请输入您要查询的百科知识：

　

词条 Lithium aluminium hydride
释义

  1. Properties, structure, preparation

     Structure  Preparation  Solubility data  Thermodynamic data  Thermal decomposition 

  2. Applications

     Use in organic chemistry  Inorganic chemistry  Hydrogen storage  Other tetrahydridoaluminiumates 

  3. See also

  4. References

  5. Further reading

  6. External links

{{Chembox
| Watchedfields = changed
| verifiedrevid = 457117309
| ImageFileL1 = lithium aluminium hydride.svg
| ImageNameL1 = Wireframe model of lithium aluminium hydride
| ImageFileR1 = Lithium-aluminium-hydride-layer-3D-balls.png
| ImageNameR1 = Unit cell ball and stick model of lithium aluminium hydride
| ImageFile2 = Lithium aluminium hydride 100g.jpg
| ImageName2 = 100 grams of lithium aluminium hydride
| ImageSize2 = 100px
| PIN = Lithium tetrahydridoaluminate(III)
| SystematicName = Lithium alumanuide
| OtherNames = Lithium aluminium hydride

Lithal

Lithium alanate

Lithium aluminohydride

Lithium tetrahydridoaluminate

Lithium tetrahydridoaluminate(III)


|Section1={{Chembox Identifiers
| Abbreviations = LAH
| InChI = 1S/Al.Li.4H/q-1;+1;;;;
| InChIKey1 = OCZDCIYGECBNKL-UHFFFAOYSA-N
| CASNo = 16853-85-3
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo1_Ref = {{cascite|correct|??}}
| CASNo1 = 14128-54-2
| CASNo1_Comment = (2H4)
| PubChem = 28112
| PubChem1 = 11062293
| PubChem1_Comment = (2H4)
| PubChem2 = 11094533
| PubChem2_Comment = (3H4)
| ChemSpiderID = 26150
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| EINECS = 240-877-9
| ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 30142
| RTECS = BD0100000
| SMILES = [Li+].[AlH4-]
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/Al.Li.4H/q-1;+1;;;;
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = OCZDCIYGECBNKL-UHFFFAOYSA-N
| Gmelin = 13167
|Section2={{Chembox Properties
| Formula = LiAlH4
| MolarMass = 37.95 g/mol
| Appearance = white crystals (pure samples)
grey powder (commercial material)
hygroscopic
| Odor = odorless
| Density = 0.917 g/cm3, solid
| Solubility = Reacts
| Solvent1 = tetrahydrofuran
| Solubility1 = 112.332 g L−1
| Solvent2 = diethyl ether
| Solubility2= 39.5 g/100 mL
| MeltingPtC = 150
| MeltingPt_notes = (decomposes)
| BoilingPt =
|Section3={{Chembox Structure
| Coordination =
| CrystalStruct = monoclinic
| SpaceGroup = P21/c
| Dipole =
|Section4={{Chembox Thermochemistry
| DeltaHf = -117 kJ/mol
| DeltaGf = -48.4 kJ/mol
| Entropy = 87.9 J/mol K
| HeatCapacity = 86.4 J/mol K
|Section7={{Chembox Hazards
| Hazards_ref = [1]
| GHSPictograms = {{GHSp|GHS02}}{{GHSp|GHS05}}
| GHSSignalWord = DANGER
| HPhrases = {{H-phrases|260|314}}
| PPhrases = {{P-phrases|223|231+232|280|305+351+338|370+378|422}}[2]
| ExternalSDS = [https://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=PL&language=EN-generic&productNumber=199877&brand=ALDRICH&PageToGoToURL=https%3A%2F%2Fwww.sigmaaldrich.com%2Fcatalog%2Fproduct%2Faldrich%2F199877%3Flang%3Dpl Lithium aluminium hydride]
| NFPA-H = 3
| NFPA-R = 2
| NFPA-F = 2
| NFPA-S = W
| NFPA_ref = [3]
| FlashPtC = 125
|Section8={{Chembox Related
| OtherFunction_label = hydride
| OtherFunction = aluminium hydride
sodium borohydride
sodium hydride
Sodium aluminium hydride
}}

Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic compound with the chemical formula LiAlH4. 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.

Properties, structure, preparation

LAH is a colorless 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. 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

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 {{chem|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]

Preparation

LiAH 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 LiAH, with subsequent precipitation of LiAlH4 to yield a product containing around 1% w/w LiCl.[10]

An alternative preparation starts from LiH, metal 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

Solubility of LiAlH4 (mol/L)[12]
SolventTemperature (°C)
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 ether – 0.56 – – –

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]

{{clear}}

Thermodynamic data

The table summarizes thermodynamic data for LAH and reactions involving LAH,[18][13] in the form of standard enthalpy, entropy, and Gibbs free energy change, respectively.

Thermodynamic data for reactions involving LiAlH4
Reaction ΔH°
(kJ/mol) 		ΔS°
(J/(mol·K)) 		ΔG°
(kJ/mol) 		Comment
Li (s) + Al (s) + 2 H2(g) → LiAlH4 (s) −116.3 −240.1 −44.7 Standard formation from the elements.
LiH (s) + Al (s) + {{frac|3|2}} H2 (g) → LiAlH4 (s) −95.6 −180.2 237.6 Using ΔH°f(LiH) = −90.579865, ΔS°f(LiH) = −679.9, and ΔG°f(LiH) = −67.31235744.
LiAlH4 (s) → LiAlH4 (l) 22 – – Heat of fusion. Value might be unreliable.
LiAlH4 (l) → {{1/3}} Li3AlH6 (s) + {{2/3}} Al (s) + H2 (g) 3.46 104.5 −27.68 ΔS° calculated from reported values of ΔH° and ΔG°.

Thermal decomposition

LAH is metastable at room temperature. During prolonged storage it slowly decomposes to Li3AlH6 and LiH.[14] This process can be accelerated by the presence of catalytic elements, such as titanium, iron or vanadium.

When heated LAH decomposes in a three-step reaction mechanism:[14][15][16]

{{NumBlk|:|3 LiAlH4 → Li3AlH6 + 2 Al + 3 H2 |{{EquationRef|R1}}}}{{NumBlk|:|2 Li3AlH6 → 6 LiH + 2 Al + 3 H2 |{{EquationRef|R2}}}}{{NumBlk|:|2 LiH + 2 Al → 2 LiAl + H2 |{{EquationRef|R3}}}}{{EquationNote|R1}} is usually initiated by the melting of LAH in the temperature range 150–170 °C,[17][18][19] immediately followed by decomposition into solid Li3AlH6, although {{EquationNote|R1}} is known to proceed below the melting point of LiAlH4 as well.[20] At about 200 °C, Li3AlH6 decomposes into LiH ({{EquationNote|R2}})[14][16][19] and Al which subsequently convert into LiAl above 400 °C ({{EquationNote|R3}}).[16] Reaction R1 is effectively irreversible. {{EquationNote|R3}} is reversible with an equilibrium pressure of about 0.25 bar at 500 °C. {{EquationNote|R1}} and {{EquationNote|R2}} can occur at room temperature with suitable catalysts.[21]

Applications

Use in organic chemistry

Lithium aluminium hydride 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.[22] 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: carbonyl reduction). Similarly, it converts amide,[23][24] nitro, nitrile, imine, oxime,[25] and azide compounds 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.[26]

LAH is most commonly used for the reduction of esters[27][28] and carboxylic acids[29] 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[30] 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.[31] 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.[32]

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.[33]

Image:LAH_rxns.png|

rect 5 12 91 74 alcohol

rect 82 178 170 240 epoxide

rect 121 9 193 69 alcohol2

rect 337 1 414 60 alcohol3

rect 458 55 526 117 alcohol4

rect 170 151 234 210 aldehyde

rect 141 259 207 279 nitrile

rect 135 281 196 300 amide

rect 128 311 204 366 amine1

rect 264 268 339 334 carboxylic acid

rect 457 362 529 413 alcohol5

rect 381 255 433 273 azide

rect 469 244 525 269 amine2

rect 321 193 401 242 ester

rect 261 141 320 203 ketone

desc none

  1. Notes:
  2. Details on the new coding for clickable images is here: Extension:ImageMap
  3. [https://web.archive.org/web/20080327003154/http://tools.wikimedia.de/~dapete/ImageMapEdit/ImageMapEdit.html?en This image editor] was used.

Lithium aluminium hydride also reduces alkyl halides to alkanes, .[34][35] 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.[36]

Lithium aluminium hydride does not reduce simple alkenes or arenes. Alkynes are reduced only if an alcohol group is nearby.[37]

Inorganic chemistry

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:[38]

LiAlH4 + 4 NaCl → 4 NaH + LiCl + AlCl3

LAH also reacts with many inorganic ligands to form coordinated alumina complexes associated with lithium ions.[38]

LiAlH4 + 4NH3 → Li[Al(NH2)4] + 4H2

Hydrogen storage

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,[39] 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.[40]

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.[40] 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|date=March 2016}}

Other tetrahydridoaluminiumates

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:[41]

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:[41]

NaAlH4 + LiCl → LiAlH4 + NaCl

KAlH4 + LiCl → LiAlH4 + KCl

"Magnesium alanate" (Mg(AlH4)2) arises similarly using MgBr2:[42]

2 LiAlH4 + MgBr2 → Mg(AlH4)2 + 2 LiBr

Red-Al (or SMEAH, NaAlH2(OC2H4OCH3)2) is synthesized by reacting sodium aluminum tetrahydride (NaAlH4) and 2-methoxyethanol:[43]

See also

{{commons category|lithium aluminium hydride}}
  • Hydride
  • Sodium borohydride
  • Sodium hydride

References

1. ^{{CLP Regulation|index=001-002-00-4|page=472}}
2. ^{{Sigma-Aldrich|id=199877|name=Lithium aluminium hydride|accessdate=2018-06-1}}
3. ^[https://cameochemicals.noaa.gov/chemical/989 Lithium aluminium hydride]
4. ^1 {{cite journal|last1=Finholt|first1=A. E.|last2=Bond|first2=A. C.|last3=Schlesinger|first3=H. I.|title=Lithium Aluminum Hydride, Aluminum Hydride and Lithium Gallium Hydride, and Some of their Applications in Organic and Inorganic Chemistry|journal=Journal of the American Chemical Society|year=1947|volume=69|issue=5|pages=1199–1203|doi=10.1021/ja01197a061}}
5. ^1 2 3 {{cite encyclopedia |author1=Gerrans, G. C. |author2=Hartmann-Petersen, P. | title = Lithium Aluminium Hydride | encyclopedia = Sasol Encyclopaedia of Science and Technology | publisher = New Africa Books | year = 2007 | page = 143 | isbn = 1-86928-384-8 | url = https://books.google.com/books?id=1wS3aWR5SO4C&pg=PA143 }}
6. ^{{cite book |author1=Keese, R. |author2=Brändle, M. |author3=Toube, T. P. | title = Practical Organic Synthesis: A Student's Guide | publisher = John Wiley and Sons | year = 2006 | page = 134 | isbn = 0-470-02966-8 | url = https://books.google.com/books?id=-fo-Z3TfB3YC&pg=PA134 }}
7. ^{{cite journal | last1 = Andreasen | first1 = A. | last2 = Vegge | first2 = T. | last3 = Pedersen | first3 = A. S. | title = Dehydrogenation Kinetics of as-Received and Ball-Milled LiAlH4 | journal = Journal of Solid State Chemistry | year = 2005 | volume = 178 | issue = 12 | pages = 3672–3678 | doi = 10.1016/j.jssc.2005.09.027 | url = http://dcwww.camd.dtu.dk/Nabiit/Dehydrogenation%20kinetics%20of%20as-received%20and%20ball-milled%20LiAlH4.pdf | bibcode = 2005JSSCh.178.3672A }}
8. ^{{cite book | last = Pohanish | first = R. P. | title = Sittig's Handbook of Toxic and Hazardous Chemicals and Carcinogens | edition = 5th | publisher = William Andrew Publishing | year = 2008 | page = 1540 | isbn = 978-0-8155-1553-1 }}
9. ^{{cite journal |author1=Løvvik, O. M. |author2=Opalka, S. M. |author3=Brinks, H. W. |author4=Hauback, B. C. | title = Crystal Structure and Thermodynamic Stability of the Lithium Alanates LiAlH4 and Li3AlH6 | journal = Physical Review B | year = 2004 | volume = 69 | issue = 13 | pages = 134117 | doi = 10.1103/PhysRevB.69.134117 |bibcode=2004PhRvB..69m4117L }}
10. ^1 {{cite book | author = Holleman, A. F., Wiberg, E., Wiberg, N. | title = Lehrbuch der Anorganischen Chemie | edition = 102nd | publisher = de Gruyter | year = 2007 | isbn = 978-3-11-017770-1 | url = https://books.google.com/books?id=mahxPfBdcxcC&printsec=frontcover }}
11. ^{{cite journal |last1=Xiangfeng |first1=Liu |last2=Langmi |first2=Henrietta W. |last3=McGrady |first3=G. Sean |last4=Craig |first4=M. Jensen |last5=Beattie |first5=Shane D. |last6=Azenwi |first6=Felix F. |title=Ti-Doped LiAlH4 for Hydrogen Storage: Synthesis, Catalyst Loading and Cycling Performance |journal=J. Am. Chem. Soc. |year=2011 |volume=133 |page=15593–15597|doi=10.1021/ja204976z}}
12. ^1 {{cite journal | last1 = Mikheeva | first1 = V. I. | last2 = Troyanovskaya | first2 = E. A. | title = Solubility of Lithium Aluminum Hydride and Lithium Borohydride in Diethyl Ether | journal = Bulletin of the Academy of Sciences of the USSR Division of Chemical Science | year = 1971 | volume = 20 | issue = 12 | pages = 2497–2500 | doi = 10.1007/BF00853610 }}
13. ^{{cite journal | last1 = Smith | first1 = M. B. | last2 = Bass | first2 = G. E. | title = Heats and Free Energies of Formation of the Alkali Aluminum Hydrides and of Cesium Hydride | journal = Journal of Chemical & Engineering Data | year = 1963 | volume = 8 | issue = 3 | pages = 342–346 | doi = 10.1021/je60018a020 }}
14. ^1 2 {{cite journal |author1=Dymova T. N. |author2=Aleksandrov, D. P. |author3=Konoplev, V. N. |author4=Silina, T. A. |author5=Sizareva |author6=A. S. | journal = Russian Journal of Coordination Chemistry | year = 1994 | volume = 20 | pages = 279 }}
15. ^{{cite journal | last1 = Dilts | first1 = J. A. | last2 = Ashby | first2 = E. C. | title = Thermal Decomposition of Complex Metal Hydrides | journal = Inorganic Chemistry | year = 1972 | volume = 11 | issue = 6 | pages = 1230–1236 | doi = 10.1021/ic50112a015 }}
16. ^1 2 {{cite journal | last1 = Blanchard | first1 = D. | last2 = Brinks | first2 = H. | last3 = Hauback | first3 = B. | last4 = Norby | first4 = P. | title = Desorption of LiAlH4 with Ti- and V-Based Additives | journal = Materials Science and Engineering B | year = 2004 | volume = 108 | issue = 1–2 | pages = 54–59 | doi = 10.1016/j.mseb.2003.10.114 }}
17. ^{{cite journal | last1 = Chen | first1 = J. | last2 = Kuriyama | first2 = N. | last3 = Xu | first3 = Q. | last4 = Takeshita | first4 = H. T. | last5 = Sakai | first5 = T. | title = Reversible Hydrogen Storage via Titanium-Catalyzed LiAlH4 and Li3AlH6 | journal = The Journal of Physical Chemistry B | year = 2001 | volume = 105 | issue = 45 | pages = 11214–11220 | doi = 10.1021/jp012127w }}
18. ^{{cite journal | last1 = Balema | first1 = V. | last2 = Pecharsky | first2 = V. K. | last3 = Dennis | first3 = K. W. | title = Solid State Phase Transformations in LiAlH4 during High-Energy Ball-Milling | journal = Journal of Alloys and Compounds | year = 2000 | volume = 313 | issue = 1–2 | pages = 69–74 | doi = 10.1016/S0925-8388(00)01201-9 }}
19. ^1 {{cite journal | last1 = Andreasen | first1 = A. | title = Effect of Ti-Doping on the Dehydrogenation Kinetic Parameters of Lithium Aluminum Hydride | journal = Journal of Alloys and Compounds | year = 2006 | volume = 419 | issue = 1–2 | pages = 40–44 | doi = 10.1016/j.jallcom.2005.09.067 }}
20. ^{{cite journal | last1 = Andreasen | first1 = A. | last2 = Pedersen | first2 = A. S. | last3 = Vegge | first3 = T. | title = Dehydrogenation Kinetics of as-Received and Ball-Milled LiAlH4 | journal = Journal of Solid State Chemistry | year = 2005 | volume = 178 | issue = 12 | pages = 3672–3678 | doi = 10.1016/j.jssc.2005.09.027 | bibcode = 2005JSSCh.178.3672A }}
21. ^{{cite journal | last1 = Balema | first1 = V. | first2 = J. W. | last2 = Wiench | first3 = K. W. | last3 = Dennis | first4 = M. | last4 = Pruski | first5 = V. K. | last5 = Pecharsky | title = Titanium Catalyzed Solid-State Transformations in LiAlH4 During High-Energy Ball-Milling | journal = Journal of Alloys and Compounds | year = 2001 | volume = 329 | issue = 1–2 | pages = 108–114 | doi = 10.1016/S0925-8388(01)01570-5 }}
22. ^{{cite journal | author = Brown, H. C. | title = Reductions by Lithium Aluminum Hydride | journal = Organic Reactions | year = 1951 | volume = 6 | page = 469 | doi = 10.1002/0471264180.or006.10 | isbn = 0471264180 }}
23. ^{{OrgSynth |author1=Seebach, D.|author2=Kalinowski, H.-O.|author3=Langer, W.|author4=Crass, G.|author5=Wilka, E.-M. | title = Chiral Media for Asymmetric Solvent Inductions. (S,S)-( + )-1,4-bis(Dimethylamino)-2,3-Dimethoxybutane from (R,R)-( + )-Diethyl Tartrate | collvol = 7 | collvolpages = 41 | year = 1991 | prep = cv7p0041 }}
24. ^{{OrgSynth |author1=Park, C. H.|author2=Simmons, H. E. | title = Macrocyclic Diimines: 1,10-Diazacyclooctadecane | collvol = 6 | collvolpages = 382 | volume = 54 | pages = 88 | year = 1974 | prep = cv6p0382 }}
25. ^{{OrgSynth |author1=Chen, Y. K.|author2=Jeon, S.-J.|author3=Walsh, P. J.|author4=Nugent, W. A. | title = (2S)-(−)-3-exo-(Morpholino)Isoborneol | volume = 82 | pages = 87 | year = 2005 | prep = v82p0087 }}
26. ^{{Cite web | url = https://www.organic-chemistry.org/chemicals/reductions/sodiumbis(2-methoxyethoxy)aluminumhydride-red-al.shtm | title = Red-Al, Sodium bis(2-methoxyethoxy)aluminumhydride | publisher = Organic Chemistry Portal }}
27. ^{{OrgSynth |author1=Reetz, M. T.|author2=Drewes, M. W.|author3=Schwickardi, R. | title = Preparation of Enantiomerically Pure α-N,N-Dibenzylamino Aldehydes: S-2-(N,N-Dibenzylamino)-3-Phenylpropanal | collvol = 10 | collvolpages = 256 | volume = 76 | pages = 110 | year = 1999 | prep = v76p0110 }}
28. ^{{OrgSynth |author1=Oi, R.|author2=Sharpless, K. B. | title = 3-[(1S)-1,2-Dihydroxyethyl]-1,5-Dihydro-3H-2,4-Benzodioxepine | collvol = 9 | collvolpages = 251 | volume = 73 | pages = 1 | year = 1996 | prep = cv9p0251 }}
29. ^{{OrgSynth |author1=Koppenhoefer, B.|author2=Schurig, V. | title = (R)-Alkyloxiranes of High Enantiomeric Purity from (S)-2-Chloroalkanoic Acids via (S)-2-Chloro-1-Alkanols: (R)-Methyloxirane | collvol = 8 | collvolpages = 434 | volume = 66 | pages = 160 | year = 1988 | prep = cv8p0434 }}
30. ^{{OrgSynth |author1=Barnier, J. P.|author2=Champion, J.|author3=Conia, J. M. | title = Cyclopropanecarboxaldehyde | collvol = 7 | collvolpages = 129 | volume = 60 | pages = 25 | year = 1981 | prep = cv7p0129 }}
31. ^{{OrgSynth |author1=Elphimoff-Felkin, I.|author2=Sarda, P. | title = Reductive Cleavage of Allylic Alcohols, Ethers, or Acetates to Olefins: 3-Methylcyclohexene | collvol = 6 | collvolpages = 769 | volume = 56 | pages = 101 | year = 1977 | prep = cv6p0769 }}
32. ^{{cite journal | last1 = Rickborn | first1 = B. | last2 = Quartucci | first2 = J. | title = Stereochemistry and Mechanism of Lithium Aluminum Hydride and Mixed Hydride Reduction of 4-t-Butylcyclohexene Oxide | journal = The Journal of Organic Chemistry | year = 1964 | volume = 29 | issue = 11 | pages = 3185–3188 | doi = 10.1021/jo01034a015 }}
33. ^{{cite book | author = Wade, L. G. Jr. | title = Organic Chemistry | edition = 6th | publisher = Pearson Prentice Hall | year = 2006 | isbn = 0-13-147871-0 }}
34. ^{{cite journal | last1 = Johnson | first1 = J. E. | last2 = Blizzard | first2 = R. H. | last3 = Carhart | first3 = H. W. | title = Hydrogenolysis of Alkyl Halides by Lithium Aluminum Hydride | journal = Journal of the American Chemical Society | year = 1948 | volume = 70 | issue = 11 | pages = 3664–3665 | pmid = 18121883 | doi = 10.1021/ja01191a035 }}
35. ^{{cite journal | last1 = Krishnamurthy | first1 = S. | last2 = Brown | first2 = H. C. | title = Selective Reductions. 28. The Fast Reaction of Lithium Aluminum Hydride with Alkyl Halides in THF. A Reappraisal of the Scope of the Reaction | journal = The Journal of Organic Chemistry | year = 1982 | volume = 47 | issue = 2 | pages = 276–280 | doi = 10.1021/jo00341a018 }}
36. ^{{cite book | author = Carruthers, W. | title = Some Modern Methods of Organic Synthesis | publisher = Cambridge University Press | year = 2004 | page = 470 | isbn = 0-521-31117-9 | url = https://books.google.com/books?id=ti7yMYYW7CMC&pg=PA470 }}
37. ^{{OrgSynth |author1=Wender, P. A.|author2=Holt, D. A.|author3=Sieburth, S. Mc N. | title = 2-Alkenyl Carbinols from 2-Halo Ketones: 2-E-Propenylcyclohexanol | collvol = 7 | collvolpages = 456 | volume = 64 | pages = 10 | year = 1986 | prep = cv7p0456 }}
38. ^1 2 {{cite book | last = Patnaik | first = P. | title = Handbook of Inorganic Chemicals | publisher = McGraw-Hill | year = 2003 | page = 492 | isbn = 978-0-07-049439-8 }}
39. ^{{cite journal | last1 = Bogdanovic | first1 = B. | last2 = Schwickardi | first2 = M. | title = Ti-Doped Alkali Metal Aluminium Hydrides as Potential Novel Reversible Hydrogen Storage Materials | journal = Journal of Alloys and Compounds | year = 1997 | volume = 253–254 | pages = 1–9 | doi = 10.1016/S0925-8388(96)03049-6 }}
40. ^1 {{cite book | last1 = Varin | first1 = R. A. | last2 = Czujko | first2 = T. | last3 = Wronski | first3 = Z. S. | title = Nanomaterials for Solid State Hydrogen Storage | edition = 5th | year = 2009 | pages = 338 | publisher = Springer | isbn = 978-0-387-77711-5 }}
41. ^1 {{cite journal | last1 = Santhanam | first1 = R. | last2 = McGrady | first2 = G. S. | title = Synthesis of Alkali Metal Hexahydroaluminate Complexes Using Dimethyl Ether as a Reaction Medium | journal = Inorganica Chimica Acta | year = 2008 | volume = 361 | issue = 2 | pages = 473–478 | doi = 10.1016/j.ica.2007.04.044 }}
42. ^{{cite book |author1=Wiberg, E. |author2=Wiberg, N. |author3=Holleman, A. F. | title = Inorganic Chemistry | year = 2001 | page = 1056 | publisher = Academic Press | isbn = 0-12-352651-5 | url = https://books.google.com/books?id=vEwj1WZKThEC&pg=PA1056 }}
43. ^{{cite journal |author1=Casensky, B. |author2=Machacek, J. |author3=Abraham, K. | journal = Collection of Czechoslovak Chemical Communications | year = 1971 | volume = 36 | pages = 2648 }}

Further reading

  • {{cite book |author1=Wiberg, E. |author2=Amberger, E. | title = Hydrides of the Elements of Main Groups I-IV | publisher = Elsevier | year = 1971 | isbn = 0-444-40807-X }}
  • {{cite book | author = Hajos, A. | title = Complex Hydrides and Related Reducing Agents in Organic Synthesis | publisher = Elsevier | year = 1979 | isbn = 0-444-99791-1 }}
  • {{cite book | editor = Lide, D. R. | title = Handbook of Chemistry and Physics | publisher = CRC Press | year = 1997 | isbn = 0-8493-0478-4 }}
  • {{cite book | author = Carey, F. A. | title = Organic Chemistry with Online Learning Center and Learning by Model CD-ROM | publisher = McGraw-Hill | year = 2002 | isbn = 0-07-252170-8 | url = http://www.chem.ucalgary.ca/courses/351/Carey5th/Carey.html }}
  • {{cite book | author = Andreasen, A. | title = Hydrogen Storage Materials with Focus on Main Group I-II Elements | chapter = Chapter 5: Complex Hydrides | publisher = Risø National Laboratory | year = 2005 | isbn = 87-550-3498-5 | url = http://www.risoe.dk/rispubl/AFM/afmpdf/ris-phd-21.pdf | deadurl = yes | archiveurl = https://web.archive.org/web/20120819163021/http://www.risoe.dk/rispubl/AFM/afmpdf/ris-phd-21.pdf | archivedate = 2012-08-19 | df = }}

External links

{{Wiktionary}}
  • {{cite web | title = Usage of LiAlH4 | url = http://www.orgsyn.org/orgsyn/chemname.asp?nameID=36257 | publisher = Organic Syntheses }}
  • {{cite web | url = https://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=28112 | publisher = PubChem | title = Lithium Tetrahydridoaluminate - Compound Summary (CID 28112) }}
  • {{cite web | url = http://webbook.nist.gov/cgi/cbook.cgi?Formula=LiAlH4&NoIon=on&Units=SI | title = Lithium Tetrahydridoaluminate | publisher = NIST | work = WebBook }}
  • {{cite web|url=http://msds.ehs.cornell.edu/msds/MSDSDOD/A441/M220131.htm |title=Materials Safety Data Sheet |publisher=Cornell University |deadurl=yes |archiveurl=https://web.archive.org/web/20060308045012/http://msds.ehs.cornell.edu/msds/MSDSDOD/A441/M220131.htm |archivedate=March 8, 2006 }}
  • {{cite web|url=http://hydpark.ca.sandia.gov/ |publisher=Sandia National Laboratory |title=Hydride Information Center |deadurl=yes |archiveurl=https://web.archive.org/web/20050507175350/http://hydpark.ca.sandia.gov/ |archivedate=May 7, 2005 }}
  • {{cite web|url=http://www.chem2.bham.ac.uk/labs/cox/Teaching/4th_Year/II/Reduction_Reactions.pdf |archive-url=http://arquivo.pt/wayback/20160523233903/http://www.chem2.bham.ac.uk/labs/cox/Teaching/4th_Year/II/Reduction_Reactions.pdf |dead-url=yes |archive-date=May 23, 2016 |title=Reduction Reactions |publisher=University of Birmingham |work=Teaching Resources - 4th Year }}
{{Lithium compounds}}{{aluminium compounds}}

4 : Lithium compounds|Aluminium complexes|Metal hydrides|Reducing agents
随便看

　

开放百科全书收录14589846条英语、德语、日语等多语种百科知识，基本涵盖了大多数领域的百科知识，是一部内容自由、开放的电子版国际百科全书。

　

Copyright © 2023 OENC.NET All Rights Reserved
京ICP备2021023879号 更新时间：2024/11/11 3:54:44