Preparation of Vitamin K3 in Mo–V–P Heteropoly Acid Solutions by Diene Synthesis

Article abstract of DOI:10.1134/S0023158420010012

Abstract: The possibility of obtaining vitamin K₃ (2-methyl-1,4-naphthoquinone, menadione) by diene synthesis from accessible substrates such as 2-methylphenol (o-cresol) and 2-methylaniline (o-toluidine) was shown. The bifunctional catalysts of these processes are the aqueous solutions of Mo–V–P heteropoly acids, which allow the oxidation and diene synthesis to be performed as a one-pot process.

Full text of DOI:10.1134/S0023158420010012

ISSN 0023-1584, Kinetics and Catalysis, 2020, Vol. 61, No. 2, pp. 276–282. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Kinetika i Kataliz, 2020, Vol. 61, No. 2, pp. 254–261.
Preparation of Vitamin K in Mo–V–P Heteropoly Acid Solutions
3
by Diene Synthesis
L. L. Gogin * and E. G. Zhizhina
а,
а
а
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
е-mail: gogin@catalysis.ru
Received June 14, 2019; revised July 1, 2019; accepted July 4, 2019
*
Abstract—The possibility of obtaining vitamin K (2-methyl-1,4-naphthoquinone, menadione) by diene syn-
3
thesis from accessible substrates such as 2-methylphenol (o-cresol) and 2-methylaniline (o-toluidine) was
shown. The bifunctional catalysts of these processes are the aqueous solutions of Mo–V–P heteropoly acids,
which allow the oxidation and diene synthesis to be performed as a one-pot process.
Keywords: hydroquinone, naphthoquinones, heteropoly acids, oxidation, diene synthesis
DOI: 10.1134/S0023158420010012
INTRODUCTION
-Methyl-1,4-naphthoquinone (vitamin K ,
bandry to increase the productivity of all types of ani-
mals [1]. The growing demand for K group vitamins
has stimulated a search for effective methods for their
synthesis.
2
3
menadione, MD) is a fat-soluble vitamin of vitamin K
group. It is necessary for the biosynthesis of pro-
thrombin and other blood coagulation factors and is
involved in bone tissue mineralization processes.
Menadione is a parent compound for all K group vita-
mins: vicasol—a water-soluble (bisulfite) form of vita-
Industrial Methods for the Synthesis of Vitamin K3
The main method for the industrial production of
min K —and vitamins K and K are obtained from it. MD is the noncatalytic oxidation of 2-methylnaph-
3
4
1
MD in the form of vicasol is widely used in medicine thalene (MN) with a chromium mixture by reaction (I)
for treatment of many diseases and in animal hus- using a fivefold excess of CrO
[2].
3
O
CH3
2CrO + 3H SO
4
CH3
+ Cr2(SO4)3 + 4H2O.
+
(I)
3
2
O
MN
MD
The production of vitamin K by this technology is
Many other methods for the synthesis of menadi-
3
not environmentally friendly because of the abun- one by oxidation of MN were proposed in addition to
dance of wastewater containing toxic chromium com- the above process [3–6], but all of them did not
pounds, tar, and acids. The production is also uneco- become more effective than the existing industrial
nomical as the selectivity of the target reaction (I) is method. Also, there are developments in which diene
below 50%. 2-Methylnaphthalene is an inaccessible synthesis followed by the oxidation of adducts is used
raw material: it is isolated from coal tar together with to obtain vitamin K
[7, 8]. The disadvantage of these
3
1
-methylnaphthalene, after which the desired isomer methods is the multistage and environmentally non-
is separated by freezing.
friendly process. Thus, in the patent [7], it was pro-
Abbreviations: MD, 2-methyl-1,4-naphthoquinone (vitamin K , menadione); MN, 2-methylnaphthalene; HPA, heteropoly acid;
3
Su, substrate; х, the number of V atoms in the HPA; m, the degree of reduction of HPA-х equal to the number of accepted electrons or
IV
the number of V ions; Е, redox potential of the HPA-х solution; MBQ, 2-methyl-1,4-benzoquinone; DMSO, dimethyl sulfoxide;
SHE, standard hydrogen electrode.
276

PREPARATION OF VITAMIN K3
posed that vitamin K be synthesized from 1-acetoxy-
277
3
m 2Su + m 2H O+ HPA-x
2
(
II)
1
,3-butadiene and 2-methyl-1,4-benzoquinone (toluqui-
none), forming a mixture of isomeric adducts with a
yield of ~60%. The resulting adducts can be oxidized
→
m 2SuO+ H HPA-x.
m
It is very important for catalysis that the HPA-x
to menadione with either 30% nitric acid or a mixture solutions are characterized by reversible oxidizability;
i.e., their reduced forms (H HPA-x, where m is the
of sodium nitrite and acetic acid at 50–60°C with a
m
yield of ~80%. However, neither the starting diene nor degree of reduction of HPA-x equal to the number of
IV
quinone are ready-made industrial products, and they accepted electrons or the number of V ions) are capable
also need to be synthesized: diene is synthesized from of being oxidized by molecular oxygen with regeneration
crotonic aldehyde and acetic anhydride, and quinone of the initial form of HPA-x by the reaction
is obtained by the oxidation of o-toluidine.
Н HPA-x + m 4O → HPA-х + m 2H O. (III)
m
2
2
Therefore, in the presence of HPA-x solutions, a
unique opportunity to close the catalytic cycle of the
two-stage oxidation (IV) of Su with oxygen appears, in
which the reversibly acting oxidant (HPA-x) actually
acts as a catalyst. Note that in Mo–V–P HPA-x solu-
tions, only the vanadium atoms are involved in the
Synthesis of Menadione
in Мо–V–P Heteropoly acid Solutions
In the search for new technologies for the produc-
tion of menadione in the late 1990s, an original solu-
tion to this problem was proposed at Boreskov Insti-
tute of Catalysis, Siberian Branch, Russian Academy
of Sciences [9, 10]. The new low-waste technology for
V
IV
redox transformations: V ꢀ V .
HPA-x
Su + 1 2O ⎯ ⎯ ⎯ ⎯ →SuO.
(IV)
2
The HPA-x solutions have high stability [20, 21];
therefore, the HPA-x solution regenerated by reaction
the synthesis of vitamin K , later called Vikasib (Sibe-
3
rian Vikasol), is based on the use of aqueous solutions
(
III) can be repeatedly used in the target reaction (II)
of Mo–V–P heteropoly acids (H
PMo
V O ,
3
+ x
12 – x x 40
in the second and subsequent cycles, including reac-
HPA-x, where x is the number of V atoms in HPA-x) as
the catalysts of oxidation. In the new process, the oxi-
dized substrate (Su) was 2-methylnaphthol-1, in contrast
to 2-methylnaphthalene used in the industrial process.
tions (II) + (III).
The reversible oxidizability of HPA-x solutions (in
contrast to CrO used in industrial reaction (I))
3
became the main distinction of the new low-waste
The HPA-х solutions are used as selective catalysts Vikasib technology [22]. Optimization of the process
of partial oxidation of various organic compounds provided 90% selectivity of the oxidation of 2-methyl-
with oxygen [11–19], occurring by the equation
naphthol-1 to menadione by reaction (IIa).
OH
O
CH3
CH3
m/4
+ m/4 H O + HPA-x
m/4
+ HmHPA-x.
(IIa)
2
O
MD
The use of this technology in Russia, however, is
The present study shows that by combining the
limited by the shortage of raw materials because naph- acid-catalyzed diene synthesis and oxidation in the
thol-1, from which 2-methylnaphthol-1 could be presence of HPA-x solutions, it is possible to obtain
obtained by methylation [23], is not produced in Rus- menadione in one technological stage from 2-methyl-
sia. Therefore, we sought for alternative methods for phenol (o-cresol) or 2-methylaniline (o-toluidine) in
the synthesis of menadione from more accessible sub- the presence of 1,3-butadiene.
strates in HPA-x solutions.
EXPERIMENTAL
Previously, we showed that HPA-x solutions,
which are strong Brönsted acids, are capable of exhib-
iting bifunctional (acid and oxidative) properties, cat-
Menadione was synthesized by reaction (II) in a
thermostatted two-necked 100 mL glass flask while
alyzing both diene syntheses and oxidations [16]. In stirring the reaction mixture with a magnetic stirrer in a
HPA-x solutions in an atmosphere of 1,3-butadiene, 1,3-butadiene atmosphere. An exact sample of o-cresol
9
,10-anthraquinone can be synthesized from 1,4- or the calculated volume of o-toluidine was placed in
naphthoquinone or hydroquinone. In this case, the the flask with a certain amount of 0.25 M HPA-x solu-
oxidation and Diels–Alder reaction proceed in one tion (the number of vanadium atoms x in HPA-x was
technological stage [16].
varied). The flask was connected to a chamber filled
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2
78
GOGIN, ZHIZHINA
8
.1 8.0 7.9 7.8 7.7 7.6
ppm
9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 ppm
1
Fig. 1. H NMR spectrum of the isolated menadione in CCl .
4
with 1,3-butadiene and blown through a long tube finely dispersed black precipitate, which was the prod-
lowered to the solution surface; the second throat was uct of the oxidative polymerization of o-toluidine.
closed, and the reaction was conducted at a given tem-
perature (20–60°C). The reaction progress was moni-
tored by GLC using a Khromos GKh-1000 chromato-
graph (Khromos, Russia; SE-Z0 type capillary col-
umn, thermal programming in the range 100–250°C).
The by-products of the conversion of 1,3-butadi-
ene in the HPA-x solution were identified by chro-
mato-mass spectrometry. The spectra were recorded
on a GCMS-QP2010 Ultra spectrometer (Shimadzu,
Japan).
The state of the catalyst was controlled by the pro-
The Мо−V−P-HPA-х (х ≥ 4) solutions of various
cedure described in [20, 24], intermittently monitoring (Keggin and modified) compositions were prepared
the decrease in the redox potential (E) of the HPA-x by the procedure described in [25, 26], and the solu-
solution during the reaction. The reaction products were tions were regenerated in an autoclave at 160−180°C
extracted with benzene or diethyl ether (3 × 20 mL),
dried over calcium chloride, then the solvent was dis-
tilled off, and the residue was weighed. The choice of
extractant made it possible to almost quantitatively
extract the reaction products from the reaction mix-
ture (which was confirmed by GLC). The quantitative
extraction of menadione was performed by chromatogra-
phy through silica gel (chloroform as an eluent), the sol-
vent was distilled off, the amount of MD (in grams) was
under oxygen pressure (P = 4 atm) by the procedure
O2
of [27]. The regenerated HPA-x solutions completely
recovered their initial activity (initial E value); there-
fore, they were repeatedly used (for up to 30 cycles) in
the target reaction (II). During the multicycle experi-
ments, no vanadium-containing substance precipi-
tated from solution. Low-vanadium HPA-x (x ≤ 3)
solutions were not used as the rate of their regenera-
tion was significantly lower than that of the HPA-4
solution.
1
determined, and the yield was calculated. Then the H
NMR spectrum was recorded in CCl (Fig. 1).
4
The purity of the isolated product was at least 98%.
Silufol UV-254 plates were also used for express deter-
mination of MD. The IR spectra of the product were
RESULTS AND DISCUSSION
Here, we solved the problem of synthesizing MD
recorded on an IR-Affinity-1 spectrometer (Shi- by diene synthesis from accessible substrates such as
madzu, Japan) in KBr pellets.
o-cresol (2-methylphenol) and o-toluidine (2-meth-
ylaniline) (Scheme 1). At the first stage of the study,
When o-toluidine was used as a substrate, the reac-
tion mixture was filtered at the end of the reaction the Keggin solution of HPA-4 (H PMo V4O40) [28]
7 8
(before the extraction of the products) to separate the was used as a bifunctional catalyst for this process.
X
O
O
O
O
CH3
CH3
CH3
CH3
CH3
HPA-x
HPA-x
HPA-x
−2H, −2e−
HPA-x
−2H, −2e−
−
+
−
2H, −2e
(H )
O
O
O
O
МD
X = OH, NH2
Scheme 1. One-pot synthesis of menadione from о-cresol and о-toluidine
in Мо−V−P-HPA-х solutions in a 1,3-butadiene atmosphere.
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PREPARATION OF VITAMIN K3
279
Table 1. Preparation of vitamin K from о-cresol and о-toluidine by diene synthesis in the 0.2 М HPA-4 solution
3
Substrate, g/mmol
HPA-4, mL
HPA-4 : substrate molar ratio
Т, °C
Yield of MD, %
о-Cresol, 0.27/2.5
18.8
1.5
1.5
1.5
2.0
1.0
2.0
2.0
2.0
3.75
80
60
40
40
80
80
60
40
40
18.9
20.9
16.7
18.0
20.0
27.1
28.5
24.3
21.1
18.8
18.8
25.1
о-Toluidine, 0.13/1.25
6.5
1
1
1
2
2.5
2.5
2.5
3.5
Reaction conditions: 1,3-butadiene atmosphere, 2 h, 100% conversion of the substrate.
When these substrates are introduced in the HPA-4
Table 1 presents the results of the study of the total
solution in a 1,3-butadiene atmosphere (Scheme 1), synthesis of vitamin K in accordance with Scheme 1.
3
they are first quickly oxidized to toluquinone, which is According to these data, the yield of MD does not
then condensed with 1,3-butadiene by the Diels– exceed 21% when it is synthesized from o-cresol in the
Alder reaction. At the final stages of the process, HPA-4 0.2 M solution of HPA-4 in the presence of 1,3-buta-
oxidizes the adducts of diene synthesis and is itself diene and 29% in the synthesis from o-toluidine. In
gradually reduced. The depth and rate of the process the case of o-cresol, which has high reactivity, tar
according to Scheme 1 are determined by the oxidiz- forms in large amounts.
ing capacity of the HPA-x solution, which can be
Both methods for the synthesis of vitamin K cer-
3
expressed by the product [HPA-x] × Δm, where Δm is
tainly have disadvantages. Nevertheless, the synthesis
the change in the degree of reduction of HPA-x during
from o-toluidine by diene synthesis looks slightly more
the one-pot process [20]. We believed that the high
promising than the synthesis from o-cresol. We
V
concentration of V in the HPA-x solution would
expected that optimization of this process would make
allow complete oxidation of the adducts of diene syn-
it possible to reduce polymer formation and thereby to
thesis and a shift of the process according to Scheme 1
increase the yield of MD.
toward menadione.
In the case of o-toluidine, the low yield of MD was
A distinction of the new processes is that they are determined by the formation of a black precipitate of
performed in one technological stage (i.e., are one-pot polytoluidine due to the oxidative polymerization of
processes), and the ability of HPA-x solutions to be o-toluidine in HPA-4 solution at the first stage of the
regenerated with oxygen by reaction (III) ensures the process simultaneously with the formation of the
environmental friendliness of the method for the pro- desired product according to Scheme 1. The IR spec-
duction of vitamin K . In addition, thorough washing trum of the obtained polymer is shown in Fig. 2.
3
of the organic phase and reaction products with water
–1
The bands in the range 3200–3500 cm are prob-
from possible impurities ensures the absence of traces
ably related to the vibrations of the N–H bond; the
of heavy metals (Mo, V) in the resulting vitamin K .
3
–1
bands at 1600–1650 cm are due to the C=N bond
1
Figure 1 shows the H NMR spectrum of the isolated
vibrations. The precipitate partially dissolved during
the process and was oxidized to toluquinone. How-
ever, the bulk of it remained unchanged; thus, some
part of the substrate was actually pulled out of the tar-
get process, which reduced the yield of MD.
menadione.
Before studying the one-pot processes described by
Scheme 1, the oxidations of o-cresol and o-toluidine
to 2-methyl-1,4-benzoquinone (MBQ) were studied
separately, and it was shown that these substrates were
The conditions of the one-pot synthesis of MD
oxidized to MBQ with low yields (20–30%). It was from o-toluidine were varied in order to reduce the
assumed that in the presence of 1,3-butadiene, the contribution of the side reactions of substrate polym-
rates of side processes, in particular, tar formation, erization and an increase in the formation rate of vita-
could be reduced due to the fact that the Diels–Alder min K . In particular, o-toluidine was introduced in
3
acid-catalyzed reaction would proceed simultaneously the reaction mixture in one portion and also by gradu-
with the oxidation of o-cresol and o-toluidine in the ally dropping its dimethyl sulfoxide (DMSO) solution
HPA-x solution. In this case, the instant concentra- to reduce the instant concentration of the substrate in
tions of the highly reactive radical particles in solution the HPA-4 solution. DMSO was chosen because of
will be lower, due to which higher yields of MBQ and, the partial solubility of polytoluidine in it; this was
accordingly, vitamin K can be obtained in a one-pot expected to facilitate further oxidation of the polymer
3
process.
to toluquinone. It turned out, however, that the intro-
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2
80
GOGIN, ZHIZHINA
Wave number, cm–1
1500 1000 500
4000
3500
3000
2500
2000
100
8
0
0
0
0
0
1173.0
301.6
513.08
1
6
4
2
1
573.8
1056.1
3214.9
1650.9
8
73.03
9
51.9
795.96
Transmission, arb. units
Fig. 2. IR spectrum of polytoluidine that precipitated from the HPA-4 solution during the preparation of vitamin K from o-tolu-
3
idine by diene synthesis in the presence of 1,3-butadiene.
duction of o-toluidine in the reaction mixture had icant amounts. The total amount of by-products
almost no effect on the amount of the polymer prod- formed from 1,3-butadiene in the one-pot process in
uct and, accordingly, on the final yield of MD.
HPA-x solutions according to Scheme 1 did not
exceed 2%.
For the same purpose, the one-pot process accord-
ing to Scheme 1 was studied in the presence of an
additional organic solvent (DMSO) in the reaction
mixture. In this case again, however, the desired char-
acteristics of MD synthesis from o-toluidine could not
be improved. This suggests that polymerization of the
substrate proceeds much more readily than its oxida-
tion to toluquinone. Nevertheless, it is important that
polytoluidine, which forms as a by-product in the oxi-
dation of o-toluidine, does not completely drop out of
the reaction. It can be separated from the reaction
mixture, oxidized to 2-methyl-1,4-benzoquinone,
and again introduced in the reaction according to
Scheme 1. It also important that polytoluidine, like
polyaniline, is a very valuable product: it has high elec-
tric conductivity and can be used as a current conduc-
tor in electric engineering [29].
In the case of o-cresol used as a substrate in the
process according to Scheme 1, the main contribution
to the formation of by-products is made by the oxida-
tive polymerization of 2-methylphenol. Similar reac-
tions of the oxidative polymerization of 2-methyl-
naphthol-1 were studied in [30], where it was shown
that the selectivity of the catalyst based on the HPA-x
solution with respect to menadione depends on the
ratio of the rates of oxidative polymerization of inter-
mediates and the formation of the desired product.
The ratio, in turn, depends on the composition of
HPA-x and the reaction method and conditions. In
the developed Vikasib technology [30], a significant
increase (from 45 to 90%) in the yield of menadione
during the oxidation of 2-methylnaphthol-1 was
achieved. We believed that the synthesis of vitamin K
3
For the one-pot processes using o-cresol and from o-cresol according to Scheme 1 could also be
o-toluidine as substrates, the temperature was varied optimized.
from 40 to 80°C. According to Table 1, the optimum
To solve this problem, modified HPA-x solutions
temperature is 60°C in both cases.
of non-Keggin compositions with higher vanadium
To obtain a complete picture of possible products contents (x = 7, 10) were chosen at the second stage of
during the diene synthesis, we studied the possibility the study of the possibility of using accessible raw
of side reactions of 1,3-butadiene in HPA-x solutions. materials for producing vitamin K in HPA-x solutions
3
For this purpose, blank experiments were performed, by diene synthesis [25]. High vanadium concentra-
in which 1,3-butadiene was fed, in the absence of other tions in the modified solutions guarantee their
substrates, into the HPA-x solutions (HPA-3, GPA-4, increased oxidative capacity and hence productivity.
and GPA-6) for 5 h. An analysis of the reaction products
showed that hydration of 1,3-butadiene into 3-buten-2-
ol occurred at low rates, and the latter was further con-
verted into methyl vinyl ketone (Scheme 2).
V
For example, the V concentration in the 0.30 M
modified solution of HPA-7 (Н Р Мо V O ) is
10
3
18
7
84
2
.6 times higher than in the 0.2 М solution of HPA-4
(
Н РМо V О ) often used in catalytic reactions. Due
7
8
V
4
40
to this V concentration, the modified HPA-x solu-
tions retain their high oxidative potential E [20]
throughout the whole process according to Scheme 1,
guaranteeing complete oxidation of the adducts of
CH =CH−CH=CH
2
2
→
CH =CH−CH
(
OH
)
−CH → CH =CH−COCH
3
2
3
2
Scheme 2. Transformation of 1,3-butadiene in aqueous
solutions of Мо−V−P-HPA-х.
diene synthesis to vitamin K .
3
In addition, linear and branched oxygen-contain-
Another important fact is high stability of the mod-
ing products of polymerization of 1,3-butadiene ified HPA-x solutions; they remain homogeneous up
(
molecular mass 122, 164, 166) were found in insignif- to 180°C (the maximum temperature for fast regener-
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PREPARATION OF VITAMIN K3
281
Table 2. Preparation of vitamin K from о-toluidine by diene
Analyzing the results, we can conclude that the
optimum temperature of the one-pot synthesis of MD
from o-toluidine in modified high-vanadium HPA-x
solutions is 60°C, as in the presence of Keggin HPA-4.
3
synthesis in the 0.25 М solutions of HPA-7, HPA-10, and
HPA-4
о-
HPA-х :
о-toluidine Т, °C
molar ratio
HPA-х,
mL
Yield
of MD, %
Toluidine,
g/mmol
V
It can be seen that excess V concentration is not
required for complete oxidation of the adducts of
diene synthesis in accordance with Scheme 1, as in the
HPA-7 and HPA-10 solutions. For these HPAs-x, the
highest yields of MD (~32%) are observed at a molar
ratio of HPA-x to o-toluidine of 2–3. The oxidative
potential of these solutions remains high enough
throughout the one-pot process (above 0.85 V relative
to SHE), providing complete oxidation of the adducts.
Clearly, due to the side reactions at the first stage of
the process, the amount of these adducts is only ~30%
of the theoretical value.
0
0
0
0
.107/1.0 HPA-7; 20
5
3
3
3
5
5
3
3
3
2
5
5
2
40
40
60
80
60
40
40
60
80
60
60
60
60
27.2
28.1
32.4
30.0
31.2
28.0
28.5
32.8
29.9
32.3
32.6
27.3
28.0
.107/1.0 HPA-7; 12
.107/1.0 HPA-7; 12
.107/1.0 HPA-7; 12
0.064/0.6 HPA-7; 12
0.107/1.0 HPA-10; 20
0.107/1.0 HPA-10; 12
0.107/1.0 HPA-10; 12
0.107/1.0 HPA-10; 12
0.107/1.0 HPA-10; 8
Another possibility of increasing the MD yield in
the overall process according to Scheme 1 was studied.
For this purpose, an organic solvent dioxane was
added to the reaction mixture before the experiment,
which is effective in two-phase organic reactions [31].
It was assumed that a water-miscible solvent would
facilitate the mixing of the two phases, reduce the sub-
strate concentration in the organic phase, and thus
would reduce the side processes of condensation. It
was found, however, that the presence of dioxane did
not affect the final yield of MD in any way.
0.064/0.6 HPA-10; 12
0
0
.107/1.0 HPA-4; 20
.107/1.0 HPA-4; 8
Reaction conditions: 1,3-butadiene atmosphere, 2 h, 100% con-
version of the substrate.
ation of HPA-x solutions), providing long life of cata-
lysts based on them [20]. Based on all these factors, we
believed that the catalysts based on modified HPA-x
could be promising for use in one-pot processes
according to Scheme 1.
Thus, it was shown that vitamin K can be obtained
3
from o-toluidine in solutions of modified Мо−V−P-
HPAs-x with a yield of up to 33% according to Scheme 1.
The polytoluidine by-product obtained in this pro-
cess may be used, for example, in electrotechnical
industry [29].
Note that when MD was obtained from o-cresol in
the presence of both HPA-7 and HPA-10, it was
impossible to obtain a higher yield of the desired prod-
uct than with HPA-4 (21%). With this substrate, the
side processes of tar formation in HPA-x solutions
occur much more easily than diene synthesis,
although the acidity of the modified HPA-x solutions
is significantly higher than that of the HPA-4 solution
CONCLUSIONS
The possibility of the catalytic production of vita-
min K in the presence of HPA-x solutions in one
3
[
20]. It was assumed that by increasing the acidity of
technological stage from o-cresol and o-toluidine in a
the catalyst solution it would be possible to increase
1
,3-butadiene atmosphere was shown. In this case,
the rate of the reaction of o-cresol and 1,3-butadiene
HPA-x acts as a bifunctional (acid and oxidative) cat-
(
acid-catalyzed reaction), but this did not happen.
alyst. Despite the low yield of the desired product
Therefore, there is some other reason for the low yield
of MD. The acidity of the HPA-4 solution was already
high enough for effective diene synthesis; neverthe-
(
below 33%), the new method is attractive because
menadione is synthesized from accessible raw materi-
als and the multistage process is performed in one
less, the rate of the side reactions of o-cresol conden- technological stage. The regeneration of HPA-x solu-
sation was high in all HPA-x (Keggin and modified) tions with oxygen opens up prospects for the develop-
solutions. Therefore, our study focused on the synthe- ment of new methods for the synthesis of vitamin K
3
sis of MD from o-toluidine.
in the presence of HPA-x as a bifunctional catalyst.
Table 2 presents the data obtained by studying the
one-pot synthesis of vitamin K in accordance with
3
FUNDING
Scheme 1 from o-toluidine in the presence of 1,3-butadi-
ene in solutions of modified high-vanadium HPA-7
This study was performed under government contract at
the Institute of Catalysis, Siberian Branch, Russian Acad-
emy of Sciences (project no. АААА-А17-117041710081-1).
(
Н Р Мо V O ) and HPA-10 (H P Mo V O ). For
10 3 18 7 84 17 3 16 10 89
comparison, the table gives the data for HPA-4.
KINETICS AND CATALYSIS Vol. 61 No. 2 2020

2
82
GOGIN, ZHIZHINA
18. Zhizhina, E.G., Odyakov, V.F., and Simonova, M.V.,
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No. 2
2020