EP0162908A4

EP0162908A4 - Preparation of alkaline earth metal organometallic compounds.

Info

Publication number: EP0162908A4
Application number: EP19850900283
Authority: EP
Inventors: Conrad W Kamienski
Original assignee: Lithium Corp of America Inc
Current assignee: Lithium Corp of America Inc
Priority date: 1983-11-15
Filing date: 1984-11-13
Publication date: 1986-04-15
Also published as: AU3741185A; CA1244044A; WO1985002176A1; EP0162908A1; IT1199223B; IT8449173A1; IT8449173A0

Abstract

Stable liquid hydrocarbon-soluble novel alkaline earth metal alkoxide compositions, and complexes thereof with, for example, alkyllithiums, dialkylmagnesiums, trialkylaluminums and the like, useful as or in the preparation of polymerization catalysts and initiators for the polymerization of alpha-olefins and diolefins, which are prepared, for instance, by reacting certain organomagnesium or other alkaline earth metal organo-compounds in liquid hydrocarbon solvents with (a) aliphatic 2-alkyl-substituted C4-C12 monohydric primary alcohols, or (b) mixtures of (a) with C3-C12 aliphatic secondary alcohols. Alternatively, these alcohols may be substituted by 2-alkoxyalkanols. Illustrative examples of the novel alkaline earth metal alkoxides are magnesium and barium 2-methyl-1-pentyloxide. An illustrative organometallic complex of the said alkaline earth metal alkoxides is that made by mixing n-butyllithium in heptane solution with magnesium 2-methylpentyoxide in heptane solution.

Description

PREPARATION OF ALKALINE EARTH METAL ORGANOMETALLIC COMPOUNDS

DESCRIPTION

Technical Field

This invention is directed to the preparation of novel alkaline earth metal alkoxides and to complexes thereof with metal alkyl of Groups I , II and III of the Periodic Table.

Background Prior Art

Alkaline earth metal alkoxides and their metal alkyl complexes have a variety of applications. For example, it has heretofore been known that certain barium alkoxides in conjunction with alkyllithium or dialkylmagnesium compounds promote the polymerization and copolymerization of, for example, 1,3-butadiene to a polymer having a high trans-1,4 microstrueture and possessing unique beneficial properties in its use as a tire rubber.

It has also heretofore been known that the barium or calcium compounds, particularly for the foregoing purposes, must be present as an alkoxide and that, generally, the barium or calcium alkoxide interacts strongly with the alkyllithium or dialkylmagnesium compounds to form complexes of, presumably, alkylbarium or alkylcalcium alkoxides with the alkyllithium or dialkylmagnesium compounds.

For maximum efficiency in this interchange reaction and for use as a polymerization initiator, it is particularly advantageous to employ barium alkoxides which possess a high solubility in liquid hydrocarbon media. Initial experimental work was done utilizing barium tert-butoxide (A. Onishi et al, U.S. Patent No. 3,629,213, December 21, 1971). However, barium tert-butoxide, by itself, was found to possess a low order of solubility in liquid aliphatic hydrocarbon solvents (U.S. Patent No. 4,044,900, July 5, 1977); while barium ethoxide is even less soluble (Z.M. Baydakova, et al (a) High Molecular Wt. Compounds 1976 Vol. (A) XVIII, No. 9 (Russian) (b) Vysokomol.Soedin. Series B 1977, 19 (10) 767-70 (Russian). Later, others (U.S. Patent No. 4,355,156) have shown that barium tert-butoxide, in conjunction with barium tert-decanolate and barium hydroxide, has a superior solubility in toluene over barium tert-butoxide-barium hydroxide alone (I.G. Hargis, R.A. Livigni and S.L. Aggarwal, ACS Symposium Series, 1982, No. 193 (Elastomers Rubber Elasticity). Barium or calcium alkoxides are generally prepared by reacting a solution of barium or calcium metal in liquid ammonia or methylamine, with the desired alcohol, followed by evaporation of the solvent and subsequent drying in vacuo. Solutions of the barium or calcium alkoxides are then made up in the desired hydrocarbon solvent.

In another example of the utility of alkaline earth metal alkoxides, certain magnesium alkyl alkoxides and magnesium dialkoxides have been found to possess utility as precursors for magnesium chloride support materials utilized in the preparation of Ziegler-Natta catalysts for alpha-olefin polymerization.

For example, ethylene has been polymerized at 80° C. in hexane using a magnesium alcoholate-TiCl₄ reaction product (MgCl₂) and a trialkylaluminum as the catalyst system. (M. Bahadir, S. Lutze, W. Payer, P. Schneller, Ger. Offen.. DE 3,120,186, Dec. 9, 1982 to Ruhrchemie.) In another application, solid magnesium diethoxide, suspended in carbon tetrachloride, is treated with ethyl benzoate and titanium tetrachloride, and the resulting solid product is used in combination with trialkylaluminum and p-methoxybenzoate as a catalyst to polymerize propylene (B. L. Goodall, A. vander Nat, and W. Sjardyn, U.S. Patent No. 4,414,132, to Shell Oil Co.).

Certain magnesium alkyl alkoxides and dialkoxides have also been generated by reaction of complexed magnesium dialkyls, coated on an inert support material, with an alcohol. These supported magnesium alkoxides are then further reacted with HCl and/or titanium tetrachloride to give a supported magnesium chloride catalyst which can be dried and used to polymerize ethylene (R. Hoff , U.S. Patent No. 4,402,861 and R. A. Dombro, U.S. Patent No. 4,378,304 to Chemplex Co.; and M. Bahadir and W. Payer, Ger. Offen. DE 3223331, to Ruhrchemie). Certain magnesium dialkoxides, soluble in hydrocarbon solvents, have known utility for the preparation of MgCl₂ which forms a useful support for catalysts to polymerize alpha-olefins, as shown by Goodall (U.S. Patent Nos. 4,216,383; 4,426,316; and 4,387,200).

D. Gessell (U.S. Patent Nos. 4,246,383; 4,426,316; and 4,244,838, to Dow Chemical Company) also describes the preparation of a useful alpha-olefin polymerization catalyst by reacting a dialkylmagnesium compound (in the presence of at least 50 mole % of a trialkylaluminum compound) with sufficient n-propyl alcohol to convert all of the alkyl groups to n-propoxy groups, thus forming a hydrocarbon-soluble solution of magnesium and aluminum n-propoxides, followed by reaction of the resulting solution with a titanium ester and a chlorinating agent, ethylaluminum dichloride, to give an MgCl₂-supported titanium catalyst.

It is also known to employ a mixture of certain dialkylmagnesiums and either lithium alkoxide, sodium alkoxide or potassium alkoxide in the polymerization and telomerization of butadiene to form low molecular weight liquid polymers, useful in the coating and also in the impregnation and encapsulation of electrical transformers and other metal parts to protect them from corrosion (C. W. Kamienski and J. F. Eastham, U.S. Patent No. 3,742,077; U.S. Patent No. 3,822,219; and U.S. Patent No. 3,847,833). Other patents describing the formation of polymeric products from similar catalyst systems are U.S. Patent Nos. 4,139,490 and 4,429,090 (to Firestone Tire & Rubber Co.), and U.S. Patent No. 3,716,495 (to Phillips Petroleum Co. ) . A known interchange of alkoxy and alkyl groups occurs on mixing these reagents to yield, in essence, a lithium, sodium or potassium alkyl and a magnesium alkoxide, as shown below:

Although certain magnesium alkyl alkoxides are known to be soluble in hydrocarbon solvents, as described in U.S. Patent Nos. 4,410,742 and 4,133,824, and by G. E. Coates, J. A. Heslop, M. E. Redwood and D. Ridley, J. Chem. Soc, 1968, 1118 (see also B. J. Wakefield in Advances in Inorganic Chemistry and Radiochemistry, Vol. ii, 1968, p. 396 (Academic Press) , little is known about the solubility of magnesium dialkoxides. It is known that both magnesium methoxide and ethoxide are insoluble in ethers and hydrocarbon solvents, as described in Kirk Othmer's Encyclopedia of Chemical Technology, vol. 2, p. 12, 3rd Edition, John Wiley, 1978. Magnesium isopropoxide was found by D. Bryce-Smith and B. J. Wakefield, J. Chem. Soc., 1964, 2483, to be insoluble in methylcyclohexane, benzene and ether, and only sparingly soluble in isopropanol. Magnesium t-butoxide is not soluble in ethyl ether ( see Coates reference, as well as D. C. Bradley in Advances in Inorganic Chemistry and Radiochemistry, Vol. 15, 1972, p. 265 (Academic Press), and, thus, presumably, would be even less soluble in hydrocarbons. Solubility of magnesium alkoxides is not improved by the addition of aluminum alkyls (B. V. Johnson, N. M. Karayannis (EPA 95,290, to Standard Oil Company). From the dearth of information on magnesium dialkoxides, it would appear that these materials are, as a class, generally insoluble and intractable in most organic solvents. C. G. Screttas (U.S. Patent No. 3,932,545) describes, among other things, the preparation of magnesium 2-ethoxyethoxide in an excess of 2-ethoxyethanol; and, further, its use in dry form as an additive to promote the hydrocarbon solubility of arylmetallics such as phenylsodium, but does not teach its preparation and solubility in hydrocarbon solvents without such additives. (See, also, article in Organometallics, Vol. 3, 904-907, 1984) .

It has now been discovered that, under certain conditions, certain magnesium dialkoxides can be prepared directly in liquid hydrocarbon or chlorinated hydrocarbon solvents, and possess a relatively high solubility therein.

Thus, it is one object of my invention to make available alkaline earth metal alkoxides possessing a particularly high solubility in liquid hydrocarbon or chlorinated hydrocarbon solvents, and in the liquid hydrocarbon and chlorinated hydrocarbon solvent solutions thereof. It is another object of my invention to provide a simplified process for the preparation of alkaline earth metal alkoxides directly in the liquid hydrocarbon or chlorinated hydrocarbon solvents. Another object of my invention is to prepare liquid hydrocarbon or chlorinated hydrocarbon-soluble stable complexes of magnesium alkoxides with other metallic alkoxides, such as those of aluminum, boron, zinc, lithium, sodium, potassium, calcium, and barium.

A still further object of my invention is to provide a process for the preparation of liquid hydrocarbon or chlorinated hydrocarbon-soluble stable complexes of these alkaline earth metal alkoxides with alkyllithium, alkylsodium, alkylpotassium, dialkylmagnesium and trialkylaluminum compounds and mixtures thereof.

Summary of the-Invention

In accordance with my invention, certain alcohols are reacted with alkaline earth metals, barium, calcium, and strontium amides, and magnesium dialkyls or alkylmagnesium alkoxides in liquid aliphatic or aromatic hydrocarbon or chlorinated hydrocarbon solvent media to form highly soluble, stable solutions of novel and highly useful alkaline earth metal alkoxides.

Whereas, linear alkaline earth metal primary alkoxides possess little or essentially no solubility in liquid hydrocarbon or chlorinated hydrocarbon solvents, those with 2-alkyl-substituents in the alcohol moiety of said alkoxides possess a much higer solubility when the alkaline earth metal is magnesium. This solubility is promoted by the presence of minor amounts of aluminum alkoxides and lithium or potassium alkoxides derived from the same said alcohol moiety; that is, those alcohols with 2-alkyl substituents. In the case of calcium or barium alkoxides of this type (see my copending U.S. Patent Application Serial No. 551,917, filed November 15, 1983), chelating tertiary di- or polyamines, such as N,N,N',N'-tetramethylethylenediamine (hereafter and in the Claims referred to as TMEDA) , were found to enhance the solubility.

Equi¬

Barium molar

Alkoxide Solvent Cone (M) TMEDA

2-Ethyl- 1-butoxide Toluene 0.55 +

2-Methyl- Cyclo- 1-pentyloxide hexane 0.63 +

2-Ethyl- Cyclo- 1-hexyloxide hexane 0.66 -

2-Ethyl-4 Cyclo methyl-1- hexane 0.75 - pentyloxide

Whereas, in the aforementioned U.S. Patent No. 4,355,156, barium tert-alkoxides were found to possess a high solubility in hydrocarbon solvents, in my hands this was not the case. For example, the solubility of barium tert-butoxide in toluene was found by me to be only 0.37M at ambient temperature; that of barium tert-amylate, 0.23M in toluene; and that of barium 3-methyl-3-pentanolate, only 0.08M in cyclohexane. In addition, the stability of these solutions deteriorated with time (precipitation of product within a few days).

As was found with respect to the corresponding barium alkoxides, magnesium tert-alkoxides possess a low to intermediate solubility in liquid hydrocarbon or chlorinated hydrocarbon solvents when prepared by the process of my invention:

Physical

Magnesium Solvent Cone Description of Alkoxide Type (M) Reaction Mixture tert- Cyclohexane Thick slurry

Butoxide forms which sets to solid mass on standing.

3-Methy1- Heptane- 0.26 Solid slurry. 3-Pentyl- Cyclohexane oxide or Toluene

tert- Heptane- 0.38 Solid slurry.

Amyloxide Cyclohexane

I have found that barium salts of certain secondary alcohols have an improved solubility in liquid hydrocarbon solvents compared with the solubility of barium tert-alkoxides. Barium see-butoxide and barium 4-methyl-2-pentyloxide can be dissolved in cyclohexane to the extent of 0.8M, or even higher, at ambient temperature, without the aid of agents such as TMEDA. Contrastingly, the highly-branched secondary alkoxide, barium 2,6-dimethyl-4-heptyloxide, sterically hindered like the tertiary alkoxides, was found to have a low solubility in these solvents, even in the presence of TMEDA.

Unlike the soluble barium secondary alkoxides, magnesium secondary alkoxides were found to be of a low order of solubility in hydrocarbon or chlorinated hydrocarbon solvents:

Physical

Magnesium Solvent Cone Description of Alkoxide Type (M) Reaction Mixture

Isoprop- Heptane- Solid gel. oxide Cyclohexane or Toluene

sec- Heptane- 0.38 Fluid slurry

Butoxide Cyclohexane of fine particles.

4-Methyl- Cyclohexane - Thick 2-Pentyl- gelatinous mass oxide which solidifies on standing.

2,6- Heptane- 0.44 Thin suspension

Dimethyl- Cyclohexane of a fine white 4-Heptyl- ppt. oxide

By contrast, I have determined that, for example, 2-alkyl-substituted magnesium primary alkoxides possess a substantially higher solubility in liquid hydrocarbon or chlorinated hydrocarbon solvents.

Physical

Magnesium Solvent Cone Description of Alkoxide (a) Type (M) Reaction Mixture

(b)

2-Methyl- Cyclohexane 1.3 Mobile, 1-Pentyl- water-clear oxide solution.

(b)

2-Ethyl- Cyclohexane 1.3 Viscous, 1-Hexyl- water-clear oxide solution.

(c)

2-Ethyl- Heptane- 0.66 Viscous, 4-Methyl- Cyclohexane water-clear 1-Pentyl- solution. oxide

Mixtures of these 2-alkyl-substituted magnesium primary alkoxides and other branched alkoxides prepared in this manner were also determined by me to possess a substantial solubility in hydrocarbon or chlorinated

hydrocarbon solvents:

Physical

Magnesium Solvent Cone Description of Alkoxide (a) Type (M) Reaction Mixture

(b)

2-Methyl- Heptane- 0.66 Clear ,

1-Pentyl- Cyclohexane mobile, oxide solution.

Isopropoxide

(1:1)

(b)

2-Methyl- Heptane- 0.66 Clear,

1-Pentyl- Cyclohexane viscous oxide solution.

Isobutoxide

(2:1)

(c)

2-Ethyl- Heptane- 0.66 Clear , 1-Butoxide Cyclohexane viscous Isopropsolution. oxide (1:1)

(b)

2-Methyl- Heptane- 0.66 Clear,

1-Pentyl- Cyclohexane viscous oxide solution. sec-Butoxide

(1:1)

(b)

2-Ethyl- Heptane- 0.66 Clear ,

1-Hexyl- Cyclohexane viscous oxide solution.

Isopropoxide)

(1:1)

2-Ethyl- Heptane- 0.6 Slightly

1-Butoxide/ Cyclohexane hazy solution. sec-Butoxide/

2-Methyl-

1-Pentyloxide

( 2 : 1 : 1)

(a) Prepared by slow addition of neat alcohol to either n-butyl-sec-butylmagnesium or di-n-hexylmagnesium in a liquid hydrocarbon or chlorinated hydrocarbon solvent.

(b) Not necessarily the upper limit of solubility. (c) Solubility at 50° C.

In one method of the practice of my invention, a dialkylmagnesium dissolved in a liquid hydrocarbon solvent is treated first with a catalytic amount (about 3 mole %, based on magnesium) of a trialkylaluminum compound, and then with slightly more than twice the molar equivalent, based on magnesium, of a C₄-C₁₂ 2-alkyl-substituted primary monohydric alkanol or alcohol, or a mixture of these alkanols or alcohols, either neat or in solution in a liquid hydrocarbon or chlorinated hydrocarbon solvent. Alkanes are rapidly generated, and can be driven off by heating to the boiling point if low boiling (ca 0-5° C) , or absorbed by the solution itself.

In another method of the practice of my invention, barium or calcium amide is suspended in the liquid hydrocarbon solvent of choice; and a slightly less than stoichiometric quantity of 2-alkyl substituted C₄-C₁₂ normal monohydric alcohol, or in admixture with various proportions of C₃-C₁₂ secondary monohydric alcohol in which the OH group is attached to the second carbon atom, alone as to such alcohols or in solution in a liquid hydrocarbon solvent, are added to the stirred barium amide or calcium amide suspension. Ammonia is rapidly evolved; and the mixture is heated to the boiling point for such period of time (commonly several hours) to be certain that essentially all ammonia is gone from the solution. TMEDA, or equivalent agents, may be added during the reaction as a complexing agent, as required, to promote solubility, especially in the case of the lower molecular weight (C₄ and C₅) 2-alkyl-substituted alkoxides.

The resulting barium or calcium alkoxide solutions are filtered to remove unreacted barium or calcium amide and other solid impurities.

In place of part of the 2-alkyl-substituted primary alcohol, secondary alcohols can be used, such as isopropanol or sec-butanol, most favorably, up to about a 1:1 molar ratio, based on the 2-alkyl-substituted primary alkanol, although somewhat more may be employed. The excess of 2-alkyl-substituted primary alkanol employed, over and above twice the molar equivalent (based on magnesium) , is generally in the range of 0.01 to 2.0 molar equivalents, based on magnesium, but will more preferably lie in the range of 0.1-1.0 molar equivalents. This addition of an excess of the 2-alkyl-substituted primary alkanol possesses an unusually beneficial action on the viscosity and/or solubility of many of these branched magnesium dialkoxides and mixtures thereof.

In place of aluminum alkoxides, one can substitute other metallic alkoxides of Groups I, II and III of the Periodic Table to effect the solubility of magnesium alkoxides in liquid hydrocarbon or chlorinated hydrocarbon solvents. For example, the addition of as little as 5 mole % of lithium, sodium or potassium 2-methylpentyloxide (based on magnesium) to a gelatinous mixture of magnesium 2-methylpentyloxide in heptane effects the immediate dissolution of the gel and the formation of a clear, mobile solution of the magnesium alkoxide in the heptane. Other metallic alkoxides which can be used, for example, are those of Na, K, Ca, Ba, B and Zn.

In addition to the 2-alkyl-substituted 1-alkanols shown above, such as, for example, 2-methyl-1-pentanol, I have also found it possible to employ

2-alkoxy-substituted 1-alkanols, such as 2-methoxy-1-ethanol and 2-ethoxy-1-ethanol, to prepare liquid hydrocarbon or chlorinated hydrocarbon solvent-soluble alkaline earth metal 2-alkoxyalkoxides by reaction with suitable alkaline earth metal-containing precursors, such as magnesium and calcium metals, magnesium and barium amides, dialkylmagnesium compounds and magnesium and calcium monoalkoxides, such as magnesium ethoxide. In this modification, no added aluminum, lithium or potassium compounds or TMEDA are necessary to maintain solubility and fluidity of the resulting liquid hydrocarbon or chlorinated hydrocarbon solvent solutions of the alkaline earth metal 2-alkoxyalkoxides .

In a novel preparative method in accordance to one particular facet of my invention, the magnesium-2-alkoxyalkoxides are prepared by simple mixing of solid magnesium monoalkoxides, such as magnesium diethoxide, with slightly more than two molar equivalents of the 2-alkoxyalkanol, such as 2-ethoxyethanol, followed by dissolution of the liquid product in the desired hydrocarbon or chlorinated hydrocarbon solvent. Advantages over other processess (including that of the aforesaid Screttas patent) are as follows: 1. My above procedure involves only simple mixing of said components to convert the solid hydrocarbon or chlorinated hydrocarbon-insoluble magnesium monoalkoxides to hydrocarbon or chlorinated hydrocarbon solvent-soluble magnesium-2-alkoxyalkoxides.

2. The process is less expensive and less hazardous than that which uses dialkylmagnesium compounds, as contrasted to a lengthy reaction using magnesium metal in place of the lower magnesium alkoxides.

3. The hydrocarbon or chlorinated hydrocarbon solvent-soluble magnesium-2-alkoxyalkoxides can be prepared from relatively less expensive and generally more readily available starting materials.

4. The magnesium-2-alkoxyalkoxide can be prepared free of hydrocarbon solvent (neat) to give a liquid or fluid product, Mg(OCH₂CHR'OR)₂ (R"OH)_x, in which R and R" are C₁-C₁₂ hydrocarbyl groups and R' is hydrogen or C₁-C₃ hydrocarbyl group. (x = 0-2). Thus, magnesium 2-ethoxy-ethoxide prepared by reaction of magnesium ethoxide with slightly more than two equivalents of 2-ethoxy-ethanol in the absence of solvents such as heptane or chlorobenzene has been found to be a clear, mobile, liquid product, essentially corresponding to the chemical formula Mg(OCH₂CH₂OCH₂CH₃)₂ (CH₃CH₂OH)₂ , a novel product having utility in catalyst (α-olefin) preparations. For example, the product can be dispersed in mineral oil and chlorinated to give essentially uniformly-sized particles of magnesium chloride which can serve as a support for a deposited titanium catalyst for alpha-olefin polymerization.

This form of magnesium alkoxide is totally different from the solid product produced by the above-mentioned Screttas patent, and is also different from the chlorobenzene solution of the magnesium 2-ethoxyethoxide produced by reaction of slightly more than two equivalents of 2-ethoxyethanol with magnesium metal in an essentially neat reaction, followed by dissolution of the resulting product in a minimum of chlorobenzene, according to my invention. Similar results are obtained, for instance, with calcium and barium 2-ethoxyethoxide.

In another novel facet of my present invention, alkaline earth metal alkoxides in a hydrocarbon or chlorinated hydrocarbon solvent-soluble form, when mixed with alkyllithium, aIkyIsodium, dialkylmagnesium, alkylpotassium and trialkylaluminum compounds form stable, soluble complexes which are useful mixtures thereof. Preferred

2-alkyl-substituted primary monohydric normal alcohols or alkanols are 2-methyl-1-pentanol and 2-ethyl-1-hexanol and mixtures thereof. Other alcohols, which advantageously can be admixed with the above 2-alkyl-substituted primary alkanols and co-reacted with alkaline earth metals and their compounds are C₃-C₁₂ aliphatic secondary and tertiary alcohols, notably C₃-C₁₂ aliphatic secondary or tertiary branched alcohols such as isopropanol, sec-butanol, 4-methyl-2-pentanol,

2-pentanol, 2-hexanol, 5-methyl-2-hexanol,

4 , 6-dimethy1-2-heptanol, tert-butanol, tert-amylalcohol, 3-methyl-3-pentanol, 2,6-dimethyl-4-heptanol and the like. Cycloaliphatic alcohols may also be used, such as cyclopentanol and cyclohexanol.

Still other alcohols which may be mixed with the above 2-alkyl-substituted primary alcohols and co-reacted with alkaline earth metals and their compounds are C₁-C₁₂ aliphatic primary (linear, unsubstituted) alcohols, such as, for example, methanol, ethanol, n-butanol, n-hexanol, n-octanol and the like. The amounts of said primary (unsubstituted), secondary and tertiary alcohols, which are co-reacted with said C₄-C₁₂ 2-alkyl-substituted primary alcohols may be varied from 0.1 to 2 moles per mole of said C₄-C₁₂ 2-alkyl-substituted primary alcohols, but will preferably be in the range of 0.5 to 1 mole per mole of said alcohol, and most in the preparation of polymerization initiators.

Additionally, hydrocarbon or chlorinated hydrocarbon solvent-soluble magnesium alkoxides ean be readily mixed with hydrocarbon or chlorinated hydrocarbon solvent-soluble magnesium alkyls to form soluble alkylmagnesium alkoxides which are useful in the preparation of halogen-free Ziegler catalysts which are useful as co-catalysts for the polymerization of olefins, diolefins, or olefin oxides. Such a procedure for forming alkylmagnesium alkoxides is deemed superior to that described in either Malpass (U.S. Patent No. 4,133,824) or Mueller (U.S.

Patent No. 4,410,742 to Schering A.G.) in that no insoluble magnesium alkoxide need be employed which would tend to slow the reaction with dialkylmagnesium compounds or incompletely react therewith. The resulting alkyl-magnesiurm alkoxides, when complexed with alkali metal alkyls, also form useful initiators for the polymerization of 1,3-dienes and vinylaromatic compounds. 2-alkyl-substituted primary monohydric (normal) alcohols or alkanols (C₄-C₁₂) , which are reacted with alkaline earth metals or their compounds in various of the embodiments of my invention are exemplified by isobutyl alcohol, 2-methyl-1-pentanol,

2-ethy1-1-butanol, 2-ethyl-1-pentanol,

2-ethy1-1-hexanol, 2-ethyl-4-methyl-1-pentanol,

2-propy1-1-heptanol, 2-methyl-1-hexanol,

2-ethyl-5-methyl-1-octanol, and the like, orr In those instances where the alcohols used in accordance with my invention are 2-alkoxy-1-alkanols or α -alkoxy-poly (ethyleneoxy)-1-ethanols, lower C₁-C₃ barium and calcium alkoxides such as ethoxide may be used in place of the respective metal or metal amides. The resulting products are lower C₁-C₃ alcohol solvates of the calcium and barium 2-alkoxy-1-alkoxides, and show the aforementioned structure

M(OCH₂-CH(R' )OR₂- (R"OH)_x, or calcium and barium α -alkoxy-poly (ethyleneoxy)-1-ethoxides, M(OCH₂)OCH₂CH₂)_nOR)₂ (R'OH)_x where x = zero to 2. Advantageously, an excess of the alcohol or mixture of alcohols, above that necessary to react with all of the alkaline earth metal precursors present, is employed in order to gain an increased fluidity or solubility of the resulting alkaline earth metal alkoxides in hydrocarbon or chlorinated hydrocarbon solutions. This excess of alcohol can vary from 0.01 to 2 moles of alcohol per mole of alkaline earth metal precursor reacted, but preferably varies from 0.05 to 1 mole of alcohol per mole of alkaline earth metal precursor reacted, and most advantageously from 0.1 to 0.5 moles of alcohol per mole of alkaline earth metal precursor reacted. The said alcohols can be added to the alkaline earth metals or their compounds in either neat form or dissolved in a liquid hydrocarbon or chlorinated hydrocarbon solvent of choice. favorably in the range of 0.7 to 1 mole per mole of said alcohol.

In addition to the alcohols mentioned above, which can be coacted with alkaline earth metals and their compounds, are

2-alkoxyl-1-alkanols, ROCH₂CHR'OH (R is C₁-C₁₂ hydrocarbyl and R' is hydrogen or C₁-C₃ hydrocarbyl), such as, for example, 2-methoxy-1-ethanol, 2-ethoxy-1-ethanol, 2-butoxy-1-ethanol,

2-butoxy-1-methy1-1-ethanol,

2-hexyloxy-1-ethanol, and the like, commonly referred to in the art as "Cellosolve" solvents (Union Carbide Corp.). Also effectively useful in the practice of my present invention are the alkanols or alcohols which are known as "Carbitols" (Union Carbide Corp.). These include, by way of illustration, 2-ethoxyethoxyethanol and

2-butoxyethoxyethanol. In general, these are alcohols of the type belonging to the generic group of α -alkoxy poly(ethyleneoxy)-1-ethanols, RO(CH₂CH₂O)_nCH₂CH₂OH, where R is C₁-C₁₂ hydrocarbyl but most desirably ethyl, n-butyl and n-hexyl, and n may vary from 0 to 4. One can employ mixtures of these alcohols with each other, in the proportions referred to herein, in admixture with the aliphatic 2-alkyl substituted C₄-C₁₂ primary monohydric alcohols referred to and described and illustrated above. In those cases where lower alkaline earth metal alkoxides (C₁-C₃) are reacted with two molar equivalents of 2-alkoxy-1-alkanols, ROCH₂CHR'OH, two molar equivalents of the C₁-C₃ lower alcohol are generated per alkaline earth metal 2-alkoxy-1-alkoxide formed and, beneficially, promote the solubility of the said alkoxide.

The dialkylmetallic compounds employed in the reaction with the above alcohols can be varied widely. For convenience, they are generally soluble in liquid hydrocarbon or chlorinated hydrocarbon media, although it is not outside the scope of this invention to employ dialkylmetallic compounds or even arylmetallic compounds which are insoluble in liquid hydrocarbon or chlorinated hydrocarbon media. Included are typical dialkylmagnesiums, such as n-butyl-sec-butylmagnesium, n-butyl-ethylmagnesium, di-n-hexylmagnesium, diisopropylmagnesium, di-n-butylmagnesium, di-sec-butylmagnesium, di-2-methyl-butylmagnesium, di-n-amylmagnesium, n-butyl-n-octylmagnesium, ethyl-isoamyl-magnesium, and typical arylmagnesium compounds, such as diphenylmagnesium, phenylmagnesium chloride and the like. Also included are phenylcalcium iodide, isopropylcalcium bromide, isopropylcalcium chloride, and the like.

These dialkylmetallic compounds, when they are dialkylmagnesium compounds, can also contain sufficient added trialkylaluminum compounds to maintain solubility and fluidity of the resulting magnesium alkoxides in the liquid hydrocarbon or chlorinated hydrocarbon solutions after reaction with the desired alcohols. It is, in any case, preferred that such trialkylaluminum compounds be added to the said dialkylmagnesium compounds, when not originally present, prior to reaction with said alcohols. Generally, amounts of trialkylaluminum to be added or maintained can be varied from 0.005 to 2 moles per mole of magnesium compound, but are preferably in the range of 0.01 to 1 mole per mole of magnesium compound, and most advantageously in the range of 0.02 to 1 mole of trialkylaluminum per mole of dialkylmagnesium compound. Typical trialkylaluminum compounds employable are triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethyl-n-butylaluminum, tri-n-octylaluminum, and the like. Instead of adding the trialkylaluminum to the dialkylmagnesium compound prior to reaction with the desired alcohol, aluminum trialkoxide or trialkylaluminum can be added after reaction of the alcohol with the dialkylmagnesium is complete and then further reacted with the alcohol or alcohols, if required.

In place of the trialkylaluminum compounds mentioned above, which are added to the dialkylmagnesium compounds prior to reaction with the desired alcohols, there can be added other organometallic compounds or metallic alkoxides, such as trialkylboron, dialkylzinc, alkyllithium, alkylsodium, potassium alkoxide, sodium alkoxide, calcium alkoxide, and barium alkoxide compounds and the like to maintain solubility and fluidity of the resulting magnesium alkoxides in the liquid hydrocarbon or chlorinated hydrocarbon solvent solutions. Other compounds containing said metals can be added, as well, which are reactive with the added alcohol, as, for example, sodium amide, sodium hydride, potassium hydride, calcium amide, barium amide, and the like. Generally, amounts of added organometallic compound, metallic alkoxide or other metal derivative can be varied in the range of 0.005 to 2 moles per mole of magnesium compound, but are preferably in the range of 0.01 to 1 mole per mole of magnesium compound, and most advantageously in the range of 0.02 to 0.1 mole of organometallic compound, metallic alkoxide, or metal derivative per mole of dialkylmagnesium compound.

Typical organometallic compounds employable are methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, phenylsodium, n-amylsodium, triethylboron, tri-n-butylboron, diethylzinc, di-n-butylzinc, and the like, and mixtures thereof.

Typical metallic alkoxides employable are lithium tert-butoxide, lithium

2-methyl-1-pentyloxide, lithium sec-butoxide, sodium tert-butoxide, sodium tert-amyloxide, sodium 2-methyl-1-pentyloxide, potassium tert-butoxide, potassium tert-amyloxide, potassium 2-methyl-1-pentyloxide, calcium

2-ethyl-1-hexyloxide, calcium

2-methyl-1-pentyloxide, barium

2-ethyl-1-hexyloxide, barium 2-methyl-1-pentyloxide, tri-n-butoxyboron, tri-2-methyl-1-pentyloxyboron, zinc di-2-methyl-1-pentyloxide, and the like, and mixtures thereof.

It is generally preferable (although not essential) to add organometallic compounds or metallic alkoxides which are soluble in the liquid hydrocarbon or chlorinated hydrocarbon medium employed.

It is also within the scope of my present invention to react the said alcohols used in accordance with my invention with alkaline earth metals and their compounds other than dialkylmetallics. For example, alkaline earth metal amides, such as Ca(NH₂)₂, Sr(NH₂)₂ and Ba(NH₂)₂, can be reacted with said alcohols in a liquid hydrocarbon or chlorinated hydrocarbon medium.

The magnesium amide, barium amide, calcium amide and strontium amide can be produced by any convenient means, but are advantageously obtained in a finely-divided form.

One novel method for the preparation of the barium amide, for example, which is particularly useful, involves dissolution of barium metal in liquid ammonia, followed by addition of an aromatic solvent, such as toluene. This addition converts the dissolved barium metal to a slurry of barium amide, which can be filtered and dried, or the ammonia evaporated off, residual ammonia being removed by subsequent heating of the slurry to the boiling point of the aromatic solvent. A finely-divided slurry of barium amide in the aromatic solvent is obtained which can be used directly in the preparation of barium alkoxides.

The reaction of the aforesaid amides, particularly desirably barium and calcium amides, with the aforesaid alcohols to produce the desired hydrocarbon- or chlorinated hydrocarbon-soluble barium and calcium alkoxides can be carried out at any convenient temperature. Preferably, the reaction is carried out at room temperature; and the reaction mixture is then heated to reflux for a period of time (usually 1 to 4 hours) to complete the removal of by-product ammonia. Other methods for the preparation of alkaline earth metal alkoxides include reaction of said alcohols with alkaline earth metal or alkaline earth metal hydrides, transalcoholysis of lower C₁-C₃ alkaline earth metal alkoxides with said alcohols, or reaction of the alkali metal alkoxide derivatives of said alcohols with alkaline earth metal halide salts. It is, further, within the scope of my present invention to react Grignard reagents such as RMgX, RCaX, etc., with said alcohols to produce useful alkoxyalkaline earth metal compounds. Obviously, for optimal economy in the production of the resulting alkaline earth metal alkoxides, the lowest priced alkaline earth metal precursors (coupled with the simplest process parameters) will be most advantageous.

In regard to the complexing solubilizer for the alkaline earth metal alkoxides, especially the barium and calcium alkoxides, while TMEDA is especially satisfactory for use in the practice of the present invention, other aliphatic tertiary amines can be utilized, among which may be mentioned azaoxa-alkanes, aza-alkyloxacycloalkanes or

oxa-alkylazacycloalkanes of the formulas:

where R¹, R² and R³ are the same or different alkyls, each containing from 1 to 4 carbon atoms, namely, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl; X is a non-reactive group, such as or other divalent aliphatic hydrocarbon or alkylene radical, preferably containing from 2 to 4 carbon atoms; and w is 1 to 4. Illustrative examples include, for instance, 2-dimethylaminoethylmethyl ether [ (CH₃)₂N-CH₂-CH₂-OCH3], 2-diethylaminoethylmethyl ether [ (C₂H₅ )₂N-CH₂-CH₂-OCH₃], and 2-dimethylaminopropylmethyl ether [ (CH₃)₂N-CH₂-CH₂-CH₂-OCH₃ ] .

TMEDA and generally functionally-equivalent aliphatic tertiary amines are disclosed in U.S. Patent No. 3,451,988. Such aliphatic tertiary amines, as there disclosed, include, among others, those which are represented by the formulas:

wherein R¹, R¹, R¹ and R¹ are the same or 2 3 4 different alkyl radicals of 1 to 5 carbon atoms, inclusive; A is a non-reactive group;

R¹¹, R¹¹, R¹¹ and R¹¹ are the 1 2 3 4 same or different alkyl radicals of 1 to 3 carbon atoms, inclusive; and n is an integer between 1 and 4, inclusive. The disclosure of said aliphatic tertiary amines in said patent is incorporated herein by reference.

The reaction of the aforementioned alcohols, used in accordance with my present invention, with dialkylmagnesium or other alkaline earth metal compounds, or other compounds disclosed and contemplated by the present invention, can be carried out at any convenient temperature. Generally, it is preferred to carry out the reactions at lower temperatures, i.e., below the boiling point of the liquid hydrocarbon or chlorinated hydrocarbon solvent employed. The said alcohols, for instance, can be added to the dialkylmagnesium compound, or the dialkylalkaline earth metal compound, or vice versa. Addition is generally carried out incrementally.

A wide variety of liquid hydrocarbon and chlorinated hydrocarbon solvents can be employed in the practice of my invention. Aliphatic or cycloaliphatic solvents, such as, for example, isopentane, n-pentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, and the like, are preferred. However, aromatic solvents can also be employed, such as, for example, benzene, toluene, xylene, mesitylene, and the like, or mixtures thereof with aliphatic or cylcoaliphatic solvents. Among the illustrative liquid chlorinated hydrocarbon solvents are 1,1,1-trichloroethane; 1,1-dichlorobutane; 1,4-dichlorobutane; 1-chlorohexane; chlorocyclohexane; mono- and polychlorobenzenes; 3 , 4-di-chlorotoluene; 1-chloropentane; 1,3-dichlorohexane; carbon tetrachloride; chloroform; and the like.

It is also within the scope of my invention to employ minor quantities of ethereal solvents in the formulation of the magnesium or other alkaline earth metal alkoxide solutions, such as, for example, diethyl ether, THF, methyl tert-butyl ether, di-n-butyl ether and the like, or monofunctional tertiary amines, such as, for example, trimethylamine, triethylamine, N-methylpiperidine and the like. Other co-solvents, compatible with alkaline earth metal alkoxides, can also be employed, such as, for example, chlorobenzene, carbon tetrachloride, chloroform, dimethylacetamide, dimethylformamide, hexamethylphosphorus triamide, and the like.

Various organometal reagents may be admixed with the aforesaid metal alkoxides of this invention. Within the scope of my invention are organolithium compounds generally soluble in hydrocarbon media, such as ethyllithium, isopropyllithium, n-hexyllithium, n-octyllithium and mixtures of these, such as n-butyllithium and ethyllithium, which form novel products soluble in hydrocarbon or chlorinated hydrocarbon solvents.

Other organoalkali compounds not normally soluble in liquid hydrocarbon or chlorinated hydrocarbon solvents can also be admixed with the magnesium alkoxides of my present invention, including, for example, n-butylsodium, n-butylpotassium, n-amylsodium, n-hexylsodium, n-hexylpotassium and the like, and mixtures of these with organolithium compounds in the range of 0.01 to 10 moles per mole of magnesium alkoxide, but more preferably in the range of 0.05 to 2 moles per mole of magnesium alkoxide. In place of, or in admixture with, the organolithium or other organoalkali compounds, one can employ diorganomagnesium compounds soluble in liquid hydrocarbon or chlorinated hydrocarbon media for interaction with the alkaline earth metal alkoxides of my invention. Examples of these diorganomagnesium compounds are diethylmagnesium, n-butyl-ethylmagnesium, diisopropylmagnesium, n-butyl-sec-butylmagnesium, n-butyl-n-octylmagnesium, di-n-hexylmagnesium, di-sec-butyImagnesium, di-2-methylbutylmagnesium and di-n-octylmagnesium, and the like, and mixtures thereof. Products formed by this interaction with magnesium alkoxides are alkylmagnesium alkoxides, which also can be formed by adding only one-half the stoichiometric amount of the alcohol to a dialkylmagnesium compound, according to my invention. In admixture with the alkaline earth metal alkoxides of my present invention are also included triorganoaluminum compounds normally soluble in liquid hydrocarbon or chlorinated hydrocarbon media, such as TIBAL, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum and the like, and mixtures thereof in the range of 0.01 to 10 moles per mole of magnesium alkoxide, but more preferably in the range of 0.05 to 2 moles per mole of alkaline earth metal alkoxide.

There is generally no particularly superior order of admixing these reagents, except that good agitation be maintained throughout said admixture. For example, the aforesaid metal alkoxide may be added to the organometal, or vice versa. Generally, addition of one reagent to the other is carried out incrementally (i.e., not all at once) so as to maintain good contact of the reagents throughout.

ANALYTICAL TECHNIQUES

Barium, magnesium, lithium and aluminum are assayed in the presence of each other in the following Examples. Aluminum is determined complexometrically by addition of an excess of either EDTA or CDTA at pH 5 to 6 and back titration of the excess with standard Zn⁺⁺ solution to a colored end point. Magnesium is determined by precipitation of the Al as Al(OH)₃, and Ba as Ba SO₄, followed by complexometric titration with EDTA at pH 10; while barium is determined by subtracting the Mg value obtained from a separate determination of both Mg and Ba via back titration of an excess of EDTA with Zn⁺⁺. The following Examples are illustrative of various facets of my present invention, showing the preparation of novel, stable liquid hydrocarbon or chlorinated hydrocarbon solvent-soluble alkaline earth metal alkoxides. It will, of course, be understood that many other novel, stable liquid hydrocarbon or chlorinated hydrocarbon solvent-soluble alkaline earth metal alkoxides can be made pursuant to my present invention, utilizing different alkaline earth metal alkoxides or alkaline earth metal dialkoxides; different complex-forming solubilizers; and different organometallics than the particular alkyllithiums, dialkylmagnesiums or trialkylaluminums used in the Examples; different liquid hydrocarbon solvents, or chlorinated hydrocarbon solvents; and different reaction temperatures, etc., without departing from the guiding principles and teachings disclosed herein. All temperatures recited are in degrees Centigrade.

EXAMPLE I

PREPARATION OF HYDROCARBON-SOLUBLE MAGNESIUM 2-METHYL-1-PENTYLOXIDE (PENTANOLATE)

(a) To a volume of 100 ml of 1.024 Molar n-butyl-sec-butyl-magnesium in heptane (DBM, Lithium Corporation of America) is added 3.3 ml of 0.92 Molar TIBAL in heptane (Texas Alkyls, Inc.) To the stirred solution cooled in an ice bath, there is slowly added 25.3 ml (0.2048 moles) of 2-methyl-1-pentanol, diluted with an equal volume of cyclohexane. The reaction proceeds smoothly with vigorous gas evolution, but no spattering on the walls of the flask, to give a crystal-clear, water-white, somewhat viscous solution. Titration of the resulting solution for Mg shows the solution to contain 0.66 moles of magnesium per liter of solution.

A 2 ml sample of the solution is treated with about 0.5 ml of neat titanium tetra-isopropylate, resulting in an immediate gelation, but no color change, indicating reaction of all alleyl groups with the alcohol.

The viscosity of the magnesium 2-methyl-1-pentyloxide solution is noticeably reduced by the addition of 1.2 ml (0.01 moles) of 2-methyl-1-pentanol. (b) . To a volume of 10 ml of 1.156

Molar n-butyl-sec-butyl-magnesium (11.56 mmoles) there is added 1.43 ml (11.56 mmoles) of 2-methyl-1-pentanol, diluted to 5 ml with heptane. Then, 0.6 ml of 0.99 Molar (0.59 mmoles) of potassium tert-amylate in cyclohexane solution is added, followed by an additional 1.43 ml of 2-methyl-1-pentanol (11.56 mmoles). A pale yellow, clear, slightly viscous solution of magnesium 2-methyl-1-pentyloxide is obtained. No excess of 2-methyl-1-pentanol is added as in comparative Example 1(a).

(c) To 10 ml of a solution of 4.33 ml of 2-methyl-1-pentanol in heptane there is added 0.4 ml of 1.91 Molar n-butyllithium in cyclohexane. To the cloudy mixture, there is added, slowly and with good mixing, 15 ml of a 1.036 Molar solution of n-butyl-sec-butylmagnesium in heptane. A clear, colorless, viscous solution of magnesium 2-methyl-1-pentyloxide is obtained.

Comparative Example I-A

To a volume of 100 ml of 1.024M DBM solution in heptane there is slowly added 25.3 ml (20.9 g, 0.2048 moles) of neat 2-methyl-1-pentanol while stirring and cooling in an ice bath. Vigorous gas evolution occurs, with spattering of viscous, gel-like material on the walls of the flask. The main body of the solution remains fluid, at least through the half-way point in the addition of the alcohol. After this point is reached, the solution becomes increasingly viscous, then gels near the end of the addition to a clear solid mass. A volume of 100 ml of cyclohexane is added, but the gel does not dissolve. The mixture is heated to reflux; but, again, no thinning or solution of the product occurs. Next, 50 ml of toluene is added, again with no effect. Finally, two consecutive 15 ml (0.1 mole) additions of TMEDA is made, also with little or no effect. The mix is decomposed by pouring the heavy, viscous, taffy-like mass into ice water.

Example 1(a) shows the beneficial effect of the addition of a very small amount of trialkylaluminum to the DBM prior to its reaction with 2-methyl-1-pentanol, while ExampIes I(b) and (c) show the beneficial effects of the addition of a small amount of potass or lithium alkoxide during the reaction.

Comparative Example I-B

To a solution of 104 ml of

2-methyl-1-pentanol (0.84 moles) in 180 ml of chlorobenzene there is added 13.2 ml of an 0.92M solution of TIBAL in heptane (t = 25°). After reaction is complete, a volume of 252 ml of a 1.6M solution of n-butyl-sec-butylmagnesium in heptane is slowly added over a 40-minute period, the temperature of the solution rising to 90°. The clear, colorless, viscous solution is cooled to 25° and 110 ml of heptane is added, along with an additional 2 ml of 0.92M TIBAL. Assay of the solution for magnesium content shows a content of 0.67 moles per liter.

This Example shows that the TIBAL can be prereacted with the alcohol before reaction with dibutylmagnesium.

EXAMPLE II

PREPARATION OF HYDROCARBON- SOLUBLE

MAGNESIUM 2-ETHYL-1-HEXYL0XIDE (HEXANOLATE )

To 10 ml of 1. 355M di-n-hexylmagnesium in cyclohexane ( already containing 3 mole % TIBAL based on contained Mg) is added, dropwise, 4.24 ml (3.53 g, 0.027 moles) of neat 2-ethy1-1-hexanol. No visible precipitate appears at any point during the addition. The solution is heated to reflux briefly and cooled to room temperature in a cold water bath. Then 5 ml of cyclohexane is added to give a crystal-clear, water-white, quite viscous solution containing approximately 0.9 moles Mg/liter (1.8N). Further dilution with 10 ml of cyclohexane decreases the viscosity somewaht. Addition of 3 mmoles of aluminum isopropoxide in solution in cyclohexane does not reduce the viscosity further; nor does the addition of 1 mmole of TIBAL. Addition of 1 ml (0.006 mole) of neat 2-ethyl-1-hexanol significantly reduces the viscosity.

EXAMPLE III

PREPARATION OF HYDROCARBON-SOLUBLE BARIUM 2-ETHYLHEXYLOXIDE

A. Preparation of Barium Amide

Into 200 ml of liquid ammonia at -60° is added, slowly, 50 g (0.365 g at.) of bar ium metal (broken crowns). After stirring for about 1 hour, 50 ml of toluene is added slowly below -50°. Within 30 minutes, evidence of reaction is noted, the reddish-bronze color of the metal-ammonia solution changing to green and then to yellow. The mixture is stirred at -50 ° to -60 ° for 1 hour longer and then allowed to warm up , ammonia slowly being driven off overnight .

To the flask containing a slurry of yellow solids is added 50 ml of toluene; the mixture is heated and stirred to distill off toluene. About 50 ml of toluene is distilled off, after which no further odor of ammonia is noted. The mixture is cooled, filtered, washed with pentane twice, and blown dry under an argon stream. The product is transferred to 125 ml Wheaton bottles in a glove bag. Total recovered product = 59.34 g (0.35 moles, 96%). Found for Ba: 80.1 wt. %; Theory - 81.1%.

Preparation of Barium-2-Ethyl-1-Hexyloxide (Hexanolate)

13.4 g (0.0791 moles) of Ba(NH₂)₂ is suspended in 100 ml of cyclohexane and mechanically stirred while neat 2-ethylhexanol (20.5 g, 24.7 ml, 0.158 moles) is added slowly, via syringe. All of the solid reacts and goes into solution. The mixture is heated to boiling for about 4 to 5 hours to remove NH₃; cooled; filtered; and analyzed for barium. Several analyses are run, resulting in an average molarity value of 0.65 M. The total volume of clear, light amber filtrate is about 110 ml. Yield of recovered Ba in solution = 0.0715 moles (90%). PMR of the alkoxide solution shows alkoxide protons (OCH₂) at 5.0δ relative to the cyclohexane protons as 2.85δ. EXAMPLE IV

PREPARATION OF A HYDROCARBON-SOLUBLE COMPLEX OF BARIUM 2-METHYL-PENTYLOXIDE AND TMEDA

12.47 g, 15.1 ml (0.122 moles) of 2-methyl-1-pentanol are added gradually to a stirred slurry of 10.34 g (0.061 moles) of barium amide in 55 ml of cyclohexane. Severe thickening of the reaction mixture occurs after addition of the first 6 ml of the alcohol, resulting in a foaming problem. In order to allow completion of the reaction, 8.5 ml (0.056 moles) of TMEDA is added to the mixture. The addition of TMEDA causes the mixture to become quite fluid, thus mixture occurs after addition of the first 6 ml of the alcohol, resulting in a foaming problem. In order to allow completion of the reaction, 8.5 ml (0.056 moles) of TMEDA is added to the mixture. The addition of TMEDA causes the mixture to become quite fluid, thus allowing the completion of the alcohol addition. After stirring for a further period of about 1 hour, an additional 1 ml of TMEDA is added (total TMEDA present - 0.063 moles); and the mixture is heated overnight in an oil bath at about 80° (just below reflux point of the solution) . No discernable solids are present. The mixture is then heated to a full reflux to drive off dissolved ammonia; cooled; filtered; and analyzed for barium: Found: Ba - 0.83 Molar Total volume = 85 ml Recovered: Ba = 0.054 Moles Yield - 88% EXAMPLE V

PREPARATION OF HYDROCARBON-SOLUBLE MIXED ALKOXIDES OF MAGNESIUM 2-METHYL-1-PENTYLOXIDE AND MAGNESIUM ISOPROPOXIDE

From (1:1) 2-Methyl-1-Pentanol/Isopropanol

To 10 ml of 1.085M DBM in heptane and 0.33 ml of 0.92M TIBAL (as above) is slowly added a mixture of 2-methyl-1-pentanol (1.34 ml, 10.85 mmoles) and isopropanol (0.82 ml, 10.85 mmoles) diluted to 5 ml with cyclohexane. Again, a clear, stable solution results at room temperature.

EXAMPLE VI

1. PREPARATION OF HYDROCARBON-SOLUBLE MAGNESIUM 2-ETHOXYETHOXIDE

(a) From Dibutylmaqnesium (DBM)

To 10 mmoles of a DBM solution in 10 ml of heptane there is added, dropwise, 21 mmoles (2.0 ml) of 2-ethoxyethanol ("Cellosolve") diluted to 5 ml with heptane. A hazy, quite mobile solution is obtained, which, on centrifugation, gives 12 ml of a clear, water-white, non-viscous solution containing 0.825 mmoles of magnesium per ml of solution (analysis by EDTA titration) representing essentially all of the initial magnesium reagent.

(b) From Magnesium Ethoxide

68.6 g (0.6 moles) of solid magnesium ethoxide, Mg(OC₂H₅)₂ is mixed with 120 ml of heptane and 112 ml (1.15 moles) of 2-ethoxyethanol, with stirring. As the mixture is stirred the temperature slowly rises to about 40° over a period of 15 minutes, then drops off to below 30° within the next hour. The mixture is then stirred for a period of 3 hours during which most of the contained solids dissolve. The resulting mixture is filtered, and the clear filtrate diluted with an additional 160 ml of heptane. Analysis of the solution shows it to contain 1.16 moles of magnesium per liter.

(c) From Magnesium Metal

7.3 g of magnesium metal chips and 64 ml of "Cellosolve" are placed together in a flask, a few crystals of iodine added, and the mixture reacted at 70-80° C for 18 hours. A light, creamy, viscous mass results, which is readily dissolved in 30 ml of chlorobenzene to give a 2.09 Molar solution. 2. PREPARATION OF A LIQUID MAGNESIUM

2-ETHOXYETHOXIDE PRODUCT COMPLEXED WITH ETHANOL

To 34.3 g (0.3 moles) of magnesium ethoxide (Mg(OEt)₂) is added 61 ml of "Cellosolve" (2-ethoxyethanol) and the mixture stirred. After about 15 minutes, the temperature rises to 40°, and most of the Mg(OEt)₂ goes into solution. The mix is heated to 50° for 1 hour, then allowed to cool and settle. The dark, greyish-black liquid is analyzed for magnesium content and found to be 3.32 Molar in Mg. The product is soluble in chlorobenzene and heptane.

EXAMPLE VII

Preparation of Magnesium 2-n-Hexyloxy-1-Ethoxide

34.5 g (0.3 moles) of magnesium ethoxide, 104 ml, 92 g (0.63 moles) of n-Hexyl "Cellosolve", and 200 ml of heptane are stirred together for 5 hours at room temperature. Most of the solids dissolve, except for some grey fines. The product solution is filtered, and the filtrate is analyzed for magnesium content. Found: 0.92 Moles Mg/liter. EXAMPLE VIII

PREPARATION OF A HYDROCARBON-SOLUBLE COMPLEX OF MAGNESIUM 2-ETHOXYETHOXIDE AND MAGNESIUM 2-HEXYLOXYETHOXIDE

80 ml of an 0.82 Molar solution of magnesium 2-ethoxyethoxide in heptane and 75 ml of the product solution of EXAMPLE VII are combined, stirred thoroughly, then stripped of solvent, and heated to 125-130° C for 2.5 hours under full vacuum. The residual product is a clear, viscous liquid at this temperature. On cooling to room temperature, the product solidifies to a clear glass, which is readily dissolved in 50 ml of methylcyclohexane.

EXAMPLE IX

PREPARATION OF HYDROCARBON-SOLUBLE CALCIUM 2-ETHOXY-1-ETHOXIDE

To 8.02 g (0.2 g moles) of calcium metal pellets suspended in 175 ml of cyclohexane and 45 ml of toluene is added a crystal of iodine and the mixture heated to reflux. A solution of 40 ml (0.41 moles) of 2-ethoxyethanol in an equal volume of cyclohexane is added over a 1-hour period. The grey fluid suspension is further refluxed and stirred for 12 hours. After cooling and filtration, 140 ml of a light amber-colored solution is obtained which is 0.77M in calcium (53%). EXAMPLE X

PREPARATION OF A HYDROCARBON-SOLUBLE COMPLEX OF SODIUM TRIHEXYLMAGNESIATE AND MAGNESIUM 2-METHYL-1-PENTYLOXIDE

A 6 ml portion of the heptane-cyclohexane solution of magnesium 2-methyl-1-pentyloxide (3.9 mmoles) of EXAMPLE I is added to 9.5 ml of an 0.4M (3.8 mmoles) solution of sodium tri-n-hexylmagnesiate in cyclohexane. A clear, colorless solution of an approximately 1:1 complex of sodium tri-n-hexyl magnesiate and magnesium 2-methyl-1-pentyloxide, NaMgHex₃ Mg(O-3MP)₂, is obtained (2MP = 2-Methylpentyl). Alternatively, this complex can be written as NaHex [HexMg-O-2MP]₂.

EXAMPLE XI

PREPARATION OF A HYDROCARBON-SOLUBLE COMPLEX OF TRIISOBUTYLALUMINUM (TIBAL) AND MAGNESIUM 2-METHYL-1-PENTYLOXIDE

A 10 ml portion of the heptane-cyclohexane solution of magnesium 2-methyl-1-pentyloxide (6.6 mmoles) of EXAMPLE I is added to 7.3 ml of an 0.92M solution (6.6 mmoles) of TIBAL in heptane. A clear, colorless solution of an approximately 1:1 Molar complex of triisobutylaluminum and magnesium 2-methyl-1-pentyloxide is obtained (Mg(O-2MP)₂ Al (IsoBu)₃). Alternatively, this complex can be written as MgAl(O-2MP)₂ · (IsoBu)₃ or IsoBuMg-O-2MP· (IsoBu)₂Al (O-2MP) .

EXAMPLE XII

PREPARATION OF A HYDROCARBON-SOLUBLE COMPLEX OF POTASSIUM TERT-BUTOXIDE AND MAGNESIUM 2-METHYL-1-PENTYLOXIDE

To 0.74 g (6.6 mmoles) of solid potassium tert-butoxide there is added 10 ml of 0.66 Molar magnesium 2-methyl-1-pentyloxide in heptane. The product thickens to a gel; then, on further mixing, thins out to form a completely clear, fluid, pale yellow solution having the composition KOt-Bu-Mg(O-2MP)₂ or KMg(O-2MP)₂(O-tert-Bu).

EXAMPLE XIII

PREPARATION OF A HYDROCARBON-SOLUBLE COMPLEX OF LITHIUM 2-METHYL-1-PENTYLOXIDE AND MAGNESIUM 2-METHYL-1-PENTYLOXIDE

To a solution of 5 ml of 1.6 Molar n-butyl-sec-butylmagnesium in heptane and 4.2 ml of 1.9 Molar n-butyllithium in cyclohexane there is added, incrementally, three 1.0 ml portions of 2-methyl-1-pentanol. The solution remains clear after each addition. During the addition of the last 1.0 ml increment, the solution becomes quite thick, then thins out on further mixing. An additional 10 ml of heptane is added. A clear, colorless, slightly viscous solution of LiMg(O-2MP)₃ is obtained.

EXAMPLE XIV

PREPARATION OF A COMPLEX OF A HYDROCARBON-SOLUBLE MAGNESIUM ALKOXIDE AND A DIALKYLMAGNESIUM COMPOUND

A 10 ml portion of the heptane-cyclohexane solution of magnesium 2-methyl-1-pentyloxide (6.6 mmoles) of EXAMPLE I is mixed with 6.1 ml of 1.085M DBM solution in heptane. A clear solution of the 1:1 Molar complex of magnesium 2-methyl-1-pentyloxide and n-butyl-sec-butylmagnesium is obtained. Assuming total scrambling of alkyl and alkoxy groups, this complex can be represented as (n,s)-butylmagnesium 2-methylpentyloxide. The complex can also be prepared by the addition of 13.2 mmoles (1.63 ml) of neat

2-methyl-1-pentanol to 13.2 mmoles (12.2 ml) of 1.085M DBM solution in heptane.

EXAMPLE XV

PREPARATION OF A COMPLEX OF A HYDROCARBON-SOLUBLE MAGNESIUM ALKOXIDE AND AN ALKYLLITHIUM COMPOUND

A 10 ml portion of the heptane-cyclohexane solution of magnesium 2-methyl-1-pentyloxide (6.6 mmoles) of EXAMPLE I is added to 3.5 ml of 1.92M n-butyllithium in 5 ml of cyclohexane to give a crystal-clear, mobile, colorless solution of the 1:1 complex of n-butyllithium and magnesium

2-methyl-1-pentyloxide

( n-BuLi· Mg(O-2MP)₂) ( 2MP = 2-Methylpentyl).

Alternatively, this complex may be written as

LiMg(O-2MP)₂(Bu).

EXAMPLE XVI

PREPARATION OF A HYDROCARBON-SOLUBLE COMPLEX OF BARIUM 2-METHYLPENTYLOXIDE (PENTANOLATE) TMEDA WITH

DI-NORMAL-HEXYLMAGNESIUM (DNHM) AND TIBAL

To 17.5 ml of an 0.36 M solution of di-normal-hexylmagnesium solution in heptane, there is added 10 ml of 0.63 M barium 2-methylpentyloxide TMEDA solution in cyclohexane with cooling at 0°. A light hazing is noted. Next, a volume of 7.6 ml of 0.92 M TIBAL is added, and the mixture is allowed to stand overnight. A clear yellow-amber solution results. Analysis shows that this solution contains 6.81 mmoles of Al (Theory = 6.99), 6.95 mmoles of Mg (Theory = 6.30), and 5.90 mmoles of Ba (Theory = 6.30).

COMPARATIVE EXAMPLE XVII

PREPARATION OF BARIUM ISOBUTOXIDE

5.65 g (0.033 moles) of barium amide is slurried in 55 ml of cyclohexane; and 6 ml (4.9 g. 0.065 moles) of isobutanol is added slowly with evolution of ammonia. The mixture is heated at reflux until no more ammonia is given off. The mixture is cooled and filtered, and the filtrate analyzed for Ba content. Found: 0.22 M or 8 mmoles Ba in the filtrate. This represents only 25% of the theoretical quantity of barium isobutoxide produced in the reaction.

EXAMPLE XVIII

PREPARATION OF A HYDROCARBON-SOLUBLE COMPLEX OF BARIUM ISOBUTOXIDE AND DI-N-HEXYLMAGNESIUM (DNHM)

To the undissolved solids remaining on the filter in the above barium isobutoxide preparation, there is added 50 ml of 0.37 M di-n-hexylmagnesium in heptane, and the mixture is stirred. Very little of the solids dissolve, and plugging of the filter plate occurs on attempted filtration. Next, 4 ml of TMEDA is added, and the mixture is stirred again. Most of the solids appear to dissolve. A red-brown solution is obtained on filtration, which shows the presence of 16 mmoles (88%) Mg and 13.5 mmoles Ba.

This example teaches that, in the absence of the TMEDA, barium alkoxides of low solubility in hydrocarbon solvents do not react rapidly with organometallic compounds to produce hydrocarbon-soluble complexes. EXAMPLE XIX

PREPARATION OF CALCIUM ISOBUTOXIDE

10 g (0.25 gram atoms) of calcium metal turnings, 40 ml of isobutanol, 50 ml of tetrahydrofuran (THF) and a crystal of I₂ are heated together at reflux and stirred vigorously with a nichrome wire stirrer for 3 days. The solvent and most of the excess isobutanol are azeotroped out of the mixture with the aid of cyclohexane. The mixture (lumps) is filtered, and the solid is washed with cyclohexane (total volume of filtrate, about 200-250 ml, total alkalinity = 0.83 N, representing a yield of calcium isobutoxide of 33%). The cake is washed twice with a 50:50 mixture of cyclohexane and isobutanol and all the filtrates combined. Solvents are azeotroped off using toluene. On cooling, a white product crystallizes out. After filtration, the solids are washed once with toluene, 3 times with pentane, and then dried under vacuum to give 18.3 g of a crystalline light yellow solid, having an N.E. of 97 (theory for Ca(O iso-C₄H₉)₂ = 93). The filtrate is evaporated to dryness, leaving 5.7 g of a dark-red, semi-solid residue [combined yield of calcium isobutoxide = 52% (based on calcium metal)] . EXAMPLE XX

CALCIUM ISOBUTOXIDE AND N-BUTYLLITHIUM

6.4 g (34.4 mmoles) of calcium isobutoxide is placed in a 250 ml flask, and 29 ml of 2.44 N n-butyllithium in hexane is added (68 mmoles). Heat is generated. 30 ml of hexane is added, but the solid does not go into solution. Then 60 ml of benzene is added, and the mixture is heated to reflux for 10-15 minutes. Some solid goes into solution. The mixture is allowed to cool to room temperature overnight, a deep red supernatant solution resulting. Analysis of the clear supernatant shows the presence of Ca (0.24M) and Li (0.56M) (2Li/Ca).

EXAMPLE XXI

PREPARATION OF A HYDROCARBON-SOLUBLE COMPLEX OF CALCIUM ISOBUTOXIDE AND SEC-BUTYLLITHIUM

3.86 g (20.7 mmol) is treated with 11.4 ml of 1.82 N sec-butyllithium in hexane (20.7 mmol) and 9 ml of benzene. The solid slowly dissolves, giving off heat and turning the solution a deep, red-brown color. Analysis of the clear supernatant solution (after centrifugation) shows an Li concentration of 0.72 N, and a Ca concentration of 0.34 M (2Li/Ca). A considerable amount of solid does not dissolve. (Addition of 3 ml of TMEDA dissolves most of this solid.) The clear solution is stored for several weeks at ambient temperature with no evidence of thermal decomposition, as would occur with sec-butyllithium alone (elimination of LiH) . The illustrative Example shown here for calcium isobutoxide and its reaction products with n- and sec-butyllithium teach the following:

(1) The reaction of solid calcium alkoxides of low solubility in hydrocarbon solvents with organo-metallics, such as n- and sec-butyllithium, is slow and requires aromatic solvents to achieve solubilization.

(2) TMEDA promotes solubility and reactivity of organometallics with calcium alkoxides of low solubility.

Claims

AMENDED CLAIMS

[receivd by the International Bureau on 09 April 1985 (09.04.85); original claims 1-43 replaced by new claims 1-28 (11 pages follow) ],

1. In a process for the preparation of hydrocarbon- or chlorinated hydrocarbon-solvent solutions of magnesium, calcium, strontium and barium alkoxides, the steps which comprise contacting a suspension of corresponding metal or metal amide or dialkylmetallic compound in a volatile hydrocarbon or chlorinated hydrocarbon solvent with an alcohol selected from the group of aliphatic 2-alkyl substituted C₄-C₁₂ primary monohydric alcohols and removing hydrogen or ammonia which forms during the reaction.

2. The process of Claim 1, in which the alcohol is at least one member selected from the group of isobutyl alcohol, 2-methyl-1-pentanol, 2-ethyl-1-butanol, 2-ethyl-1-pentanol, 2-ethyl-1-hexanol, 2-ethyl-4-methyl-1-pentanol, 2-propyl-1-heptanol, 2-methyl-1-hexanol and 2-ethyl-5-methyl-1-octanol.

3. The process of Claim 1, in which there is included in the reaction mixture, when using barium amide or calcium amide, an aliphatic tertiary amine complexing solubilizer.

4. The process of Claim 3, in which said solubilizer is TMEDA.

5. The process of Claim 1, in which the dialkylmetallic compound is a dialkylmagnesium compound and is selected from the group of n-butyl-sec-butyl magnesium, n-butyl-ethylmagnesium, di-n-hexylmagnesium, n-butyl-n-octylmagnesium, and mixed ethyl, butyl, hexyl and octylmagnesiums.

6. The process of Claim 1, in which there is included in the reaction mixture, when employing magnesium metal or a dialkylmagnesium compound, a minor amount of a complexing solubilizer in the form of a member selected from the group of trialkylaluminum compounds and alkyllithium compounds.

7. The process of Claim 1, in which there is included in the reaction mixture, when employing magnesium metal or a dialkylmagnesium compound, a minor amount of a complexing solubilizer selected from the group of alkali metal alkoxides.

8. The process of Claim 1, in which an excess of said alcohols above that necessary to react with all of the alkaline earth metal, metal amide or dialkylmetallic compound present, is employed, the excess of said alcohol or alcohols being in the range of 0.01 to 2 moles of alcohol per mole of alkaline earth metal compound reacted.

9. The process of Claim 6, in which the amount of the trialkylaluminum compound, which is added to the magnesium metal or dialkylmagnesium present, is in the range of 0.01 to 0.1 moles per mole of the magnesium present.

10. The process of Claim 7, in which the alkali metal alkoxide is potassium alkoxide, and the amount of said potassium alkoxide, which is added to the magnesium metal or dialkylmagnesium, is in the range of 0.01 to 0.1 mole per mole of the magnesium present.

11. The process of Claim 6, in which the alkyllithiums are n-alkyllithiums, and the amount of said n-alkyllithium, which is added to the magnesium metal or dialkylmagnesium, is in the range of 0.01 to 0.1 mole per mole of the magnesium present.

12. The process of Claim 7, in which the said alkali metal alkoxides are selected from the group of lithium isopropoxide, lithium sec-butoxide, lithium tert-butoxide, lithium 2-methyl-1-pentyloxide, sodium tert-butoxide, sodium tert-amyloxide, sodium 2-methyl-1-pentyloxide, potassium tert-butoxide, potassium tert-amyloxide and potassium 2-methyl-1-pentyloxide, and the amount of said metal alkoxides, added to the magnesium metal or dialkylmagnesium, is in the range of 0.01 to 0.1 mole per mole of magnesium.

13. In a process for the preparation of hydrocarbon or chlorinated hydrocarbon solvent-soluble alkaline earth metal alkoxides, the steps which comprise reacting a suspension of alkaline earth metal, or alkaline earth metal amide, or C₁-C₃ alkaline earth metal alkoxides in a volatile hydrocarbon or chlorinated hydrocarbon solvent, or a solution of an alkaline earth dialkylmetallic compound in said solvent, with a

2-alkoxy-substituted-1-alkanol (R0CH₂CHR' OH) where R is a C₁-C₁₂ hydrocarbyl and R' is hydrogen or C₁-C₃ hydrocarbyl; or a member of the group of α -alkoxy-poly (ethyleneoxy) -1-ethanols

(ROCH₂CH₂OH)_nCH₂CH₂OH where R is a C₁-C₁₂ hydrocarbyl group and n is from 0 to 4; or a mixture thereof with each other or with any of the alcohols of Claim 1; and removing hydrogen or ammonia which results from the reaction.

14. The process of Claim 13, in which said 2-alkoxy-substituted-1-alkanols are selected from the group of 2-methoxy-1-ethanol, 2-ethoxy-1-ethanol, 2-butoxy-1-ethanol and 2-hexyloxy-1-ethanol.

15. The process of Claim 13, in which said α-alkoxy-poly(ethyleneoxy)-1-ethanols are selected from the group of 2-ethoxyethoxy-1-ethanol, 2-butoxyethoxy-1-ethanol and 2-hexyloxyethoxy-1-ethanol.

16. A process for the preparation of hydrocarbon or chlorinated hydrocarbon solvent solutions of alkaline earth metal 2-alkoxyalkoxides, which comprises contacting a solid alkaline earth metal dialkoxide of the formula M^II(OR)₂ in which R is a C₁-C₁₂ hydrocarbyl group, with at least two molar equivalents of a

2-alkoxy-substituted-1-alkanol, ROCH₂CHR' OH, where R is a C₁-C₁₂ hydrocarbyl group and R' is hydrogen or a C₁-C₃ hydrocarbyl group, isolating the resultant mobile liquid product, and then dissolving same in a hydrocarbon or chlorinated hydrocarbon solvent.

17. A process for the preparation of hydrocarbon or chlorinated hydrocarbon solvent solutions of alkaline earth metal 2-alkoxyalkoxides, which comprises reacting an alkaline earth metal or alkaline earth dialkylmetallic compound with at least 2 molar equivalents of a

2-alkoxy-substituted-1-alkanol, ROCH₂CHR' OH, or mixtures of such alkanols , in which R is a C₁-C₁₂ hydrocarbyl group and R' is H or a C₁-C₃ hydrocarbyl group, and then dissolving the product in a hydrocarbon or chlorinated hydrocarbon solvent containing a minor amount of an alcohol.

18. A chemical composition selected from the group of liquid hydrocarbon or chlorinated hydrocarbon solvent-soluble compounds and complexes of alkaline earth metal aliphatic 2-alkyl-substituted C₄-C₁₂ primary (normal) alkoxides.

19. A chemical composition selected from the group of liquid hydrocarbon or chlorinated hydrocarbon solvent-soluble compounds and complexes of (i) magnesium 2-methylpentyloxide, (ii) magnesium 2-ethylhexyloxide, (iii) magnesium 2-methylpentyloxide, (iv) magnesium 2-methylpentyloxide, (v) magnesium 2-methylpentyloxide, (vi) calcium 2-methylpentyloxide, (vii) barium

2-methylpentyloxide, (viii) calcium 2-ethyIhexyloxide, and (ix) barium 2-ethylhexyloxide.

20. A composition soluble in hydrocarbon or chlorinated hydrocarbon solvents selected from the group of alkaline earth metal 2-alkoxy-alkoxides, M^II(OCH(R')CH₂OR)₂· (R"OH)_x in which R and R" are C₁-C₁₂ hydrocarbyl groups, R' is hydrogen or C₁-C₃ hydrocarbyl group, and x is 0-2.

21. A composition selected from the group of alkaline earth metal α -alkoxy-poly ( ethyleneoxy)-1-ethoxides, M¹¹(OCH₂CH₂(OCH₂CH₂)_nOR)₂· (R'OH)_x in which R and R' are C₁-C₁₂ hydrocarbyl groups, R' is hydrogen or a C₁-C₃ hydrocarbyl group, and x = 0-2, said composition being soluble in hydrocarbon or chlorinated hydrocarbon solvents.

22. A composition according to Claim 20, in which the alkaline earth metal 2-alkoxy-1-alkoxide is magnesium 2-ethoxyethoxide, the alcohol of complexation (solvation) is ethanol and x is 2, said composition existing as a mobile liquid at ordinary temperatures and in the absence of added solvents.

23. A composition according to Claim 20, in which the alkaline earth metal 2-alkoxy-1-alkoxide is magnesium, calcium or barium 2-ethoxyethoxide, and x is zero, said composition being a solution of said alkoxide in a hydrocarbon or chlorinated hydrocarbon solvent.

.

24. A composition according to Claim 20, in which a mixture of two magnesium 2-alkoxy-1-alkoxides is cogenerated, the mixture consisting of a 1:1 molar complex of magnesium 2-ethoxyethoxide and magnesium

2-hexyloxyethoxide, said mixture being free of solvent and existing as a liquid at elevated temperature.

25. A chemical complex comprising magnesium alkoxides and organometallic compounds selected from the group of liquid hydrocarbon or chlorinated hydrocarbon solvent-soluble complexes of

(i) Magnesium 2-methylpentyloxide and n-butyl-sec-butylmagnesium; (ii) Magnesium 2-methylpentyloxide and n-butyllithium;

(iii) Magnesium 2-methylpentyloxide and triisobutylaluminum; (iv) Magnesium 2-methylpentyloxide and sodium tri-n-hexylmagnesiate;

(v) Magnesium 2-methylpentyloxide, n-butyllithium and n-butylsodium; (vi) Magnesium 2-methylpentyloxide and lithium

2-methylpentyloxide; (vii) Magnesium 2-methylpentyloxide and potassium 2-methylpentyloxide.

26. A chemical complex comprising barium and calcium alkoxide salts, alkylmetallic compounds including alkyllithiums, dialkylmagnesiums, and trialkylaluminums, and TMEDA, selected from the group of liquid hydrocarbon- or chlorinated hydrocarbon-soluble complexes of (i) barium isobutoxide, di-n-hexylmagnesium and TMEDA, (ii) barium 2-methylpentyloxide·TMEDA, butylethyl-magnesium and triisobutylaluminum, (iii) barium 4-methyl-2-pentyloxide, butyloctylmagnesium, triisobutylaluminum and TMEDA, (iv) barium 2-methylpentyloxide, di-n-hexylmagnesium, triisobutylaluminum and TMEDA, and (v) calcium isobutoxide, sec-butyllithium and TMEDA.

27. A chemical complex comprising barium and calcium alkoxides, and organometallic compounds, including alkyllithiums, dialkylmagnesiums, and trialkylaluminums selected from the group of liquid hydrocarbon or chlorinated hydrocarbon solvent-soluble complexes of: (i) barium 2-ethylhexyloxide and n-butyl-sec-butylmagnesium, (ii) barium 2-ethylhexyloxide, n-butyllithium, and triisobutylaluminum, (iii) barium 2-ethylhexyloxide, butyloctylmagnesium, and triisobutylaluminum, (iv) barium 2-ethylhexyloxide/4-methyl-2-pentyloxide, n-butyl-sec-butylmagnesium and triisobutylaluminum, (v) barium isobutoxide/cyclohexyloxide and n-butyl-sec-butylmagnesium, and (vi) calcium 2-ethylhexyloxide and n-butyl-sec-butylmagnesium.

28. An organometallic complex composition soluble in hydrocarbon or chlorinated hydrocarbon solvent solutions, said composition being produced by reacting a solution of a magnesium alkoxide resulting from the reaction of a mixture of magnesium metal, magnesium amide or a solution of a dialkylmagnesium compound in a volatile hydrocarbon or chlorinated hydrocarbon solvent, with a minor amount of a trialkylaluminum, n-alkyllithium or potassium alkoxide and with alcohols as such or in solution in a volatile liquid hydrocarbon or chlorinated hydrocarbon, said alcohols selected from the group of (a) aliphatic 2-alkyl-substituted C₄-C₁₂ primary monohydric alcohols; and (b) mixtures of said (a) alcohols with C₃-C₁₂ aliphatic secondary or tertiary alcohols; said composition being essentially free from hydrogen or ammonia which formed during the reaction.