Decarboxylation Processes Using Mixed Metal Oxide Catalysts

The following are related, commonly assigned pending applications, except where noted, filed on an even date herewith:

U.S. Patent application Ser. No. 07/585,561; U.S. Patent application Ser. No. 07/585,560; U.S. Patent application Ser. No. 07/585,455; U.S. Patent application Ser. No. 07/585,563; U.S. Patent application Ser. No. 07/585,564; U.S. Patent application Ser. No. 07/585,551; U.S. Patent application Ser. No. 07/585,456; U.S. Patent application Ser. No. 07/585,565; and U.S. Patent application Ser. No. 07/585,555 now U.S. Pat. No. 5,104,987, all of which are incorporated herein by reference.

1. Technical Field

This invention relates to a decarboxylation process which comprises contacting a carboxylated compound with a metal oxide catalyst under conditions effective to decarboxylate the carboxylated compound.

2. Background of the Invention

Decarboxylation, that is, elimination of the --COOH group as CO.sub.2, is a known process. March, J., Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 1968, pp. 435-436, 477-480 and 878-879, describes various decarboxylation reactions. At pages 435-436, it is stated that aromatic acids can be decarboxylated by heating with copper and quinoline. At pages 477-480, it is stated that aliphatic acids which undergo successful decarboxylation have certain functional groups or double or triple bonds in the alpha or beta positions such as malonic acids, alpha-cyano acids, alpha-nitro acids, alpha-aryl acids, alpha-keto acids, alpha-trihalo acids, beta-keto acids, beta,gamma-olefinic acids and the like. At pages 878-879, oxidative decarboxylation is described in which lead tetraacetate cleaves carboxyl groups, replacing them with acetoxy groups, which may be hydrolyzed to hydroxyl groups. It is stated that compounds containing carboxyl groups on adjacent carbons (succinic acid derivatives) can be bisdecarboxylated with lead tetraacetate. It is also stated that compounds containing geminal carboxyl groups (malonic acid derivatives) can be bisdecarboxylated with lead tetraacetate, gem-diacetates (acylals) being produced, which are hydrolyzable to ketones.

Tamura, Y. et al., Synthesis, 1975, 641-642, relates to the preparation of unsymmetrical sulfides by the alkylation of thiols with alkyl carbonates in the presence of sodium ethoxide and ethanol under refluxing conditions.

Taylor, Roger, Tetrahedron Letters, No. 8, 1975, 593-596, discloses the thermal decomposition of carbonates to ethers utilizing a palladium-charcoal catalyst.

Witt, H. et al., Angew. Chem., 1970, 82, 79, describes the preparation of substituted diphenyl ethers from ortho- and para-substituted diphenyl carbonates in the presence of small amounts of potassium carbonate and at a temperature of 180.degree. C.-260.degree. C.

Tundo, Pietro et al., Ind. Eng. Chem. Res., 1988, 27, 1565-1571, describes the reaction of dialkyl carbonates with phenols, thiophenols and mercaptans under gas-liquid phase-transfer conditions (continuous flow of gaseous reactants over a solid bed supporting a liquid phase-transfer catalyst) to produce the corresponding ethers and thioethers. The solid bed consisted of potassium carbonate coated with 5 weight percent of CARBOWAX.RTM. poly(oxyethylene)glycol 6000 for one set of experiments and alpha-alumina pellets coated with 5 weight percent of potassium carbonate and 5 weight percent of CARBOWAX.RTM. poly(oxyethylene)glycol 6000 for another set of experiments. Tundo et al. state at page 1568, right hand column, lines 33-42, that the reaction of alcohols with dialkyl carbonates produces only transesterification.

Dow Chemical U.S.A., Experimental Ethylene Carbonate XAS-1666.00L Product Bulletin (1982), pp. 4-6, discloses hydroxyethylation reactions in which ethylene carbonate reacts with compounds containing active hydrogen to give hydroxyethyl derivatives. Compounds containing active hydrogen include phenols, thiophenols, alcohols, mercaptans, carboxylic acids, amines and amides. The reactions are carved out at temperatures of from 100.degree. C. to 200.degree. C. in the presence of metal salts such as potassium carbonate. Carbon dioxide is the principle by-product. It is stated that ethylene carbonate yields, in most cases, the mono-ethylene oxide insertion product. At pages 5-7, it is stated that aromatic amines can be reacted with ethylene carbonate to form N-(2-hydroxyethyl) derivatives. It is stated that with primary amines such as aniline, a mixture of mono- and di-substituted derivatives can be prepared. It is also stated that carbamates and imidazolidinones can be produced through the reaction of ethylene carbonate with aliphatic mono- and diamines. At pages 8-9, the use of ethylene carbonate as a monomer for the synthesis of a variety of polymers is disclosed. It is stated that polycarbonates can be produced from the polymerization of ethylene carbonate in the presence of a base and small amounts of diols. It is also stated that polyoxyethylenes or polyglycols can be produced by the homopolymerization of ethylene carbonate at an elevated temperature in the presence of carbonates and bicarbonates of alkali metals and inert materials with a large surface area, e.g., ground glass. Alcohols can also react with excess ethylene carbonate to form polyglycol derivatives. At page 12, the preparation of ethylene sulfide from the reaction of ethylene carbonate with potassium thiocyanate at a temperature of 100.degree. C. is disclosed. It is stated that 2-oxazolidinones can be prepared from the reaction of aryl or alkyl isocyanates with ethylene carbonate in the presence of a catalyst. It is also stated that ethylene carbonate slowly decomposes to ethylene oxide in quantative yields at a temperature above 200.degree. C. and that this reaction is accelerated by the presence of catalysts such as inorganic and organic salts.

Texaco Chemical Company, TEXACAR.RTM. Ethylene and Propylene Carbonates Product Bulletin (1987), pp. 22-23, describes the reaction of ethylene carbonate and propylene carbonate with primary and secondary aliphatic amines at low temperatures to yield carbamates. It is stated that ethylene carbonate and propylene carbonate can react with amines to give the corresponding hydroxyethyl and hydroxypropyl derivatives. At page 23, hydroxyalkylation reactions are described in which ethylene carbonate and propylene carbonate react with compounds which contain an active hydrogen, i.e., alcohols, mercaptans, phenols, thiophenols, amines and carboxylic acids, to give the corresponding hydroxyethyl and hydropropyl derivatives. The reactions are run at temperatures of 100.degree. C. to 200.degree. C. employing a basic catalyst such as potassium carbonate at a 0.5 weight percent level. At page 24, it is stated that linear polycarbonates may be formed by reacting ethylene carbonate with aliphatic, cycloaliphatic or araliphatic dioxy compounds such as 1,4-dimethylcyclohexane or with ethylene glycol. Also at page 24, the reaction of ethylene carbonate with glycerine to give glycidol is described. It is stated that this reaction probably proceeds through the cyclic carbonate ester of glycerine. It is also stated that ethylene carbonate may be reacted with potassium thiocyanate at elevated temperature to give ethylene sulfide.

Enichem Synthesis SpA, Dimethyl Carbonate Product Bulletin, pp. 9-13, discloses the reaction of aromatic amines with dimethyl carbonate to give N-methyl and N,N'-dimethyl aromatic amines. It is stated that the reaction is carried out under the same conditions as used for the methylation of phenols. The reaction of phenols with dimethyl carbonate is carried out in the presence of a basic catalyst such as NaOH, Na.sub.2 CO.sub.3, NaOCH.sub.3, tertiary amines and heterocyclic nitrogenous compounds. Reaction temperatures of at least 140.degree. C. are required. It is stated that the speed of reaction can be accelerated with catalytic quantities of organic and inorganic halides. At page 12, it is stated that dimethyl carbonate reacts with amines (aliphatic or aromatic, primary or secondary) to produce carbamates and ureas. At page 13, it is stated that aminoalcohols can react with dimethyl carbonate in the presence of sodium or potassium alkoxides to yield 2-oxazolidinones. At page 9, it is stated that dimethyl carbonate can react with glycols or diphenols to yield oligomers or polycarbonates.

Trotta, F. et al., J. Org. Chem., 1987, 52, pp. 1300-1304, relates to selective mono-N-alkylation of aromatic amines by dialkyl carbonate under gas-liquid phase-transfer catalysis conditions (continuous flow process). The catalyst is a polyethylene glycol in the presence of a base (K.sub.2 CO.sub.3).

This invention relates to a decarboxylation process which comprises contacting a carboxylated compound with a metal oxide catalyst under conditions effective to decarboxylate the carboxylated compound.

This invention also relates to a decarboxylation process which comprises contacting an active hydrogen-containing compound with a CO.sub.2 synthon in the presence of a metal oxide catalyst under conditions effective for decarboxylation.

This invention further relates to a decarboxylation process which comprises (i) contacting an active hydrogen-containing compound with a CO.sub.2 synthon under conditions effective to produce a carboxylated compound, and (ii) contacting the carboxylated compound with a metal oxide catalyst under conditions effective to decarboxylate the carboxylated compound.

The decarboxylation processes of this invention is useful for the production of numerous organic compounds, e.g., alcohols, ethers, esters, amines, amides, carboxylic acids and the like, which have a wide variety of applications.

For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 67th Ed., 1986-87, inside cover. Also, for purposes of this invention, Group IIIB metal oxides embraces the lanthanides and actinides. As used herein, the term "oxide" embraces oxides, hydroxides and/or mixtures thereof. Also, as used herein, the term "CO.sub.2 synthon" embraces SO.sub.2 synthons such as sulfurous acids and sulfurous acid esters. Further, for purposes of this invention, the term "hydrocarbon" is contemplated to include all permissible compounds having at least one hydrogen and one carbon atom. In a broad aspect, the permissible hydrocarbons include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic organic compounds which can be substituted or unsubstituted.

As indicated above, this invention relates to a decarboxylation process which comprises contacting a carboxylated compound with a metal oxide catalyst under conditions effective to decarboxylate the carboxylated compound.

As also indicated above, this invention relates to a decarboxylation process which comprises contacting an active hydrogen-containing compound with a CO.sub.2 synthon in the presence of a metal oxide catalyst under conditions effective for decarboxylation.

As further indicated above, this invention relates to a decarboxylation process which comprises (i) contacting an active hydrogen-containing compound with a CO.sub.2 synthon under conditions effective to produce a carboxylated compound, and (ii) contacting the carboxylated compound with a metal oxide catalyst under conditions effective to decarboxylate the carboxylated compound.

When an active hydrogen-containing compound and CO.sub.2 synthon are employed as starting materials, it is believed that a transesterification reaction followed by a decarboxylation reaction occurs to provide the desired product. The exact reaction mechanism is not fully appreciated but what is appreciated is that an active hydrogen-containing compound starting material and CO.sub.2 synthon starting material can be contacted in the presence of a metal oxide catalyst under conditions effective for decarboxylation to provide a desired product. It is also appreciated that a carboxylated compound can be contacted with a metal oxide catalyst under conditions described herein to provide a decarboxylated compound product.

Step (i) of certain processes of this invention can in general be referred to as a transesterification reaction. Any suitable transesterification catalyst can be employed in step (i). Such transesterification catalysts are known and include, for example, basic metal oxides, alkoxides and other basic metal salts such as potassium carbonate, sodium titanate and the like. Other suitable transesterification catalysts include, for example, Bronsted acids such as sulfuric acid and Lewis acids such as aluminum triisopropoxide. As discussed hereinafter in regard to the decarboxylation catalyst, the transesterification catalyst employed in this invention likewise may also contain support(s), binding agent(s) or other additives to stabilize or otherwise help in the manufacture of the catalyst. Both homogeneous and heterogeneous catalysts can be employed in the step (i) reaction. The amount of transesterification catalyst used in step (i) is dependent on the particular catalyst employed and can range from about 0.01 weight percent or less to about 10 weight percent or greater of the total weight of the starting materials.

Suitable active hydrogen-containing compound starting materials which can be employed in the step (i) transesterification reaction include any permissible substituted or unsubstituted active hydrogen-containing organic compound(s). Illustrative active hydrogen-containing compound starting materials useful in this invention include, for example, substituted and unsubstituted alcohols, phenols, carboxylic acids, amines and the like. The molar ratio of active hydrogen-containing compound to CO.sub.2 synthon is not narrowly critical and can range from about 0.05:1 or less to about 50:1 or greater, preferably from about 0.1:1 to about 10:1.

Suitable active hydrogen-containing compounds include substituted and unsubstituted alcohols (mono-, di- and polyhydric alcohols), phenols, carboxylic acids (mono-, di- and polyacids), and amines (primary and secondary). Other suitable active hydrogen-containing compounds include substituted and unsubstituted thiophenols, mercaptans, amides and the like. Frequently, the organic compounds contain 1 carbon to about 100 or 150 carbons (in the case of polyol polymers) and can contain aliphatic and/or aromatic structures. Most often, the organic compounds are selected from the group of mono-, di- and trihydric alcohols having 1 to about 30 carbon atoms. The organic compounds having active hydrogens can be the product of hydroformylation/hydrogenation reactions.

Suitable alcohols include primary and secondary monohydric alcohols which are straight or branched chain such as methanol, ethanol, propanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, isopropyl alcohol, 2-ethylhexanol, sec-butanol, isobutanol, 2-pentanol, 3-pentanol and isodecanol. Particularly suitable alcohols are linear and branched primary alcohols (including mixtures) such as produced by the "Oxo" reaction of C.sub.3 to C.sub.20 olefins. The alcohols may also be cycloaliphatic such as cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, as well as aromatic substituted aliphatic alcohols such as benzyl alcohol, phenylethyl alcohol, and phenylpropyl alcohol. Other aliphatic structures include 2-methoxyethanol and the like.

Phenols include alkylphenols of up to 30 carbons such as p-methylphenol, p-ethylphenol, p-butylphenol, p-heptylphenol, p-nonylphenol, dinonylphenol and p-decylphenol. The aromatic radicals may contain other substituents such as halide atoms.

Alcohols (polyols) having 2 or more hydroxyl groups, e.g., about two to six hydroxyl groups and have 2 to 30 carbons, include glycols such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, neopentylene glycol, decylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol. Other polyols include glycerine, 1,3-propanediol, pentaerythritol, galactitol, sorbitol, mannitol, erythritol, trimethylolethane and trimethylolpropane.

Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid. Other carboxylic acids include benzoic acid, cyclohexane carboxylic acid, phenylacetic acid, toluic acid, chlorobenzoic acid, bromobenzoic acid, nitrobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, hydroxybenzoic acid, anthranilic acid, aminobenzoic acid, methoxybenzoic acid and the like.

Amines include methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propylamine, isopropylamlne, n-butylamine, isobutylamine, cyclohexylamine, piperazine, benzylamine, phenylethylamine, monoethanolamine, diethanolamine, aminoethylethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylenediamine and hexamethylenediamine. Other amines include aniline, methylaniline, toluidine, anisidine, chloroaniline, bromoaniline, nitroaniline, diphenylamines, phenylenediamine, benzidine, aminobenzoic acid, sulfanilic acid and sulfanilamide. Still other amines include acetanilide, benzanilide, aceto-toluidide, nitroacetanilide and the like.

Suitable CO.sub.2 synthon starting materials which can be employed in the step (i) transesterification reaction include any permissible substituted or unsubstituted carboxyl-containing compound(s) or carbonyl-containing compound(s) which are capable of reacting with an active hydrogen-containing compound under the process conditions described herein. Illustrative CO.sub.2 synthons include, for example, substituted and unsubstituted carbonates, chlorocarbonates, carbonic acids, carbamates, carbamic acids, oxalates, 2-oxazolidinones, ureas, esters, phosgene, chloroformates, carbon dioxide, orthocarboxylates, sulfurous acids, sulfurous acid esters and the like. For purposes of this invention, carbon monoxide is also considered a CO.sub.2 synthon for appropriate oxidative carbonylation reactions. Preferred CO.sub.2 synthons include, for example, diethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, diphenyl carbonate, 2-oxazolidinone, ethylene sulfite, urea, phosgene and the like. The use of CO.sub.2 synthons prepared in situ such as the reaction of ethylene carbonate and monoethanolamine to give 2-oxazolidinone is encompassed within the scope of this invention.

The step (i) transesterification reaction can be conducted over a wide range of pressures ranging from atmospheric or subatmospheric pressures to superatmospheric pressures. However, the use of very high pressures has not been observed to confer any significant advantages but increases equipment costs. Further, it is preferable to conduct the step (i) reaction at reduced pressures of from about 1 mm Hg to less than about 760 mm Hg. The step (i) transesterification reaction is preferably effected in the liquid or vapor states or mixtures thereof.

The temperature of the step (i) transesterification reaction may be as low as about ambient temperature to about 300.degree. C. Preferably, the reaction temperature ranges from about 50.degree. C. to about 200.degree. C., and most preferably from about 60.degree. C. to about 120.degree. C.

Suitable carboxylated compounds prepared by the step (i) transesterification reaction include any permissible substituted or unsubstituted carboxylated compounds which are capable of eliminating carbon dioxide under the process conditions described herein, e.g., esters, carbonates, carbamates and the like. Illustrative carboxylated compounds useful in this invention include, for example, substituted and unsubstituted carboxylated alcohols and phenols; carboxylated amines; carboxylated amides; carboxylated ethers and epoxides; carboxylated esters; carboxylated carboxylic acids and anhydrides; carboxylated ketones; carboxylated olefins; carboxylated acetylenes; carboxylated halides and sulfonates; carboxylated aldehydes; carboxylated nitriles; carboxylated hydrocarbons; and the like. The amount of carboxylated compound(s) employed in step (ii) is dependent on the amount of metal oxide catalyst employed.

The carboxylated compounds prepared by the step (i) transesterification reaction may undergo one or more transesterifications prior to the step (ii) decarboxylation reaction. For example, an active hydrogen-containing compound different from the active hydrogen-containing compound starting material may be reacted with the originally prepared carboxylated compound under conditions effective to prepare a different carboxylated compound. This invention is not intended to be limited in any manner by the step (i) transesterification reaction.

Step (ii) of certain processes of this invention can in general be referred to as a decarboxylation reaction. Suitable decarboxylation catalysts which can be employed in step (ii) include one or more metal oxides. A magnesium:aluminum mixed metal oxide is a preferred metal oxide catalyst as more fully described below. Both homogeneous and heterogeneous catalysts can be employed in the step (ii) reaction. The amount of decarboxylation catalyst used in step (ii) is not narrowly critical and is dependent on whether step (ii) is conducted batchwise or continuously. If batchwise, the catalyst employed can range from about 0.01 weight percent or less to about 10 weight percent or greater of the total weight of the starting materials. If continuously, generally a fixed bed is employed.

Suitable decarboxylation catalysts for use in the processes of this invention comprise one or more metal oxides, preferably mixed metal oxides containing two or more metal oxides. Illustrative of such metal oxides include, for example, one or more of the following: Group IA metal oxides, Group IIA metal oxides, Group IIIB metal oxides (including lanthanides and actinides), Group IVB metal oxides, Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, Group VIII metal oxides, Group IB metal oxides, Group IIB metal oxides, Group IIIA metal oxides, Group IVA metal oxides, Group VA metal oxides or Group VIA metal oxides. Certain of these metal oxides may also be used as transesterification catalysts in accordance with this invention such as Group IIA and IIIA metal oxides. Preferred metal oxides and mixed metal oxides are amphoteric or basic. Preferred metal oxides which may be utilized as decarboxylation catalysts include, for example, one or more oxides of magnesium, aluminum, calcium, strontium, gallium, beryllium, barium, scandium, yttrium, lanthanum, cerium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, lutetium, ytterbium, niobium, tantalum, chromium, molybdenum, tungsten, titanium, zirconium, hafnium, vanadium, iron, cobalt, nickel, zinc, silver, cadmium, boron, indium, silicon, germanium, t[n, lead, arsenic, antimony and bismuth.

Group IIA metal oxides such as magnesium oxide and calcium oxide and Group IIIA metal oxides such as aluminum oxide and gallium oxide are Preferred mixed metal oxides for use in this invention. For mixed metal oxides in which at least one of the metals is magnesium, suitable metals in association with magnesium may include, for example, one or more of the following: Group IIIA metals such as boron, aluminum, gallium and indium, Group IIIB metals such as scandium, yttrium and lanthanum including the lanthanides, Group VB metals such as niobium and tantalum, Group VIB metals such as chromium, molybdenum and tungsten, Group VIII metals such as iron, cobalt and nickel, Group IIB metals such as zinc and cadmium, Group IVA metals such as silicon, germanium, tin and lead, Group VA metals such as arsenic, antimony and bismuth, and Group IVB metals such as zirconium and hafnium. For mixed metal oxides in which at least one of the metals is calcium, suitable metals in association with calcium may include, for example, one or more of the following: Group IIIA metals such as boron, aluminum, gallium and indium, Group IVA metals such as silicon, germanium, tin and lead, Group VB metals such as niobium and tantalum, and Group VIB metals such as chromium, molybdenum and tungsten.

Illustrative of mixed metal oxides which may be used as decarboxylation catalysts include, for example, MgO-Al.sub.2 O.sub.3, MgO-SiO.sub.2, MgO-CdO, MgO-Bi.sub.2 O.sub.3, MgO-Sb.sub.2 O.sub.5, MgO-SnO.sub.2, MgO-ZrO.sub.2, MgO-BeO, MgO-TiO.sub.2, MgO-CaO, MgO-SrO, MgO-ZnO, MgO-Ga.sub.2 O.sub.3, MgO-Y.sub.2 O.sub.3, MgO-La.sub.2 O.sub.3, MgO-MoO.sub.3, MgO-Mn.sub.2 O.sub.3, MgO-Fe.sub.2 O.sub.3, MgO-Co.sub.3 O.sub.4, MgO-WO.sub.3, MgO-V.sub.2 O.sub.5, MgO-Cr.sub.2 O.sub.3, MgO-ThO.sub.2, MgO-Na.sub.2 O, MgO-BaO, MgO-CaO, MgO-HfO.sub.2, MgO-Li.sub.2 O, MgO-Nb.sub.2 O.sub.5, MgO-Ta.sub.2 O.sub.5, MgO-Gd.sub.2 O.sub.3, MgO-Lu.sub.2 O.sub.3, MgO-Yb.sub.2 O.sub.3, MgO-CeO.sub.2, MgO-Sc.sub.2 O.sub.3, MgO-PbO, MgO-NiO, MgO-CuO, MgO-CoO, MgO-B.sub.2 O.sub.3, CaO-SiO.sub.2, CaO-Al.sub.2 O.sub.3, CaO-SnO, CaO-PbO, CaO-Nb.sub.2 O.sub.5, CaO-Ta.sub.2 O.sub.5, CaO-Cr.sub.2 O.sub.3, CaO-MoO.sub.3, CaO-WO.sub.3, CaO-TiO.sub.2, CaO-HfO.sub.2, MgO-SiO.sub.2 -Al.sub.2 O.sub.3, MgO-SiO.sub.2 -ZnO, MgO-SiO.sub.2 -ZrO.sub. 2, MgO-SiO.sub.2 -CuO, MgO-SiO.sub.2 -CaO, MgO-SiO.sub.2 -Fe.sub.2 O.sub.3, MgO-SiO.sub.2 -B.sub.2 O.sub.3, MgO-SiO.sub.2 -WO.sub.3, MgO-SiO.sub.2 -Na.sub.2 O, MgO-SiO.sub.2 -Ga.sub.2 O.sub.3, MgO-SiO.sub.2 -La.sub.2 O.sub.3, MgO-SiO.sub.2 -Nb.sub.2 O.sub.5, MgO-SiO.sub.2 -Mn.sub.2 O.sub.3, MgO-SiO.sub.2 -Co.sub.3 O.sub.4, MgO-SiO.sub.2 -NiO, MgO-SiO.sub.2 -PbO, MgO-SiO.sub.2 -Bi.sub.2 O.sub.3, MgO-Al.sub.2 O.sub.3 -ZnO, MgO-Al.sub.2 O.sub.3 -ZrO.sub.2, MgO-Al.sub.2 O.sub.3 -Fe.sub.2 O.sub.3, MgO-Al.sub.2 O.sub.3 -WO.sub.3, MgO-Al.sub.2 O.sub.3 -La.sub.2 O.sub.3, MgO-Al.sub.2 O.sub.3 -Co.sub.3 O.sub.4, CaO-SiO.sub.2 -Al.sub.2 O.sub.3, CaO-SiO.sub.2 -SnO, CaO-SiO.sub.2 -Nb.sub.2 O.sub.5, CaO-SiO.sub.2 -WO.sub.3, CaO-SiO.sub.2 -TiO.sub.2, CaO-SiO.sub.2 -MoO.sub.3, CaO-SiO.sub.2 -HfO.sub.2, CaO-SiO.sub.2 -Ta.sub.2 O.sub.5, CaO-Al.sub.2 O.sub.3 -SiO.sub.2, CaO-Al.sub.2 O.sub.3 -PbO, CaO-Al.sub.2 O.sub.3 -Nb.sub.2 O.sub.5, CaO-Al.sub.2 O.sub.3 -WO.sub.3, CaO-Al.sub.2 O.sub.3 -TiO.sub.2, CaO-Al.sub.2 O.sub.3 -MoO.sub.3, CaO-HfO.sub.2 -Al.sub.2 O.sub.3, CaO-HfO.sub.2 -TiO.sub.2, and the like. Other suitable mixed metal oxides embraced within the scope of this invention are disclosed by Tanabe et al., Bulletin of the Chemical Society of Japan, Vol. 47(5), pp. 1064-1066 (1974).

The metal oxides described herein which can be used as decarboxylation catalysts may contribute to product selectivity and/or catalytic activity of the reaction and/or stability of the catalyst. As discussed hereinafter, the decarboxylation catalyst employed in this invention may also contain support(s), binding agent(s) or other additives to stabilize or otherwise help in the manufacture of the catalyst.

The decarboxylation catalysts which comprise one or more metal oxides may be prepared in a wide variety of ways. For example, the one or more metal oxides can be provided from metal salts which can either be heated or precipitated to form the metal oxides. Also, one or more metal oxides may be provided as a partial condensate on a support, such as a silica or alpha, beta or gamma alumina, silicon carbide, and the like, and then condensed by heating to effect polymerization to the desired oxide form. The one or more metal oxides may be condensed from hydrolyzable monomers to the desired oxide(s), indeed, to form oxide powders which can thereafter be compressed in the presence of a condensation catalyst to form pellets and larger structures of the metal oxide decarboxylation catalyst. A blend of the powders and condensation catalyst can be made into a shapeable paste which can be extruded and cut into pellets according to conventional procedures. The extrudate may thereafter be fired to cure the condensation catalyst and fix the structure. The cut extrudate may be blended with a support material such as those characterized above, and the blend fired to fuse the metal oxide catalyst to the support.

In an embodiment of this invention, a magnesium salt, e.g., magnesium nitrate, and an aluminum salt, e.g., aluminum nitrate, are precipitated using ammonium hydroxide. The material is then washed with deionized water and calcined at a temperature of from about 350.degree. C. to about 450.degree. C. to afford the desired magnesium:aluminum mixed metal oxide catalyst.

In another embodiment, a magnesium oxide, e.g., magnesium carbonate hydroxide pentahydrate, and an aluminum oxide, e.g., aluminum hydroxide hydrate, are added to deionized water and thoroughly mixed to from a paste. The paste is then calcined at a temperature of from about 350.degree. C. to about 450.degree. C. to afford the desired magnesium:aluminum mixed metal oxide catalyst.

A preferred catalyst structure comprises a Group IIA and IIIA mixed metal oxide having a surface area of at least about 100 m.sup.2 /gm which may or may not be bonded to a support material. The decarboxylation catalysts on a support preferably have a surface area greater than about 20 m.sup.2 /gm to as high as about 260 m.sup.2 /gm, or greater depending upon which metal oxides are employed. In the case of magnesium:aluminum oxides, the surface area can be greater than about 50 m.sup.2 /gm to as high as about 260 m.sup.2 /gm, more preferably, greater than about 100 m.sup.2 /gm to as high as about 260 m.sup.2 /gm, determined according to the single point N.sub.2 method.

The term "support," as used herein and in the claims, means a solid structure which does not adversely affect the catalytic properties of the catalyst and is at least as stable as the catalyst to the reaction medium. The support can function as a decarboxylation catalyst independent of the metal oxide catalyst used herein, although it may have lower catalytic activity to the reaction. The support may act in concert with the catalyst to moderate the reaction. Some supports may contribute to the selectivity of the reaction. The catalyst structure can comprise from about 2 to about 60 percent by weight or greater of the support, more preferably from about 10 to about 50 percent by weight of the support, the remainder being the weight of the metal oxide(s). Included in the weight of the support is the weight of any binding agent such as phosphates, sulfates, silicates, fluorides, and the like, and any other additive provided to stabilize or otherwise help in the manufacture of the catalyst. The support may be particles as large or larger than the catalyst component and "glued" to the decarboxylation catalyst by virtue of a binding medium.

The support may constitute a separate phase in the process of extruding the catalytic structure. In this embodiment, the support forming material, preferably as a paste is blended with a paste of the decarboxylation catalyst or a partial condensate thereof. The paste may comprise the oxide forms of the support and the decarboxylation catalyst, each blended with water, and/or binding agents. The extrudate of the blend is passed through a multiorificed die and chopped into pellets of the desired sizes. The particles may be doughnut shaped, spherical, and the like. Then the particles are calcined to dry them and complete any condensation reaction in the support and/or the metal oxide decarboxylation catalyst.

A preferred group of mixed metal oxide catalysts for use in this invention include materials having the formula:

wherein M is at least one divalent metal cation; Q is at least one trivalent metal cation; and A is at least one anion providing a valence (n.sup.-), wherein n is at least 1, e.g., between 1 and 4 and most often between 1 and 3, and wherein a is a positive number, M, Q, and A are provided in a proportion such that x/y is a number equal to or greater than 1, z has a value greater than zero and 2x+3y-nz is a positive number. M, Q and A may be selected to provide a layered structure. Preferably, x/y is in the range of 1 to 12, more preferably x/y is in the range of 1 to 6 and most preferably is in the range of 1 to 4. Preferably, z has a value such that x/z is between n and 12n, more preferably between n and 6n and most preferably between n and 4n.

Suitable divalent metal cations, M, broadly include elements selected from the Transition elements and Groups IIA and IVA of the Periodic Table as well as certain Group IIIB elements. As specific examples can be mentioned magnesium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, palladium, platinum, copper, zinc, cadmium, mercury, tin and lead. Divalent metal cations which are particularly suitable are magnesium, nickel, cobalt, zinc, calcium, strontium and copper. Suitable trivalent metal cations, Q, broadly include elements selected from the Transition elements and Groups IIIA and VA of the Periodic Table as well as certain Group IIIB elements. As specific examples can be mentioned aluminum, antimony, titanium, scandium, bismuth, vanadium, yttrium, chromium, iron, manganese, cobalt, ruthenium, nickel, gold, gallium, thallium, and cerium. Trivalent metal cations which are particularly suitable can be selected from aluminum, boron, gallium and lanthanum.

The composition of formula (I) also can include a wide range of anions, A. Any anion or combination of anions which can balance the charge of the cations can be used. Suitable anions include inter alia, halides (such as chloride, fluoride, bromide, and iodide), nitrite, nitrate, sulfite, sulfate, sulfonate, carbonate, chromate, cyanate, phosphite, phosphate, molybdocyanate, bicarbonate, hydroxide, arsenate, chlorate, ferrocyanide, borate, cyanide, cyanaurate, cyanaurite, ferricyanide, selenate, tellurate, bisulfate, as well as organic anions such as oxalate, acetate, hexanoate, sebacate, formate, benzoate, malonate, lactate, oleate, salicylate, stearate, citrate, tartrate, maleate, and the like. The class of metalate anions described in U.S. Pat. No. 4,667,045, including metavanadate, orthovanadate, molybdate, tungstate, hydrogen pyrovanadate and pyrovanadate, also are suitable as anion A. Anions suitable for use in combination with the metal cations previously identified as being particularly suitable are carbonate, halide, phosphate, chromate, sulfate, hydroxide, oxalate, acetate, nitrate, hexanoate, sebacate, vanadate, molybdate, tungstate and ferrocyanate.

The foregoing lists of suitable divalent and trivalent cations and suitable anions are meant to be illustrative and not exclusive. Those skilled in the art will recognize that other cations and anions can be used provided that the specific type of cations and their relative amounts (x/y ratio) and the specific type of anions and their relative amount result in a mixed metal oxide composition.

Included in the materials identified above are those based on exchangeable anionic clay minerals. For example, compositions of formula (I) wherein M is magnesium and Q is aluminum are related to hydrotalcites, while compositions in which M is nickel and A is aluminum are related to takovites. In fact, mixed metal oxides prepared using magnesium, nickel or cobalt as the divalent cation and aluminum as the trivalent cation exhibit the typical X-ray diffraction pattern of a hydrotalcite.

In a more preferred aspect, the processes of this invention can utilize mixed metal oxide catalyst compositions prepared by calcining at an elevated temperature compositions according to formula (I). Suitable calcined compositions have the general formula:

wherein M, Q, x, y, z and n have the same meanings defined above in connection with formula (I), and D is at least one nonvolatile anion. Nonvolatile anions may include, inter alia. halides, nitrates, phosphites, phosphate, vanadate, molybdate, tungstate, sulfite, sulfate, chromate, arsenate, borate, chlorate and the like. This list is illustrative and not exclusive.

Heat treating the formula (I) compositions to prepare the calcined mixed metal oxide compositions of formula (II) can be done, for example, at a temperature in the range of 200.degree. C. to 800.degree. C. for a period of time of about 12 to 24 hours under an inert atmosphere such as nitrogen or in appropriate cases under an oxidizing atmosphere such as air.

Calcination of the mixed metal oxide composition dehydrates the composition and converts at least partially the metal hydroxides to metal oxides. Any nonvolatile anions may be present in the calcined material.

Provided the calcination temperature is not excessive, the mixed metal oxide can be rehydrated to the mixed metal hydroxide with water. Generally, the mixed metal oxide can be restored readily if the calcination temperature does not exceed about 600.degree. C. Mixed metal oxides which are calcined under more severe conditions are not easily rehydrated and lower surface area materials are obtained.

Certain compositions falling within formula (I), such as hydrotalcite, which comprises a magnesium-aluminum hydroxide carbonate, and takovite, which comprises a nickel-aluminum hydroxide carbonate, are naturally occurring compositions. However, such compounds, as well as their related compositions, also can be prepared synthetically from inexpensive starting materials using well-known coprecipitation techniques. Procedures for direct synthesis of such materials are described in Itaya et al., Inorg. Chem. (1987) 26:624-626; Taylor, R. M., Clay Minerals (1984) 19:591-603; Reichle, U.S. Pat. No. 4,476,324; Bish, D. L., Bull, Mineral (1980), 103:170-175 and Miyata et al., Clays and Clay Minerals (1977), 25:14-18. Using direct synthesis one has the ability to vary within wide limits the M.sup.+2 /Q.sup.+3 atomic ratio as well as the anion.

For example, a composition of formula (I) where M.sup.+2 is nickel or magnesium, Q.sup.+3 is aluminum and A.sup.n- is carbonate can be prepared by adding, as aqueous solutions, (a) a mixture of nitrates, sulfates or chlorides of nickel or magnesium and aluminum in a desired atomic ratio of nickel or magnesium to aluminum, e.g. 6 atoms of nickel as nickel chloride to 2 atoms of aluminum as aluminum chloride, to (b) an aqueous solution of a stoichiometric amount of sodium hydroxide and a water soluble salt of the desired anion, e.g., sodium carbonate. The two solutions are mixed at a temperature of about 25.degree. C. to 35.degree. C. with vigorous stirring over a several-hour period to produce a slurry. The slurry then is heated for about 18 hours at a temperature within the range of about 50.degree. C. to 200.degree. C. (preferably between about 60.degree. C. to 75.degree. C.) in order to control crystallization and the ultimate particle size of the resulting crystals. After filtering, and thorough washing and drying, the solids are recovered, typically as a powder.

As noted above, this procedure can be adapted to a wide variety of cations, cation atomic ratios and anion substitutions. For example, water soluble salts of divalent magnesium, cobalt, zinc, copper, iron and calcium can be substituted for the nickel chloride illustrated above, while water soluble salts of trivalent gallium and lanthanum can replace the aluminum chloride. A wide variety of other combinations also will be apparent to those skilled in the art. Generally, the rate of metal ion addition to the aqueous caustic/anion solution is not critical and can be varied widely. For example, a preferred preparation method is described in Schaper, H. et al., Applied Catalysis, 54, 1989, 79-90, the disclosure of which is incorporated herein by reference. The reaction temperature also is not critical, although the temperature during the reaction preferably is kept below about 100.degree. C. An important feature of the procedure is the use of efficient agitation during the mixing procedure to avoid the formation of undesired by-products.

Loading of an anion A or D into the mixed metal oxide compositions is influenced by a variety of factors including (i) the amount of anion used in the preparation relative to the metal cations, (ii) the atomic ratio of the metal cations (x/y) in the preparation procedure, (iii) the size of the cations and anions and (iv) the preparation procedure. As used herein, "loading" is defined as the amount of available valences provided by a desired anion A or D expressed as a percentage of the total available valences for anion A or D. For example, carbonate loading in a hydrotalcite-type catalyst can be maximized by (i) using an excess (e.g., a greater than 3:1 molar ratio) of sodium carbonate to aluminum chloride during catalyst preparation and (2) adjusting the atomic ratio of magnesium to aluminum cations to about 2:1.

Mixed metal oxide compositions suitable as catalysts also can be prepared from the native or synthetic hydrotalcite-type compositions by ion exchange. For example, hydrotalcite can be treated at ambient conditions with 0.01N phosphoric acid for about 18 hours to replace the carbonate anion with phosphate anion. A halide analog of hydrotalcite prepared directly or by anion-exchange could be contacted with molybdic acid or a water soluble salt thereof, or with a water soluble salt of tungstic acid or vanadic acid in order to substitute the transition metal anion for the halide anion in the catalyst structure thereby to produce a mixed metal oxide composition of formula (I). Other ion exchanges will be apparent to those skilled in the art.

Calcined mixed metal oxide compositions may exhibit a higher level of selectivity/activity than uncalcined compositions. If a calcined mixed metal oxide catalyst composition experiences any decline in selectivity, it can be regenerated by a heat treatment in the presence of air to restore at least a portion of its initial level of selectivity/activity enhancement and reused. Conditions discussed above for calcining the hydrated mixed metal oxide compositions are suitable for regenerating compositions which have experienced a decline in activity.

Catalysts having the formulas (I) and (II) above wherein M is at least one of magnesium and calcium, Q is aluminum or gallium, A is at least one of carbonate, bicarbonate, phosphate, sulfate and nitrate, x/y is between 1 and 20, z has a value which satisfies the relationship: x/z is between n and 12n, and a is a positive number, are generally preferred for vapor phase decarboxylation due to their combination of activity (conversion of precursor) and selectivity. A preferred process involves a vapor phase process using mixed metal oxide catalyst wherein M.sup.2+ is magnesium, Q.sup.3+ is aluminum, A.sup.n- is carbonate, x/y is about 1, and z is about 1.

A group of preferred mixed metal oxide catalyst compositions which can be employed in the processes of this invention is disclosed in copending U.S. Patent application Ser. No. 125,134, filed Nov. 25, 1987 now abandoned in favor of continuation application Ser. No. 527,375, filed May 23, 1990 now U.S. Pat. No. 5,064,804, the disclosure of which is incorporated herein by reference.

The step (ii) decarboxylation reaction may be effected in the liquid or vapor or supercritical liquid states or mixtures thereof. In this context, the vapor phase reaction is intended to refer to the general vapor state of the starting materials. Though the step (ii) decarboxylation reaction conditions may range from subatmospheric or atmospheric to superatmospheric conditions, it is desirable to run the step (ii) reaction from about 1 mm Hg to about 5,000 mm Hg, preferably from about 100 mm Hg to about 2,500 mm Hg.

The temperature of the step (ii) decarboxylation reaction may be as low as about 150.degree. C. to about 500.degree. C. Preferably, the reaction temperature ranges from about 175.degree. C. to about 375.degree. C., and most preferably from about 225.degree. C. to about 350.degree. C.

Suitable carboxylated compounds for use in the step (ii) decarboxylation reaction can be prepared by the step (i) transesterification reaction or by other methods such as the carbonylation of suitable compounds with carbon monoxide and oxygen at elevated temperatures in the presence of certain copper salts. Such a carbonylation process can be an alternative to the step (i) transesterification reaction and is encompassed within the generic scope of this invention. It is also appreciated that two or more CO.sub.2 synthons can be reacted under conditions effective to produce a carboxylated compound.

The step (ii) decarboxylation reaction can be conducted in the presence of an inert diluent which can be either a liquid or gas. When a liquid diluent is employed, it should preferably be a good solvent for the starting materials, inert under the reaction conditions, and of such a nature that separation from the decarboxylated compound product will not be difficult. For instance, the boiling points of the diluent and the decarboxylated compound product should differ by an adequate amount and there should be no tendency of the diluent to form an azeotrope with the desired decarboxylated compound product.

Examples of useful liquid diluents that meet the foregoing qualifications include benzene, toluene, xylene, ethylbenzene, anisole, heptane, octane, nonane, decane, dibutyl ether, and the like. Hydrocarbons are preferred.

Illustrative gaseous diluents include for example, nitrogen, methane, hydrogen, carbon monoxide or carbon dioxide. The gaseous diluent should of course be chosen so that it does not prevent the preparation of the desired products.

While the use of such diluents may be beneficial, the processes of this invention can be operated using pure starting material(s) as a liquid or gaseous feed. The degree of dilution of the starting materials with various diluents may vary considerably depending upon any process constraints restricting the use of the diluent. For example, in commercial production, the use of very large quantities of some gaseous diluents may be disadvantageous due to the cost of pumping large volumes of the gaseous diluent and increased difficulty in isolating the product, which increase the energy costs of the process. With liquid diluents, the use of very large quantities may be disadvantageous due to the energy cost associated with large recovery and recycle. If the processes of this invention are to be carried out using a gaseous diluent, in general it is recommended that the starting material(s) constitute from about 1 to about 95, and preferably about 5 to about 50, mole percent of the starting material/carrier feed. Increasing the dilution of the starting material with a gaseous diluent such as hydrogen may tend to increase the selectivity of the reaction to the particular products desired. The amount of liquid diluent can vary widely, for instance, from no diluent to about 90 weight percent or greater of the total weight of the starting materials.

For processes of this invention in which a carboxylated compound is contacted with a metal oxide catalyst under conditions effective to decarboxylate the carboxylated compound or an active hydrogen-containing compound and a CO.sub.2 synthon are contacted in the presence of a metal oxide catalyst under conditions effective for decarboxylation or other related processes described herein, it is understood that the process conditions described herein for the step (ii) decarboxylation reaction can desirably be employed for such processes.

The processes of this invention are useful for preparing substituted and unsubstituted decarboxylated compounds. Illustrative compounds prepared by the processes of this invention include, for example, substituted and unsubstituted alcohols or phenols; amines; amides; ethers or epoxides; esters; carboxylic acids or anhydrides; ketones; olefins; acetylenes; halides or sulfonates; aldehydes; nitriles; and hydrocarbons.

Illustrative of suitable compounds which can be prepared by the processes of this invention include those permissible compounds which are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, 1984, the pertinent portions of which are incorporated herein by reference. Other suitable compounds are described in Harrison, I. T. and Harrison, S., Compendium of Organic Synthetic Methods, 1971, the pertinent portions of which are incorporated herein by reference.

The decarboxylated compound products produced by the processes of this invention can be separated by distillation. For example, a crude reaction product can be subjected to a distillation-separation at atmospheric or reduced Pressure through a packed distillation column. Reactive distillation may be useful in conducting the step (i) transesterification reaction.

The processes of this invention may be carried out using, for example, a fixed bed reactor, a fluid bed reactor, or a slurry reactor. The optimum size and shape of the catalyst will depend on the type of reactor used. In general, for fluid bed reactors, a small, spherical catalyst particle is preferred for easy fluidization. With fixed bed reactors, larger catalyst particles are preferred so the back pressure within the reactor is kept reasonably low.

The processes of this invention can be conducted in a batch or continuous fashion, with recycle of unconsumed starting materials if required. The reaction can be conducted in a single reaction zone or in a plurality of reaction zones, in series or in parallel or it may be conducted batchwise or continuously in an elongated tubular zone or series of such zones. The materials of construction employed should be inert to the starting materials during the reaction and the fabrication of the equipment should be able to withstand the reaction temperatures and pressures. Means to introduce and/or adjust the quantity of starting materials or ingredients introduced batchwise or continuously into the reaction zone during the course of the reaction can be conveniently utilized in the processes especially to maintain the desired molar ratio of the starting materials. The reaction steps may be effected by the incremental addition of one of the starting materials to the other. Also, the reaction steps can be combined by the joint addition of the starting materials to the decarboxylation catalyst. When complete conversion is not desired or not obtainable, the starting materials can be separated from the product, for example by distillation, and the starting materials then recycled back into the reaction zone.

The processes are conducted for a period of time sufficient to produce the decarboxylated compound products. The exact reaction time employed is dependent, in part, upon factors such as temperature, nature and proportion of starting materials, and the like. The reaction time will normally be within the range of from about one-half to about 100 hours or more, and preferably from less than about one to about ten hours.

The processes may be conducted in either glass lined, stainless steel or similar type reaction equipment. The reaction zone may be fitted with one or more internal and/or external heat exchanger(s) in order to control undue temperature fluctuations, or to prevent any possible "runaway" reaction temperatures.

Illustrative of suitable reactants in effecting the processes of this invention include by way of example:

AL--alcohols

CA--carboxylic acids

PH--phenols

TPH--thiophenols

MER--mercaptans

AMN--amines

AMD--amides

CN--carbonates

CLCN--chlorocarbonates

CNA--carbonic acids

CM--carbamates

CMA--carbamic acids

OX--oxalates

OXZ--2-oxazolidinones

UR--ureas

ES--esters

PH--phosgene

CH--chloroformates

CD--carbon dioxide

OC--orthocarboxylates

SA--sulfurous acids

SAE--sulfurous acids esters

CAL--carboxylated alcohols

CPH--carboxylated phenols

CTPH--carboxylated thiophenols

CMER--carboxylated mercaptans

CAMN--carboxylated amines

CAMD--carboxylated amides

CET--carboxylated ethers

CEP--carboxylated epoxides

CES--carboxylated esters

CCA--carboxylated carboxylic acids

CANH--carboxylated anhydrides

CKET--carboxylated ketones

COLE--carboxylated olefins

CACE--carboxylated acetylenes

CHAL--carboxylated halides

CSUL--carboxylated sulfonates

CALD--carboxylated aldehydes

CNIT--carboxylated nitriles

CHC--carboxylated hydrocarbons

Illustrative of suitable products prepared by the processes of this invention include by way of example:

AL--alcohols

PH--phenols

TPH--thiophenols

MER--mercaptans

AMN--amines

AMD--amides

ET--ethers

EP--epoxides

ES--esters

CA--carboxylic acids

ANH--anhydrides

KET--ketones

OLE--olefins

ACE--acetylenes

HAL--halides

SUL--sulfonates

ALD--aldehydes

NIT--nitriles

HC--hydrocarbons

Illustrative of permissible reactions encompassed within the scope of this invention include, for example, the following reactant/product combinations:

As used herein, the term "substituted" is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic anc cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen and the like in which the number of carbons can range from 1 to about 20 or more, preferably from 1 to about 12. The permissible substituents can be one or more than the same or different for appropriate organic compounds. This invention is not intended to be limited in any manner by the permissible substituents of organic compounds.

Certain of the following examples are provided to further illustrate the processes of this invention.

A total of 79.4 grams (0.34 moles) of magnesium nitrate hexahydrate and 12.0 grams (0.032 moles) of aluminum nitrate nonahydrate were dissolved in 200 milliliters of deionized water to give a first solution. A total of 0.95 grams of sodium carbonate and 18 grams of sodium hydroxide were dissolved in 150 milliliters of deionized water to give a second solution. About 100 milliliters of distilled water was heated in a flask at a temperature of 40.degree. C. and the first and second solutions were combined simultaneously with good agitation using a mechanical stirrer. The rates of addition of the first and second solutions were

adjusted to maintain a pH of 9-10. The total addition took 3 minutes and a final pH of 9 was obtained. The contents were stirred at a temperature of 48.degree. C. for a period of 30 minutes. The filter cake was washed with 300 milliliters of deionized water and dried at a temperature of 60.degree. C. overnight to give a total of 20.1 grams of material. The dried filter cake was washed (ca. 200 milliliters three times) with deionized water at a temperature of 60.degree. C. until the pH of the wash was neutral. The filter cake was then dried at a temperature of 80.degree. C. overnight. The weight of the dried filter cake was 11.8 grams. The filter cake was then calcined in air at a temperature of 400.degree. C. overnight to afford 7.3 grams of the catalyst having a magnesium/aluminum ratio of 10:1 and a surface area of 130 square meters per gram. This catalyst is referred to hereinafter as Catalyst A.

A total of 88.2 grams (0.34 moles) of magnesium nitrate hexahydrate and 132.0 grams (0.35 moles) of aluminum nitrate nonahydrate were dissolved in 400 milliliters of deionized water to give a first solution. A total of 10.6 grams of sodium carbonate and 60.8 grams of sodium hydroxide were dissolved in 400 milliliters of deionized water to give a second solution. About 100 milliliters of distilled water was heated in a flask at a temperature of 40.degree. C. and the first and second solutions were combined simultaneously with good agitation using a mechanical stirrer. The rates of addition of the first and second solutions were adjusted to maintain a pH of 9-10. The total addition took 10 minutes. An additional 50 milliliters of 1 molar sodium hydroxide was added to obtain a final pH of 9. The contents were stirred at a temperature of 40.degree. C. for a period of 30 minutes. The filter cake was dried at a temperature of 80 .degree. C. overnight to give a total of 94.7 grams of material. The dried filter cake was washed (ca. 300 milliliters three times) with deionized water at a temperature of 60.degree. C. until the pH of the wash was neutral. The filter cake was then dried at a temperature of 80.degree. C. overnight. The weight of the dried filter cake was 38.1 grams. The filter cake (12.0 grams) was then calcined in air at a temperature of 400.degree. C. for a period of 3 hours to afford 1.6 grams of the catalyst having a magnesium/aluminum ratio of 1:1 and a surface area of 265 square meters per gram. This catalyst is referred to hereinafter as Catalyst B.

A total of 10 grams of filter cake prepared in Example 2 (prior to calcination at a temperature of 400.degree. C.) was calcined in air at a temperature of 700.degree. C. for a period of 3 hours to afford 5.9 grams of the catalyst having a magnesium/aluminum ratio of 1:1 and a surface area of 201 square meters per gram. This catalyst is referred to hereinafter as Catalyst C.

A total of 170.2 grams (0.66 moles) of magnesium nitrate hexahydrate and 12.6 grams (0.033 moles) of aluminum nitrate nonahydrate were dissolved in 400 milliliters of deionized water to give a first solution. A total of 1.02 grams of sodium carbonate and 32.0 grams of sodium hydroxide were dissolved in 400 milliliters of deionized water to give a second solution. About 100 milliliters of distilled water was heated in a flask at a temperature of 40.degree. C. and the first and second solutions were combined simultaneously with good agitation using a mechanical stirrer. The rates of addition of the first and second solutions were adjusted to maintain a pH of 9-10. The total addition took 2 minutes and a final pH of 8.4 was obtained. The contents were stirred at a temperature of 40.degree. C. for a period of 30 minutes. The filter cake was dried at a temperature of 80.degree. C. overnight to give a total of the 64.8 grams of material. The dried filter cake was washed (ca. 300 milliliters three times) and deionized water at a temperature of 60.degree. C. until the pH of the wash was neutral. The filter cake was then dried at a temperature of 80.degree. C. overnight. The weight of the dried filter cake was 24.4 grams. The filter cake (8.5 grams) was then calcined in air at a temperature of 700.degree. C. for a period of 3 hours to afford 5.0 grams of the catalyst having a magnesium/aluminum ratio of 20:1 and a surface area of 104 square meters per gram. This catalyst is referred to hereinafter as Catalyst D.

A total of 132.3 grams (0.51 moles) of magnesium nitrate hexahydrate and 66.0 grams (0.17 moles) of aluminum nitrate nonanhydrate were dissolved in 400 milliliters of deionized water to give a first solution. A total of 9.3 grams of sodium carbonate and 48.0 grams of sodium hydroxide were dissolved in 400 milliliters of deionized water to give a second solution. About 100 milliliters of distilled water was heated in a flask at a temperature of 40.degree. C. and the first (350 milliliters) and second solutions were combined simultaneously with good agitation using a mechanical stirrer. The rates of addition of the first and second solutions were adjusted to maintain a pH of 8-9. The total addition took 8 minutes and a final pH of 8.5 was obtained. The contents were stirred at a temperature of 48.degree. C. for a period of 15 minutes. The filter cake was dried at a temperature of 80.degree. C. overnight to give a total of 86.0 grams of material. The dried filter cake was washed (ca. 300 milliliters three times) with deionized water at a temperature of 60.degree. C. until the pH of the wash was neutral. The filter cake was then dried at a temperature of 80.degree. C. overnight. The weight of the dried filter cake was 41.8 grams. The filter cake (12.0 grams) was then calcined in air at a temperature of 400.degree. C. for a period of 3 hours to afford 7.3 grams of the catalyst having a magnesium/aluminum ratio of 3:1 and a surface area of 113 square meters per gram. This catalyst is referred to hereinafter as Catalyst E.

A total of 29.2 grams (0.11 moles) of magnesium nitrate hexahydrate and 87.0 grams (0.23 moles) of aluminum nitrate nonahydrate were dissolved in 200 milliliters of deionized water to give a first solution. A total of 7.0 grams of sodium carbonate and 32.0 grams of sodium hydroxide were dissolved in 200 milliliters of deionized water to give a second solution. About 100 milliliters of distilled water was heated in a flask at a temperature of 40.degree. C. and the first (180 milliliters) and second (180 milliliters) solutions were combined simultaneously with good agitation using a mechanical stirrer. The rates of addition of the first and second solutions were adjusted to maintain a pH of 8-9. The total addition took 12 minutes and a final pH of 8.2 was obtained. The contents were stirred at a temperature of 40.degree. C. for a period of 20 minutes. The filter cake was dried at a temperature of 80.degree. C. overnight to give a total of 39.1 grams of material. The dried filter cake was washed (ca. 300 milliliters three times) with deionized water at a temperature of 60.degree. C. until the pH of the wash was neutral. The filter cake was then dried at a temperature of 80.degree. C. overnight. The weight of the dried filter cake was 22.0 grams. The filter cake (12.0 grams) was then calcined in air at a temperature of 400.degree. C. for a period of 3 hours to afford 7.8 grams of the catalyst having a magnesium/aluminum ratio of 1:2 and a surface area of 270 square meters per gram. This catalyst is referred to hereinafter as Catalyst F.

A total of 85.1 grams (0.33 moles) of magnesium nitrate hexahydrate and 6.3 grams (0.16 moles) of aluminum nitrate nonahydrate were dissolved in 200 milliliters of deionized water to give a first solution. A total of 0.5 grams of sodium carbonate and 16.0 grams of sodium hydroxide were dissolved in 200 milliliters of deionized water to give a second solution. About 100 milliliters of distilled water was heated in a flask at a temperature of 40.degree. C. and the first and second solutions were combined simultaneously with good agitation using a mechanical stirrer. The rates of addition of the first and second solutions were adjusted to maintain a pH of 8-9. The total addition took 8 minutes and a final pH of 8.8 was obtained. The contents were stirred at a temperature of 42.degree. C. for a period of 15 minutes. The filter cake was dried at a temperature of 80.degree. C. overnight to give a total of 24.4 grams of material. The dried filter cake was washed (ca. 300 milliliters three times) with deionized water at a temperature of 60 .degree. C. until the pH of the wash was neutral. The filter cake was then dried at a temperature of 80.degree. C. overnight. The weight of the dried filter cake was 12.6 grams. The filter cake (12.4 grams) was then calcined in air at a temperature of 400.degree. C. for a period of 3 hours to afford 8.0 grams of the catalyst having a magnesium/aluminum ratio of 20:1 and a surface area of 163 square meters per gram. This catalyst is referred to hereinafter as Catalyst G.

A total of 7.7 grams (0.03 moles) of magnesium nitrate hexahydrate and 118.53 grams (0.3 moles) of aluminum nitrate nonahydrate were dissolved in 200 milliliters of deionized water to give a first solution. A total of 9.5 grams of sodium carbonate and 48.0 grams of sodium hydroxide were dissolved in 200 milliliters of deionized water to give a second solution. About 100 milliliters of distilled water was heated in a flask at a temperature of 40.degree. C. and the first and second solutions were combined simultaneously with good agitation using a mechanical stirrer. The rates of addition of the first and second (175 milliliters) solutions were adjusted to maintain a pH of 8-9. The total addition took 8 minutes and a final pH of 11.1 was obtained. The contents were stirred at a temperature of 48.degree. C. for a period of 15 minutes. The filter cake was dried at a temperature of 80.degree. C. overnight to give a total of 58.3 grams of material. The dried filter cake was washed (ca. 300 milliliters three times) with deionized water at a temperature of 60.degree. C. until the pH of the wash was neutral. The filter cake was then dried at a temperature of 80.degree. C. overnight. The weight of the dried filter cake was 17.8 grams. The filter cake (12.0 grams) was then calcined in air at a temperature of 400.degree. C. for a period of 3 hours to afford 9.2 grams of the catalyst having a magnesium/aluminum ratio of 1:10 and a surface area of 298 square meters per gram. This catalyst is referred to hereinafter as Catalyst H.

A total of 44.1 grams (0.17 moles) of magnesium nitrate hexahydrate and 66.0 grams (0.17 moles) of aluminum nitrate nonahydrate were dissolved in 200 milliliters of deionized water to give a first solution. A total of 4.8 grams of ammonium carbonate and 60 milliliters of ammonium hydroxide (28 weight percent) were dissolved in 200 milliliters of deionized water to give a second solution. About 100 milliliters of distilled water was heated in a flask at a temperature of 40.degree. C. and the first and second solutions were combined simultaneously with good agitation using a mechanical stirrer. The rates of addition of the first and second solutions were adjusted to maintain a PH of 9-10. The total addition took 15 minutes and a final pH of 9.5 was obtained. The contents were stirred at a temperature of 41.degree. C. for a period of 40 minutes. The filter cake was washed (ca. 300 milliliters three times) with deionized water at temperature of 60 .degree. C. until the pH of the wash was neutral. The filter cake was then dried at a temperature of 80.degree. C. overnight. The weight of the dried filter cake was 30.5 grams. The filter cake was washed (ca. 300 milliliters three times) again with deionized water at a temperature of 60.degree. C. and dried overnight at a temperature of 80.degree. C. The weight of the dried filter cake was 21.6 grams. The filter cake (12.0 grams) was then calcined in air at a temperature of 400.degree. C. for a period of 3 hours to afford 7.6 grams of the catalyst having a magnesium/aluminum ratio of 1:1 and a surface area of 223 square meters per gram. This catalyst is referred to hereinafter as Catalyst I.

A magnesium/aluminum material having a 2:1 magnesium/aluminum ratio was obtained from United Catalysts Inc., Louisville, Ky. This material was calcined in air at a temperature of 450.degree. C. for a period of 3 hours to afford the catalyst having a surface area of 192 square meters per gram. This catalyst is referred to hereinafter as Catalyst J.

A magnesium/aluminum material having a 1:1 magnesium/aluminum ratio was obtained from United Catalysts Inc., Louisville, Ky. This material was calcined in air at a temperature of 450.degree. C. for a period of 3 hours to afford the catalyst having a surface area of 161 square meters per gram. This catalyst is referred to hereinafter as Catalyst K.

A total of 256.0 grams (1.0 moles) of magnesium nitrate hexahydrate and 125.0 grams (0.33 moles) of aluminum nitrate nonahydrate were dissolved in 700 milliliters of deionized water to give a first solution. A total of 100 grams of sodium carbonate and 140 grams of sodium hydroxide were dissolved in 1000 milliliters of deionized water to give a second solution. The first and second solutions were combined simultaneously with good agitation using a mechanical stirrer at or below a temperature of 35.degree. C. over a period of 4 hours. The contents were then heated to a temperature of 65.degree. C. and stirred overnight. The filter cake was washed (ca. 300 milliliters two to three times) with deionized water at a temperature of 60.degree. C. until the sodium content of the resulting solid material was below 0.1 percent (dry basis). The solid material was then dried at a temperature of 125.degree. C. under vacuum overnight. This material was calcined in air at a temperature of 400.degree. C. for a period of 3 hours to afford the catalyst having a magnesium/aluminum ratio of 3:1 and a surface area of 164 square meters per gram. This catalyst is referred to hereinafter as Catalyst L.

A total of 5.0 grams (0.01 moles) of magnesium carbonate hydroxide pentahydrate and 10.0 grams (0.13 moles) of aluminum hydroxide hydrate were combined, 32 grams of deionized water was added to form a paste and the contents were then thoroughly mixed. The paste was calcined in air at a temperature of 400.degree. C. for a period of 3 hours to afford 8.1 grams of the catalyst having a magnesium/aluminum ratio of 1:1. This catalyst is referred to hereinafter as Catalyst M.

A total of 89.1 grams (1 mole) of 2-(N,N-dimethylamino)ethanol, 19.7 grams (0.167 moles) of diethyl carbonate and 1.0 gram of sodio 2-dimethylaminoethoxide (0.01 moles) were combined in a 250 milliliter round bottom flask equipped with a straight distillation head and magnetic stirrer. A vacuum was established and maintained at 50 mm Hg and the flask was heated to reflux. Initial reaction temperatures at reflux were 40.degree. C. at the head and 48.degree. C. on the kettle. Ethanol was removed over a period of 5.5 hours and trapped using a dry ice/acetone bath. After this time, a sample was removed from the kettle and analyzed by capillary gas chromatography. The kettle analyzed (area percent) for: 0.5 percent ethanol, 69.7 percent 2-(N,N-dimethylamino)ethanol, 0.1 percent diethyl carbonate, 0.1 percent bis[2-(N,N-dimethylamino)ethyl]ether, 1.5 percent 2-(N,N-dimethylamino)ethyl ethyl carbonate, and 28.1 percent bis[2-(N,N-dimethylamino)ethyl]carbonate. The reaction mixture was heated again for a period of 4.5 hours at reflux, after which time the head temperature rose to 56.degree. C. and the kettle temperature rose to 60.degree. C. A total of 15.6 grams of distillate was obtained. The distillate analyzed (area percent) by capillary gas chromatography for: 87.6 percent ethanol, 0.6 percent ethyl carbonic acid, 3.7 percent 2-(N,N-dimethylamino)ethanol and 7.9 percent diethyl carbonate. After 9 hours at reflux, the 2-(N,N-dimethylamino)ethanol was removed overhead (56.degree. C.-60.degree. C. head temperature) slowly. After a period of 45 minutes, 58.2 grams of distillate was collected. The distillate analyzed (area percent) by capillary gas chromatography for 2-(N,N-dimethylamino)ethanol (98.8 percent) with minor amounts of ethanol and bis[2-(N,N-dimethylamino)ethyl]carbonate. The kettle (35.08 grams) analyzed (area percent) by capillary gas chromatography for bis[2-(N,N-dimethylamino)ethyl]carbonate (97.7 percent) with minor amounts of 2-(N,N-dimethylamino)ethanol, diethyl carbonate, 2-(N,N-dimethylamino)ethyl ethyl carbonate and bis[2-(N,N-dimethylamino)ethyl]ether. A total of 34.4 grams of the kettle material was charged to a 50 milliliter round bottom flask equipped with a distillation head and magnetic stirrer. The Pressure was reduced to 8 mm Hg and the material was distilled overhead. The first fraction contained 4.6 grams of material. A second fraction containing 1.4 grams of material was obtained (maximum head temperature of 103.degree. C. at 8 mm Hg) and a final fraction (head temperature of 108 .degree. C.-109.degree. C. at 8 mm Hg) containing 25.2 grams of material was collected. A total of 2.2 grams was left as kettle residue. The last fraction analyzed (area percent) by capillary gas chromatography for bis[2-(N,N-dimethylamino)ethyl]carbonate (98.2 percent) with a minor amount of 2-(N,N-dimethylamino)ethanol (1.1 percent). A total material balance of greater than 99 percent was obtained and a theoretical yield of 73.8 percent (based on the final fraction of distillate) of bis[2-(N,N-dimethylamino)ethyl]carbonate was obtained.

In the examples set forth in Table I below, an Applied Test Systems, Inc. Model 3620 Split Test Oven equipped with a preheater (stainless steel 1/8 inch o.d. .times.2 feet) and 1/2 inch (o.d.) stainless steel reactor tube (8 inch length) was packed with catalyst and heated to the desired reaction temperature using a Honeywell Dial-A-Trol temperature controller. The temperatures at the top of the reactor and the bottom were monitored using a digital temperature readout. The liquid feed of neat bis[2-(N,N-dimethylamino)ethyl]carbonate was added (downflow) to the reactor via a Fluid Metering Inc. RP-G20 drive pump equipped with an 1/8 inch pump head. The system was maintained under nitrogen, which was introduced prior to the liquid preheater and was monitored with a rotometer. The product mixture was collected in a 100 milliliter round bottom flask, vented first to a dry ice/acetone trap and then a Firestone valve. Analysis was performed by capillary gas chromatography (FID) using a DB-1701 column. The process conditions and product analyses are set forth in Table I.

A total of 28.8 grams (0.22 moles) of 4-(2-hydroxyethyl)morpholine, 9.0 grams (0.1 moles) of dimethyl carbonate and 0.38 grams of anhydrous potassium carbonate were combined in a 50 milliliter 3-neck round bottom flask equipped with a 12 inch vacuum-jacketed column packed with stainless steel screens and a distillation head. The contents were heated to reflux under nitrogen. An initial kettle temperature of 128.degree. C. and a head temperature of 61.degree. C. were observed. The contents were heated at reflux for a period of about 1.5 hours at which time the kettle temperature rose to 131.degree. C. After this time, methanol (with some dimethyl carbonate) was slowly removed overhead for a period of about 50 minutes. Capillary gas chromatographic analysis showed about 50 percent of the desired product. The flask was then cooled to a temperature of 80.degree. C. and an additional 3.0 grams of dimethyl carbonate was added. The contents were again heated to reflux for a period of about 30 minutes while removing methanol overhead to give a final kettle temperature of 200.degree. C. A total of 4.3 grams of distillate was obtained. The kettle was filtered (vacuum) to remove the potassium carbonate. A total of 26.2 grams of this material was added to a 50 milliliter flask equipped with a 4 inch vacuum-jacketed column packed with stainless steel screens and a distillation head. The flask was heated under vacuum (4 mm Hg) to remove the last traces of 4-(2-hydroxyethyl)morpholine (80.degree. C. at 4mm Hg). The kettle fraction analyzed (area percent) by capillary gas chromatography as follows: 85.6 percent bis(2-N-morpholinoethyl)carbonate, 9.1 percent 2,2-dimorpholinodiethylether, and 2.1 percent 4-(2-hydroxyethyl)morpholine.

Using the apparatus employed in Examples 15-27, a 20 percent (volume) solution of bis(2-N-morpholinoethyl)carbonate prepared in Example 28 in cyclohexane was passed through 6.0 grams of Catalyst J at a temperature of 300.degree. C. and a liquid feed rate of 0.32 milliliters per minute. A total of 7.8 grams of product was recovered. Capillary gas chromatographic analysis (area percent) of this material showed 62.7 percent selectivity to 2,2-dimorpholinodiethylether at 97.5 percent bis(2-N-morpholinoethyl)carbonate conversion.

A total of 13.1 grams (0.1 moles) of 4-(2-hydroxyethyl)morpholine, 27.0 grams (0.3 moles) of dimethyl carbonate and 0.4 grams of anhydrous Potassium carbonate were combined in a 50 milliliter 3-neck round bottom flask equipped with a 4 inch vacuum-jacketed vigreaux column and a distillation head. The contents were heated to reflux under nitrogen, and after a period of 15 minutes (kettle temperature of 93.degree. C. and a head temperature of 63.degree. C.) methanol (with some dimethyl carbonate) was slowly removed overhead. After a period of about 2.5 hours, an additional 4.5 grams of dimethyl carbonate was added and the contents heated to reflux for another 1.5 hours. Capillary gas chromatographic analysis showed complete reaction of 4-(2-hydroxyethyl)morpholine. The flask was then cooled, filtered to remove potassium carbonate and charged to a clean 50 milliliter round bottom flask. The contents were distilled under vacuum (5 mm Hg) to give 9.14 grams (boiling point 117-119.degree. C. at 5 mm Hg) of 4-(2-hydroxyethyl)morpholine methyl carbonate (99 percent). The kettle residue (4.3 grams) analyzed (area percent) by capillary gas chromatography as follows: 4-(2-hydroxyethyl)morpholine methyl carbonate (32.8 percent) and bis(2-N-morpholinoethyl)carbonate (65.5 percent).

Using the apparatus employed in Examples 5-27, a 20 percent (volume) solution of 4-(2-hydroxyethyl)morpholine methyl carbonate prepared in Example 30 in cyclohexane was passed through 6.0 grams of Catalyst J at a temperature of 300.degree. C. and a liquid feed rate of 0.27 milliliters per minute. A total of 7.4 grams of product was recovered. Capillary gas chromatographic analysis (area percent) of this material showed 67.7 percent selectivity to 4-(2-methoxyethyl)morpholine at 100 percent 4-(2-hydroxyethyl)morpholine methyl carbonate conversion.

A total of 118.2 grams (1 mole) of 2-butoxyethanol, 120.1 grams (1.5 moles) of dimethyl carbonate, and 1.0 gram of potassium carbonate were combined in 300 milliliter round bottom three-neck flask equipped with a straight distillation head and a magnetic stirrer. The flask contents were heated to reflux at an initial temperature of 64.degree. C. at the head and 89.degree. C. in the kettle. A methanol/dimethyl carbonate azeotrope was slowly removed overhead. A total of 99.5 grams of material was removed overhead (64.degree. C.-90.degree. C.) over a period of about 13 hours after which time the kettle temperature rose to 228.degree. C. After this time, the flask contents were cooled (132.2 grams) and filtered into a 200 milliliter round bottom flask. The flask contents were then placed under vacuum. The desired product was collected at a temperature of 135.degree. C.-142.degree. C. at 6 mm Hg. A total of 96.6 grams (73.7 percent yield) of bis(2-butoxyethyl)carbonate was obtained at a purity of greater than 99 percent as analyzed by capillary gas chromatography on a DB-1701 column.

Using the apparatus employed in Examples 15-27, bis(2-butoxyethyl)carbonate prepared above was passed through a catalyst bed containing 10.8 grams of a magnesium:aluminum mixed metal oxide (3/16 inch tablets, Mg/Al 3:1) at a reaction temperature indicated in Table II below and at a liquid feed rate of about 0.3 milliliters/minute. The feed was continued for a period of 1 hour and then analyzed by capillary gas chromatography on a DB-1701 column. The results are given in Table II.

Bis(sec-butyl)carbonate was prepared from 2-butanol and dimethyl carbonate via the following procedure. A total of 51.88 grams (0.7 mol) of 2-butanol, 64.22 grams (0.71 mol) of dimethyl carbonate, and 1.0 gram (0.003 mol) of di-n-butyltin dimethoxide were combined in a 250 milliliter 3-neck flask equipped with a distillation head and vigreaux column. The reaction mixture was refluxed under nitrogen overnight (kettle temperature 84.degree. C., head temperature 80.degree. C.). With a head temperature of 63.degree. C. (kettle 74.degree. C.), the condensate was taken over slowly. A total of 46.2 grams of distillate was collected while maintaining a head temperature of less than 73.degree. C. A second distillate fraction of 5.7 grams was collected at a head temperature of 73-94.degree. C. At this point the relative amount of methyl sec-butyl carbonate to bis(sec-butyl)carbonate was about 2:1. The flask was cooled and an additional 14.8 grams (0.2 mol) of 2-butanol was added and the reaction mixture heated to reflux. The condensate was again taken over slowly at a head temperature less than 74.degree. C. to afford an additional 13.7 grams of distillate. At this point the head temperature reached 133.degree. C. and the kettle temperature was 169.degree. C. A small distillate fraction (5.7 grams) was taken overhead followed by a second distillate fraction (53.5 grams) which contained bis(sec-butyl)carbonate (head temperature 161.degree. C., kettle temperature 174.degree. C.). Analysis by capillary gas chromotography showed 93% (area) purity of bis(sec-butyl)carbonate with 7% (area) methyl sec-butyl carbonate.

Using the apparatus employed in Examples 15-27, bis(sec-butyl)carbonate was passed through a catalyst bed containing 11.5 grams of a magnesium:aluminum mixed metal oxide (3/16 inch tablets, Mg/Al 3:1) at a reaction temperature indicated in Table III below and at a liquid feed rate of about 0.3 milliliters/minute. The feed was continued for a period of 1 hour and then analyzed by capillary gas chromatography on a DB-1701 column. The results are given in Table III.

A total of 76.1 grams (1 mole) of 2-methoxyethanol, 67.6 grams (0.75 moles) of dimethyl carbonate, and 0.5 grams of dibutyltin dimethoxide were combined in a 250 milliliter round bottom three-neck flask equipped with a straight distillation head and a magnetic stirrer. The flask contents were heated to reflux at an initial temperature of 73.degree. C. at the head and 102.degree. C. in the kettle. After seven minutes at reflux, a methanol/dimethyl carbonate azeotrope was slowly removed overhead. A total of 55.9 grams of material was removed overhead (64.degree. C.-88.degree. C.) over a period of about 21 hours after which time the kettle temperature rose to 145.degree. C. After this time, the flask contents were cooled and put under vacuum. The desired product was collected at a temperature of 97.degree. C.-105.degree. C. at 3 mm Hg. A total of 77.98 grams (87.5 percent yield) of bis(2-methoxyethyl)carbonate was obtained at a purity of greater than 99 percent as analyzed by capillary gas chromatography on a DB-1701 column.

Using the apparatus employed in Examples 15-27, bis(2-methoxyethyl)carbonate was passed through a catalyst bed containing 11.5 grams of a magnesium:aluminum mixed metal oxide (3/16 inch tablets, Mg/Al 3:1) at a reaction temperature indicated in Table IV below and at a liquid feed rate of about 0.3 milliliters/minute. The feed was continued for a period of 1 hour and analyzed by capillary gas chromography on a DB-1701 column. The results are given in Table IV.

Using the apparatus employed in Examples 15-27, a mixture of cyclohexanol (1 mole) and dimethyl carbonate (3 mole) was passed through 11.5 grams of a magnesium:aluminum mixed metal oxide (3/16 inch pellets, Mg/Al 3:1) at a temperature of 250.degree. C. and at a liquid feed rate of 0.32 milliliters/minute. After a period of one hour, a total of 31 grams of liquid was collected. Analysis was performed by capillary gas chromatography (FID) using a DB-1701 column. The results were (area %) as follows:

5.9% methanol

3.0% dimethyl carbonate

77.3% cyclohexyl methyl ether

7.1% cyclohexanol.

Using the apparatus employed in Examples 15-27, a mixture of 2-(2-ethoxyethoxy)ethanol (1 mole) and diethyl carbonate (3 mole) was passed through 11.5 grams of a magnesium:aluminum mixed metal oxide (3/16 inch pellets, Mg/Al 3:1) at a temperature of 225.degree. C. and at a liquid feed rate of 0.29 milliliters/minute. After a period of one hour, a total of 30.2 grams of liquid was collected. Analysis was performed by capillary gas chromatography (FID) using a DB-1701 column. The results were (area %) as follows:

19.1% diethyl ether

16.0% ethanol

14.3% diethyl carbonate

41.2% diethylene glycol diethyl ether

3.3% tetraethylene glycol diethyl ether.

Using the apparatus employed in Examples 15-27, a mixture of 1-decanol (1 mole) and dimethyl carbonate (3 mole) was passed through 11.5 grams of a magnesium:aluminum mixed metal oxide (3/16 inch pellets, Mg/Al 3:1) at a temperature of 250.degree. C. and at a liquid feed rate of 0.34 milliliters/minute. After a period of 1.1 hour, a total of 36.5 grams of liquid was collected. Analysis was performed by capillary gas chromatography (FID) using a DB-1701 column. The results were (area %) as follows:

2.5% methanol

0.7% dimethyl carbonate

75.6% n-decyl methyl ether

9.0% 1-decanol

2.2% n-decyl methyl carbonate

4.5% bis(n-decyl)ether.

Using the apparatus employed in Examples 15-27, a mixture of 1-methoxy-2-propanol (1 mole) and dimethyl carbonate (4 mole) was passed through 11.5 grams of a magnesium:aluminum mixed metal oxide (3/16 inch pellets, Mg/Al 3:1) at a temperature of 250.degree. C. and at a liquid feed rate of 0.35 milliliters/minute. After a period of 1 hour, a total of 30.6 grams of liquid was collected. Analysis was performed by capillary gas chromatography (FID) using a DB-1701 column. The results were (area %) as follows:

12.5% methanol

0.6% dimethyl carbonate

75.7% propylene glycol dimethyl ether

8.7% 1-methoxy-2-propanol.

A total of 144.2 grams (1.2 mol) of 2-(2-methoxyethoxy)ethanol, 400 grams (4.4 mol) of dimethyl carbonate and 3 grams (0.05 mol) of sodium methoxide were combined in a 1-liter 3-neck round bottom flask equipped with a 14 inch distillation column, distillation head, and magnetic stirbar. The system was evacuated and purged three times with nitrogen using a Firestone valve, and left under a constant nitrogen atmosphere. After a period of 1.5 hours at reflux (kettle temperature 84.degree. C.), methanol (boiling point 64.degree. C.) was slowly removed overhead to drive the equilbrium. A total of 49.8 grams of methanol was removed over a period of 3 hours, after which time the stopcock was closed and the reaction mixture was allowed to reflux overnight. The mixture was then cooled to room temperature, filtered and charged (429 grams) to a 500 milliliter round bottom flask equipped with a distillation head and magnetic stirbar. Excess dimethyl carbonate (boiling point 90.degree. C.) was removed overhead. The flask was then cooled, put under vacuum (10-11 mm Hg), and methyl 2-(2-methoxyethoxy)ethyl carbonate removed overhead (boiling point 115-125.degree. C.). A total of 193 grams (ca. 90% yield) was obtained. Gas chromatography analysis of this material showed 97.74% purity (remainder was 2-(2-methoxyethoxy)ethanol).

Chunks of magnesium:aluminum mixed metal oxide (Mg/Al 3:1) materials were crushed to a fine powder and calcined at a temperature of 400.degree. C. overnight. A total of 2.5 grams of the calcined magnesium:aluminum mixed metal oxide (Mg/Al 3:1) materials was charged to a 7.5 inch stainless steel tube (3/8 inch o.d.) which was then connected to a preheater installed in a Hewlett Packard GC oven. The temperature was set at 275.degree. C. and, after reaching reaction temperature, the methyl 2-(2-methoxyethoxy)ethyl carbonate prepared above (generally 10 grams) was fed via a FMI piston pump at 0.5 milliliters/minute with a nitrogen sweep. The material at the reactor outlet was allowed to condense in a sample bottle (cooled in dry ice/acetone) equipped with an outlet vented to the hood. Products were analyzed on a gas chromatograph and the results are given in Table V below.

Using the apparatus employed in Examples 15-27, a solution containing 1.72 grams (0.02 mol) of piperazine and 7.21 grams (0.08 mol) of dimethyl carbonate in 20 milliliters of methanol was passed through a catalyst bed containing 2.0 grams of a magnesium:aluminum mixed metal oxide (3/16 inch tablets, Mg/Al 3:1) at a temperature of 250.degree. C and a flow rate of about 0.3 milliliters per minute. After a period of 1 hour, the reaction was stopped and the product analyzed. The results are given in Table VI below.

Using the apparatus employed in Examples 15-27, a 30 weight percent solution of ethyl 1-piperazinecarboxylate in cyclohexane was passed through a catalyst bed containing 6.0 grams of a magnesium:aluminum mixed metal oxide (1/8 inch tablets, Mg/Al 3:1) at a temperature of 325.degree. C. and a liquid feed rate of 0.32 milliliters per minute. After a period of 0.5 hours, the cyclohexane was removed under vacuum and the product mixture (liquid and solid) was dissolved in water. The results are given in Table VII below.

Into a 10 milliliter round bottom reaction flask equipped with a distillation column, thermometer and mechanical stirrer was added 2.16 grams of trimethylene carbonate and 0.257 grams of a magnesium:aluminum mixed metal oxide having a magnesium:aluminum ratio of 3:1. The flask contents were heated to a temperature of 250.degree. C. in an oil bath. The products distilled from the flask as they were formed and collected in a cold trap cooled to a temperature of -78.degree. C. Analysis was performed by a capillary gas chromatograph (FlD) using a DB-1701 column. The collected products consisted of 0.825 grams (65 percent theoretical yield) of a 50/50 mixture of oxetane and allyl alcohol.

Into a 10 milliliter round bottom reaction flask equipped with a distillation column, thermometer and mechanical stirrer was added 2.06 grams of poly(trimethylene carbonate) and 0.255 grams of a magnesium:aluminum mixed metal oxide having a magnesium:aluminum ratio of 3:1. The flask contents were heated to a temperature of 250.degree. C. in an oil bath. The products distilled from the flask as they were formed and collected in a cold trap cooled to a temperature of -78.degree. C. Analysis was performed by a capillary gas chromatograph (FlD) using a DB-1701 column. The collected products consisted of oxetane and allyl alcohol (0.76 ratio of oxetane/allyl alcohol).

Into a 25 milliliter round bottom reaction flask equipped with a distillation column, thermometer and mechanical stirrer was added 2.01 grams of poly(trimethylene carbonate), 0.51 grams of a magnesium:aluminum mixed metal oxide having a magnesium:aluminum ratio of 3:1, and 10.03 grams of tetraglyme as a solvent. The flask contents were heated to a temperature of 250.degree. C. in an oil bath. The products distilled from the flask as they were formed and collected in a cold trap cooled to a temperature of -78.degree. C. Analysis was performed by a capillary gas chromatograph (FlD) using a DB-1701 column. The collected products consisted of oxetane and allyl alcohol (0.99 ratio of oxetane/allyl alcohol).

Into a 25 milliliter round bottom reaction flask equipped with a distillation column, thermometer and mechanical stirrer was added 1.0 gram of poly(trimethylene carbonate), 0.25 grams of a magnesium:aluminum mixed metal oxide having a magnesium:aluminum ratio identified in Table VIII below, and optionally an amount of tetraglyme solvent identified in Table VIII. The flask contents were heated to a temperature of 250.degree. C. in an oil bath. The products distilled from the flask as they were formed and collected in a cold trap cooled to a temperature of -78.degree. C. Analysis was performed by a capillary gas chromatograph (FlD) using a DB-1701 column. The collected products consisted of oxetane and allyl alcohol. The oxetane/allyl alcohol ratios are set forth in Table VIII.

Into a 25 milliliter round bottom reaction flask equipped with a distillation column, thermometer and mechanical stirrer was added 1.0 gram of trimethylene carbonate, 0.25 grams of a magnesium:aluminum mixed metal oxide having a magnesium:aluminum ratio identified in Table IX below, and optionally an amount of tetraglyme solvent identified in Table IX. The flask contents were heated to a temperature of 250.degree. C. in an oil bath. The products distilled from the flask as they were formed and collected in a cold trap cooled to a temperature of -78.degree. C. Analysis was performed by a capillary gas chromatograph (FlD) using a DB-1701 column. The collected products consisted of oxetane and allyl alcohol. The oxetane/allyl alcohol ratios are set forth in Table IX.

Into a 25 milliliter round bottom reaction flask equipped with a distillation column, thermometer and mechanical stirrer was added 1.0 gram of trimethylene carbonate and 0.25 grams of a magnesium:aluminum mixed metal oxide having a magnesium:aluminum ratio of 2:1. The flask contents were heated to a temperature identified in Table X below in an oil bath. The products distilled from the flask as they were formed and collected in a cold trap cooled to a temperature of -78.degree. C. Analysis was performed by a capillary gas chromatograph (FlD) using a DB-1701 column. The collected products consisted of oxetane and allyl alcohol. The oxetane/allyl alcohol ratios are set forth in Table X.

A total of 180.0 grams (2.0 moles) of dimethyl carbonate, 17.4 grams (0.1 mole) of 1,4-bis(2-hydroxyethyl)piperazine, and 1.0 gram (0.007 mole) of potassium carbonate were combined in a 250 milliliter round bottom flask equipped with a straight distillation head and a magnetic stirrer. The flask contents were heated to reflux under a nitrogen atmosphere. Initial reaction temperatures at reflux were 80.degree. C. at the head and 88.degree. C. in the kettle. A methanol/dimethyl carbonate azeotrope was removed overhead over a period of 7.5 hours. After this time, the flask contents were cooled and the kettle contents were analyzed by capillary gas chromatography (FlD) using a DB-1701 column. The 1,4-bis(2-hydroxyethyl)piperazine was totally converted to a mixture of 1,4-bis(2-hydroxyethyl)piperazine methyl carbonate and 1,4-bis(2-hydroxyethyl)piperazine dimethyl carbonate. The kettle contents were heated for an additional period of 2.5 hours after which the reaction was stopped. The kettle contents were concentrated in vacuo at 20 mm Hg and a temperature of 60.degree. C. using a rotary evaporator. A total of 26.6 grams of material which was about 88 percent pure in 1,4-bis(2-hydroxyethyl)piperazine dimethyl carbonate was obtained. The major by-products were 1,4-bis(2-hydroxyethyl)piperazine methyl carbonate (ca. 1.5 percent) and di-[1,4-bis(2-hydroxyethyl)piperazine]carbonate (ca. 9.9 percent).

Using the apparatus employed in Examples 15-27, a 30 percent (volume) solution of 1,4-bis(2-hydroxyethyl)piperazine dimethyl carbonate in 1,2-dimethoxypropane was passed through a catalyst bed containing 6.0 grams of a magnesium:aluminum mixed metal oxide (2:1 Mg/Al) at a temperature of 350.degree. C. and a liquid feed rate of 0.28 milliliters per minute. After a period of 31 minutes, the reaction was stopped and a total of 7.1 grams of product was recovered. Gas chromatographic analysis (area %) of this material showed 33.4 percent selectivity to triethylenediamine at 100 percent conversion of 1,4-bis(2-hydroxyethyl)piperazine dimethyl carbonate. A major by-product included 1,4-bis(2-methoxyethyl)piperazine (7.5 percent).

Using the apparatus employed in Examples 15-27, a mixture of triethylene glycol (0.2 moles) and dimethyl carbonate (0.2 moles) was passed through 6.0 grams of 1/8 inch magnesium:aluminum mixed metal oxide extrudates (Mg/Al 2:1) at a temperature of 275.degree. C. and at a liquid feed rate of 0.32 milliliters per minute. After a period of 30 minutes, the reaction was stopped and the product analyzed. The results are given in Table XI below.

Although the invention has been illustrated by certain of the preceding examples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof.