A combined experimental and density functional study of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes reactivity towards the allylic chlorine

Article abstract of DOI:10.1002/poc.3425

Nucleophilic substitution and dehydrochlorination reactions of a number of the ring-substituted 1-(arylsulfonyl)-2-R-4-chloro-2-butenes are studied both experimentally and theoretically. The developed synthetic procedures are characterized by a general ra

Full text of DOI:10.1002/poc.3425

Research Article
Received: 31 October 2014,
Revised: 17 December 2014,
Accepted: 24 January 2015,
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI: 10.1002/poc.3425
A combined experimental and density
functional study of 1-(arylsulfonyl)-2-R-4-
chloro-2-butenes reactivity towards the
allylic chlorine
Sergey V. Bondarchuka*, Victor V. Smaliusa and Boris F. Minaeva,b
Nucleophilic substitution and dehydrochlorination reactions of a number of the ring-substituted 1-(arylsulfonyl)-2-R-4-
chloro-2-butenes are studied both experimentally and theoretically. The developed synthetic procedures are characterized
by a general rapidity, cheapness, and simplicity providing moderate to high yields of 1-arylsulfonyl 1,3-butadienes
(48–95%), 1-(arylsulfonyl)-2-R-4-(N,N-dialkylamino)-2-butenes (31–53%), 1-(arylsulfonyl)-2-R-2-buten-4-ols (37–61%), and
bis[4-(arylsulfonyl)-3-R-but-2-enyl]sulfides (40–70%). The density functional theory B3LYP/6-311++G(2d,2p) calculations of
the intermediate allylic cations in acetone revealed their high stability occurring from a resonance stabilization and
hyperconjugation by the SO2Ar group. The reactivity parameters estimated at the bond critical points of the diene/allylic
moiety display a high correlation (R2 > 0.97) with the Hammett (σp) constants. 1-Arylsulfonyl 1,3-butadienes are character-
ized by a partly broken π conjugated system, which follows from analysis of the two-centered delocalization (δ) and locali-
zation (λ) index values. The highest occupied molecular orbital energies of 1-arylsulfonyl 1,3-butadienes are lower than
those of 1,3-butadiene explaining their low reactivity towards the Diels–Alder condensation. Copyright © 2015 John Wiley
& Sons, Ltd.
Keywords: 1-(arylsulfonyl)-2-R-4-chloro-2-butenes; 1-arylsulfonyl 1,3-dienes; conceptual density functional theory; electrophile-
nucleophile interactions; quantum theory of atoms in molecules
2-(methylaminosulfonyl)-1-(arylsulfonyl)hydrazines,[19] 1-(sulfonyl)-
INTRODUCTION
5-(arylsulfonyl)indoline,[20] N-arylsulfonyl-N-methyl-N′-(2,2-dimethyl-
2H-1-benzopyran-4-yl)ureas[21], and aryl sulfonyl fluorides[22] were
Recently, a renewed growing interest is observed towards the
successfully evaluated as myorelaxants and anticancer agents. Thus,
we suspect that the products of SN reactions of 1-(arylsulfonyl)-2-R-4-
chloro-2-butenes with the studied nucleophiles might be predicted
as biologically active compounds.
synthetic capabilities of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes
(1a–1j). This is because of their use in the synthesis of coenzyme
Q10[1,2] and of highly functionalizable 1-arylsulfonyl 1,3-dienes.[3–
10]
The 4-chloro-2-methyl-1-phenylsulfonyl-2-butene species is
an intermediate in the synthesis of coenzyme Q10,[1,2,11] and
the latter dienes were found to react efficiently with aryl diazo-
nium salts at the 3 and 4 positions.[3–10,12,13] A further dehydro-
chlorination of this reaction product will result in the formation of
a more complex diene and so on. As it follows from our present un-
published results, these dienes are efficient rubber additives for car
tires increasing adhesion to the tire cord. Meanwhile, the studied bu-
tenes possess effective herbistatic properties against Echinochloa
crus-galli L., Amaranthus retroflexus L., and Chenopodium album L.
at typical concentrations of 0.1–0.001%.
As a synthetic route to yield 1-(arylsulfonyl)-2-R-4-chloro-2-
butenes the Asscher–Vofsi reaction is usually applied.[2]
Another method leading to a broad variety of 1-(arylsulfonyl)-
2-R-4-chloro-2-butenes is represented as the Michael addition
of nucleophiles to 1-arylsulfonyl 1,3-dienes.[15,23] Earlier, we
have developed an alternative method for preparing
1-(arylsulfonyl)-2-R-4-chloro-2-butenes using arylation of conju-
gated dienes with aryl diazonium salts in the SO2 saturated
solution.[3–13] In contrast to the previously developed methods,
this protocol is very simple, relatively fast, and does not need
expensive reactants or catalysts.[2,15,23]
In contrast to the mentioned butenes, the 2-arylsulfonyl
1,3-dienes, 1,3-bis(arylsulfonyl) 1,3-dienes and, especially, 2,3-
bis(arylsulfonyl) 1,3-diene compounds are studied much bet-
ter.[14,15] In two recent exhaustive reviews, Flick and Padwa
described a broad variety of syntheses towards azapolycyclic
ring systems and piperidone derivatives.[16,17] One should note
that the molecules containing the arylsulfonyl moiety are well
known as physiologically active compounds, for example, sulfon-
amide drugs. The recent pharmacological evaluations, however,
reveal that the other arylsulfonyl-containing molecules – very differ-
ent structurally – also possess biological activity. In particular,
1-aroyl(1-arylsulfonyl)-4-bis(trifluoromethyl)alkyl semicarbazides,[18]
* Correspondence to: S. V. Bondarchuk, Department of Organic Chemistry,
Bogdan Khmelnitsky Cherkasy National University, blvd. Shevchenko 81,
18031 Cherkasy, Ukraine.
E-mail: bondchem@cdu.edu.ua
a S. V. Bondarchuk, V. V. Smalius, B. F. Minaev
Department of Organic Chemistry, Bogdan Khmelnitsky Cherkasy National
University, blvd. Shevchenko 81, 18031, Cherkasy, Ukraine
b B. F. Minaev
Department of Theoretical Chemistry and Biochemistry, Royal Institute of
Technology, AlbaNova, S-106 91, Stockholm, Sweden
J. Phys. Org. Chem. 2015
Copyright © 2015 John Wiley & Sons, Ltd.

S. V. BONDARCHUK, V. V. SMALIUS AND B. F. MINAEV
1-(Arylsulfonyl)-2-R-4-chloro-2-butenes and 1-arylsulfonyl 1,3-
dienes are also interesting compounds from theoretical point of
view. The former contains a strong electron-withdrawing (ArSO2)
group and the allylic chlorine atom. Therefore, their SN reactions
are expected to be rather efficient. On the other hand,
1-arylsulfonyl 1,3-dienes possess the conjugated π system, which
is bound with the ArSO2 group. Thus, their reactivity towards the
Diels–Alder or polar addition is of special current interest.[24–29] In
order to study the influence of the latter group, we have per-
formed a series of SN reactions of 13 various 1-(arylsulfonyl)-2-R-
4-chloro-2-butenes with such nucleophiles as diethylamine,
diethanolamine, morpholine, potassium hydroxide, and sodium
sulfide as well as the dehydrochlorination reaction yielding the cor-
responding 1-arylsulfonyl 1,3-dienes followed by the Diels–Alder
addition with maleic anhydride. Although 1-arylsulfonyl 1,3-dienes
are expected to match better in the inverse electron demand
Diels–Alder reaction, we have selected maleic anhydride as a
dienophile because the latter yields crystalline adducts, which are
used for the diene identification by characteristic melting points.
In the present study, the reactivity parameters of the studied
compounds and the reactive intermediates have been determined
in terms of conceptual density functional theory (DFT). Because the
SN reactions are generally described as electrophile–nucleophile
interactions, the Mayr–Patz equation[30–33] has been applied to
estimate the corresponding reaction rate. Recently, we have exam-
ined this method for the aryl cations reactions with π-nucleophiles
and have approved its reliability.[34–36] A rationale of the depen-
dence between the reaction rates and isolated yields has been pro-
posed on the ground of the obtained log k values. Meanwhile, the
topological analysis of the electron density and the global/local
electronic structure descriptors has enabled us to explain peculiar
reactivity of 1-arylsulfonyl 1,3-dienes towards addition reactions.
Although some of the presented reactions are not principally
new,[15] we propose synthetic procedures that are much faster,
cheaper, and simpler than the previously developed synthesis.
The described computational approach will be useful for study-
ing chemical reactivity in the electrophile–nucleophile reactions
of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes, 1-arylsulfonyl 1,3-
dienes, and the related compounds.[16,17,37–40]
Scheme 1. Formation of 1-arylsulfonyl 1,3-dienes 2a–2j by dehydro-
chlorination of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes 1a–1j
Information). We have calculated the nuclear chemical shift
according to the following definition:[41]
sample
TMS
iso
δ ¼ σ
ꢀ σiso
(1)
sample
iso
TMS
iso
where σ
and σ
are the values of isotropic shielding for
protons in the studied molecule (2f) and tetramethylsilane as a
reference, respectively. The isotropic shielding is the average of
the diagonal elements of the shielding tensor:[41]
À
Á
σiso ¼ σxx þ σyy þ σzz =3
(2)
We used the B3LYP/6-311++G(d,p) approach in terms of the
gauge-independent atomic orbital method. As it follows from
Table S1, the semi-quantitative (qualitative) agreement
between calculated and experimental NMR chemical shifts per-
mits us to make definite assignments. The most interesting
results concern the aromatic protons assignment in the 2f
species. The proton H(22) (the hydrogen atom labeling is given
in Fig. S2 in the Supporting Information) demonstrates the
largest low-field chemical shift and is separated from other
aromatic protons (probably because of perturbation from the
nearby oxygen atom). Our DFT calculation reproduces this
peculiarity pretty well, which supports the total reliable NMR
assignment.
Our joint researches with the Institute of Macromolecular
Chemistry (National Academy of Sciences of Ukraine) have dem-
onstrated that the diene 2h well copolymerizes with isoprene.
The obtained copolymer bears the nitro group in the benzene
nucleus; this can increase adhesion to the rubber fillers and tire
cord.
RESULTS AND DISCUSSION
Experimental study of the 1-(arylsulfonyl)-2-R-4-chloro-2-
butenes reactivity
As our experiments revealed, the allylic chlorine atom in
1-(arylsulfonyl)-2-R-4-chloro-2-butenes, containing different sub-
stituents at the ortho, meta, and para positions of the benzene
ring, can undergo dehydrochlorination as well as nucleophilic
substitution in the reaction with alkylamines, potassium hydrox-
ide, and sodium sulfide. Thus, heating of 1-(arylsulfonyl)-2-R-4-
chloro-2-butenes with an equimolar amount of triethylamine in
a solution of benzene or acetone leads to the elimination of
hydrogen chloride and subsequent formation of 1-arylsulfonyl
1,3-dienes 2a–2j (Scheme 1).
The structures of the sulfonyl-containing dienes 2f and 2j
have been confirmed using the proton nuclear magnetic reso-
nance (1Н NMR) spectroscopic analysis. Recorded spectrum of
the diene 2j is illustrated in Fig. S1 in the Supporting Information,
and the spectra assignment is discussed in the related text.
Application of DFT, described in the succeeding text, explains
the detected NMR spectra pretty well (Table S1 in the Supporting
Taking into account a significant weakening of the π-
conjugation in the dienes 2a–2j, we have tried to study their re-
activity towards the Diels–Alder condensation. It was found that
the studied dienes react poorly with maleic anhydride. Heating
of the reactants in benzene or xylene in the presence of iodine
failed. Only a sustainable melting of equimolar amounts of the
dienes 2a–2j with freshly sublimed maleic anhydride have
yielded crystal 1-(arylsulfonyl)-1,4,5,6-tetrahydrophthalic anhy-
drides 3g–3j (Scheme 2).
Because of instability of the dienes 2a–2e at high tempera-
tures, we could not obtain the corresponding adducts. On the
other hand, the diene 2f does not react with maleic anhydride
too. This is caused by a strong electron withdrawing effect of
the 2-nitro substituent with respect to the conjugated π system
of the diene moiety. Such electron depletion is the reason why
the dienes 2 do not undergo the Knoevenagel–hetero-Diels–
Alder condensation.[42] It is worthwhile noting that the energy
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THE CHLORINE REACTIVITY IN 1-(ARYLSULFONYL)-2-R-4-CHLORO-2-BUTENES
alcohols. Thus, treating an acetone solution of 1-(arylsulfonyl)-
2-R-4-chloro-2-butene with a 10% water solution of potassium
hydroxide yields the corresponding 1-(arylsulfonyl)-2-R-2-buten-
4-ol (Scheme 4). The obtained alcohols 7 can be reconverted to
the initial chlorides 1 up to 90% yield when treating with thionyl
chloride (Scheme 4). The results of elemental analysis of the
obtained alcohols 7 revealed zero chlorine content.
Scheme 2. The Diels–Alder reaction of the dienes 2 with maleic
A mixing of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes obtained
using arylation of 1,3-butadiene and isoprene with aryl diazo-
nium salts in the SO2 saturated solution and those obtained
according to Scheme 4 has suggested no melting point depres-
sion; this justifies an identity of the mixed solids. The corre-
sponding values of melting point of the chlorides 1 can be
found elsewhere.[3–5,13]
Additionally, 1-(arylsulfonyl)-2-R-4-chloro-2-butenes easily react
with sodium sulfide to give the corresponding sulfonyl-containing
fatty-aromatic sulfides. Thus, when treating an acetone solution of
the corresponding butene with a water solution of Na2S, a nucleo-
philic substitution of the allylic chlorine in two butene molecules
smoothly occurred; this yields bis[4-(arylsulfonyl)-3-R-but-2-enyl]
sulfides 8g–8j and 8’h (Scheme 5).
anhydride
of cis–trans isomerization of the dienes 2g–2j are the following:
2g (3.43 kcal/mol), 2h (3.45 kcal/mol), 2i (3.43 kcal/mol), and 2j
(3.45 kcal/mol). Because, these energy values are rather small,
these can be easily overcome under the reaction conditions.
The structure of adducts 3g and 3h was confirmed by proton
nuclear magnetic resonance (1H NMR) spectroscopy. Recorded
spectrum of the adduct 3g is illustrated in Fig. S3 in the
Supporting Information, and the spectra assignment is discussed
in the related text.
Heating of the acetone solutions of the 1-(arylsulfonyl)-4-chloro-
2-butenes 1e and 1j (R4 = H) and 1-(arylsulfonyl)-4-chloro-2-
methyl-2-butenes 1’a, 1’g, and 1’h (R4 = CH3) with secondary
amines leads to sulfonyl-containing fatty-aromatic tertiary amines.
Thus, the reactions with equimolar amounts of diethylamine,
morpholine, and diethanolamine yield 1-(arylsulfonyl)-2-R-4-N,
N-diethylamino-2-butenes (4e, 4j, and 4’g), 1-(arylsulfonyl)-2-R-4-
N-morpholyl-2-butenes (5j, 5’a, and 5’h), and 1-(4-sulfamoyl-
phenylsulfonyl)-4-N,N-hydroxyethyl-2-butene 6j, respectively
(Scheme 3).
The composition of fatty-aromatic sulfides 8g and 8h was de-
termined by the 1Н NMR spectroscopic analysis. Recorded spec-
trum of the sulfide 8g is illustrated in Fig. S5 in the Supporting
Information, and the spectra assignment is discussed in the re-
lated text.
Quantum-chemical calculations
The structure of compounds 5’a and 5’h was confirmed by
means of 1H NMR spectroscopy. Recorded spectrum of the com-
pound 5’a is illustrated in Fig. S4 in the Supporting Information,
and the spectra assignment is discussed in the related text.
1-(Arylsulfonyl)-2-R-4-chloro-2-butenes (1g, 1h, 1j, and 1’h)
also undergo hydrolysis to form the corresponding primary
The DFT calculations performed within this study have been aimed
to explain the peculiarities of reactivity of 1-(arylsulfonyl)-2-R-4-
Scheme 4. Reversible transformations between 1-(arylsulfonyl)-2-R-4-
chloro-2-butenes (1) and 1-(arylsulfonyl)-2-R-2-buten-4-ols (7)
Scheme 3. Substitution of the active chlorine atom of the butenes 2 by
the diethylamine, morpholine, and diethanolamine moieties
Scheme 5. Nucleophilic substitution of the allylic chlorine with sodium
sulfide yielding bis[4-(arylsulfonyl)-3-R-but-2-enyl]sulfides (8)
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S. V. BONDARCHUK, V. V. SMALIUS AND B. F. MINAEV
chloro-2-butenes (1) as well as 1-arylsulfonyl 1,3-dienes (2). Be-
cause the nucleophilic substitution of chlorine is accompanied
with an intermediate formation of the allylic cations (1+), the reac-
tivity of the butenes 1 towards SN reactions is best described in
terms of the Mayr–Patz electrophile quantification scheme.[30–33]
DFT calculations support the general assumption of the SN1 mech-
anism of the reactions presented in Scheme 1; thus, the rate con-
stant logarithm of the electrophile–nucleophile reaction can be
expressed as in Eqn (3)
Table 1. Adiabatic ionization energies (IE), electron affinities
(EA), electronic chemical potential (μ), chemical hardness (η),
and global electrophilicity index (ω) of the alyllic cations (1+
and 1’+) (in eV) calculated at the B3LYP/6-311++G(2d,2p)
level of theory in acetone
Entry
IE
EA
μ
η
ω
1a+
1b+
1c+
1d+
1e+
1f+
7.73
7.51
7.02
7.66
7.56
8.07
8.24
8.19
7.92
7.92
7.71
8.23
8.20
5.64
5.62
5.58
5.67
5.67
5.75
5.73
5.74
5.70
5.71
5.34
5.43
5.44
ꢀ6.69
ꢀ6.56
ꢀ6.30
ꢀ6.66
ꢀ6.61
ꢀ6.91
ꢀ6.99
ꢀ6.97
ꢀ6.81
ꢀ6.82
ꢀ6.53
ꢀ6.83
ꢀ6.82
2.09
1.89
1.44
1.99
1.89
2.32
2.51
2.45
2.22
2.22
2.37
2.80
2.76
10.67
11.38
13.82
11.14
11.59
10.27
9.74
À
Á
log k ¼ s E þ Nexper ∝ ω þ Nad
(3)
where Nexper is the relative reactivity, E is the nucleophile indepen-
dent electrophilicity parameter, and s is the empirical parame-
ter.[30–33] The experimentally derived parameters E and Nexper are
proportional to the adiabatic global electrophilicity (ω) and nucle-
ophilicity indexes (Nad).
1g+
1h+
1i+
9.92
10.43
10.47
8.99
8.33
8.41
1j+
The former is calculated according to the well-known Parr
scheme;[43] it includes electron chemical potential (μ)[44] and
chemical hardness (η).[45] Consequently, after simplification,
one obtains the following expression:
1’a+
1’g+
1’h+
2
ðIE ꢀ EAÞ
ω ¼
(4)
8ðIE ꢀ EAÞ
Table 2. The calculated log k values for the nucleophile–
electrophile reactions yielding products 4–8
Herein, IE and EA are the adiabatic ionization energy and elec-
tron affinity.[34–36]
Product
log k
Product
log k
Product
log k
IE ¼ UXnþ1 ꢀ UXn
4j
16.50
17.61
14.36
16.49
14.43
5’a
6j
7j
7’h
7g
15.01
16.43
16.61
14.55
15.88
7h
8h
8g
8i
16.06
17.56
17.39
18.07
18.12
ꢀ
ꢁ
ꢀ
ꢁ
¼
Eenleþc1ðXÞ þ ZPVEXnþ1
ꢀ
EnelecðXÞ þ ZPVEnX
(5)
(6)
4e
4’g
5j
EA ¼ UnX ꢀ UnXꢀ1
5’h
8j
ꢀ
ꢁ
ꢀ
ꢁ
¼
EnelecðXÞ þ ZPVEnX
ꢀ
Eenlꢀec1ðXÞ þ ZPVEXnꢀ1
The results are listed in Table 2. The nucleophilicity indexes for
the studies reactants, calculated according to Eqn (7), are the
following: diethylamine (6.03 eV), morpholine (6.02 eV),
diethanolamine (5.96 eV), potassium hydroxide (6.14 eV), and so-
dium sulfide (7.65 eV), respectively. We should stress that the cal-
culated absolute log k values cannot be directly compared with
the experimentally obtained values. These can either serve as
the semi-quantitative reactivity descriptors or need a calibration
with some related reference systems.
In order to check how the calculated log k values describe the
obtained reaction yield, we have built a plot (Fig. 1). As expected,
high log k values correspond to the higher yields. Taking into
account that a yield equals to zero when log k = 0, we have
approximated the obtained data with two curves. The red curve
(Fig. 1(a)) includes all the product yields, except ones corre-
sponding to the cations 1j+ and 1e+. The latter products are
better described with another similar function (Fig. 1(b)). This is
likely due to some synthetic peculiarities that cannot be
accounted within these calculations.
The adiabatic values are much more accurate than ones ob-
tained within the “vertical” approach.[34–36] Finally, the adiabatic
nucleophilicity index has been calculated as the following:[46]
Nad ¼ 11:79 ꢀ IENu
(7)
Herein, IENu is the adiabatic ionization energy of the corre-
sponding nucleophile, and the number 11.79 corresponds to
the IE value (in eV) of the tetracyanoethylene molecule as a
reference.[47]
Thus, we have calculated the IE, EA, μ, η, and ω parameters for
the studied allylic cations. The data obtained are listed in Table 1.
It is interesting that the ω values rise when the corresponding
ring substituent possesses the higher electron-donating ability.
Moreover, the methyl group in the cations 1’+ decreases the ω
values significantly (Table 1). The Hammett constants (σp),[48]
however, do not correlate with the latter values, but strongly cor-
relate with the EA values (R2 = 0.9748). The correlation plot is pre-
sented in Fig. S6 in the Supporting Information. The absolute
values of global electrophilicity index are somewhat lower than
those of the singlet and triplet aryl cations (9–21 eV).[34] Conse-
quently, one may suspect that SN reactions of the allylic cations
1+ and 1’+ are not diffusion controlled. Thus, we have calculated
the log k values for the products 4–8 because these reactions
can be presented as electrophile–nucleophile addition between
the studied allylic cations and the corresponding nucleophile.
The optimized structure of the cation 1a+ is illustrated in Fig. 2,
while the structural parameters of all the studied allylic cations
are presented in Fig. S7 in the Supporting Information. As it fol-
lows from the molecular electrostatic potential (ESP) 3D map, a
uniform positive charge delocalization occurs onto the allylic
moiety (Fig. 2). Although, an electron depletion, caused by the
arylsulfonyl group, results in higher ESP values at the C(2) atom
rather than at the C(4), the condensed Fukui function (f +) values
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THE CHLORINE REACTIVITY IN 1-(ARYLSULFONYL)-2-R-4-CHLORO-2-BUTENES
Recently, we have found that a number of local Quantum
Theory of Atoms in Molecules properties are convenient for the
structure-activity description in benzidine and its singly and dou-
bly oxidized forms.[49,50] Being calculated in the bond critical
points (BCP), these can clarify the electron distribution and, con-
sequently, the reactivity. Among these AIM quantities, we have
used the electron density ρ(r), its Laplacian ∇2ρ(r), energy densi-
ties he(r), g(r), and v(r),[51] bond ellipticity ε(r),[51] average local
ionization energy Ī(r),[52] localized orbital locator,[53] and electron
localization function (ELF).[54] Figure 2(b) illustrates BCPs where
the local descriptors are studied. The calculated data regarded
to BCP1 are collected in Table 3, and the rest results (for BCP2
and BCP3) are included in the Supporting Information (Tables
S3 and S4, respectively).
In contrast to the global molecular properties listed in Table 1,
all the local descriptors, excluding several peculiar cases, do
strongly correlate with the corresponding (σp) constants. The av-
erage value of R2 is higher than 0.95 for all three BCPs. Actually,
the correlation coefficients are even higher and often approach
to 0.999, but such regression analysis requires more decimals
to be accounted because the obtained values are very sensitive
to rounding. The high R2 values suggest that every local molec-
ular characteristics itself can serve as a reactivity descriptor, but
the obtained absolute values should be compared with a proper
reference structure. For this purpose, we have applied 2-butenyl
cation (denoted as a blank). Thus, we can estimate how the
whole arylsulfonyl group affects the pure 1,3-butadiene
reactivity.
Figure 1. Yields of the nucleophilic substitution reactions forming the
products 4–8 versus the corresponding reaction rate logarithms (log k)
calculated by the Mayr–Patz equation
Surprisingly, the local descriptors suggest that the electron
density is donated to the C(1)–C(2), C(2)–C(3), and C(3)–C(4)
bonds compared with the blank (see the corresponding ρ(r)
values in Tables 3, S3, and S4). Thus, one can conclude that the
SO2Ar group behaves as an electron-donating substituent. This
also follows from the highest ESP values of the cation 1a+ and
of the blank (the bold values in Fig. 2). As one can see in Fig. 2,
the blank values of ESP are higher; this suggests that the ArSO2
group stabilizes the cation 1a+ (the highest and lowest values
of ESP for the rest cations that are listed in Table S2 in the
Supporting Information). Such interesting effect might be due
to the cation stabilization by resonance, which can be illustrated
in Scheme S1 (structures I–VIII) in the Supporting Information.
Additionally, the effect of hyperconjugation explains such be-
havior of the ArSO2 group. Indeed, the dihedral angle φ (Fig. S7)
in the cation 1a+ is equal to 99.1°, and the lCꢀS = 1.927 Å, that is
noticeably higher than in the butene 1a (1.840 Å). Moreover,
the ρ(r) values at BCP corresponding to the C–S bond are equal
to 0.1513 (1a+) and 0.1866 (1a), respectively. These structural
and topological peculiarities prove the presence of an electron
donation towards the allylic moiety and importance of
hyperconjugation as a stabilizing factor (structures IX and X in
Scheme S1). It is worthwhile noting that the increased Ī(r) and
ELF values in the cations 1+ can be ascribed to the inductive
effect of the oxygen atoms counterbalancing to some extent
hyperconjugation.
Figure 2. The structure of the cation 1a+ together with molecular elec-
trostatic potential 3D map (a) and diene 2a (b) optimized at the B3LYP/6-
311++G(2d,2p) level of theory in acetone. Magenta circles indicate the
bond critical points (BCP) in the compounds 1+ and 2 where the local de-
scriptors are estimated.
It is interesting that the electronic effect of the CH3 group in
the cations 1’+ results in decreasing ρ(r) values at BCP1 and
BCP2, but its small increase at BCP3 (Tables 3, S3, and S4). This
suggests an increased contribution of the resonance structure
II (Scheme S1 in the Supporting Information). It is important that
in the cation l’a+ the C–S bond elongation is less pronounced,
possibly because the methyl group concurs to donate electron
density via hyperconjugation: lCꢀS are equal to 1.902 Å (l’a+) vs.
suggest the latter atom as a more preferable site for nucleophilic
attack (0.167 vs. 0.134). The latter f + values for the rest cations
are listed in Table S2 in the Supporting Information. It is worth-
while noting that the ring substituents slightly affect the ESP
values on the allylic fragment, while the CH3 group in the cations
1’+ causes a rather drastic effect. This also follows from the lower
ω indexes (Table 1).
J. Phys. Org. Chem. 2015
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S. V. BONDARCHUK, V. V. SMALIUS AND B. F. MINAEV
Table 3. The local molecular properties (in a. u.) of the cations 1+ and 1’+ calculated at the r1 point (BCP1)
Entry
ELF(r)
LOL(r)
Ī(r)
∇2ρ(r)
he(r)
v(r)
g(r)
ε(r)
ρ(r)
Blank
1a+
1b+
1c+
1d+
1e+
1f+
0.9531
0.9563
0.9559
0.9555
0.9565
0.9565
0.9574
0.9573
0.9573
0.9568
0.9570
0.9582
0.9590
0.9590
0.9665
0.8184
0.8239
0.8231
0.8224
0.8243
0.8243
0.8258
0.8256
0.8257
0.8248
0.8251
0.8273
0.8288
0.8286
0.9602
0.6228
0.6468
0.6456
0.6436
0.6476
0.6476
0.6486
0.6503
0.6507
0.6489
0.6494
0.6350
0.6379
0.6383
0.9529
ꢀ0.7548
ꢀ0.7734
ꢀ0.7809
ꢀ0.7866
ꢀ0.7701
ꢀ0.7690
ꢀ0.7489
ꢀ0.7566
ꢀ0.7562
ꢀ0.7636
ꢀ0.7619
ꢀ0.7171
ꢀ0.7040
ꢀ0.7047
0.9675
ꢀ0.2662
ꢀ0.2714
ꢀ0.2744
ꢀ0.2768
ꢀ0.2701
ꢀ0.2697
ꢀ0.2620
ꢀ0.2647
ꢀ0.2645
ꢀ0.2675
ꢀ0.2667
ꢀ0.2509
ꢀ0.2456
ꢀ0.2459
0.9673
ꢀ0.3437
ꢀ0.3494
ꢀ0.3536
ꢀ0.3570
ꢀ0.3476
ꢀ0.3471
ꢀ0.3368
ꢀ0.3417
ꢀ0.3399
ꢀ0.3441
ꢀ0.3430
ꢀ0.3224
ꢀ0.3153
ꢀ0.3156
0.9651
0.0775
0.0780
0.0792
0.0802
0.0775
0.0774
0.0748
0.0755
0.0754
0.0766
0.0763
0.0716
0.0696
0.0697
0.9588
0.0407
0.0573
0.0629
0.0676
0.0556
0.0552
0.0438
0.0471
0.0468
0.0515
0.0500
0.0428
0.0354
0.0355
0.9483
0.2825
0.2901
0.2918
0.2931
0.2894
0.2892
0.2851
0.2865
0.2864
0.2880
0.2876
0.2794
0.2765
0.2767
0.9641
1g+
1h+
1i+
1j+
1’a+
1’g+
1’h+
R2
The boldface style has been chosen to readily discriminate the R2 values from that of descriptors, which are often very similar.
Table 4. The local molecular properties of the dienes 2 calculated at the r1 point (BCP1)
Entry
ELF(r)
LOL(r)
Ī(r)
∇2ρ(r)
he(r)
v(r)
g(r)
ε(r)
ρ(r)
Blank
2a
2b
2c
2d
2e
2f
2g
2h
2i
0.9324
0.9299
0.9298
0.9298
0.9300
0.9300
0.9306
0.9302
0.9303
0.9301
0.9302
0.9895
0.7879
0.7846
0.7845
0.7845
0.7847
0.7847
0.7855
0.7850
0.7851
0.7849
0.7850
0.9745
0.5845
0.6237
0.6230
0.6223
0.6252
0.6252
0.6265
0.6278
0.6281
0.6261
0.6269
0.9957
ꢀ0.9993
ꢀ0.9742
ꢀ0.9744
ꢀ0.9744
ꢀ0.9734
ꢀ0.9735
ꢀ0.9717
ꢀ0.9725
ꢀ0.9722
ꢀ0.9731
ꢀ0.9728
0.9748
ꢀ0.3794
ꢀ0.3739
ꢀ0.3741
ꢀ0.3741
ꢀ0.3735
ꢀ0.3735
ꢀ0.3723
ꢀ0.3730
ꢀ0.3727
ꢀ0.3733
ꢀ0.3731
0.9803
ꢀ0.5090
ꢀ0.5043
ꢀ0.5046
ꢀ0.5047
ꢀ0.5037
ꢀ0.5037
ꢀ0.5016
ꢀ0.5028
ꢀ0.5023
ꢀ0.5032
ꢀ0.5030
0.9865
0.1296
0.1304
0.1305
0.1305
0.1302
0.1302
0.1293
0.1298
0.1296
0.1300
0.1299
0.9649
0.3319
0.3179
0.3185
0.3191
0.3171
0.3169
0.3114
0.3153
0.3139
0.3157
0.3152
0.9882
0.3425
0.3397
0.3398
0.3398
0.3396
0.3396
0.3392
0.3393
0.3392
0.3395
0.3394
0.9595
2j
R2
The boldface style has been chosen to readily discriminate the R2 values from that of descriptors, which are often very similar.
1.927 Å (la+). Although the local descriptors in the cations 1+ and
1’+ behave in a different manner compared with the blank, the
global electrophilicity parameter takes into account all the sub-
stituents effects, which is seen in the correlation between the
Scheme 6. Resonance structures of the diene 2a
ω values and the local descriptors.
Another aim of the present work is to study the peculiar reac-
tivity of the dienes 2. The optimized structures of the latter com-
pounds together with the selected structural and infrared
spectral parameters are presented in Fig. S8 in the Supporting In-
formation. On one hand, the latter compounds hardly react in
the Diels–Alder condensation (see the previous section). When
reacting with aryl diazonium salts in the SO2 saturated medium,
these compounds behave as isolated rather than conjugated di-
enes.[3–6] Thus, the carbon atoms C(3) and C(4) appear to be op-
erating and crucial, not the C(1) and C(4) atoms. Similar to the
consideration of the allylic cations, we have calculated the local
molecular properties at the BCPs (Fig. 2) of the dienes 2 in order
to rationalize their reactivity. The obtained data are listed in
Tables 4, S5, and S6. In contrast to the cations 1+, the electron
distribution in dienes 2 behaves in a slightly different manner.
A small electron depletion is observed in BCP1 and BCP3 com-
pared with the blank (1,3-butadiene). Meanwhile, the ρ(r) value
at BCP2 is higher. This is in accord with the rise of the polar
resonance structure contribution (Scheme 6, structure b).
It is worth noting that the ring substituent in the dienes 2 has
almost no effect on the structural parameters (Fig. S8 in the
Supporting Information). Such shifting of the electron density
towards the ArSO2 group (Scheme 6) should partly break the
conjugated system. Among the great variety of methods for es-
timating the π-electron conjugation, we have used two-centered
delocalization index δ (2c-DI)[55–57] and localization index λ (LI)[55]
as the most reliable descriptors. As one can see in Table 5, the
three key descriptors, namely, 2c-DI, LI, and LAB do exhaustively
suggest a partial breaking of the conjugated system in the
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THE CHLORINE REACTIVITY IN 1-(ARYLSULFONYL)-2-R-4-CHLORO-2-BUTENES
Table 5. The two-centered delocalization (2c-DI) and localization (LI) indexes, Laplacian bond orders (LAB), and frontier molecular
orbital energies of the dienes 2
a
a
Entry
2c-DI (δ)
C2–C3 C3–C4
LI (λ)
LAB
EHOMO
eV
,
ELUMO,
eV
C1–C2
C1
C2
C3
C4
C1–C2 C2–C3 C3–C4
Blank
2a
2b
2c
2d
2e
2f
2g
2h
2i
1.8741
1.6903
1.6913
1.6921
1.6877
1.6875
1.6770
1.6842
1.6818
1.6856
1.6842
0.9927
1.2145 1.8741 4.374
1.2082 1.8534 4.005
1.2081 1.8539 4.004
1.2080 1.8544 4.003
1.2086 1.8521 4.005
1.2085 1.8520 4.005
1.2088 1.8493 4.007
1.2093 1.8504 4.008
1.2097 1.8493 4.008
1.2089 1.8512 4.006
1.2091 1.8504 4.006
4.106
4.028
4.029
4.030
4.026
4.026
4.020
4.024
4.022
4.024
4.023
4.106 4.374
4.105 4.340
4.105 4.340
4.105 4.341
4.105 4.338
4.105 4.338
4.105 4.334
4.105 4.336
4.105 4.334
4.105 4.337
4.105 4.336
1.9157 1.3180
1.8128 1.3149
1.8140 1.3109
1.8130 1.3131
1.8087 1.3153
1.8077 1.3142
1.8028 1.3170
1.8097 1.3169
1.8054 1.3148
1.8077 1.3132
1.8056 1.3160
1.9157 ꢀ6.31
1.9155 ꢀ6.84
1.9158 ꢀ6.75
1.9153 ꢀ6.42
1.9141 ꢀ6.85
1.9117 ꢀ6.82
1.9112 ꢀ6.98
1.9160 ꢀ6.99
1.9125 ꢀ7.00
1.9123 ꢀ6.93
1.9110 ꢀ6.96
ꢀ0.69
ꢀ1.79
ꢀ1.76
ꢀ1.70
ꢀ1.88
ꢀ1.89
ꢀ2.85
ꢀ2.84
ꢀ2.97
ꢀ2.20
ꢀ2.11
2j
R2
0.9506 0.9941 0.8979 0.9958
—
0.9701 0.9013 0.3569 0.6848
0.7249
0.7293
aCalculated using the DFT(B3LYP)/6-31G(d) method in acetone.
The boldface style has been chosen to readily discriminate the R2 values from that of descriptors, which are often very similar.
Table 6. Radical (f0), electrophilic (f+), and nucleophilic (fꢀ) Fukui functions condensed to the diene carbon atoms in the dienes 2
Entry
fAþ
fA0
fAꢀ
C(1)
C(2)
C(3)
C(4)
C(1)
C(2)
C(3)
C(4)
C(1)
C(2)
C(3)
C(4)
2a
2b
2c
2d
2e
2f
2g
2h
2i
0.091
0.095
0.101
0.085
0.086
0.006
0.002
0.007
0.038
0.042
0.194
0.102
0.104
0.106
0.097
0.099
0.019
0.008
0.018
0.055
0.060
0.112
0.064
0.067
0.071
0.060
0.060
0.007
0.003
0.007
0.028
0.030
—
0.135
0.140
0.146
0.127
0.127
0.020
0.010
0.020
0.065
0.070
—
0.098
0.090
0.068
0.087
0.081
0.065
0.064
0.067
0.077
0.077
0.198
0.086
0.083
0.072
0.079
0.076
0.046
0.042
0.046
0.063
0.063
0.115
0.078
0.069
0.051
0.068
0.062
0.058
0.058
0.060
0.065
0.068
—
0.141
0.130
0.102
0.126
0.117
0.095
0.091
0.096
0.113
0.114
—
0.105
0.084
0.035
0.089
0.075
0.124
0.126
0.126
0.117
0.113
0.202
0.070
0.062
0.037
0.062
0.054
0.074
0.076
0.074
0.072
0.066
0.118
0.091
0.072
0.030
0.077
0.064
0.110
0.112
0.113
0.103
0.105
—
0.146
0.120
0.058
0.126
0.107
0.169
0.173
0.173
0.161
0.158
—
2j
Blank
dienes 2. When compared with the blank, the aforementioned
parameters in the bond C(1)–C(2) are sharply decreased. The
far the bond is distant from the ArSO2 group, the more the calcu-
lated values approach to those of the blank. The high correla-
tions of the 2c-DI, LI, and LAB values with the corresponding
Hammett (σp) constants indicate that the influence of the SO2Ar
group does proceed through the π system. The electron density
depletion from the diene moiety in compounds 2 decreases sig-
nificantly their reactivity towards the Diels–Alder condensation
(Scheme 2). A simple descriptor – the highest occupied molecu-
lar orbital energy value (EHOMO) – has been used to elucidate the
relative ability of the dienes 2 in the latter reaction. When com-
pared with the blank, all the EHOMO values are lower (Table 5);
this means that the more energy is needed for breaking the con-
jugated system. Indeed, the dienes 2 require melting at rather
high temperatures to undergo the Diels–Alder reaction (Experi-
mental Section). Thus, the obtained theoretical results
completely confirm the experimental findings.
f 0, f + values of the dienes 2 compared with bare 1,3-butadiene
(Table 6), is that these are less reactive towards the addition
reactions. Secondly, despite the electron withdrawing nature of
the ArSO2 group, the electrophilic addition to the dienes 2 is a
more preferable reaction pathway, than the radical and, espe-
cially, nucleophilic attack. Moreover, the highest values of the
Fukui functions are characteristic to the C(4) atoms; thus, taking
into account the partly broken conjugated system, we can
confirm computationally that the addition to the dienes 2 does
proceed via the C(4) and C(3) carbon atoms.[3–6]
CONCLUSIONS
In the present work, we have studied reactivity of 13 various
ring-substituted 1-(arylsulfonyl)-2-R-4-chloro-2-butenes towards
both nucleophilic substitution and elimination reactions. The
experiments have revealed that these dienes easily undergo SN
reactions with amines (diethylamine, morpholine, and
diethanolamine), KOH, and Na2S. The high reactivity has been
rationalized in terms of an effective resonance stabilization of
Finally, we have calculated the Fukui functions condensed to
the carbon atoms in the diene moiety; the results are listed in
Table 6. The first conclusion, which follows from the lower f ꢀ
,
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S. V. BONDARCHUK, V. V. SMALIUS AND B. F. MINAEV
the intermediate allylic cations, which has been determined from
the ESP values and the local reactivity descriptors, namely, ρ(r), Ī
(r), and ELF. The obtained reaction yields correlate with the the-
oretical log k values computed by means of the Mayr–Patz equa-
tion, which has included the global electrophilicity index (ω) and
the adiabatic nucleophilicity index (Nad). The good linear correla-
tions (R2 ~ 0.97) of the reactivity parameters of the allylic cations
with the corresponding Hammett σp constants of the ring
substituents have indicated that their influence predominantly
proceeds via the π system.
Compound 2a
Yield 73% (based on triethylamine), oily compound (crystallizes upon
cooling in ice water). Anal. Calcd for С10Н10O2S: S, 16.50. Found: S,
16.41; Calcd: С, 61.83. Found: C, 62.05; Calcd: H, 5.19. Found: H, 5.27.
Compound 2b
Yield 87% (based on triethylamine), oily compound (crystallizes upon
cooling in ice water). Anal. Calcd for С11Н12O2S: S, 15.39. Found: S,
15.22; Calcd: С, 63.43. Found: C, 63.68; Calcd: H, 5.81. Found: H, 5.96.
The elimination of hydrogen chloride from 1-(arylsulfonyl)-2-R-
4-chloro-2-butenes has yielded the corresponding 1-arylsulfonyl
1,3-dienes. These compounds were characterized experimentally
as poor dienes in the Diels–Alder condensation. The calculations
have revealed that these have lower HOMO energies compared
with bare 1,3-butadiene that explains their general inactivity.
The computed values of the 2c-DI and LI of the studied
dienes have allowed us to elucidate why these compounds
behave as isolated rather than conjugated dienes in addition
reactions.[3–5] The mechanism of the latter reactions with aryl
diazonium salts in the SO2 saturated medium, however, is still
not yet completely clear.
Compound 2c
Yield 83% (based on triethylamine), oily compound (crystallizes upon
cooling in ice water). Anal. Calcd for С11Н12O3S: S, 14.29. Found: S,
14.16; Calcd: С, 58.91. Found: C, 58.98; Calcd: H, 5.39. Found: H, 5.60.
Compound 2d
Yield 53% (based on triethylamine), oily compound (crystallizes upon
cooling in ice water). Anal. Calcd for С10Н9ClO2S: Cl, 15.50. Found: Cl,
15.20; Calcd: S, 14.02. Found: S, 14.24; Calcd: С, 52.52. Found: C, 52.83;
Calcd: H, 3.97. Found: H, 4.08.
Obushak et al.[58–61] put forward the most exhaustive pro-
posal, which included an intermediate formation of the radical
cation of the reaction substrate (diene). At the same time, we
have recently found that the transition state of addition reaction
to the double C¼C bond of π-nucleophiles has a multireference
Compound 2e
Yield 69%, mp: 44–45 °C. Anal. Calcd for С10Н9BrO2S: Br, 29.25. Found: Br,
28.84; Calcd: S, 11.74. Found: S, 12.05; Calcd: С, 43.97. Found: C, 44.21;
Calcd: H, 3.32. Found: H, 3.40.
3
nature with a high contribution of the triplet ππ* state of the
latter.[35] Consequently, the triplet states of π-nucleophiles
should be considered when estimating the activation barrier of
this reaction.[35,62–67] Moreover, our recent results suggest that
the aforementioned 3ππ* states can be achieved under the
“dark” conditions by the action of catalyst (copper fine
particles).[68] Therefore, the complete understanding of the
dienes 2 reactivity still remains to be a puzzle for both experi-
mentalists and theoreticians.
Compound 2f
Yield 62%, mp: 79–80 °C. 1H NMR (600 MHz, CDCl3) δ: 5.67–5.70 (d, Ј =
9 Hz, 1Н, СН2), 5.76–5.82 (d, Ј = 17.1 Hz, 1Н, СН), 5.42–6.54 (m, 1Н, СН),
6.86–6.91 (d, Ј = 15 Hz, 1Н, СН), 7.29–7.32 (m, 1Н, СН), 7.77–7.83 (m, 3Н,
о-О2NС6Н4), 8.16–8.19 (dd, 1Н, o-О2NС6Н4); The 1H NMR spectrum of
1
the diene 2j: H NMR (600 MHz, CDCl3) δ: 4.92 (s, 2Н, NН2), 5.67–5.70 (d,
J = 9.0 Hz, 1Н, СН), 5.78–5.82 (d, J = 17.0 Hz, 1Н, СН), 6.37–6.40–6.44
(m, 2Н, СН2), 7.30–7.32–7.33–7.35 (dd, J1 = 11.0, J2 = 11.5 Hz, 1Н, СН),
8.04–8.06 (d, J = 8.0 Hz, 2Н, С6Н4), 8.09–8.11 (d, J = 7.5 Hz, 2Н, p-Н-
2NSО2С6Н4); Anal. Calcd for С10Н9NO4S: N, 5.55. Found: N, 5.70; Calcd:
S, 13.40. Found: S, 13.27; Calcd: С, 50.20. Found: C, 50.29; Calcd: H,
3.79. Found: H, 3.93.
EXPERIMENTAL SECTION
General
The 1H NMR spectra were recorded using Varian VXR-300 and Varian
Gemini-400 spectrophotometers in СDСl3, DMSO-d6, or Me2CO-d6
solvents. Reaction solvents were dried and distilled under nitrogen using
standard procedures. All commercially available reactants were
purchased form Aldrich, ALSI Ltd. Kiev, Ukraine and used without further
purification. 1-(Arylsulfonyl)-4-chloro-2-butenes were prepared according
to our previously developed protocol[69] and were recrystallized before use.
Compound 2g
Yield 76%, mp: 61–62 °C. Anal. Calcd for С10Н9NO4S: N, 5.55. Found: N,
5.76; Calcd: S, 13.40. Found: S, 13.65; Calcd: С, 50.20. Found: C, 50.41;
Calcd: H, 3.79. Found: H, 3.95.
Compound 2h
Yield 95%, mp: 102–103 °C. Anal. Calcd for С10Н9NO4S: N, 5.55. Found: N,
5.76; Calcd: S, 13.40. Found: S, 13.60; Calcd: С, 50.20. Found: C, 50.38;
Calcd: H, 3.79. Found: H, 3.87.
General procedure for the synthesis of 1-arylsulfonyl
1,3-butadienes (2a–2j)
To a solution of the corresponding 1-(arylsulfonyl)-4-chloro-2-butene
(0.05 mol) in 130 mL of benzene, a solution of 6.9 mL of triethylamine
(0.05 mol) in 20 mL of benzene was added dropwise. The reaction mix-
ture was refluxed on a water bath at 70–80 °С for 3 h. After cooling the
reaction mixture, a precipitate of triethylamine hydrochloride was sepa-
rated, then benzene was distilled off under reduced pressure, and the
residue was recrystallized. Solvents for recrystallization of the com-
pounds 2a–2c, 2d–2g, 2h–2i, and 2j were the following: hexane,
ethanol–water 2/1 mixture, ethanol–water 1/2 mixture, and ethanol–
water 1/1 mixture, respectively.
Compound 2i
Yield 92%, mp: 174–175 °C. Anal. Calcd for С11Н10O4S: S, 13.45. Found: S,
13.20; Calcd: С, 55.45. Found: C, 55.20; Calcd: H, 4.23. Found: H, 4.06.
Compound 2j
Yield 48%, mp: 184–185 °C. Anal. Calcd for С10Н11NO4S2: N, 5.12. Found:
N, 5.02; Calcd: S, 23.46. Found: S, 23.73; Calcd: С, 43.94. Found: C, 44.05;
Calcd: H, 4.05. Found: H, 4.29.
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THE CHLORINE REACTIVITY IN 1-(ARYLSULFONYL)-2-R-4-CHLORO-2-BUTENES
General procedure for the synthesis of anhydrides of 1-
Compound 4’g
(arylsulfonyl)-1,4,5,6-tetrahydrophthalic acid (3g–3j)
Yield 37%, mp: 163–164 °C. Anal. Calcd for С15Н22N2O4S: N, 8.56. Found:
N, 8.58; Calcd: S, 9.82. Found: S, 10.03; Calcd: С, 55.19. Found: C, 55.27;
Calcd: H, 6.72. Found: H, 6.83.
The corresponding 1-arylsulfonyl 1,3-butadiene (0.01 mol) was mixed
with 1 g (0.01 mol) of freshly sublimed maleic anhydride, and then the
mixture was alloyed for 6 h. After cooling, the solid melt was separated
and recrystallized. The compound 3g was recrystallized from benzene
and the compounds 3h–3j form glacial acetic acid.
Compound 5j
Yield 32%, mp: 168–169 °C. Anal. Calcd for С14Н20N2O5S2: N, 7.63. Found:
N, 7.77; Calcd: S, 17.79. Found: S, 17.60; Calcd: С, 46.65. Found: C, 46.44;
Calcd: H, 5.59. Found: H, 5.49.
Compound 3g
Yield 15%, mp: 133–134 °C. 1H NMR (600 MHz, CDCl3) δ: 2.56 (m, 2Н, СН2),
3.84 (m, 2Н in СНСО), 5.03 (t, 1Н, СН), 5.67 (t, 1Н, СН), 6.29 (m, 1Н in
СНSO2), 7.94–7.95–7.97 (t, J1 = 7.5, J2 = 8.0 Hz, 1Н, m-О2NС6Н4),
8.26–8.28 (d, 1Н, J = 8.0 Hz, m-О2NС6Н4), 8.57 (d, 1Н, m-О2NС6Н4), 8.59
(s, 1Н, m-О2NС6Н4). The 1H NMR spectrum of the adduct 3h: 1H NMR
(600 MHz, CDCl3) δ: 2.49–2.55 (m, 1Н, СН), 2.59 (m, 1Н, СН), 3.85 (m, 2Н,
СН2), 4.98–4.99–5.01 (t, 1Н, СН), 5.62 (t, 1Н, СН), 6.28 (m, 1Н, СН),
8.12–8.13 (d, J = 9.0 Hz, 2Н, p-О2NС6Н4), 8.44–8.46 (d, J = 9.0 Hz, 2Н,
Compound 5’a
Yield 53%, mp: 98–99 °C. 1H NMR (600 MHz, CDCl3) δ: 1.85 (s, 3Н, СН3),
2.29 (t, 4Н, СН2), 2.93–2.94 (d, J = 6.5 Hz, 2Н, СН2), 3.66 (t, 4Н, СН2), 3.81
(s, 2Н, СН2), 5.25 (t, 1Н, СН), 7.55–7.57–7.58 (t, J1 = 7.0, J2 = 7.5 Hz, 2Н,
С6Н5), 7.64–7.66–7.67 (t, 1Н, С6Н5), 7.87–7.89 (d, J = 8.0 Hz, 2Н, С6Н5);
Anal. Calcd for С15Н21NO3S: N, 5.00. Found: N, 4.74; Calcd: S, 10.85. Found:
S, 10.89; Calcd: С, 60.99. Found: C, 61.10; Calcd: H, 7.16. Found: H, 7.28.
p-О2NС6Н4); Anal. Calcd for С14Н11NO7S: N, 4.15. Found: N, 4.12; Calcd:
S, 9.50. Found: S, 9.66; Calcd: С, 49.85. Found: C, 50.07; Calcd: H, 3.29.
Found: H, 3.45.
Compound 5’h
Yield 41%, mp: 137–138 °C. 1H NMR (600 MHz, CDCl3) δ: 1.71 (s, 3Н, СН3),
2.07 (s, 4Н, СН2), 2.78–2.79 (d, J = 7.0 Hz, 2Н, СН2), 3.34–3.50 (m, 4Н, СН2),
4.23 (s, 2Н, СН2), 5.19 (t, 1Н, СН), 8.12–8.14 (d, J = 9.5 Hz, 2Н, p-О2NС6Н4),
8.42–8.44 (d, J = 8.5 Hz, 2Н, p-О2NС6Н4); Anal. Calcd for С15Н20N2O5S: N,
8.44. Found: N, 8.23; Calcd: S, 9.42. Found: S, 9.39; Calcd: С, 52.93. Found:
Compound 3h
Yield 17%, mp: 203–204 °C. Anal. Calcd for С14Н11NO7S: N, 4.15. Found: N,
3.92; Calcd: S, 9.50. Found: S, 9.70; Calcd: С, 49.85. Found: C, 50.10; Calcd:
H, 3.29. Found: H, 3.47.
C, 53.12; Calcd: H, 5.92. Found: H, 5.98.
Compound 3i
Yield 11%, mp: 257–280 °C (decomposition). Anal. Calcd for С15Н12O7S: S,
9.53. Found: S, 9.36; Calcd: С, 53.57. Found: C, 53.71; Calcd: H, 3.59. Found:
H, 3.68.
Compound 6j
Yield 31%, mp: 191–192 °C. Anal. Calcd for С14Н22N2O6S2: N, 7.35. Found:
N, 7.40; Calcd: S, 8.47. Found: S, 8.28; Calcd: С, 44.43. Found: C, 44.80;
Calcd: H, 5.86. Found: H, 5.99.
Compound 3j
Yield 19%, mp: 200–250 °C (decomposition). Anal. Calcd for С14Н13NO7S2:
N, 3.77. Found: N, 3.62; Calcd: S, 17.27. Found: S, 17.44; Calcd: С, 45.28.
Found: C, 45.50; Calcd: H, 3.53. Found: H, 3.77.
General procedure for the synthesis of 1-(arylsulfonyl)-2-R-2-
buten-4-ols (7)
To a solution of the corresponding 4-substituted 1-(arylsulfonyl)-2-butene
(0.02 mol) in 30 mL of acetone, a solution of 1.12 g (0.02 mol) of potassium
hydroxide in 10 mL of water was added dropwise. The reaction mixture was
heated until dissolving and left at room temperature for 1 h. Then it was
poured in 100 mL of water. The formed solid phase was separated and
recrystallized. The compounds 7g and 7’h were recrystallized from a mixture
of acetic acid-water 1/2, the compound 7h from a mixture of ethanol–water
1/1, and the compound 7j from a mixture of ethanol–water 1/2.
General procedure for the synthesis of 1-(arylsulfonyl)-4-N,
N-dialkylamino-2-butenes (4–6)
To a solution of the corresponding 1-(arylsulfonyl)-2-R-4-chloro-2-butene
(0.02 mol) in 20 mL of acetone a solution of the corresponding secondary
amine (0.02 mol) in 5 mL of acetone was added dropwise. The reaction
mixture was refluxed on a water bath at 70–80 °С for 1 h. After cooling,
the reaction mixture was poured into 50 mL of water, and then sodium
carbonate was added until a slightly alkali reaction. The formed precipi-
tate was separated and recrystallized. Solvents for recrystallization of
the compounds were the following: ethanol–water 2/1 mixture (4e),
ethanol–water 1/2 mixture (4j), ethanol–water 1/1 mixture (4’g and 6j),
and neat water (5j, 5’a, and 5’h).
Compound 7g
Yield 59%, mp: 71–72 °C. Anal. Calcd for С10Н11NO5S: N, 5.44. Found: N,
5.18; Calcd: S, 12.46. Found: S, 12.22; Calcd: С, 46.69. Found: C, 46.74;
Calcd: H, 4.31. Found: H, 4.52.
Compound 7h
Compound 4e
Yield 61%, mp: 109–110 °C. Anal. Calcd for С10Н11NO5S: N, 5.44. Found: N,
Yield 34%, mp: 198–199 °C. Anal. Calcd for С14Н20BrNO2S: N, 3.97. Found:
5.24; Calcd: S, 12.46. Found: S, 12.20; Calcd: С, 46.69. Found: C, 46.77;
N, 4.04; Calcd: Br, 23.07. Found: Br, 22.90; Calcd: S, 9.26. Found: S, 9.43;
Calcd: H, 4.31. Found: H, 4.49.
Calcd: С, 48.56. Found: C, 48.72; Calcd: H, 5.82. Found: H, 5.95.
Compound 4j
Compound 7j
Yield 31%, mp: 219–220 °C. Anal. Calcd for С14
Н22N2O4S2: N, 7.94. Found:
Yield 37%, mp: 165–166 °C. Anal. Calcd for С10Н13NO5S2: N, 4.80. Found:
N, 8.08; Calcd: S, 18.51. Found: S, 18.70; Calcd: С, 48.53. Found: C, 48.67;
N, 4.87; Calcd: S, 22.01. Found: S, 22.20; Calcd: С, 41.22. Found: C, 41.48;
Calcd: H, 6.40. Found: H, 6.45.
Calcd: H, 4.50. Found: H, 4.59.
J. Phys. Org. Chem. 2015
Copyright © 2015 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/poc

S. V. BONDARCHUK, V. V. SMALIUS AND B. F. MINAEV
Compound 7’h
To describe the studied interactions as a realistic feature of condensed
phase, the polarizable continuum model simulations have been in-
cluded.[76] Acetone was chosen as a model medium because it is used
in the studied synthesis. To define cavities the universal force field radii
were used.[76] The overlap index and a minimum radius of the spheres
were specified as 0.8 and 0.5 Å, respectively. The DFT calculations of
the closed-shell species were performed using the spin-restricted
Kohn–Sham formalism, while the open-shell species were calculated in
terms of the spin-unrestricted Kohn–Sham approach.
The Quantum Theory of Atoms in Molecules properties[51] have been
calculated using the AIMQB program within the AIMStudio suite using
the Proaim basin integration method.[77] A part of post-SCF analyses
were performed with a recently developed Multiwfn program pack-
age.[78] The condensed Fukui functions and the dual descriptor values
have been computed using the atomic charges determined by the
Hirshfeld population analysis.[79] This part of calculations was treated
using the DFT(BLYP)/TNP method implemented in Materials Studio 5.5
suite of programs.[80] Wherein, the polar medium simulation was
performed using a conductor-like screening model.[81]
Yield 43%, mp: 89–90 °C. Anal. Calcd for С11Н13NO5S: N, 5.16. Found: N,
5.22; Calcd: S, 11.82. Found: S, 11.60; Calcd: С, 48.70. Found: C, 48.68;
Calcd: H, 4.83. Found: H, 4.73.
General procedure for the synthesis of bis[4-(arylsulfonyl)-3-
R-but-2-enyl]sulfides (8)
To a solution of the corresponding 1-(arylsulfonyl)-2-R-4-chloro-2-butene
(0.02 mol) in 40 mL of acetone, a solution of 2.4 g (0.01 mol) of Na2S 9H2O
in 15 mL of water was added dropwise. The reaction mixture was left at
room temperature for 1 h and then poured in 100 mL of water. The
formed solid phase was separated and recrystallized. The compounds
8g, 8h, 8j, and 8’h were recrystallized from glacial acetic acid and the
compound 8i from a mixture of acetic acid–water 1/2.
Compound 8g
Yield 66%, mp: 158–159 °C. 1H NMR (600 MHz, CDCl3) δ 2.86–2.87 (d,
4Н, СН2), 4.26–4.27 (d, 4Н, СН2), 5.36 (m, 2Н, СН), 5.51 (m, 2Н, СН),
7.93–7.95–7.96 (t, J1 = 8.0, J2 = 8.0 Hz, 2Н, m-О2NС6Н4), 8.26–8.28 (d,
J = 6.5 Hz, 2Н, m-О2NС6Н4), 8.53–8.55–8.57 (t, J1 = 9.5, J2 = 9.5 Hz, 4Н,
Acknowledgements
m-О2NС6Н4); Anal. Calcd for С20Н20N2O8S3: N, 5.46. Found: N, 5.39;
Calcd: S, 18.77. Found: S, 18.50; Calcd: С, 46.86. Found: C, 46.57; Calcd:
H, 3.93. Found: H, 3.84.
This work was supported by the Ministry of Education and
Science of Ukraine, Research Fund (Grant No. 0113U001694).
We thank Professor Hans Ågren (KTH, Stockholm) for the PDC
supercomputer use. The computations were performed on
resources provided by the Swedish National Infrastructure for
Computing (SNIC) at the Parallel Computer Center (PDC) through
the project “Multiphysics Modeling of Molecular Materials,” SNIC
020/11-23.
Compound 8h
Yield 65%, mp: 191–192 °C. 1H NMR (600 MHz, CDCl3) δ 2.87–2.88 (d, 4Н,
СН2), 4.25–4.26 (d, 4Н, СН2), 5.34 (m, 2Н, СН), 5.53 (m, 2Н, СН), 8.11–8.12
(d, J = 8.5 Hz, 4Н, p-О2NС6Н4), 8.43–8.45 (d, J = 9.0 Hz, 4Н, p-О2NС6Н4).
Anal. Calcd for С20Н20N2O8S3: N, 5.46. Found: N, 5.33; Calcd: S, 18.77.
Found: S, 18.49; Calcd: С, 46.86. Found: C, 46.51; Calcd: H, 3.93. Found:
H, 3.72.
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