DE2610035A1 - PROCESS FOR THE PRODUCTION OF AETHYLIDEN DIACETATE - Google Patents

Description

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1086 A

Halcon International / Inc., New York, New Jersey, V, St.A.

Process for the production of Äthylidendia acetate

The invention relates to a method for producing Ethylidene diacetate (1,1-diacetoxyethane) by carbonylation of dimethyl ether and / or methyl acetate in the presence of hydrogen.

Ethylidene diacetate is a chemical intermediate of considerable commercial importance as it is readily available can be converted into a number of different chemicals that come on the market in tons. For example, ethylidene diacetate can easily be converted into vinyl acetate plus acetic acid using a conventional conversion process convict (compare Kirk-Othmer "Encyclopedia of Chemical Technology, "(Second Edition), Volume 21, page 321, Interscience, New York (197O)). With the help of another, well known method, ethylidene diacetate can be converted into acetic anhydride plus acetaldehyde (compare Kirk-Othmer "Encyclopedia of Chemical Technology," (second edition), Volume 8, pages 410-413, Interscience, New York (1965)). Reference is also made to US Pat. No. 2,425,389, which explains the wide range of uses of ethylene diacetate emerges as a chemical intermediate.

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So far, however, the utilization of ethylidene diacetate is considered chemical intermediate is significantly restricted by that there is no economical process for its production readily available, inexpensive starting materials are available. A method of making ethylidene diacetate comprises the reaction of acetaldehyde and acetic anhydride to form ethylidene diacetate, which is an intermediate is used for the production of vinyl acetate; d. H. a process which, to a limited extent, is technically Scope has been carried out, including on "Hydrocarbon Process." 44 (11) (1965) 287, may be referred to. Another method includes the reduction of acetic anhydride with hydrogen, see U.S. Patent 3,579,566.

As a result, ethylidene diacetate was not used as a chemical intermediate, since its manufacture is quite the application requires expensive raw materials over which can only be disposed of to a limited extent. Furthermore, modern chemical technology has an interest in its exploitation of ethylene as a starting material for the production of acetic anhydride, acetaldehyde, vinyl acetate and acetic acid directed. The production of ethylene depends of course on the use of petroleum fractions, which are also not in any Quantities are available where ethylene cannot readily be made from carbon or methane.

The use of non-petroleum feedstocks for the manufacture of materials used in commercial Extent of ethylene derived, like the four products above, has been and is the subject of considerable research, which are mainly directed to the application of carbonylation techniques, ie. the implementation of carbon monoxide (in the presence or in the absence of hydrogen) with organic materials. With the help of such carbonylation techniques were successfully produced a variety of materials, at least on a laboratory scale. Much of the early work

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in this area goes back to Reppe ("Acetylene Chemistry", PB Report-18852-s, Charles A. Meyer & Co., Inc. (translation), Pages 162 and following (1949)). In none of these early works is there any suggestion that ethylidene diacetate is used could produce by a carbonylation process. According to later work, including, for example, the U.S. Patent 2,727,902 to Reppe et al. be referenced, methanol, carbon monoxide and hydrogen were under carbonylation conditions converted to "Acetaldehyddimethy! acetal", which is also known as Ethylidendiraethyläther (compare Merck Index, 8th Edition, page 374, Merck & Co., New Jersey (1968)). In fact, the acetals are the only gem-compounds of which it is known that they can be prepared by carbonylation processes (see US Pat. Nos. 3,285,948 and 3 689 533).

Overall, considerable research has been devoted to carbonylation reactions, with In no case have carbonylation processes been described for the preparation of ethylidene diacetate, although this Material is highly desirable as a chemical intermediate.

There has now been a process for the preparation of ethylidene diacetate found, which is the subject of the invention and which consists in that one

(a) methyl acetate and / or dimethyl ether,

(b) carbon monoxide and

(c) hydrogen

under essentially anhydrous conditions with a halide source implements. According to the invention, the halide used is bromide or iodide or mixtures of bromide and iodide, where Iodide is preferred.

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The invention therefore relates to a process for the production of ethylidene diacetate, which is characterized in that he

(a) methyl acetate and / or dimethyl ether,

(b) carbon monoxide and

(c) hydrogen

under essentially anhydrous conditions in the presence of a catalyst promoting the formation of ethylidene diacetate brings in a reaction zone with a halide source in contact, the at least one member from the group bromide and contains iodide.

The process according to the invention can be carried out in the vapor phase or in the liquid phase, the latter being preferred is. When working in the vapor phase, carbon monoxide, hydrogen and methyl acetate (and / or dimethyl ether) are combined with the halide source in the reaction zone in which the materials come into contact with one another and with one another react. According to the preferred embodiment of the process carried out in the liquid phase, carbon monoxide is added, Hydrogen and methyl acetate (and / or dimethyl ether) with one present in the reaction zone, in the liquid phase present reaction medium in contact and maintains this contact for a period of time necessary for the reaction to proceed sufficient. According to this preferred embodiment (carried out in the liquid phase), the halide source can be a constituent of the reaction medium present in the liquid phase so that they are not introduced with the reactants got to. Part of the reaction medium present in the liquid phase, which now contains ethylidene diacetate, can then be extracted withdrawn from the reaction zone and worked up to obtain ethylidene diacetate. The ethylidene diacetate can

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then sold as such or converted to acetaldehyde plus acetic anhydride and / or vinyl acetate plus acetic acid.

The overall reaction / that when using methyl acetate as a reaction participant seems to expire can be represented by the following chemical equation:

2 methyl acetate + 2CO + H ₂ > ethylidene diacetate + acetic acid.

If, instead of methyl acetate, dimethyl ether is used as the reactant, the overall reaction proceeds somewhat differently and can be represented by the following chemical equation:

2 dimethyl ether + 4CO + H ₂ ^ ethylidene diacetate + acetic acid.

Mixtures of methyl acetate and dimethyl ether can of course also be used insert. Furthermore, the above equations show that acetic acid is the primary reaction by-product, other by-products are often obtained instead of or in addition to acetic acid. The others often observed primary by-products are acetic anhydride and / or acetaldehyde. The nature and distribution of these by-products depends on as will be explained in more detail below, to a large extent on the carbon monoxide / hydrogen ratio used away. It should be noted, however, that ethanol and other ethyl derivatives are not formed to any significant extent. although traces of these products can be found.

The mechanism of the reaction or reactions taking place is not known. Because of the behavior of the invention Reaction system in the presence of particularly preferred catalyst systems, it is unlikely that the desired ethylidene diacetate predominantly by the reaction (reduction) of acetic anhydride with that in the system

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any hydrogen present is formed, a reaction described in U.S. Patent 3,579,566. According to recognized postulates preferred with regard to the reaction mechanisms Catalyst systems (compare Khan and Martell, "Homogeneous Catalysis of Metal Complexes", Volume I, Academic Press, New York (1974), rarely 49 and 315) it is to be expected that the formation of organometallic complexes of such catalysts with acid anhydrides would be far less favored than the formation of such complexes with the expected reaction intermediates, like Acy! halides. The smooth formation of such complexes with Acyl halides lead to a slight reduction of the acyl halide, what the occurrence of a reduction of the anhydride as a significant factor in the observed ethylene diacetate formation reaction would rule out.

It should also be noted that in the carbonylation reaction acetic acid occurring as a by-product can be easily obtained, for example by distillation processes, and can be purified to use as such and / or with methanol to the methyl acetate reactant can implement. The purification of the acetic acid obtained as a by-product is particularly simple since the reaction medium is anhydrous, so that it is not necessary to use water separated in order to achieve concentrations corresponding to the glacial acetic acid. If one uses acetic acid for the production of recirculating more methyl acetate, one has in practice a method which does not produce any by-products for the production of ethylidene diacetate.

Since methanol is readily available with the aid of procedures known per se converted into methyl ether and / or methyl acetate can, the inventive method is a simple method for converting methanol into ethylidene diacetate. Furthermore, since methanol need not be made from petroleum-based materials, the advantages are

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of the present process compared to the conventional techniques for the production of acetic anhydride, acetaldehyde, Vinyl acetate and acetic acid are readily apparent.

The reactions described by the above equations are advantageously carried out in the presence of suitable catalyst systems carried out. The catalyst systems based on catalysts of the noble metals of group VIII, in particular based on catalysts based on palladium, iridium and rhodium, and most preferably on palladium and / or rhodium are particularly advantageous. The effectiveness of these preferred noble metal catalyst systems is particularly evident in terms of the rate of reaction and the concentration of the desired products through the simultaneous Use of organic promoters capable of interacting with the Group VIII noble metal catalyst to enter into a coordination connection. Suitable organic promoters are organic non-hydrocarbon materials, which have one or more electron-rich atoms in their molecular structure that have one or more electron pairs, which are available for the formation of coordinative compounds with the noble metal catalyst. Most Organic promoters of this type can be viewed as Lewis bases for the particular anhydrous reaction system employed will. The increase in catalyst performance is also achieved through the use of inorganic (especially metallic) promoters that are used instead of or together with the organic promoters. Suitable metallic promoters include the elements and / or compounds of elements having an atomic weight of more than 5 of the groups IA, HA, HIA, IVB, VIB, the non-precious metals of the group VIII and the metals of Lanthanide and actinide groups of the periodic table, that in the "Handbook of Chemistry and Physics", 42nd Edition, Chemical Rubber Publishing Co., Cleveland, Ohio (1960), Pages 448 to 449. The preferred

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If you use the organic starting material (of course in addition to Carbon monoxide and hydrogen) dimethyl ether is used to assume (although not proven) that the initial stage in the carbonylation of the ether with the formation of Methyl acetate. Although one is thus dirnethyl ether without further as starting material for the method according to the invention can use is the use of methyl acetate (as such or in the form of a mixture with dimethyl ether) particularly preferred.

If you use dimethyl ether as a starting material for the inventive Process used, the reaction can be carried out in one or more reaction zones. Thus would a preferred procedure according to this embodiment comprise the use of two reaction zones, wherein in the first reaction zone to dimethyl ether by carbonylation Methyl acetate would be converted, while the ethylidene diacetate formation reaction proceed in the second reaction zone would. With this procedure you can use different reaction 'conditions for (a) the conversion of dimethyl ether to methyl acetate and (b) the conversion of methyl acetate to ethylidene diacetate apply so that each of the two reaction zones can be operated under conditions suitable for those carried out therein Reactions are optimal.

However, the use of separate reaction zones is not necessary because of the conversion of dimethyl ether to methyl acetate can be achieved simultaneously with the formation of the ethylidene diacetate and in the same reaction zone.

In addition to dimethyl ether and / or methyl acetate, necessary components for the formation of ethylidene diacetate are carbon monoxide and to use hydrogen. These starting materials can be introduced into the reaction zone (s) together or separately. When working in the vapor phase it is of course necessary to have the halide source together with the reactants

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inorganic promoters include the metals of group VIB and the non-noble metals of group VIII, especially chromium, Iron, cobalt and nickel, and most preferably chromium.

Similar catalyst systems are also used for carbonylation reactions in systems in which hydrogen (although it may only be present in trace amounts) is not essential Is part of the patent applicant filed by the same applicant of Nabil Rizkalla with the title "Process for the preparation of carboxylic acid anhydrides" (1087A) (patent application P).

The surprising feature of the present invention is also evident from a comparison of those that take place herein Carbonylation reactions with those described in U.S. Patent 3,689,533. Following the procedure of this patent specification will be Catalysts used which are similar to those preferred according to the invention, in this. Case of water-containing reaction systems can be used. Nevertheless, despite the use of substantial amounts of hydrogen in conjunction with Carbon monoxide in the carbonylation reaction (compare in particular Example 10 of this patent specification) is not specified, that ethylidene diacetate would be formed. It is surprising that the simultaneous use of essentially anhydrous reaction system and of hydrogen influence the course of the reaction to such an extent would suggest that one can obtain a product that has not previously been in any way suspected that it could be obtained by a carbonylation process could be made.

As already indicated, the invention provides a process for the preparation of ethylidene diacetate by reacting carbon monoxide and created hydrogen with dimethyl ether and / or methyl acetate. This reaction takes place in the vapor phase or in liquid phase, the reaction in the liquid phase being preferred.

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to be introduced, which in turn can be introduced together with the other reactants or separately.

It should be noted that the hydrogen, in addition to carbon monoxide a necessary reactant for the manufacture of ethylene diacetate is not necessary for the conversion of dimethyl ether to methyl acetate. if it is assumed that carbon monoxide and hydrogen are introduced separately into the reaction zone in which the ethylidene diacetate is formed, the starting materials are preferably used in a substantially pure form, such as those commercially available are available. In any case, however, if desired, inert diluents such as carbon dioxide, nitrogen, methane can be used and / or inert gases (for example helium, argon, neon, etc.) may be present. The presence of inert diluents this type does not affect the desired carbonylation reactions, although it is necessary in the presence of these gases may be to increase the total pressure to achieve the desired carbon monoxide and hydrogen partial pressures.

All components, d. H. Carbon monoxide, hydrogen as well as methyl acetate and / or dimethyl ether) should essentially be anhydrous as this will facilitate the maintenance of the essentially anhydrous conditions in the reaction zone. The presence of small amounts of water, however, such as found in commercially available reactants, for example, is acceptable. Normally however, it is intended to avoid the presence of more than 5 mole percent water in one or more of the reactants v / earth, the presence of less than 3 mole percent water being desired and the presence of less than 1.0 mole percent water is preferred. More important than the amount of water in the feed or in the circuit guided streams introduced into the reaction zone respectively, is the concentration of free water plus alcoholic hydroxyl groups (which are formed in situ with the formation of Water), which is present in the reaction zone. In the

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In practice, the molar ratio of (a) water plus the molar equivalents of alcoholic hydroxyl groups to (b) the number of moles of dimethyl ether and / or methyl acetate in the reaction zone is the most appropriate measure to define this concentration. Based on this definition, the ratio should preferably _{not exceed O #} 1: 1. Lower values of this ratio are advantageous, with optimum results being obtained when this ratio is from about 0 to about 0.05: 1. When working in the vapor phase, this ratio can easily be controlled by the content of water and / or free alcohol (for example methanol) in all streams that are introduced into the reaction zone, depending on the amount of ether introduced. and / or ester reactant appropriately. In the preferred mode of operation in the liquid phase, this ratio can readily be controlled by keeping the reaction medium present in the reaction zone and present in the liquid phase in an essentially anhydrous state.

The presence of common organic impurities in the commercial grades of dimethyl ether and / or Methyl acetate are present, however, are not a problem for the practice of the invention.

As previously indicated, the process according to the preferred embodiment is in the liquid phase in the presence of an essentially anhydrous, liquid reaction medium carried out. Since water is not a product of the reaction, can one can easily maintain substantially anhydrous conditions in the liquid reaction medium achieve that by introducing the necessary reactants into the reaction zone and / or in the circuit directed streams (which will be explained in more detail below) are reasonably dry and free of alcoholic Holds hydroxyl groups (i.e. free alcohol). That

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The reaction medium present in the liquid phase thus contains reactants (carbon monoxide, hydrogen, dimethyl ether and / or methyl acetate), reaction products (ethylene diacetate and acetic acid) and that for the implementation halide required for the desired reaction and any by-products formed, which are usually Include acetaldehyde and / or acetic anhydride.

To facilitate the reaction in the liquid phase one can Use solvents or thinners. The solvents or diluents are preferably materials required in the reaction system, such as excess dimethyl ether or excess methyl acetate and / or methyl halide and / or acetyl halide (the preferred halide sources) and / or by-products, which are usually formed in the reaction system, such as acetic acid, acetaldehyde and / or acetic anhydride, Excess dimethyl ether and / or excess dimethyl acetate are the preferred reaction diluents, with the preferred materials used alternately are acetic acid and / or acetic anhydride.

It is also possible to use organic solvents or diluents which are inert with regard to the reactions taking place. The most suitable inert solvents or diluents are the hydrocarbons free of olefinic unsaturation, especially the paraffinic, cycloparaffinic and aromatic hydrocarbons such as octane, benzene, toluene, the xylenes, cyclododecane and the like. Other suitable solvents include chloroform, carbon tetrachloride and acetone. If you look at the Solvents or diluents not involved in the reaction are used, they are preferably selected in such a way that that the solvent or diluent has a boiling point which is sufficiently different from the constituents the reaction mixture differs so that the

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Separation of the constituents of the reaction mixture from the diluent or the solvent is facilitated.

As already indicated, the reaction requires the presence of a halide which, according to the preferred embodiment of working in the liquid phase, is a component of the is present in the liquid phase reaction medium. Suitable halides are bromide or iodide or mixtures thereof, iodide is preferred. The halide is usually and predominantly in the form of methyl halide, acetyl halide, Hydrogen halide or mixtures thereof are present and can be introduced into the liquid reaction medium in such a form will. However, it is sufficient, especially in the case of batchwise operation, to transfer the materials into the liquid phase in such a form to introduce that one or more of the said materials, i. H. Methyl halide, acetyl halide and / or hydrogen halide) be formed in situ. Materials in situ with the other components of the liquid phase React reaction medium with the formation of methyl halide, acetyl halide and / or hydrogen halide, close inorganic halide materials, for example salts such as the alkali metal salts and the alkaline earth metal salts, as well as elemental iodine and elemental bromine. In the continuous operation, in which the reaction by-products separated (for example by distillation and / or extraction techniques) and circulated into the reaction medium are recycled, organic halides, such as methyl halide and / or acetyl halide, are components of the liquid Phase present reaction medium present and can be recovered and returned as such to the reaction zone so that only a small amount of fresh halide has to be added in order to reduce the amount that occurs during the recovery Compensate for losses.

The amount in which the halide should be contained in the reaction medium present in the liquid phase,

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depends on the amount of that introduced into the reaction zone Ether and / or ester reactant, but may vary within a wide range. Typically 0.5 to 1000 moles of ester or ether are used per equivalent of the halide, more preferably 1 to 300 moles per equivalent, and even more preferably 2 to 100 moles per equivalent. In general higher ratios of halide to ether and / or ester reactants result in increased Reaction speed. According to a typical practical embodiment, that contains in the liquid phase Reaction medium, apart from water and solvents used which do not occur during the reaction or diluents, usually the following materials in the stated concentration ranges, which are expressed as mole percent unless otherwise specified:

Halide, weight percent

(as contained amount) 0.1 to 75%

Acetaldehyde 0 to 40%

Acetic acid 1 to 75%

Acetic anhydride 0 to 8O%

Ethylidene diacetate 1 to 6O%

Dimethyl ether 0 to 50%

Methyl acetate 5 to 9O%

If you use solvents that do not occur in the reaction, these normally make up 5 to 95 percent by weight, more preferably 10 to 90 percent by weight, and even more preferably 15 to 80 percent by weight of that in the liquid phase present reaction medium from.

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In the above list are the amounts of dissolved Colon monoxide and hydrogen not contained, which are present in the reaction medium present in the liquid phase must allow the desired reaction or reactions to occur.

It should be noted that the reaction media present in the liquid phase, the specified concentration ranges meet, can easily be worked up to obtain ethylidene diacetate, as they make a considerable difference the volatility of the materials it contains. Methyl halides are generally highly volatile materials. They can therefore easily be separated off and recovered with the aid of distillation and / or extraction techniques and return to the reaction zone. Even those in that Acetic acid present in the system and the acetic anhydride present in the system can be easily recovered. Ethylene diacetate has a much lower volatility and can therefore in any desired purity be won. The inert solvents or diluents; if any, can be readily available in terms of be selected for their volatility so as to facilitate their recovery and reuse.

As already mentioned, the method according to the invention is preferred carried out in the presence of a reaction medium present in the liquid phase, which is contained in a reaction zone. Man can be a single reaction zone or a multitude of in series or use reaction zones connected in parallel. The procedure can in turn be run intermittently, semi-continuously or continuously. The reaction zone can be one or multiple autoclaves or a longer tubular zone or series of such zones. Of course, the reaction zone should be designed so that it is able to withstand the reaction temperature and pressure and should be made of materials that are inert to the reaction conditions. Suitable inert materials

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tantalum, zirconium, various stainless steels, Hastelloys and the like are used to implement the reaction zone. the The reaction zone is suitably equipped with internal and / or external means for removing heat, which the Absorbing heat from the exothermic reaction and maintaining appropriate temperature control during the process facilitate the response. The reaction zone is suitably designed so that there is sufficient mixing, so that there is adequate contact between the carbon monoxide and hydrogen reactants and the ether-Z acetate reactants results. Any mixing device known to those skilled in the art can be used, including vibratory, Shaking and stirring techniques, etc. Usually the reactants will introduced into the reaction zone at a point which is below the level of the liquid present in the zone State of the present reaction medium, so that the mixing and the appropriate contact by gas introduction techniques is achieved.

The process according to the invention can be carried out within a wide temperature range. For example, temperatures of 20 to 500 ⁰ C suitable, and temperatures is desired and from 80 to 350 ° C. Tempraturen are preferably from 100 to 250 ⁰ C. Temperatures lower than those mentioned can be used, although this results in lower reaction rates. It is also possible to use higher temperatures than those mentioned, although this does not result in any significant practical advantages.

The reaction time is not an essential parameter of the invention Process and depends to a large extent on the temperature used as well as the concentration of the reactants away. Appropriate reaction times (i.e. times sufficient for the ethylidene diacetate formation reaction to proceed) for the in liquid phase carried out embodiment are normally

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in a range from 0.05 to 20 hours. The reaction time in a batch system is clear in itself. In the case of continuous operation, the dwell time is defined as the quotient that is obtained by dividing the volume
of the liquid reaction medium present in the reaction zone by the rate (in units of volume per hour) at which the dimethyl ether and / or methyl acetate (both fresh feed and any recycled material) are introduced into the reaction zone.

In the preferred embodiments, those in the liquid phase
are carried out, the total pressure of the reaction is also an unimportant process parameter, provided that the pressure is high enough to keep the reaction medium in the liquid phase and the appropriate carbon monoxide and hydrogen partial pressures are achieved. The appropriate carbon monoxide

and hydrogen partial pressures are each preferably in βίο
In the range of 0.35 to 352 kg / cm (5-500 psi), more preferred

2
in a range of 1.76 to 211 kg / cm (25-3000 psi). Man

however, it can employ wider partial pressure ranges, with a range of 0.007 to 1050 kg / cm (0.1-15,000 psi) being applicable are. Although even higher partial pressures can be used, there is little benefit and considerable costs are necessary to create devices that can withstand such higher pressures.

The stoichiometry of the chemical equations given above suggests that the reaction leading to the formation of ethylidene diacetate requires a molar ratio of carbon monoxide to hydrogen of 2: 1 to 4: 1 and depends on whether you use dimethyl ether or methyl acetate (or mixtures thereof) Starting material is used. It has been found, however, that one can obtain much broader molar ratios of carbon monoxide
Can apply hydrogen, roughly speaking in a range from 1: 100 to 100: 1, more advantageously in a range from
50: 1 to 1:50 and preferably in a range of 10: 1 to 1:10. The best results are achieved with

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1 Q _

IO

Carbon dioxide / hydrogen mixtures / the stoichiometric Carbon monoxide / hydrogen ratio are approximated. Carbon monoxide / hydrogen molar ratios in the range from 0.5: 1 to 5: 1 are therefore particularly preferred.

The molar ratio of carbon monoxide to hydrogen also affects the nature of the by-products obtained. The above Equations indicate that acetic acid is formed as a by-product. However, other by-products can also be formed such as especially acetic anhydride and acetaldehyde. For example you can if you look at the other conditions keeps constant in a liquid phase system by increasing it the molar ratio of carbon monoxide to hydrogen is the molar ratio of acetic anhydride formed to that formed Increase acetic acid. You can do otherwise by reducing the carbon monoxide / hydrogen molar ratio Increase the molar ratio of acetaldehyde formed to acetic acid formed. Consequently the process according to the invention enables considerable flexibility with regard to the distribution of the available by-products,

When operating in the liquid phase, the molar ratios used are from carbon monoxide plus hydrogen to dimethyl ether and / or methyl acetate is dictated by the partial pressure criteria given above, as the * partial pressure and concentration this normally gaseous reactant in liquid Phase are directly proportional.

After the reaction is carried out, the reaction effluent becomes withdrawn from the reaction zone and transferred to a distillation zone comprising one or a series of distillation columns may have. In these columns, ethylidene diacetate and the acetic acid (and / or acetic acid and / or acetaldehyde) obtained while unreacted and partially reacted materials and the halogen-containing Recovered constituents of the reaction medium and into the

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Reaction zone are recycled. The catalyst can also recovered and, if desired, returned to the reaction zone.

As already mentioned, the ethylidene diacetate formation reaction according to the invention advantageously carried out in the presence of a carbonylation catalyst. According to a preferred embodiment this carbonylation catalyst is based on the use of one or more catalysts of the noble metals Group VIII, d. H. Ruthenium, rhodium, palladium, osmium, iridium and / or platinum. The catalysts based on Palladium, iridum and rhodium are preferred, the products based on rhodium and / or palladium being particularly advantageous and are therefore particularly preferred.

The carbonylation catalyst, which is suitably a noble metal of Group VIII of the Periodic Table, can be used in any suitable form, that is, in the valence state of zero or a higher valence form. For example, the catalyst can be used as a metal in finely divided form or in the form of a carbonate, an oxide, a hydroxide, a nitrate, a bromide, an iodine, a chloride, a low molecular weight alcoholate (for example an alcoholate with 1 to 5 carbon atoms, such as methylate or ethylate), a phenolate or a metal carboxylate in which the carboxylation is derived from an alkanecarboxylic acid having 1 to 20 carbon atoms. In a similar way, one can use complexes of the metals, for example the metal carbonyls such as iridium and rhodium carbonyls, and also other complexes such as the carbonyl halides, for example iridium tricarbonyl chloride / Ir (CO) ₃ C] ₁ Z ₂ , or the acetylacetonates, for example rhodium acetylacetonate , Rh (C ₅ H ₇ O ₂ ) O, use. It is also possible to use preformed ligand-like complexes such as dichloro-bis (triphenylphosphine) -palladium, dichloro-bis- {triphenylphosphine) -rhodium and trichloro-tris (pyridine) -rhodium. Taking rhodium as an exemplary representative of the preferred noble metal carbonylation catalysts are examples

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of forms in which the noble metal carbonylation catalyst
can be fed to the system, in addition to those already mentioned
Forms rhodium oxide (Rh ₃ O ₃ ), tetrarhodium dodecacarbonyl, dirhodium octacarbonyl, hexarhodium hexadecacarbonyl (Rh _g (CO) * g), rhodium (II) formate. Rhodium (II) acetate, rhodium (II) propionate, rhodium (II) butyrate, rhodium (II) valerate, rhodium (III) naphthenate, rhodium dicarbonylacetylacetonate, rhodium trihydroxide, indenylrhodium dicarbonyl, rhodium dicarbonyl (1-pheny! -1,3-dione), tris (hexane-2,4-dione) rhodium (III), tris (heptane-2,4-dione) rhodium (III), tris (1-phenylbutane-1,3-dione) rhodium (III), tris (3-methylpentane-2,4-dione) rhodium (III) and tris (1-cyclohexylbutane-i, 3-dione) rhodium (III).

For reaction systems in the liquid phase, the noble metal catalyst can be used in a form that is present in the liquid phase from the beginning or over time
Reaction medium dissolves, so that a homogeneous catalyst system is obtained. Alternatively, the catalyst can also be used in insoluble (or only partially soluble) form, so that a
creates heterogeneous catalyst system. Amounts of the carbonylation catalyst (calculated as the noble metal contained, based on the total amount of the reaction medium present in the liquid phase) of only about 1-10 "percent by weight (1 ppm) are effective, although amounts of
at least 10 ppm, suitably at least 25 ppm and more preferably at least 50 ppm. The upper limit of concentration on the amount of carbonylation catalyst is selected by economic considerations rather than rate or selectivity advantages. These limits usually suggest that no more than about
Noble metal containing 50,000 ppm is normally used
will. An optimal compromise between response speed and economic criteria would normally be the
Use of amounts of the noble metal contained in the carbonylation catalyst, based on the total weight of the in
liquid phase present reaction medium between about

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10 and about 50,000 ppm, suitably between about 100 and 25,000 ppm and more preferably between about 500 and 10,000 ppm recommend.

The effectiveness of these preferred noble metal catalyst systems can, as already mentioned, especially in relation to the reaction rate and the concentration of the desired products can be increased by simultaneously Promoters used. Effective promoters are inorganic or organic, whereby mixtures (or compounds) can use organic and inorganic components.

Suitable organic promoters are non-hydrocarbon materials, capable of coordinating with the Group VIII noble metal of the catalyst and which have one or more electron pairs in their molecular structure which are necessary for the formation of coordinate bonds with the noble metal catalyst are available. These promoters can be shared with the respondents and the Introduce reaction zone or can feed them together with the noble metal of Group VIII by ligand complexes with the noble metal forms before the noble metal-ligand complex is introduced into the reaction zone. If you have preformed ligand complexes used, the simultaneous use of promoters (either organic or inorganic origin) is not necessary, although you can of course make use of it.

Suitable organic promoters are organophosphine compounds, organoanoarsine compounds, organostibine compounds, Organonitrogen compounds and organo-oxygen compounds. The organophosphine and organonitrogen promoters are the preferred promoters.

Suitable oxygen-containing compounds that are able to to act as organic promoters in this system are those

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Compounds / containing functional groups, such as phenolic Hydroxyl groups, carboxyl groups, carbonyloxy groups, carbony groups and the like. Suitable organonitrogen compounds are compounds containing amino groups, imino groups and nitrile groups. You can also use materials which have both oxygen atoms and nitrogen atoms contain.

Examples of oxygen-containing organic promoters are, without this list being exhaustive, glycol, methoxyacetic acid, ethoxyacetic acid, diglycolic acid, thiodiglycolic acid. Benzoic acid, pyromellitic acid, toluic acid, tetrahydrofuran, dioxane, tetrahydropyran, catechol, citric acid, 2-methoxyethanol, 2-ethoxyethanol, 2-n-propoxyethanol, 2-n-butylethanol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 2,3-dihydroxynaphthalene, cyclohexane-1,2-diol, 1,3-epoxypropane, 1,2-dimethoxybenzene, 1,2-diethoxybenzene, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-di-n-propoxyethane, 1,2-di-n-butoxyethane, Pentane-2,4-dione, hexane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, 1-phenylbutane-1,3-dione, 3-methylpentane-2,4-dione and the mono- and dialkyl ethers of propylene glycol, diethylene glycol and dipropylene glycol and the same.

Suitable nitrogen-containing organic promoters include, for example: pyrrole, pyrrolidine, pyridine, piperidine, pyrimidine, the picolines, pyrazine (and its N-lower alkyl-substituted derivatives, where "lower alkyl" stands for an alkyl group having 1 to 5 carbon atoms, such as N-methylpyrrolidine), Benztriazole, N, N, N ¹ , N'-tetramethylethylenediamine, N, N, N ¹ , N'-tetraethylethylenediamine, N, N, N ¹ , N'-tetra-n-propylethylenediamine, N, N, N ¹ , N '-Tetramethylmethylenediamine, Ν, Ν, Ν', Ν ¹ -tetraethylmethylenediamine, N, N, N ', N'-tetraisobutylmethylenediamine, piperazine, N-methylpiperazine, N-ethylpiperazine, 2-methyl-N-methylpiperazine, 2,2' -Bipyridyl, methyl-substituted 2,2'-bipyridyl, uhy! Substituted 2,2'-bipyridyl, 1,4-diazabicyclo- / 2.2.2 / octane, methyl-substituted 1 ^ -di

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Purine, 2-aminopyridine, 2- (dimethylamino) -pyridine, 1,1O-phenanthroline, methyl-substituted 1,10-phenanthroline, 2- (dimethylamino) -6-methoxy-quinoline, 7-chloro-i, 10-phenanthroline, 4-triethylsilyl-2,2'-bipyridyl, 5- (thiapentyl) -1,10-phenanthroline, tri-n-butylamine and the like.

Suitable organic promoters which contain both oxygen atoms and nitrogen atoms are ethanolamine, diethanolamine, isopropanolamine, di-n-propanolamine, Ν, Ν-dimethylglycine, N, N-diethylglycine, 1-methyl-2-pyrrolidinone, 4-methylmorpholine, Ν , Ν, Ν ¹ , N'-tetramethylurea, iminodiacetic acid, N-methyliminodiacetic acid, N-methyldiethanolamine, 2-hydroxypyridine, methyl-substituted 2-hydroxypyridine, picolinic acid, methyl-substituted picolinic acid, nitrilotriacetic acid, 2,5-dicarboxypiperazine (2-dicarboxypiperazine) -iminodiacetic acid, ethylenediaminetetraacetic acid, 2,6-dicarboxypyridini, 8-hydroxyquinoline, 2-carboxyquinoline, cyclohexane-1,2-diamine-N, N, N *, N'-tetraacetic acid, the tetramethyl ester of ethylenediaminetetraacetic acid and the like.

Stibines and arsines that are suitable are illustrated by the following materials exemplified: trimethylarsine, Triethylarsine, triisopropylstibine, ethyldiisopropylstibine, Tricyclohexylarsine, triphenylstibine, tri (o-tolyl) -stibine, phenyldiisopropylarsine, Phenyldiamylstibine, diphenylethylarsine, tris- (diethylaminomethyl) -stibine, Ethylene-bis (diphenylarsine), hexamethylene-bis (diisopropylarsine), Pentamethylene bis (diethylstibine) etc.

Preferred organic promoters are the organonitrogen or organophosphorus compounds in which the nitrogen atoms or the phosphorus atoms are at least in part trivalent. Many of these preferred compounds may also contain oxygen atoms, such as 1-methyl-2-pyrolienone and Ν, Ν, Ν ', Ν ¹ -etramethylurea. The tertiary amines of the following general formula are particularly preferred

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- OA -

R ¹ .R ³

12 3
in which R, R and R, which can be identical or different, denote alkyl groups, cycloalkyl groups or aryl groups each having not more than about 10 carbon atoms. The heterocyclic amines of the pyridine type, such as pyridine itself, the picolines, quinoline and methylquinoline, are also particularly preferred. The tertiary phosphines of the following general formula

R * R ⁶

4 5 6
in which R, R and R have the same meanings as the

12 3

Groups R, R and R are also particularly preferred. Examples for particularly suitable phosphines are trimethylphosphine, Tri- (tert-butyl) -phosphine, tri- (n-butyl) -phosphine, tricyclohexylphosphine and tripheny! phosphine "

The amount of organic promoter used depends on the amount of noble metal catalyst present in the reaction zone. Normally the amount is adjusted so that at least 0.1, suitably at least 0.2 and preferably at least 0.3 moles of the promoter compound are present per mole of the noble metal in the reaction zone. On the other hand, there is little benefit in using a large excess of the organic promoter per mole of the noble metal catalyst. Normally, not more than 500 moles of promoter per mole of noble metal catalyst are used in the reaction zone during operation. Desirably there are less than 200 moles of promoter per mole of noble metal, and more preferably less than 100 moles of promoter per mole

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of the noble metal catalyst used. Particularly beneficial results is obtained by counting the number of moles of organic promoter per mole of noble metal catalyst present in the reaction zone in the range between 0.2 and 200 moles per mole, and more preferably between 0.3 and 100 moles per mole holds.

The stated proportions of organic promoter to noble metal naturally assume that the promoter and the noble metal introduced into the reaction zone in the form of separate compounds will. If, which is also indicated as feasible, preformed ligand complexes from the organic promoter and the noble metal are formed, the amount of promoter will of course be determined by the stoichiometry of the complex. Man however, in order to promote the maintenance of the stability complex, an additional promoter can either be desired if desired feed periodically or continuously during the course of the reaction into the reaction zone.

Another type of organically promoted noble metal catalyst, which are suitable as carbonylation catalysts for the process according to the invention are those compounds in which the metal of the noble metal catalyst is bound to a polymeric substrate, which can be organic or inorganic in nature. Such Metal-polymer complexes are to be addressed as heterogeneous because of their insolubility in the physical sense, even though they are have chemical properties that correspond more to homogeneous than heterogeneous catalysis. Such metal-polymer complexes and processes for their preparation are known, including reference to Z. M. Michalska and D. E. Webster, "Supported Homogeneous Catalysts ", CHEMTECH, February 1975, pages 117 to 122 and the reference should be made to the literary positions mentioned therein. Contain the complexes particularly suitable for the process according to the invention a silica, polyvinyl chloride, or crosslinked polystyrene-divinylbenzene substrates via phosphine, SiIy1-, amine or Precious metal bound to sulfide bonds.

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Effective inorganic promoters include the elements (and the compounds of elements) with an atomic weight greater than 5 of groups IA, HA, IIIA, IVB, VIB, the non-precious metals of Group VIII and the metals of the lantanide and actinide groups of the periodic table given in the above-mentioned "Handbook of Chemistry and Physics". Particularly preferred are the metals of these low molecular weight groups; H. those metals with an atomic weight of less than 100, the metals of group IVB and the non-noble metals of group VIII being particularly preferred. In general the most preferred elements are silicon, magnesium, calcium, titanium, chromium, iron, cobalt, nickel and aluminum. Most preferred are lithium, chromium, cobalt, iron and nickel and especially chromium.

The inorganic promoters can be in elemental form, i.e. H. in the form of finely divided or powdered metals or they can be in the form of compounds of various kinds, both organic and inorganic in nature can be, use which are suitable for introducing the element as a cation into the reaction system under the reaction conditions. Typical compounds of promoter elements are the oxides, the hydroxides, the halides (preferably the bromides and the iodides), the oxyhalides, the hydrides, the carbonyls, the alcoholates, the nitrates, the nitrites, the phosphates, the Phosphites and the like. Particularly preferred organic compounds are the salts of organic, aliphatic, cycloaliphatic, naphthenic and araliphatic monocarboxylic acids, for example alkanecarboxylic acid salts, such as the acetates, the butyrates, the decanoates, the laurates, the stearates, the Benzoates and the like. Other suitable compounds include the alkyl metal compounds as well as the chelates, association compounds and enol salts. The elemental forms, the bromides and the iodides and the are particularly preferred Salts of organic acids, preferably the acetates. One can

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if desired, mixtures of inorganic promoters as well use, especially mixtures of elements from different groups of the periodic table.

The amount of the organic promoter can be within wide ranges but is preferably so large that 0.0001 moles to 100 moles, more preferably 0.1 to 10 moles, of the promoter per mole of the noble metal catalyst contained in the reaction zone of Group VIII are present.

Of course, it can also be carried out and in certain cases is advantageous, in addition to the noble metal catalyst, both organic and also to use inorganic promoters. For example (in connection with the particularly preferred palladium and rhodium noble metal catalysts) purely organic systems, such as tertiary amines, heterocyclic nitrogen compounds use pyridine-type or tertiary phosphines as promoters. Instead of the organic promoters you can also use inorganic promoters, especially chromium, iron, nickel or cobalt, and most preferably chromium. However that is Use of phosphine or amine promoters in conjunction with chromium, iron, nickel or cobalt, and most preferably with Chromium suitable and extremely effective.

The. The following examples serve to further illustrate the invention. The term "liquid" as used in these examples Phase "stands for the liquid portion of the reaction mixture without the dissolved catalyst components (including the Halide source) that may be present and without any solvent used.

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example 1

Charge a 3.8 liter (1 gallon) autoclave equipped with a turbine stirrer is, with 60 parts by weight of methyl acetate, one part by weight of rhodium chloride trihydrate, 3 parts by weight of 3-picoline and 20 parts by weight Methyl iodide. The autoclave is then closed

2 and pressurizes it with carbon monoxide to 36.2 kg / cm (500 psig). Then hydrogen is introduced into the autoclave

2, thereby increasing the pressure of the autoclave to 71.3 kg / cm (1000 psig). The autoclave and its contents are then on Heated to 150 ° C. and left at this temperature for 3 hours, after which the autoclave is allowed to cool and ventilated and the liquid phase contained therein by gas chromatography examined. It is found that the liquid phase is 44 percent by weight of sthylidene diacetate and 6.5 percent by weight of acetic anhydride and contains 0.6 weight percent acetaldehyde in addition to a substantial amount of acetic acid. The rest of the liquid phase consists predominantly from unreacted components of the starting material.

Example. 2

The procedure and the device of Example 1 are used, with 60 parts by weight of methyl acetate, 1.6 parts by weight of palladium acetate, 10 parts by weight of triphenylphosphine and 20 parts by weight of methyl iodide starting out, 'Man. - .. _s feeds carbon monoxide and hydrogen in the same way up to the same pressure as indicated in Example 1. The reaction is carried out ^{at 135 ° C. for 17 hours.} The gas chromatographic analysis of the reaction products shows that the reaction effluent contains 34 percent by weight of ethylidene diacetate and 5.3 percent by weight of acetaldehyde in addition to a substantial amount of acetic acid. The remainder of the liquid phase consists predominantly of unreacted components from the starting charge.

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Example 3

The procedure and apparatus of Example 1 are followed, using as the initial charge 60 parts by weight of methyl acetate, 5 parts by weight of dichlorobis (triphenylphosphine) palladium, 2 parts by weight of triphenylphosphine and 20 parts by weight of methyl iodide. Then carbon monoxide and hydrogen are introduced in the same manner and up to the same pressure as described in Example 1. The reaction is carried out ^{at 135 ° C. for 17 hours.} Analysis of the reaction products by gas chromatography indicates that the reaction effluent contains 31 percent by weight of ethylidene diacetate and 9.6 percent by weight of acetaldehyde in addition to a substantial amount of acetic acid. The remainder of the liquid phase consists predominantly of unreacted components from the initial charge.

Example 4

The procedure and apparatus of Example 1 are used, with maxi using 60 parts by weight of methyl acetate, 1 part by weight of rhodium chloride trihydrate, 3 parts by weight of chromium carbonyl and 20 parts by weight of methyl iodide as the initial charge. Then carbon monoxide and hydrogen are introduced in the same manner and up to the same pressure as described in Example 1. The reaction is carried out for 4 hours at 15O ⁰ C. Analysis of the reaction products by gas chromatography shows that the reaction effluent contains 13 percent by weight ethylidene diacetate, 0.6 percent by weight acetaldehyde and 17.8 percent by weight acetic anhydride, in addition to a substantial amount of acetic acid. The remainder of the liquid phase consists predominantly of unreacted components from the initial charge.

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- 3O -

Example 5

The procedure and apparatus of the example are used 1, with 60 parts by weight of methyl acetate, one part by weight of rhodium chloride trihydrate and 20 parts by weight of methyl iodide are used. Then you give carbon monoxide and hydrogen in the same manner and up to the same pressure as described in Example 1. The reaction is carried out for three hours at 150 C, after which the Gas chromatographic analysis of the reaction effluent shows that no reaction products were obtained. This example illustrates the · advantages that can be obtained through the simultaneous Use of an organic and / or inorganic promoter and a noble metal catalyst achieved in the preceding Examples were applied.

Example 6

The procedure and apparatus of Example 1 are used with an initial charge of 60 parts by weight Methyl acetate, 2 parts by weight dichloro-bis (triphenylphosphine) rhodium, 3 parts by weight of triphenylphosphine and 20 parts by weight of methyl iodide are used. Then there will be carbon monoxide and hydrogen in the manner described in Example 1 and supplied until the same pressure is achieved. The reaction will be during Carried out for 3 hours at 150 ° C. The gas chromatographic Analysis of the reaction products shows that the reaction effluent is 13 percent by weight of ethylene diacetate and 7.4 percent by weight Contains acetaldehyde in addition to a substantial amount of acetic acid. The rest of the liquid phase consists mainly of unreacted Components of the initial charge.

Example7

The procedure and the device of the example are ended 1, with an initial charge of 60 parts by weight

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Methyl acetate, one part by weight of palladium chloride, 3 parts by weight of chromium carbonyl, 3 parts by weight of 3-picoline and 20 parts by weight of methyl iodide are used. Then carbon monoxide and hydrocarbon are introduced in the manner and to the pressure as described in Example 1. The reaction is carried out ^{at 150 °} C. for 3 1/2 hours. The gas chromatographic analysis of the reaction products shows that the reaction effluent contains 2 percent by weight ethylidene diacetate and 7 percent by weight acetaldehyde in addition to a substantial amount of acetic acid. The remainder of the liquid phase consists predominantly of unreacted components from the initial charge. This experiment is repeated with the reaction being carried out for only 2 hours. Gas chromatographic analysis of the liquid phase obtained in this way shows that it contains 10 percent by weight ethylidene diacetate and 10 percent by weight acetaldehyde, the remainder again a substantial amount of acetic acid and unreacted constituents of the initial charge, no acetic anhydride being present.

Example

The procedure and apparatus of Example 1 are used, the initial charge being 60 parts by weight of methyl acetate, 1.2 parts by weight of palladium chloride and 20 parts by weight of methyl iodide. Then carbon monoxide and hydrogen are introduced in the same manner and up to the same pressure as described in Example 1. The reaction is carried out for 17 hours at 135 ^° C., after which the gas chromatographic analysis of the reaction effluent shows that no products have been obtained. This example, like example 5, thus illustrates the advantages that result from the simultaneous use of an organic and / or inorganic promoter and a noble metal catalyst.

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Example 9

The procedure and apparatus of Example 1 are used, the initial charge being 60 parts by weight of methyl acetate, 2 parts by weight of trichlorotris (pyridine) rhodium and 20 parts by weight of methyl iodide. Then carbon monoxide and hydrogen are introduced in the same manner and to the same pressure as described in Example 1. The reaction is carried out for 3 hours at 155 ⁰ C, after which gas chromatographic analysis of Reaktionspodukte shows that the reaction effluent contains 25 weight percent and 42 weight percent acetic anhydride Äthylidendiacetat addition of a substantial amount of acetic acid. The remainder of the liquid phase consists predominantly of unreacted components from the initial charge. No acetaldehyde can be detected.

Example 10

The procedure and apparatus of Example 1 are used with an initial charge of 60 parts by weight Methyl acetate, 1.3 parts by weight of palladium chloride, 6 parts by weight of tri- (η-butyl) phosphine and 20 parts by weight. Runs out of methyl iodide. Then carbon monoxide and hydrogen according to the procedure described in Example 1 are used supplied, with the difference that one pressures

2 2

of 22.1 kg / cm and 43.2 kg / cm (300 and 600 psig), respectively. The reaction is carried out ^{at 135 ° C. for 17 hours.} The gas chromatographic analysis of the reaction products shows that the reaction effluent contains 12.4 percent by weight ethylidene diacetate and 12 percent by weight acetaldehyde in addition to a substantial amount of acetic acid. The remainder of the liquid phase consists predominantly of unreacted components from the initial charge.

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Example 11

The procedure and apparatus of Example 1 are used, the initial charge being 100 parts (molar basis) methyl acetate, 17 parts (molar basis) methyl iodide and 0.4 part (molar basis) of a preformed rhodium-pyridine ligand complex of the formula RhCl ₃ (pyridine ) ₃ begins. Then carbon monoxide and hydrogen are introduced according to the procedure described in Example 1 and up to the same pressures. The reaction is carried out ^{at 150 ° C. for 17 hours.} Gas chromatographic analysis of the reaction products shows that the reaction effluent contains 13 mol percent ethylidene diacetate, no acetaldehyde and no acetic anhydride. The effluent, however, contains a substantial amount of acetic acid and the remainder consists of the liquid phase comprising predominantly unreacted components of the initial charge. This example illustrates the use of a preformed noble metal ligand complex instead of the use of an organic promoter added as such.

Example 12

The procedure and apparatus of Example 1 are used, the initial charge being 60 parts by weight of methyl acetate, 1.6 parts by weight of palladium acetate, 10 parts by weight of triphenyl phosphine and 20 parts by weight of methyl bromide begins. Carbon monoxide and hydrogen are added according to the procedure described in Example 1, with

2 the difference that pressures of 22.1 and 43.2 kg / cm (300 or 600 psig). The reaction is carried out at 135 ° C. for 17 hours. Gas chromatographic analysis the reaction products show that the reaction effluent is 14 weight percent Ethylidene diacetate, 0.4 weight percent acetaldehyde and 2 weight percent acetic anhydride in addition to one contains a substantial amount of acetic acid. The rest of the liquid phase consists mainly of unreacted components the initial charge.

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Example 13

The procedure and apparatus of Example 1 are followed and 60 parts by weight are used as the initial charge Methyl acetate, 1.6 parts by weight of palladium diacetate, 2 parts by weight of imidazole and 20 parts by weight of methyl iodide. Then carbon monoxide and hydrogen are added according to the procedure described in Example 1, with the inter-

2 decided that pressures of 22.1 and 43.2 kg / cm (300 and 600 psig) were used. The reaction is carried out ^{at 135 ° C. for 17 hours.} The gas chromatographic analysis of the reaction products shows that the reaction effluent contains 3.4 percent by weight of ethylidene diacetate and 6.1 percent by weight of acetaldehyde in addition to substantial amounts of acetic acid. The remainder of the liquid phase consists predominantly of unconverted components from the initial charge.

Example 14

The procedure and apparatus of Example 1 are used, the initial charge being 60 parts by weight of methyl acetate / 1.6 parts of palladium diacetate, 3 parts by weight of chromium carbonyl, 15 parts by weight of Ν, Ν-dimethylacetamide and 20 parts by weight of methyl iodide. Carbon monoxide and hydrogen are then added according to the procedure described in Example 1 and using the same pressures. The reaction is carried out ^{at 135 ° C. for 17 hours.} A gas chromatographic analysis of the reaction products shows that the reaction effluent contains 27 percent by weight of ethylidene diacetate and 3.3 percent by weight of acetaldehyde in addition to a substantial amount of acetic acid. The remainder of the liquid phase consists predominantly of unreacted constituents from the initial charge.

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Example 15

The procedure and apparatus of Example 1 are used with an initial charge of 60 parts by weight Methyl acetate, 1.6 parts by weight of palladium diacetate, 10 parts by weight of hexamethylphosphoramide and 20 parts by weight Methyl iodide is used. Then carbon monoxide and hydrogen are used in the same way using the same Pressures carried out as described in Example 1. The reaction is carried out at 135 ° C. for 17 hours. Gas chromatographic analysis of the reaction products shows that the reaction effluent is 21.7 percent by weight ethylidene diacetate and contains 1.6 weight percent acetaldehyde in addition to a substantial amount of acetic acid. The rest of the liquid Phase consists mainly of unreacted components of the initial charge. The one used in this example Hexamethylphosphoramide is an example of a nitrogen promoter and not a phosphorus promoter as in this one Compound the phosphorus atom is in the +6 valence state and has no electron pair necessary for formation a coordinative bond with the noble metal catalyst is available.

Example 16

The procedure and apparatus of Example 1 are used, 60 parts by weight of methyl acetate, 1.6 parts by weight of palladium diacetate, 10 parts by weight of Ν, Ν-dicyclohexylmethylamine and 20 parts by weight of methyl iodide being used as the initial charge. Carbon monoxide and hydrogen are then used in the same manner using the same pressures as described in Example 1. The reaction is carried out ^{at 135 ° C. for 17 hours.} Gas chromatographic analysis of the reaction products shows that the reaction effluent is 14.6

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Contains percent by weight ethylidene diacetate and 4.9 percent by weight acetaldehyde in addition to a substantial amount of acetic acid. The remainder of the liquid phase comprises predominantly unreacted Components of the initial charge.

Example 17

The procedure and apparatus of Example 1 are used, starting with 30 parts by weight of dimethyl ether, 43 parts by weight of methyl acetate, 2 parts by weight Palladium dichloride, 10 parts by weight of triphenylphosphine and 31 parts by weight of methyl iodide are used. then carbon monoxide and hydrogen are introduced according to the procedure described in Example 1, with the difference

2 2

that pressures of 22.1 kg / cm or * 22.1 kg / cm (300 or 300 psig). The reaction is carried out at 150 ° C. for 17 hours. Gas chromatographic analysis of the Reaction products shows that the reaction effluent is 2 percent by weight Contains ethylidene diacetate and 44 percent by weight methyl acetate in addition to a substantial amount of acetic acid. The rest the liquid phase consists predominantly of unreacted components from the initial charge.

Example 18

The procedure and apparatus of Example 1 are used with an initial charge of 60 parts by weight Methyl acetate, 3 parts by weight of chromium carbonyl, 3 parts by weight of rhodium trichloride trihydrate and 26 parts by weight of N-methylpyridinium iodide are used. Then become carbon monoxide and hydrogen introduced in the procedure described in Example 1, with the difference that one

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2 2

Pressures of 22.1 kg / cm and 22.1 kg / cm (300 psig and 300 psig, respectively) applies. The reaction is carried out at 150 ° C. for 17 hours carried out. The gasChromatograph! See analysis of the reaction products shows that the reaction effluent is 41.2 percent by weight ethylidene diacetate and 19 percent by weight acetic anhydride in addition to a substantial amount of acetic acid. The rest of the liquid phase consists mainly of unreacted Components of the initial charge.

Example 19

The procedure and the device of Example 1 are used, 60 parts by weight of methyl acetate, 3 parts by weight of rhodium chloride trihydrate and 20 ", 5 parts by weight of chromium iodide (CrI ₇ ) being used as the initial charge. Carbon monoxide and hydrogen are then fed in according to the procedure described in Example 1, with the difference that

2 2

pressures of 22.1 kg / cm and 22.1 kg / cm (300 and 300 psig) are used. The reaction is carried out ^{at 150 ° C. for 17 hours.} The gas chromatographic analysis of the reaction products shows that the reaction effluent contains 5.2 percent by weight of ethylidene diacetate and 10 percent by weight of acetic anhydride in addition to a substantial amount of acetic acid. The remainder of the liquid phase consists predominantly of unreacted components from the initial charge.

Examples 18 and 19 illustrate the flexibility of the process with respect to the halide source, in no example any methyl halide, acetyl halide or hydrogen halide can be added. Example 18 illustrates the fact that organic halogen-containing compounds as suitable halogen sources are suitable, while Example 19 describes the use of inorganic materials as Halide sources illustrated.

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Example 2O

The procedure and apparatus of Example 1 are used, starting with 100 parts (molar basis) methyl acetate, 17 parts (molar basis) methyl iodide, 0.9 parts (molar basis) palladium acetate (Pd (C ₂ H ₅ O ₂ ) ₂ ) and 4 parts (mole basis) benzotriazole are used. Then carbon monoxide and hydrogen are fed in according to the procedure described in Example 1, with the difference that pressures of

2 2

Applies 22.1 kg / cm and 22.1 kg / cm (300 and 300 psig), respectively. the The reaction is carried out at 152 ° C. for 16 hours. the Gas chromatographic analysis of the reaction products shows that the reaction effluent is 20 percent by weight ethylidene diacetate, Contains 2 percent by weight acetic anhydride, 3 percent by weight acetaldehyde in addition to a substantial amount of acetic acid. The rest of the liquid phase consists mainly of unreacted Components of the initial charge.

The portion of the effluent obtained in this example that occurs at the gas chromatographic analysis corresponds to the ethylidene diacetate absorption peak, is carried out after desorption an ice-water trap to condense ethylidene diacetate and win. The ethylidene diacetate obtained in this way is analyzed by infrared spectroscopy and shows a Infrared spectrum that is identical to that of a sample of a commercially available, pure ethylidene diacetate, so that the identity of the product and the validity of the gas chromatography used in this and other examples Analysis is proven.

Example 21

A glass-lined pressure vessel is charged with 100 parts by weight of methyl acetate, 36.6 parts by weight of methyl iodide, 3.5 parts by weight of palladium acetate, 8 parts by weight

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Triphenylphosphine and 24 parts by weight of chromium carbonyl, after which the vessel at room temperature with carbon monoxide and hydrogen (in a weight ratio of 95: 5) on one

2
Bring pressure of 43.2 kg / cm (600 psig), seal the jar and heat to 150 ° C. with stirring for 6 hours. A carbon monoxide / hydrogen mixture (weight ratio 95: 5) is continuously fed in to keep it in the vessel

maintain a total pressure of 71.3 kg / cm (1000 psig). After a reaction time of 6 hours, the Gas chromatographic analysis of the liquid phase shows that it is 14.2 percent by weight ethylidene diacetate, 19.1 percent by weight Methyl acetate, 59.8 percent by weight acetic anhydride and Contains 6.9 percent by weight acetic acid.

Example 22

A pressure vessel lined with glass is also charged 100 percent by weight methyl acetate, 27 parts by weight methyl iodide, 2.6 parts by weight of palladium acetate, 6 parts by weight of triphenylphosphine and 17.9 parts by weight of chromium carbonyl, after which the Vessel at room temperature with carbon monoxide and hydrogen

2 (weight ratio 97.5: 2.5) (600 psig) brings to a pressure of 43.2 kg / cm, whereupon the vessel is sealed and heated for 6 hours under stirring to 150 ⁰ C. A carbon monoxide / hydrogen mixture (weight ratio 97.5: 2.5) is continuously fed in to keep a constant in the vessel

Maintain a total pressure of 71.3 kg / cm (1000 psig).

After the 6-hour reaction time has elapsed, the gas chromatographic Analysis of the liquid phase that it contains 7.1 percent by weight ethylidene diacetate, 24.9 percent by weight methyl acetate, Contains 63.8 percent by weight acetic anhydride and 4.2 percent by weight acetic acid.

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Example 23

A pressure vessel lined with glass is charged with 100 parts by weight Methyl acetate, 12.5 parts by weight methyl iodide, 18 parts by weight chromium carbonyl, 5.5 parts by weight triphenylphosphine and 2.3 parts by weight of palladium acetate, after which the vessel with a gas mixture of 97.3 percent by weight carbon monoxide and 2.7 weight percent hydrogen on one print

2
of 53.7 kg / cm (750 psig). The contents of the vessel are stirred for 14 hours at 150 ° C., after which the gas chromatographic analysis of the liquid phase shows that it contains 10% by weight of ethylidene diacetate, 18% by weight of methyl acetate, 68% by weight of acetic anhydride and 4% by weight of acetic acid.

Example 24

A pressure reaction vessel lined with glass is charged with 100 parts by weight of methyl acetate, 12.5 parts by weight of methyl iodide, 18 parts by weight of chromium carbonyl, 5.5 Parts by weight of triphenylphosphine and 2.3 parts by weight of palladium acetate and brings the vessel with a gas mixture from 98.7 percent by weight carbon monoxide and 1.3 percent by weight

2 percent hydrogen to a pressure of 53 _r 7 kg / cm (750 psig). The vessel is stirred for 14 hours at 150 ⁰ C, after which gas chromatographic analysis of the liquid phase shows that these 7 weight percent Äthylidendiacetat, 15 weight percent methyl acetate, 75 weight percent acetic anhydride and acetic acid containing 3 weight percent.

Example 25

A glass-lined pressure reaction vessel is charged with 100 parts by weight of methyl acetate, 12.5 parts by weight. Methyl iodide, 18 parts by weight of chromium carbonyl, 5.5 parts by weight of triphenylphosphine and 2.3 parts by weight of palladium acetate and brings it with a gas mixture of 93.3 percent by weight carbon monoxide and 6.7 percent by weight hydrogen to a pressure of 53.7 kg / cm (750 psig). The vessel is stirred for 3 hours at 150 ° C., after which the gas chromatographic Analysis of the liquid phase shows that

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these 21 percent by weight ethylidene diacetate, 38 percent by weight methyl acetate, 29 percent by weight acetic anhydride and contains 12% weight percent acetic acid.

Example 26

A pressure vessel made of Hastelloy-C is charged with 100 parts by weight Methyl acetate, 14 parts by weight of methyl iodide., 2.7 parts by weight of palladium acetate, 6.2 parts by weight of triphenylphosphine and 20.6 parts by weight of chromium carbonyl and bring the vessel at room temperature with carbon monoxide and Hydrogen (weight ratio 3: 1) to a pressure of

2
43.2 kg / cm (600 psig) after which the jar is capped and

heated ^{to 150 °} C. for 9 hours with stirring. A carbon monoxide / hydrogen mixture is continuously

2 to ensure a constant total pressure of 64.3 kg / cm (900 psig) in the vessel, using amounts such that a carbon monoxide / Hydrogen ratio of 3: 1 is present. After the 9-hour reaction time shows the gas chromatographic analysis of the liquid phase that it contains 42 percent by weight ethylidene diacetate, 16 percent by weight methyl acetate, 1 percent by weight acetaldehyde, 23 percent by weight acetic anhydride and Contains 18 percent by weight acetic acid.

Example 27

A pressure vessel made of Hastelloy-C is charged with 100 parts by weight Methyl acetate, 18.8 parts by weight of methyl iodide, 34 parts by weight of acetic anhydride, 3.6 parts by weight of palladium acetate, 8 parts by weight of triphenylphosphine and 55 parts by weight of chromium iodide and bring the vessel to room temperature with carbon monoxide and hydrogen (weight ratio 2: 1)

2
to a pressure of -43.2 kg / cm (600 psig), whereupon the vessel is closed and heated to 160 ° C. with stirring for 2½ hours. A carbon monoxide / hydrogen mixture (weight ratio 2: 1) is fed in continuously to

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a constant total pressure of 64.3 kg / cm (900 psig). After the reaction time of 2 1/2 hours shows the gas chromatographic analysis of the liquid phase that it contains 30 percent by weight of ethylidene diacetate, 33 percent by weight methyl acetate, 0.3 percent by weight acetaldehyde, 20 percent by weight acetic anhydride and 16.7 percent by weight Contains acetic acid.

Example 28

A pressure vessel made of Hastelloy-C is charged with 100 parts by weight of methyl acetate, 65 parts by weight of methyl iodide, 5.2 parts by weight of palladium acetate, 7.9 parts by weight of triphenylphosphine, 9.5 parts by weight of chromium carbonyl and 130 parts by weight of ethylene glycol diacetate as a solvent, bring the vessel at room temperature with carbon monoxide and hydrogen (weight ratio 1: 1)

to a pressure of 43.2 kg / cm (600 psig), the jar closes then heated to 150 ° C. with stirring for 10 hours. Carbon monoxide and hydrogen are constantly being added to the vessel a total pressure of 60.8 kg / cm (850 psig) and a carbon monoxide / hydrogen ratio of 1: 1. After the reaction time of 10 hours has elapsed, the gas chromatographic Analysis of the liquid phase to be 48.8 percent by weight ethylene diacetate, 0.6 percent by weight acetaldehyde, 13 percent by weight Methyl acetate, 11.6 percent by weight acetic anhydride and Contains 26 percent by weight acetic acid.

Example 29

A pressure reactor lined with glass is charged with 100 parts by weight of methyl acetate, 34 parts by weight of methyl iodide, 17 parts by weight of triphenylphosphine and 1.7 parts by weight of palladium acetate and brings it with a gas mixture of 70 percent by weight carbon monoxide and 30 percent by weight hydrogen

2
to a pressure of 71.3 kg / cm (1000 psig). The vessel is stirred for 6 hours at 150 ⁰ C, after which gas chromatographic analysis of the liquid phase shows that it contains 33 weight percent Äthylidendiacetat, 43 weight percent methyl acetate, 19 weight percent acetic acid and 5 weight percent acetaldehyde.

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Claims (64)

Claims Process for the preparation of ethylidene diacetate, thereby marked that one (a) methyl acetate and / or dimethyl ether, {b> carbon monoxide and
(c) hydrogen under essentially anhydrous conditions in the presence a catalyst promoting the formation of ethylidene diacetate brings in a reaction zone with a halide source in contact, the at least one representative from the Group contains bromide and iodide. 2. The method according to claim 1, characterized that contacting in the presence of an essentially anhydrous, in liquid Fiber present reaction medium takes place, which is contained in the reaction zone. 3. The method according to claim 1, characterized that the catalyst contains a noble metal of group VIII of the periodic table. 4. The method according to claim 2, characterized that the catalyst contains a noble metal of group VIII of the periodic table. 603839/1083 5 .. The method according to claim 4, characterized in that the noble metal of group VIII of the periodic table used in conjunction with a promoter. 6. The method according to claim 5, characterized in that that the promoter is an organic non-hydrocarbon -Material used in its molecular structure has at least one electron-rich atom that has at least one electron pair * that for the formation of a coordinative bond with the noble metal of group VIII of the periodic table is available, 7. The method according to claim 6, characterized in that the promoter is at least uses a representative of the group, the organophosphine, organoarsine, organostibine, organonitrogen and organo-oxygen compounds includes, 8- The method according to claim 7, characterized / That one uses an organonitrogen compound as a promoter, the at least one functional Group selected from the group comprising amino groups, imino groups and nitrile groups. 9, the method according to claim 7, characterized in that g e k e η η draws that the promoter is an organo-oxygen compound uses, which has at least one functional group that consists of phenolic hydroxyl groups, carboxyl groups, Carbonyloxy groups and carbonyl groups is selected. 609839/1063 10. The method according to claim 8, characterized that one uses as a promoter at least one representative of the group that (a) tertiary amines of the general formula ¹ R ³ E ¹ N
/ R ² 12 3
wherein R, R and R, which can be identical or different, denote alkyl groups, cycloalkyl groups or aryl groups, and (b) pyridine-type heterocyclic amines. 11. The method according to claim 10, characterized in that - 12 3 indicates that the groups R, R and R each contain no more than about 10 carbon atoms. 12. The method according to claim 7, characterized in that a tertiary phosphine of the general formula is used as the promoter R ⁴ R ⁶ R ⁵ 609839/1 069 4 5 6
in which R, R and R, which can be identical or different, denote alkyl groups, cycloalkyl groups and aryl groups. 13. The method according to claim 12, characterized in that - 4 5 6 indicates that the groups R, R and R each contain no more than about 10 carbon atoms. 14. The method according to claim 5, characterized in that an inorganic promoter is used which contains at least one element with an atomic weight of more than 5 from groups IA, HA, ΠΙΑ, IVB, VIB, the base metals of group VIII, the Metals
the lanthanide series and the metals of the actinide series of the periodic table. 15. The method according to claim 14, characterized that the element has an atomic weight of less than 100. 16. The method according to claim 14, characterized in that at least one metal from the group is used as the inorganic promoter, the metals of group VIB and the base metals of group VIII of the periodic table. 17. The method according to claim 16, characterized in that the inorganic promoter
at least one representative of chromium, cobalt, and iron
Includes Nickel Comprehensive Group. 609839/1069 18. Expire according to claim 17, characterized in that - k e η η ζ- e i chnet that one as an inorganic promoter Chromium used. 19. The method according to claim 6, characterized in that the organic Prontotor is used in an amount of at least 0.1 mol per mol of the noble metal present in the reaction zone. 20. The method according to claim 19, characterized that the amount of the organic promoter used is not more than 500 moles of promoter per mole of the noble metal catalyst present in the reaction zone. 21. The method according to claim 14, characterized in that the inorganic promoter in an amount of O, CX) OI moles to 1O0 moles per mole of the in The noble metal catalyst of Group VIII of the Periodic Table present in the reaction zone is used. 22. The method according to claim 1, characterized in that the halide is an iodide ■ used. 23. The method according to claim 4, characterized in that " at least one representative of the group comprising palladium and rhodium is used as the noble metal. 609839/1069 ~ ⁴⁸ ~ 261003 24. The method according to claim 23, characterized in that the noble metal is palladium and used as the halide iodide. 25. The method according to claim 23, characterized in that the noble metal is rhodium and used as the halide iodide. 26. The method according to claim 2, characterized in that there is a molar ratio of (a) Water plus the molar equivalents of alcoholic hydroxyl groups to (b) the number of moles of dimethyl ether plus methyl acetate applied in the reaction medium present in the liquid phase of not more than 0.8: 1 27. The method according to claim 26, characterized that the ratio of 0.5: 1 is not exceeds. 28. The method according to claim 26, characterized in that the ratio 0.1: 1 is not exceeds. 29. The method according to claim 2, characterized in that the halide is in a form is introduced into the reaction zone that under the reaction conditions at least one representative of the group. Forms methyl halide, acetyl halide and hydrogen halide. 609839/1069 30. The method according to claim 2, characterized in that the ratio of the number the moles of dimethyl ether introduced into the reaction zone and Methyl acetate to the number of equivalents of the halide in the reaction medium present in the liquid phase 0.5: 1 to 1000: 1. 31. The method according to claim 30, characterized that the ratio is 1: 1 to 300: 1 amounts to. 32. The method according to claim 31, characterized in that that the ratio is 2: 1 to 100: 1. 33. The method according to claim 2, characterized that one works at a reaction temperature of 20 to 5OO °. 34. The method according to claim 33, characterized in that a temperature of 80 to 350 ⁰ C is used. 35. The method according to claim 34, characterized in that one works at a temperature of 100 to 250 ^0C . 36. The method according to claim 2, characterized in that carbon monoxide and hydrogen partial pressures in a range from 0.35 to 2
352 kg / cm applies. 60983 9/1069 37. The method according to claim 36, characterized in that at partial pressures in 2
Range from 1.76 to 211 kg / cm works. 38. The method according to claim 36, characterized in that there is a molar ratio of Applying carbon monoxide to hydrogen from 10: 1 to 1:10. 39. The method according to claim 38, characterized that a molar ratio of carbon monoxide to hydrogen of 0.5: 1 to 5: 1 is used. 40. The method according to claim 4 _f, characterized in that the noble metal of group VIII of the periodic table in an amount between about 10 ppm (weight) and about 50,000 ppm (weight), based on the total weight of the liquid phase present in the reaction zone Reaction medium used. 41. Process for the preparation of ethylidene diacetate, d a ■ characterized by being in the presence one present in the reaction zone, present in the liquid phase. Reaction medium (a) methyl acetate and / or dimethyl ether, (b) carbon monoxide, (c) hydrogen, 609839/1069 under essentially anhydrous conditions and in the presence a carbonylation catalyst that is a noble metal of Group VIII of the Periodic Table, with a source of halide brings into contact, which contains at least one member from the group of bromide and iodide. 42. The method according to claim 41, characterized in that iodide is used as the halide. 43. The method according to claim 41, characterized in that the noble metal of the group VIII of the periodic table uses at least one member of the palladium and rhodium group. 44. The method according to claim 43, characterized that iodide is used as the halide. 45. The method according to claim 43, characterized in that the carbonylation catalyst sator additionally contains a promoter, which is an organic non-hydrocarbon material, which has at least one electron-rich atom in its molecular structure that has at least one electron pair, that for the formation of a coordinative bond with the noble metal Group VIII is available. 46 »Method according to claim 45, characterized that at least one representative of the group is used as a promoter, the organophosphines Organoarsine, organostibine, organonitrogen and organo-oxygen compounds includes. 609839/1069 47. The method according to claim 46 »characterized "That at least one representative of the group is used as a promoter" the (a) tertiary amines of the general formula 12 3 in which E ', E and R »which are the same or different can mean »Älkylgnappen» CyeloaUcylgarappeii or ürylgnuippen, and heterocyclic amines of the pyridine type includes- 48. The method of claim 46 'characterized in that as _w iPromotor a tertiary phosphine of the general formula S * R ⁶ in which R ,, R and R, which are the same or "different can mean, alkyl groups;, cycloalkyl groups or & ryl groups » is used. 49. "The method according to claim 43» characterized in that the carbonylation catalyst additionally contains an inorganic promoter which contains at least one element with an atomic weight wq more than 5 » 809839/1069 selected from groups IA, HA, HIA, IVB, VIB, the Group VIII base metals, the metals of the lanthanide series and the metals of the actinide series of the periodic table is selected, contains. 50. The method according to claim 49, characterized that at least one metal from the group is used as the inorganic promoter, the metals of group VIB and base metals of group VIII of the periodic table. 51. The method according to claim 50, characterized that at least one representative of the group is used as the inorganic promoter, the chromium, Includes cobalt, iron and nickel. 52. The method according to claim 51, characterized in that the inorganic promoter Chromium used. 53. The method according to claim 45, characterized in that at least 0.1 mol of the organic promoter per mole of that present in the reaction zone Noble metal, but not more than 500 moles of promoter per mole of noble metal catalyst present in the reaction zone used. 54 .. The method according to claim 47, characterized that the organic promoter in an amount of at least 0.1 mole per mole of the in the However, not in an amount of more than 500 moles of the promoter per mole of the noble metal present in the reaction zone noble metal catalyst present in the reaction zone is used « 609839/1069 55. The method according to claim 48, characterized that the organic promoter in an amount of at least 0.1 mole per mole of that in the reaction zone noble metal present but in an amount not more than 500 moles of promoter per mole of that in the reaction zone existing noble metal catalyst uses. 56. The method according to claim 49, characterized that the inorganic promoter in an amount of 0.0001 moles to 100 moles per mole of the noble metal catalyst of Group VIII of the Periodic Table used in the reaction zone. 57. The method according to claim 51, characterized in that the inorganic promoter is used in an amount of 0.0001 mol to 100 mol per mol. of the noble metal catalyst present in the reaction zone of group VIII of the periodic table. 58. The method according to claim 44, characterized in that a molar ratio of (a) water plus the molar equivalents of alcoholic hydroxyl groups to (b) the number of moles of dimethyl ether plus methyl acetate in the reaction medium present in the liquid phase of not more than 0, 1: 1 applies and works at a reaction temperature of 20 to 500 ° C. 59. The method according to claim 58, characterized in that a temperature of 100 to 250 ⁰ C is used. 609839 / 1.06.9 2810035 6O. Procedure according to an spoke 58, thereby g e keaa marked that one dear in a relationship Number of moles of di- methyl ether land methyl acetate, to the number of equivalents of the halide in the reaction medium present in the liquid phase from 0.5: 1 to 1000: 1 works 61. The method according to claim 6O, characterized that with a ratio of the moles of the ether edge of the acetate to the equivalents of the halide from 2: 1 to 1 © ö = 1 works. 62. The method according to claim 6O, characterized in " that carbon nano oxide and water" fabric — uses partial pressures of 0.35 to 352 kg / approx. 63. The method according to claim 62, characterized that a molar ratio of carbon monoxide to hydrogen of 10s 1 to 1s IO is used. 64. The method according to claim 63, characterized in that itnan is a noble metal of the group VIIJ of the Periodic Table in the reaction zone in an amount between about 1 © ppm (weight) and about 50,000 ppm (weight), based on the total weight of the liquid phase Reaction medium used. 809339/1069 i. ORIGINAL JNSPECTSD