D
2
 8
1
1
2)
".
P
u
b
C
h
e
m
.
 "
Li
th
iu
m
T
et
ra
h
y
dr
id
o
al
u
m
in
at
e
". 
W
e
b
B
o
o
k.
N
I
S
T.
 "
M
at
er
ia
ls
S
af
et
y
D
at
a
S
h
e
et
".
C
or
n
el
l
U
ni
v
er
si
ty
.
A
rc
hi
v
e
d
fr
o
m 
th
e
or
ig
in
al 
o
n
M
 ar
c
h
8,
2
0
0
6.
 "
H
y
dr
id
e
In
fo
r
m
at
io
n
C
e
nt
er
".
S
a
n
di
a
N
at
io
n
al
L
a
b
or
at
or
y.
A
rc
hi
 v
e
d
fr
o
m 
th
e
or
ig
in
al 
o
n
M
a
y
7,
2
0
0
5.
 "
R
e
d
u
ct
io
n
R
e
a
ct
io
n
s" 
(P
D
F)
. 
T
e
a
c
hi
n
g
R
e
s
o
ur
c
e
s
-
4t
h
Y
e
ar
.
U
ni
v
er
si
ty
of
Bi
r
m
in
g
h
a
m
.
A
rc
hi
v
e
d
fr
o
m 
th
e
or
ig
in
 al 
(P
D
F) 
o
n
M
a
y
2
3,
2
0
1
6.
show

Lithium compounds (list)

show

Aluminium compounds
Categories: 
 Lithiu
m
comp
ound
s
 Alumi
nium
comp
lexes
 Metal
hydri
des
 Redu
cing
 agent
s
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