FR2485521A1 - PROCESS FOR THE PREPARATION OF ALIPHATIC CARBOXYLIC ACIDS - Google Patents

Abstract

THE OBJECT OF THE INVENTION IS A PROCESS FOR THE PREPARATION OF HOMOLOGATED ALIPHATIC CARBOXYLIC ACIDS IN CAC, CONSISTING OF HEATING THESE ACIDS WITH CARBON OXIDE AND HYDROGEN IN THE PRESENCE OF A TRANSITION METAL AS A CATALYST AND D IODIDE OR BROMIDE AS AN ACTIVATOR, AT A PRESSURE OF AT LEAST 35.5 BARS. THIS PROCESS IS CHARACTERIZED IN THAT THIS CATALYST IS A COMPOUND CONTAINING NICKEL OR PALLADIUM ASSOCIATED WITH A TERTIARY LIGAND DONOR OF THE VB GROUP.

Description

The present invention relates to a process for the preparation of acids

  carboxylic acids by conversion to homologues of aliphatic carboxylic acids with synthesis gas using a particular catalyst system. There is a growing need for a wide variety of aliphatic carboxylic acids

  having carbon numbers and different structures

  rents, which have become important commercial products. The many processes leading to the preparation of these acids include the oxidation of saturated and unsaturated hydrocarbons, the carboxylation of monoolefin, particularly α-olefins, and dienes such as conjugated dienes such as 1,3-butadiene.

  and the carbonylation of lower aliphatic alcohols.

  The Applicant now discloses a novel route for the preparation of short chain aliphatic acids involving conversion to aliphatic carboxylic acid homologues of lower molecular weight. The transformation into homologues is carried out by treatment of these carboxylic acids with synthesis gas (also known as "syngas",

  mixture of carbon monoxide and hydrogen).

  The transformation into homologues of car-

  However, in the patent application No. 8013436, which is also under examination, the transformation into homologues is not known to us in the presence of the particular catalytic system of the invention. of these same acids using synthesis gas and in the presence of a catalyst containing ruthenium and an iodide or a

  bromide as an activating agent has been exposed.

  Transformation into alcohol homologs

  saturated alkyl benzyls and benzyl alcohols

  stored by the synthesis gas to give the alcohols

2485521-

  corresponding molecular mass, has been the subject of extensive studies. As appropriate examples,

  the transformation of methanol into its homo-

  ethanol, and the transformation of ethanol into iso-

  of propanol, butanol and pentanol (see nCar-

  good Monoxide in Organic Synthesis ", by J. Falbe, 59-

  62 and I. Wender, Catal. Rev. Sci. Eng., 14, 97-129 (1976)).

  Cobalt carbonyls, with or without phosphine or metal

  as modifiers, are commonly used as catalysts

  in these transformation reactions into homologues

  alcohols (see: DOS 2,625,627 and U.S.

No. 4,111,837).

  Related homogeneous cobalt carbonyl catalysts are also effective for the synthesis of aliphatic carboxylic acids by carbonylation of lower aliphatic alcohols. More recently,

  Soluble rhodium catalysts have become catalysts

  of choice, for example in the synthesis of acetic acid by carbonylation of methanol (Chem.

p. 605, October 1971).

  Another relevant homologous transformation technology is the recently reported transformation of dimethyl ether and methyl acetate to ethyl acetate (see G. Braca et al., 9, Amer. Chem.

Soc., 100, 6238 (1978).

  One of the aims of the invention is to provide

  a new process for converting carboxylic acids

  short-chain aliphatic species in their counterparts

  by means of a single catalytic system.

  The feedstock used in this process comprises synthesis gas together with the acid which is

turned into counterparts.

  The present invention provides a method of

  preparation of higher homologues of carboxylic acids

  C2 to C6 aliphatic materials which comprises heating the starting aliphatic carboxylic acid with carbon monoxide and hydrogen in the presence of a catalytic amount of a compound containing palladium or nickel associated with a ligand tertiary donor of group VB and in the presence of an iodide or bromide agent

  activation at a pressure of at least 35.5 bar.

  The process of the invention can be illustrated by converting acetic acid to higher homologues according to equation 1: ## STR1 ## Other lower aliphatic acids, such as propionic acid and other C 2 to C 6 acids may also be converted into homologues

  following a similar procedure.

  The method of the invention which comprises the

  preparation of higher homologues of carboxylic acids

  C2 to C6 aliphatics comprises the steps of contacting the starting aliphatic acids with at least a catalytic amount of a compound containing palladium or associated nickel

  to a tertiary donor ligand of the VB group and in pre-

  the presence of iodide or bromide as an activating

  and heating the reaction mixture obtained under a pressure of at least 35.5 bar with carbon monoxide and hydrogen until a substantial formation of the desired acids containing at least 3 atoms

of carbon has been obtained.

  When carrying out the transformation reaction

  In order to produce the higher homologues of the introduced aliphatic carboxylic acids, it is desirable to provide at least a quantity of carbon monoxide.

  and sufficient hydrogen to satisfy the stoichiology

  higher homologues of desired carboxylic acids, although an excess of carbon monoxide or hydrogen over stoichiometric

to be present.

- 2485521

  It has been found that the conversion reaction to homologues is carried out only with a synthesis gas mixture, and that the carbon monoxide alone is not sufficient (unlike the prior art processes involving carboxylation of carbon dioxide). aliphatic alcohols

  lower in carboxylic acids).

  It has further been found that an iodide or bromide acting as an activating agent is necessary for the reaction of transformation into homologues to proceed according to the general scheme outlined above. Finally, and surprisingly, it has been found that a lower alkyl organic iodide or bromide is much more effective as an activating agent than iodides or bromides of metals.

  alkalis such as cesium iodide.

  The process will be described in more detail below.

of the invention.

  Catalysts usable in practice

  of the invention contain palladium or nickel.

  They can be chosen from organic or inorganic compounds, complexes etc ... very diverse, as will be shown and illustrated below. It is sufficient that the precursor of the catalyst actually used contains palladium or nickel in any of its ionic states. It is then assumed that the effective catalytically active chemical species comprises palladium or nickel in complex combination with carbon monoxide and hydrogen. The most effective catalyst is obtained when the palladium or nickel-hydrocarbonyl species is solubilized in the carboxylic acid used as coreactant to satisfy

  to the stoichiometry of equation 1.

  The precursors of the palladium catalyst

  can take many different forms.

  For example, palladium may be added to the reaction mixture as an oxide such as palladium (II) oxide (PdO). It may also be added in the form of a salt of a mineral acid, such as palladium (II) chloride (PdCl 2), palladium (II) bromide (PdBr 2), palladium iodide (II) ) (Pdd2), anhydrous palladium (II) chloride (PdCl2), or palladium nitrate (Pd (NO2) 2, xH2O), or under the

  form of a salt of a suitable organic carboxylic acid

  such as palladium (II) acetate or

palladium (II) tylacetonate.

  Preferred palladium compounds include palladium oxides, palladium salts of a mineral acid and palladium salts of organic carboxylic acids. Of these, we prefer

  palladium (II) acetate, acetyl

  palladium acetonate and palladium oxide.

  The precursors of the nickel catalyst

  can also take many different forms.

  For example, nickel may be added to the reaction mixture in the form of an oxide such as nickel (II) oxide (NiO), nickel (II) oxide (Ni 2 O 3, 6H 2 O), and oxide of nickel (II, III) (NiO, Ni 2 O 3) It may also be added in the form of a salt of a mineral acid such as nickel (II) chloride (NiCl 2), nickel (II) chloride hydrated (NiCl2, 6H20), nickel bromide (II) (NiBr2), hydrated nickel bromide (II) (NiBr2, xH2O), nickel iodide (NiI2), or nickel nitrate (II) hydrated (Ni (NO 3) 2, 6H 2 O) or in the form of a salt of a suitable organic carboxylic acid, for example nickel (II) formate, nickel (II) acetate, nickel propionate ( II), nickel naphthenate (II), nickel (III) acetylacetonate, etc. Nickel may also be added to the reaction zone in the form of a carbonyl or hydrocarbonyl derivative, in which case nickel carbonyl (Ni (CO) 4), hydrocarbons bony and substituted carbonyls such as bis (triphenylphosphine) nickel dicarbonyl

  and bis- (triphenylphosphite) nickel dicarbonyl.

  Preferred nickel-containing compounds are nickel oxides, inorganic acid nickel salts, carbon acid nickel salts, and the like.

  organic xylics and carbonyl or hydro-

  carbonyls of nickel. Of these, it is particularly preferred

  nickel (II) acetylacetonate, nickel (II) acetate, nickel (II) propionate and

nickel carbonyl.

  In the invention, if desired

  add palladium or nickel to the reaction zone

  in the form of one or more oxides, salts or carbonyl derivatives in the form of a complex with one or more tertiary donor ligands of group VB. If desired, however, the ligand can be added separately to the reaction mixture. The main elements of the VB group ligands include nitrogen, phosphorus, arsenic and antimony. These elements, in their trivalent oxidation states, in particular tertiary phosphorus and nitrogen, may be bonded to one or more aliphatic, cycloaliphatic, aromatic, substituted aromatic, aryloxy, alkoxy or mixed aliphatic-aromatic radicals, each containing up to to 12 carbon atoms, or they may be part of a heterocyclic ring system, or mixtures thereof. Examples of suitable ligands that may be used in the invention include triphenylphosphine, tri-n-butylphosphine, triphenyl phosphite, triethyl phosphite, trimethylphosphite, trimethylphosphine, tri-p-methoxyphenylphosphine, triethylphosphine,

  trimethylarsine, triphenylarsine, tri-p-tolyl-

  phosphine, tricyclohexylphosphine, dimethylphenyl

  phosphine, trioctylphosphine, tri-o-tolylphosphine, 1,2bis (diphenylphosphino) ethane, triphenylstibine, trimethylamine, triethylamine, tripropylamine, tri-n-octylamine, pyridine, 2,2'-dipyridyl ,

  1,10-phenanthroline, quinoline, N, N'-dimethylamine,

  thylpiperazine, 1,8-bis (dimethylamino) naphthalene

and N, N-dimethylaniline.

  One or more of these VB group palladium or nickel-tertiary donor ligand combinations may

  be preformed, before addition to the reaction zone-

  as in the case, for example, bis (triphenylphosphine) palladium chloride, bis (triphenylphosphine) palladium (II) acetate and tetrakis (triphenylphosphine) palladium (O), bis (1, 2-diphenylphosphino) ethane nickel (II), from

  dicarboxyl bis (triphenylphosphine) nickel and tetra-

  kis (triphenylphosphite) nickel (O). The complexes may also be formed in situ, the palladium or nickel containing compound and the ligand being added separately. The preparation of these palladium or nickel-donor complex ligand VB group combinations as a complex is described more fully in

  U.S. patents Nos. 3,102,899 and 3,560,539.

  The amounts of the VB group tertiary donor ligand used with the palladium or nickel compound, for example, the stoichiometric amount required to form a complex with the palladium or nickel compound, to be varied within 5 times, can be varied widely. or more molar amount

  necessary to form the complex.

  Iodide or bromide acting as an active agent

  which have been found to be necessary to effect the desired conversion reaction of acids to homologues, may be in combined form with palladium or nickel, as for example in palladium (II) chloride or iodide nickel, but it is generally preferred to have an excess of halogen

  in the catalyst system, as an activating agent.

  By "excess" is meant an amount of halogen greater than 3 halogen atoms per palladium or nickel atom in the catalyst system. This activating component of the catalytic system may be composed of a halogen and / or a halogenated compound, which may be introduced into the reaction zone in gaseous or liquid form, or of saturated solution in a suitable solvent or reagent. Suitable halogenated activating agents include hydrogen halides such as hydrogen iodide and gaseous iodide, alkyl, aryl and aralkyl halides containing up to 12 carbon atoms. such as methyl iodide, ethyl iodide ,. 1-iodopropane, 2-iodobutane, 1-iodobutane, ethyl bromide, iodobenzene and benzyl iodide,

  as well as acyl iodides such as acetyl iodide

  the. The quaternary ammonium and phosphonium halides are also suitable as halogenated coreactant;

  examples of these are tetrahydrofuran iodide.

  methylammonium and tetrabutylphosphonium iodide.

  Alkali and alkaline earth metal halides, such as cesium iodide, can also be used, but they are generally not as effective as the other activating agents listed

  for this transformation into counterparts.

  Activating agents consisting of C1-C6 alkyl iodides or bromides are the preferred activating agents for the acid-to-palladium or nickel catalyzed reaction reaction according to the invention. Iodide is preferred

methyl and ethyl iodide.

  The starting carboxylic acids that can be used

  in the process of the invention are aliphatic acids

  C2 to C6. These acids are preferably also useful as solvents for palladium or nickel catalysts. Suitable carboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, trimethylacetic acid and caproic acid, as well as C2-6 aliphatic dicarboxylic acids such as oxalic, malonic, succinic and adipic acids. The invention further relates to the use of substituted aliphatic acids containing one or more functional substituents such as lower alkoxy, chloro, fluors, phenyl, substituted phenyl, cyano, alkylthio and amino functional groups, for example acetoacetic acid, dichloroacetic and trifluoroacetic acids, chloropropionic acid, trichloroacetic acid, monofluoroacetic acid, etc. It is also possible to use mixtures of these carboxylic acids in any ratio in the process of the invention. The preferred carboxylic acids for the purpose of the homologous conversion according to the invention are acetic acid and propionic acid, acetic acid

being the preferred one.

  The amount of palladium or nickel compound used in the present invention is not critical, and can be varied over a wide range. In general, the process of the invention is advantageously carried out in the presence of a catalytically effective amount of one or more of the active compounds of palladium or nickel, which gives the desired products with reasonable yields. The reaction operates when only 1 x 10-6% by weight, or even less, of palladium or nickel is used, based on the total weight of the reaction mixture. The maximum concentration is imposed by various factors including the cost of the catalyst, the partial pressures of carbon monoxide and hydrogen, the temperature at which one operates and the carboxylic acid chosen as diluent / reagent. A catalyst concentration of 1 x 10-5 to 10% by weight of palladium or nickel, based on the total weight of the reaction mixture, is generally

  advantageous in the practice of the invention.

  The temperature range which can be usefully employed in these syntheses is a variable which depends on other experimental factors, among which the choice of the carboxylic acid used as coreactant, the pressure and the concentration, as well as the particular species. selected catalyst, among others. The operating range is from 100 to about 350 ° C., when operating under the pressure of synthesis gas. A smaller interval of about

  at around 2500C, is the temperature range

res preferred.

  Pressures of at least 35.5 bar result in high yields of higher homologues of aliphatic carboxylic acids of interest by the process of the invention. A preferred operating range is from 69.9 to 518.2 bar, although pressures above 5108.2 bar also provide useful yields of the desired acid. The pressures discussed here represent the total pressure produced by all the reagents, although they are largely due to the carbon monoxide and hydrogen fractions

in these examples.

  The relative amounts of carbon monoxide and hydrogen that may be initially present in the synthesis gas mixture are variable,

  and can be varied in a wide range.

  In general, the CO: H2 molar ratio is in the

  range from 20: 1 to 1:20, preferably from 5: 1 to 1: 5, although it is also possible to use

  reports outside these ranges. In operation

  In particular, but also in batch experiments, it is also possible to use the gaseous carbon-carbon oxide gas mixtures in combination with up to 50% by volume of one or more other gases. These other gases may comprise one or more inert gases such as nitrogen, argon, neon, etc., or gases that may or may not react under the conditions of the hydrogenation of CO, such as gas. carbonic, hydrocarbons such as methane, ethane, propane etc ... ethers such as dimethyl ether, methylethyl ether and diethyl ether, alkanols such as methanol

  and esters such as methyl acetate.

  In all these syntheses, to achieve a high degree of selectivity, the amount of carbon dioxide and hydrogen present in the mixture

  The reaction must be at least sufficient to satisfy

  do with the stoichiometry of equation (1). An excess of carbon monoxide and / or hydrogen with respect to stoichiometric quantities may be present if

the desire.

  As far as can be determined, and without being limited by the invention, the one-step process of conversion to homologues described herein results in the formation of acidic products containing primarily one atom

  more carbon than the starting material. Quantities

  Minor counterparts of higher homologs of acids containing two or three additional carbon atoms are usually present as well. When the coreactant is acetic acid, the main products are propionic acid, butyric acid, and valeric acid. By-products such as water and ethyl acetate are also detected in the liquid product fraction. When the acidic reagent is propionic acid, the main products are n-butyric acid and isobutyric acid. The ratio of isomeric acids n to iso is usually about 3: 1. The novel process of the invention can be carried out

  kill in a discontinuous, semi-continuous or continuous manner.

  The catalyst can be introduced initially into the reaction zone batchwise, or introduced continuously or intermittently in this zone at

  during the synthesis reaction. Operating conditions

  res can be adjusted to optimize the

  formation of the desired ester, and this product can be

  recovered by methods well known in the art,

  such as distillation, fractionation, extrac-

  etc. It is then possible to recycle, if desired in the reaction zone, a constituent fraction of the palladium or nickel catalyst, and form

additional products.

  The products were identified in this work by one or more of the following analytical techniques; gas-liquid chromatography (cgl), infrared (ir), mass spectrometry, nuclear magnetic resonance (nmr) and elemental analysis, or a combination of these techniques. The analysis results are given for the most part in parts.

  weight, all temperatures are in degrees centrigra-

  and all the pressures in bars.

  The following nonlimiting examples are

  given by way of illustration of the invention.

EXAMPLE I

  To a liquid mixture, swept with nitrogen, acetic acid (25 g) and methyl iodide (8.0 g, 56 mmol) placed in a glass jacket, 0.4 g of palladium acetate is added. (1.8 mmol of Pd) and 4.0 g of triphenylphosphine (15 mmol). The mixture is stirred to partially dissolve the palladium acetate, and the glass jacket and its contents are introduced into a 450-lb swing autoclave. The reactor is swept with a gaseous mixture containing equimolar amounts of carbon monoxide and hydrogen at a pressure of 138.9 bars with

  the same gas mixture and heated with

  at 2200C. At this temperature, the pressure is raised to 435.5 bar with the gas mixture carbon monoxide / hydrogen and is kept constant throughout the rest of the test by gradual addition of the mixture

  gas from a large buffer tank.

  After cooling, lowering the reactor pressure, and taking samples of the off-gas, 32.6 grams of a clear, dark red liquid product is collected in the glass jacket. A small amount (less than 1 ML) of a lighter liquid phase is also detected. The analysis of the largest phase with cgl shows the presence of 13.2% propionic acid 1.1% butyric acid 0.5% valeric acid 16.0% water

  47.8% unreacted acetic acid.

  Typical samples of gas released show the presence of:% carbon monoxide 22% hydrogen 13% carbon dioxide

15% methane.

EXAMPLES 2 to 4

  By following the general procedure of

  Example 1, other catalyst combinations are used.

particularly,

  1) Examples 2 and 3 illustrate the use of

  various initial molar ratios of the acetate

  from palladium (II) to triphenylphosphine, in

  in the reactor an initial pressure of 276.8 bar, with a mixture containing equimolar amounts of carbon monoxide and hydrogen and carrying out the conversion to homologues of acetic acid

  under varying pressure conditions.

  b) Example 4 illustrates the use of bis (triphenylphosphine) -palladium (II) chloride

as precursor of the catalyst.

EXAMPLES A-H

  Following the general procedure of Example 1, a number of experiments were carried out using various additional catalysts with methyl iodide as the activating agent and

  acetic acid as starting carboxylic acid.

  The results summarized in Table 1 below

  below show that platinum, cobalt, iron, manganese, rhenium, molybdenum and chromium catalysts are inefficient for

  from acetic acid to higher homologs.

TABLE I

  COMPOSITION OF THE LIQUID PRODUCT (% by wt.) Acid Agent Ligand Example Catalyst VB activation group Aliphatiaue Pd (OAc) 2 Pd (OAc) 2 Pd (OAc) 2 8 Ph3P 8 Ph3P 4 Ph3P Pd (PPh3) 2C12 K2PtC14-3PPh3 CoI 2 Co 2 (CO) 8 Fe (AcAc) 3 Mn 2 (CO) 10 Re 2 (CO) 10 Mo (AcAc) 3 Cr (AcAc) 3 -31 MeI-31 MeI-31 Mel -31 MeI-28 MeI-10 MeI - MeI-10 MeI-5 MeI-10 MeI-10 MeI HOAc HoAc HOAc HOAc HOAC HOAc HOAc HOAc HOAc HOAC HOAc H20 16.0, 8 0.5, 1k 0.9 13.81, 1 2, 4 3.9 2.3 0.5 0.7 1.1, 4 HOAC 47.8 64, 8 27.9 48.8k 37.4 63.41, 1, 4, 1, 2 97.8 97, 5 93.6 89.7

  _____________________________________ I

  HOPr 13.2 13.2 8.0, 0k 6.3 7.11 HOBu Iso

0.7 0.4

0.7 0.4

  1,3_ 0,21 0,2 0,5 0,5 0,41 tert 1,0 a) test load: aliphatic acid, 25g; activating agent (iodide), 56 mmol catalyst b) test load: aliphatic acid, 50 g activating agent (iodide) 40 mmol catalysis c) test load: aliphatic acid, 50 g; activating agent (iodide), 112 mroles; cat1lye d) test load: aliphatic acid, 50g; activating agent (iodide) 20 mmol; catalysis e) conditions of the test: initial pressure 276.8 bar CO / H (* 1), 220 C, 18h f) 2d6, igbatios: O / H 2 (1: 1,2, 8h)

  (f) designations: propionic acid, HOPr; butyric acid, HOBu y and valeric acid, HOVa.

  g) test conditions: constant pressure 435.5 bar CO / l (1: 1), 220 C, 18h.

  (h) two-phase liquid product, the heaviest phase (k) accounts for 86% of the sample.

  i) the two phase liquid product, the heavier phase (1) constitutes 94% of the sample.

  a small amount of a liquid phase plus a drastically larger amount of liquid.

  HOVa iso I 0.9 I 0.41 0.1 0.6 n i 0.5 0.8 0'4k C, 31 0.1 0.2 I.- '

1.8 mmoles.

eur, 4.0 mmol.

3seur, 4.0 mmoles.

eur, 4 # 0 mmoles.

  Co Co L L L L ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro. r |. '_

EXAMPLE 5

  Example 1 is repeated except that 0.50 g of nickel (II) acetate (2 mmol of Ni) is used and

  1.43 g of triphenylphosphine (5.4 mmol).

  After cooling, lowering the reactor pressure and taking samples of the off-gas, 33.9 g of a dark brown liquid product is collected in the glass jacket. The analysis with cgl shows the presence of: 7.6% propionic acid, 0.6% butyric acid, 0.4% valeric acid, 8.2% water,

  1% unreacted acetic acid. Typical samples of gas evolved show the presence of; 57%

  carbon monoxide, 34% hydrogen, 2% carbon dioxide,

2% methane.

EXAMPLE 6

  Following the general procedure of Examples 1 and 5, a second example is carried out using a triphenylphosphine and nickel carbonyl complex, (Ni (PPh 3) 2 (CO) 2). The results

  are summarized in Table 2 below.

TABLE 2

  Catalyst Ni (OAc) 2 Ligand of Activating Group VB 3Ph3P Ni (Ph3P) 2 (CO) 2 -28 MeI -10 MeI Aliphatic Acid HOAC HOAc COMPOSITION OF LIQUID PRODUCT (% wt) 8.2, 2, 1 82.7 HOPr 7.6 4.9 HOBu Iso n 0.2 0.4 0.4 HOVa tert3, iso 3 ni - II _

0.2 1 0.2

0.9 0.1 J

  k) test load: aliphatic acid, 25g; activating agent (iodide), 56 mmol; catalyst, 2.0 mmol.

  1) test load: aliphatic acid, 50g; activating agent (iodide), 40 mmol; catalyst, 4.0 mmol

  catalyst and ligand added as a complex.

  m) test conditions: constant pressure (435.5 bar) of CO / H2 (1: 1), 220 C, 18h.

co CO Ul N ru -.o

Example

1, m 21,

1 HOAC

- 2485521

Claims (10)

  1. Method for preparing higher homologs   of C2 to C6 aliphatic carboxylic acids,   both to heat the starting aliphatic carboxylic acid with carbon monoxide and hydrogen in the presence of a transition metal catalyst and an iodide or bromide as an activation agent under a pressure at least 35.5 bar, characterized in that the catalyst is a compound containing palladium or nickel associated with a donor ligand tertiary group VB.   2. Process according to claim 1, characterized   rised by heating at a temperature from 100 to 3500C.   3. Process according to any one of the   1 and 2, characterized in that the pressure is 69.9 at 518.2 bars.   4. Process according to any one of the   1 to 3, characterized in that the compound containing   Palladium oxide is a palladium oxide, a palladium salt of a minetal acid or a palladium salt. of an organic carboxylic acid.   5. Process according to claim 4, characterized   in that the compound containing palladium is palladium (II) acetate, palladium (II) acetylacetonate, palladium (II) chloride or palladium oxide.   6. Process according to any one of the   1 to 3, characterized in that the compound containing   nickel is a nickel oxide, a nickel salt of a mineral acid, a nickel salt of a carboxylic acid,   organic or a nickel carbonyl or hydrocarbonyl.   7. The process of claim 6, wherein   characterized in that the nickel-containing compound is nickel (II) chloride, nickel (II) oxide, nickel (II) acetylacetonate, nickel acetate   (II), nickel propionate (II) or nickel carbonyl.   8. Process according to any one of   Claims 1 to 7, characterized in that the ligand   tertiary donor group VB is triphenylphosphine, trimethylphosphine, tri-n-butylphosphine, triphenyl phosphite, triethylphosphite, triphenylarsine, trimethylamine, triethylamine,   tripropylamine or tri-n-octylamine.   9. Process according to any one of the   1 to 8, characterized in that the iodide or bromide used as an activating agent is a   iodide or C1-C6 alkyl bromide.   10. Process according to any one of   Claims 1 to 9, characterized in that the acid   The starting aliphatic carboxylic acid is acetic acid.