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US3255224A - Process for the production of complex alkali aluminum alkyls or alkali aluminum alkyl hydrides - Google Patents

Process for the production of complex alkali aluminum alkyls or alkali aluminum alkyl hydrides Download PDF

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Publication number
US3255224A
US3255224A US45526A US4552660A US3255224A US 3255224 A US3255224 A US 3255224A US 45526 A US45526 A US 45526A US 4552660 A US4552660 A US 4552660A US 3255224 A US3255224 A US 3255224A
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aluminum
alkali
complex
metal
hydride
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US45526A
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Ziegler Karl
Lehmkuhl Herbert
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ZIEGLER AG
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ZIEGLER AG
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    • 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
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/065—Aluminium compounds with C-aluminium linkage compounds with an Al-H linkage

Definitions

  • aluminum alkyls form complex compounds with various substances.
  • such com plexes are formed from aluminum alkyls and ethers, thioothers or tertiary amines, but also from the organic aluminum compounds and alkali halides, more especially alkali fluorides, alkali cyanides, alkali hydrides and alkali alkyls. All these complexes can be produced by simple combination and perhaps also by joint heating of the complex formers and aluminum alkyls.
  • the sodium hydride cannot be used for the complex formation, because otherwise this metal alkyl compound, that is to say, for example the lead tetraethyl, would decompose.
  • a reaction with alkali alkyl is possible and can also be carried out practically.
  • the exploitation of this possibility on a large industrial scale is however precluded by the fact that the alkali alkyls can only be prepared with difliculty, so that the provision of adequate quantities of alkali alkyls is only possible with practical difficulties, at least at the present time.
  • the working up of the primary electrolysis products is thus eilected by way of other complex compounds of aluminum triethyl, but these compounds are not the aforementioned most important complex electrolytes.
  • lead tetraethyl using an electrolyte of sodium-aluminum tetraethyl at the lead anode, a mixture of 1 mol of lead tetraethyl and 4 mols of aluminum triethyl isobtained.
  • the lead tetraethyl can be separated out from this mixture in pure form by converting the aluminum triethyl into its complex compounds with sodium fluoride and/ or sodium cyanide, as described in the patent application 40,134, filed July 1, 1960, and now abandoned (.Process for Separating Aluminum Triethyl From Other Metal Ethyl Compounds).
  • the lead tetraethyl is sparingly soluble in these compounds and can be separated out in liquid form.
  • T he aluminum triethyl is thus a decomposition product of the electrolyte used during the electrolysis. Consequently, if it is desired to operate economically, it must be supplied to the electrolyte again in the original form as sodium-aluminum tetraethyl. This can only be eiiected by the alkali fluoride or alkali cyanide complexes being again transformed into sodium aluminum tetraethyl.
  • Another working up method for the said mixture of for example aluminum triethyl and lead tetraethyl consists in treating the mixture with a suitable tertiary amine, more especially tributylamine, as described in US. Patent 3,119,854, issued January 28, 1964 (Method of Separating Aluminum Triethyl From Other Metal Ethyl Compounds and to a Novel Aluminum Complex Compound).
  • the tributylamine compound of aluminum triethyl is solid at a sufficiently low temperature and it can be separated out by the cooling of lead tetraethyl; the necessity then exists of reconverting this tributylamine compound of the aluminum triethyl into the original electrolyte (sodiumaluminum tetraethyl). Problems of similar nature frequently arise in the course of modern electrolytic processes for the production of metal alkyls.
  • the complex compounds of the aluminum trialkyls I converted into a mixture of sodium fluoride and aluminum triethy1-triethylamine.
  • the etherates of the aluminum trialkls for example aluminum triethyldiethyl etherate, can be split for example by potassium fluoride into potassium fluoride complexes of aluminum triethyl and free ether. It is not possible in practise to formulate any laws which regulate the stability of the various aluminum alkyl complexes. It was not possible to foresee how perhaps the sequence of the complex stability would he when comparing a series of substances which are capable of forming complexes.
  • the present invention is based on the unexpected and surprising fact that alkali hydrides in combination with the aluminum trialkyls, are stronger complex formers even than tertiary amines and the alkali fluorides and cyanides. It has surprisingly also been found that these very stable complexes can be split by alkali hydrides, the corresponding alkali aluminum alkyls then being formed.
  • the present invention provides a process for the production of alkali aluminum alkyls or alkali aluminum alkyl hydrides, wherein other aluminum trialkyl complex or addition compounds are reacted with alkali hydrides if desired in the presence-of oleflnes.
  • Particularly suitable starting materials for this reaction are the alkali halide complexes, more especially the alkali fluoride complexes of the aluminum trialkyls, the alkali cyanide complexes and the trialkylamine addition compounds of the aluminum trialkyls or mixtures containing these compounds.
  • the aluminum complexes can be split with alkali hydrides, if necessary in the presence of olefines.
  • it is the alkali aluminum alkyl complexes which are formed and not the aluminum alkyl hydride complex. It is preferable to use an olefine which corresponds to the alkyl residue. It is alsopreferred to use sodium hydride.
  • the complex formers originally combined in complex form with the aluminum alkyls and liberated by the alkali hydrides or alkali alkyls can be separated very easily from cially with aluminum triethyl, sodium hydride not only forms a 1:1 complex, but also a 1:2 complex with the composition NaH-2Al(C H This complex has been proved to be more stable than even the 1:1 complex of aluminum triethyl with sodium cyanide. Consequently, if 1 mol of sodium hydride is added to the compound NaCN-2Al(C H sodium cyanide immediately precipitates. Sodium cyanide can also be precipitated from the 2:1 complex of aluminum triethyl and sodium cyanide by adding the compound Na[Al(C H H]. In this second case, the complex compound of the sodium hydride with the aluminum triethyl operates approximately in the manner of a dissolved sodium hydride.
  • the direct treatment of the complex aluminum compounds with solid hydride is subject substantially to the general difficulty peculiar to all reactions in which, under the action of a solid substance on a liquid, the first solid substance disappears and a second solid substance is formed. Under such circumstances, incrustation of the first solid substance by the second substance being separated out can very readily occur, and this means that even if the main part of the reaction proceeds fairly quickly, a relatively long time may be necessary until a complete conversion has taken place.
  • either the liberated inorganic complex former is directly obtained or the so-called 1:1 complex compounds are obtained as second reaction component.
  • the combination NaF-2Al(C H with triethylamine gives sodium fluoride and aluminum triethyltriethylaminate.
  • the compound KF-2Al(C I-I only 1 mol of aluminum triethyl is split off as triethylaminate, and the 1:1 compound KF-Al'(C H is obtained.
  • Ethers such as diethyletber, diisopropyl ether, di-sec.-butylether or di-n-butylether, generally provide the 1:1 compounds as well as 1 molecule of the corresponding etherates from the complex fluorides of aluminum trialkyl.
  • a condition for carrying out this form of the process is obviously that the complex initial aluminum compounds can be split by adding ether or tertiary amine.
  • predictions can scarcely be made here for the special case, but it is nevertheless possible from ,case to case to establish easily, by a small initial experiment, whether this form of the invention can be used.
  • the aluminum trialkyl etherates or aluminum trialkyl trialkylaminates are not solvents for alkali fluorides or cyanides. Even if the cleavage extends to below these salts, it is only necessary to pour off the liquid aluminum compounds from the solid phase or perhaps remove the said compounds by way of a filter candle. If the cleavage only extends to the 1:1 compounds, the etherates or trialkylaminates can be separated with extreme case by distillation, preferably a continuous vacuum distillation, from the complex 1:1 compounds.
  • the second stage in this form of the process according to the invention i.e. the final regeneration to the complex electrolytes, proceeds extremely quickly and easily, since it is now only necessary for the sodium hydride to dissolve during the reaction and no solid substance is separated out during this reaction.
  • the alkali halide complex compounds and the alkali hydride used for the splitting or cleavage contain dilferent alkali metals the cleavage generally takes place in such a way that the alkali metal with the highest atomic number remains in the alkali aluminum alkyl and the halide of the alkali metal with the lower atomic number if separated out.
  • Example 2 150 cc. of a suspension of NaH in parafiin oil is added at 90 C. and while stirring to 215 g. (:1 mol) of aluminum triethyl-triethylaminate in a 500 cc. flask filled with nitrogen. The content of sodium hydride in the suspension was fixed at 15.3 g. of NaH per 100 cc. of suspension. All the NaH is dissolved in a short time. The reaction mixture is transferred under nitrogen into an autoclave with a reaction chamber having a capacity of '1 litre and heated to 160 C. Ethylene is introduced at a pressure of substantially 10 atm.
  • the pressure in the autoclave is expediently kept constant by connecting the reaction vessel by way of a pressure-tight metal capillary tube to a larger storage vessel in which there is an ethylene pressure of 10 atm. Thorough mixing of the reaction components is assured by shaking the autoclave. Experience shows that the absorption of ethylene ceases after about 5 hours. In order to check this, the supply of ethylene is stopped and it is observed whether there is any further decrease in pressure in the sealed reaction vessel. The excess ethylene is blown off while hot and the liquid contents of the autoclave are emptied out under nitrogen or ethylene pressure while hot.
  • the reaction mixture is heated under a vacuum of 10 mm. Hg to 120 C., a total of 100 g. (:1 mol) of triethylamine being distilled olf.
  • the reaction mixture consists of two immiscible liquid phases, of which the lower phase solidifies on cooling (M.'P. about 120 (3;). It is practically pure sodium aluminum tetraethyl.
  • the top phase is parafiin oil containing only a little sodiumaluminum tetraethyl and can be immediately employed again for the preparation of a sodium hydride suspension.
  • Example 3 0.95 mol of sodium hydride suspension in Decalin (400 g. NaH/kg. suspension) are added to 270 g. (:1 mol) of the sodium fluoride-aluminum ethyl 1:2-compound at a temperature of from 80 to 100 C. After 30 minutes, the sodium hydride has dissolved. The Decalin is removed at 2 to 3 mm. Hg (bath temperature up to 120 C.), and the mixture of sodium-aluminum triethyl hydride and sodium fluoride-aluminum triethyl is obtained.
  • 1 mol of sodium hydride (solid or in Decalin suspension) is initially added to 1 mol of sodium fluoride-aluminum triethyl 1:2, as described in Example 3, then another 0.95 mol of sodium hydride is added, the mixture is placed in a shaker-type autoclave and treated at 180 C. for more than 20 hours with an ethylene pressure of 15 atm. After emptying out the contents of the autoclave, these mixtures can be separated at C. in 2 hours by settlement.
  • the sodium-aluminum tetraethyl can be cleanly separated from the sodium fluoride which quickly settles on the bottom.
  • the Decalin can be first of all extracted as a top layer above the sodium-aluminum tetraethyl and can be used again for preparing a fresh sodium hydride suspension.
  • Example 5 2 mols of sodium hydride are added to 1 mol of sodium cyanide-aluminum triethyl 1:2 at 120 C. while stirring. After 5 hours at 120 C., the sodium hydride has dissolved and 1 mol of sodium cyanide has separated out. The sodium cyanide is removed from the sodiumaluminum triethyl hydride by centrifuging and is washed with benzene to eliminate the residues of organometallic substances.
  • Example 6 1.95 mols of sodium hydride are added to -1 mol of sodium hydride-aluminum triethyl 1:2. The mixture is placed under nitrogen pressure in a 500 cc. autoclave.
  • the mixture reacts at Crand an ethylene pressure of 15 atm. in 4 hours to sodium-aluminum tetraethyl.
  • the contents of the autoclave can be separated at 150 C. and the pure sodium-aluminum tetraethyl is extracted.
  • Example 7 1 mol of dry potassium hydride is added to 1 mol of potassium-aluminum tripropyl fluoride. and heated while stirring to 90 C. After about 2 to 3 hours, potassium hydride is no longer present in the solid phase and instead an equivalent quantity of KF has precipitated. The potassium fluoride precipitate is allowed to settle at 90 C. and the clear supernatant liquid is siphoned off, this liquid being pure potassium-aluminum tripropyl hydride. The yield of potassium-aluminum tripropyl hydride is g. (:97% of the theoretical).
  • Example 1 2 mols of sodium hydride are added at 130 C. to 1 mol of potassium fluoride-aluminum triethyl 1:2 and stirred for 5 hours. 1 mol of sodium fluoride is precipitated and this is separated out by allowing it to settle at 90 C. The supernatant mixture contains 1 mol of potassium-aluminum triethyl-hydride as well as 1 mol of sodium-aluminum triethyl hydride.
  • Example 11 202 g. of dry triethylamine are carefully added while stirring at room temperature to 270 g. of
  • the precipitated sodium fluoride is allowed to settle and it is separated from the formed aluminum triethyl-triethylaminate by decanting.
  • the sodium fluoride can be washed with a little benzene and after removing the last traces of benzene in vacuo, it can be obtained in pure form with a yield of 100% of the calculated quantity, and in addition there are obtained 220 g. of aluminum triethyl-triethylaminate, i.e. 98% of the theoretical. This is further processed in accordance with Example 2.
  • Example 12 102 g. of diisopropylether are added at room temperature to 270 g. of NaF-2Al(C H The homogeneous liquid mixture is thereafter heated in vacuo at mm. Hg to 100 to 130 C. (measured in the liquid) and 220 g. of aluminum triethyl diisopropyl etherate distil off. The distillation residue consists of 156 g. of
  • diisopropyl ether instead of diisopropyl ether, it is also possible to use diethyl ether, .but in this case the danger of an ether loss is greater than with the diisopropyl ether, which has a higher boiling point.
  • Process for the production of alkali-metal-alumi num-tetra-al'kyl-complex compounds which comprises reacting a complex of aluminum-trialkyl with a member selected from the. group consisting of alkali-metal-halides, alkali-metal-cyanides, and trialkyl amines, with an alkali metal hydride and reacting the resulting product with an olefin, and recovering the alkali-metal-aluminumtetraalkyl compound formed.
  • Process for the production of alkali-metal-tetraalkyl-complex compounds which comprises the step-s of (1) reacting a complex of aluminum-trialkyl with a member selected from the group consisting of alkylmetal-halides, alkali-metal-cyanides, and trialkyl amines,
  • Process according to claim 1 which comprises effecting said reaction with stoichiometric amounts of said aluminum-trialkyl-complex and alkali-metal-hydride reactants.
  • Process for the production of alkali-metal-alurninum-alkyl-hydride-complex compounds which comprises reacting a complex of aluminum-trialkyl with a member selected from the group consisting of alkali-metal-halides and alkali-metal-cyanides with a member selected from the group consisting of ethers and tertiary amines, to form the corresponding trialkyl-aluminum-complex with the second-mentioned member, and thereafter reacting the latter with an alkali-metal-hydride, and recovering the alkali-metal-aluminum-alkyl-hydride compound formed.
  • a tertiary amine is reacted with the first-mentioned complex to form aluminum trialkyl aminate and liberate a compound selected from the group consisting of alkali metal halides and alkali metal cyanides, said tertiary amine is separated from the liberated compound and is thereafter reacted with said alkali metal hydride.

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US45526A 1959-07-31 1960-07-27 Process for the production of complex alkali aluminum alkyls or alkali aluminum alkyl hydrides Expired - Lifetime US3255224A (en)

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DEZ7460A DE1153755B (de) 1959-07-31 1959-07-31 Verfahren zur Herstellung von Alkalialuminiumalkylhydriden und gegebenenfalls Alkalialuminiumalkylen

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3538135A (en) * 1964-06-15 1970-11-03 Thiokol Chemical Corp Process for preparing stabilized forms of trialkynyl aluminums
US3655536A (en) * 1969-11-06 1972-04-11 Continental Oil Co Anodic process for the preparation of tetraalkyl lead compounds
US3696136A (en) * 1970-10-09 1972-10-03 Ethyl Corp Method of stabilizing sodium aluminum diethyl hydride
EP1371653A1 (de) * 2002-06-13 2003-12-17 Crompton GmbH Verfahren zur Herstellung von Alkalitetraalkylaluminaten und deren Verwendung
US6960677B1 (en) * 2003-10-28 2005-11-01 Albemarle Corporation Preparation of aluminates

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2786860A (en) * 1952-05-13 1957-03-26 Ziegler Preparation of organic aluminum compounds
US2915541A (en) * 1952-04-21 1959-12-01 Ziegler Karl Production of alkyl aluminum hydrides and their complex compounds with alkali hydrides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2915541A (en) * 1952-04-21 1959-12-01 Ziegler Karl Production of alkyl aluminum hydrides and their complex compounds with alkali hydrides
US2786860A (en) * 1952-05-13 1957-03-26 Ziegler Preparation of organic aluminum compounds

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3538135A (en) * 1964-06-15 1970-11-03 Thiokol Chemical Corp Process for preparing stabilized forms of trialkynyl aluminums
US3655536A (en) * 1969-11-06 1972-04-11 Continental Oil Co Anodic process for the preparation of tetraalkyl lead compounds
US3696136A (en) * 1970-10-09 1972-10-03 Ethyl Corp Method of stabilizing sodium aluminum diethyl hydride
EP1371653A1 (de) * 2002-06-13 2003-12-17 Crompton GmbH Verfahren zur Herstellung von Alkalitetraalkylaluminaten und deren Verwendung
US6960677B1 (en) * 2003-10-28 2005-11-01 Albemarle Corporation Preparation of aluminates

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GB955253A (en) 1964-04-15
NL254207A (de)
DE1153755B (de) 1963-09-05

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