Nonadditive effects of structural factors in reactions of aryloxiranes with arenesulfonic acids. Observation of isoparametricity phenomenon

Article abstract of DOI:10.1134/S107042801105006X

In reactions of aryloxiranes XC₆H₄₍₃₎CH(O)CH ₂ with arenesulfonic acids YC₆H₄SO₃H in a mixture of dioxane with diglyme (1 : 1) at 265 K the nonadditive effects of substituents X and Y were strongly revealed, therefore it was possible to observe experimentally the isoparametricity phenomenon: In the isoparametric point σ _X ^IP = 1.42 with respect to the X substituent constant the rate of the oxirane ring opening did not depend on the structure of Y (ρ_Y^X = 0). Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S107042801105006X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 5, pp. 687−693. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © I.V. Shpan’ko, I.V. Sadovaya, N.V. Kulikova, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 5, pp. 685−691.
Nonadditive Effects of Structural Factors in Reactions
of Aryloxiranes with Arenesulfonic Acids.
Observation of Isoparametricity Phenomenon
I. V. Shpan’ko, I. V. Sadovaya, and N. V. Kulikova
Donetsk National University, Donetsk, 83001 Ukraine
e-mail: shpanko09@rambler.ru
Received July 27, 2010
Abstract—In reactions of aryloxiranes XC6H4(3)CH(O)CH2 with arenesulfonic acids YC6H4SO3H in a mixture
of dioxane with diglyme (1 : 1) at 265 K the nonadditive effects of substituents X and Y were strongly revealed,
therefore it was possible to observe experimentally the isoparametricity phenomenon: In the isoparametric point
σXIP = 1.42 with respect to the X substituent constant the rate of the oxirane ring opening did not depend on the
structure of Y (ρYX = 0).
DOI: 10.1134/S107042801105006X
Scheme 1.
The versatility and features of the mechanisms of
oxirane reactions, their unique synthetic possibilities and
practical value have attracted the attention of researchers
for several decades. The interest in oxirane chemistry is
still strong nowadays as show the numerous recent pub-
lications (see, e.g., [1]). However although the research
on oxiranes is very versatile, the quantitative aspects of
their reactions are still poorly understood. The establish-
ment of quantitative laws taking into account the effect
of the structure, solvent, temperature, pH of the medium
and the other internal and external factors on the rate
and regioselectivity of reactions of oxirane substrates
with reagents of diverse character is a topical problem.
In this respect a special attention should be paid to cross
reaction series where occurs the interaction (nonadditiv-
ity) of effects of mutually varied factors. These series
should be described with the use of polylinear equations
with cross terms whose coefficients take into account
such interactions and therefore their prognostic value
significantly grows [2].
X
CH CH2OH
OSO2
X
CH CH2
O
Iа_If
+
Y
IIIа_IIIo
X
Y
CH CH2
SO3H
IIа_IIe
OH OSO2
Y
Y
IVа_IVj
IVa–IVj
I, X = H (a), 3-Br (b), 4-Br (c), 4-NO2 (d), 4-Br-3-NO2
(e), 3,5-(NO2)2 (f); II, Y = 4-OMe (a), 4-Me (b), H (c),
4-Cl (d), 3-NO2 (e); III, X = H, Y= 4-OMe (a), 4-Me (b),
H (c); X = 3-Br, Y= 4-OMe (d), 4-Me (e), H (f), 4-Cl (g);
X = 4-Br, Y = 4-OMe (h), 4-Me (i), H (j), 4-Cl (k); X =
4-NO2, Y = 4-OMe (l), 4-Me (m), H (n), 4-Cl (o), 3-NO2
(p); IV, X = 4-Br-3-NO2, Y = 4-OMe (a), 4-Me (b), H
(c), 4-Cl (d), 3-NO2 (e); X = 3,5-(NO2)2, Y = 4-OMe (f),
4-Me (g), H (h), 4-Cl (i), 3-NO2 (j).
The goal of this work is the study of the combined
effect of substituents X and Y on the reaction rate of
substituted aryloxiranes with substituted arenesulfonic
acids in a mixture dioxane–bis(2-methoxyethyl) ether
(diglyme), 1:1 (Scheme 1).
687

SHPAN’KO et al.
688
In this mixed solvent the reaction rate proved to be
substituents X. The results of processing kinetic data
(Table 1) using these equations are compiled in Table 2.
They show that in going from one fixed substituent X
(Y) to another the sensitivity factors ρYX (ρYX) consider-
ably change. This shows the interaction of mutual effects
of substituents X and Y in the studied reactions, i.e.,
their nonadditive influence on the process. However the
uniformity of such interaction is not retained within the
total range of variation of substituents X in the oxirane
substrate, as is demonstrated in Fig. 1 where the deviation
is shown of the kinetic data of oxirane Ie, If reactions
from the linear correlations in the coordinates of equation
(1). Consequently, the reactions involving these substrates
cannot be included into the main cross reaction series
(CRS 1). This is due to the above mentioned change in
the regioselectivity of the opening of the oxirane ring
effected by strong electron-acceptor substituents X =
4-Br-3-NO2, 3,5-(NO2)2.
convenient for measurement in a wide range of variation
of substituents at 265 K. In reactions of aryloxiranes
Ia–Id with arenesulfonic acids IIa–IIe products formed
resulting from the α-opening of the oxirane ring, primary
alcohols 2-aryl-2-arylsulfonyloxyethanols IIIa–IIIp [3].
The formation of 2,2-disubstituted ethanol derivatives
was also observed in the reactions of these aryloxiranes
with benzoic acids [4], HNO3 [5], and the other acid
reagents [6]. However with aryloxiranes Ie, If with
electron-acceptor substituent X more powerful than
1
4-NO2 according to the H NMR data (see below) the
products of the β-opening of the oxirane ring, secondary
alcohols 1-aryl-2-arylsulfonyloxyethanols IVa–IVj were
obtained. The observed change I in the reaction regio-
selectivity is in agreement with the stated in a number
of publications [7] β-opening of the oxirane ring in the
presence in the aryloxiranes of strong electron-acceptor
substituents.
The quantitative estimation of the mutual effects of
substituents X and Y in CRS 1 was performed applying
the equation of the cross correlation for two-parametric
polylinear principle [2]:
All reactions have the overall third order, first with
respect to oxirane and second for the acid. The values
of the rate constants kXY l2 mol–2 s–1 of these reactions
are compiled in Table 1. To evaluate quantitatively the
effect on the rate of substituents X and Y were used the
respective equations:
log kXY = log kHH + ρXY=HσX + ρYX=HσY + ρXYσXσY, (3)
where kHH is the rate constant of the standard reaction
of oxirane Ia with acid IIc (X = Y = H, σX = σY = 0),
ρYX=H and ρYX=H are the sensitivity factors of the standard
reaction series, ρYX is the factor of the cross interaction.
The performance of the cross correlation analysis of the
results of the multifactor kinetic experiment according to
equation (3) along the program of multilinear regression
analysis furnished the following result:
Y
log kXY = log kHY + ρX σX
logkXY = log kXH + ρYXσY.
(1)
(2)
Equation (1) describes the partial reaction series
with variable substituents X and fixed subsstituents Y,
and equation (2), with variable substituents Y and fixed
log kXY = (1.47 ± 0.03) – (5.35 ± 0.06)σX
+ (3.1 ± 0.2)σY – (2.9 ± 0.2)σXσY
R 0.998, s 0.066, F 2418, n 16.
(4)
Table 1. Rate constants kXY × 102 (l2 mol–2 s–1) of reactions
between aryloxiranes Ia–If and arenesulfonic acids IIa–IIe in
the mixture of dioxane with diglyme (1 : 1) at 265 K
Oxirane
Acid
Ia
Ib
Ic
Id
Ie
If
IIa
IIb
IIc
IId
IIe
415 39.4
840 72
6.06 0.112 0.24
0.0212
8.46 0.140 0.365 0.021
3520 183
20.3
55.2
–
0.23
0.38
0.84
0.644 0.022
Fig. 1. Dependence of log kXY on σX of substituents X for reac-
tions of aryloxiranes XC6H4(3)CH(O)CH2 with arenesulfonic
acids YC6H4SO3H [Y = 4-Cl (1), H (2), 4-Me (3), 4-OMe (4)]
in the mixture of dioxane with diglyme, 1 : 1, at 265 K.
–
–
700
–
1.24
4.26
0.0219
0.0218
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NONADDITIVE EFFECTS OF STRUCTURAL FACTORS IN REACTIONS OF ARYLOXIRANES
689
Table 2. Values of sensitivity factors ρXY and ρYX in equations (1) and (2) for reactions of aryloxiranes XC6H4(3)CH(O)CH2 with
arenesulfonic acids YC6H4SO3H in the mixture of dioxane with diglyme, 1 : 1, at 265 K
Y (σY)
4-OCH3 (–0.27)
4-CH3 (–0.17)
H (0)
ρXY
r
X (σX)
H (0)
ρYX
r
–4.59 ± 0.07
–4.9 ± 0.1
–5.4 ± 0.1
–5.9 ± 0.3
0.999
0.999
0.999
0.999
3.5 ± 0.2
2.48 ± 0.02
1.96 ± 0.07
0.89 ± 0.07
0.999
0.999
0.999
0.993
4-Br (0.23)
3-Br (0.39)
4-NO2 (0.78)
4-Cl (0.23)
3-NO2 (0.71)
–
–
4-Br-3-NO2 (0.94)
3,5-(NO2)2 (1.42)
1.25 ± 0.060
0
0.997
–
Owing to the statistically valid factor of the cross
interaction ρXY regression (4) exhibits the isoparametric
properties. Its attributes are isoparametric points (IPP)
of oxirane ring opening with the formation of primary
alcohols IIIa–IIIp in CRS 1 we suggest a stage mecha-
nism (Scheme 2) that is in agreement with the overall
third order of these reactions, partial first with respect to
oxirane substrate and partial second with respect to acid
reagent HA (YC6H4SO3H). This mechanism involves
the formation in the first reversible stage of complex A
with an H-bond. In the second stage limiting the rate kα
the activated substrate suffers the nucleophilic attack of
the second acid molecule on the α-carbon atom of the
oxirane ring, located in the benzyl position, to form the
trimolecular transition state B. Just this direction of the
oxirane ring opening corresponds to the formation of
primary alcohols IIIa–IIIp in reactions involving ary-
loxiranes Ia–Id.
corresponding to substituents constants, for X (σXIP
=
–1
–1
–ρYX=HρXY = 1.07) and Y (σYIP = –ρXY=HρXY = –1.84),
and also the same rate constant value kXY in both IPP
IP
–1
(log k = log kHH – ρYX=HρYX=HρXY = –4.25). As seen
XY
from the calculation data, IPP fall to the region of low
reactivity of the system. The experimental attainment of
IPP σYIP where the process rate should not depend on the
structure of substituents X (ρYX = 0) is not possible for
it requires the introduction into the molecule of arene-
sulfonic acid improbably powerful electron-donor sub-
stituents Y with ΣσY –1.84. As to IPP σXIP where the rate
should not be affected by the changes in the structure of
substituents Y (ρYX = 0) we attempted to test the possibil-
ity of its existence using as the substrate oxirane Ie with
summary value of constants of substituent X (ΣσX 0.94)
close to isoparametrical. However the reactions involv-
ing this oxirane showed abnormally high sensitivity to
the change of substituents Y (Table 2). This is due to the
distortion of the uniformity of the interaction of structural
factors because of the changed regioselectivity of reac-
tions (Scheme 1), therefore the experimental test of this
IPPfailed. Yet we succeeded to prove a complete absence
of the effect of substituent Y on the opening rate of oxi-
rane ring involving oxirane If where ρYX = 0. Evidently
the value ΣσX 1.42 of constants of substituent X = 3,5-
(NO2)2 corresponds to the value of the experimentally
attainable IPP σXIP 1.42 in another cross reaction series
partially investigated in this work (CRS 2) that includes
the formation of secondary alcohols IVa–IVj involving
oxiranes Ie, If. From the data of Table 2 it is possible to
calculate for CRS 2 the approximate value of the factor
of the cross interaction: ρXY = ΔρYX/ΔσX = –2.6.
In keeping with the two-stage mechanism kXY = Kkα
that means ρYX = ρY1 + ρX2. Taking into account the nature
of the first stage a conclusion is possible that ρX1 <0. The
second stage proceeds along the mechanism of concerted
nucleophilic substitution ANDN with the electrophilic
assistance to the C–O bond cleavage in the oxirane ring.
The transition state B is by its character dissociative.
There the cleavage of the C–O bond largely surpasses
the formation of the O–C bond leading to the appearance
of a positive charge on the α-carbon atom of the oxirane
ring, and consequently ρX2 <0 (the strengthening of the
electron-acceptor properties of substituents X destabi-
lizes the transition state B). Inasmuch as both stages of
the process are characterized by negative values of the
sensitivity factor with respect to the effect of substituents
X, the effective value ρYX is expressed by large negative
values for the studies partial reaction series (Table 2).
The sensitivity parameter ρYX is also a combined value:
ρYX = ρY1 + ρY2, where ρY1 > 0, and the sign and magnitude
of ρY2 is determined by the prevalence of either the forma-
tion of the O–C bond or the cleavage of the C–O bond in
For the described regressions (4) of the reactions
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 5 2011

SHPAN’KO et al.
690
Scheme 2.
X
X
K
CH CH2
O
+
HA
CH CH2
O
HA
А
=/
H
A
X
X
ka
CH CH2
CH CH2OH
A
O
H
A
B
A + HA
=/
H
A
X
X
kb
CH CH2
CH CH2A
OH
O
H
A
C
the transition state B. The electron-acceptor substituents
Y impede the formation of the O–C bond (ρO–C <0) and
facilitate the cleavage of the C–O bond (ρC–O >0) by the
electrophilic assistance to this process in the transition
state B, therefore ρY2 = (–ρO–C) + ρC–O. Since as already
mentioned the transition state B is dissociative it is pre-
sumable that |ρA–C| < ρC–O and ρY2 >0. Inasmuch as both
sensitivity parameters ρY1 and ρY2 with respect to the effect
of substituents Y prove to be positive for both stages, it
is reasonable that the observed effective ρYX value for
the partial reaction series forming CRS 1 is also positive
(Table 2).
above reasoning it is possible to conclude that in the stage
of the formation of complex A to IPP with respect to the
constants of substituents X (σXIP(A) = –ρY1/ρX1Y >0) and
Y (σYIP(A) = –ρX1/ρX1Y <0) would correspond respectively
weak proton acceptors (aryloxiranes with the electron-
acceptor substituents X) and inactive proton donors
(arenesulfonic acids with electron-donor substituentsY).
In this event the H-bond can become so weak that it would
result in parameters ρX1 and ρY1 equal zero in IPP σYIP(A)
and σXIP(A) respectively. Just this situation is characteristic
of the cross reaction series under consideration, whose
attribute is IPP σXIP 1.07 and σYIP –1.84 corresponding to
IP
low reactivity of the system (log kXY –4.25). A similar
The stage character of the process governs also the
sign and the magnitude of the factor of cross interaction
ρXY. In the first stage of the process the increase in the
electron-acceptor properties of substituents X (ΔσX >0)
would result in the decrease in the electron density on
the oxygen atom of the oxirane ring and therefore to the
weakening of the H-bond in complex A resulting in the
diminishing of ρY1 (ΔρY1 <0), hence ρX1Y = ΔρY1/ΔσX < 0.
On the other hand, the strengthening of the electron-
acceptor properties of substituents Y (ΔσY >0) would
favor the strengthening of the H-bond and consequently
would increase the negative value of ρX1 (ΔρX1 < 0) and,
as a result, ρX1Y = ΔρX1/ΔρY < 0. Taking into account the
relationship in the interaction of mutual structural effects
was observed in the acid-base interaction of substituted
pyridines with substituted phenols with the formation of
H-complexes [8].
The ANDN mechanism of the second limiting stage is
resembling that of the nucleophilic substitution at the
benzyl carbon atom where the negative values of ρXY and
IPPcorresponding to maximum reactivity of the substrate
and the nucleophile are characteristic [9]. Since in CRS
1 the cleavage of the oxirane ring occurs involving the
α-carbon atom located in the benzyl position, analogously
to the benzyl systems we should expect ρX2Y <0 for this
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NONADDITIVE EFFECTS OF STRUCTURAL FACTORS IN REACTIONS OF ARYLOXIRANES
691
stage. At the same time the contribution of ρX2Y into the
effective value ρXY in equation (4) should be insignificant,
for in the opposite case the calculated values of IPP σX
and σYIP for CRS 1 would not correspond to the minimum
the calculated by semiempirical method PM3 (Mopac
97) ehthalpy of formation in reaction of aryloxiranes
with acid IIc of secondary alcohols XC6H4(3)CH(OH)
CH2OSO2C6H5 [–ΔHII = 597.7, 477.7, 438.6, 406.7,
466.7, 406.7, 477.5, 430.0, 501.6 kJ mol−1 in the series
of X = 4-OCH3, 4-CH3, H, 4-Br, 3-Cl, 3-Br, 4-NO2,
4-Br-3-NO2, 3,5-(NO2)2] and their isomers primary
alcohols XC6H4(3)CH(OSO2C6H5)CH2OH (–ΔHI =
596.1, 476, 436.6, 404.3 463.9, 403.8, 473.5, 421.7,
490.9 kJ mol−1 respectively in the same series of sub-
stituents X). As seen from Fig. 2, the difference δXΔH =
ΔHII – ΔHI is in a fair linear dependence on constants
σX in the range of σX from –0.27 (X = 4-OCH3) to 0.78
(X = 4-NO2):
IP
of reactivity.
Hence from the above reasoning it is possible to con-
clude that in the studied CRS 1 the nonadditive effect
of substituents X and Y on the rate of the process is due
mainly to the interaction of their electronic effects in the
stage of the formation of H-complex A.
As to the reactions involving aryloxiranes Ie, If
forming CRS 2, their first stage consists in appearance
of H-complex A similar to that in CRS 1, which in the
second limiting stage kβ suffers the nucleophilic attack of
the second acid molecule on the spatially more accessible
β-carbon atom of the methylene group of the oxirane ring
with the formation of the transition state C. The similarity
of the first stage of both types of the oxirane ring opening
results in same sign and close values of the factor of cross
interaction in CRS 1 (ρXY –2.9) and CRS 2 (ρXY –2.6),
confirming for another time the conclusion of the ap-
pearance just in this stage of the nonadditive effects of
substituents X and Y.
δXΔH = (2.08 ± 0.07) + (2.2 ± 0.2)σX
r 0.983, s 0.167, n 7.
(5)
The points for substituents X = 4-Br-3-NO2 and 3,5-
(NO2)2 deviate from this correlation. The comparison
for them the values δXΔH (4.1 and 5.3) obtained by
equation (5) and calculated from the difference δXΔH =
ΔHII – ΔHI (8.3 and 10.7) shows that the secondary
alcohols IVc, IVh formed at the β-opening of oxiranes
are by 4.2 and 5.4 kJ mol−1 respectively more stable
than the corresponding primary alcohols if they would
have formed by the α-opening of the oxirane ring. It is
therefore not surprising that in the presence of powerful
electron-acceptor substituents X in the oxirane substrate
the regioselectivity of reactions changes to the forma-
The β-opening of the oxirane ring caused by the
powerful electron-acceptor substituents X results in sig-
nificant acceleration of the oxirane ring opening (Fig. 1)
compared with the rate extrapolated for the α-opening.
Thus in the case of oxirane If the experimental value of
the rate constant of the formation of secondary alcohol
IVh involving acid IIc (Table 1) is 295-fold larger than
that calculated by equation (4) for the α-opening of the
oxirane ring to form the primary alcohol (log kXY
=
–6.127, kXY 7.46 × 10–7 l2 mol–2 s–1). This significant
decrease in the rate of α-opening of the oxirane ring is
caused by the destabilizing effect of powerful electron-
acceptor substituents X in the process of formation of
the transition state B of the carbocation character with
a significant part of the positive charge on the benzyl
carbon atom.
The transition from the α-opening of the oxirane ring
to the β-opening at introduction into the molecule of
aryloxirane of powerful electron-acceptor substituents
X = 4-Br-3-NO2 and 3,5-(NO2)2 is accompanied by
abnormally large growth of the thermodynamic stability
of the forming in CRS 2 secondary alcohols compared
with the stability of the products of the α-opening (pri-
mary alcohols) in CRS 1. This statement is illustrated by
Fig. 2 where versus σX is plotted the difference between
Fig. 2. Plot vs. σX of the difference δXΔH =ΔHII –ΔHI between
calculated values of enthalpy of formation in reactions of
aryloxiranes XC6H4(3)CH(O)CH2 with benzenesulfonic acid
PhSO3H of secondary alcohols XC6H4(3)CH(OH)CH2OSO2C6H5
(ΔHII, kJ mol−1) and isomeric primary alcohols XC6H4(3)
CH(OSO2C6H5)CH2OH (ΔHI, kJ mol−1) in the series X = 4-OMe
(1), 4-Me (2), H (3), 4-Br (4), 3-Cl (5), 3-Br (6), 4-NO2 (7),
4-Br-3-NO2 (8), 3,5-(NO2)2 (9).
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SHPAN’KO et al.
692
tion of the thermodynamically significantly more stable
secondary alcohols.
by TLC on Silufol UV-254 plates (development in iodine
vapor, eluent cyclohexane–dichloromethane, 7:3). The
products of reactions between oxiranes Ie, If and acids
IIb,IIc were synthesized in conditions similar to the
kinetic runs.
EXPERIMENTAL
1H NMR spectra were registered on a spectrometer
Bruker Avance-400 (400 MHz) in CDCl3, internal ref-
erence TMS. Dioxane of “pure for analysis” grade and
diglyme of “pure” grade were dried with KOH and dis-
tilled over Na (diglyme at reduced pressure). Commercial
(Merck) phenyloxirane (98% of the main substance) was
used without additional purification. Technical 4-nitro-
phenyloxirane was twice recrystallized from hexane,
mp 85–86°C [10]. The other aryloxiranes were obtained
from the corresponding phenacyl bromides by known
procedures [11].Arenesulfonic acids of “pure” grade were
dried by long (10 h) boiling of their benzene solutions
with water separation on a Dean–Stark trap and were
stored in a vacuum desiccator over P2O5.
1-(4-Bromo-3-nitrophenyl)-2-tosyloxyethanol
(IVb). A solution of 0.122 g (0.5 mmol) of oxirane Ie
and 0.860 g (5 mmol) of acid IIb in 50 ml of a mixture
of dioxane with diglyme, 1 : 1, was maintained for 72 h
at –8°C till the disappearance of oxirane (TLC monitor-
ing, the absence of reaction with HBr). Then the reaction
mixture was diluted with 100 ml of water, the reaction
product was extracted with ether (3 × 20 ml), the com-
bined ether extracts were washed with water till neutral
reaction of washings, and dried with anhydrous MgSO4,
the solvent was distilled off at a reduced pressure. Yield
1
0.198 g (95%), light yellow oily substance. H NMR
spectrum, δ, ppm: 2.38 s (3H, CH3), 3.54 d.d (1H, CH2,
3J 7.0, 2J 11.2 Hz), 3.62 d.d (1H, CH2, 3J 4.1, 2J 11.2 Hz),
3.86 d.d (1H, CH, 3J1 7.0, 3J 4.1 Hz), 7.33 d (2H, H3,5,
C6H4, J 8.0 Hz), 7.73 d (2H, H2,6 C6H4, J 8.0 Hz), 9.06 d.d
(1H, H6, C6H3, J6,2 2.1, J6,5 9.0 Hz), 9.42 d (1H, H5, C6H3,
J6,5 9.0 Hz), 9.45 d (1H, H2 C6H3, J6,2 2.1 Hz). Found,
%: C 43.45; H 3.28; Br 19.11; N 3.43; S 7.83. C15H-
14BrNO6S. Calculated, %: C 43.27; H 3.36; Br 19.23; N
3.36; S 7.69.
The measurement of the reaction rate was car-
ried out by sampling, the addition to the sample of
HBr solution in glacial acetic acid to stop the pro-
cess. Then the mixture was cooled to 265 K and after
180 min the excess HBr unreacted with residual oxirane
was determined by potentiometric titration with water
solution ofAgNO3 [3]. The reaction kinetics were studied
at 10-fold and over excess of arenesulfonic acids with
respect to the initial concentrations of aryloxiranes (S):
[HA]0 >> [S]0 = 0.001 – 0.008 mol l−1. Under these con-
centration conditions the reaction is of the first order with
respect to oxirane substrate and of the second order with
respect to acid reagent, and the process rate is described
by the equation
1-(3,5-Dinitrophenyl)-2-phenylsulfonyloxy-
ethanol (IVh) was similarly obtained from 0.105 g
(0.5 mmol) of oxirane If and 0.791 g (5 mmol) of
acid IIc. Yield 0.171 g (93%), light yellow oily
1
substance. H NMR spectrum, δ, ppm: 4.17 d.d
3
2
(1H, CH2, J 6.8, J 10.9 Hz), 4.27 d.d (1H, CH2,
3J 3.9, 2J 10.9 Hz), 5.22 d.d (1H, CH, 3J 3.9, 3J 6.8 Hz),
7.45–7.83 m (5H, Ph), 8.42 d (2H, H2,6, C6H3, J 4.3 Hz),
8.93 t (1H, H4, C6H3, J 4.3 Hz). Found, %: C 45.93;
H 3.19; N 7.79; S 8.53. C14H12N2O8S. Calculated, %:
C 45.65; H 3.26; N 7.61; S 8.69.
–d[S]/dt = k[S] = kXY[S][HA]02,
(6)
where k (s–1) and kXY (l2 mol–2 s–1) are rate constants of
pseudofirst and third order respectively. In all kinetic
runs the apparent rate constants k remained constant in
the course of the process till the conversion of oxirane
was 70–80% (the error in the constant measurement did
not exceed 5%). The constants kXY characterizing the
combined effect of substituents X and Y on the rate of
the process were evaluated by extrapolation to zero of
linear dependences k = kXY[HA]02 for four and more dif-
ferent concentrations of HA (r ≥ 0.995). The statistical
processing of experimental data was performed at the
confidence range 0.95.
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