Model of selectivity to methyl pelargonate in hydrocarbomethoxylation of 1-octene in the presence of the Pd(PPh3)2Cl2—PPh3—p-toluenesulfonic acid catalytic system

Article abstract of DOI:10.1007/s11172-020-2935-z

The model of selectivity to methyl pelargonate was developed for the hydrocarbomethoxylation of 1-octene catalyzed by the Pd(PPh₃)₂Cl₂—PPh₃—p-toluenesulfonic acid system (378 K). The ratio of the rate of methyl pelargonate formation to the sum of the rates of formation of three isomeric esters (reaction products) was accepted as the differential selectivity of the reaction. The model represents a system of equations relating the differential selectivity of the reaction to the CO pressure and concentrations of methanol, PPh₃, and p-toluenesulfonic acid. The model adequately depicts the experimental data in a wide range of 1-octene conversions up to 95.5%. The regularities of a change in the reaction selectivity were substantiated using the hydride multiroute mechanism of hydrocarbomethoxylation of 1-octene.

Full text of DOI:10.1007/s11172-020-2935-z

Russian Chemical Bulletin, International Edition, Vol. 69, No. 8, pp. 1561—1568, August, 2020
1561
Model of selectivity to methyl pelargonate in hydrocarbomethoxylation of 1-octene
in the presence of the Pd(PPh3)2Cl2—PPh3—p-toluenesulfonic acid
catalytic system
S. A. Batashev and N. T. Sevostyanova
Tula State Lev Tolstoy Pedagogical University,
125 prosp. Lenina, 300026 Tula, Russian Federation.
Fax:+7 (487 2) 65 7807. E-mail: piligrim.tula.ru@gmail.com
The model of selectivity to methyl pelargonate was developed for the hydrocarbometh-
oxylation of 1-octene catalyzed by the Pd(PPh3)2Cl2—PPh3—p-toluenesulfonic acid system
(378 K). The ratio of the rate of methyl pelargonate formation to the sum of the rates of forma-
tion of three isomeric esters (reaction products) was accepted as the differential selectivity of
the reaction. The model represents a system of equations relating the differential selectivity of
the reaction to the CO pressure and concentrations of methanol, PPh3, and p-toluenesulfonic
acid. The model adequately depicts the experimental data in a wide range of 1-octene conver-
sions up to 95.5%. The regularities of a change in the reaction selectivity were substantiated
using the hydride multiroute mechanism of hydrocarbomethoxylation of 1-octene.
Key words: hydrocarbomethoxylation, 1-octene, methyl pelargonate, palladium catalyst,
selectivity model.
The hydrocarbalkoxylation of 1-octene and its isomers
attracts attention of researchers, since this reaction pro-
vides a possibility of the simple one-pot synthesis of esters,
in particular, methyl pelargonate (1), from alkene, CO,
and alcohol under mild conditions.1—6 Methyl pelargonate
(product 1) is of practical interest as a potential half-
product in pharmaceutical synthesis.4—6 The homogeneous
systems including the catalytic palladium precursor and
promoter additives of organophosphines and acids are the
most efficient catalysts of hydrocarbalkoxylation.2—13 The
presence of phosphines imparts thermal stability needed
to the catalytic palladium complexes in the redox medium,
which is formed during hydrocarbalkoxylation under the
action of alcohols, CO, and water, and makes it possible
to achieve high rates and yields of target products being,
as a rule, linear.2,3,6—9 Triphenylphosphine and a series
of diphosphines manifest the highest promoting ability
among organophosphines. For example, high conversions
and enhanced selectivities to the linear products were
observed for the hydrocarbomethoxylation of terminal and
internal alkenes catalyzed by the Pd2(dba)3—bis(di-tert-
butylphosphinemethyl)benzene—methanesulfonic acid
system.2 For cyclohexene hydrocarbomethoxylation, the
promoter additives of diphosphines of the norbornane and
norbornene structures with Pd(OAc)2 provided a possibil-
ity to achieve higher reaction rates than those obtained
when triphenylphosphine was used. These parameters were
actually observed for the P/Pd ratios by 8—65 times lower.
The presence of trans-diphosphines, for instance, trans-
2,3-bis(diphenylphosphinemethyl)norbornane, favors the
acceleration of cyclohexene hydrocarbomethoxylation
compared to cis-diphosphines.10 A substantial drawback
of many diphosphines is their high cost, which diminishes
the attractivity for engagement in development of industri-
ally important processes. Another type of promoter addi-
tives to the palladium catalysts of hydrocarbalkoxylation
is presented by acids, such as mainly strong protonic acids
(mainly p-toluenesulfonic acid)2,6—13 and Lewis ac-
ids.3—5,7—9 Strong H-acids act as a hydrogen source
participating in the formation of hydride palladium com-
plexes, which are the key intermediates in the hydride
mechanism of hydrocarbalkoxylation. An increase in the
concentration of H-acids results in a significant increase
in the hydrocarbalkoxylation rate, but alkene isomerization
is simultaneously accelerated and the reaction selectivity
decreases.6,7,13 Nevertheless, high selectivity to the yield
of linear esters can be obtained in the presence of strong
protonic acids in particular cases.2 No alkene isomeriza-
tion occurs, as a rule, in the presence of Lewis acids,3—5
but the selectivity to the linear product does not always
remain high.4,5 Unfortunately, the influence of various
factors on the selectivity of hydrocarbalkoxylation is poorly
studied and that hanpers the attempts to elucidate the
quantitative regularities of the reaction course.
This work is a continuation of our study6,14 of the
hydrocarbomethoxylation of 1-octene catalyzed by the
Pd(PPh3)2Cl2—PPh3—p-toluenesulfonic acid (TsOH)
system (Scheme 1).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1561—1568, August, 2020.
1066-5285/20/6908-1561 © 2020 Springer Science+Business Media LLC

Batashev and Sevostyanova
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Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
Scheme 1
The main attention has previously6,14 been given to
the initial reaction rates, while no distinct rules character-
izing a change in the selectivity were revealed. However,
the regularities of the reaction proceeding during the whole
course to the range of deep conversions of the reactants
are of interest from the practical point of view. Therefore,
this work is devoted to the development of the model
of selectivity of 1-octene hydrocarbomethoxylation to
product 1.
products (r1 + r2 + r3), the following equation can be
written:
.
The S value was calculated as a slope ratio of the linear
dependence of the methyl pelargonate concentration С1
on the total concentration of esters (С1 + С2 + С3) in
a wide range of conversions. The correlation coefficients
of the straight lines were varied from 0.992 to 1.000. Thus,
S did not change in time during each experiment, and
its value was determined by the initial experimental con-
ditions only: CO pressure and concentrations of methanol
and components of the catalytic system. The empirical
equations were selected experimentally to the obtained
dependences of the selectivity S on each varied parameter
of the system on the basis of high determination factor
R2 using the Sigma Plot program.
Experimental
The hygroscopic reagents were dehydrated prior to use.
1-Octene was dried over anhydrous CaCl2 and distilled. Methanol
was dried over CaO and then distilled. The Pd(PPh3)2Cl2 catalyst
was synthesized using a known procedure.15 Triphenylphosphine
and p-toluenesulfonic acid (existing as monohydrate TsOH•H2O)
were commercial products (Sigma—Aldrich) with the major
substance content 99.0 and 98.5%, respectively.
All experiments were carried out in toluene at constant tem-
perature (378 K). The procedures of kinetic experiment and GLC
analysis of the reaction mixture were earlier described com-
pletely.14 The concentrations of 1-octene and products 1—3 were
calculated using the internal standard method. o-Xylene as the
internal standard was introduced in the known concentration
into the reaction mixture before the experiment onset.
For example, the dependence of S on the methanol
concentration passes through a minimum (Fig. 1) and
is described by Eq. (I) with the determination coefficient
R2 = 0.971.
(I)
Results and Discussion
In a series of experiments on the influence of the
methanol concentration on the reaction selectivity, the
conversion of 1-octene reached 92.1% and the yield of
product 1 was 69.2%.
The influence of the CO pressure on the differential
selectivity of 1-octene hydrocarbomethoxylation is de-
scribed by the empirical equation (II), viz., third-power
polynomial (Fig. 2), with the determination coefficient
R2 = 0.999.
The one-factor experiments on studying the influence
of the CO pressure and concentrations of methanol,
Pd(PPh3)2Cl2, PPh3, and TsOH•H2O on 1-octene hydro-
carbomethoxylation were carried out.6,14 In the present
work, we used the obtained results6,14 to determine the
differential selectivity to methyl pelargonate (1) during
the whole reaction course. The current concentrations of
esters 1—3 were measured at various time moments dur-
ing each experiment. For this purpose, on the average
8—11 samples of the reaction mixture were taken. The
dependences of the methyl pelargonate concentration С1
on the total concentration of esters (С1 + С2 + С3) turned
out linear during the whole reaction course until the 1-oc-
tene conversion equal to 85.6—95.5% was achieved
within 70—150 min. Since the differential selectiv-
ity (S) is the ratio of the rate of formation of target prod-
uct 1 (r1) to the total rate of formation of all reaction
S (%) = (87.2 1.2) – (13.1 1.6)•10–6•PCO
+
+ (3.90 0.58)•10–12•P2
–
.
CO
– (0.404 0.064)•10–18P3
(II)
CO
It was found in a series of experiments on the variation
of the CO pressure that the conversion of 1-octene reached
85.6% and the yield of product 1 was 62.4%.

Selectivity model of hydrocarbomethoxylation
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1563
S (%)
S (%)
80
82
76
72
68
64
78
74
1
2
3
CPPh •102/mol L–1
3
0
0.2
0.4
C(MeOH)/mol L–1
Fig. 3. Differential selectivity of 1-octene hydrocarbomethoxyl-
ation vs PPh3 concentration; PCO = 2.0•106 Pa; concentra-
tions (mol L–1): C0(C8H16) = 0.10, С0(MeOH) = 0.15,
Fig. 1. Differential selectivity of 1-octene hydrocarbomethoxyl-
ation vs methanol concentration; PCO = 2.0•106 Pa; concentra-
tions (mol L–1): C0(C8H16) = 0.10, С0(Pd(PPh3)2Cl2) =
C0(Pd(PPh3)2Cl2) = 1.0•10–3, and C0(TsOH) = 1.2•10–2
.
= 2.0•10–3, С0(PPh3) = 8.0•10–3, and C0(TsOH) = 2.4•10–2
.
S (%)
.
(III)
78
76
74
72
70
The conversion of 1-octene in experiments on varying
the PPh3 concentration reaches 81.7%, and the yield of
product 1 is 63.8%.
The dependence of the selectivity to methyl pelargo-
nate on the TsOH concentration (Fig. 4) is described by
Eq. (IV) with the determination coefficient R2 = 0.974:
.
(IV)
1
2
3
4
PCO•10–6/Pa
Fig. 2. Differential selectivity of 1-octene hydrocarbomethoxyl-
ation vs CO pressure; concentrations (mol L–1): C0(C8H16) =
S (%)
80
= 0.10, С0(MeOH) = 0.15, C0(Pd(PPh3)2Cl2) = 1.0•10–3
,
C0(PPh3) = 6.0•10–3, and C0(TsOH) = 1.2•10–2
.
75
70
65
60
The differential selectivity to ester 1 is nearly con-
stant (63.5 2.4%) in the studied concentration range:
C(Pd(PPh3)2Cl2) = (0.1—1.5)•10–2 mol L–1. The
yield of ester 1 and 1-octene conversion remain al-
most unchanged: 52.8 4.3% and 81.9 5.0%, res-
pectively. The initial concentrations (mol L–1) of
other components of the system in experiments on
studying the influence of Pd(PPh3)2Cl2 were as fol-
lows: С0(С8Н16) = 0.1, С0(MeОН) = 0.15, С0(PPh3) =
=
6•10–3
, and С0(TsOH) = ; PCO =
1.2•10–2
= 2.0•106 Pa.
2
4
CTsOH•102/mol L–1
The influence of PPh3 on the selectivity of 1-octene
hydrocarbomethoxylation (Fig. 3) is described by the
empirical equation (III) with the determination coefficient
R2 = 0.922:
Fig. 4. Differential selectivity of 1-octene hydrocarbomethoxyl-
ation vs TsOH concentration; PCO = 2.0•106 Pa; concen-
trations (mol L–1): C0(C8H16) = 0.10, С0(MeOH) = 0.15,
C0(Pd(PPh3)2Cl2) = 1.0•10–3, and С0(PPh3) = 6.0•10–3
.

Batashev and Sevostyanova
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Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
When the TsOH concentration is varied, the conversion
of 1-octene attains 95.5%, and the yield of product 1
is 56.6%.
formed almost without induction period.14 It is most
likely that the "delayed" formation of product 3 is due to
a slow isomerization of 1-octene to 2-octene via reac-
tion (4).
Equations (I)—(IV) represent the model of selectivity
to product 1. The model is valid under the following con-
ditions: Т = 378 K, PCO = (1.0—5.0)•106 Pa, and concen-
trations (mol L–1): C0(C8H16) = 0.10, С0(Pd(PPh3)2Cl2) =
= (1.0—2.0)•10–3, С0(PPh3) = (0.4—4.8)•10–2, and
(4)
C0(TsOH) = (0.6–6.0)•10–2
.
The obtained results can be explained in terms of the
multiroute hydride mechanism involving palladium com-
plexes X0—X19 (reactions (4)—(26)) supplemented by
the reactions of ligand exchange between the palladium
complexes6—8,11,12,14,16—26 (Eqs (27)—(32)). The con-
secutive reactions (5)—(8), as well as reaction (19) and
(20), afford the palladium hydride complexes initiat-
ing the catalytic cycles of hydrocarbomethoxylation
(Schemes 2—4). The target product (ester 1) is formed
via two routes (see Scheme 2, reactions (9)—(11) and
Scheme 4, reactions (21)—(23)). Product 2 can be formed
as a result of sequential reactions (12)—(14) (see Scheme 2)
and reactions (24)—(26) (see Scheme 4) from 1-octene
or from 2-octene hydrocarbomethoxylation the prod-
uct of the acid-catalyzed isomerization of 1-octene (see
reaction (4); Scheme 3, reactions (15), (13), and (14)).
In turn, reactions (16)—(18) (see Scheme 3) afford ester 3.
The formation of this product is preceded by a notice-
able induction period of 5—10 min or 50—60 min in
some experiments, whereas products 1 and 2 are
( 5)
(6)
(7)
(8)
Scheme 2

Selectivity model of hydrocarbomethoxylation
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1565
Scheme 3
* Reactions (13) and (14) were duplicated from Scheme 2.
(19)
(20)
Scheme 4

Batashev and Sevostyanova
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Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
of these features assumes that not only TsOH but also
water molecules are involved in the generation of the
hydride complexes, since p-toluenesulfonic acid was in-
troduced into the reaction mixture in the form of mono-
hydrate.25 For this reason, water acts as a ligand-forming
agent in reaction (7). An increase in the TsOH•H2O
concentration induces the shift of equilibrium of reaction
toward hydride complex Х2, which finally accelerates the
hydrocarbomethoxylation reaction. The established de-
crease in the regioselectivity to product 1 with an increase
in the TsOH concentration is related to an increase in the
contribution of 1-octene isomerization to 2-octene (see
reaction (4)), the consequence of which is an increase in
the fraction of branched esters.
The curves with maxima describing the dependences
of the initial rate of 1-octene hydrocarbomethoxylation
on the CO pressure and MeOH and PPh3 concentrations
has previously6,14 been found. Similar dependences of the
hydrocarbomethoxylation rate on the concentrations of
MeOH and PPh3 and CO pressure were also obtained for
the reaction involving cyclohexene.14,17,25 On the one
hand, MeOH and CO act as reactants in the catalytic
cycles (see Schemes 2—4). On the other hand, they are
involved in the ligand exchange reactions (28)—(31) af-
fording the inactive palladium forms and removal of
a portion of the catalyst from the catalytic cycles. Owing
to this, the dependences of the hydrocarbomethoxylation
rates on the MeOH concentration and CO pressure are
described by the curves with maxima.
(27)
(28)
(29)
(30)
(31)
(32)
As follows from Fig. 1, the curve of the dependence of
the selectivity to methyl pelargonate on the methanol
concentration passes through a minimum. As the methanol
concentration increases to not very high values, the ob-
served decrease in the regioselectivity to product 1 can be
related to an increase in the solvating ability of the medium.
According to the presented Schemes 2—4, the intermedi-
ates of the catalytic cycles of 1-octene hydrocarbometh-
oxylation are cationic species containing weakly coordi-
nated TsO– anion in the external sphere. These interme-
diates are prone to nonspecific solvation by polar MeOH
molecules, and intermediates Х3, X4, X10, and X11 contain-
ing the unbranched alkyl and acyl substituents are solvated
Complex Х2 (m = 0 (X2), 1 (X2´)) gives rise to the
catalytic cycles presented in Schemes 2 and 3.
Under CO excess conditions, according to Eqs (19)
and (20), the formation of carbonyl-containing hydride
intermediates X9 (n = 1 (X9), 2 (X9´)) is possible, which
gives rise to the catalytic cycle presented in Scheme 4.
Strong protonic acids play the key role in the genera-
tion of the hydride catalytic complexes.11,12 We have found
earlier that the dependence of the initial rate of formation
of product 1 on the TsOH concentration is described by
the curve with a weakly pronounced maximum, whereas
the formation rates of products 2 and 3 ascend nonlinearly
with an increase in the TsOH concentration approaching
a constant value.6,14 In the range of low TsOH concentra-
tions, the dependences of the partial rates on the toluene-
sulfonic acid concentration are described by parabolic
curves, which indicates the second order of the reaction
with respect to TsOH. The dependences of rate of cyclo-
hexene hydrocarbalkoxylation have a similar shape in the
range of low TsOH concentrations.17,25,27 An explanation
more strongly than their branched analogs X5—Х8, X12
,
and X13. A consequence of this is an increase, most likely,
in the fraction of the branched reaction products and
a decrease in the regioselectivity to product 1, which are
observed at a slight increase in the MeOH concentration.
At the same time, complex Х2 can be formed via reaction
(8) in the case of specific solvation. It can be assumed that
reaction (8) contributes substantially to the generation of
the hydride complexes in the range of high methanol
concentrations. The MeOH molecule acting as a ligand
in the coordinate sphere of palladium are characterized
by the electron-donor properties. Therefore, the catalytic
cycles involving the methanol-containing complexes (see

Selectivity model of hydrocarbomethoxylation
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1567
Scheme 2) should result in the predominant formation of
the linear product thus increasing the selectivity to prod-
uct 1 in the range of high MeOH concentrations.
dependence was explained by an increase in the contribu-
tion of the formation of catalytically inactive complex Х19
.
To conclude, the model of selectivity to the most valu-
able linear product, methyl pelargonate, was developed
for the hydrocarbomethoxylation of 1-octene catalyzed
by the Pd(PPh3)2Cl2—PPh3—TsOH system. The model
represents the system of equations relating the differential
selectivity of the reaction to the CO pressure and concen-
trations of MeOH, PPh3, and p-toluenesulfonic acid. In
each experiment, the dependence of the current methyl
pelargonate concentration on the total current concentra-
tion of esters during the whole reaction course to the
1-octene conversions 85.6—95.5% turned out to be linear,
which was confirmed by the correlation coefficient values.
The differential selectivity equal to the slope ratio of these
straight lines remained constant during the whole reaction
course in each experiment and changed depending on the
initial conditions. Therefore, it can be asserted that the
developed model of differential selectivity adequately fits
experimental data in a wide range of 1-octene conversions
up to 95.5%. The hydride multiroute mechanism of 1-oc-
tene hydrocarbomethoxylation was used to explain the
regularities of changes in the reaction selectivity to methyl
pelargonate.
The earlier obtained6,14 curves with maxima describing
dependences of the partial hydrocarbomethoxylation rates
on the triphenylphosphine concentration are the result of
different effects of PPh3 on the direction of reactions
(27)—(29). On the one hand, an increase in the PPh3
concentration induces the shift of the equilibrium of re-
actions (28) and (29) toward complex Х1 responsible
for the generation of the hydride catalytic complexes.
On the other hand, as the concentration of this pro-
moter increases, the contribution of reaction (27) leading
to the formation of catalytically inactive complex Х14
increases.
The observed increase in the regioselectivity of the
process with an increase in the PPh3 concentration in the
system and a decrease in the regioselectivity with an in-
crease in the CO pressure are consistent with the published
data on the hydrocarbalkoxylation.8,28—31 The authors of
these works advanced the following explanation. When
the water, MeOH, or PPh3 molecules in the coordinate
sphere of the hydride palladium complexes are substituted
by the CO molecule (see Eqs (19) and (20)), the hydrogen
atom in carbonyl intermediates Х9 begins to manifest acidic
properties under the action of the electron acceptor CO.
Consequences of this are the predominant formation of
the branched alkylpalladium intermediate and a decrease
in the regioselectivity of the reaction to ester 1. At the
same time, an increase in the PPh3 concentration in the
system induces an opposite effect: increases the fraction
of the intermediates containing no carbonyl, whose reac-
tion with 1-octene molecules results in the predominant
formation of the n-alkylpalladium complexes and an ob-
served increase in the regioselectivity to product 1.
A multidirectional effect of CO and PPh3 on the selec-
tivity of hydrocarbomethoxylation is also in agreement
with the concepts on the steric factor: an increase in the
concentration in the system of less bulky carbonylpalla-
dium intermediate decreases the selectivity to the linear
product, whereas in increase in the more bulky phosphine-
palladium complexes induces an increase in the selectiv-
ity to product 1. However, an opposite character of the
influence of the substituent volume in the monophosphine
ligands has previously been found9: the yield of the linear
product decreased with an increase in the volume of these
substituents. It is most likely that the steric factor has no
decisive significance for the selectivity of alkene hydro-
carbomethoxylation.
This work was financially supported by the Government
of the Tula Region (Agreement No. DS/130 of October 29,
2018).
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Received December 15, 2019;
in revised form June 28, 2020;
accepted July 6, 2020