A facile synthesis of stable phosphorus ylides containing chlorine and sulfur derived from 6-chloro-2-benzoxazolethiol and 2-chloro-phenothiazine

Article abstract of DOI:10.1080/10426500802275093

Stable crystalline phosphorus ylides containing chlorine and sulfur were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylene-dicarboxylates in the presence of 6-chloro-2-benzoxazolethiol and 2-chl

Full text of DOI:10.1080/10426500802275093

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A Facile Synthesis of
Stable Phosphorus Ylides
Containing Chlorine and Sulfur
Derived from 6-Chloro-2-
benzoxazolethiol and 2-Chloro-
phenothiazine
Malek Taher Maghsoodlou a , Nourollah Hazeri
a , Sayyed Mostafa Habibi Khorasani a , Hadi
Mahmoudi Moghaddam a , Mahmoud Nassiri a & Jaber
Salehzadeh a
a Department of Chemistry , The University of Sistan
and Baluchestan , Zahedan, Iran
Published online: 22 Jun 2009.
To cite this article: Malek Taher Maghsoodlou , Nourollah Hazeri , Sayyed Mostafa
Habibi Khorasani , Hadi Mahmoudi Moghaddam , Mahmoud Nassiri & Jaber Salehzadeh
(2009) A Facile Synthesis of Stable Phosphorus Ylides Containing Chlorine and
Sulfur Derived from 6-Chloro-2-benzoxazolethiol and 2-Chloro-phenothiazine,
Phosphorus, Sulfur, and Silicon and the Related Elements, 184:7, 1713-1721, DOI:
10.1080/10426500802275093
To link to this article: http://dx.doi.org/10.1080/10426500802275093
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Phosphorus, Sulfur, and Silicon, 184:1713–1721, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802275093
A Facile Synthesis of Stable Phosphorus Ylides
Containing Chlorine and Sulfur Derived from
6-Chloro-2-benzoxazolethiol and 2-Chloro-phenothiazine
Malek Taher Maghsoodlou, Nourollah Hazeri, Sayyed
Mostafa Habibi Khorasani, Hadi Mahmoudi Moghaddam,
Mahmoud Nassiri, and Jaber Salehzadeh
Department of Chemistry, The University of Sistan and Baluchestan,
Zahedan, Iran
Stable crystalline phosphorus ylides containing chlorine and sulfur were obtained
in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and
dialkyl acetylene-dicarboxylates in the presence of 6-chloro-2-benzoxazolethiol and
2-chloro-phenothiazine. These stable ylides exist in solution as a mixture of two
geometrical isomers. This is caused by the conjugation of the ylide moiety with the
adjacent carbonyl group, which results in a restricted rotation around the respective
carbon-carbon bond.
Keywords Acetylenic ester; geometrical isomers; NH-acids; stable phosphorus ylides;
triphenylphosphine
INTRODUCTION
The synthesis of phosphorus ylides is important in organic chemistry
because of the application of these compounds in the synthesis of or-
ganic products,1–14 especially in the synthesis of naturally occurring
products with biological and pharmacological activity.15–19 Phosphorus
ylides are usually prepared by deprotonation of phosphonium salts,
which can be obtained by the reaction of triphenylphosphine with an
alkyl halide.1–3 In recent years, a three-component method has been
developed20–30 for the synthesis of organophosphorus compounds us-
ing a novel approach that employs vinylphosphonium salts. Here we
Received 17 April 2008; accepted 15 June 2008.
We gratefully acknowledge financial support from the Research Council of the Uni-
versity of Sistan and Baluchestan.
Address correspondence to Malek Taher Maghsoodlou, Department of Chemistry,
The University of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan, Iran. E-mail:
mt maghsoodlou@yahoo.com
1713

1714
M. T. Maghsoodlou et al.
describe an efficient synthetic route to stable phosphorus ylides de-
rived from 6-chloro-2-benzoxazolethiol and 2-chloro-phenothiazine. The
benzoxazole and phenothiazine moieties as well as their derivatives
are widely used in making medicines.31,32 Thus, the reaction of triph-
enylphosphine 1 and dialkyl acetylenedicaboxylates 2 in the presence of
compounds 3 leads to the corresponding stable heterocyclic phosphorus
ylides 4 in excellent yields (see Scheme 1).
SCHEME 1
RESULTS AND DISCUSSION
The reaction of 6-chloro-2-benzoxazolethiol and 2-chloro-phenothiazine
with dialkyl-acetylenedicarboxylates 2 in the presence of triph-
enylphosphine 1 proceeded in ethyl acetate as solvent at room tem-
perature and was completed within a few hours. The 1H and 13C NMR
spectrum of the crude product clearly indicated the formation of the
stable phosphorus ylides 4. No product other than 4 could be detected
by NMR spectroscopy. The structures of compounds 4a–e were deter-
mined from the IR, 1H, 13C, and 31P NMR spectra. The 1H, 13C, and 31
P
NMR spectra of ylides 4a–e are consistent with the presence of two iso-
mers. The ylide moiety of these compounds is strongly conjugated with
the adjacent carbonyl group resulting in a hindered rotation around
the C-C bond connecting these two groups. Interconversion of the ge-
ometrical isomers (E)-4 and (Z)-4 is slow on the NMR time scale at
1
ambient temperature (see Scheme 2). Selected H, 13C, and 31P NMR

Synthesis of Stable Phosphorus Ylides
1715
chemical shifts and coupling constants for the major (M) and the minor
(m) geometrical isomers of compounds 4a–e are shown in Table I.
SCHEME 2
As can be seen, only one geometrical isomer was observed for the di-
tert-butyl derivatives of 4, presumably, because of the bulky tert-butyl
groups.
On the basis of the well established chemistry of trivalent phospho-
rus nucleophiles,1–3 it is reasonable to assume that the formation of the
phosphorus ylides 4 is initiated by the addition of triphenylphosphine
to the corresponding acetylenic esters. Protonation of the resulting 1:1
adduct by the acid Z-H followed by addition of the conjugated base Z−
yields the phosphoranes 4 (see Scheme 3).
SCHEME 3
1
The H NMR spectrum of 4a showed four sharp lines at δ = 3.21,
3.80, 3.81, and 3.83 ppm arising from the methoxy protons. The sig-
nal for methine protons appeared as doublet at δ = 5.78 ppm (3JPH
=
TABLE I Selected 1H, 13C, and 31P NMR Chemical Shifts (δ in ppm)
and Coupling Constants (J in Hz) for 2-H, OR, CO2R, C-2, and C-3 in
the Major (M) and Minor (m) Isomers of Compounds 4a–e
Isomer
H-2 (3JPH
)
OR
CO2R
C-2 (2JPC
)
C-3 (1JPC
)
31P
4a
4a
4b
4b
4c
4d
4d
4e
4e
M
m
M
m
M
M
m
M
m
5.78 (17.3)
5.72 (17.0)
5.74 (17.8)
5.57 (19.8)
5.56 (18.5)
4.21 (14.6)
4.14 (16.1)
4.19a
3.21
3.81
3.78
3.82
1.00
3.81
3.93
3.44
3.80
3.80
3.83
4.25
4.34
1.57
3.96
3.98
4.28
4.44
62.8 (17.4)
63.3 (14.1)
62.9 (17.5)
63.2 (5.9)
63.5 (17.9)
65.4 (14.7)
64.8 (14.6)
65.0 (16.9)
65.6 (14.9)
40.5 (124.0)
41.9 (131.9)
40.2 (123.6)
40.7 (132.2)
39.6 (123.8)
41.4 (124.2)
41.6 (135.5)
40.3 (123.6)
41.3 (135.2)
23.9
25.0
23.9
25.4
23.5
24.5
23.5
24.8
23.5
4.24a
aBroad signal.

1716
M. T. Maghsoodlou et al.
17.3 Hz) and 5.72 ppm (3JPH = 17.0 Hz) for the E and Z isomers, respec-
tively. The 13C NMR spectrum of 4a displayed 26 distinct resonances
in good agreement with the presence of a mixture of the two conforma-
tional isomers.
The 1H and 13C NMR spectra of compounds 4b–e are similar to those
of 4a, except for the signals resulting from the ester group, which are
characteristic for the respective substituent R. The structural assign-
1
ments made for compounds 4a–e on the basis of the H and 13C NMR
spectra were supported also by the IR spectra. The carbonyl region of
the spectra exhibits absorption bands for each compound. Of special
interest is the ester absorption of these compounds at 1731–1612 cm−1
.
Conjugation with the ylide moiety accounts for the shift of the carbonyl
absorption bands to lower wave numbers.
In summary, we have prepared novel phosphorus ylides using a one-
pot reaction between triphenylphosphine and dialkyl acetylenedicar-
boxylates in the presence of 6-chloro-2-benzoxazolethiol or 2-chloro-
phenothiazine. The present method carries the advantage that not
only is the reaction performed under neutral conditions, but the sub-
stances also can be mixed without any activation or modifications.
The 6-chloro-2-benzoxazolethiol and 2-chloro-phenothiazine containing
phosphorus ylides 4a–e may be considered as potentially useful syn-
thetic intermediates. The procedure described here might be employed
as a general method for the preparation of phosphoranes with variable
functionalities.
EXPERIMENTAL
Melting points and IR spectra of all compounds were measured on an
Electrothermal 9100 apparatus and a Shimadzu IR-460 spectrometer,
1
respectively. The H, 13C, and 31P NMR spectra were obtained with a
Bruker DRX-300 Avance instrument in CDCl3 as solvent at 300.1, 75.4,
and 121.5 MHz, respectively. The mass spectra were measured with a
GCMS-QP 5050A mass spectrometer operating at an ionization po-
tential of 70 eV. Dialkyl acetylenedicarboxylates, triphenlphosphine,
6-chloro-2-benzoxazolethiol, and 2-chloro-phenothiazine were pur-
chased from Fluka, and were used without further purification.
General Procedure
To a magnetically stirred solution of triphenylphosphine (0.26 g,
1 mmol) and 6-chloro-2-benzoxazolethiol (1 mmol) or 2-chloropheno-
thiazine (1 mmol) in 10 mL of dry ethyl acetate, a solution of the

Synthesis of Stable Phosphorus Ylides
1717
corresponding acetylenedicarboxylate (1 mmol) in 4 mL of dry ethyl
acetate was added dropwise over a period of 10 min. After approxi-
mately 6 h of stirring at room temperature, the product was filtered
and washed with cold diethyl ether (3 × 5 mL).
Dimethyl-2-(6-chloro-2-benzoxazolethiol-N-yl)-3-(triphenyl-
phosphanylidene)-butanedioate (4a)
Colorless crystals; mp: 162–164◦C; yield: 0.54 g (92%). IR (KBr) (νmax
,
cm−1): 1728, 1617 (C O). MS (m/z, %): 471 (M-2CO2Me, 31), 408 (M-
C7H3ClNOS, 22), 262 (PPh3, 100), 183 (PPh2, 94), 108 (PPh, 43), 77
(Ph, 16). Anal. Calcd. for C31H25ClNO5PS (590.0): C, 63.10; H, 4.27; N,
2.37%. Found: C, 63.33; H, 4.48; N, 2.29%.
1
Major Isomer (72%): H NMR (CDCl3): δ = 3.21 (s, 3H, CH3), 3.80
3
(s, 3H, CH3), 5.78 (d, JPH = 17.3 Hz, 1H, P=C-CH), 7.28–7.86 (m,
1
18H,arom-H). 13C NMR (CDCl3): δ = 40.5 (d, JPC = 124.0 Hz, P=C),
49.6 (CH3), 52.3 (CH3), 62.8 (d, 2JPC = 17.4 Hz, P=C-CH), 110.2, 114.2,
1
3
124.9, 125.6 (d, JPC = 92.0 Hz, C-i), 129.2 (d, JPC = 12.7 Hz, C-m),
129.8, 132.0, 132.6 (C-p), 133.4 (d, 2JPC = 9.7 Hz, C-o), 147.2, 169.9 (d,
3JPC = 11.4 Hz, C=O ester), 170.0 (d, JPC = 11.3 Hz, P-C=C), 180.0
2
(C=S). 31P NMR (CDCl3): δ = 23.9.
Minor Isomer (28%): 1H NMR (CDCl3): δ = 3.81, (s, 3H, CH3), 3.83
3
(s, 3H, CH3), 5.72 (d, JPH = 17.0 Hz, 1H, P=C-CH), 6.88–7.86 (m,
18H, arom-H). 13C NMR (CDCl3): δ = 40.9 (d, JPC = 131.9 Hz, P=C),
1
53.0 (CH3), 53.6 (CH3), 63.3 (d, 2JPC = 14.1 Hz, P=C-CH), 110.5, 113.3,
124.5 124.9 (d, 1JPC = 92.0 Hz, C-i), 125.5, 129.2 (d, 3JPC = 12.7 Hz, C-
m), 130.0, 132.2, 132.6 (C-p), 133.5 (d, 2JPC = 8.6 Hz, C-o), 147.4, 169.6
3
2
(d, JPC = 13.9 Hz, C=O), 170.4 (d, JPC = 12.9 Hz, P-C= C), 180.3
(C=S). 31P NMR (CDCl3): δ = 25.0.
Diethyl-2-(6-chloro-2-benzoxazolethiol-N-yl)-3-(triphenyl-
phosphanylidene)-butanedioate (4b)
White solid; mp: 149–151◦C; yield: 0.56 g (90%). IR (KBr) (νmax, cm−1):
1731, 1620 (C O). MS (m/z, %): 433 (M-PPh2, 21), 282 (M-PPh2 and
CO2Et, 38), 262 (PPh3, 100), 183 (PPh2, 83), 108 (PPh, 44), 77 (Ph, 9).
Anal. Calcd. for C33H29ClNO5PS (618.1): C, 64.13; H, 4.73; N, 2.27%.
Found: C, 64.27; H, 4.79; N, 2.11%.
1
3
Major Isomer (78%): H NMR (CDCl3): δ = 0.49 (t, JHH = 7.1 Hz,
3H, CH3), 1.29 (t, 3JHH = 7.1 Hz, 3H, CH2), 3.76–3.80 (m, ABX3 system,
3
CH2), 4.16–4.34 (m, ABX3 system, CH2), 5.74 (d, JPH = 17.8 Hz, 1H,
P=C-CH), 7.27–7.90 (m, 18H, arom-H). 13C NMR (CDCl3): δ = 14.0

1718
M. T. Maghsoodlou et al.
1
(CH3), 14.2 (CH3), 40.2 (d, JPC = 123.6 Hz, P=C), 58.4 (CH2), 61.8
2
(CH2), 62.9 (d, JPC = 17.5 Hz, P=C-CH), 110.2, 114.3, 124.8, 125.8
1
3
(d, JPC = 92.0 Hz, C-i), 129.1 (d, JPC = 12.2 Hz, C-m), 129.9, 132.0,
132.5 (d, 4JPC = 2.3 Hz, C-p), 133.5 (d, 2JPC = 9.7 Hz, C-o), 147.2, 169.2
3
2
(d, JPC = 13.2 Hz, C=O), 169.5 (d, JPC = 12.4 Hz, P-C= C), 180.1
(C=S).31P NMR (CDCl3): δ = 23.9.
1
3
Minor Isomer (22%): H NMR (CDCl3): δ = 1.21 (t, JHH = 7.1 Hz,
3
3H, CH3), 1.34 (t, JHH = 7.1 Hz, CH3), 3.75–3.82 (m, ABX3 system,
3
CH2), 4.30–4.40 (m, ABX3 system, CH2), 5.57 (d, JPH = 19.8 Hz, 1H,
P=C-CH), 6.85–7.90 (m, 18H, arom-H). 13C NMR (CDCl3): δ = 14.1
1
(CH3), 14.8 (CH3), 40.7 (d, JPC = 132.2 Hz, P=C), 61.3 (CH2), 61.7
2
(CH2), 63.2 (d, JPC = 5.9 Hz, P=C-CH), 110.5, 113.4, 124.3, 125.2
(d,1JPC = 92.4 Hz, C-i), 128.5 (d, JPC = 12.2 Hz, C-m), 130.1, 132.1,
3
4
2
132.5 (d, JPC = 2.3 Hz, C-p), 133.5 (d, JPC = 9.7 Hz, C-o), 147.4,
3
2
169.5 (d, JPC = 13.6 Hz, C=O), 170.0 (d, JPC = 17.8 Hz, C=O), 180.4
(C=S).31P NMR (CDCl3): δ = 25.4.
Di-tert-buthyl-2-(6-chloro-2-benzoxazolethiol-N-yl)-3-
(tri-phenylphosphanylidene)-butanedioate (4c)
White solid; mp: 161–163◦C; yield: 0.63 g (94%). IR (KBr) (νmax
,
cm−1): 1725, 1613 (C=O). MS (m/z, %): 572 (M-CO2CMe3, 32), 377
(M-C7H3ClNOS and 2 CMe3, 42), 288 (M-PPh2 and 2 CO2CMe3, 25),
262 (PPh3, 100), 183 (PPh2, 63), 108 (PPh, 33), 57 (CMe3, 57). Anal.
Calcd. for C37H37ClNO5PS (674.2): C, 65.92; H, 5.53; N, 2.08%. Found:
C, 66.07; H, 5.72; N, 2.03%.
1H NMR (CDCl3): δ = 1.00 (s, 9H, CH3), 1.57 (s, 9H, CH3), 5.56 (d,
3JPH = 18.5 Hz, 1H, P=C-CH), 7.24–8.40 (m, 18H, arom-H). 13C NMR
1
(CDCl3): δ = 28.1 (CH3), 28.3 (CH3), 39.6 (d, JPC = 123.8 Hz, P=C),
2
63.5 (d, JPC = 17.9 Hz, P=C-CH), 78.0 (CMe3), 81.7 (CMe3), 110.0,
1
3
114.3, 124.7, 126.2 (d, JPC = 91.7 Hz, C-i), 128.9 (d, JPC = 12.2 Hz,
4
2
C
−m), 130.0, 132.0, 132.4 (d, JPC = 2.2 Hz, C-p), 133.5 (d, JPC = 9.7
3
2
Hz, C-o), 147.2, 167.7 (d, JPC = 13.1 Hz, C=O), 169.0 (d, JPC = 11.8
Hz, P-C= C), 180.2 (C=S). 31P NMR (CDCl3): δ = 23.5.
Dimethyl-2-(2-chloro-phenothiazine-N-yl)-3-(triphenyl-
phosphanylidene)-butanedioate (4d)
Yellow powder; mp: 134–136◦C; yield: 0.61 g (95%). IR (KBr) (υmax
,
cm−1): 1735, 1629 (C=O). MS (m/z, %): 519 (M-2CO2Me, 25), 345 (M-
PPh3 and OCH3, 23), 262 (PPh3, 100), 183 (PPh2, 97), 108 (PPh, 43),

Synthesis of Stable Phosphorus Ylides
1719
77 (Ph, 23). Anal. Calcd. for C36H29ClNO4PS (638.1): C, 67.76; H, 4.58;
N, 2.20%. Found: C, 67.80; H, 4.65; N, 2.18%.
1
Major Isomer (54%): H NMR (CDCl3): δ = 3.81 (s, 3H, CH3), 3.96
3
(s, 3H, CH3), 4.21 (d, JPH = 14.6 Hz, 1H, P=C-CH), 6.65–7.72 (m,
22H, arom-H). 13C NMR (CDCl3): δ = 41.4 (d, 1JPC = 124.2 Hz, P= C),
49.1 (CH3), 52.8 (CH3), 65.4 (d, 2JPC = 14.7 Hz, P=C-CH), 113.3, 114.6,
1
115.1, 120.1, 122.2, 124.0, 126.4 (d, JPC = 92.0 Hz, C-i), 126.1, 126.4,
3
4
126.9, 128.5 (d, JPC = 12.3 Hz, C-m), 131.8 (d, JPC = 2.7 Hz, C-p),
132.0, 132.1, 132.61, 133.4 (d, 2JPC = 9.7 Hz, C-o), 169.0 (d, 3JPC = 13.2
Hz, C=O), 173.6 (d, JPC = 17.6 Hz, P-C= C).31P NMR (CDCl3): δ =
2
24.5.
1
Minor Isomer (46%): H NMR (CDCl3): δ = 3.93 (s, 3H, CH3), 3.98
(s, 3H, CH3), 4.14 (d, 3JPH = 16.1 Hz, 1H, P=C-CH), 6.65-7.72 (m, 22H,
arom-H). 13C NMR (CDCl3): δ = 41.6 (d, JPC = 135.5 Hz, P= C), 52.6
1
2
(CH3), 52.9 (CH3), 64.8 (d, JPC = 14.6 Hz, P=C-CH), 113.3, 114.6,
1
115.1, 120.1, 122.2, 124.0, 125.2 (d, JPC = 91.8 Hz, C-i), 126.2, 126.5,
3
127.0, 128.5 (d, JPC = 12.2 Hz, C-m), 131.8 (d4, JPC = 2.7 Hz, C-p),
132.1, 132.2, 132.7, 133.5 (d, 2JPC = 9.8 Hz, C-o), 168.9 (d, 3JPC = 13.5
Hz, C=O), 173.8 (d, 2JPC = 16.8 Hz, C=O). 31P NMR (CDCl3): δ = 23.5.
Diethyl-2-(2-chloro-phenothiazine-N-yl)-3-(triphenyl-
phosphanylidene)-butanedioate (4e)
White powder; mp: 153–155◦C; yield: 0.61 g (91%). IR (KBr) (υmax
,
cm−1): 1722, 1612 (C=O). MS (m/z, %):MS (m/z, %): 520 (M-2CO2Et,
26), 440 (M-C12H7ClNS, 19), 359 (M-PPh3 and OEt, 31), 262 (PPh3,
100), 183 (PPh2, 97), 108 (PPh, 48), 77 (Ph, 17). Anal. Calcd. for
C38H33ClNO4PS (666.2): C, 68.51; H, 4.99; N, 2.10%. Found: C, 68.64;
H, 5.13; N, 2.06%.
1
Major Isomer (60%): H NMR (CDCl3): δ = 0.43 (broad, 3H, CH3),
1.32 (broad, 3H, CH3), 3.44 (broad, 2H, CH2), 4.19 (broad, 1H, P=C-
CH), 4.28 (broad, 2H, CH2), 6.66–7.96 (m, 22H, arom-H). 13C NMR
1
(CDCl3): δ = 14.1 (CH3), 14.3 (CH3), 40.3 (d, JPC = 123.6 Hz, P=C),
57.7 (CH2), 61.3 (CH2), 65.0 (d, 2JPC = 16.9 Hz, P=C-CH), 113.5, 114.7,
1
115.2, 121.5, 121.6, 122.4, 125.6, 126.0, 126.3, 126.8 (d, JPC = 92.4
3
4
Hz, C-i), 128.4 (d, JPC = 11.7 Hz, C-m), 131.7 (d, JPC = 2.7 Hz, C-
2
3
p), 132.0, 132.1, 132.6, 133.5 (d, JPC = 9.7 Hz, C-o), 168.2 (d, JPC
=
13.3 Hz, P-C=C), 172.9 (d, 2JPC = 12.4 Hz, C=O).31P NMR (CDCl3): δ =
24.8.
1
Minor Isomer (40%): H NMR (CDCl3): δ = 1.34 (broad, 6H, CH3),
3.80 (broad, 2H, CH2), 4.24 (broad, 1H, P=C-CH), 4.44 (broad, 2H,
CH2), 6.66–7.96 (m, 22H, arom-H).13C NMR (CDCl3): δ = 13.9 (CH3),

1720
M. T. Maghsoodlou et al.
14.0 (CH3), 41.3 (d, 1JPC = 135.2 Hz, P=C), 60.9 (CH2), 61.3 (CH2), 65.6
2
(d, JPC = 14.9 Hz, P=C-CH), 113.4, 114.5, 115.3, 121.4, 121.7, 122.4,
125.5, 126.2, 126.4, 126.6 (d, 1JPC = 92.3 Hz, C-i), 128.4 (d, 3JPC = 12.5
4
Hz, C-m), 131.7 (d, JPC = 2.7 Hz, C-p), 132.0, 132.1, 132.7, 133.5 (d,
3
2
2JPC = 9.7 Hz, C-o), 168.7 (d, JPC = 12.6 Hz, C=O), 173.4 (d, JPC
=
13.1 Hz, P-C= C). 31P NMR (CDCl3): δ = 23.5.
REFERENCES
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