Intramolecular electrophilic cyclization of functional derivatives of unsaturated compounds: II. Synthesis and transformation of N-{(2Z)-5- [(arylsulfanyl)methyl]dihydrofuran-2(3H)-ylidene}-N-alkyl(aryl)aminium perchlorates

Article abstract of DOI:10.1134/S1070428012020078

N-Alkyl(aryl)amides of allylacetic acid when reacting with arylsulfenyl chlorides in acetic acid in the presence of lithium perchlorate undergo a selective cyclization to form N-{(2Z)-5-[(arylsulfanyl)methyl] dihydrofuran-2(3H)-ylidene}-N-alkyl-(aryl)aminium perchlorates. Treating of the latter with sodium acetate leads to the formation of the corresponding 5-[(arylsulfanyl)methyl]lactones, and with sodium ethylate, to 5-[(arylsulfanyl) methyl]-2-iminolactones. In reaction with secondary cycloalkylamines in the presence of water a transamidation and tetrahydrofuran ring opening occurs to afford 5-arylsulfanyl-4-hydroxypentanoic acid amides. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012020078

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 2, pp. 193−201. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.I. Vas’kevich, N.M. Tsizorik, E.B. Rusanov, V.I. Staninets, M.V. Vovk, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48,
No. 2, pp. 206−213.
Intramolecular Electrophilic Cyclization of Functional
Derivatives of Unsaturated Compounds: II.*
Synthesis and Transformation of
N-{(2Z)-5-[(Arylsulfanyl)methyl]dihydrofuran-2(3H)-
ylidene}-N-alkyl(aryl)aminium Perchlorates
A. I. Vas’kevich, N. M. Tsizorik, E. B. Rusanov, V. I. Staninets, and M. V. Vovk
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, 02094 Ukraine
e-mail: vaskevich@ioch.kiev.ua
Received July 23, 2011
Abstract—N-Alkyl(aryl)amides of allylacetic acid when reacting with arylsulfenyl chlorides in acetic acid in
the presence of lithium perchlorate undergo a selective cyclization to form N-{(2Z)-5-[(arylsulfanyl)methyl]
dihydrofuran-2(3H)-ylidene}-N-alkyl-(aryl)aminium perchlorates. Treating of the latter with sodium acetate leads to
the formation of the corresponding 5-[(arylsulfanyl)methyl]lactones, and with sodium ethylate, to 5-[(arylsulfanyl)
methyl]-2-iminolactones. In reaction with secondary cycloalkylamines in the presence of water a transamidation
and tetrahydrofuran ring opening occurs to afford 5-arylsulfanyl-4-hydroxypentanoic acid amides.
DOI: 10.1134/S1070428012020078
The electrophilic intramolecular cyclization (EIC) of
unsaturated carboxylic acids at the treatment with sulfe-
nyl chlorides is a convenient method of the synthesis of
sulfanyl-substituted lactones [2, 3]. Yet the regularities of
the cyclosulfenylation of the amides of unsaturated car-
boxylic acids are virtually unstudied [4, 5], although the
process may take two routes involving two nucleophilic
sites (N and O atoms), which may result in sulfanyl-
containing lactams or lactones. The commonly adopted
scheme of the formation of the lactone ring involving EIC
postulates the participation of the corresponding iminium
salts [6] that as a rule without isolation are subjected to
hydrolysis into the target compounds. This kind interme-
diate compounds formerly practically were not objects
of investigations in various chemical reactions except
for [7] where the opening of the furanylideneiminium
salt was described in the presence of collidine in an
aprotic solvent. Therefore it seems reasonable to look
for a model EIC reaction that would result in relatively
stable iminium salts important both in the theoretical and
synthetic aspects.
To this end we chose as cyclization objects N-substi-
tuted allylacetamides whose reaction with the oxidating
system diphenyl disulfide–manganese(ІІІ) acetate had
been successfully applied to the preparation of 5-(sulfa-
nylmethyl)dihydro-2(3H)-furanones [8]. In the reaction of
allylacetamides Іa–Id with arylsulfenyl chlorides ІІa–IIc
in acetic acid in the presence of the equimolar amount
of LiClO4 as “dopant” [9, 10] a region- and stereoselec-
tive intramolecular cyclization occurred at the oxygen
atom of the amide group. As a result crystalline or oily
N-alkyl(aryl)-N-{5-[(arylsulfanyl)methyl]dihydrofuran-
2(3H)-ylidene}aminium perchlorates ІІІa–IIIl formed in
67–84% yields (Scheme 1).
The structure of obtained salts ІІІa–IIIl was confirmed
1
by spectral data. In particular, the H NMR spectra of
these compounds contain a set of multiplets of protons of
the dihydrofuran ring in the ranges 2.10–2.45, 2.40–2.70
(C4H2), 3.05–3.45 (C3H2), 5.20–5.60 (C5H) ppm and
of protons of exocyclic methylene group in the region
––––––––––––––––
* For Communucation I, see [1].
193

VAS’KEVICH et al.
194
Scheme 1.
bond. Therewith the sum of the bond angles at the atom
N2 is 360°. The lengths of the C–S bonds are not equal
evidently because of dissimilar hybridization of the atoms
C1 and C7, i.e., because of the conjugation of the unshared
electron pair of the sulfur atom with the π-system of the
phenyl substituent.
ClO_4
+
HN R
LiClO4
+
ArSCl
Ar S
C
NH
O
O
R
Iа_Id
IIa_IIc
IIIа_IIIl
In the crystal of compound IIIf hydrogen bonds N2–
I, R = Bu (a), i-Pr (b), Ph (c), 4-MeOC6H4 (d); II, Ar =
C6H5 (a), 4-MeC6H4 (b), 4-NO2C6H4 (c); III, R = Bu,Ar =
C6H5 (a), 4-MeC6H4 (b), 4-NO2C6H4 (c); R = i-Pr, Ar =
C6H5 (d), 4-MeC6H4 (e), 4-NO2C6H4 (f); R = Ph, Ar =
C6H5 (g), 4-MeC6H4 (h), 4-NO2C6H4 (i); R = 4-MeOC6H4,
Ar = C6H5 (j), 4-MeC6H4 (k), 4-NO2C6H4 (l).
4A
2
2N
4B
2
2N
H2N O and N –H
N
O were found [N –H 0.79(3),
...
...
2
4A
2
4B
2
2N
...
...
...
O 2.932(8), N O 2.837(8) Å, angles N –H
O4A 159(3), N2–H2N
4B 161(3)°].
...
O
The hydrolytic stability of salts ІІІa–IIIl depends on
the character of the substituent at the iminium nitrogen
atom. Compounds ІІІa–IIIf with the alkyl substituents
that decrease the electrophilicity of the iminium group are
stable to the moisture in air and organic solvents. In con-
trast, compounds ІІІg–IIIl containing aryl substituents
according to the 1H NMR spectra under these conditions
are readily converted into the corresponding lactones IV.
For the preparative synthesis of lactones IVa–IVc it is
advisable to treat the iminium salts with sodium acetate
in aqueous ethanol.
3.35–3.70 ppm. In the 13C NMR spectra the carbon atoms
of the dihydrofuran ring give rise to signals in the region
26–27 (C4), 30–31 (C3), 90–93 (C5), 178–180 (C2) ppm,
and of the methylene group of the fragment ArSCH2, at
34–38 ppm. However these data are not sufficient for the
evaluation of the spatial arrangements of compounds III,
in particular, of the configuration of the exocyclic iminium
bond. Therefore we carried out an XRD investigation of
compound IIIf, which proved the Z-configuration of the
synthesized iminium salts (see the figure).
In the study of the reaction of salts ІІІa, IIIi, IIIk,
IIIl with sodium ethylate we found that maintaining the
reagents for 15–20 min in anhydrous ethanol resulted in
the formation of 5-[(arylsulfanyl)methyl]dihydro-2(3H)-
furanylidenes Va–Vd, most probably along the scheme
of addition-elimination of an ethoxy anion. The 1H and
13C NMR spectra of furan imino derivatives Va–Vd
contain a double set of materially all proton and carbon
signals showing that these compounds exist as mixtures
of Z- and E-isomers.
The central five-membered heterocycle has the en-
velope configuration: The group of atoms O7C9C10C11
is planar within 0.058(2) Å and forms with the atoms
O7C8C9 an angle of 18.43(35)°.
The distribution of the bond distances and angles in
the molecule of compound IIIf indicates the delocaliza-
tion of the electron density on the atoms O7C11N2. For
instace, the bond O7–C11 is notably shorter than the bond
O7–C8, whereas the length of the bond N2–C11 1.28 Å
is characteristic of a standard double bond C=N. The
strong shortening of the O7–C11 bond is apparently due
to an efficient conjugation of the unshared electron pair
of the oxygen with the π-system of the double C11–N2
Furanylideneamines Va–Vd were however unstable
with respect to acid reagents, and at treating with sulfuric
acid in ethanol they are cleanly converted into lactones
IVa–IVc (Scheme 2).
A promising preparative process consists in the reac-
tion of iminium salts ІІІa–IIIi with highly basic cyclic
secondary amines VIa–VIc in the presence of water. The
reaction readily occurs with excess amine at room tem-
perature and furnishes 5-arylsulfanyl-4-hydroxypentanoic
acids amides VІІa–VIIi in 69–73% yields (Scheme 3);
some representatived of the latter compounds has been
obtained formerly [11] by treating 5-sulfanylmethyllac-
tones with primary amines. We believe that the process
proceeds by the primary attack of the amine on the
electrophilic atom C2 of the furan ring with subsequent
opening of the cyclic intermediate under the action of
water. In the absence of water and in the reaction with
Structure of N-[(2Z)-5-{[(4-nitrophenyl)sulfanyl]methyl}
dihydrofuran-2(3H)-ylidene]propan-2-aminium perchlorate
(ІІІf) according to the XRD data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

INTRAMOLECULAR ELECTROPHILIC CYCLIZATION
195
Scheme 2.
H2SO4
NaOAc,
H2O
ArS
O
O
IVа_IVc
IIIа_IIIl
OC2H5
NaOC2H5
_NaClO4
H
N
N
_HOC2H5
O
O
OC2H5
R
R
SAr
SAr
Vа_Vd
ІV,Ar = C6H5 (a), 4-MeC6H4 (b), 4-NO2C6H4 (c); V, R = Bu,Ar = C6H5 (a); R = Ph,Ar = 4-NO2C6H4 (b); R = 4-MeOC6H4,
Ar = 4-MeC6H4 (c); R = 4-MeOC6H4, Ar = 4-NO2C6H4 (d).
Scheme 3.
.
.
NHR'2
IIIа_IIIl
+
NHR'2
ArS
+
NH
O
VIа_VIc
R
ClO4
S
+
OH
NR'2
H
H2O
Ar
..
O
ArS
+
NH
NH3RClO4
O
H2O
R
_
NR'
ClO4
VIIа VIIi
2
VI, R’2 = (CH2)4 (a), (CH2)5 (b), (CH2)2O(CH2)2 (c); VII, R'2 = (CH2)4,Ar = C6H5 (a), 4-MeC6H4 (b), 4-NO2C6H4 (c); R'2 =
(CH2)5, Ar = C6H5 (d), 4-MeC6H4 (e), 4-NO2C6H4 (f); R'2 = (CH2)2O(CH2)2, Ar = C6H5 (g), 4-MeC6H4 (h), 4-NO2C6H4 (i).
1
primary aliphatic and aromatic amines forms an intrac-
table mixture of products.
UR-20 from pellets with KBr. The H and 13C NMR
spectra were registered on a spectrometer Bruker Ad-
vance DRX-500 (500.13, 125.75 MHz respectively),
internal reference TMS. Mass spectra were measured
on an instrumentAgilent 110\DAD\HSD\VLG 119562.
Crystals of compound IIIf are monoclinic,
space group P21/C, a 13.5116(14), b 11.3367(11),
c 11.8852(12) Å, β 95.634(3)°, V 1811.7(3) Å3, Z 4,
dc 1.447, μ 0.364 mm–1, F(000) 824. XRD experiment
In the 1H NMR spectra of amides VIIa–VIIi alongside
the multiplets of the methylene groups protons the multi-
plets are present of the protons C4H at 3.54–3.75 ppm and
doublets (the multiplets) of OH protons at 4.93–5.16 ppm.
The 13C NMR spectra are characterized by the signals of
atoms C4 in the range 62–68 ppm. In the IR spectra of
amides VIIa–VIIi the stretching vibrations band of C=O
groups is observed in the range 1635–1610 cm–1.
Scheme 4.
5-Arylsulfanyl-4-hydroxypentanoic acid amides
VIIa–VIIi are easily converted into derivatives of 5-aryl-
sulfonyl-4-acetoxypentanoic acids [12, 13]. Compounds
VІІc, VIIf, VIIi at the oxidation with oxone are selec-
tively transformed into sulfones VIIIa–VIIIc (Scheme 4).
OH
O
O
KHSO5
S
VIIc, VIIf, VIIi
O
Ar
NR2
VIIIа_VIIIc
EXPERIMENTAL
VIII, Ar = 4-NO2C6H4, R2 = (CH2)4 (a), (CH2)5 (b),
(CH2)2O(CH2)2 (c).
IR spectra were recorded on a spectrophotometer
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

VAS’KEVICH et al.
196
was carried out on a single crystal of linear dimensions
0.08 × 0.40 × 0.43 mm at room temperature on a dffrac-
tometer Bruker SmartApex II (λMoKα-radiation, graphite
monochromator, θmax 26.45°, spheric segment 16 ≤ h ≤
16, –13 ≤ k ≤ 14, –14 ≤ l ≤ 14. Overall 17400 reflections
were collected, among them 3735 independent (R-factor
of averaging 0.0539). The correction for extinction was
introduced by multiscanning method along SADABS
program (ratio of minimal to maximal correction
Tmin/Tmax 0.783550). The structure was solved by the
direct method and refined by least-squares method in
the anisotropic approximation for all nonhydrogen atoms
applying software BRUKER SHELXTL [14]. Three
oxygen atoms of the perchlorate anion are disordered
by two positions with the occupancies 55.7 and 44.3%.
All hydrogen atoms were placed geometrically, their
positions and thermal parameters were refined with the
positions and thermal parameters of the corresponding
carbon atoms, only the hydrogen linked to the nitrogen
atom involved in the hydrogen bonds was revealed
objectively and refined isotropically. In the refinement
2366 reflections were involved with I > 2σ(I); 260 refined
parameters, 9.1 reflection per parameter, weight scheme
ω = 1/[σ2(Fo2) + (0.0716P)2 + 1.209P] was used where
P = (Fo2 + 2Fc2)/3, the ratio of the maximum (average)
shift to the error in the last cycle 0.001 (0.000). The final
values of the divergence factors are R1(F) 0.0554, wR2(F2)
0.1366 with respect to reflections with I > 2σ(I) and R1(F)
0.0960, wR2(F2) 0.1618, GOF 1.017 for all reflections.
The residual electron density from the difference Fourier
series after the last cycle was 0.52 and –0.33 e/Å3.
2(3H)-ylidene}butan-1-aminium perchlorate (IІIa).
Yield 84%, oily substance. 1H NMR spectrum (DMSO-
d6), δ, ppm: 0.86 t (3H, CH3, J 7 Hz), 1.23–1.29 m (2H,
CH2), 1.39–1.45 m (2H, CH2), 2.08–2.21 m (1H, CH),
2.39–2.51 m (1H, CH), 3.12–3.21 m (4H, 2CH2), 3.35–
3.48 m (2H, CH2), 5.24–5.28 m (1H, CH), 7.23–7.56 d
(5Harom), 11.88 s (1H, NH). 13C NMR spectrum (DMSO-
d6), δ, ppm: 13.35 (CH3), 19.76 (CH2), 26.58 (C3), 29.45
(C4), 30.86 (CH2), 37.61 (CH2S), 44.43 (NCH2), 91.56
(C5), 127.09, 129.16, 130.42, 134.30 (6Carom), 180.08
(C2). Mass spectrum: m/z 365 [M + 1]+. Found, %:
C 49.39; H 6.01; N 3.72. C15H21ClN2O7S. Calculated,
%: C 49.51; H 6.09; N 3.84. M 363.9.
N-[(2Z)-5-{[(4-Methylphenyl)sulfanyl]methyl}
dihydrofuran-2(3H)-ylidene]butan-1-aminium per-
1
chlorate (IІIb). Yield 81%, oily substance. H NMR
spectrum (DMSO-d6), δ, ppm: 0.86 t (3H, CH3, J 7 Hz),
1.21–1.30 m (2H, CH2), 1.36–1.44 m (2H, CH2),
2.12–2.20 m (1H, CH), 2.26 C (3H, CH3), 2.40–2.52 m
(1H, CH), 3.10–3.19 m (4H, 2CH2), 3.39–3.46 m
(2H, CH2), 5.20–5.24 m (1H, CH), 7.18 d (2Harom
,
J 10.5 Hz), 7.35 d (2Harom, J 10.5 Hz), 11.87 s (1H, NH).
Mass spectrum: m/z 379 [M + 1]+. Found, %: C 50.74;
H 6.35; N 3.59. C16H24ClNO5S. Calculated, %: C 50.85;
H 6.40; N 3.71. M 377.9.
N-[(2Z)-5-{[(4-Nitrophenyl)sulfanyl]methyl}dihy-
drofuran-2(3H)-ylidene]butan-1-aminium perchlo-
rate (IIІc). Yield 71%, mp 72°C. IR spectrum, ν, cm–1:
1
1700 (C=N). H NMR spectrum (CDCl3), ppm: 0.84 t
(3H, CH3, J 7 Hz), 1.24–1.29 m (2H, CH2), 1.40–1.52 m
(2H, CH2), 2.26–2.33 m (1H, CH), 2.55–2.61 m (1H, CH),
3.15–3.53 m (6H, 3CH2), 5.35–5.38 m (1H, CH), 7.47 d
(2Harom, J 10.5 Hz), 8.12 d (2Harom, J 10.5 Hz), 10.52 s
(1H, NH). 13C NMR spectrum (DMSO-d6), ppm: 12.83
(CH3), 19.08 (CH2), 26.56 (C3), 29.10 (C4), 30.22 (CH2),
33.91 (CH2S), 43.07 (NCH2), 90.65 (C5), 123.53, 126.84,
144.89, 145.76 (6Carom), 179.58 (C2). Mass spectrum:
m/z 410 [M + 1]+. Found, %: C 43.95; H 5.09; N 6.77.
C15H21ClN2O7S. Calculated, %: C 44.06; H 5.18; N 6.85.
M 408.9.
Compounds IIIa–IIIl. General procedure. To a so-
lution of 2 mmol of amide Ia–Id in 10 ml of acetic acid
was added in succession at stirring solutions of 0.23 g
(2.2 mmol) of lithium perchlorate in 5 ml of acetic acid
and 2.2 mmol of arylsulfenyl chloride IIa–IIc in 3 ml
of acetic acid. The reaction mixture was stirred at room
temperature over 4 h. The precipitated crystals of com-
pounds IIIf, IIIi, IIIk, IIIl were filtered off, washed on
the filter with acetic acid and hexane. In the case of the
other products the solvent was distilled off in a vacuum,
the residue was treated with 10 ml of water. The organic
phase was extracted with chloroform (2×10 ml), dried
with MgSO4, filtered, and evaporated. Compounds IIIa,
IIIb, IIId, IIIg were obtained as oils, and IIIc, IIIg, IIIj
were isolated as solids after treating the oily residues
with hexane.
N-{(2Z)-5-[(Phenylsulfanyl)methyl]-dihydrofuran-
2(3H)-ylidene}propan-2-aminium perchlorate (IIІd).
Yield 68%, oily substance. 1H NMR spectrum (DMSO-
d6), δ, ppm: 1.08 d (3H, CH3, J 6.8 Hz), 1.17 d (3H, CH3,
J 6.8 Hz), 2.05–2.19 m (1H, CH), 2.37–2.46 m (1H, CH),
3.08–3.16 m (2H, CH2), 3.42–3.57 m (2H, CH2), 3.61–
3.70 m (1H, CH), 5.24–5.28 m (1H, CH), 7.25–7.52 m
(5Harom), 11.74 s (1H, NH). Mass spectrum: m/z 351 [M +
N-{(2Z)-5-[(Phenylsulfanyl)methyl]-dihydrofuran-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

INTRAMOLECULAR ELECTROPHILIC CYCLIZATION
197
1]+. Found, %: C 47.96; H 5.70; N 3.91. C14H19ClN2O7S.
Calculated, %: C 48.07; H 5.76; N 4.00. M 349.8.
(2Harom, J 7.6 Hz), 7.19–7.36 m (7Harom), 11.14 s (1H,
NH). Mass spectrum: m/z 430 [M + 1]+. Found, %:
C 54.24; H 3.98; N 3.41. C18H20ClNO5S. Calculated, %:
C 54.33; H 5.07; N 3.52. M 428.8.
N-[(2Z)-5-{[(4-Methylphenyl)sulfanyl]methyl}
dihydrofuran-2(3H)-ylidene]propan-2-aminium per-
chlorate (ІIIe). Yield 73%, mp 55–56°C. IR spectrum,
N-[(2Z)-5-{[(4-Nitrophenyl)sulfanyl]methyl}dihy-
drofuran-2(3H)-ylidene]phenylaminium perchlorate
(IІIi). Yield 79%, mp 135°C. IR spectrum, ν, cm–1: 1680
1
ν, cm–1: 1705 (C=N). H NMR spectrum (DMSO-d6),
δ, ppm: 1.09 d (3H, CH3, J 7 Hz), 1.16 d (3H, CH3,
J 7 Hz), 2.06–2.20 m (1H, CH), 2.40–2.48 m (1H,
CH), 3.08–3.17 m (2H, CH2), 3.30–3.47 m (2H, CH2),
3.55–3.63 m (1H, CH), 5.21–5.24 m (1H, CH), 7.20 d
(2Harom, J 10.5 Hz), 7.37 d (2Harom, J 11 Hz), 11.74 s
(1H, NH). 13C NMR spectrum (DMSO-d6), δ, ppm: 20.39
(CH3), 20.69 (CH3), 20.80 (CH3), 26.26 (C3), 30.23 (C4),
36.33 (CH2S), 46.62 (NCH), 91.23 (C5), 129.48, 129.82,
130.88, 136.23 (6Carom), 178.33 (C2). Mass spectrum:
m/z 365 [M + 1]+. Found, %: C 49.38; H 6.02; N 3.75.
C15H22ClNO5S. Calculated, %: C 49.51; H 6.09; N 3.84.
M 363.9.
1
(C=N). H NMR spectrum (CD3CN), δ, ppm: 2.32–
2.44 m (1H, CH), 2.63–2.77 m (1H, CH), 3.38–3.53 m
(2H, CH2), 3.55–3.60 m (1H, CH), 5.59–5.62 m (1H, CH),
7.30 d (2Harom, J 7 Hz), 7.39–7.41 m (3H arom), 7.50 d
(2Harom, J 8.5 Hz), 7.98 d (2Harom, J 8.5 Hz), 10.96 s (1H,
NH). 13C NMR spectrum (CD3CN), δ, ppm: 25.89 (C3),
32.35 (C4), 34.88 (CH2S), 94.45 (C5), 122.31, 123.87,
127.64, 129.03, 129.64, 130.22, 133.17, 144.82 (12Carom),
180.01 (C2). Mass spectrum: m/z 430 [M + 1]+. Found,
%: C 47.68; H 3.87; N 6.43. C17H17ClN2O7S. Calculated,
%: C 47.62; H 4.00; N 6.53. M 428.8.
N-[(2Z)-5-{[(4-Nitrophenyl)sulfanyl]methyl}
dihydrofuran-2(3H)-ylidene]propan-2-aminium
perchlorate (IІIf). Yield 74%, mp 140°C. IR spectrum,
N-{(2Z)-5-[(Phenylsulfanyl)methyl]-dihydrofuran-
2(3H)-ylidene}-4-methoxyphenylaminium perchlorate
(ІIIj). Yield 67%, mp 94°C. 1H NMR spectrum (CDCl3),
δ, ppm: 2.23–2.30 m (1H, CH), 2.56–2.65 m (1H, CH),
3.35–3.56 m (4H, 2CH2), 3.84 C (3H, CH3), 5.39–5.47 m
(1H, CH), 7.03 d (2Harom, J 9 Hz), 7.24–7.38 (5Harom),
7.45 d (2Harom, J 8 Hz). 13C NMR spectrum (CDCl3),
δ, ppm: 27.42 (C4), 33.35 (C3), 38.13 (CH2S), 56.58
(OCH3), 94.95 (C5), 115.98, 125.23, 127.92, 128.40,
130.61, 131.31, 135.79, 161.04 (12Carom), 179.89 (C2).
Mass spectrum: m/z 415 [M + 1]+. Found, %: C 52.11;
H 4.78; N 3.29. C18H20ClN2O6S. Calculated, %: C 52.23;
H 4.87; N 3.38. M 413.9.
1
ν, cm–1: 1705 (C=N). H NMR spectrum (DMSO-d6),
δ, ppm: 1.09 d (3H, CH3, J 7 Hz), 1.16 d (3H, CH3,
J 7 Hz), 2.07–2.25 m (1H, CH), 2.40–2.55 m (1H, CH),
3.10–3.25 m (2H, CH2), 3.60–3.80 m (3H, CH + CH2),
5.34–5.37 m (1H, CH), 7.67 d (2Harom, J 10.5 Hz), 8.17 d
(2Harom, J 11 Hz), 11.64 s (1H, NH). 13C NMR spectrum
(DMSO-d6), δ, ppm: 20.73 (CH3), 20.75 (CH3), 26.40
(C3), 30.30 (C4), 34.01 (CH2S), 46.75 (NCH), 90.47 (C5),
123.46, 127.23, 144.94, 145.56 (6Carom), 178.36 (C2).
Mass spectrum: m/z 396 [M + 1]+. Found, %: C 42.51;
H 4.72; N 7.03. C14H19ClN2O7S. Calculated, %: C 42.59;
H 4.85; N 7.10. M 394.8.
N-[(2Z)-5-{[(4-Methylphenyl)sulfanyl]methyl}
dihydrofuran-2(3H)-ylidene]-4-methoxyphenylamin-
ium perchlorate (IІIk). Yield 69%, mp 131–132°C.
N-{(2Z)-5-[(Phenylsulfanyl)methyl]-dihydrofuran-
2(3H)-ylidene}phenylaminium perchlorate (IIІg).
Yield 73%, oily substance. 1H NMR spectrum (CDCl3),
δ, ppm: 2.51–2.63 m (2H, CH2), 3.34–3.40 m (2H,
CH2), 3.51–3.61 m (2H, CH2), 5.41–5.48 m (1H, CH),
7.13–7.40 m (10Harom), 10.96 s (1H, NH). Mass spectrum:
m/z 385 [M + 1]+. Found, %: C 53.09; H 4.65; N 3.54.
C17H18ClNO5S. Calculated, %: C 53.20; H 4.73; N 3.65.
M 383.8.
1
IR spectrum, ν, cm–1: 1675 (C=N). H NMR spectrum
(CD3CN), δ, ppm: 2.25 s (3H, CH3), 2.26–2.39 m (1H,
CH), 2.52–2.67 m (1H, CH), 3.25–3.43 m (2H, CH2),
3.53–3.67 m (2H, CH2), 3.80 C (3H, CH3), 5.40–5.52 m
(1H, CH), 6.80 d (2Harom, J 9.5 Hz), 7.05 d (2Harom
,
J 9.5 Hz), 7.20–7.34 m (4Harom, J 9 Hz), 11.68 s (1H, NH).
13C NMR spectrum (CD3CN), δ, ppm: 20.93 (CH3), 25.98
(C3), 32.33 (C4), 38.57 (CH2S), 55.30 (OCH3), 93.34 (C5),
114.36, 123.80, 126.30, 129.98, 130.24, 131.40, 137.98,
159.57 (12Carom), 177.69 (C2). Mass spectrum: m/z 429
[M + 1]+. Found, %: C 53.21; H 5.12; N 3.16. C19H22Cl-
NO6S. Calculated, %: C 53.33; H 5.18; N 3.27. M 427.9.
N-[(2Z)-5-{[(4-Methylphenyl)sulfanyl]methyl}
dihydrofuran-2(3H)-ylidene]phenylaminium per-
1
chlorate (IІIh). Yield 74%, oily substance. H NMR
spectrum (CDCl3), δ, ppm: 2.20 s (3H, CH3), 2.47–
2.58 m (2H, CH2), 3.24–3.41 m (2H, CH2), 3.52–
3.59 m (2H, CH2), 5.41–5.49 m (1H, CH), 6.98 d
N-[(2Z)-5-{[(4-Nitrophenyl)sulfanyl]methyl}dihy-
drofuran-2(3H)-ylidene]-4-methoxyphenylaminium
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VAS’KEVICH et al.
198
perchlorate (ІIIl). Yield 72%, mp 152°C. IR spectrum,
was added at stirring 1 mmol of sodium ethylate obtained
by dissolution of 0.023 g of sodium in 5 ml of ethanol.
After 30 min the reaction mixture was evaporated (yellow
crystals of compound Vb were filtered off ), 5 ml of an-
hydrous chloroform was added, the precipitate of sodium
perchlorate was filtered off, the filtrate was evaporated
in a vacuum.
1
ν, cm–1: 1685 (C=N). H NMR spectrum (CD3CN), δ,
ppm: 2.30–2.45 m (1H, CH), 2.57–2.71 m (1H, CH),
3.35–3.49 m (2H, CH2), 3.52–3.57 m (1H, CH), 3.67–
3.71 m (1H, CH), 3.80 s (3H, CH3), 5.53–5.64 m (1H,
CH), 6.88 d (2Harom, J 9.5 Hz), 7.21 d (2Harom, J 9.5 Hz),
7.49 d (2Harom, J 9 Hz), 7.97 d (2Harom, J 9 Hz). 13C NMR
spectrum (CD3CN), δ, ppm: 25.92 (C4), 32.04 (C3),
34.96 (CH2S), 55.10 (OCH3), 93.69 (C5), 114.62, 123.75,
123.81, 126.03, 127.65, 144.90, 145.76, 159.75 (12Carom),
178.80 (C2). Mass spectrum: m/z 460 [M + 1]+. Found,
%: C 47.02; H 4.12; N 6.03. C18H19ClN2O8S. Calculated,
%: C 47.11; H 4.17; N 6.10. M 458.9.
N-Butyl-N-{5-[(phenylsulfanyl)methyl]dihydro-
furan-2(3H)-ylidene}amine (Va). Yield 84%, oily sub-
stance. 1H NMR spectrum (CDCl3), δ, ppm: 0.84–0.88 m
(3H, CH3), 1.23–1.34 m (2H, CH2), 1.35–1.51 m (2H,
CH2), 1.65–1.75 m, 1.76–1.88 m (1H, CH), 2.13–2.22 m,
2.23–2.40 m (1H, CH), 2.46–2.57 m (2H, CH2), 2.91–3.29
m (4H, 2CH2), 4.32–4.39 m, 4.44–4.53 m (1H, CH),
7.15–7.47 m (5Harom). 13C NMR spectrum (CDCl3), δ,
ppm: 13.74, 13.96 (CH3), 20.07, 20.63, 26.90, 28.08,
28.42, 28.93, 31.59, 33.08, 38.62, 41.26, 46.91, 50.31
(CH2), 77.49, 80.31 (CH), 126.10, 126.63, 128.93,
129.02, 129.74, 130.00, 135.47, 136.14 (Carom), 161.81,
165.10 (C2). Mass spectrum: m/z 329 [M + 1]+. Found,
%: C 68.31; H 7.98; N 5.21; S 12.11. C15H21NOS. Cal-
culated, %: C 68.40; H 8.04; N 5.32; S 12.17. M 263.4.
Compounds IVa–IVc. a. To a solution of 1 mmol
of iminium salt IIIa–IIIl in 3 ml of ethanol was added
a solution of 1.5 mmol of sodium acetate in 2 ml of wa-
ter, and the mixture was left standing over 12 h. Ethanol
was evaporated, the organic phase insoluble in water was
extracted with chloroform (2×5 ml), dried with MgSO4,
filtered, and evaporated. Compound IVc was crystallized
from hexane.
b. Iminolactone Va–Vd, 1 mmol, and 0.1 mmol of
sulfuric acid in 10 ml of ethanol were boiled at stirring
for 1 h. The filtrate was evaporated in a vacuum, washed
with water, extracted with 5 ml of chloroform (at the
preparation of compound IVc from compounds Vb, Vd
the reaction product was crystallized from water). The
extract was dried with MgSO4 and evaporated.
N-[5-{[(4-Nitrophenyl)sulfanyl]methyl}dihydrofu-
ran-2(3H)-ylidene]-N-phenylamine (Vb). Yield 94%,
mp 127–128°C. IR spectrum, ν, cm–1: 1685 (C=N).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.89–2.05 m
(1H, CH), 2.26–2.34 m, 2.48–2.53 m (1H, CH), 2.74–
2.80 m (2H, CH2), 3.46–3.56 m (2H, CH2), 4.68–4.72,
4.74–4.77 m (1H, CH), 6.81–6.82, 6.84–6.65 d (2Harom
,
5-[(4-Phenylsulfanyl)methyl]dihydrofuran-2(3H)-
2-one (IVa). Yield 71% (a), 76% (b), oily substance (mp
45°C [11, 15]).
J 9 Hz), 6.92–6.95, 7.01–7.04 m (1Harom), 7.12–7.16,
7.26–7.30 (1Harom), 7.54 d, 7.63 d (2Harom, J 9 Hz),
8.03 d, 8.17 d (2Harom, J 9 Hz). 13C NMR spectrum
(DMSO-d6), δ, ppm: 25.05, 26.97 (C4), 27.76, 29.26 (C3),
34.91, 35.00 (CH2S), 78.49, 81.15 (C5), 120.88, 122.35,
122,75, 123.61, 123.82, 126.68, 128.16, 128.84 144.51,
144.63, 146.51, 146.59, 146.91, 48.97(Carom), 162.01,
167.68 (C2). Mass spectrum: m/z 329 [M + 1]+. Found,
%: C 62.03; H 4.87; N 8.46; S 9.65. C17H16N2O3S. Cal-
culated, %: C 62.18; H 4.91; N 8.53; S 9.76. M 328.4.
5-[(4-Tolylsulfanyl)methyl]dihydrofuran-2(3H)-2-
one (IVb). Yield 75% (a), 69% (b), oily substance [8, 11].
5-{[(4-Nitrophenyl)sulfanyl]methyl}dihydro-
furan-2(3H)-2-one (IVc). Yield 65%, mp 83°C. IR
1
spectrum, ν, cm–1: 1760 (C=O). H NMR spectrum
(DMSO-d6), δ, ppm: 1.93–2.11 m (1H, CH), 2.31–2.43
m (1H, CH), 2.52–2.60 m (2H, CH2), 3.53 d (2H,
CH2, J 6 Hz), 4.71–4.80 m (1H, CH), 7.61 d (2Harom
,
N-(4-Methoxyphenyl)-N-[5-{[(4-methylphenyl)
sulfanyl]methyl}dihydrofuran-2(3H)-ylidene]amine
J 8.7 Hz), 8.16 d (2Harom, J 8.7 Hz). 13C NMR spec-
trum (DMSO-d6), δ, ppm: 26.46 (C4), 27.97 (C3), 35.18
(CH2S), 77.88 (C5), 123.82, 126.68, 144.68, 146.39
(6Carom), 176.53 (C2). Found, %: C 51.99; H 4.30;
N 5.43. C11H11NO4S. Calculated, %: C 52.16; H 4.38;
N 5.53.
1
(Vc). Yield 92%, mp 77–78°C. H NMR spectrum
(CDCl3), δ, ppm: 1.86–2.06 m (1H, CH), 2.33 C (3H,
CH3), 2.41–2.57 m (1H, CH), 2.73–2.86 m (2H, CH2),
2.97–3.06 m (1H, CH), 3.24–3.44 m (1H, CH), 3.80 s
(3H, CH3), 4.54–4.66 m (1H, CH), 6.77–6.90 m (2Harom),
7.06–7.18 m (4Harom), 7.28–7.34 m (2Harom). 13C NMR
spectrum (CDCl3), δ, ppm: 21.04 (CH3), 25.45, 27.48
Compounds Va–Vd. General procedure. To 1 mmol
of iminium salt IIIa–IIIl in 3 ml of anhydrous alcohol
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INTRAMOLECULAR ELECTROPHILIC CYCLIZATION
199
(C4), 28.44, 30.24 (C3), 38.87, 39.10 (CH2S), 55.40,
55.49 (OCH3), 79.28, 81.65 (C5), 113.77, 114.30, 114.43,
122.11, 124,42, 125.75, 129.87, 129.91, 129.94, 130.67,
130.79, 130.97, 131.33, 137.10, 139.58 (Carom), 156.08,
161.62 (C2). Mass spectrum: m/z 328 [M + 1]+. Found, %:
C 69.54; H 6.37; N 4.21; S 9.65. C19H21NO2S. Calculated,
%: C 69.69; H 6.46; N 4.28; S 9.79. M 327.4.
1.62 m (1H, CH), 1.68–1.80 m (1H, CH), 1.84–1.92 m
(3H, CH + CH2), 2.24–2.38 m (5H, CH3 + CH2), 2.88 m
(2H, CH2), 3.23–3.28 m (2H, CH2), 3.55–3.64 m (1H,
CH), 4.93–5.03 m (1H, OH), 7.12 d (2Harom, J 8.0 Hz),
7.25 d (2Harom, J 7.5 Hz). 13C NMR spectrum (DMSO-
d6), δ, ppm: 20.16 (CH3), 23.85 (CH2), 25.51 (CH2),
30.07 (C3), 30.93 (C2), 40.43 (C5), 45.12 (CH2), 45.78
(CH2), 68.51 (C4), 128.34, 129.38, 133.08, 134.90 (Carom),
170.32 (C1). Mass spectrum: m/z 294 [M + 1]+. Found,
%: C 65.33; H 7.79; N 4.71; S 10.81. C16H23NO2S. Cal-
culated, %: C 65.49; H 7.90; N 4.77; S 10.93. M 293.4.
N-(4-Methoxyphenyl)-N-[5-{[(4-nitrophenyl)
sulfanyl]methyl}dihydrofuran-2(3H)-ylidene]amine
1
(Vd). Yield 92%, oily substance. H NMR spectrum
(CDCl3), δ, ppm: 1.94–2.12 m (1H, CH), 2.31–2.47 m
(1H, CH), 2.52–2.66 m, 2.76–2.89 m (2H, CH2),
3.24–3.53 m (3H, CH + CH2), 3.79 C (3H, CH3),
4.65–4.83 m (1H, CH), 6.76–6.80 m (4Harom), 6.84 d,
6.99 d (2Harom, J 9 Hz), 7.37 d, 7.45 d (2Harom, J 9 Hz),
8.03 d, 8.16 d (2Harom, J 9 Hz). 13C NMR spectrum
(CDCl3), δ, ppm: 25.43, 27.53 (C4), 28.57, 30.18 (C3),
36.38, 36.80 (CH2S), 55.36, 55.50 (OCH3), 78.33,
80.99 (C5), 113.68, 114.37, 114.87, 116.42, 123.93,
124.14, 124.23, 127.11, 127.22, 127.38, 139.25, 145.66
(Carom), 156.21, 160.76 (C2). Mass spectrum: m/z 359
[M + 1]+. Found, %: C 60.21; H 5.01; N 7.71; S 8.87.
C18H18N2O4S. Calculated, %: C 60.32; H 5.06; N 7.82;
S 8.95. M 358.4.
4-Hydroxy-5-[(4-nitrophenyl)sulfanyl]-1-
(pyrrolidin-1-yl)pentan-1-one (VІІc). Yield 83%, mp
1
125–126°C. H NMR spectrum (DMSO-d6), δ, ppm:
1.54–1.93 m (6H, 3CH2), 2.26–2.40 m (2H, CH2), 3.15–
3.60 m (6H, 3CH2), 3.63–3.75 m (1H, CH), 5.10–5.27 m
(1H, OH), 7.53 d (2Harom, J 8.5 Hz), 8.11 d (2Harom
,
J 7.0 Hz). 13C NMR spectrum (DMSO-d6), δ, ppm: 23.86
(CH2), 25.51 (CH2), 30.02 (C3), 31.22 (C2), 38.47 (C5),
45.14 (CH2), 45.79 (CH2), 67.64 (C4), 123.45, 126.00,
144.15, 148.28 (Carom), 170.22 (C1). Mass spectrum:
m/z 325 [M + 1]+. Found, %: C 55.42; H 6.12; N 8.48;
S 9.75. C15H20N2O4S. Calculated, %: C 55.54; H 6.21;
N 8.64; S 9.88. M 324.4.
Compounds VІІa–VIIi. General procedure. To 1 ml
of amine VIa–VIc containing 4–5 drops of water was
added 1 mmol of iminium salt IIIa–IIIl, the mixture was
left standing for 12 h, then 10 ml of water was added.
The formed oily product was extracted with chloroform
(2×5 ml), the extract was dried with MgSO4. The solvent
was evaporated, compounds VІІb, VIIc, VIIe–VIIi were
crystallized from hexane .
4-Hydroxy-5-(phenylsulfanyl)-1-(piperidin-1-
yl)pentan-1-one (VІІd). Yield 84%, oily substance.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.36–1.63 m
(7H, 3CH2 + CH), 1.77–1.87 m (1H, CH), 2.28–2.45 m
(2H, CH2), 3.01 d (2H, CH2), 3.37–3.45 m (4H, 2CH2),
3.57–3.68 m (1H, CH), 5.00 m (1H, OH), 7.13–7.19 m
(1Harom), 7.28–7.35 m (4Harom). 13C NMR spectrum
(DMSO-d6), δ, ppm: 23.81 (CH2), 25.03 (CH2), 25.81
(CH2), 28.53 (C3), 31.35 (C2), 39.40 (C5), 41.62
(CH2), 45.60 (CH2), 68.33 (C4), 124.86, 127.38,
128.38, 136.72 (Carom), 169.99 (C1). Mass spectrum:
m/z 294 [M + 1]+. Found, %: C 65.42; H 7.81; N 4.67;
S 10.75. C16H23NO2S. Calculated, %: C 65.49; H 7.90;
N 4.77; S 10.93. M 293.4.
4-Hydroxy-5-(phenylsulfanyl)-1-(pyrrolidin-
1-yl)pentan-1-one (VІІa). Yield 72%, oily sub-
1
stance. H NMR spectrum (DMSO-d6), δ, ppm:
1.48–1.60 m (1H, CH), 1.70–1.92 m (5H, CH +
+ 2CH2), 2.25–2.39 m (2H, CH2), 2.91 m (2H, CH2),
3.18–2.45 m (4H, 4CH2), 3.56–3.62 m (1H, CH), 5.04 d
(1H, OH), 7.10–7.37 m (5Harom). 13C NMR spectrum
(DMSO-d6), δ, ppm: 23.87 (CH2), 25.54 (CH2), 30.11
(C3), 31.02 (C2), 39.33 (C5), 45.16 (CH2), 45.83 (CH2),
68.27 (C4), 125.07, 127.67, 128.67, 136.92 (Carom),
170.39 (C1). Mass spectrum: m/z 280 [M + 1]+. Found,
%: C 64.35; H 7.46; N 4.91; S 11.34. C14H21NO3S. Cal-
culated, %: C 64.48; H 7.58; N 5.01; S 11.48. M 279.4.
4-Hydroxy-5-[(4-methylphenyl)sulfanyl]-1-
(piperidin-1-yl)pentan-1-one (VІІe). Yield 79%, mp
1
60°C. H NMR spectrum (DMSO-d6), δ, ppm: 1.33–
1.58 m (7H, 3CH2 + CH), 2.26 s (3H, CH3), 2.30–2.44 m
(2H, CH2), 3.01 d (2H, CH2), 3.35–3.42 m (4H, 2CH2),
3.54–3.63 m (1H, CH), 4.97 m (1H, OH), 7.12 d (2Harom
,
J 8.0 Hz), 7.23 d (2Harom, J 7.5 Hz). 13C NMR spectrum
(DMSO-d6), δ, ppm: 20.44 (CH3), 23.99 (CH2), 25.22
(CH2), 26.00 (CH2), 28.69 (C3), 31.46 (C2), 39.35 (C5),
41.80 (CH2), 45.79 (CH2), 68.19 (C4), 128.36, 129.43,
4-Hydroxy-5-[(4-methylphenyl)sulfanyl]-1-
(pyrrolidin-1-yl)pentan-1-one (VІІb). Yield 69%, mp
68–69°C. 1H NMR spectrum (DMSO-d6), δ, ppm: 1.52–
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200
133.05, 134.92 (Carom), 170.20 (C1). Mass spectrum:
m/z 308 [M + 1]+. Found, %: C 66.33; H 8.12; N 4.44;
S 10.29. C17H25NO2S. Calculated, %: C 66.41; H 8.20;
N 4.56; S 10.43. M 307.5.
102–103°C. IR spectrum, ν, cm–1: 1620 (C=O). 1H NMR
spectrum (DMSO-d6), δ, ppm: 1.55–1.69 m (1H, CH),
1.76–1.90 m (1H, CH), 2.31–2.64 m (2H, CH2), 3.07–
3.25 m (2H, CH2), 3.30–3.54 m (8H, 4CH2), 3.66–3.75 m
(1H, CH), 5.16 d (1H, OH), 7.52 d (2Harom, J 9.6 Hz),
8.12 d (2Harom, J 9.0 Hz). 13C NMR spectrum (DMSO-d6),
δ, ppm: 28.29 (C3), 31.52 (C2), 38.35 (C5), 41.36 (CH2),
45.29 (CH2), 66.00 (2CH2), 67.77 (C4), 123.48, 126.06,
144.17, 148.18 (Carom), 170.69 (C1). Mass spectrum:
m/z 341 [M + 1]+. Found, %: C 52.78; H 5.84; N 8.09;
S 9.28. C15H20N2O5S. Calculated, %: C 52.93; H 5.92;
N 8.23; S 9.42. M 340.4.
4-Hydroxy-5-[(4-nitrophenyl)sulfanyl]-1-
(piperidin-1-yl)pentan-1-one (VІІf). Yield 91%,
mp 112°C. IR spectrum, ν, cm–1: 1635 (C=O). 1H NMR
spectrum (DMSO-d6), δ, ppm: 1.35–1.67 m (7H, 3CH2 +
+ CH), 1.76–1.88 m (1H, CH), 2.31–2.46 m (2H,
CH2), 3.06–3.13 m (1H, CH), 3.17–3.25 m (1H, CH),
3.34–3.43 m (4H, 2CH2), 3.66–3.75 m (1H, CH), 5.15 m
(1H, OH), 7.13 d (2Harom, J 8.5 Hz), 8.13 d (2Harom
,
J 8.5 Hz). 13C NMR spectrum (DMSO-d6), δ, ppm: 23.99
(CH2), 25.23 (CH2), 26.01 (CH2), 28.63 (C3), 31.78
(C2), 38.37 (C5), 41.83 (CH2), 45.78 (CH2), 67.89 (C4),
123.49, 126.00, 144.17, 148.28 (Carom), 170.10 (C1). Mass
spectrum: m/z 339 [M + 1]+. Found, %: C 56.67; H 6.46;
N 8.13; S 9.35. C16H22N2O4S. Calculated, %: C 56.78;
H 6.55; N 8.28; S 9.48. M 338.4.
Compounds VІІІa–VIIIc. General procedure. To
a solution of 1 mmol of amide VІІc, VIIf, VIIi in 5 ml
of methanol was added at stirring 4 mmol of oxone dis-
solved in 5 ml of water. The reaction mixture was stirred
for 5 h, the formed precipitate was filtered off, washed
with 50% aqueous methanol, and dried.
4-Hydroxy-5-[(4-nitrophenyl)sulfonyl]-1-
(pyrrolidin-1-yl)pentan-1-one (VІІІa). Yield 97%,
mp 185°C. IR spectrum, ν, cm–1: 1630 (C=O). 1H NMR
spectrum (DMSO-d6), δ, ppm: 1.50–1.54 m (1H, CH),
1.70–1.89 m (3H, CH + CH2), 1.80–1.89 m (2H, CH2),
2.24–2.36 m (2H, CH2), 3.21–3.27 m (2H, CH2), 3.33–
3.59 m (4H, 2CH2), 3.93–4.01 m (1H, OH), 8.17 d (2Ha-
rom, J 8.8 Hz), 8.43 d (2Harom, J 8.4 Hz). Mass spectrum:
m/z 357 [M + 1]+. Found, %: C 50.37; H 5.57; N 7.74;
S 8.91. C15H20N2O6S. Calculated, %: C 50.55; H 5.66;
N 7.86; S 9.00. M 356.4.
4-Hydroxy-5-(phenylsulfanyl)-1-(morpholin-1-yl)
pentan-1-one (VІІg). Yield 91%, mp 49–50°C. IR spec-
trum, ν, cm–1: 1610 (C=O). 1H NMR spectrum (DMSO-
d6), δ, ppm: 1.50–1.64 m (1H, CH), 1.77–1.91 m (1H,
CH), 2.32–2.50 m (2H, CH2), 2.99 m (2H, CH2), 3.37–
3.70 m (9H, 4CH2 + CH), 5.01 m (1H, OH), 7.12–7.22 m
(1Harom), 7.27–7.38 m (4Harom). 13C NMR spectrum
(DMSO-d6), δ, ppm: 28.34 (C3), 31.30 (C2), 39.20 (C5),
41.34 (CH2), 45.31 (CH2), 65.99 (2CH2), 67.98 (C4),
125.06, 127.92, 128.58, 136.83 (Carom), 170.77 (C1). Mass
spectrum: m/z 296 [M + 1]+. Found, %: C 60.89; H 7.05;
N 4.68; S 10.72. C15H21NO3S. Calculated, %: C 60.99;
H 7.17; N 4.74; S 10.86. M 295.4.
4-Hydroxy-5-[(4-nitrophenyl)sulfonyl]-1-
(piperidin-1-yl)pentan-1-one (VІІІb). Yield 98%, mp
1
174°C. IR spectrum, ν, cm–1: 1630 (C=O). H NMR
4-Hydroxy-5-[(4-methylphenyl)sulfanyl]-1-
spectrum (CDCl3), ppm: 1.50–1.65 m (7H, 3CH2 +
CH), 1.86–1.93 m (2H, CH2), 2.41–2.63 m (2H, CH2),
3.24–3.28 m (1H, CH), 3.37–3.54 m (5H, 2CH2 + CH),
4.18–4.23 m (1H, CH), 4.82–4.92 m (1H, OH), 8.13 d
(2Harom, J 8.0 Hz), 8.37 d (2Harom, J 8.0 Hz). Mass spec-
trum: m/z 371 [M + 1]+. Found, %: C 51.76; H 5.91;
N 7.45; S 8.54. C16H22N2O6S. Calculated, %: C 51.88;
H 5.99; N 7.56; S 8.66. M 370.4.
(morpholin-1-yl)pentan-1-one (VІІh). Yield 92%, mp
1
78–79°C. IR spectrum, ν, cm–1: 1610 (C=O). H NMR
spectrum (DMSO-d6), δ, ppm: 1.47–1.63 m (1H, CH),
1.76–1.90 m (1H, CH), 2.27 s (3H, CH3), 2.31–2.46 m
(2H, CH2), 3.39–3.65 m (9H, CH + 4CH2), 5.00 d (1H,
OH, J 5.1 Hz), 7.14 d (2Harom, J 7.8 Hz), 7.24 d (2Harom
,
J 7.8 Hz). 13C NMR spectrum (DMSO-d6), δ, ppm: 20.12
(CH3), 28.33 (C3), 31.22 (C2), 38.80 (C5), 41.33 (CH2),
45.29 (CH2), 65.98 (2CH2), 68.12 (C4), 128.35, 129.34,
132.99, 134.89 (Carom), 170.78 (C1). Mass spectrum:
m/z 310 [M + 1]+. Found, %: C 62.02; H 7.38; N 4.46;
S 10.23. C16H23NO3S. Calculated, %: C 62.11; H 7.49;
N 4.53; S 10.36. M 309.4.
4-Hydroxy-5-[(4-nitrophenyl)sulfonyl]-1-
(morpholin-1-yl)pentan-1-one (VІІІc). Yield 95%,
mp 161°C. IR spectrum, ν, cm–1: 1610 (C=O). 1H NMR
spectrum (DMSO-d6), δ, ppm: 1.55–1.56 m (1H,
CH), 1.68–1.74 m (1H, CH), 2.28–2.37 m (2H, CH2),
3.36–3.43 m (4H, 2CH2), 3.49–3.60 m (6H, 3CH2),
3.91–4.02 m (1H, CH), 4.96 d (1H, OH, J 6.0 Hz), 8.17 d
(2Harom, J 8.4 Hz), 8.43 d (2Harom, J 8.4 Hz). Mass spec-
4-Hydroxy-5-[(4-nitrophenyl)sulfanyl]-1-
(morpholin-1-yl)pentan-1-one (VІІi). Yield 93%, mp
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

INTRAMOLECULAR ELECTROPHILIC CYCLIZATION
201
trum: m/z 373 [M + 1]+. Found, %: C 48.30; H 5.32;
N 7.44; S 8.53. C15H20N2O7S. Calculated, %: C 48.38;
H 5.41; N 7.52; S 8.61. M 309.4.
7. Iitagawa, O., Hanano, T., Hirata, T., Inoue, T., and
Tagushi, T., Tetrahedron Lett., 1992, vol. 33, p. 1299.
8. Abd, El-Samii, Z.K.,Al,Ashmawy, M.I., and Mellor, J.M.,
J. Chem. Soc., Perkin, Trans. 1, 1988, p. 2517.
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