CA1254190A - Ruthenium-promoted cobalt catalysts for the dealkoxyhydroxymethylation of formaldehyde acetals to form glycol ethers - Google Patents

Abstract

ABSTRACT

The invention is a catalyst composition useful in the dealkoxyhydroxymethylation of formaldehyde acetals prepared by a specific method. The catalyst is precipitated from the reaction mixture resulting from the dealkoxyhydroxymethyla-tion of a formaldehyde acetal with syngas in presence of a mixture of Co2(CO)8 and Ru3(CO)12 as catalyst.
The precipitated catalyst has better activity than a mixture of Co2(CO)8 and Ru3(CO)12.

Description

lZS~ ~9() BACKGROUND OF THE INVENTION

SCOPE OF THE INVENTION

This invention relates to the dealkoxyhydroxymethylation of acetals.
More particularly, it relates to a novel process for the dealkoxyhydroxymethylation of certain dialkyl-, dicycloalkyl-, or diaryl-formaldehyde acetals by reacting said acetals with syngas, i.e., hydrogen and carbon monoxide, in the presence of novel ruthenium carbonyl-promoted cobalt carbonyl catalysts to form the corresponding ethylene glycol monoethers. Still more particularly, it relates to the catalysts per se and methods for preparing the same. The methylal described herein may be added directly or formed in _tu from the corresponding formaldehyde and alcohol precurors.

The glycol ethers described herein encompass ~nown classes of compounds having various uses, as for example as jet fuel additives, cleaners, coatings solvents, intermediates in the production of certain diphthalates, and the like.

DESCRIPTION OF THE PRIOR ART

One current well-known method of manufacturing ethylene glycol monoethers such as monoalkyl ethers consists of reacting ethylene oxide with the alcohol corresponding to the desired alkyl ether, employing various known catalyst system~.

LS317 -2- ~:e Alternatively, the cobalt-catalyzed reaction of aldehydes or their dialkyl acetals with syngas, i.e., a carbon monoxide-hydrogen mixture, to form the corresponding glycol ether i~ also described in the art. Thus, for example, a method of making ethylene glycol ethers is described in U.S. Patent No. 2,525,793 which employs cobalt oxide to catalyze the reaction of methylal with syngas to provide a reaction mixture which, after hydrogenation over nickel, gives relatively uneconomical conversions on the order of 25-33%.

Numerous attempts have been made to obtain more practical yields of glycol ethers from aldehydes or their dialkylacetals. A number of promoters have been used in conjunction with variou cobalt catalysts in an effort to improve reaction rates and product yields. U.S.
Patent 4,062,898, for example, discloses a ruthenium chloride-promoted cobalt iodide catalyst which hydrocarbonylstes formaldehyde dimethylacetal (methylal) to ethylene glycol monomethyl ether (EGMME) in yields of 10% or less. The reaction temperature required is 185~C at 20 atm. or above. A second method, described in J~ Kokai Tokkyo Xoho 81 83,432 (1981) uses substantial quantities of 2,4,6- collidine or similar aromatic amines to promote the cobalt carbonyl catalyzed hydrocarbonylation of methylal in benzene as a solvent. The reaction of methylal with highly pressurized syngas in this process at 190C for 10 hours gave 44% selectivity to EGMME at 98~ conversion. A further patent, Euro. Pat. Appln. EP 34,374 (1981) uses both iodine and triphenyl or tricyclohexylphosphine together with RuC13 N20 to promote the Co(Ac)2 4H20 - catalyzed hydrocarbonylation of methylal using 3000 psig LS317 _3_ l~Si~t9U

of syngas, and temperatures of between 150 snd 175C to obtain results nearly comparable to those of the Japanese.

More recently, Knifton has found that cobalt carbonyl promoted with a Group VIB donor ligand catalyzes the hydrocarbonylation of an aldehyde in an alcohol to make ethylene glycol monoethers; U.S. 4,308,403. Yields of ethylene glycol monobutyl ether (EGMB~) as high as 61% were reported in this patent. A cyclopentadienyl-ligated cobalt catalyst is slso effective for these reactions giving glycol ethers in up to 54~ yield;
U.S. 4,317,943-Propylene glycol monoalkyl ethers are formed by contacting high pressuremixtures of carbon monoxide and hydrogen with either an acetal or an aldehyde and an alcohol using a cobalt catalyst promoted with a tin- or germanium-containing compound; U.S. 4,356,3~7. Yields of glycol ethers up to 31% were reported in this patent. Ethylene glycol ethers were also formed from a formaldehyde acetal or formaldehyde and an alcohol using tin or germanium promoters for cobalt carbonyl; U.S. 4,357,477. The highest glycol ether yield (EGMBE) was 53% in this case.

Finally, propylene glycol monoalkyl ethers were formed by hydrocarbonylation of acetaldehyde acetals or acetaldehyde and alcohols using rhodium, ruthenium or nickel compounds to promote either cobalt carbonyls or cobalt compounds having group V ligand systems attached.
Glycol ether yields up to 28% were realized when these promoters were used; Knifton, U.S. 4,390,734 (1983).

LS317 ~4~

1~4~90 Thus, the use of various promoters for the cobalt-catalyzed hydrocarbonylation of aldehydes or acetals has resulted in glycol ether yields of from 10-61%, depending on the glycol ether produced. The highest reported yield of EGMME is 44%, of EGMBE is 61% and PGi~EE is 28%.

SUMMARY 0~ THE INVE~TION

In accordance with the present invention, there is provided an improved process for the reaction of certain dialkyl-, dicycloalkyl-, or diaryl-formaldehyde acetals or their formaldehyde-alcohol precursors with syngas in the presence of novel ruthenium carbonyl-promoted cobalt carbonyl catalysts, to form the corresponding ethylene glycol monoethers.
This reaction, which may best be dcscribe(3 as the dealkoxyhydroxymethylation of an acetal formed separately or in situ by the known reaction of formaldehyde with an alcohol, may be depicted by the following general reaction scheme.

ORl OR1 CH ~ + CO + 2H2 ~ C1~2 + R20H
oR2 \ CH20H

wherein Rl and R2, which may be the same or different, and which together may be joined by one or more bridging atoms as described below to form a cyclic compound, comprise any organic moieties which are inert to the conditions of the reaction, and are selected from the group consisting of:

LS317 _5_ so a) a straight or branched chain alkyl group having from I to about 20 carbon toms, such as methyl, ethyl, propyl, isopropyl, n-bvtyl, t-butyl, 2-ethylheYyl, dodecyl, and the like;

b) a substituted or un~ubstituted cycloalkyl group having ~rom 5 to sbout 20 carbon ~toms, 6uch a~ cyclopentyl, cyclohexyl, cyclobeptyl, 3-methylcyclopentyl, 3-butylcyclohexyl, cyclooctyl, adamantyl, decalyI, 3-phenylcycloheptyl and the li~e; and c) a 6ubstituted or unsub6tituted aryl group having fr~m 6 to about 20 carbon atoms ~uch as benzyl, phenyl, naphthyl, fluoroanthryl, tetralyl, tolyl, ethylphenyl, cumyl, anisyl, chlorophenyl, and the like.

It will be under~tood that when Rl and R2 in the foregoing reaction scheme are different, the resulting products will actually be mixtures of the corresponding ethers and alcohols.

This invention i~ also described to the novel ruthenium-promoted cobalt carbonyl catalysts per se, and to methods for preparing the same.

;~1 125~9~

This process, using the novel catalysts of this invention, provides an improvement over the methods of the prior art in that the instant catalysts do not require the added presence of the iodide, amines, or phosphine promoters such as are disclosed in the prior art, and thus are less costly and easier to prepare and recover. Moreover, these novel catalysts permit the reaction to be carried out under more mild conditions of time and temperature than those of the prior art, yet most surprisingly provide rate and selectivities of de~ired product over those obtained by the use of cobalt carbonyl alone.

DESCRIPTION OF THE_PREFERRED EMBODIMENTS

The novel homogenous catalysts of this invention which may be prepared in varying ways, are ruthenium carbonyl-promoted dicobalt octacarbonyls, more specifically, triruthenium dodecacarbonyl-dicobalt octacarbonyl mixtures. This catalyst system is readily prepared by simply mixing dicobalt octacarbonyl (Co2(CO)8) with ruthenium dodecacarbonyl ~Ru3(CO)12) in the reaction medium. The molar ratios of these two components are optimally in the range of about 10:1 to 1:10, and s9 preferably about 5:1 to 1:5.

It has also been found, in accordance with this invention, that when the catalyst mixture is allowed to precipitate from the reaction medium following completion of the hydroxymethylation reaction this material unexpectedly ha6 been found to have superior catalytic activity over the initial ruthenium-cobalt carbonyl mixture in terms of rates and selectivities. This activity has been found to vary somewhat, however, ~5317 -7-~4~90 depending upon the rate at which the precipitate forms, along with other factors such as the initial concentrations, ratios, and the like. Thus, for example, when the ruthenium and cobalt carbonyl catalysts are mixed into the reaction medium in ~olar ratios of 1:1, and the mixture allowed to precipitate out of solution, following dealkoxyhydroxymethylation, for a period of 1-25 days, the re~ultin~ solid, when introduced into a methylal-syngas reaction, has equal ~r increased activity with respect to rates and selectivities for ethylene glycol monoether.

Equally surprising, it has also been found that an even more active catalyst than the precipitate described above may be obtained by heating the ruthenium and cobalt mixture for periods of from about 1 to 5 hours in the presence of an inert organic solvent, preferably a chlorinated aromatic such as chlorobenzene, o-dichlorobenzene, or the like, under pressurized syngas. The mixture, on cooling, results in an orange-colored precipitate, which when used as a catalyst in the dealkoxylhydroxyme~hylation of methylal, results in significant improvements in the rates and selectivities for the ethylene glycol ether over the original catalyst mixture. For example, when ruthenium and cobalt carbonyl are mixed in molar ratios of 1:1, heated in chlorobenzene at about 150 C. underrv 3000 psi of syngas for about 3 hours, and then cooled, the resulting precipitate has increased catalytic activity in a methylal dealkoxyhydroxymethylation reaction.

The formaldehyde acetsl dealkoxyhydroxymethylation reaction with syngas, as described above, utilizing the novel ruthenium-cobalt carbonyl catalyst mixtures of this invention, including the aforedescribed l~S4190 precipitated forms thereof, msy conveniently be conducted in a generally known manner whereby the desired ~cetal is reacted with syngas under elevated temperature and pressures for given periods of time, during which period the reaction mixture is efficiently stirred. In this reaction, the volume ratio of carbon monoxide to hydrogen in the syngas desirably is in the range of from about 1:3 to 3:1, and more preferably 1:2 to 2:1. Following rapid cooling, the reaction product i8 then recovered from the mixture in a routine manner.

In contrast to the prior art reaction conditions described above, the novel ruthenium-cobalt carbonyl catalysts of this invention advantageously permit the use of more mild operating conditions. Thus, temperatures in the range of from about 100 to 200C, and preferably about 125 to 175C, pressures of from about 500 to 5000 psi, and preferably about 1000 to 3000 psi, may satisfactorily be employed.

The ratio of the weight of catalyst mixture employed, to the weight of acetal, is desirably in the range of from about .001:0.1, and preferably .005:.05 in a batch reaction.

In a further embodiment of this invention, it has been found that highly advantageous effects may also be obtained in this dealkoxyhydroxymethylation process by the addition of solvents in combination with the catalyst system of this invention.

The solvents which may be advantageously used comprise any polar or non-polar organic solvents which are inert to the conditions of the LS31~ _9_ l~S4'1~0 reaction. Included amongst these solvents are Cl 12 alcohols, preferably those corresponding to the alkyl group of the formaldehyde acetal, such 8s methanol, ethanol, butanol, 3-ethyl~2-hexanol and the li~e; ethers which will not cleave under the conditions of the reaction, such as glyme, diglyme, diphenyl ether and the like; aromatics and substituted aromatics ~uch a6 benzene, toluene, xylene, chlorobenzene, dichlorobenzene, anisole, and the like.

The solvents may constitute anywhere from 0 to 9~ volume percent of the reaction mixture, and preferably 20 to 80 percent.

The acetal starting materials employed in this invention have the aforedescribed general formula, namely ~ORl C~
~ oR2 wherein the R and R2 groups are as defined above. These acetals can be prepared in a known manner, separately or in situ, as for example as described in E.V. Dehmlav and J. Schmidt, Tetrahedron Letters, p.95-6 (1976) B.S. Bal and H.W. Pinnick, J. _r~K~ Chem. V44 (21), p. 3727-8(1979) D.W. Hall, U.S. Patent 3,492,356, Jan. 27 (197~), by the reaction of formaldehyde with an alcohol, or mixture of alcohols, of the general formula RlOH or R20H, where again R1 and R2 are as defined above, form the correspondin~ acetal. Hereinafter, when the acetal is referred to, it will be understood that the corresponding precursors, formaldehyde and the desired alcohol, are also intended to be included.

1~S'~3S?

As also mentioned above, the organic substituents of the resulting acetal may be joined by one or more bridBin8 atoms to form such cyclic compounds as 0--fH2C ~ ~CH C ~ CH2--CH2 O - CH~ O - CH ~ ~ - CH2 - CH2 O - CH ~ O - CX2~

2 ~--CX2~' and the like, wherein X is selected from the group consisting of alkyl, aralkyl, aryl and cycloalkyl groups having from 1 to about 20 carbon atoms.

It is essential t in selecting the acetal starting material, that it not contain any substituents which are reactive under the conditions of the dealkoxyhydroxymethylation process of this invention. In other words, the R1 and R2 groups should not, for example, contain or comprise such reactive moie~ies as phosphine, arsine, amino, sulfido or carbonyl groups, acetal moieties, or olefins or acetylenic double bonds. Other like groups will be recognized or readily determined by those skilled in the art as resulting in products other than the desired monoethers.

When these acetals are dealkoxyhydroxymethylated with ~yngas in accordance with the process of this invention, there is obtained the corresponding ethylene glycol monoether in which the ether moiety will correspond to the organic moieties of the acetal starting material. Also formed in lesser amounts is the trialkoxyethane of the general formula LS317 -Il-12S4~9~

~O
RlOCH2CH
\ORl, together with the alcohol R20H, which may be recycled to form additional acetal starting material. Again, as above, if the R groups of the acetal are different, a mixture of corresponding R-substituted compounds will result.

As shown below, the selectivitie6 for ehe desired monoether over the trialkoxy by-product are in the ratio of from about 3:1 to as much as 10:1 or more.

In a preferred embodiment of this invention, the starting materials are preferably symmetrical acetals where the R groups are lower alkyl groups of 1 to 4 carbon àtoms, thereby forming the corresponding ethylene glycol mono-lower alkyl ether~ such as the monomethyl ether, the monoethyl ether, and the like.

Alternatively, the acetal may contain such Rl and R2 groups as naphthyl and phenyl. In the case of naphthyl, the reaction of the resulting formaldehyde acetal with syngas will provide 2-(2-naphthyloxy) ethanol, d known ~edative, which in turn may be oxidized ~o the corresponding 2-naphthyloxyacetic acid, a plant growth hormone.

.lZ~4~90 Likewise, the dealkoxyhydroxymethylation of the acetal, wherein Rl and R are phenyl, will produce 2-phenoxy-ethanol, a topical antiseptic, which when oxidized, results in phenoxyacetic acid, a fungicide.
Similarly, the formaldehyde acetal wherein R1 and R are 2, 4, 5-trichlorophenyl wiil yield, in accordance with this process, 2, 4, 5-trichlorophenoxyacetic acid, an herbicide. In a like manner, when R and R2 are p-nonylphenyl, p-nonylphenoxyacetic acid, a corrosion inhibitor and antifoaming sgent in gasoline and cutting oils will be formed.

Each of these aforedescribed products may be recovered routinely by methods well known in the art.

The invention will now be illustrated by, but is not intended to be limited to, the following examples.

EXAMPLES

Examples 1-21 A series of runs was carried out in which the following general procedure was employed, using as the catalyst a mixture of Co2(CO)8 and Ru3(CO)12, or Co2(C0~8 alone (for comparative purposes). In the table below, it should be noted that wheress addition of Ru3(CO)12 caused an increase in production of the glycolether, B, over that obtained with C02(CO)8 alone, other metal carbonyls had no such effect.

12S~90 To a 300 ml stainless steel autoclave equipped with a magnedrive stirrer was charged: methylal, solvent (if any), and catalyst. Carbon monoxide, S00 psig, and hydrogen, 1600 psig, were admitted and the reaction mixture was rapidly heated to the desired temperature. The mixture was stirred for the designated time at reaction temperature after which the reactor was cooled by immersion in an ice bath. When the contents reached 25C
the final pressure was recorded. After venting the gas the liquid was analyzed by GLPC.

The results are reported in Table I below. Reaction conditions, amounts, and the use of solvents were varied in accordance with the data set forth in this table.

`` LS317 -14-i2S4t9V

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Examples 22-25 In addition to the above runs, another series of runs was carried out in accordsnce with the following general procedure, using varying condi-tions 9 etc., in which the catalyst employed was precipitated from solu-tions of Co-Ru catalyzed methylal dealkoxyhydroxymethylation, with or without a solvent being present.

The catalyst system and methylal were charged to a 300 ml autoclave and the system flushed thoroughly with C0 and H2. A 1:1 CO~H2 mixture was added to a pressure of 2400 psig and the temperature rapidly raised to 150~C. The reaction mixture was stirred for the designated time period and then rapidly cooled, the pressure released, gases collected and analyzed by gcms and the liquid removed and analyzed by standardized glpc .

The results of these runs are reported in Table II below.

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l~S~90 The catalysts for Examples 23, 24 and 25 of Table II were prepared as follows:

Example 23 Catalyst The catalyst for Example 23 was prepared by allowing the liguid recovered from two runs identical to Example 18, Table l to stand for several weeks, after which an or~nge solid precipitated. Filtration of the orange solid followed by drying in vacuo ~ave a material which exhibited characteristic metal carbonyl bands in the infrared but was neither Co2(C0)8 nor Ru3(C0)12. The ir bands in the isolated solid were at 4.83,

4.92 and 4.98u. The brid8ing carbonyl of the startinB Co2(C0)8 (5.37u) had totally disappeared in forming the new active complex. The solid, 2.5 grams, was used as a catalyst for Example 23.

Example 24 Catalyst The catalyst for Example 24 was prepared by all.owing the liquid recovered from two runs identical to Example 4, Table I to stand for several weeks after which an orange solid precipitated. This solid, 2.0 grams, after filtration and drying in vacuo, was used as the catalyst for Example 24.
The solid which was isolated had characteristic metal carbonyl bands at 4.83, 4.92 and 4.98u. The bridging carbonyl of the starting Co2(C0)8 had completely disappeared.

lZ~t9~

Example 25 Catalyst The catalyst for Example 25 was prepared as indicated in footnote (c) of Table Il. The isolated orange solid had infrared bands at 4.83u, 4.92u an 4.97u indicative of a metal carbonyl complex in which there was no bridging carbonyl band at 5.37u.

In the following examples, Examples 26-32, experiments were csrried out in a manner similar to Examples 1-25, except that dibutoxymethane was substituted for methylal, and solvents and temperatures were varied as shown in Tables III and IV, to produce ethylene glycol monobutyl ether.

12S~

Examples 26-29 In Examples 26-2~ formaldehyde dibutylacetal, (CH2(0Bu)2), was dealkoxylhydroxymethylated to ethylene glycol monobutyl ether, EGMBE, using a 1:1 mixture of Co2~C0)8 and Ru3(C0)12 as the catalyst~ It can be seen from the tsbulated results of Table III that running the reaction in a solvent such as n-butyl alcohol or o-dichlorobenzene gives generally superior yields to running the reaction in neat CH2(0Bu)2.

In Table III, the examples were conducted in accordance with the following general procedure:

Dicobalt octacarbonyl, 4 mmoles, triruthenium dodecacarbonyl, 4 mmoles, CH2(0Bu)2 in the amount listed in the table and solvent in the amount listed in the table were charged to a 300 ml stirred autoclave to which 3200 psi of a 1:1 mixture of C0 and H2 were added and then heated to 150C for 3-4 hrs. The autoclave was cooled, drained and the product weighed and subjected to standardized gas chromatographic analysis.

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lZ5~19V

Examples 30-32 In Examples 30-32, the results of which are ~u~marized in Table IV, it can be seen that as the reaction temperature is raised from 125 to 175C
the EGMBE yield increases from 12 to 34.

In Table IV, the examples were conducted in accordance with the following general procedure:

Dicobalt octacarbonyl, 4 mmoles, triruthenium dodecacarbonyl, 4 mmoles, and CH2(0Bu)2, 90 ml, were charged to a 300 ml autoclave. Then 3200 p6i of a 1:1 C0/H2 mixture was added and the reaction mixture heated for 3~4 hours at the temperature listed in the Table. The autoclave was cooled, drained and the product weighed and subjected to standardized gas chromatographic analysis.

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izs~ o Example 33 In a manner similar to Example 31, except that formaldehyde dicyrlohexyl acetal is used instead of formaldehyde dibutyl acetal, ethylene glycol monocyclohexyl ether is prepared in good yield.

Example 34 In a manner similar to Example 31, except that formaldehyde diphenyl acetal is used instead of formaldehyde dibutyl acetal, ethylene glycol monophenyl ether is formed as a reaction product.

Example 35 In a manner similar to Example 31, except that dioxolane is used instead of formaldehyde dibutyl acetal, diethylene glycol is produced afi a reaction product.

Example 36-43 Approximately 6 grams of paraformaldehyde and the catalyst package in 90 moles of butanol and 10 ml of toluene were heated at the temperatures given in Table V at the pressures of hydrogen and CO indicated for two hours. After this time the reaction mixtures were analyzed by gas chromatography showing the major product to be ethylene glycol monobutyl ether. Results are tabulated in Table V.

12.~ 90 TABLE V
REACTIONS OF FORMALDEHYDE, SYNGAS AND BVTANOL
TO GIVE ETHYLENEGLYCOL MONOBUTYL ETHER, EGMBE
EXAMPLE CATALYST COMPONENTS INITIAL PRESSURES REACTION REACTlON PRODUCTS (GC Area ~) Co2(CO)g RU3(C)12 H CO T. ~CCH30C5Hg ECNBE C~2~DC4H9~2 36 4 4 1600 800 150 2.0 9.4 tr 37 4 4 1600 800 150 2.0 9.7 0.3 38 2 4 1600 800 150 1.7 9.6 0.5 39 2 4 1600 800 150 1.4 9.1 1.5 4 4 1600 1600 150 1.2 10.7 0.5 41 4 4 1600 1600 150 0.7 9.2 1.8 42 2 4 1600 1600 150 0.7 9.2 1.8 43 4 4 1600 800 175 2.3 9.6 a) EGMB = Ethylene glycol ~onobutyl ether

Claims (6)

The invention claimed is:

1. A composition useful as a catalyst for the dealkoxyhydroxymethylation of formaldehyde acetals prepared by precipitating a ruthenium and cobalt carbonyl complex from a reaction mixture formed by the dealkoxyhydroxy-methylation of a formaldehyde acetal with syngas in the presence of a catalyst comprising a mixture of Co2(CO)8 promoted with RU3(Co)12.

2. The composition of Claim 1 wherein the molar ratio of the cobalt to ruthenium carbonyl components of the precipitated catalyst is in the range of from about 10:1 to 1:10.

3. A composition useful as a catalyst fox the dealkoxyhydroxymethylation of formaldehyde acetals prepared by precipitating a ruthenium and cobalt carbonyl complex from a reaction mixture formed by the dealkoxyhydroxy-methylation of a formaldehyde acetal with syngas in the presence of an inert organic solvent and a catalyst comprising a mixture of Co2(CO)8 promoted with RU3(CO)12.

4. The composition of Claim 3 wherein the molar ratio of the cobalt to ruthenium carbonyl components of the precipitated catalyst is in the range of from about 10:1 to 1:10.

5. A composition useful as a catalyst for the dealkoxyhydroxymethylation of formaldehyde acetals prepared by precipitating a ruthenium and cobalt carbonyl complex from a reaction mixture formed by the treatment of a mixture of Co2(CO)8 and Ru3(CO)12 in a chlorinated aromatic hydrocarbon with syngas at elevated temperature and pressure.

6. The composition of Claim 5 wherein the molar ratio of the cobalt to ruthenium carbonyl components of the precipitated catalyst is in the range of from about 10:1 to 1:10.