NL7905114A - PROCESS FOR THE SIMULTANEOUS PREPARATION OF ALCOHOL AND VICINAL GLYCOL ESTERS. - Google Patents

Description

• m -1- 20773 / Vk / iv r

Applicant: Texaco Development Corporation, White Plains, New York, United States of America

Short designation: Process for the simultaneous preparation of alcohol and vicinal glycol esters.

5

The invention relates to a process for the simultaneous preparation of alcohol and vicinal glycol esters. In particular, the invention relates to an improved process for the preparation of alcohol and vicinal glycol esters, including ester derivatives of ethylene glycol, by reacting oxides of carbon with hydrogen.

In particular, the invention relates to the selective co-synthesis of alcohol and glycol esters such as the ester derivative of ethylene glycol, methanol and ethanol and the method according to the invention is characterized in that a reaction mixture of carbon monoxide and hydrogen with sufficient carbon monoxide and hydrogen can suffice the stoichiometric amounts required for the desired ester synthesis, a liquid medium with one or more carboxylic acids and a catalyst containing ruthenium, osmium or a mixture thereof, is heated at a temperature of 100-350 ° C and an elevated pressure of at least 34 atmosphere..

For example, the process can be carried out, but is not limited to, by effecting a one-step co-synthesis of ethylene glycol diacetate, methyl acetate and ethyl acetate from carbon monoxide and hydrogen in the presence of acetic acid as the liquid medium according to the stoichiometric equations 1-3 , which are listed below.

25 CH20Ac 2 CO + 3 H- + 2 HOAc- * I + 2 H.0 1.

CH20Ac 2 CO + 4 H2 + HOAc-> CH3CH20Ac + 2 HgO 2.

CO + 2 H2 + HOAc- »CH30Ac + H20 3.

30

Methyl acetate, ethyl acetate and glycol diacetate are products of commercial value, especially as chemical intermediates and solvents for effecting extraction. Methyl acetate and ethyl acetate are used on a large scale as a solvent, especially for coating compositions. Ethylene glycol diacetate is suitable for the preparation of ethylene * 7905114'f -2-20773 / Vk / iv glycol, an important compound for the preparation of polyester fibers, and anti-freeze compositions. Free glycol can be obtained from the diacetate derivative via hydrolysis as indicated, for example, in the Belgian patent 749 * 685.

One of the objects of the invention is to obtain new preparations of an alcohol and diol ester using a mixture with carbon monoxide and hydrogen, hereinafter referred to as synthesis gas or syngas, in particular, such a process is suitable when the methyl acetate, ethyl acetate and glycol diacetate is the main products according to equations 1-3 as indicated above, because in this case acetic acid is the co-reaction medium and an opportunity for the preparation of acetic acid is via the methanol carbonylation from synthesis gas as described in "Trends in Petrochemical Technology ”by AM Brownstein, Chapter 5 (1976).

Numerous patents are known which relate to the synthesis of low molecular weight hydrocarbons, olefins and. alcohols by starting from synthesis gas. Specifically, U.S. Pat. No. 2,636,046 discloses the synthesis of polyhydric alcohols and their derivatives by a reaction between carbon monoxide and hydrogen at elevated pressures above 1500 atmospheres and temperatures up to 400 ° C, using certain cobalt-containing catalysts. More recently, Belgian Patent 793,086 and U.S. Patent 3,940,432 disclose the co-synthesis of methanol and ethylene glycol from mixtures of carbon monoxide and hydrogen using a rhodium-catalyst. The C0 hydrogenation is typically accomplished at 544 atmospheres and a H 1 / CO synthesis gas of 25 1: 1 at a temperature of 220 ° C using tetraethylene glycol methyl ether as a solvent and dicarbonylacetylacetonator sodium (I) in combination with an organic Lewis base as a catalyst precursor. For an overview, please refer to R.L. Purett, Annals New York Academy of Sciences, Vol. 295 p. 239 (1977) Although other Group VIII metals of the Periodic Table 30 have been investigated for activity under similar conditions including cobalt, ruthenium, copper, manganese, iridium and platinum have only been shown to have a slight activity with cobalt. In particular, due to the use of ruthenium compounds, it has proved impossible to obtain polyfunctional products such as ethylene glycol. This is disclosed in U.S. Pat. No. 3,833,634 to solutions of tri-7905114 * -3-20773 / Vk / iv ruthenium dodecarbonyl.

The use of ruthenium, osmium or mixtures thereof forms part of the method according to the invention. According to a preferred method, the reaction mixture as cocatalyst contains one or more alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, iminium salts or quaternary phosphonium salts.

Further details regarding the process of the invention are: a) The catalyst composition.

Catalysts useful in the practice of the process of the invention contain osmium or ruthenium or mixtures of these metals.

The ruthenium or osmium containing catalysts can be selected from a wide variety of organic or inorganic compounds or complexes as explained below. It is only necessary that the catalyst precursor actually used contain the transition metal, namely ruthenium or osmium, in one of the ionic states. The catalytic actives used contain ruthenium or osmium in complex combination with carbon monoxide and hydrogen. The most effective catalysis is obtained when ruthenium® osmium hydrocarbonyl is dissolved in the carboxylic acid as a co-reactant, complying with the stoichiometry of equations 1-3 as mentioned above.

Although the invention is further elucidated below on the basis of certain ruthenium-containing forms or substances, it is clear that osmium can also be used in comparable forms, namely within the scope of the invention. --------- -------

The preferred ruthenium catalyst as a precursor can exist in many different forms. For example, ruthenium can be added to the reaction mixture in an oxide form, such as, for example, ruthenium (IV) oxide, hydrate, anhydrous ruthenium (IV) dioxide and ruthenium (VIII) tetraoxide. Alternatively, it can be added as the salt of a mineral acid such as ruthenium (III) chloride hydrate, ruthenium (III) bromide, anhydrous ruthenium (III) chloride and ruthenium nitrate or as a salt of a suitable organic carboxylic acid, as mentioned under b), for example ruthenium (III) acetate, ruthenium (III) proprionate, ruthenium butyrate, ruthenium (III) trifluoroacetate, ruthenium octaate, ru theniuranaphthenate, ruthenium valerate and ruthenium (III) acetylacetonate.

790 5 1 1 4

V.

m -4- 20773 / Vk / iv

Ruthenium can also be added to the reaction zone in the form of a carbonyl or hydrocarbonyl derivative. Suitable examples of this include triru-thenium dodecacarbonyl * hydrocarbonyl such as HgRu (iCO) ^ and H ^ Ru ^ iCO) ^ and substituted carbonyl compounds such as the tricarbonyl ruthenium (II) chloride dimer 5 [HuiCOjgClg '] 2 ·

In a preferred embodiment of the invention, ruthenium is added to the reaction zone in the form of an oxide, salt or carbonyl derivative in combination with one or more tertiary donor ligands selected from group VB of the Periodic Table. The ligands 10 to be named, not an element of group VB of the Periodic Table, are nitrogen, phosphorus, arsenic and antimony. These elements in their trivalent oxidation state, especially tertiary phosphorus and nitrogen, may also be bonded to one or more alkyl groups, cycloalkyl groups, aryl groups, substituted aryl, aryloxyde, alkoxide, alkaryl or aralkyl radicals, each having 1-12 carbon atoms or they can be 15 are part of a heterocyclic ring system or mixtures thereof. Examples of suitable ligands that can be used in the context of the invention are triphenylphosphine, tri-n-butylphosphine, triphenylphosphite, triethylphosphite, trimethylphosphite, trimethylphosphine, tri-p-methoxyphenylphosphine, triethylphosphine, trimethylarsine, triphenyl-triphenyl , tricyclo-20 hexylphosphine, dimethylphenylphosphine, trioctylphosphine, tri-o-tolylphosphine, 1,2-bis (diphenylphosphino) ethane, triphenylstibine, trimethylamine, triethylamine, tripropylamine, tri-n-octylamine, pyridine , 10-phenanthroline, quinoline, N, N * -dimethylpiperazine, 1,8-bis (dimethylamino) naphthalene and N, N-dimethylaniline.

One or more of these ruthenium-tertiary group VB donor-ligand combinations may be preformed, for addition to the reaction mixture or as with tris (triphenylphosphine) ruthenium (II) chloride and tricarbonyl bis (triphenylphosphine) ruthenium, these complexes may also be be formed in situ.

The behavior of each of these ruthenium catalyst precursors is further illustrated in the examples below. "

Similar catalyst combinations with osmium instead of ruthenium as the transition metal component are also suitable for the desired synthesis of alcohol and polyhydric alcohol esters from the synthesis gas.

b) Carbonzpur.

Carboxylic acids which are suitable in the process according to the invention v 7905114 -5- 20773 / Vk / iv φ form the acidic agent for the desired methyl, ethyl and glycol ester products.

The preferred acids are also suitable as a solvent for the transition metal catalysts, especially the ruthenium catalyst combinations.

Suitable carboxylic acids include aliphatic acids, alicyclic monocarboxylic acids, heterocyclic acids and aromatic acids, both substituted and unsubstituted. The invention particularly relates to the use of aliphatic monocarboxylic acids with 1-12 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, capric acid, perlargonic acid and lauric acids, as well as aliphatic dicarboxylic acids with 2-6 carbon atoms such as oxalic acid , malonic acid, succinic acid and adic acid. On the other hand, substituted aliphatic monocarboxylic acids with one or more functional substituents such as chlorine or fluorine atoms or alkoxy, cyano, alkylthio or amino groups can be used. Examples of such acids include acetoacetic acid, dichloroacetic acid, trifluoroacetic acid, chloropropionic acid, trichloroacetic acid and monofluoroacetic acid. Benzoic acid, naphthoic acid, tolulinic acid, chlorobenzoic acid, amino benzoic acid and phenylacetic acid can be mentioned as suitable aromatic acids. The alicyclic monocarboxylic acids can contain 3-6 carbon atoms in the substituted or unsubstituted ring and can contain one or more carboxyl groups such as cyclopentanecarboxylic acid or hexahydrobenzoic acid.

The heterocyclic acids can contain 1 to 3 composite rings which may or may not be substituted together with one or more carboxylic acid groups, such as quinoline, furoin and picolinic acids. Mixtures of such types of carboxylic acids in any ratio can also be used in the process of the invention. The preferred carboxylic acids are aliphatic acids such as acetic acid, propionic acid and butyric acid and substituted aliphatic acids such as trifluoroacetic acid.

c) The concentration of the catalyst.

The amount of ruthenium or osmium catalyst used in the process of the invention is not critical and can vary within wide limits.

In general, it is desirable to perform the process in the presence of a catalytically effective amount of the active ruthenium or osmium containing substance to yield the desired ester products in a reasonable yield. The reaction takes place when a small amount such as 1 x 10 6 wt% and even smaller amounts of ruthenium or osmium are used based on the total weight of the reaction mixture. The top cont% 7905114 ψ -6- 20773 / Vk / iv · »entration is determined by a number of factors such as the catalyst cost, the partial pressure of carbon dioxide and hydrogen, the temperature and the choice of the carboxylic acid as diluent or reactant. A concentration of 1 x 10 to 10 wt% ruthenium or osmium based on the total weight of the reaction mixture is generally desirable when performing the method of the invention.

d) The temperature.

The temperature range that can be suitably used during ester synthesis is variable and depends on the other experimental factors including the choice of the carboxylic acid as co-reactant, the pressure and concentration and the particular choice of the catalyst as the most important variables. When ruthenium is used as the active metal, the process is carried out at a temperature of 100-350 ° C when an overpressure is applied to the syngas. A more limited temperature limit of 150-260 ° C represents the preferred temperatures when the main products are methyl, ethyl and glycol acetate. Table A shows at which temperatures the method is preferably used.

e) Press.

Overpressure of 34 atmospheres or higher leads to significant yields of desired alcohol and vicinal glycol ester by using the method of the invention. A preferred pressure for solutions of ruthenium (III) acetylacetonate in acetic acid ranges from 68 to 510 atmospheres, although pressures above 510 atmospheres also provide a suitable yield of the desired ester. Table A also provides further information about the pressures to be used. The pressure intended in this context represents the total pressure generated by all reactants, although the pressure is primarily effected by carbon monoxide and hydrogen.

f) The composition of the gas.

The relative amounts of carbon monoxide and hydrogen initially present in the syngas mixture are variable and these amounts can be varied within wide limits. Generally, the CO to Hg molar ratio is between 20: 1 to 1:20, preferably 5: 1 to 1: 5, although ratios outside these ranges can also be used. In particular in continuous operations, but also in batch operations, carbon monoxide-hydrogen gaseous mixtures may be used together with up to 50 volume% of a 7905114-77777 / Vk / iv or more other gases. These other gases may include one or more inert gases such as nitrogen, argon or neon and may also include gases which undergo reaction under the CO hydrogenation conditions such as carbon dioxide, hydrocarbons such as methane, ethane or propane, ethers such as di- 5 methyl ether, methyl ethyl ether and diethyl ether, alcohols such as methanol and acid esters such as methyl acetate.

In the synthesis to be carried out, the amount of carbon monoxide and hydrogen present in the reaction mixture must be sufficient to satisfy the stoichiometric equations 1) -3) mentioned above.

10 g) Product distribution.

The hydrogenation of CO in one step with the aid of ruthenium or osmium catalysts, insofar as it is determinable, without limiting the invention, leads to the formation of three kinds of primary products, in particular the methanol, ethanol and ethylene glycol ester derivatives of the corresponding co reactant 15 carboxylic acids. When acetic acid is the co-reactant, the most important product is methyl acetate, ethyl acetate and ethylene glycol diacetate. Smaller amounts of by-products are determined in the liquid product fraction, especially smaller amounts of water, glycol monoacetate, propyl acetate and dimethyl ether. Carbon dioxide, methane and dimethyl ether can be determined in the off-gas together with unreacted carbon monoxide and hydrogen.

h) Method of carrying out the method.

The method according to the invention can be effected batchwise, semi-continuously or continuously. The catalyst can first be fed to the reaction zone, which can be accomplished batchwise or continuously or intermittently to the reaction zone during the synthesis reaction. The processing conditions can be adjusted to optimize the formation of the desired ester product and the material can be recovered by known methods such as distillation, fractionation, extraction and the like. A fraction rich in ruthenium or osmium catalyst components can then be recycled to the reaction zone if desired and additional ester products are obtained by the CO hydrogenation.

i) Analyzes to be performed.

The products obtained by the hydrogenation of carbon monoxide can be identified by one or more of the analytical assays listed below, namely gas-liquid phase chromatography (glc), infrared 7905114 r-8- 20773 / Vk / iv ♦ »(ir ), race spectrometry, nuclear magnetic resonance (nmr) and elemental analysis or a combination of these methods, j) Co-catalyst.

There are a number of classes of suitable cocatalysts that can be used in the process of the invention. One such class that can be added to the reaction mixtures to improve the activity of the dissolved ruthenium or osmium as a catalyst are salts of alkali metals and alkaline earth metals. Particular examples of effective alkali metal salts include the alkali metal halides, for example, the fluoride, chloride, bromide or iodine salts, and alkali and alkaline earth metal salts of suitable carboxylic acids. The preferred alkali and alkaline earth metal carboxylates are the acetate, propionates and butyrate in the form of the sodium salt, potassium salt, barium salt and cesium salt. These salts can be added within wide concentration ranges, from 0.01 to 100 moles of alkali or alkaline earth salt per gram atom of ruthenium or osmium present in the reaction mixture. The most preferred ratios are between 5: 1 and 15: 1 (see Table B).

The following are some combinations of ruthenium co-catalyst corabinations suitable in the process of the invention: ruthenium chloride-cesium acetate, ruthenium (IV) oxide-cesium acetate, ruthenium chloride-cesium trifluoroacetate, ruthenium chloride-sodium acetate, ruthenium chloride-cesium propylene carbonate ruthenium oxide-cesium fluoride.

The operation of this is stated in Examples XVIII-XXVIII.

Quaternary ammonium and phosphonium cation salts are also effective as cocatalysts in the process of the invention. Suitable quaternary phosphonium salts are those which are substantially inert under the CO hydrogenation conditions and can be represented by the formula:

j (R1) (R2) P- (R3) (R4) JV

wherein R 2, R 2, R 2 and R 2 are organic radicals bonded to the phosphorus atom by a saturated aliphatic carbon atom and X is an anionic substance, preferably a carboxylic acid as mentioned below. The organic radicals 7905114 * r * -9-20773 / Vk / iv which are suitable include radicals of 1-20 carbon atoms in a branched or linear alkyl chain. These are in particular the methyl, ethyl, n-butyl, iso-butyl, octyl, 2-ethylhexyl and dodecyl radicals. Tetramethylphosphonium acetate and tetrabutylphosphonium acetate are the commercially available phosphonium salts to be mentioned by name. The corresponding quaternary phosphonium and ammonium hydroxides, nitrates and halides such as the corresponding chlorides, bromides and iodides can be used successfully as quaternary ammonium salts of carboxylic acids. such as tetra-n-butylammonium acetate and tetra-n-octrylammonium propionate as well as the corresponding iminium salts such as bis (triphenylphosphine) -10 iminium acetate. Examples XVII, XVIII, XXXII and XXXIII mention the effectiveness of the ruthenium chloride-tetrabutylphosphonium acetate combinations.

Similar catalyst combinations with osmium instead of ruthenium as the transition metal component are also suitable for the desired synthesis of alcohol and polyhydric alcohol esters from the synthesis gas.

The invention is further elucidated by means of the following examples which should not be regarded as limiting. The percentages listed are percentages by weight if not the contrary.

Example I

To 50 ml of a degassed sample of acetic acid in a reactor with a 300 ml glass inner wall which can be pressurized and equipped with a stirrer and heating means is charged 0.40 g (1.0 ramol) under nitrogen. ruthenium acetylacetonate was added. The reactor is closed, purged with CO / H 2 and pressurized to 184 atmospheres with synthesis gas (1: 1 CO / Hg). The mixture is then heated to 220 ° C with stirring for 18 hours and then cooled. The gas absorption is 27.2 atmospheres.

A sample of the excess of the gas is taken and the remainder drained to give a yellow-red liquid product which is analyzed gas-liquid bromato-graphically, showing that it contains 1.9% methyl acetate, 0.3¾ ethyl acetate 1, 4¾ ethylene glycol diacetate.

Yellow crystalline triruthenium dodecacarbonyl slowly precipitates from the resulting solution after standing in air. The analysis of the discharged gases indicates that they consist of 35 7905114 * ♦ -10-20773 / Vk / iv / 47% hydrogen, 48% carbon monoxide, 1.3% carbon dioxide, 2.2% methane.

Example II

Here, a CO hydrogenation is carried out as mentioned in example I, except that the mixture supplied consists of 0.426 g (0.66 mmol) tri-ruthenium dodecacarbonyl dissolved in 50 ml acetic acid. The analysis of the liquid product by carrying out a gas-liquid chromatography indicates the presence of 4.2% methyl acetate, 0.5% ethyl acetate, 0.4% ethylene glycol diacetate.

Example III

The hydrogenation of CO is carried out as indicated in Example I except that the feed mixture consists of 0.71 g (1.0mmol) tricarbonyl bis (triphenylphosphine) ruthenium in 50 ml glacial acetic acid. The analysis of the obtained liquid product indicates the presence of 3.4 wt% methyl acetate, 0.8 wt% ethyl acetate, 0.2 wt% ethylene glycol diacetate.

Example IV

The hydrogenation of CO is carried out as indicated in Example I except that the feed mixture consists of 0.722 g (1 mmol) of ruthenium 25 (III) hexafluoroacetylacetonate in 50 ml of acetic acid. The analysis of the liquid product indicates the presence of 5.7% methyl acetate, 0.2% ethyl acetate, 0.26% ethylene glycol diacetate.

30 Example V

The hydrogenation of CO is carried out as indicated in Example 1 except that the feed mixture consists of 0.40 g (1 mmol) ruthenium (III) acetylacetonate, 0.40 g tri-n-butylphosphine and 50 ml acetic acid. Analysis of the obtained liquid product shows the presence of a significant amount of methyl acetate, ethyl acetate and ethylene glycol diacetate.

7905114 -11- 20773 / Vk / iv

Example VI

The hydrogenation of CO is carried out as described in Example I except that a mixture consisting of 0.598 g (0.66 mmol) trisodium dodecacarbonyl dissolved in 50 ml acetic acid is supplied. The analysis of the liquid product obtained, which analysis is effected by gas-liquid chromatography, shows the presence in the product of methyl acetate and ethylene glycol diacetate.

Examples VII-XII

Hereby are followed the procedures mentioned in example 1, 10 wherein the temperature and the pressure is varied and the yield is determined and the degree of presence of the acetic acid ester products is de- indicated. investigated. The standard catalyst used herein is ruthenium (III) acetylacetonate in an amount of 1-2 mmole dissolved in glacial acetic acid.

The results obtained herein are summarized in Table A. It is clear from the data reported in Table A that the methyl acetates, ethyl acetates and ethylene glycol acetates can be obtained by hydrogenating CO with the dissolved ruthenium catalyst at the processing temperature of 180-260 ° C and a pressure of 88.5-500 atomosphere.

Table A

Example temperature maximum pressure components in liquid product (wt%) temperature (° C) (atmosphere) HgO MeOAc EtOAc (CH2OAc) 2 1 '. 1 'I' ...... 1 "" "" "VII 180 470 0.7 0.7 0.1 0.1 VIII 220 88.5 0.2 0.7 0.5 0.1 25 IX 220 161.5 1.0 3.4 0.7 0.5 X 220 296 2.5 3.5 0.8 0.4 XI 220 463 2.0 15.6 0.8 1.0 XII 260 500 5 , 1 47.7 2.9 0.8 30 Example XIII _________

Following the procedure of Example 1, 0.80 g (2.0 mmol) of ruthenium acetylacetonate was added to a degassed mixture of 50 ml of acetic acid placed in the glass-lined reactor of 300 ml capacity. The reactor was closed, purged with CO / H 2 and pressurized to 272 atmospheres with 1: 1 synthesis gas. The mixture was then heated to 220 ° C with stirring for 8 hours and then cooled, 7905114 [- 12 - 20773 / Vk / iv #. The gas uptake was 68 atmospheres. The excess gas was vented and a 1 L sample was taken to perform the analysis. The data from the gas liquid chromatographic determination indicated the presence of 12.3% methyl acetate, 1.0% ethylene glycol diacetate, 0.5% ethyl acetate.

The remainder of the liquid product was recycled to the 300 ml reactor, repressurized with 1: 1 synthesis gas and the hydrogenation of CO was accomplished as noted above. The final product was analyzed after repeated cycling and found to contain 44.9% methyl acetate, 2.2% ethylene glycol diacetate, 1.4% ethyl acetate 15 together with unreacted acetic acid and an aqueous by-product. The methyl acetate, ethyl acetate and ethylene glycol diacetate were recovered as overhead fractions by distillation under a reduced pressure of 0.1-10 mm mercury. The bottom fractions in an amount of 2 g plus 0.2 g of crystallized triruthenium dodecacarbonyl were recycled to the reactor with 50 ml of fresh acetic acid and the conversion of CO / H 2 to acetate esters was performed as described above. The recovered clear, yellow product in the form of 46 ml of liquid was found to contain II, 6% methyl acetate, 2.2% ethylene glycol diacetate, 0.5% ethyl acetate.

Examples XIV and XV listed below serve as comparative examples, showing that cobalt and rhodium-based equivalent-looking catalysts are relatively ineffective in carrying out such a process.

Example XIV (for comparison)

To a degassed sample of 50 ml of acetic acid placed in a reactor provided with a glass inner wall with a volume of 300 ral, which reactor can be pressurized and provided with heating and stirring elements, is added 0.8 g (1 under nitrogen) .0 mmol) rhodium (III) acetylacetonate.

7905114 * * Λ -13- 20773 / Uk / iv

The reactor is closed, purged with CQ / H 2 and pressurized to 184 atmospheres with synthesis gas (1: 1 C0 / H 2). The mixture is then heated to 220 ° C with stirring for 18 hours and then cooled.

The excess amount of gas is vented after a sample is taken and the liquid product is analyzed by gas-liquid chromatography, which shows the presence of 0.5% methyl acetate, 1.2% ethyl acetate, 0.1% glycol diacetate.

10 Example XV (for comparison)

The hydrogenation of CO was carried out as described in Example XIV, except that 0.34 g (1 mmol) of dikobalt octacarbonyl and 50 ml of acetic acid were charged. The analysis of the obtained liquid product in an amount of 49 ml, which analysis was performed by gas-liquid chromatography, indicated the presence of 0.7% methyl acetate, 2.7% ethyl acetate, 0.1% glyclodiacetate.

Example XVI

Following the procedure outlined in Example I, 0.40 g of ruthenium (III) acetylacetonate (1.0 mmol) and 50 ml of trifluoroacetic acid were fed to a 450 ml reactor fitted with a glass coating. The reactor was closed, rinsed with CO / Hg, pressurized to 272 atmospheres with CO / H 2 (1: 1) and heated to a temperature of 220 ° C overnight. The gas absorption was found to be 95.25 atmospheres. After cooling, a green liquid product containing suspended solids was obtained, which product was analyzed by gas-liquid chromatography. This analysis showed that the product contained 37% methyl trifluoroacetate, 2.3% ethyl trifluoroacetate, 2.2% ethylene glycol di (trifluoroacetate), 43.0% unreacted trifluroacetic acid.

Examples XVII-XXXVI below show a process according to the invention using a cocatalyst.

> 7905114 "# -14- 20773 / Vk / iv r

Example XVII

An autoclave consisting of a reactor equipped with a pressurized glass inner wall, heated and equipped with coolers and stirrers was charged with 1.04 g (4.0 mmol) of ruthenium chloride, 5 hydrate, 12.7 g (40 mmol) tetrabutylphosphonium acetate and 50 g acetic acid. After stirring, all solids dissolved and a clear, deep red solution was obtained. The reactor was then closed, purged with CO / Hg and pressurized to 272 atmospheres with synthesis gas (a mixture of hydrogen and carbon monoxide in a 1: 1 ratio). After a period of 60-75 minutes, the autoclave was heated with stirring to 220 ° C and kept at this temperature overnight. Total gas uptake was found to be 122.5 atmospheres. After cooling, the excess of gases was vented after a sample was taken and 58 ml of deep red liquid was obtained which was analyzed. No solid product was present. The gas-liquid chromatographic analysis of the liquid product carried out indicated the presence of 63.9% by weight methyl acetate, 6.28% by weight ethylene glycol diacetate, 5.9% by weight ethyl acetate, 19.7% by weight unreacted acetic acid,

Example XVIII

To a 300 ml autoclave equipped with a pressurized glass coating containing heating and stirring elements was added 0.52 g (2.0 mmol) ruthenium chloride hydrate, 19 GBg (60 mmol) * tetrabutylphosphonium acetate and 25 g acetic acid are added. The mixture was stirred to dissolve the solids, the reactor was closed, rinsed with CO / H 2 and pressurized to 272 atmospheres with synthesis gas (1: 1 CO / Hg) over a period of 60 The autoclave was heated to 220 ° C with stirring for 75 minutes and kept at this temperature overnight. The total gas uptake was found to be 105.5 atmospheres. After cooling, the excess gas was vented and 43 ml of deep red liquid product was obtained from the reactor. The gas-liquid chromatographic analysis of the liquid fraction carried out indicated the presence of 52.3 wt% methyl acetate, 6.71 wt% ethylene glycol diacetate, 4.2. wt% ethyl acetate, 25.4 wt% unreacted acetic acid.

7905114. r -15- 20773 / Vk / iv

A similar product distribution was accomplished using an equivalent amount of ruthenium (IV) dioxide as a catalyst precursor and tetrathylphosphonium acetate of tetramethylphosphonium acetate as a cocatalyst component.

5 Example XIX

To the autoclave indicated in Example XVII, 1.04 g (4.0 mmol) of ruthenium chloride hydrate, 8.0 g of cesium acetate and 50 g of acetic acid were added. After stirring, all solids dissolved and a clear, deep red solution was obtained. The reactor was then closed, purged with CO / 10 H 2 and pressurized to 272 atmospheres with synthesis gas (1: 1 Hg / CO). The autoclave was heated under stirring to a temperature of 220 ° C for a period of 90 minutes and kept at this temperature overnight. Total gas uptake was found to be 68 atmospheres. After cooling, the excess gases were vented after a sample was taken and the liquid product analyzed. The gas-liquid chromatographic analysis showed that the product contained 42.0 wt% methyl acetate, 5.7 wt% ethyl acetate, 3.2 wt% ethylene glycol diacetate, 48.4 wt% unreacted acetic acid.

Examples XX-XXV

Using the procedure set forth in Example XIX, 1.04 g (4.0 mmol) of ruthenium chloride hydrate, 50 g of acetic acid and various amounts of cesium acetate (0-60 mmol) were added to the glass-walled reactor. The reactor was closed, rinsed with CO / Hg, pressurized to 272 atmospheres with H 2 / CO (1: 1) and heated to a temperature of 220 ° C overnight. After cooling, the liquid product was collected and gas-liquid was analyzed chromatographically. The results obtained are summarized in Table B. The formation of methyl acetate and ethylene glycol diacetate both appeared to be most abundant due to the addition of the cesium salt. Both ruthenium chloride and cesium acetate are easily dissolved in acetic acid and the initial Cs / Ru ratios of 5 to 15 were found to produce the highest yields of glycol diacetate.

7905114 35 -16- 20773 / Vk / iv ".

, -r

Table B

example cesium salt Cs / Ru components present in liquid product (wt%) (mmol) ratio HgQ MeOAc EtOAc (CHgOAc ^ 5 XX 0 0 6.8 19.9 23.1 0.22 XXI 4 1 1.1 18.4 15.6 0.18 XXII 12 3 0.4 23.0 3.8 0.86 XXIII 20 5 0.3 38.9 4.2 2.28 XXIV 40 10 0.4 42.0 5.7 3, 2 10 XXV 60 15 0.5 33.1 5.6 2.66

Example XXVI

0.383 g (2.0 mmol) ruthenium oxide hydrate, 4.0 g cesium acetate and 4.0 g cesium acetate were added to an autoclave equipped with a 450 ml glass pressurized coating, heated and equipped with cooling and stirring devices. 25 g of glacial vinegar are done. The reactor was then quenched, rinsed with CO / Hg and pressurized to 272 atmospheres with synthesis gas (1: 1, CO / Hg). After the autoclave was heated to 220 ° C with stirring for a period of 90 minutes, this temperature was maintained overnight. The gas absorption was found to be 54.5 atmospheres. After cooling, a sample of the residual gas was taken and then vented and 28 g of a brown liquid product with solids suspended therein was analyzed. The liquid fraction was found to contain 7.3 wt% methyl acetate, 2.59 wt% ethylene glycol diacetate, 1.8 wt% ethyl acetate.

The residual gases were found to contain 44% hydrogen, 39% carbon monoxide, 11% carbon dioxide, 3.3% methane.

Example XXVII

Following the procedure set forth in Example XIX, 7905114 • ψ -17- 20773 / Vk / iv gave 1.04 g (4.0 mmol) of ruthenium chloride hydrate, 3.28 g (40 mmol) of sodium acetate and 50 g of acetic acid done in a reactor fitted with a glass cladding. The reactor was flushed with CO / H 2 and pressurized to 272 atmospheres with CO / H 2 (1: 1) and kept at 220 ° C overnight. The gas absorption was found to be 54.5 atmospheres. After cooling, the resulting liquid product was analyzed by gas-liquid chromatography, which showed that this product contained 27.8 wt.% Methyl acetate, 1.8 wt.% Ethyl acetate, 1.67 wt.% Ethylene glycol diacetate.

Example XXVIII

Following the procedure described in Example XIX, 1.04 g (4.0 mmol) of ruthenium chloride hydrate, 2.1 g of cesium propionate (10 mmol) and 25 ml of propionic acid were charged in a 450 ml reactor with a glass upholstery done. The reactor was closed, rinsed with CO2 / H2, pressurized to 272 atmospheres with CO2 / H2 (1: 1) and heated to a temperature of 220 ° C overnight. After cooling, a yellow liquid product was obtained which was analyzed by gas-liquid chromatography and found to contain 28.1% methyl propionate, 1.30% ethylene glycol dipropionate, 0.3% ethyl propionate, 64.9% unreacted propionic acid.

The residual waste gas mainly consisted of unreacted carbon monoxide and hydrogen, viz. 47% hydrogen, 43% carbon monoxide, 7.2% carbon dioxide.

A similar product distribution was obtained using an equivalent amount of barium propionate as cocatalyst instead of cesium propionate.

Example XXIX

Following the procedure set forth in Example XXVI, 0.763 g (4.0 mmol) of ruthenium oxide hydrate, 12.0 g of bis (triphenylphosphine) iminium-790 5 1 1 4% 5 * ♦ -18-20773 / Vk / iv acetate and 50 g acetic acid fed to a reactor equipped with a glass cladding. The reactor was flushed with CO / H 2 i pressurized to 272 atmospheres with CO / H 2 (1: 1) and heated to 220 ° C overnight.

After cooling, the liquid product was collected and gas-liquid chromatography was analyzed. It was found from this that this product contained 26.7 wt% methyl acetate, 9.5 wt% ethyl acetate, 7.6 wt% water, 1.39 wt% glycol diacetate.

Comparable methyl, ethyl and glycol acetate yields were obtained using an equivalent amount of bis (triphenylphosphine) iminium nitrate, trimethylammonium acetate and / or tetrapropylammonium acetate as a cocatalyst component instead of bis (triphenylphosphine) iminium acetate.

Example XXX

The methods, ruthenium catalyst and solvent were used as mentioned in example XVII, but the reactor was pressurized to 280 atmospheres with a mixture of hydrogen and carbon monoxide in a ratio of 2: 1. After heating to 220 ° C with stirring, a cooled liquid product was obtained with the following composition: 29.4 wt% methyl acetate, II, 4 wt% ethyl acetate, 0.9 wt% ethylene glycol diacetate, 5.4 wt% water, 48.3 wt% unreacted acetic acid.

Example XXXI

The procedure described in Example XVII was followed, but the reactor was pressurized to 272 atmospheres with a mixture of hydrogen and carbon monoxide in a 1: 2 ratio. After the mixture was heated to a temperature of 220 ° C with stirring, the liquid was cooled and after analysis 33.6 wt% methyl acetate, 11.8 wt% ethyl acetate, 2.60 wt% ethylene glycol diacetate, 47.4 wt% .% to contain unreacted acetic acid.

790 5 1 14 * · -19- 20773 / Vk / iv «k

Example XXXII

An autoclave equipped with a 850 ml pressurized glass liner equipped with heaters, coolers, and stirrers was used to make 1.04 g (4.0 mmol) of ruthenium chloride 5 hydrate, 12, 7 g of tetrabutylphosphonium acetate and 50 g of glacial acetic acid were added. The reactor was then closed, purged with CO / H 2 and pressurized to 136 atmospheres with synthesis gas (1: 1, CO / H 2). The reactor was heated and the contents were stirred while the temperature was raised to 220 ° C, the pressure to 429 atmospheres with synthesis gas in a 1: 1 ratio. The temperature was maintained at 220 ° C overnight and the pressure at a value of 408-429 atmospheres by continuously feeding syngas. After cooling, the excess amount of gases was vented after a sample was taken and 62g of deep red liquid product was analyzed. No solid product was present.

The liquid fraction that was analyzed by gas-liquid chromatography was found to contain 61.9 wt% methyl acetate, 8.2 wt% ethyl acetate, 5.61 wt% ethylene glycol diacetate, 18.3 wt% unreacted acetic acid.

Example XXXIII

Following the procedure described in Example XXXII, 1.04 g (4.0 molarol) ruthenium chloride hydrate, 50 g glacial acetic acid and 10.72 g tetrabutylphosphonium acetate yvers were prepared from tri-n-butylphosphine and n-butyl acetate, in an autoclave, fitted with a glass coating, with a volume of 850 ml. The reactor was closed, rinsed with CO / H 2 and pressurized to 136 atmospheres with synthesis gas (1: 1, CO / H). Heat was supplied to the reactor and the mixture was stirred and after the temperature reached 220 ° C, the pressure was raised to 429 atmospheres with 1: 1 synthesis gas. The temperature was kept at 220 ° C overnight, the pressure at 408-429 atmospheres by continuously adding synthesis gas. After cooling, the excess gases were vented after a sample was taken and 62 g of a deep red liquid product were obtained which was further analyzed. No solid was found to be present. The liquid fraction analyzed by gas-liquid chromatography was found to be 7905114 * -20-20773 / Vk / iv 66.8 wt% methyl acetate, 7.3 wt% ethyl acetate, 6.11 wt% ethylene glycol diacetate, 2.07 wt% ethylene glycol monoacetate 5.

Example XXXIV

Following the procedure as described in Example XXX, 1.04 g (4.0 mmol) of ruthenium chloride hydrate, 50 g of acetic acid together with 40 mmol of cesium acetate and 12 mmol of triethyl phosphite were placed in a glass lined reactor. The reactor was closed, rinsed with CO / H 2, pressurized to 272 atmospheres with CO / H 2 (1: 1) and kept at 220 ° C overnight. After cooling, a deep red liquid product was obtained which was analyzed by gas-liquid chromatography. The product was found to contain 22.1 wt% methyl acetate, 17.6 wt% ethyl acetate, 2.86 wt% ethylene glycol diacetate, 54.5 wt% unreacted acetic acid.

Example XXXV

Following the procedure outlined in Example XIX, 1.04 g (4.0 mmol) of ruthenium chloride hydrate, 50 g of acetic acid, 40 mmol of cesium acetate and 12 mmol of triphenyl phosphite were placed in a glass lined reactor. The reactor was closed, rinsed with CO / H 2, pressurized to 272 atmospheres with CO / H 2 (1: 1) and heated overnight to a temperature of 220 ° C. After cooling, 52 ral deep red liquid product Obtained gas-liquid chromatographic analysis which showed that the product contained 26.6 wt% methyl acetate, 16.5 wt% ethyl acetate, 2.55 wt% ethylene glycol diacetate, 50.8 wt% unreacted glacial acetic acid.

Example XXXVI

By following the procedure described in Example XIX

7905114-21- 20773 / Vk / iv, 1.04 g (4.0 mmol) of rutheniura chloride hydrate, 50 g of acetic acid, 40 mmol of ethyl acetate and 4 mmol of triethylamine were placed in a glass lined reactor. The reactor was closed, rinsed with CO / H 2 (1: 1), pressurized to 272 atmospheres with CO / Hg (1: 1) and heated to a temperature of 220 ° C overnight. After cooling, a deep red liquid product was obtained, which was analyzed by gas-liquid chromatography, which showed that the product contained 38.1 wt.% Methyl acetate, 8.1 wt.% Ethyl acetate, 2.69 wt.% Ethylene glycol diacetate, 47.6 wt.% Unreacted acetic acid contained.

- CONCLUSIONS - 7905114

Claims (8)

0 Μ -22- 20773 / Vk / iv -CONCLÜSIES- Process for the simultaneous preparation of alcohol and vicinal glycol esters, characterized in that a reaction mixture of carbon monoxide and hydrogen with sufficient carbon monoxide and hydrogen to meet the stoichiometric amounts required for the desired ester synthesis is a liquid medium with one or more carboxylic acids and a catalyst containing ruthenium, osmium or a mixture thereof, is heated to a temperature of 100-350 ° C and an elevated pressure of at least 34 atmospheres. 2. Process according to claim 1.1, characterized in that a ruthenium oxide or ruthenium salt is used as the catalyst. Process according to claims 1-2, characterized in that the ruthenium-containing catalyst also contains one or more tertiary donor ligands with an element of group VB of the Periodic System. 4. Process according to claims 1-3, characterized in that the carboxylic acid co-reactant is an aliphatic or substituted aliphatic carboxylic acid with 1-12 carbon atoms. 5. Process according to claims 1-4, characterized in that as ruthenium catalyst a residual catalyst is used from previously used alcohol-vial glycol ester synthesis from CO / E mixtures. The method of claims 1 to 5, wherein the reaction mixture contains a co-catalyst selected from alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, ammonium salts and quaternary aliphatic phosphonium salts. Process according to claim 6, characterized in that an alkali metal salt of a carboxylic acid or a quaternary ammonium salt or phosphonium salt of a carboxylic acid is used as the co-catalyst. Process according to claims 6-7, characterized in that the reaction mixture contains 5-15 moles of cocatalyst per gram atom of ruthenium or osmium. 30 7905114