Sulfenyl halides in the synthesis of heterocycles. 3. Interaction of perfluoro-1-ethyl-2-methyl-1-propenyl-iminochloromethanesulfenyl chloride with 1-allyl-2-methoxybenzene

Article abstract of DOI:10.1007/s10593-006-0247-3

Reaction of perfluoro-1-ethyl-2-methyl-1-propenyliminochloromethanesulfenyl chloride with 1-allyl-2-methoxybenzene in methylene chloride and nitromethane gives as the main products β-and γ-chloro sulfides plus derivative of 2,3-dihydrobenzofuran. The reaction in nitromethane in the presence of lithium perchlorate gave a product of addition of sulfur-containing electrophiles to the double bond-a derivative of 1,3-thiazolidin-2-one-in preference to the cycloaddition product.

Full text of DOI:10.1007/s10593-006-0247-3

Chemistry of Heterocyclic Compounds, Vol. 42, No. 10, 2006
SULFENYL HALIDES IN THE SYNTHESIS
OF HETEROCYCLES. 3*. INTERACTION OF
PERFLUORO-1-ETHYL-2-METHYL–1-PROPENYL-
IMINOCHLOROMETHANESULFENYL CHLORIDE
WITH 1-ALLYL-2-METHOXYBENZENE
A. V. Borisov, V. K. Belsky, V. K. Osmanov, G. N. Borisova, and Zh. V. Matsulevich
Reaction of perfluoro-1-ethyl-2-methyl-1-propenyliminochloromethanesulfenyl chloride with 1-allyl-2-
methoxybenzene in methylene chloride and nitromethane gives as the main products β- and γ-chloro
sulfides plus derivative of 2,3-dihydrobenzofuran. The reaction in nitromethane in the presence of
lithium perchlorate gave a product of addition of sulfur-containing electrophiles to the double bond – a
derivative of 1,3-thiazolidin-2-one – in preference to the cycloaddition product.
Keywords: alkenes, sulfenyl chlorides, heterocyclization.
Iminochloromethanesulfenyl chlorides are very promising synthons for the synthesis of heterocycles
[2-10], however only N-phenyliminochloromethanesulfenyl chloride was used, as a rule, in the investigation of
reactions of this class of compounds with alkenes.
In the present work we have produced the first example of a perfluorinated α,β-unsaturated
N-substituted iminochloromethanesulfenyl chlorides – perfluoro-1-ethyl-2-methyl-1-propenyliminochloro-
methanesulfenyl chloride (1) and have studied its reaction with 1-allyl-2-methoxybenzene (2).
We have established that when the sulfenyl chloride 1 reacted with allylanisole 2 at 20°C a number of
products were formed, the ratio of which depended of the reaction conditions. For example, in methylene
chloride products of 1,2-addition of the sulfenyl chloride both according to Markovinkov's rule and contrary to it
are formed – β-chloro sulfides 3 and 4 respectively, addition with a 1,2-shift of the aryl group – the γ-chloro
sulfide 5, and cyclization brought about by the nucleophilic part of the substrate, o-methoxyanisole – derivatives
of 2,3-dihydrobenzofuran 6. In nitromethane products of cyclization with ring closure at nitrogen atom of the
sulfenyl fragment – derivatives of 1,3-thiazolidin-2-one (7) – were formed along with the products mentioned
above. The formation the heterocycle 7 is the main direction of the reaction of sulfenyl chloride 1 with
allylanisole 2 in nitromethane in the presence of lithium perchlorate. The composition of the reaction mixtures
produced determined by 1H NMR spectroscopy and the yields of isolated products are cited in Table 1.
_______
* For paper 2 see [1].
__________________________________________________________________________________________
Nizhni Novgorod Technical University, Nizhni Novgorod 603606, Russia; e-mail: ifxf@nntu.nnov.ru.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1558-1564, October, 2006. Original article
submitted November 11, 2004; revision submitted March 24, 2006.
1346
0009-3122/06/4210-1346©2006 Springer Science+Business Media, Inc.

OMe
Cl
Cl
OMe
Cl
OMe
Cl
NRF
S
+
RFN
+
NRF
S
Cl
SCl
1
2
3
4
OMe
NRF
Cl
S
O
OMe
+
+
+
Cl
S
R
F N
S
NRF
7
Cl
O
6
5
F3C
F3C
C2F5
RF =
TABLE 1. Results of the Reaction of the Sulfenyl Chloride 1 with 1-Allyl-2-
methoxybenzene 2 (20°C)
Composition of the reaction mixture (yield, %)
Medium
3
4
5
6
7
CH2Cl2
22 (12)
20
9 (3)
18
60 (38)
9 (5)
10
—
3
MeNO2
49
5
MeNO2–LiClO4
13 (5)
15 (9)
5
62 (47)
Fig. 1. General view of the molecule of compound 7.
1347

Fig. 2. Packing of compound 7 in the crystal structure
viewed along the 0Y axis (H atoms are not shown).
In the reactions of sulfenyl chlorides, products of rearrangement and cyclization can be obtained either
directly in the AdE reactions or as a result of conversions of the products of 1,2-addition – β-chlorosulfides [1, 9-
12]. In this connection the stability of the products 3 and 4 under the reaction conditions was investigated and it
was established they underwent no appreciable conversions. Consequently all of the products obtained were
formed by the AdE process.
The composition and structure of the compounds synthesized were confirmed by elemental analysis, IR,
1H and 13C NMR, and mass spectra. The spatial and molecular structure of the heterocycle were established by
X-ray crystallography (Tables 2 and 3).
Two symmetrically independent molecules of compound 7 occupy the unit cell in the crystalline state.
The general view of one of the independent molecules is shown in Fig. 1. Packing of the molecules in the crystal
is shown in Fig. 2. The assignment of the signals in the NMR spectra of the synthesized compounds agrees with
literature characteristics of allylbenzenes with sulfenyl substituents in the ring [13-15].
1348

TABLE 2. Bond Lengths (d) in the Molecule of Compound 7
Bond
d, Å
Bond
d, Å
S(1)–C(1)
S(1)–C(2)
1.750(5)
1.805(5)
1.207(5)
1.358(5)
1.415(6)
1.397(5)
1.415(5)
1.492(5)
1.319(6)
1.332(5)
1.329(6)
1.311(6)
1.328(6)
1.313(6)
1.340(5)
1.341(5)
1.324(6)
F(10)–C(17)
F(11)–C(17)
C(2)–C(3)
1.322(6)
1.303(6)
1.512(6)
1.517(5)
1.509(6)
1.384(6)
1.379(6)
1.399(7)
1.359(8)
1.347(7)
1.399(6)
1.334(6)
1.504(7)
1.540(7)
1.529(6)
1.522(7)
O(1)–C(1)
O(2)–C(10)
O(2)–C(11)
N(1)–C(1)
N(1)–C(15)
N(1)–C(3)
F(1)–C(13)
F(2)–C(13)
F(3)–C(13)
F(4)–C(14)
F(5)–C(14)
F(6)–C(14)
F(7)–C(16)
F(8)–C(16)
F(9)–C(17)
C(3)–C(4)
C(4)–C(5)
C(5)–C(10)
C(5)–C(6)
C(6)–C(7)
C(7)–C(8)
C(8)–C(9)
C(9)–C(10)
C(12)–C(15)
C(12)–C(13)
C(12)–C(14)
C(15)–C(16)
C(16)–C(17)
TABLE 3. Bond Angles (ω) in the Molecule of Compound 7
Angle
ω,deg.
Angle
ω,deg.
C(1)–S(1)–C(2)
C(10)–O(2)–C(11)
C(1)–N(1)–C(15)
C(1)–N(1)–C(3)
C(15)–N(1)–C(3)
O(1)–C(1)–N(1)
O(1)–C(1)–S(1)
N(1)–C(1)–S(1)
C(3)–C(2)–S(1)
N(1)–C(3)–C(2)
N(1)–C(3)–C(4)
C(2)–C(3)–C(4)
C(5)–C(4)–C(3)
C(10)–C(5)–C(6)
C(10)–C(5)–C(4)
C(6)–C(5)–C(4)
C(5)–C(6)–C(7)
C(8)–C(7)–C(6)
C(9)–C(8)–C(7)
C(8)–C(9)–C(10)
O(2)–C(10)–C(5)
O(2)–C(10)–C(9)
C(5)–C(10)–C(9)
C(15)–C(12)–C(13)
C(15)–C(12)–C(14)
C(13)–C(12)–C(14)
F(1)–C(13)–F(3)
92.1(2)
118.2(4)
116.7(3)
115.8(3)
126.4(3)
124.6(4)
125.0(3)
110.4(3)
107.4(3)
104.4(3)
112.7(3)
112.1(3)
111.9(3)
118.2(4)
120.2(4)
121.6(4)
120.8(5)
119.4(5)
121.2(5)
120.0(5)
115.8(4)
123.8(4)
120.4(4)
122.2(4)
125.1(5)
112.7(4)
107.2(5)
F(1)–C(13)–F(2)
F(3)–C(13)–F(2)
F(1)–C(13)–C(12)
F(3)–C(13)–C(12)
F(2)–C(13)–C(12)
F(4)–C(14)–F(6)
F(4)–C(14)–F(5)
F(6)–C(14)–F(5)
F(4)–C(14)–C(12)
F(6)–C(14)–C(12)
F(5)–C(14)–C(12)
F(1)–C(13)–F(3)
C(12)–C(15)–N(1)
C(12)–C(15)–C(16)
N(1)–C(15)–C(16)
F(8)–C(16)–F(7)
F(8)–C(16)–C(17)
F(7)–C(16)–C(17)
F(8)–C(16)–C(15)
F(7)–C(16)–C(15)
C(17)–C(16)–C(15)
F(11)–C(17)–F(10)
F(11)–C(17)–F(9)
F(10)–C(17)–F(9)
F(11)–C(17)–C(16)
F(10)–C(17)–C(16)
F(9)–C(17)–C(16)
105.0(5)
106.0(4)
115.6(4)
113.4(5)
109.0(5)
108.6(6)
106.1(4)
107.4(4)
113.7(4)
112.2(4)
108.4(5)
107.2(5)
119.8(4)
125.8(4)
114.1(4)
105.9(4)
108.3(4)
106.4(4)
111.3(4)
109.3(4)
115.0(4)
108.9(4)
107.9(5)
106.9(5)
112.7(4)
110.3(4)
109.9(4)
1349

EXPERIMENTAL
1
IR spectra of KBr disks or thin films were recorded on a Specord M-80 instrument. H NMR spectra
were recorded with Bruker WM-250 (250 MHz), 13C NMR spectra with a AM-300 (75 MHz), and 19F NMR
spectra with a Bruker WP-200 SY (188 MHz) in CDCl3 solution with TMS (1H and 13C NMR spectra) and
CF3COOH (19F NMR spectra) internal standards.
Perfluoro-1-ethyl-2-methyl-1-propenyliminochloromethanesulfenyl Chloride (1). Liquid chlorine
(2 ml, 44 mmol) and a catalytic amount iron powder were added to perfluoro-1-ethyl-2-methylpropenyl
isothiocyanate (13.6 g, 40 mmol) (prepared by method [16]) cooled to -78°C in an ampule. The ampule was
sealed and heated for 4 h in a water bath at 70°C. The excess chlorine was removed on a rotary evaporator. The
residue was distilled in vacuum to give sulfenyl chloride 1 (11.8 g, 72%); bp 90-93°C (1 mm Hg). IR spectrum
(film), ν, cm-1: 1660 (C=C, C=N). 19F NMR spectrum, δ, ppm: -23.2 (m, CF3C=C); -19.6 (m, CF3C=C); 2.3 (m,
CF3CF2); 33.2 (m, CF2). Found, %: C 19.88; F 49.94; N 3.25; S 7.51. C7Cl2F11NS. Calculated, %: C 20.50;
F 50.97; N 3.42; S 7.82.
Reactions of 1 and 2. A. In methylene chloride or nitromethane. A solution of the unsaturated
compound 2 (0.74 g, 5 mmol) in 30 ml of solvent was added to the sulfenyl chloride 1 (2.05 g, 5 mmol) in 30 ml
of solvent at 20°C. The solvent was removed in vacuum after 15 h. The residue was chromatographed on an
L40/100 silica gel column (40 × 2 cm) with a 10:1 mixture of hexane–methylene chloride.
B. In a nitromethane–lithium perchlorate system. A solution of LiClO4 (2.12 g, 20 mmol) in
nitromethane (50 ml) and a solution of compound 2 (0.74 g, 5 mmol) in nitromethane (10 ml) were added to a
solution of sulfenyl chloride 1 (2.95 g, 5 mmol) in nitromethane (15 ml) at 20°C. The solvent was removed in
vacuum after 3 h. Methylene chloride (50 ml) was added to the reaction mixture, the residue of LiCl and LiClO4
was filtered off and washed many times on the filter with methylene chloride. The filtrate was evaporated and
the residue was chromatographed as in method A.
N-(Perfluoro-1-ethyl-2-methylpropen-1-yl)-2-chloro-3-(2-methoxyphenyl)propylsulfanylchloro-
1
methanimine (3). Oil, Rf 0.62. IR spectrum (film), ν, cm-1: 1660 (C=C, C=N). H NMR spectrum, δ, ppm
3
2
(J, Hz): 7.34-6.84 (4H, m, Ar); 4.40 (1H, m, CHCl); 3.82 (3H, s, CH3O); 3.48 (1H, dd, J = 5.5, J = 14.5,
2
CH2S); 3.31 (1H, m, CH2S); 3.17 (2H, d, J = 7.0, CH2Ar). 19F NMR spectrum, δ, ppm: -23.6 (m, CF3C=C),
-19.9 (m, CF3C=C); 1.9 (m, CF3CF2); 32.6 (m, CF2). Found, %: C 35.88; H 2.05; F 36.79; N 2.35; S 5.87.
Calculated C17H12Cl2F11NOS. Calculated, %: C 36.58; H 2.17; F 37.44; N 2.51; S 5.74.
N-(Perfluoro-1-ethyl-2-methylpropen-1-yl)-2-chloro-1-(2-methoxybenzyl)ethylsulfanylchloro-
1
methanimine (4). Oil, Rf 0.66. IR spectrum (film), ν, cm-1: 1660 (C=C, C=N). H NMR spectrum, δ, ppm
3
(J, Hz): 7.35-6.87 (4H, m, Ar); 4.28 (1H, m, CHS); 3.81 (3H, s, CH3O); 3.73 and 3.68 (2H, both dd, J = 5.5,
3J = 3.8, 2J = 11.5, CH2Cl); 3.18 and 3.10 (2H, both dd, 3J = 8.0, 3J = 7.0, 2J = 14.0, CH2Ar). 19F NMR spectrum,
δ, ppm: -23.6 (m, CF3C=C); -19.9 (m, CF3C=C); 1.8 (m, CF3CF2); 32.3 (m, CF2). Found, %: C 36.12; H 2.09;
F 37.15; N 2.39; S 5.51. C17H12Cl2F11NOS. Calculated, %: C 36.58; H 2.17; F 37.44; N 2.51; S 5.74.
N-(Perfluoro-1-ethyl-2-methylpropen-1-yl)-3-chloro-2-(2-methoxyphenyl)propylsulfanylchloro-
1
methanimine (5). Oil, Rf 0.54. IR spectrum (film), ν, cm-1: 1660 (C=C, C=N). H NMR spectrum, δ, ppm
(J, Hz): 7.37-6.90 (4H, m, Ar); 3.90 (1H, m, CH2Cl); 3.84 (3H, s, CH3O); 3.55 (2H, m, CH2S); 3.20 (1H, m,
CHAr). 13C NMR spectrum, δ, ppm: 157.34, 129.25, 128.88, 126.50, 120.63 (Ar), 55.19 (CH3O), 46.54 (CH2Cl),
41.09 (CHAr), 36.29 (CH2S). 19F NMR spectrum, δ, ppm: -23.7 (m, CF3C=C); -20.1 (m, CF3C=C); 1.7 (m,
CF3CF2); 32.5 (m, CF2). Found, %: C 35.98; H 2.07; F 37.20; N 2.42; S 5.45. C17H12Cl2F11NOS. Calculated, %:
C 36.58; H 2.17; F 37.44; N 2.51; S 5.74.
N-(Perfluoro-1-ethyl-2-methylpropen-1-yl)-2,3-dihydrobenzo[b]furan-2-ylmethylsulfanylchlorome-
1
thanimine (6). Oil, Rf 0.44. IR spectrum (film), ν, cm-1: 1660 (C=C, C=N). H NMR spectrum, δ, ppm (J, Hz):
3
3
2
7.25-6.80 (4H, m, Ar); 5.01 (1H, m, CHO); 3.43 and 3.01 (2H, both dd, J = 7.0, J = 7.0, J = 16.0, CH2Ar);
3.38 (2H, m, CH2S). 13C NMR spectrum, δ, ppm: 158.95, 128.53, 125.36, 125.10, 121.19, 109.79 (Ar); 79.32
(CHO); 39.33 (CH2S), 34.84 (CH2Ar). 19F NMR spectrum, δ, ppm: -23.6 (m, CF3C=C); -20.0
1350

(m, CF3C=C); 1.8 (m, CF3CF2); 32.5 (m, CF2). Mass spectrum, m/z (Irel, %): 507 [M]+ (4), 472 [M - Cl]+ (12),
132 (100), 69 (10). Found, %: C 37.27; H 1.65; F 40.91; N 2.55; S 6.50. C16H9ClF11NOS. Calculated, %:
C 37.85; H 1.79; F 41.16; N 2.76; S 6.31.
4-(2-Methoxybenzyl)-3-(perfluoro-1-ethyl-2-methylpropen-1-yl)-1,3-thiazolidin-2-one
(7).
1
Mp 65-66°C (hexane). IR spectrum (KBr), ν, cm-1: 1730 (C=O), 1640 (C=C). H NMR spectrum, δ, ppm
(J, Hz): 7.35-6.87 (4H, m, Ar); 4.69 (1H, m, CHN); 3.88 (3H, s, CH3O); 3.25 (2H, m, CH2S); 3.11 (1H, dd,
2
3J = 6.8, J = 11.2, CH2Ar); 2.88 (1H, t, 2J = 11.2, CH2Ar). 13C NMR spectrum, δ, ppm: 171.43 (C=O), 157.74,
131.15, 129.25, 123.14, 120.95, 110.86 (Ar), 61.81 (CHN), 55.14 (CH3O), 34.14 (CH2S), 32.25
(CH2Ar).19F NMR spectrum, δ, ppm: -23.4 (m, CF3C=C); -17.6 (m, CF3C=C); 1.8 (m, CF3CF2); 29.3 and 31.8
(both br. d, J = 286.6, CF2). Mass spectrum, m/z (Irel, %): 503 [M]+ (12), 362 (7), 121 (100), 91 (36). Found, %:
C 40.25; H 2.30; F 41.05; N 2.59; S 6.19. C17H12F11NO2S. Calculated, %: C 40.57; H 2.40; F 41.52; N 2.78; S 6.37.
X-ray Structural Analysis of Compound 7. Crystals of 7, obtained from hexane were triclinic.
At 293 K: a = 8.861(2), b = 12.164(2), c = 19.784(4) Å; α = 87.16, β = 85.17, γ = 71.65°; V = 2016.2(7) Å3;
–
d
calc = 1.658 g/cm3; space group P1 ; Z = 4; F(000) = 1008 ( there are two symmetrically independent molecules
in the unit cell). Analysis was carried with an Enraf-Nonius CAD-4 automatic diffractometer (MoKα-radiation,
θ/2θ scanning, 2θmax = 50°). The structure was solved by direct methods using the SHELXTL programme. The
number of experimental reflexion was 3011. In the calculations 2840 reflexions with I > 3σ(I) were used in the
calculations. Refinement was carried using full matrix least squares in the anisotropic approximation. The final
value of the residual factor R = 0.29. The complete X-ray data have been deposited in the Cambridge Structural
Data Bank (deposit number CCDC 299726).
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1351