U.S. patent number 3,899,401 [Application Number 05/498,447] was granted by the patent office on 1975-08-12 for electrochemical production of pinacols.
This patent grant is currently assigned to BASF Aktiengesellschaft. Invention is credited to Fritz Beck, Heinz Nohe.
United States Patent |
3,899,401 |
Nohe , et al. |
August 12, 1975 |
Electrochemical production of pinacols
Abstract
Pinacols are prepared by electrolytic hydrodimerization of
carbonyl compounds in non-compartmented cells using a mixture of
from 5 to 75% by weight of the carbonyl compound, from 5 to 90% by
weight of the alcohol corresponding to the carbonyl compound, from
0.1 to 3% by weight of a quaternary ammonium salt and from 0 to 30%
by weight of water.
Inventors: |
Nohe; Heinz (Meckenheim,
DT), Beck; Fritz (Ludwigshafen, DT) |
Assignee: |
BASF Aktiengesellschaft
(Ludwigshafen (Rhine), DT)
|
Family
ID: |
5890758 |
Appl.
No.: |
05/498,447 |
Filed: |
August 19, 1974 |
Foreign Application Priority Data
|
|
|
|
|
Aug 25, 1973 [DT] |
|
|
2343054 |
|
Current U.S.
Class: |
205/418 |
Current CPC
Class: |
C25B
3/295 (20210101) |
Current International
Class: |
C25B
3/00 (20060101); C25B 3/10 (20060101); C07b
029/06 (); C07c 029/00 (); C07c 031/20 () |
Field of
Search: |
;204/59R,72,73R,76,77 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Wilson et al., Transactions Electrochem. Soc., Vol. 80, pp.
151-161, (1941). .
Shlotterbeck, Transactions Electrochem. Soc., Vol. 92, pp. 377-389,
(1947)..
|
Primary Examiner: Edmundson; F. C.
Attorney, Agent or Firm: Johnston, Keil, Thompson &
Shurtleff
Claims
We claim:
1. A process for the manufacture of pinacols of the formula
##SPC4##
in which R is hydrogen or a hydrocarbon radical of one to six
carbon atoms and R' is a hydrocarbon radical of one to six carbon
atoms, by electrolytic hydrodimerization of carbonyl compounds of
the formula
R'--CO--R
in which R and R' have the above meaning, in non-compartmented
cells, wherein a mixture which contains from 5 to 75% by weight of
the carbonyl compound, from 5 to 90% by weight of the alcohol
corresponding to the carbonyl compound, of the formula ##SPC5##
from 0.1 to 3% by weight of the quaternary ammonium salt and from 0
to 3% by weight of water is used for the electrolysis.
2. A process as claimed in claim 1, wherein the mixture used for
the electrolysis in addition contains from 1 to 30% by weight of
dioxan and/or from 5 to 70% by weight of methanol.
3. A process as claimed in claim 1, wherein acetone is used as the
carbonyl compound.
Description
This application discloses and claims subject matter described in
German Pat. application No. P 23 43 054.8, filed Aug. 25, 1973,
which is incorporated herein by reference.
The invention is concerned with a new and particularly advantageous
process for the electrochemical manufacture of pinacols.
It is known that organic carbonyl compounds, especially aldehydes
and ketones, can be dimerized, with simultaneous hydrogenation, to
the so-called pinacols, that is to say to derivatives of the
alkylene glycol.
This hydrodimerization can only be carried out electrochemically on
a cathode whereof the hydrogen overvoltage is not too low, or by
means of a suitable reducing agent. It cannot be carried out under
catalytic hydrogenation conditions. Photochemical synthesis of the
pinacols proves rather unsatisfactory, in particular with regard to
the energy yield. In the electrochemical synthesis of a pinacol,
the hydrogen is provided by the protons of the solvent or of an
added acid: ##SPC1##
It is also known that the formation of pinacols from aromatic or
aromatic/aliphatic carbonyl compounds gives high yields, whilst
only moderate to poor yields of the pinacol are to be expected with
purely aliphatic compounds.
This situation is related to the stability of the radical
intermediates.
Starting from acetone, tetramethylethylene glycol, referred to as
"pinacol," is obtained. This compound is converted into pinacolene
or into 2,3-dimethylbutadiene by acid-catalyzed elimination of one
or two molecules of water, respectively.
Both these products derived directly from pinacol, and pinacol
itself, are interesting intermediates for the synthesis of
polymers, pharmaceutical products and pesticides. However, a broad
use of these products has hitherto been prevented by the fact that
only unsatisfactory methods of manufacture were available.
One process for the manufacture of pinacol consists, for example,
in reacting acetone with amalgams of aluminum, magnesium or sodium.
This process is still being used to manufacture pinacol on a small
scale. The process produces a great deal of isopropanol as a
by-product and the degree of utilization of the metal is relatively
low, so that the resulting costs are high. Furthermore, the salts
produced are an objectionable ballast. While the lastmentioned
disadvantage is avoided in direct electro-reduction on lead,
lead-copper alloy or lead-tin alloy cathodes in electrolytes
containing sulfuric acid or in alkaline electrolytes, this process
has not found industrial acceptance, because it suffers from
various disadvantages. Thus, the formation of highly toxic lead
organyls ("lead oils") as by-products at the cathode cannot be
avoided. Furthermore, a compartmented cell is required, since
otherwise acetone and pinacol undergo oxidative degradation at the
Pb/PbO.sub.2 anode. In addition, only poor current efficiencies are
attainable. Further, the electrolyte has to be neutralized before
working up to prevent the acid-catalyzed elimination of water to
give pinacolene or dimethylbutadiene, and this neutralization
produces large amounts of salts. It is also a disadvantage that
some of the acetone is reduced to the valueless by-product
isopropanol and that the solutions contain a large amount of water
which must in part be evaporated during working up.
It is an object of the present invention to provide a direct
electrochemical process for the manufacture of pinacols from
carbonyl compounds which avoids the above disadvantages. This
object is achieved by the process according to the invention.
According to the process of the invention, pinacols of the formula
II, in which R is hydrogen or a hydrocarbon radical of one to six
carbon atoms and R' is a hydrocarbon radical of one to six carbon
atoms are manufactured by electrolytic hydrodimerization of
carbonyl compounds of the formula I in non-compartmented cells,
using for the electrolysis a mixture which contains from 5 to 75%
by weight of the carbonyl compound, from 5 to 90% by weight of the
alcohol corresponding to the carbonyl compound, of the formula
##SPC2##
from 0.1 to 3% by weight of a quaternary ammonium salt and from 0
to 30% by weight of water.
The hydrocarbon radicals can be straight-chain or branched radicals
and can be saturated or unsaturated. Methyl, ethyl, propyl, butyl,
isopropyl, isobutyl, hexyl and cyclohexyl may be mentioned as
examples of hydrocarbon radicals.
Examples of suitable carbonyl compounds are acetone, acetaldehyde,
methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone and
methyl cyclohexyl ketone. The use of acetone and of the
corresponding alcohol isopropanol is of particulr interest in
industry.
The mixture to be subjected to electrolysis contains from 5 to 75%
by weight, preferably from 10 to 40% by weight, of the above
carbonyl compound. It also contains from 5 to 90% by weight,
preferably from 20 to 80% by weight, of the alcohol corresponding
to the carbonyl compound.
Suitable quaternary ammonium salts, of which from 0.1 to 3% by
weight, preferably from 0.5 to 1% by weight, are present in the
mixture to be subjected to electrolysis, are, for example,
compounds of the formula ##SPC3##
in which the radicals R are alkyl, such as alkyl of one to six
carbon atoms, for example methyl, ethyl, n-propyl, i-propyl or
n-butyl, aryl, such as phenyl, or aralkyl, such as benzyl, and X is
an anion, for example a sulfate, alkylsulfate, phosphate,
carbonate, arylsulfonate such as tosylate, tetrafluoroborate,
hexafluosilicate or perchlorate anion.
Particularly suitable conducting salts of this type are
tetraethylammonium ethyl-sulfate, tetraethylammonium sulfate and
tetrabutylammonium tetrafluoborate. Within the stated range, the
concentration of these salts should be kept as low as possible to
simplify the isolation of the pinacol and avoid its anoidic
degradation.
Since an electrosynthesis can be carried out with economical
current/voltage data even at minimal concentrations of the
conducting salt if cells with closely spaced electrodes are
employed, in DT-OS (German published application) No. 1,804,809,
and in J. Appl. Electrochem. 2, 59 (1972) is particularly suitable
for the process of the invention. In the present instance, the
electrode spacing in these cells in suitably from 0.1 to 1.0 mm,
preferably from 0.2 to 0.5 mm.
In principle, it is possible to employ as the cathode material any
metal of medium or high hydrogen overvoltage, that is to say Cu,
Ag, Cd, Zn, Sn, Pb, Tl and Hg, as the pure metals or in the form of
their alloys. However, particularly advantageous cathode materials
are graphite, carbon and graphite-filled plastics. Examples which
may be mentioned are the commercially available electrode carbons
of type LEK or EXN as supplied by Conradty, Nuremberg, West
Germany, or of type DIABON N, BS 70 or P 127 from Sigri, Meitingen,
West Germany or BASCODUR from Raschig, Ludwigshafen, West Germany.
The carbon cathodes should preferably be cleaned carefully before
the electrolysis, for example by rinsing them with concentrated
hydrochloric acid and/or by brushing them with pure quartz powder.
The carbon electrodes, which are usually porous, should preferably
be stored in distilled water. The current efficiency can be
increased by depositing a very thin layer, namely from 1 to 1,000
atom layers, preferably from 30 to 100 atom layers, of certain
metals, such as Hg, Pb, Cu, Ag or Au, individually or as mixtures,
on the cathode prior to the electrolysis. For this purpose, the
electrodes, in the ready-assembled cell, are dipped into a dilute
acidified aqueous solution of the corresponding metal salt such as
Pb(NO.sub.3).sub.2, HgSO.sub.4, CuSO.sub.4, AgNO.sub.3 or
AuCl.sub.3, and the metal is deposited at current densities of from
0.1 to 1 A/dm.sup.2 for the calculated period of time, whilst
circulating the solution. The metals are more probably distributed
over the surface as islands at selected points than as a coherent
layer.
A suitable anode material is above all lead dioxide, preferably as
a composite electrode on base surfaces of graphite, carbon, lead
titanium or tantalum. Other oxide anodes, such a Fe.sub.3 O.sub.4
MnO.sub.2, Tl.sub.2 O.sub.3 or RuO.sub.2 (on Ti) can also be
employed, as can gold, graphite, carbon and the platinum metals.
The use of graphite anodes is particularly advantageous. Since
graphite cathodes are also preferred, the bipolar electrodes are
thus conveniently simple discs or plates of graphite, carbon or
graphite-filled plastics. At pH values above 7, and in particular
above 10, it is also possible to employ metals which can be
passivated, such as Fe, Co, Ni or chrome nickel steel, as the anode
material in the process according to the invention. A preferred
bipolar electrode consists of graphite plates or carbon plates
which have optionally been coated with lead dioxide (100 to 500
.mu.) on the anode side, or to which thin foils of, for example, Ti
or Ni have been glued by means of a graphite-filled adhesive.
The current density used in the process according to the invention
is not critical and is, for example, from 0.1 to 100 A/dm.sup.2,
preferably from 5 to 25 A/dm.sup.2.
The temperature is suitably maintained at from 0.degree.to
50.degree.C. Whilst low temperatures increase the current yield,
they entail technical complications. For this reason, temperatures
of from 20.degree.to 35.degree.C are preferably used.
When using carbon cathodes, the pH proves to have little influence
and can be selected to be from 1 to 14. If the pH is not regulated
externally, it assumes a value of from 2 to 4 during the
electrolysis.
Movement of the bath is advantageous, and is essential when using a
capillary gap cell. Good convection is achieved by circulating the
electrolyte by means of a pump. The rate of flow parallel to the
electrodes is preferably set to values of from 1 to 30 cm per
second.
It is advantageous to continue the electrolytic hydrodimerization
until final concentrations (or stationary concentrations, in
continuous operation) of pinacol of from 1 to 30% by weight,
preferably from 5 to 20% by weight, have been reached. Separating
the unconverted carbonyl compound from the product presents no
problems.
In working up the material issuing from the electrolysis, it is
advisable first to adjust the pH to 7 by adding a little sodium
hydroxide solution, so as to avoid the acid-catalyzed rearrangement
to pinacolone during working up. The unconverted acetone and
isopropanol are stripped off, for example under reduced pressure.
The solution which remains is cooled, for example to 0.degree.C
whilst stirring, if necessary after addition of water. The pinacol
crystallizes out as pinacol hexahydrate, which is filtered off and
washed with a little ice water. The mother liquor contains the
quaternary ammonium salt and can be recycled to the electrolysis,
if appropriate after first extracting it with ether or methylene
chloride to remove water-soluble by-products.
Current efficiencies based on pinacol of more than 50% can be
achieved by the process of the invention. Particularly high current
efficiencies are obtained when from 1 to 30% by weight, preferably
from 3 to 10% by weight, of dioxane is added as the co-solvent.
These current efficiencies are substantially in excess of the
values of 37% (U.S. Pat. No. 2,485,258) and 44% (U.S. Pat. No.
2,422,468) hitherto given in the literature for the synthesis of
pinacol. The addition of methanol, in concentrations of from 5 to
70% by weight, preferably from 10 to 40% by weight, to the reaction
mixture proves to be particularly advantageous when graphite anodes
are used.
The process according to the invention can be carried out batchwise
or continuously. In continuous operation, the reaction mixture is
circulated continuously through the cell (and, preferably, through
a heat exchanger).
The process of the invention is carried out in a non-compartmented
cell. The preferred anode process is the dehydrogenation of the
alcohol, for example in accordance with the equation
CH.sub.3 --CHOH--CH.sub.3 .fwdarw. CH.sub.3 --CO--CH.sub.3 + 2
H.sup.+ + 2 .theta.
Thus a part of the ketone which is converted at the cathode is
produced from the alcohol at the anode. If the formation of pinacol
takes place cathodically with high yield, which is desirable, a
part of the ketone to be converted is introduced in the form of the
corresponding alcohol in the process according to the invention. In
this case, the acetone is consumed at the cathode, is a
single-electron reaction, more rapidly than it can be replaced from
the isopropanol, at the anode, in a two-electron reaction. On the
other hand, if there is a high cathodic subsidiary yield of
alcohol, it suffices if relatively little of the alcohol is
introduced initially. In any case, net production of this undesired
by-product can be prevented completely. Because the alcohol is
available in sufficient concentration at the anode, the anodic
reverse decomposition of the pinacol to the carbonyl compound, an
anodic reaction which normally takes place, is -- surprisingly --
substantially prevented.
In addition to the high current efficiency, the process according
to the invention has yet other advantages over the known processes.
Thus the production of salts, which is unavoidable when the acids
are neutralized, does not arise. Because of the low concentration
of the ammonium salts in the mixture, there is no solubilizing
effect of the pinacol. Since the solutions contain relatively
little water, only little energy is required to concentrate the
material issuing from the electrolysis.
EXAMPLE 1
The cell used is a capillary gap cell consisting of a stack of
circular horizontal plates of DIABON N (Messrs. Sigri) electrode
carbon, the discs being of 117 mm diameter and 10 mm thickness. The
plates are wired bipolar in series. The anode side of the plates is
provided with a 300 .mu. thick layer of PbO.sub.2 anodically
deposited from lead nitrate solution. The interior of the stack of
plates bears a 30 mm hole, so that the effective electrode surface
is 1 dm.sup.2. A spacing of 0.25 mm is maintained between the
plates by radially applied polyester strips. The stack of plates is
suspended from the cover of the cell. The current is supplied at
the ends of the bipolar stack of plates, via an insulated middle
axial in the case of the bottom end, or directly in the case of the
upper end. The reaction solution is pumped through a union on the
cover of the cell into the center of the stack of plates, flows
radially outward through the capillary gaps and is returned into
the center of the stack of plates via a heat exchanger. The cell,
which is further provided with a thermometer, a glass electrode and
an off-gas pipeline, is described German laid-open specification
No. 1,804,809.
At the start of the electrolysis, 1 kg of a mixture consisting of
50% by weight of acetone, 39.5% by weight of isopropanol, 10% by
weight of water and 0.5% by weight of tetraethylammonium ethyl
sulfate is introduced into the cell. A total of 138.6 ampere hours
is passed through the system at a current density of 10 A/dm.sup.2,
a temperature of 20.degree.C and a pH of from 2 to 3, (which
maintains itself automatically), whilst circulating the electrolyte
at 7.5 liters per minute. Since the stack consists of 6 pairs of
electrodes, this corresponds to an electrolysis time of 2.30 hours.
In this way, the acetone initially introduced is theoretically
converted to the extent of 60%. During the electrolysis, the
potential of 55 volt (9.2 volt per electrode pair) remains
practically constant.
After termination of the electrolysis, the liquid is colorless.
After taking a sample to determine the acetone (with NH.sub.2
OH.HCl) and adjusting the pH to 7.0 by adding 4.3 ml of 1 N NaOH
solution, the acetone and the isopropanol are stripped off in a
rotary evaporator at 40.degree.C under 100 mm Hg. A further 50 g of
water are added to the residue and the mixture is cooled to
0.degree.C. Hereupon, pinacol hydrate crystallizes out and is
filtered off quickly and rinsed with a little ice water. 98.5 g of
a pure white crystalline product containing 53% of pinacol, and
thus having a composition close to that of pinacol hexahydrate, are
obtained. A further 2.5 g of pinacol can be extracted from the
mother liquor by means of ether. Accordingly, the total pinacol
yield is 52.2 + 2.5 = 54.7 g. This corresponds to a current
efficiency of 20.3%. Assuming anodic dehydrogenation of isopropanol
with 100% current efficiency, a current efficiency of 70.4% for its
cathodic formation can be calculated from the acetone balance. 6.6
g of 2-methylpentane-2,4-diol were isolated as a high-boiling
by-product from the above ether extract. The subsidiary yield of
isopropanol had no nett effect in the process according to the
invention. The pinacol hexahydrate isolated as the main fraction
melts at 44.degree.C (literature value: 45.4.degree.C).
EXAMPLE 2
The electrosynthesis described in Example 1 was repeated, varying
the acetone : isopropanol ratio and in some cases also varying the
water content in the batches. The table which follows lists the
concentrations of the components, the amounts of current, the
current efficiencies based on pinacol, designated "CE," and the
cell potentials (for six electrode pairs), designated "U.sub.c."
The results show that optimum current efficiencies based on pinacol
are obtained at low acetone concentrations and high isopropanol
concentrations. In all experiments, the current density of 10
A/dm.sup.2, the temperature of 20.degree.C, and the conducting salt
concentration of 0.5% of tetraethylammonium ethyl-sulfate (=
NEt.sub.4.EtSO.sub.4) were kept constant.
A subsidiary yield of 2-methylpentane-2,4-diol of 26.3 and 22.8 was
isolated respectively from the two batches of lower water content
at the beginning of the table.
Table
__________________________________________________________________________
(1 kg batches) Composition (% by weight) Electrolysis data Acetone
Isopropanol H.sub.2 O CE (%) based U.sub.c (V). Q (Ampere on
pinacol (6 electrode hours) pairs)
__________________________________________________________________________
.sup.+ 84.5 10 5 5.6 49 136.8 74.5 20 5 6.8 51 137.8 65 15 19.5
14.3 42 122.5 50 39.5 10 20.3 55 138.6 40 49.5 10 23.8 56 138.7 30
59.5 10 27.5 66 111 20 69.5 10 33.9 60 106.1 per 1.5 kg 10 79.5 10
41.2 64 at 5 A/dm.sup.2 111 per 3 kg
__________________________________________________________________________
.sup.+ Comparative run
EXAMPLE 3
The temperature and the current density were varied under the
experimental conditions mentioned in Example 1. The results are
listed in the table.
Table ______________________________________ (Batches containing 1%
of NEt.sub.4.EtSO.sub.4) t (.degree.C) J[A/dm.sup.2] CE (%) based
U.sub.c [V] on pinacol (6 electrode pairs)
______________________________________ 20 10 20.3 41 10 10 23.8 49
0 10 29.8 58 20 25 22.7 75.5 20 40 24.8 115
______________________________________
It can be seen that the current efficiency rises substantially with
decreasing temperature and increasing current density.
EXAMPLE 4
The influence of dioxane as a co-solvent was examined in more
detail in the series of experiments which follows. The solutions
contained 40% of acetone, 2.5% of water, 1% of NEt.sub.4.EtSO.sub.4
and the amounts of dioxan listed in the table which follows, the
remainder consisting of isopropanol. The penultimate column
compares the initial potential with the final potential. The
experiments showed a slight tendency for the potential to rise, and
indicated the formation of small amounts of an acid by-product, but
no covering layers were detectable on the electrodes at the end of
the experiment. 138.7 ampere hours were used per kg of batch,
corresponding to a theoretical conversion of 60%. The current
density, temperature and other conditions of electrolysis were the
same as in Example 1.
______________________________________ % by wt. U.sub.c [V] of CE %
based (6 elec- Color of the crude solvent on pinacol trode pairs)
product after stripping ______________________________________ 27
dioxane 51 54/62 Yellow 20 dioxane 45 47/60 Light yellow 10 dioxane
43 53/59 Light yellow 5 dioxane 39 50/58 Light yellow 2 dioxane 37
52/58 Light yellow 1 dioxane 27 52/57 Light yellow
______________________________________
EXAMPLE 5
The cathode materials listed in the first column of the table which
follows were employed in order to investigate the influence of the
cathode material. In other respects, the experimental conditions
and the cell were identical with those in Example 1.
Table ______________________________________ (1 kg batches) Cathode
Atom layers CE (%) U.sub.c [V] for 6 of foreign based on electrode
metal pinacol pairs ______________________________________ DIABON N
(Messrs. Sigri) -- 20.3 55 DIABON N 30 Hg 27.5 55 DIABON N 100 Hg
29.1 54 DIABON N 300 Hg 26.8 54 DIABON N 100 Pb 27.7 55 CONRADTY
LEK -- 19.5 55 CONRADTY LEK 100 Hg 31.1 54 BASCODUR (Raschig) --
21.5 54 SIGRI BS 70 -- 15.0 53
______________________________________
In some experiments, the cathode was coated with foreign metals
prior to the electrolysis. Hg was deposited from a solution of 100
g of HgSO.sub.4 and 60 g of H.sub.2 SO.sub.4 per liter at 0.5
A/dm.sup.2, whilst circulating the solution. This required a
deposition time of 6 seconds for 100 atom layers of Hg, if it is
assumed that one atom layer contains 10.sup.15 atoms per cm.sup.2.
The lead was deposited from an acid lead tetrafluoborate bath,
using the same current density.
Comparison of the unmodified types of graphite shows that BASCODUR
and DIABON N give more advantageous results than LEK or BS 70.
However, coating LEK with Hg gives better current efficiencies that
coating DIABON N.
EXAMPLE 6
The experiments which follow and are summarized in the table were
carried out in the cell described in Example 1. The conditions of
electrolysis were the same as in Example 1, but the conducting salt
and the water concentration were varied. In the case of the
experiments with low water content and the experiments with
virtually anhydrous systems, 2-methylpentane-2,4-diol was again
obtained as a by-product, in the yields shown in the table. The
results show that the best current efficiencies based on pinacol
are obtained in the presence of tetrabutylammonium tetrafluoborate
(= NBu.sub.4 .BF.sub.4) with 2.5% of water. These conditions also
resulted in relatively little of the by-product
2-methylpentane-2,4-diol.
Table
__________________________________________________________________________
(1 kg batches) Conducting salt % H.sub.2 O % Ac % IP Pinacol
2,4-Dimethyl- Q (ampere) U.sub.c (%) g CE (%) pentane-2,4- hours)
diol (g) [V]
__________________________________________________________________________
0.5 NEt.sub.4.EtSO.sub.4 --* 59.5 40 51 16.9 24 137.7 60 " 2.5 57
40 50.5 17.2 20 132 57 " 19.5 40 40 53.4 18.6 -- 138.5 52 1.0
NBu.sub.4.BF.sub.4 --** 59 40 85.5 28.6 10.3 136.5 54 " 2.5 56.5 40
89.8 31.0 10.8 132 49 " 19.5 40 40 68.5 22.5 -- 138.5 47
__________________________________________________________________________
*Water content at end of experiment: 0.12% **Water content at end
of experiment: 0.23%
EXAMPLE 7
1 kg of a reaction mixture composed of 50% of methyl ethyl ketone,
39.5% of sec. butanol, 10% of water and 0.5% of NEt.sub.4.SO.sub.4
was introduced into the capillary gap cell described in EXample 1,
but consisting of four electrode pairs. The DIABON-N cathodes were
coated with "100 atom layers" of mercury -- as in Example 5 --
prior to the experiment. The electrolysis was carried out at 10
A/dm.sup.3 and 20.degree.C until an amount of current of 111.8
ampere hours had been passed through, corresponding to a
theoretical conversion of 60%. Accordingly, the electrolysis time
was 2.8 hours. During the electrolysis, the cell potential rose
from 50.5 to 55 volt. The pH at the end of the electrolysis was
5.0. For working up, the low-boiling constituents of the
electrolyte were distilled off under reduced pressure. 77.2 g of a
brown crude product were left; this was examined directly by gas
chromatography. It contained 12.3% = 9.5g of pinacol
(1,2-dimethyl-1,2-diethyl glycol), corresponding to a current
efficiency of 3.1%.
EXAMPLE 8
The capillary gap cell described in Example 1 consists in this case
of a stack of DIABON-N discs (6 .times. 1 dm.sup.2, d = 250.mu.).
Thus, in this experiment, the anode is also composed of graphite.
At the start of the electrolysis, 1 kg of reaction mixture A or B
is introduced into the cell.
______________________________________ A 50% of acetone 39% of
isopropanol 10% of water 1% of NEt.sub.4.EtSO.sub.4 B 50% of
acetone 20% of methanol 19% of isopropanol 1% of
NEt.sub.4.EtSO.sub.4 ______________________________________
These reaction mixtures are reacted as in Example 1, at 10
A/dm.sup.2, 20.degree.C and a pH of from 3 to 4, which maintains
itself automatically, the amount of current being 138.6 ampere
hours (corresponding to an electrolysis time of 2.3 hours and a
theoretical conversion of 60%).
In case A, the potential assumes a total value of 44 volt. During
the electrolysis, the anodic graphite suffers some attack and the
electrolyte turns black due to dispersed graphite particles. After
the electrolysis, a total amount of 4.5 g of graphite dust can be
isolated. The current efficiency based on pinacol is found to be
21.5% and the energy requirement for pinacol formation is found to
be 15.5 kWh/kg.
In case B, the potential is only 37 volt (at the 6 electrode
pairs). During the electrolysis, the anodic graphite is hardly
attacked and the liquid remains almost clear. The graphite dust
filtered off after the electrolysis weighs 0.1 g. Pinacol is formed
with a current efficiency of 19.0%. The energy required for pinacol
formation is 14.7 kWh/kg.
* * * * *