Process for preparing carbonyl compounds by catalysed oxidation of olefins and catalysts present microemulsions

Carbonyl compounds can be prepared by catalytic oxidation of olefins with oxygen or oxygen-containing gases in a microemulsion (ME) as reaction medium and catalyst support. The catalysts present in ME and used for this purpose are characterized by a content of 0.0001-10% by weight of a Pd compound and by a content of 0.0005-20% by weight of a subgroup metal compound or a quinone, based on the total weight of the catalysts present in the ME.

BACKGROUND OF THE INVENTION 
The present invention relates to the oxidation of open-chain or cyclic 
olefins in a microemulsion as reaction medium and catalyst support with 
formation of compounds containing a carbonyl function (open-chain or 
cyclic aldehydes and ketones), and also the catalysts present in 
microemulsions. 
A known and generally usable process is the oxidation of C--C double bonds 
using ozone as oxidate (Houben-Weyl: Methoden der Organischen Chemie 
Methods of Organic Chemistry!, Stuttgart 1952, Volume 7/1, Page 333 f). 
This process has often been employed for the solution of chemical problems 
in the laboratory, but has not been able to achieve any industrial 
importance since the preparation and handling of ozone is very complicated 
and the handling of the highly explosive ozonides obtained as 
intermediates entails considerable risks. 
Further oxidants which have been described for the reaction of C--C double 
bonds are, for example, potassium permanganate, chromic acid, nitric acid, 
osmium tetroxide, hydrogen peroxide/osmium tetraoxide, lead tetraacetate 
and periodic acid, which have been used specifically for the solution of 
individual problems (Houben-Weyl: Methoden der Organischen Chemie Methods 
of Organic Chemistry!, Stuttgart 1952, Volume 7/1, Pages 347, 351 f). 
All these methods are very complicated, require expensive oxidants and are 
linked to specific structural prerequisites. 
For the oxidation of olefins on an industrial scale, both in the gas phase 
and in the liquid phase, a number of catalytic processes have become known 
from the patent literature. 
In carrying out oxidations of olefins in the gas phase in the presence of 
solid catalysts, the selectivities achieved are generally unsatisfactory. 
Such processes therefore do not come into question for many compounds 
(U.S. Pat. No. 3,946,081 (1976); Ullmann's Encyklopadie der technischen 
Chemie Ullmann's Encyclopedia of Industrial Chemistry!, 4th Edition, 
Volume 17, Page 483 f). 
In carrying out oxidation reactions in the liquid phase, the introduction 
of the catalyst (usually inorganic compounds) into the reaction mixture 
generally presents a serious problem owing to the low solubility of 
inorganic compounds in the organic compounds. Owing to the low catalyst 
concentration associated therewith, the reactions are carried out at 
relatively high temperatures and therefore only low conversions and 
unsatisfactory selectivities are often obtained (DE-OS (German Published 
Specification) 2 618 055; DE-OS (German Published Specification) 2 805 
402). 
In the Wacker-Hoechst process, ethylene is oxidized on an industrial scale 
with oxygen or air in an aqueous phase in the presence of palladium 
chloride and copper chloride at 90.degree.-130.degree. C. and a pressure 
of up to 10 bar to give acetaldehyde (German Patent Specification 1 049 
845, 1 061 767, 1 080 994; see also Winnacker-Kuchler, Chemische 
Technologie Chemical Technology!, Volume 6, 4th Edition, Page 66 f 
(1982)). The process is carried out in either one or two stages (in the 
two-stage process, the reoxidation of the catalyst solution is carried out 
in a separate stage). It is an elegantal process used worldwide, but it is 
fundamentally desirable to be able to work at significantly lower 
temperatures. 
Furthermore, DE-OS (German Published Specification) 3 305 000 describes the 
oxidation of cyclopentene to cyclopentanone in the presence of 
Wacker-Hoechst catalysts in alcoholic solutions. However, the solubility 
of the catalyst salts, which are fed in the solid state into the reaction 
vessel, is very low in organic alcoholic systems, their concentration is 
therefore undefined. 
SUMMARY OF THE INVENTION 
In contrast, it has now been found that the oxidation of olefins to form 
carbonyl compounds (open-chain or cyclic aldehydes and ketones) can be 
carried out with high selectivity by reacting the olefins with oxygen or 
oxygen-containing gases at low temperatures in the presence of catalysts 
in microemulsions as reaction media. 
The invention provides a process for preparing carbonyl compounds of the 
formula 
##STR1## 
by catalytic oxidation of olefins of the formula 
##STR2## 
where, in the formulae R.sup.1, R.sup.2 and R.sup.3 are, independently of 
one another, hydrogen; straight-chain or branched C.sub.1 -C.sub.8 -alkyl 
which is unsubstituted or monosubstituted or disubstituted by halogen, 
hydroxy, cyano, COO--C.sub.1 -C.sub.4 -alkyl, CO--C.sub.1 -C.sub.4 -alkyl, 
SO.sub.2 --O--C.sub.1 -C.sub.2 -alkyl or phenyl; or phenyl or naphthyl 
which are unsubstituted or monosubstituted or disubstituted by halogen, 
hydroxy, nitro, cyano, C.sub.1 -C.sub.4 -alkyl, COO--C.sub.1 -C.sub.4 
-alkyl, CO--C.sub.1 -C.sub.4 -alkyl or SO.sub.2 --O--C.sub.1 -C.sub.4 
-alkyl, 
and 
R.sup.1 and R.sup.3 or R.sup.2 and R.sup.3 can furthermore together form an 
alkylene chain .paren open-st.CH.sub.2 .paren close-st..sub.m where m=3-10 
and 1-2 of the alkylene chain C-atoms can be substituted by halogen, 
hydroxy, C.sub.1 -C.sub.4 -alkyl, COO--C.sub.1 -C.sub.4 -alkyl, 
CO--C.sub.1 -C.sub.4 -alkyl, SO.sub.2 --O--C.sub.1 -C.sub.4 -alkyl or 
phenyl, 
by oxygen or oxygen-containing gases, which is characterized in that the 
oxidation is carried out at 0.degree.-200.degree. C. and 0.2-200 bar in 
the presence of a catalyst system comprising a palladium compound and one 
or more reoxidizing agents from the group of compounds of further subgroup 
metals and quinones, in a microemulsion as reaction medium and catalyst 
support. 
DETAILED DESCRIPTION OF THE INVENTION 
The olefins to be reacted according to the invention can be introduced into 
reaction media comprising organic components, water and surfactants to 
form a single-phase system (microemulsion ME). Single-phase ME can also 
take up as catalysts the inorganic salts otherwise not soluble in organic 
systems. The ME is thus simultaneously reaction medium and catalyst 
support. 
The invention accordingly further provides catalysts present in ME, in 
particular catalysts for reactions in which both starting materials and 
products are gaseous. After the reaction is complete, the products and any 
starting materials which have not completely reacted leave the catalyst 
present in the ME, so that the catalyst is available for further 
reactions. This is formally analogous to heterogeneous solid catalysts; in 
contrast to these the contact between the catalysts present in ME and 
starting materials is much more intensive as a result of the "solubility 
of the starting materials in the catalysts". 
Oxidations in single-phase systems have advantages over oxidations in 
two-phase or multiphase systems. The ME forms spontaneously even under 
gentle stirring from a mixture of water, organic compounds, for example 
the olefin to be reacted and optionally further organic solvents, and the 
surfactant. The dispersion formed is optically transparent and 
thermodynamically stable, i.e. even after long periods there is no 
separation of the ME into two phases (Angewandte Chemie 97, (1985), 655; 
Ullmann, Vol. 9, Page 310; Rompp, Chemie Lexikon Encyclopedia of 
Chemistry!, p. 2779). The droplet size of the ME is established as a 
function of the composition in the range from 5 to 100 nm and is 
independent of the power input by means of which dispersion is carried 
out. Since the droplet size is far below the wavelength of visible light, 
the ME is optically transparent like a true solution, although droplets 
are present as in an emulsion. The difference from a normal emulsion is, 
on the one hand, in the size of the droplets (ME: from 5 to 100 nm; other 
emulsions: from 0.5 to 10 .mu.m) and, on the other hand, in the 
thermodynamic stability of the ME. While an appreciable amount of 
mechanical energy has to be used for preparing a normal emulsion, a ME 
spontaneously forms from the components with gentle stirring. This 
preparative process for the ME is comparable with the mixing of two 
miscible liquids. 
It has been found that for the formation of the ME required according to 
the invention it is important that the composition and the temperature of 
the mixture is within the single-phase region of the phase diagram of the 
system in question. Each ternary mixture of water, olefin (and optionally 
additional organic solvent) and a surfactant has its own phase diagram. In 
these various phase diagrams, the single-phase region is in each case 
found at different temperatures and compositions. The temperature range of 
the single-phase region is determined by the hydrophilicity of the 
surfactant, i.e. is shifted to higher temperatures with increasing 
hydrophilicity. The use of surfactant mixtures enables the temperature 
range of the single-phase region to be adjusted specifically to a desired 
temperature. 
For the reaction mixtures, the surfactant (or surfactant mixture) is 
selected so that the single-phase region extends over the desired 
compositions and the desired temperature range (e.g. room temperature). 
Adjacent to the single-phase region are two-phase regions in which normal, 
unstable emulsions occur. 
Ionic and nonionic surfactants are suitable for preparing the ME. A single 
surfactant or a mixture of a plurality of surfactants, preferably from 1 
to 3 can be used. 
Specific examples which may be mentioned are: n-(C.sub.8 
-C.sub.18)-alkyl-sulphonates, n-(C.sub.8 
-C.sub.18)-alkyl-benzene-sulphonates, n-(C.sub.8 
-C.sub.18)-alkyl-trimethyl-ammonium salts, di(n-(C.sub.8 
-C.sub.18)-alkyl)dimethyl-ammonium salts, n-(C.sub.8 
-C.sub.18)-alkyl-carboxylates, oligoethylene oxide-EO.sub.2-30 
-mono-n-(C.sub.6 -C.sub.18)-alkyl ethers, n-(C.sub.8 
-C.sub.18)-alkyl-dimethylamine oxide, n-(C.sub.8 
-C.sub.18)-alkyldimethylphosphine oxide or oligoethylene oxide monoaryl 
ethers. The n-alkyl chains can also be replaced by partially unsaturated 
chains. 
The ME comprises (i) from 1 to 20% by weight of water, (ii) from 60 to 97% 
by weight of one or more inorganic components from the group of olefins to 
be reacted and organic solvents and (iii) from 2 to 20% by weight of one 
or more surfactants, all based on the total weight of the ME. 
Suitable catalysts for the process of the invention are a palladium 
compound and, as cocatalyst, at least one reoxidizing agent from the group 
of compounds of the transition metals of the first, second and third 
transition series, and also the actinides, as are described in DE-OS 
(German Published Specification) 26 18 055 and Hollemann-Wiberg, Lehrbuch 
der anorganischen Chemie Textbook of Inorganic Chemistry!, 1971, Pages 
672 to 680, and of quinones. The reoxidizing agents effect a reoxidation 
of the Pd catalyst which has itself been reduced by the oxidation of the 
olefin; the reoxidizing agent reduced in this way is then reconverted into 
the oxidized state by means of oxygen. The quinones can also be used in 
the form of the corresponding hydroquinones. Suitable quinones are o- and 
p-benzoquinone, naphthoquinone, anthraquinone and others known to those 
skilled in the art; they can be substituted by from 1 to 4 halogen atoms 
(F, Cl, Br), C.sub.1 -C.sub.4 -alkyl groups or C.sub.1 -C.sub.4 -alkoxy 
groups, including different ones of these. Preferably, transition metal 
compounds which occur in various oxidation states as reoxidizing agent. 
The reoxidizing agents are hereinafter referred to as cocatalyst. 
Preference is given to using compounds of the following elements in 
combination with Pd as catalyst: iron, cobalt, nickel, copper, chromium, 
tin, antimony, cerium, rhodium, platinum, gold. 
Suitable compounds of the abovementioned transition elements are (DE-OS 
(German Published Specification) 2 618 055): 
salts of inorganic adds, 
salts of organic carboxylic acids, 
complex salts of the elements, 
alkoxides of aliphatic, cycloaliphatic, araliphatic and aromatic alcohols. 
Of course, it is also possible to use mixtures of the various 
abovementioned cocatalysts. 
In place of the compounds of the transition elements as cocatalyst, it is 
also possible to use organic compounds such as, for example, quinones. 
The process of the invention is preferably carried out in the presence of a 
catalyst system comprising palladium chloride or palladium nitrate and 
iron nitrate. 
The concentration of the salts in the catalyst system in the ME can be 
varied within wide limits. The amount of palladium compound added can be, 
for example, from 0.0005 to 10% by weight, preferably from 0.05 to 1% by 
weight, of the ME. The concentration of the cocatalyst can be below or 
above the concentration of the palladium compound, for example 0.0001-20% 
by weight of the ME. Advantageously, the concentration of the cocatalyst 
is set higher than that of the palladium compound, preferably by a factor 
of from 2 to 100. 
The catalyst is introduced into a ME by starting with an aqueous solution 
which forms a single-phase solution with the ME. The catalyst can also be 
dissolved directly in the ME. 
Suitable olefins for the process of the invention are, for example, those 
of the above formula (II) with the scope of definitions specified. 
Preferred olefins are those of the formula 
##STR3## 
where R.sup.11 and R.sup.12 are, independently of one another, hydrogen; 
straight-chain or branched C.sub.1 -C.sub.4 -alkyl which is unsubstituted 
or substituted by halogen, hydroxy, COO--CH.sub.3, CO--CH.sub.3 or phenyl; 
or phenyl which is unsubstituted or substituted by halogen, hydroxy, 
nitro, CH.sub.3, C.sub.2 H.sub.5, COO--CH.sub.3 or CO--CH.sub.3, and 
R.sup.13 is hydrogen or methyl; and 
R.sup.11 and R.sup.13 or R.sup.12 and R.sup.13 can together form 
trimethylene, tetramethylene or pentamethylene. 
The organic part of the ME can be made up only of the olefin to be reacted. 
However, it is also possible to use, in addition, an oxidation-resistant 
organic water-immiscible solvent in an amount of 10-1000% by weight of the 
amount of the olefin to be reacted. Such solvents are, for example: 
C.sub.4 -C.sub.20 -alkanes or C.sub.6 -C.sub.10 -aromatics, which can also 
be substituted by halogen, nitro or ester groups and are well known to 
those skilled in the art as typical organic solvents. 
In general, in the process of the invention, temperature and pressure can 
be varied within wide limits. 
Thus, the process of the invention can be carried out in a temperature 
range between 0.degree. and 200.degree. C. It is advantageously carried 
out in the temperature range from about 10.degree. to 80.degree. C., in 
particular at 15.degree.-40.degree. C. (vicinity of room temperature). 
Carrying out the reaction in the vicinity of room temperature is termed 
cold oxidation. 
The reaction can be carried out at atmospheric pressure, reduced or 
increased pressure; in general, the pressure range between 0.2 and 200 bar 
is suitable. The reaction is advantageously carried out in the pressure 
range from 0.5 to 100 bar, in particular from 1 to 10 bar. 
The oxidant used in the process of the invention can be pure oxygen. It can 
also be used as a mixture with one or more inert gases such as nitrogen, 
argon, carbon dioxide, of course also in the form of air. 
The reaction time in the process of the invention can be varied within wide 
limits. It can be, for example, from 0.1 to 20 hours, preferably from 0.25 
to 10 hours, and depends, inter alia, on the batch size. 
To carry out the process of the invention, the ME can be formed together 
with the olefin to be oxidized, for example with cyclopentene or 
cyclohexene, and the desired catalyst is then introduced into the 
microemulsion. The entire system here remains as a single phase. This 
system is then brought into intimate contact with oxygen or an 
oxygen-containing gas mixture by means of fine distribution. The process 
of the invention can here be carried out batchwise in the simplest manner 
in a stirred autoclave under an appropriate oxygen pressure and suitable 
temperature, with the oxygen pressure having to be at least high enough 
for the amount of oxygen to be sufficient for achieving the desired 
conversion. However, it is generally more advantageous, even when carrying 
out the process of the invention in an intrinsically batchwise manner, to 
pass oxygen continuously into the liquid phase and to maintain the gas 
stream at constant pressure and constant flow rate by means of a valve 
system for gas supply and gas discharge (DE-OS (German Published 
Specification) 26 18 055). 
To achieve a high selectivity for the desired reaction product, it can be 
advantageous to carry out the reaction in such a way that only a partial 
conversion is achieved; this can be achieved in a known manner, for 
example, by appropriate selection of the reaction conditions, pressure and 
temperature, but also of the composition of the liquid phase or gas phase, 
and the type and amount of catalyst. 
After reaching the desired conversion, the reaction mixture is worked up. 
This can be carried out, for example, by distillation. 
The great advantage of the procedure according to the invention of working 
in ME is that the work-up of the reaction mixture for isolating the 
product can be carried out significantly more simply as a result of the 
chemical and physical properties of ME. The work-up is preferably carded 
out as follows: lowering the temperature compared with the reaction 
temperature causes the ME to separate into a first phase containing the 
predominant part of the surfactant and of the water (including the 
catalyst) and into a second phase in which the product and unreacted 
olefin (possibly together with an additional solvent) are present. The 
latter phase is worked up by distillation. The catalyst-containing phase 
can be admixed with fresh starting material and recirculated to the 
reaction. The phase separation can be caused in part just by the formation 
of the reaction production at reaction temperature. Depending on the type 
of olefin reacted, the product has a different degree of influence on the 
stability of the ME, so that temperature changes of different sizes are 
necessary for the separation of the ME into the two phases. Such a 
separation can also be carried out continuously. 
If the olefins to be reacted and products are gaseous at reaction 
temperature, the process of the invention is, in a preferred embodiment, 
carried out as follows: the prepared ME containing the catalyst is first 
placed without the olefin to be reacted in a suitable reaction vessel, for 
example in an autoclave. The gas mixture containing both the olefin to be 
reacted and also the oxidant, for example the oxygen, is then continuously 
passed into, and mixed with, this ME. The gas stream can here be 
maintained at constant pressure with constant flow rate by means of a 
valve system for gas supply and gas discharge. The flow rate of the gas 
mixture enables any desired reaction time ("contact time") corresponding 
to the desired conversion to be set. The gas mixture flowing out contains 
the reaction product which is conducted away for work-up. The work-up is 
thus restricted only to the gas mixture leaving the reactor, which can be 
carried out in a known manner. According to this variant of the process of 
the invention, the ME is used as catalyst support, similar to a solid 
catalyst support material, continuously over a relatively long period of 
time. 
The process of the invention has the advantage compared with the prior art 
that olefins can, in a simple manner, be oxidized continuously or 
batchwise at a high selectivity. 
Compounds which can be prepared by the process of the invention, namely 
open-chain or cyclic aldehydes and ketones, are used, as is known, in many 
organic syntheses as intermediates.

EXAMPLES 
Apparatus 
In the following examples, use was made of a commercial autoclave of 
stainless steel (from Carl Roth) having a volume of 200 ml. The autoclave 
was designed for a working pressure of up to 100 bar and a working 
temperature of up to 300.degree. C. The desired operating temperature was 
set by means of a heating mantle kept constant by means of an electrical 
regulator. The gases (air, oxygen) were taken from a steel bottle via a 
pressure valve. For this purpose, Teflon pipes sheathed with steel fabric 
were used. The desired working pressure was set by means of valves of a 
pressure gauge. So as not to exceed the operating pressure of 100 bar, a 
safety valve set to 95 bar was additionally installed between the 
autoclave and the steel bottle. The reaction solution was placed in the 
autoclave in a glass beaker having a volume of 40 ml and was stirred from 
the outside using a magnetic stirrer. The rotation speed of the stirrer 
allowed a fine distribution of the gas in the reaction solution. The 
cleaning of the autoclave was carried out in the cold state using ethanol. 
The autoclave and the venting valve were blown out with dry and pure 
nitrogen before each experiment. Furthermore, glass vessels were cleaned 
in an ultrasonic bath. After closing the autoclave, it was pressurised to 
the desired working pressure with the oxidizing gas (air or oxygen) from a 
steel bottle. The inlet valve was then closed so that further feed of gas 
was no longer possible. The magnetic stirrer was then turned on and the 
contents of the autoclave were heated to the desired temperature. After 
the reaction time had expired, the autoclave was taken from the heating 
mantle and cooled in ice water. After cooling, the glass vessel together 
with its contents was then removed and analyzed. 
Reaction media 
The reaction media used were microemulsions (ME) which were formed together 
with the compounds to be oxidized (cyclopentene or cyclohexene) and 
catalysts. The compositions of these ME are shown in Table 1. 
TABLE 1 
______________________________________ 
Microemulsions (ME), Total 100% by weight without catalyst 
Composition 
% by weight! 
ME1 ME2 ME3 ME4 ME5 ME6 ME7 
______________________________________ 
Cyclopentene 
39.3 32.1 32.1 30.6 -- -- -- 
Cyclohexene -- -- -- -- 30.2 30.2 30.2 
n-Heptane 39.3 32.1 32.1 30.6 -- -- -- 
n-Octane -- -- -- -- 30.2 30.2 30.2 
Igepal* 10.1 8.3 8.3 11.8 -- -- -- 
Triton** 3.5 6.7 6.7 5.8 18.8 18.8 18.8 
n-Propanol -- 14.4 14.4 14.2 14.8 14.8 14.8 
Water 7.8 6.4 -- 7 6 -- -- 
1N Hydrochloric acid 
-- -- 6.4 -- -- 6 -- 
0.5N Sodium acetate 
-- -- -- -- -- -- 6 
______________________________________ 
*Igepal CA 520: 4(C.sub.8 H.sub.17)C.sub.6 H.sub.4 O(CH.sub.2 CH.sub.2 
O).sub.4 CH.sub.2 CH.sub.2 OH (from Aldrich) 
**Triton X 100: 4(C.sub.8 H.sub.17)C.sub.6 H.sub.4 O(CH.sub.2 CH.sub.2 
O).sub.9 CH.sub.2 CH.sub.2 OH (from Aldrich) 
Analysis 
In carrying out the following examples, the identity of the compounds 
obtained was confirmed by gas-chromatographic and mass-spectroscopic 
analysis in comparison with authentic samples. Use was made of a gas 
chromatograph HP 5890 Series II fitted with a flame ionisation detector 
and automatic sample injection device. Separation columns used were 
capillary columns OV 1701. The length and the internal diameter of the 
columns were 25/50 m and 0.32 mm respectively. The injection block and the 
detector were set to 300.degree. C. The temperature of the column was 
increased from 50.degree. C. to 250.degree. C. at a heating rate of 
10.degree. C./min. The carrier gas used was helium. The flow rate of the 
helium was 1.5 ml/min. The quantitative determination was carried out by 
the internal standard method. The standard used was n-nonane or n-decane. 
The substances were identified by means of a mass-selective detector. 
Examples 1 to 19 
A batch of 17 g (about 20 ml) containing the catalyst indicated in Tables 2 
and 3 below was in each case introduced, in a 40 ml glass vessel, into the 
stirred autoclave described above and was oxidized at the temperatures and 
oxygen pressures indicated in these tables for the indicated time. 
Subsequently, the reaction product was analysed by gas chromatography and 
mass spectroscopy and also, as described further above, pure product was 
separated from the ME. The conversions and selectivities calculated from 
the gas-chromatographic analysis are likewise given in Tables 2 and 3. 
TABLE 2 
__________________________________________________________________________ 
Examples 1 to 11: Oxidation of cyclopentene; % by weight of catalyst, 
based on the total batch 
Conversion of 
Selectivite %! 
Micro- 
Catalyst composition 
T .sup.p O.sub.2 
t cyclo-pentene 
base on 
Example 
emulsion 
% by weight! 
.degree.C.! 
bar! 
h! 
%! cyclopentanone 
__________________________________________________________________________ 
1 ME 1 PdCl.sub.2 /CuCl.sub.2 : 0.8/6 
46 18. Air 
4 10.4 72 
2 ME 2 PdCl.sub.2 /CuCl.sub.2 : 0.7/4.9 
46 18. Air 
4 20 85 
3 ME 3 PdCl.sub.2 /CuCl.sub.2 : 0.7/4.9 
46 18. Air 
4 37 83 
4 ME 3 PdCl.sub.2 /CuCl.sub.2 : 0.05/4.9 
48 18. Air 
4 18 84 
5* ME 4 PdCl.sub.2 /FeCl.sub.3 : 0.7/2 
48 18. Air 
4 61 83 
6 ME 4 PdCl.sub.2 /FeCl.sub.3 : 0.7/2 
15 1 6 3,5 90 
7 ME 4 PdCl.sub.2 /Fe(NO.sub.3).sub.3 : 0.7/0.7 
15 1 6 12 83 
8 ME 4 PdCl.sub.2 /Fe(NO.sub.3).sub.3 : 0.7/1.4 
15 1 6 28 85 
9 ME 4 PdCl.sub.2 /Fe(NO.sub.3).sub.3 : 0.7/0.35 
15 1 6 7 76 
10 ME 4 PdCl.sub.2 /Fe(NO.sub.3).sub.3 : 0.1/0.35 
15 1 6 6 82 
11 ME 4 PdCl.sub.2 /Fe(NO.sub.3).sub.3 : 0.7/1.4 
20 5 0.5 
14 88 
__________________________________________________________________________ 
5*: Workup gave 2.14 g of pure cyclopentanone 
TABLE 3 
__________________________________________________________________________ 
Examples 12 to 19: Oxidation of cyclohexene, catalyst as in Table 2 
Conversion of 
Selectivity %! 
Micro- 
Catalyst composition 
T .sup.p O.sub.2 
t cyclo-hexene 
based on cyclo- 
Example 
emulsion 
% by weight! 
.degree.C.! 
bar! 
h! 
%! hexanone 
__________________________________________________________________________ 
12 ME 5 PdCl.sub.2 /CuCl.sub.2 : 0.7/4.9 
68 18. Air 
4 12 64 
13 ME 5 PdBr.sub.2 /CuCl.sub.2 : 0.7/4.9 
73 18. Air 
4 30 30 
14 ME 5 PdCl.sub.2 /FeCl.sub.3 : 0.7/2 
30 1 6 3 80 
15 ME 5 PdCl.sub.2 /Fe(NO.sub.3).sub.3 : 0.7/1.4 
30 1 6 18 62 
16 ME 5 PdCl.sub.2 /(NH.sub.4).sub.2 Ce(NO.sub.3).sub.6 : 
30 1 6 8 68 
0.5/0.8 
17 ME 5 PdCl.sub.2 /Fe(NO.sub.3).sub.3 /Ce(SO.sub.4).sub.2 : 
30 1 6 21 71 
0.7/1.4/1.4 
18 ME 6 PdCl.sub.2 /Fe(NO.sub.3).sub.3 : 0.7/1.4 
30 1 6 9 68 
19 ME 7 PdCl.sub.2 /FeCl.sub.3 : 0.7/2 
30 1 6 1.5 77 
__________________________________________________________________________ 
Example 20: Oxidation of 1-octane 
The autoclave described above was charged with 17 g of ME containing 
1-octene as compound to be oxidized and having the following composition 
(in % by weight including catalyst): 54% of 1-octene, 7.7% of Igepal, 1.9% 
of Triton 100, 19.2% of n-propanol, 10.7% of water and 0.8% of PdCl.sub.2 
/5.7% of Fe(NO.sub.3).sub.3 as catalyst. The oxidation was carried out for 
6 hours at 50.degree. C. and 1 bar using pure oxygen. Methyl hexyl ketone 
was obtained as product. The selectivity was 54% at a conversion of 14%. 
Example 21: Oxidation of ethene 
For the oxidation of ethene, the above-described apparatus was used, but a 
gas stream was maintained through the autoclave at constant pressure with 
constant flow rate by means of a valve system (gas supply and gas 
discharge). To carry out the oxidation, the autoclave was charged with 50 
g of ME comprising 39.37 g of n-heptane, 4.5 g of Igepal, 5 g of water, 1 
g of 40% strength aqueous Fe(NO.sub.3).sub.3 solution and 0.13 g of 
PdCl.sub.2, and a gas mixture comprising 85% by volume of ethene and 15% 
by volume of oxygen was passed through the ME at 12 bar and 24.degree. C. 
The flow rate was 0.8 l/h. The ME here served as catalyst support. In the 
exiting gas mixture, acetaldehyde and ethylene oxide were found as 
products by gas chromatography. In the steady state, the conversion was 
1.4% of the ethene and the selectivity (based on acetaldehyde) was 62%. 
Example 22: Oxidation of ethene 
This was carried out as described in Example 21, but the gas stream was set 
to 98% by volume of oxygen and 2% by volume of ethene. This gave a 
conversion of 14% of the ethene. The selectivity, based on acetaldehyde, 
was 54%. 
Example 23: Oxidation of propene 
This was carried out as described in Example 21, but the gas stream was set 
to 42% by volume of oxygen and 48% by volume of propene and this was 
passed through the ME at a volumetric flow rate of 0.8 l/h at 2 bar total 
pressure and room temperature. The selectivity for the product acetone was 
64%; propylene oxide was found as further product. The conversion was 0.9% 
of the propene.