Aluminium isopropoxide

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Aluminium isopropoxide
One enantiomorph of Al4(OiPr)12
Names
IUPAC name
Aluminium Isopropoxide
Other names
Triisopropoxyaluminium
Aluminium isopropanolate
Aluminium sec-propanolate
Aluminium triisopropoxide
2-Propanol aluminium salt
AIP
Identifiers
3D model (
JSmol
)
ChemSpider
ECHA InfoCard
 100.008.265 Edit this at Wikidata
EC Number
  • 209-090-8
RTECS number
  • BD0975000
UNII
  • InChI=1S/3C3H7O.Al/c3*1-3(2)4;/h3*3H,1-2H3;/q3*-1;+3 checkY
    Key: SMZOGRDCAXLAAR-UHFFFAOYSA-N checkY
  • InChI=1/3C3H7O.Al/c3*1-3(2)4;/h3*3H,1-2H3;/q3*-1;+3
    Key: SMZOGRDCAXLAAR-UHFFFAOYAV
  • CC(C)[O-].CC(C)[O-].CC(C)[O-].[Al+3]
Properties
C9H21AlO3
Molar mass 204.246 g·mol−1
Appearance white solid
Density 1.035 g cm−3, solid
Melting point Sensitive to purity:
138–142 °C (99.99+%)
118 °C (98+%)[1]
Boiling point @10 Torr 135 °C (408 K)
Decomposes
isopropanol
 Poor
Structure
monoclinic
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Flammable (F)
GHS labelling:
GHS02: Flammable
Warning
H228
P210, P240, P241, P280
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
2
1
2
Flash point 16 °C (61 °F; 289 K)
Related compounds
Other cations
 Titanium isopropoxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Aluminium isopropoxide is the

isopropyl group (–CH(CH3)2). This colourless solid is a useful reagent in organic synthesis.[1]

Structure

A tetrameric structure of the crystalline material was verified by

NMR spectroscopy and X-ray crystallography. The species is described by the formula Al[(μ-O-i-Pr)2Al(O-i-Pr)2]3.[2][3] The unique central Al is octahedral, and three other Al centers adopt tetrahedral geometry. The idealised point group symmetry
is D3.

Preparation

This compound is commercially available. Industrially, it is prepared by the reaction between isopropyl alcohol and aluminium, or aluminium trichloride:

2 Al + 6 iPrOH → 2 Al(O-i-Pr)3 +3H2
AlCl3 + 3 iPrOH → Al(O-i-Pr)3 + 3 HCl

The procedure entails heating a mixture of aluminium,

mercuric chloride. The process occurs via the formation of an amalgam of the aluminium. A catalytic amount of iodine is sometimes added to initiate the reaction.[4] The industrial route does not use mercury.[5]

Reactions

Aluminium isopropoxide is used in

aldehydes and the Oppenauer oxidation of secondary alcohols.[6] In these reactions, it is assumed that the tetrameric cluster disaggregates. It is used in the Tishchenko reaction
.

Being a basic

cyclic esters.[7]

History

Aluminium isopropoxide was first reported in the master's thesis of the Russian organic chemist Vyacheslav Tishchenko (Вячеслав Евгеньевич Тищенко, 1861–1941), which was reprinted in the Journal of the Russian Physico-Chemical Society (Журнал Русского Физико-Химического Общества) of 1899.[8] This contribution included a detailed description of its synthesis, its peculiar physico-chemical behavior, and its catalytic activity in the Tishchenko reaction (catalytic transformation of aldehydes into esters). It was later found also to display catalytic activity as a reducing agent by Meerwein and Schmidt in the Meerwein–Ponndorf–Verley reduction ("MPV") in 1925.[9][10] The reverse of the MPV reaction, oxidation of an alcohol to a ketone, is termed the Oppenauer oxidation. The original Oppenauer oxidation employed aluminium butoxide in place of the isopropoxide.[11]

Related compounds

  • Aluminium phenolate
  • Aluminium tert-butoxide, which is a dimer [(t-Bu-O)2Al(μ-O-t-Bu)]2.[12] It is prepared analogously to the isopropoxide.[13]

References

  1. ^
    ISBN 0471936235
    .
  2. doi:10.1016/S0277-5387(00)83775-4
    .
  3. doi:10.1016/0022-1902(79)80384-X
    .
  4. doi:10.1021/ja01292a033
    .
  5. ISBN 978-3527306732
    .
  6. doi:10.15227/orgsyn.035.0039
    .
  7. doi:10.1021/ma961567w
    .
  8. ^ Тищенко, B. E. (Tishchenko, V. E.) (1899). "Действие амальгамированного алюминия на алкоголь. Алкоголятов алюминия, их свойства и реакции" [Effect of amalgamated aluminium on alcohol. Aluminium alkoxides, their properties and reactions.]. Журнал Русского Физико-Химического Общества (Journal of the Russian Physico-Chemical Society) (in Russian). 31: 694–770.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  9. doi:10.1002/jlac.19254440112
    .
  10. doi:10.1002/0471264180.or002.05
    .
  11. doi:10.1002/recl.19370560206
    .
  12. ISBN 0-12-352651-5
    .
  13. doi:10.15227/orgsyn.021.0008
    .
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