EP0983278A1 - Isopropoxyalane trimere stable, son procede de preparation et son utilisation - Google Patents

Isopropoxyalane trimere stable, son procede de preparation et son utilisation

Info

Publication number
EP0983278A1
EP0983278A1 EP98925554A EP98925554A EP0983278A1 EP 0983278 A1 EP0983278 A1 EP 0983278A1 EP 98925554 A EP98925554 A EP 98925554A EP 98925554 A EP98925554 A EP 98925554A EP 0983278 A1 EP0983278 A1 EP 0983278A1
Authority
EP
European Patent Office
Prior art keywords
isopropoxyalane
oipr
solvent
stable
trimeric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98925554A
Other languages
German (de)
English (en)
Inventor
Andreas Schlegel
Heinrich Noeth
Peter Rittmeyer
Dieter Hauk
Ulrich Wietelmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
Metallgesellschaft AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemetall GmbH, Metallgesellschaft AG filed Critical Chemetall GmbH
Publication of EP0983278A1 publication Critical patent/EP0983278A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
    • C01F7/36—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts from organic aluminium salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages

Definitions

  • the invention relates to a stable trimeric isopropoxyalane, to a process for the preparation of the stable trimeric isopropoxyalane and to the use thereof.
  • Hydrogen aluminum (A1H 3 , Alan) and complex metal aluminum hydrides (Alanate) are common, strong reducing agents. They are therefore used to reduce carbonyl compounds, esters and nitro compounds.
  • the desired high reactivity towards most functional groups leads in some cases to problems due to the lack of selectivity of the reducing agents. This is the case, for example, if there are several reducible functional groups in one molecule or if the reducing agents are not only as but also act as a base.
  • the partial replacement of the hydrogen in the aluminum hydrogen or the complex metal aluminum hydrides by suitable substituents leads to a variation of the
  • Lithium-tri (tert-butoxy) aluminum hydride weakened to such an extent due to the steric shielding that carboxylic acid derivatives are only reduced to the aldehyde under certain conditions.
  • the mono- and dialkoxyalanes produced from unbranched alcohols are completely insoluble in aprotic solvents and therefore cannot be used for reduction purposes.
  • the tendency towards polymerization can be suppressed by increasing the steric space filling of the alkoxy radical.
  • the mono and di-tert. -butoxyalane very soluble in common organic solvents. Tert.
  • butoxyalanes cannot be produced economically in every case, since this is for the implementation according to the equation
  • R is an alkyl radical with 3 to 10 carbon atoms or a cycloalkyl radical with 5 to 8 carbon atoms
  • the document shows that the alkoxyalanes described there are in dimeric form. According to the publication, the known dimeric alkoxyalanes can also contain propyl and / or isopropyl radicals as radicals R.
  • DE-OS 195 29 241 proposes a process in which A1H 3 is reacted with an alcohol ROH in the presence of an inert organic solvent, the molar ratio being either essentially 1: 1 or essentially 1: 2 . This process then forms either H 2 A10R or HA1 (0R) 2 , these alkoxyalanes being present as dimers.
  • the alkoxyalanes known from DE-OS 195 29 241 are said to be used for the production of optically variable systems.
  • Isopropoxyalanes have been known for about 30 years. They can be prepared by reacting hydrogen aluminum (A1H 3 ) with isopropanol in a molar ratio of 2: 1 or 1: 1 or by reacting A1H 3 with aluminum isopropoxide.
  • A1H 3 hydrogen aluminum
  • A1H 3 aluminum isopropoxide.
  • the dimeric isopropoxyalane (H 2 A10iPr) 2 could be isolated from the reaction solution.
  • the reaction of A1H 3 with isopropanol in a 1: 2 molar ratio the HAl (OiPr) 2 is formed, which is in equilibrium with the mono- and triisopropoxyalane, but which favors the formation of the diisopropoxyalane.
  • 2HAK0iPr) 2 £ • AI (OiPr) 3 + H 2 A10iPr
  • the diisopropoxyalane dissolves in benzene approximately in trimer form and therefore has the composition H 3 A1 3 (OiPr) ⁇ .
  • the above-mentioned disproportionation equilibrium is slowly established in the trimeric diisopropoxyalane solution, as a result of which the composition of the solution changes disadvantageously.
  • the invention has for its object to provide a chemoselective, stable isopropoxyalane, which is readily soluble in common solvents, the solutions of which are stable in storage, which has an increased hydride content compared to available alkoxyalanes, which does not form any toxic by-products during hydrolysis, and which consists of inexpensive and available raw materials can be represented.
  • Form of the isopropoxyalane has a high stability; it melts at approx. 60 ° C, can sublime at 40 ° C / 0.5 mbar
  • the mol ace corresponds to the structural formula.
  • the trimeric isopropoxyalane according to the invention does not disproportionate, but is very stable and can therefore be stored in solid or, in particular, in dissolved form over a longer period of time and is therefore salable Reducing agents available.
  • the stable trimeric isopropoxyalane is dissolved in a solvent or solvent mixture in a concentration of 20 to 80 wt .-%, with ether, tertiary amines, alkylphosphines, aromatic hydrocarbons, saturated aliphatic hydrocarbons or mixtures thereof as solvents Solvents are used.
  • the trimeric isopropoxyalane is very stable, which is why these solutions are particularly suitable as a salable product.
  • the trimeric isopropoxyalane is dissolved in diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, triethylamine, toluene, hexane, cyclohexane and / or methylcyclohexane, since the abovementioned solvents are readily available, easy to handle and inexpensive, and because the trimeric isopropoxyalane is present in these solvents is particularly stable.
  • the solubility of the trimeric isopropoxyalane at 20 ° C. in toluene is approximately 45% by weight, in hexane approximately 30% by weight and in Tetrahydrofuran approx. 50% by weight, the salable solutions having an isopropoxyalane content which is slightly below the maximum solubility.
  • the object on which the invention is based is further achieved by the creation of a process for the preparation of the trimeric isopropoxyalane, in which A1H 3 with Al (OiPr) 3 or with isopropanol in a molar ratio of 5: 4 or 3: 4 in a solvent or a solvent mixture is implemented.
  • A1H 3 with Al (OiPr) 3 or with isopropanol in a molar ratio of 5: 4 or 3: 4 in a solvent or a solvent mixture is implemented.
  • the respective molar ratio according to the invention is used, the stable trimeric isopropoxyalane is formed from the starting substances and no unstable reaction products are formed.
  • the solutions prepared by the process according to the invention can be sold directly without further purification, the concentration of the trimeric isopropoxyalane in the salable solutions being quite high.
  • the variation of the molar ratios within the limits according to the invention is particularly important for carrying out the process on an industrial scale, because the starting substances often contain impurities which correspond to the Change the molar ratio of the starting substances to be aimed for by 5: 4 or 3: 4 slightly. However, this does not lead to a noticeable deterioration in the quality of the product.
  • the method according to the invention can advantageously be carried out in such a way that A1H 3 and AI (OiPr) 3 according to the equation
  • inventive method can also be carried out in such a way that A1H 3 and isopropanol according to the equation 3AlH 3 +4 (CH 3 ) 2 CHOH ---> H S A1 3 (OiPr) 4 + 4H 2 at a
  • Reaction temperature from -80 to + 80 ° C are implemented. At the reaction temperatures according to the invention, the reaction proceeds sufficiently quickly and the solvents used are easy to handle.
  • the A1H 3 is used in the form of a Lewis base adduct, ethers or tertiary amines being used as the Lewis base.
  • Open-chain, cyclic or polyfunctional ethers which can remain in the product solution serve as the Lewis base.
  • Trialkylamines R 3 N are particularly suitable as amines, where R is an alkyl radical having 1 to 6 C atoms.
  • the exact composition of the adduct consisting of A1H 3 and a Lewis base depends on the Lewis base used and the preparation of the adduct and varies within wide limits. The adduct but has a greater stability compared to the pure A1H 3 and is readily soluble and easily accessible in many solvents.
  • ethers, tertiary amines, alkylphosphines, aromatic hydrocarbons, saturated aliphatic hydrocarbons or mixtures of these solvents are used as solvents.
  • the solvents used must be liquid in a part of the temperature range from -80 to + 100 ° C and be available free of water.
  • the process according to the invention can be carried out particularly successfully if diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, triethylamine, toluene, hexane, cyclohexane and / or methylcyclohexane are used as the solvent or solvent mixture.
  • solvents are inexpensive, readily available and can be dewatered at reasonable cost and using customary methods.
  • the stable trimeric isopropoxyalane is used as a reducing agent in organic and inorganic syntheses, as a source for aluminum or aluminum oxide in the electronics and ceramic industries and for pigment production, the use in the form of solutions being preferred for synthetic chemistry.
  • Aluminum, aluminum oxide and pigments can be produced from the stable trimeric isopropoxyalane, for example by the CVD process in a reducing or oxidizing atmosphere. The subject matter of the invention is explained below using exemplary embodiments.
  • Adduct with the Lewis base diethyl ether is present in the solution.
  • 109 g (0.534 mol) of Al (OiPr) 3 are then introduced in solid form into the solution at 0 to 5 ° C. in portions. The mixture is stirred at 5 ° C for one hour and then warmed to room temperature. After the LiCl has been separated off by filtration, the diethyl ether is distilled off. After drying the product in vacuo, a colorless oil remains that slowly crystallized.
  • the yield of stable trimeric isopropoxyalane is 121.6 g; the crystalline product has the above-mentioned spectroscopic data.
  • the product contains 13.7 mmol H ' / g and 8.8 mmol Al / g. For the theoretical yield of 100%, these values are 15.5 mmol H * / g and 9.3 mmol Al / g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne l'isopropoxyalane trimère stable de la composition H5Al3(OiPr)4, où iPr est un reste (CH3)2CH. L'invention concerne également un procédé pour la préparation de cet isopropoxyalane trimère stable, dans lequel AlH3 est mis en réaction avec Al (OiPr)3 ou bien avec de l'isopropanol dans le rapport molaire de 5:4 ou 3:4 dans un solvant ou un mélange de solvants. L'isopropoxyalane trimère stable peut s'utiliser notamment comme réducteur pour les synthèses organiques et inorganiques, comme source pour l'aluminium ou l'oxyde d'aluminium dans l'industrie de l'électronique et de la céramique ou bien pour la fabrication de pigments.
EP98925554A 1997-05-13 1998-05-07 Isopropoxyalane trimere stable, son procede de preparation et son utilisation Withdrawn EP0983278A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19719809 1997-05-13
DE19719809A DE19719809C1 (de) 1997-05-13 1997-05-13 Stabiles trimeres Isopropoxyalan, Verfahren zu seiner Herstellung und seine Verwendung
PCT/EP1998/002693 WO1998051691A1 (fr) 1997-05-13 1998-05-07 Isopropoxyalane trimere stable, son procede de preparation et son utilisation

Publications (1)

Publication Number Publication Date
EP0983278A1 true EP0983278A1 (fr) 2000-03-08

Family

ID=7829208

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98925554A Withdrawn EP0983278A1 (fr) 1997-05-13 1998-05-07 Isopropoxyalane trimere stable, son procede de preparation et son utilisation

Country Status (4)

Country Link
US (1) US6191295B1 (fr)
EP (1) EP0983278A1 (fr)
DE (1) DE19719809C1 (fr)
WO (1) WO1998051691A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2329815A1 (fr) * 2005-02-11 2011-06-08 Kalamazoo Holdings, Inc. Variété capsicum présentant une hyper-accumulation de zéaxanthine et produits dérivés de cette variété

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19529241A1 (de) * 1995-08-09 1997-02-13 Basf Ag Aluminiumalkoxyhydride

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9851691A1 *

Also Published As

Publication number Publication date
DE19719809C1 (de) 1998-05-14
US6191295B1 (en) 2001-02-20
WO1998051691A1 (fr) 1998-11-19

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