Halosulfenylation of Conjugated Dienes with Arylsulfenamides in the Presence of Phosphorus Oxyhalides

Article abstract of DOI:10.1023/A:1026055717386

Electrophilic sulfenylation of cyclic and open-chain conjugated dienes effected by a system arylsulfenamide-phosphorus oxyhalide was investigated. The initially formed adducts of 1,2-halosulfenylation in the course of the reaction and also at storage and chromatograqphic purification on silica gel undergo quantitative isomerization into a mixture of stereoisomeric products of 1,4-addition. The effect of halogen nature and the character of substituents in the benzene ring of arenesulfenamide on the addition rate of sulfenamides activated by phosphorus oxyhalides to open-chain and cyclic conjugated dienes and isomerization rate of the arising 1,2-adducts was examined.

Full text of DOI:10.1023/A:1026055717386

Russian Journal of Organic Chemistry, Vol. 39, No. 4, 2003, pp. 513 526. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 4, 2003,
pp. 549 561.
Original Russian Text Copyright
2003 by Beloglazkina, Belova, Antipin, Zyk Buryak.
Dedicated to Full Member of the Russian Academy of Sciences
I. P. Beletskaya on occasion of her jubilee
Halosulfenylation of Conjugated Dienes with Arylsulfenamides
in the Presence of Phosphorus Oxyhalides
E. K. Beloglazkina1, M. A. Belova1, R. L. Antipin1,
N. V. Zyk1, and A. K. Buryak2
1Lomonosov Moscow State University, 119992 Moscow, Russia e-mail: bel@org.chem.msu.su
2Institute of Physical Chemistry, Russian Academy of Sciences, Moscow
Received July 10, 2002
Abstract Electrophilic sulfenylation of cyclic and open-chain conjugated dienes effected by a system
arylsulfenamide phosphorus oxyhalide was investigated. The initially formed adducts of 1,2-halosulfenyla-
tion in the course of the reaction and also at storage and chromatograqphic purification on silica gel undergo
quantitative isomerization into a mixture of stereoisomeric products of 1,4-addition. The effect of halogen
nature and the character of substituents in the benzene ring of arenesulfenamide on the addition rate of
sulfenamides activated by phosphorus oxyhalides to open-chain and cyclic conjugated dienes and iso-
merization rate of the arising 1,2-adducts was examined.
We have formerly described the halosulfenylation
of a homoconjugated diene, bicyclo[2.2.1]hepta-2,5-
diene, with a system arylsulfenamide phosphorus
oxyhalide [1]. A possibility to prepare various
products from the same initial reagents by modifica-
tion of reaction conditions opens wide synthetic
prospects and requires further investigation of this
reagent. In this study we examined the addition of
arylsulfenamides activated by phosphorus oxyhalides
to a number of conjugated dienes: 2,3-dimethyl-1,3-
addition occurred trans-stereospecifically in keeping
with Markownikoff rule. On storage or at heating the
1,2-products isomerized into more stable 1,4-adducts.
On the other hand the system arylsulfenamide
phosphorus oxybromide is a synthetic equivalent of
arylsulfenyl bromides whose addition to diene
systems is almost unknown.
Our study has shown that the best yields of
halosulfenylated products are obtained when excess
diene reacts with the system arylsulfenamide phos-
phorus oxyhalide (at the ratio diene sulfenylating
agent 1.5 : 1) in CH2Cl2 at 40 C. Initially formed
1,2-adducts in the course of reaction and also at
storage or when submitted to chromatography on
silica gel quantitatively isomerize into a mixture of
stereoisomeric products of 1,4-addition.
butadiene,
2-methyl-1,3-butadiene
(isoprene),
1,3-cyclohexadiene, and 1,3-cyclopentadiene.
The reagent we apply, arylsulfenamide phosphorus
oxychloride, may be regarded as
a synthetic
equivalent of arylsulfenyl chlorides. The sulfenyl
chlorides addition to conjugated dienes is sufficiently
well documented [2 8]. On a large number of
substituted 1,3-butadienes [5] and on some cyclic
diene systems [7, 8] the addition of sulfenyl chlorides
was shown to furnish 1,2-adduct. Therewith the
With cyclic dienes the reaction gives rise to a
single product of trans-1,2-addition across an only
double bond.
1070-4280/03/3904-0513$25.00 2003 MAIK Nauka/Interperiodica

514
BELOGLAZKINA et al.
Table 1. Yields and ratio of reaction products obtained by treating 1,3-cyclopentadiene with sulfenamides activated
with phosphorus oxyhalides
Ratio of reaction products, %
Overall
POHlg3 Sulfenamide, Ar
Index
Reaction time, h
yield, %
I
III
IV
POBr3
POCl3
4-NO2C6H4
2-NO2C6H4
C6H5
a
b
c
d
2
20
2
2
22
29
28
100
63
40
42
36
38
29
36
95
95
95
80
4-NO2C6H4
After 120 h of storage
After submitting to chromatography
18
75
18
25
18
2-NO2C6H4
C6H5
e
f
3
100
62
76
50
21
40a
After 120 h of storage
38
16
42
46
24
8
8
33
80a
50
After 170 h of storage
3
a
Unreacted sulfenamide remained in the reaction mixture.
Table 2. Yields and ratio of reaction products obtained by treating 1,3-cyclohexadiene with sulfenamides activated
with phosphorus oxyhalides
Ratio of reaction products, %
Overall
POHlg3 Sulfenamide, Ar
Index
a
Reaction time, h
yield, %
II
V
VI
POBr3
4-NO2C6H4
3
50
18
10
50
66
50
77
75
83
56
50
80
After 120 h of storage
After boiling in CHCl3
After submitting to chromatography
16
40
23
60
30
85
95
78
2-NO2C6H4
C6H5
b
c
d
18
42
25
17
23
25
100
69
63
100
67
100
66
40
1
21
25
After 120 h of storage
POCl3
4-NO2C6H4
1.5
80a
After 15O h of storage
31
37
5
4
86
2-NO2C6H4
C6H5
e
f
93a
After 120 h of storage
33
42
4
90a
60
34
60
After 120
h
of storage
a
Unreacted sulfenamide remained in the reaction mixture.
The data on yields and composition of reaction
products obtained from 1,3-cyclopentadiene and
1,3-cyclohexadiene treated with the system aryl-
sulfenamide phosphorus oxyhalide are compiled in
Tables 1 and 2 respectively.
1,3-cyclopentadiene resulted in a mixture of trans-
and cis-isomers of 5-arylsulfanyl-3-halocyclopent-1-
ene with significant prevalence of trans-isomer III.
However in the case of 4-(o-nitrophenylsulfanyl)-3-
chlorocyclopent-1-ene (Ie) was obtained almost sole
isomerization
product,
trans-5-(o-nitrophenyl-
The isomerization of 4-arylsulfanyl-3-halocyclo-
sulfanyl)-3-chlorocyclopent-1-ene (IIIe), cis-isomer
pent-1-enes (Ia f) obtained by halosulfenylation of
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HALOSULFENYLATION OF CONJUGATED DIENES
515
IVe formed only in trace amount. Apparently the
nitro group in the ortho position of benzene ring
interacts with the arising carbocation and prevents the
attack of the chloride ion from the exo-side.
It should be noted that this effect is not observed
isomerization
enes (IIb, d f) (1,3-cyclohexadiene adducts) afforded
exclusively trans-5-arylsulfanyl-3-halocyclohex-1-
enes (Vb, d f). Probably here one unshared pair of
sulfur atom can interact with a carbocation site arising
in the fourth position of the cyclohexane ring.
of 4-arylsulfanyl-3-halocyclohex-1-
with
3-bromo-4-(o-nitrophenylsulfanyl)cyclopen-1-
ene (Ib). Apparently the attack on the carbocationic
site of bromide anion which is a stronger nucleophile
than chloride ion occurred faster than nitro group
coordination. The data compiled in Table 2 show that
cis-Isomer VI was obtained only from 3-bromo-
anion on the carbocation site as compared to the other
nucleophiles (e.g., unshared electron pairs of sulfur).
5-(p-nitrophenylsulfanyl)cyclohex-1-ene
(a)
and
3-bromo-5-phenylsulfanylcyclohex-1-ene (c). Same
as with isomerization of cyclopentadiene adducts here
assumption is possible of faster attack of bromide
The halosulfenylation of the symmetrical 2,3-di-
methyl-1,3-butadiene similarly to reaction with cyclic
dienes afforded a single 1,2-adduct that isomerized
into E- and Z-isomers of 4-arylsulfanyl-1-halo-2,3-
dimethyl-1-butene.
amides activated with phosphorus oxyhalides are
listed in Table 3.
The yields and ratio of reaction products obtained
from 2,3-dimethyl-1,3-butadiene and arylsulfen-
With unsymmetrical 1,3-diene, isoprene, the situa-
tion is far more complicated since are presumable two
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516
BELOGLAZKINA et al.
Table 3.Yields and ratio of reaction products obtained by treating 2,3-dimethyl-1,3-butadiene with sulfenamides
activated with phosphorus oxyhalides
Ratio of reaction products, %
Overall
POHlg3 Sulfenamide, Ar
Index
Reaction time, h
yield, %
VII
(E)-VIII (Z)-VIII
POBr3
POCl3
4-NO2C6H4
2-NO2C6H4
C6H5
4-NO2C6H4
2-NO2C6H4
a
b
c
d
e
2
17
2
27
17
21
3
10
40
40
50
7
14
20
9
40
60
50
19
28
40
9
57
90
87
85
59a
32a
75
74
58
40
82
C6H5
f
a
Unreacted sulfenamide remained in the reaction mixture.
Table 4.Yields and ratio of reaction products obtained by treating isoprene with sulfenamides activated with phosphorus
oxyhalides
Reaction
time, h
Ratio of reaction products, %
Overall
yield, %
POHlg3 Sulfenamide, Ar
Index
IX
X
(Z)-XI
(E)-XI
(E)-XI
POBr3
POCl3
4-NO2C6H4
2-NO2C6H4
C6H5
4-NO2C6H4
2-NO2C6H4
C6H5
a
b
c
d
e
f
2
18
2
27
27
2
10
15
11
23
20
23
60
48
53
27
34
38
30
16
20
96
90
77
95
51a
89
21
16
50
33
9
13
38
a
Unreacted sulfenamide remained in the reaction mixture.
1,2-adducts arising in keeping with Markownikoff
rule, and 4 isomers of 1,4-adduct (see Table 4).
and (E)-(XII) of which only isomer (E)-(XII) is
obtained.
It is clear, that E- and Z-isomers of compound XI
arise as a result of adduct IX isomerization, and
isomerization of adduct X can furnish (Z)-(XII)
The data in Table 4 show that arenesulfenamides
activated with phosphorus oxyhalides react pre-
dominantly with the more substituted double bond of
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HALOSULFENYLATION OF CONJUGATED DIENES
517
the isoprene. As a result forms compound IX, and its
isomerization gives rise to isomers (Z)-(XI) and
(E)-(XI). Product X originating from the reaction at
the less substituted isoprene double bond forms in
considerably smaller amount and almost does not
suffer isomerization.
conformation where C4 atom is outside the plane
formed by the other four carbon atoms [9]. This fact
significantly simplifies the interpretation of coupling
constants in the course of structural assignment.
In the 1H NMR spectra of compounds I (Table 5)
the signals of protons at the double bond appear as
two multiplets, and methylene protons have quite
different chemical shifts (3.30 3.15 and 2.50
2.40 ppm) and forms (doublet of doublets of quartets
and doublet of doublets of triplets respectively). By
an example of compound Ie it was established apply-
ing the homonuclear double resonance procedure that
the coupling constant of olefin protons is 5.8 Hz,
and the constants of their coupling with the protons
of CH2 group are 1.5 2.0 Hz. The proton signals of
substituents in compounds I look as follows: H CHlg
is a broadened singlet or a triplet with a coupling
constant of about 2.0 Hz , H CS is a doublet with a
coupling constant of 7.0 Hz. According to published
data [9] substituted cyclopentenes have the values of
We revealed certain laws governing reactions with
all dienes studied. The rate of reaction with dienes
of sulfenamides activated with POHlg3 depends not
only on the proper structure of the diene but also on
the character of the halogen and of substituents in the
benzene ring of the sulfenamide. The cyclic dienes
react with the sulfenamides activated with phosphorus
oxyhalides faster, than open-chain analogs (2,3-di-
methyl-1,3-butadiene and isoprene). The reaction of
N-(o-nitriphenylsulfanyl)morpholine activated with
POHlg3 (Hlg = Cl, Br) with dienes is about 10 times
slower than reactions of N-(p-nitrophenyl)- and
N-phenylsulfanylmorpholine.
Sulfenamides react faster in the presence of POBr3
than POCl3 resulting in higher yilds of bromosulfides
as compared to chlorosulfides. Besides 1,2-adducts of
bromosulfenylation easier undergo isomerization into
1,4-adducts that the chlorosulfides because bromide
anion is a better leaving group than chloride anion,
and the primarily formed bromosulfides easier trans-
form into the corresponding carbocations than the
respective chlorosulfides.
3
3Jtrans 3.0 4.0 and Jcis 6.0 8.0 Hz. The lack of large
coupling constant by H CHlg atom and a common
large coupling constant by H CS and by one of the
protons of the CH2 group (7.0 Hz) allow assignment
to compounds I a structure of 1,2-trans-adduct of
1,3-cyclopentadiene.
The structure of 1,4-adducts was assigned to
products III and IV by analogy with the published
data [7, 8, 11]. The signals from olefin protons of
compounds III and IV appear as a sole multiplet.
The signals from the other four protons of compounds
III and IV (H CHlg, H CS and CH2) are dissimilar
in form and chemical shifts (Tables 6 and 7). As
already mentioned, the coupling constants in the
spectra of substituted cyclopentenes have values 3Jtrans
It should be noted that isomerization of products
obtained by bromo- and chlorosulfenylation by
N-phenylsulfanylmorpholine occurs faster than the
isomerization of halosulfenylation products prepared
with the use of nitro-substituted arylsulfenamides.
Apparently the PhS group as a better donor than
O2NC6H4S group provides better stabilization of the
arising carbocation and thus facilitates the isomeriz-
ation.
3
3.0 4.0 and Jcis 6.0 8.0 Hz [9]. The comparison of
these values with the sets of coupling constants of
isomers III and IV given in tables shows that the
protons H4 and H4 in compound III are in different
configurational relations to protons H3 and H5,
whereas in the isomer IV the protons H3 and H5 are
configurationally equivalent with respect to protons
H4 and H4 . Consequently compounds III are trans-
isomers, and compounds IV cis-isomers of 5-aryl-
sulfanyl-3-halocyclopent-1-enes.
The structure of products obtained was deduced
from the 1H NMR spectra. The analysis of spectra
and their subsequent description were based on the
1
1
published data, on the values of the H H coupling
constants, and also on the results of homonuclear
double resonance spectra. The chemical shifts of
protons and coupling constants in the 1H NMR
spectra of compounds synthesized are compiled in
Tables 5 15.
The structure of compounds IId and Va (Table 8)
was established applying the method of homonuclear
1
Configuration assignments of compounds I, III,
1H H double resonance. It was shown that the
3
IV were based on analysis of coupling constants J
proton H CS in compound IId is coupled with the
proton H CCl and the protons of the adjacent CH2
group whereas the H CCl is coupled with H CS and
with one of the olefin protons. These data un-
values and on analogous published data [7 11]. Note
that conformational mobility of substituted cyclo-
pentenes is insignificant, and prevails the envelope
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522
BELOGLAZKINA et al.
1
1
Table 12. Chemical shifts of H nuclei ( , ppm ) and coupling constants 1H H (J Hz) of compounds VIIIa f
Compd. no.
VIIIa
Isomer
H1
H4
H3C5
H3C6
H(Ar)
E
Z
E
Z
E
Z
E
Z
E
Z
E
Z
4.02 s
4.00 s
4.04 s
4.01 s
3.94 s
3.75 s
4.08 s
4.07 s
4.11 s
4.09 s
4.02 s
3.79 s
3.76 s
3.69 s
3.68 s
3.62 s
3.57 s
3.50 s
3.75 s
3.68 s
3.68 s
3.63 s
3.56 s
3.51 s
1.86 s
1.85 s
8.12 d (J 8.8); 7.36 d (J 8.8)
1.89 q (J 1.5) 1.83 q (J 1.5) 8.10 d (J 8.8); 7.36 d (J 8.8)
VIIIb
1.90 1.83 m
1.90 1.83 m
8.18 7.24 m
8.14 7.24 m
VIIIc
1.82 q (J 0.9) 1.76 q (J 0.9) 7.37 7.17 m
1.86 q (J 1.3) 1.56 q (J 1.4) 7.37 7.17 m
VIIId
1.91 1.79 m
1.91 1.79 m
1.96 1.83 m
1.96 1.83 m
8.09 d (J 9.2); 7.40 d (J 9.2)
8.07 d (J 9.0); 7.33 d (J 9.0)
8.32 7.20 m
VIIIe
8.32 7.20 m
7.51 7.12 m
VIIIf
1.83 s
1.74 s
1.88 q (J 1.4) 1.56 q (J 1.4) 7.51 7.12 m
1
Table 13. Chemical shifts of 1H nuclei ( , ppm ) and coupling constants 1H H (J Hz) of compounds IXb, d e
H1
H1
H2
H2C4
H3C5
H(Ar)
IXb 5.14 d(J1,2 10.7) 5.35 d (J1,2 17.3) 5.97 d.d (J2,1 17.3, J2,1 10.7) 3.22 d, 3.14 d (2J4,4 12.3) 1.85 s 8.19 7.21 m
IXd 5.19 d(J1,2 10.7) 5.37 d (J1,2 17.0) 6.03 d.d (J2,1 17.0, J2,1 10.7) 3.26 d, 3.19 d (2J4,4 13.2) 1.78 s 8.20 8.03 m,
7.41 7.29 m
IXd 5.19 d(J1,2 10.6) 5.38 d (J1,2 17.2) 6.04 d.d (J2,1 17.2, J2,1 10.6) 3.25 d, 3.17 d (2J4,4 12.5) 1.83 s 8.34 7.24 m
IXf 5.13 d(J1,2 10.7) 5.31 d (J1,2 17.2) 5.99 d.d (J2,1 17.2, J2,1 10.7) 3.19 d, 3.08 d (2J4,4 13.3) 1.76 s 7.40 7.12 m
1
Table 14. Chemical shifts of 1H nuclei ( , ppm ) and coupling constants 1H H (J Hz) of compounds Xa f
H1
H1
H3
H2C4
H3C5
H(Ar)
Xa
5.00 br.s
5.08 br.s 4.65 d.d (J3,4 9.9, J3,4 5.7) 3.63 d.d (2J4,4 13.0, J4,3 5.7), 1.83 s 8.16 8.04 m,
3.50 d.d (2J4,4 13.0, J4 ,3 9.9) 7.38 7.30 m
Xb 4.98 t (J1,1 1.2) 5.08 br.s 4.70 d.d (J3,4 10.1, J3,4 5.5) 3.59 d.d (2J4,4 13.3, J4,3 5.5), 1.85 s 8.19 7.21 m
3.45 d.d (2J4,4 13.3, J4 ,3 10.1)
Xc
5.00 t (J1,1 1.4) 5.08 br.s 4.61 d.d (J3,4 10.4, J3,4 5.4) 3.52 d.d (2J4,4 13.7, J4,3 5.4), 1.82 s 7.40 7.12 m
3.36 d.d (2J4,4 13.7, J4 ,3 10.4)
Xd 5.01 t (J1,1 1.2) 5.05 br.s 4.52 d.d (J3,4 8.6, J3,4 6.5) 3.50 d.d (2J4,4 13.5, J4,3 6.5), 1.82 s 8.20 8.03 m,
3.38 d.d (2J4,4 13.5, J4 ,3 8.6) 7.41 7.29 m
Xe
5.00 t (J1,1 1.2) 5.04 br.s 4.57 d.d (J3,4 8.8, J3,4 6.2) 3.46 d.d (2J4,4 13.2, J4,3 6.2), 1.83 s 8.34 7.24 m
3.34 d.d (2J4,4 13.2, J4 ,3 8.8)
Xf
4.97 t (J1,1 1.3) 5.00 br.s 4.43 d.d (J3,4 9.2, J3,4 6.0) 3.35 d.d (2J4,4 13.8, J4,3 6.0), 1.87 s 7.40 7.12 m
3.22 d.d (2J4,4 13.8, J4 ,3 9.2)
ambiguously indicate the structure of 1,2-adduct.
In the case of compound Va both protons H CS and
H CBr are coupled with the protons at the double
bond with a constant equal to 4.7 4.9 Hz (Table 9)
evidencing the structure of 1,4-adduct.
trans-Location of substituents in compounds IId
and Vd was proved applying -criterion. The
essence of the method consists in measuring half-
width of signals from protons attached to the sub-
1
stituents in the H NMR spectra registered in solvents
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HALOSULFENYLATION OF CONJUGATED DIENES
523
1
Table 15. Chemical shifts of 1H nuclei ( , ppm ) and coupling constants 1H H (J, Hz) of compounds XIa f, XIIc
Compd. Isomer
no.
H C =
H2CHlg
H2CS
CH3
H(Ar)
XIa
Z
E
5.77 t.q (J 8.4, J 1.2)
5.73 t (J 8.2)
3.93 d (J 8.4)
3.95 d (J 8.2)
3.64 s
3.73 s
1.83 br.s
1.90 br.s
8.16 8.04 m,
7.38 7.30 m
8.16 8.04 m,
7.38 7.30 m
XIb
XIc
XId
XIe
XIf
Z
E
Z
E
Z
5.83 t.q (J 8.4, J 1.2)
5.87 t (J 8.8)
5.54 t.q (J 8.3, J 1.2)
5.60 t (J 8.4)
3.96 d (J 8.4)
4.00 d (J 8.8)
3.91 d (J 8.3)
3.95 d (J 8.4)
4.04 d (J 8.0)
3.62 s
3.68 s
3.48 s
3.56 s
3.64 s
1.86 d (J 1.2) 8.19 7.21 m
1.93 br.s 8.19 7.21 m
1.85 d (J 1.2) 7.40 7.12 m
1.82 br.s 7.40 7.12 m
1.82 d (J 1.3) 8.20 8.03 m,
7.41 7.29 m
5.70 t.q (J 8.0, J 1.3)
Z
E
Z
E
E
5.75 t.q (J 8.0, J 1.2)
5.70 t (J 8.6)
5.42 t.q J 7.9, J 1.1)
5.47 t (J 8.0)
4.06 d (J 8.0)
4.09 d (J 8.6)
3.69 d (J 7.9)
3.97 d (J 8.0)
3.94 s
3.61 s
3.68 s
3.46 s
1.86 d (J 1.2) 8.34 7.24 m
1.93 br.s
8.34 7.24 m
1.81 d (J 1.1) 7.40 7.12 m
3.50 s
1.76 br.s
1.65 br.s
7.40 7.12 m
7.40 7.12 m
XIIc
5.89 t (J 8.6)
3.66 d (J 8.6)
1
of different polarity. Therewith for a trans-adducts
occurs simultaneous broadening or narrowing of
signals from protons linked to the substituents [12].
We recorded the spectra of compounds IId and
Vd in deuterobenzene and deuterochloroform. The
simultaneous broadening of proton signals related to
the substituents confirmed trans-configuration of the
substituents in the adducts II and V. The structure
of compounds VII XII was established basing on
published data [2, 3, 5] and on 1H H coupling
constants (Tables 10 15). Besides we measured mass
spectra of all compounds synthesized. The identifica-
tion was performed either by the search in the data-
bases or by analysis of mass spectra proceeding from
the main laws of organic compounds fragmentation
under the electron impact [13]. The main trends in
fragmentation of compounds I VI and VII XII are
given below.
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BELOGLAZKINA et al.
Table 16. Parameters of mass spectra of compounds I XII
Compd. no.
Main peaks in mass spectra, m/z (Irel, %)
I, III, IVa 45 (23) [CHS]+ , 65 (27) [C5H5]+ , 97 (38) [C5H5S]+ , 79 (85) [C6H7]+ , 171 (18), 219 (100) [M-HBr]+
I, III, IVb 45 (38) [CHS]+ , 53 (43) [C4H6]+ , 65 (27) [C5H5]+ , 138 (100) [C6H4NOS]+ , 154 (65), 174 (44), 185 (35),
219 (77) [M-HBr]+
I, III, IVc 65 (24) [C5H5]+ , 67 (100) [C5H7]+ , 77 (5) [C6H5]+ , 97 (5) [C5H5S]+ , 110 (85) [PhSH]+ , 174 (8) [M-HBr]+
I, III, IVd 39 (41) [C3H3]+ , 45 (47) [CHS]+ , 65 (51) [C5H5]+ , 97 (53) [C5H5S]+ , 128 (25), 171 (34), 219 (100)
[M-HCl]+
I, III, IVe 56 (94) [C4H8]+ , 77 (100) [C6H5]+ , 91 (14), 105 (37), 138 (10) [C6H4NOS]+ , 175 (23)
I, III, IVf 45 (21) [CHS]+ , 65 (22) [C5H5]+ , 77 (8) [C6H5]+ , 97 (29) [C5H5S]+ , 109 (85) [PhS]+ , 141 (32), 174 (100)
[M-HCl]+
II, V, VIa 44 (18) [CS]+ , 51 (14) [C4H3]+ , 65 (8) [C5H5]+ , 77 (67) [C6H5]+ , 79 (85) [C6H7]+ , 111 (24) [C6H7S]+ ,
155 (8), 171 (5), 184 (16), 233 (100) [M-HBr]+
II, V, VIb 51 (24) [C4H3]+ , 77 (34) [C6H5]+ , 92 (10), 125 (10), 139 (24), 152 (18), 167 (100), 184 (52), 231 (32)
[M-HBr H2]+
II, V, VIc 44 (24) [CS]+ , 51 (54) [C4H3]+ , 65 (27) [C5H5]+ , 77 (99) [C6H5]+ , 79 (87) [C6H7]+ , 92 (13), 110 (76)
[PhSH]+ , 155 (24), 186 (82) [M-HBr H2]+ , 188 (100) [M-HBr]+
II, V, VId 44 (21) [CS]+ , 51 (39) [C4H3]+ , 65 (22) [C5H5]+ , 77 (99) [C6H5]+ , 79 (99) [C6H7]+ , 111 (63) [C6H7S]+ ,
155 (19), 171 (14), 184 (25), 233 (100) [M-HCl]+ , 234 (42) [M-Cl]+
II, V, VIe 56 (88) [C4H8]+ , 77 (100) [C6H5]+ , 105 (36), 118 (7), 138 (10) [C6H4NOS]+ , 175 (27)
II, V, VIf 44 (28) [CS]+ , 51 (34) [C4H3]+ , 65 (19) [C5H5]+ , 77 (69) [C6H5]+ , 79 (56) [C6H7]+ , 110 (54) [PhSH]+ ,
155 (16), 186 (41) [M-HCl H2]+ , 188 (100) [M-HCl]+
VII, VIIIa 41 (56) [C3H5]+ , 53 (80) [C4H5]+ , 65 (21) [C5H5]+ , 79 (90) [C6H7]+ , 81 (95) [C6H9]+ , 99 (47), 113 (22)
[C6H9S]+ , 121 (12), 235 (100) [M-HBr]+ , 236 (29) [M-Br]+
VII, VIIIb 41 (54) [C3H5]+ , 53 (70) [C4H5]+ , 79 (66) [C6H7]+ , 81 (39) [C6H9]+ , 138 (100) [C6H4NOS]+ , 152 (29),
235 (38) [M-HBr]+
VIII, VIIIc 41 (26) [C3H5]+ , 53 (26) [C4H5]+ , 55 (31) [C4H7]+ , 65 (19) [C5H5]+ , 79 (30) [C6H7]+ , 81 (23) [C6H9]+ ,
83 (51), 99 (34), 110 (46) [PhSH]+ , 190 (100) [M-HBr]+ , 191 (16) [M-Br]+
VII, VIIId 41 (45) [C3H5]+ , 53 (62) [C4H5]+ , 65 (16) [C5H5]+ , 79 (77) [C6H7]+ , 81 (81) [C6H9]+ , 99 (32), 113 (15)
[C6H9S]+ , 235 (100) [M-HCl]+ , 236 (20) [M-Cl]+
VII, VIIIe 41 (50) [C3H5]+ , 53 (68) [C4H5]+ , 79 (66) [C6H7]+ , 81 (39) [C6H9]+ , 106 (22), 138 (100) [C6H4NOS]+ ,
152 (29), 235 (33) [M-HCl]+ , 236 (4) [M-Cl]+
VII, VIIIf 41 (27) [C3H5]+ , 53 (33) [C4H5]+ , 65 (22) [C5H5]+ , 79 (37) [C6H7]+ , 81 (23) [C6H9]+ , 99 (38), 109 (18),
110 (17) [PhSH]+ , 190 (100) [M-HCl]+ , 191 (15) [M-Cl]+
IX, X, XIa 41 (58) [C3H5]+ , 65 (21) [C5H5]+ , 67 (94) [C5H7]+ , 85 (41), 221 (100) [M-HBr]+ , 222 (17) [M-Br]+
IX, X, Xb 41 (100) [C3H5]+ , 65 (39) [C5H5]+ , 67 (71) [C5H7]+ , 78 (22) [C6H6]+ , 106 (29), 138 (77) [C6H4NOS]+ ,
156 (49), 221 (43) [M-HBr]+ , 222 (5) [M-Br]+
IX, X, XI, 41 (20) [C3H5]+ , 51 (19) [C4H3]+ , 65 (38) [C5H5]+ , 77 (11) [C6H5]+ , 99 (82) [C5H7S]+ , 176 (100)
XIIc
[M-HBr]+ , 177 (11) [M-Br]+
IX, X, XId 41 (58) [C3H5]+ , 65 (38) [C5H5]+ , 67 (70) [C5H7]+ , 85 (42), 221 (100) [M-HCl]+ , 222 (17) [M-Cl]+
IX, X, XIe 41 (91) [C3H5]+ , 65 (42) [C5H5]+ , 67 (82) [C5H7]+ , 78 (20) [C6H6]+ , 106 (32), 138 (100) [C6H4NOS]+ ,
156 (52), 221 (58) [M-HCl]+ , 222 (6) [M-Cl]+
IX, X, XIf 41 (18) [C3H5]+ , 51 (19) [C4H3]+ , 65 (35) [C5H5]+ , 77 (13) [C6H5]+ , 99 (98) [C5H7S]+ , 176 (100)
[M-HCl]+ , 177 (17) [M-Cl]+
It should be noted that in the mass spectra of all
compounds I XII the molecular ion peak is lacking.
The main primary decomposition direction of com-
ounds I XII is elimination of HHlg molecule result-
ing in appearance of peaks with m/z 219 (I, III, IVa,
b, d, e), 174 (I, III, IVc, f), 233 (II, V, VIa, b, d, e),
188 (II, V, VIc, f), 235 (VII, VIIIa, b, d, e), 190 (VII,
VIIIc, f), 221 (IX, X, XIa, b, d, e), 176 (IX, X, XIc, f,
XIIc). In the spectra of the majority of compounds
the most abundant peak is [M-HHlg]+ (Table 16).
Further character of [M-HHlg]+ fragmentation is
dissimilar and depends on the compound structure.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 4 2003

HALOSULFENYLATION OF CONJUGATED DIENES
525
The fragmentation of [M-HHlg]+ ions arising
from the sulfenylation products of 1,3-cyclohexadiene
(II, V, VI) consists in elimination of ArS and H2
resulting in appearance of strong peaks with m/z 77
[C6H5+ ] and 79 [C6H7+ ], whereas the fragmentation
of ions [M-HHlg]+ from compounds I, III, IV
occurs with elimination of ArH and ArSH to give
ions [C5H5S+ ], m/z 97, and [C5H5+ ], m/z 65.
and HP-5890 chromatograph. The velocity of spectra
registering in the range from 10 to 300 m/z or from
40 to 450 m/z varied from 1 to 2 seconds. The
chromatograms were recorded according to the total
ion current. The standard conditions for measuring
mass spectra are as follows: ion source temperature
150 C, ionizing electrons energy 70 eV, accelerating
voltage 3 kV, mass numbers range 40 400 amu.
The fragmentation of ions [M-HHlg]+ belonging
to the sulfenylation products of the open chain con-
jugated dienes (2,3-dimethyl-1,3-butadiene and
isoprene) occurs by successive ejection of ArS
and H2.
As a result form ions [C6H9+ ], m/z 81, and
[C6H7+ ], m/z 79, from compounds VII, VIIIa f, and
also [C5H7+ ], m/z 67, and [C5H5+ ], m/z 65, from
compounds IX, X, XIa f, XIIc. Besides in the mass
spectra of compounds VII, VIIIa, d is observed a
peak [C6H9S+ ], m/z 113, and for compounds IX, X,
XI, XIIc, IX, X, XIf appears a peak [C5H7S+ ],
m/z 99 originating apparently from the rupture of
C S bond in [M-HHlg]+ followed by ejection of
Ar .
Chromatographic analyses were performed on
micropacked columns of 50 0.1, 70 0.1, 70 0.08,
120 0.1 cm and on capillary column of 30 m
0.53 mm with a low polar phase DB-5 (5% of
phenylmethylsilicone), film thickness 1.5 m. The
packing used was Sterling MT of specific surface
1
7.6 m2 g and grain diameter 0.14 0.16, 0.16 0.18,
0.20 0.22 mm. Helium was applied as carrier gas,
1
flow rate 5 20 mlmin for micropacked columns
1
and 2 mlmin for capillary column The chromato-
graphic separation was carried out on the chromato-
graph HP-5890 connected to mass spectrometer, at
the use of the capillary column division was 1: 10.
The chromatographic separation was optimized by
variation of oven temperature programming: from
1
1 to 25 deg min with the micropacked columns to
0.5 to 15 deg min 1 for the capillary column.
The presence of substituents in the benzene ring
linked to the sulfur atom and their position also
affects further fragmentation of ions [M-HHlg]+ .
A characteristic peak in the mass spectra of all
products obtained by dienes sulfenylation with
N-phenylsulfanylmorpholine I VIIIc, f is that with
m/z 110 [C6H5SH+ ], whereas in compounds I XIb, e
the nitro group in the ortho-position of the benzene
ring is responsible for the specificity of their frag-
mentation ( ortho-effect [13]) and for appearance in
the spectra of these compounds of a peak with m/z
138 [C6H4NOS+ ].
Reactions of sulfenamides with dienes in the
presence of phosphorus oxyhalides. To a solution of
sulfenamide (2 mmol) in anhydrous CH2Cl2 (15 ml)
while vigorous stirring at 40 C was slowly added a
solution of 2 mmol of phosphorus oxyhalide in the
same solvent (15 ml), and the mixture was stirred for
10 min. Then a solution of diene (3 mmol) in
anhudrous CH2Cl2 (20 ml) was slowly added, the
mixture was stirred till the completion of the reaction
[TLC monitoring on fixed silica gel layer (Silufol)].
The reaction mixture was filtered through a 7 cm bed
of silica gel, and the solvent was evaporated.
EXPERIMENTAL
Data on yields and composition of the reaction
products are compiled in Tables 1 4. Chemical shifts
Commercial 2,3-dimethyl-1,3-butadiene, isoprene,
and 1,3-cyclohexadiene (Lancaster) were used with-
out additional purification. 1,3-Cyclopentadiene was
prepared just before use from its dimer (Lancaster)
by thermal decomposition along procedure [14].
Arylsulfenamides were prepared by procedure [15]
from the corresponding arylsulfenyl chlorides and
morpholine. Arylsulfenylchlorides were obtained
from the corresponding diaryl sulfides and sulfuryl
chloride [16].
1H NMR spectra were registered on Varian
VXR-400 spectrometer at operating frequency
400 MHz. GC-MS spectra were measured on JMS-
D300 instrument connected to a JMA-2000 computer
1
of 1H nuclei (ppm) and coupling constants 1H H(Hz)
of the compounds are listed in Tables 5 15. Param-
eters of mass spectra are presented in Table 16.
The authors are grateful to I. F. Leshcheva
(Chemical Department of Lomonosov Moscow State
University) for helping in registering and interpreta-
tion of the NMR spectra.
The study was carried out under financial support
of the Russian Foundation for Basic Research (grant
no. 02 03 33347) and Russian Ministry of Educa-
tion, program
no. 990879).
Universities of Russia (grant
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 4 2003

526
BELOGLAZKINA et al.
REFERENCES
p. 739.
10. Wawzonek, S. and Bennett, W.E., OMR, 1972, vol. 4,
1. Zyk, N.V., Beloglazkina, E.K., Belova, M.A.,
Leshcheva, I.F., Zefirov, and N.S., Izv. Akad. Nauk,
Ser. Khim., 2002, p. 1356.
2. Mueller, W.H. and Butler, P.E., J. Org. Chem.,
1967, vol. 32, p. 2925.
3. Mueller, W.H. and Butler P.E., J. Org. Chem., 1968,
vol. 33, p. 2642.
4. Corey, E.J. and Block E., J. Org. Chem., 1966,
vol. 31, p. 1663.
p. 73.
11. Zyk, N.V., Nikulin, A.V., Ugrak, B.I., Borisen-
ko, A.A., and Zefirov, N.S., Zh. Org. Khim., 1985,
vol. 21, p. 1189.
12. Zefirov, N.S., Samoshin, V.V., and Subbotin, O.A.,
Tetrahedron, 1978, vol. 34, p. 2953.
13. Zaikin, V.G., Varlamov, A.V., Mikaya, A.I., and
Prostakov, N.S., Osnovy mass-spektrometrii organi-
cheskikh soedinenii (Fundamentals of Mass Spectro-
metry of Organic Compounds), Moscow: MAIK
Nauka/Interperiodika , 2001, 286 p.
14. Syntheses of Organic Reagents, Moscow: Mir, 1949,
vol. 4, p. 565.
15. Billman, J.H., Garrison, J., Anderson R., and
Wolnak, B., J. Am. Chem. Soc., 1941, vol. 63,
p. 1920.
5. Schmid, G.H., Yeroushalmi, S., and Garratt D.G.,
J. Org. Chem., 1980, vol. 45, p. 910.
6. Rasteikene, L.P., Grechuite, D.I., Lin,kova, M.G., and
Knunyants, I.L., Usp. Khim., 1977, vol. 46, p. 1041.
7. Hartke, K., Jung, M.H., Zerbe, H., and Kamp-
chen, T. Lieb. Ann., 1986, p. 1268.
8. Hartke, K. and Gleim, H.U., Lieb. Ann., 1976, p. 716.
9. Cocu, F.G., Wolczunowicz, G., Bors L., and
Posternak, Th., Helv. Chim. Acta, 1970, vol. 53,
16. Mueller, W.H. and Butler, P.E., J. Org. Chem., 1968,
vol. 33, p. 1533.
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