Reaction of 2-thioxo-4-thiazolidinones toward Lawesson's reagent, phosphorus pentasulfide, dialkylaminophosphines, and phosphorus ylides

Article abstract of DOI:10.1080/10426507.2011.627898

2-Thioxo3-allyl-4-thiazolidinone 1a reacts with Lawesson's reagent (LR, 2) to give the ethylenic product 5 through a coupling reaction along with the dithioxo compound 6. Coupling reaction products of types 8 and 9 are also produced upon reacting thiazolidinones 1 and with the appropriate tris(diallkylamino) phosphine reagent (3 a,b). Reaction of the thiazolidinone 1a with the ylidenetriphenylphosphorane reagents 4 a-c proceeds according to the Wittig mechanism yielding ethylenes 10a-c, respectively. Structural elucidations for the new products were based upon compatible analytical and spectroscopic measurements as well a confirmatory single crystal X-ray structure for 5. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the related elements to view the free supplemental file.

Full text of DOI:10.1080/10426507.2011.627898

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Reaction of 2-Thioxo-4-Thiazolidinones
Toward Lawesson's Reagent, Phosphorus
Pentasulfide, Dialkylaminophosphines,
and Phosphorus Ylides
Hoda A. Abdel-Malek a
a Department of Organometallic and Organometalloid Chemistry,
National Research Centre, Giza, Egypt
Published online: 31 Jan 2012.
To cite this article: Hoda A. Abdel-Malek (2012): Reaction of 2-Thioxo-4-Thiazolidinones Toward
Lawesson's Reagent, Phosphorus Pentasulfide, Dialkylaminophosphines, and Phosphorus Ylides,
Phosphorus, Sulfur, and Silicon and the Related Elements, 187:4, 506-514
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Phosphorus, Sulfur, and Silicon, 187:506–514, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.627898
REACTION OF 2-THIOXO-4-THIAZOLIDINONES
TOWARD LAWESSON’S REAGENT, PHOSPHORUS
PENTASULFIDE, DIALKYLAMINOPHOSPHINES,
AND PHOSPHORUS YLIDES
Hoda A. Abdel-Malek
Department of Organometallic and Organometalloid Chemistry,
National Research Centre, Giza, Egypt
GRAPHICAL ABSTRACT
S
S
S
CH CH2
N
CH2
S
N
N
S
S
S
6
S
S
5
CH3
CH3
R
R
N
R
N
H3C
H3C
H3C
O
N
N
O
O
N
N
S
H3C
CH3
CH3
S
S
S
O
N
N
R
Z8
8a, R = CH2CH=CH2
b, R = C2H5
E8
c, R = CH3
R`
R`
N
R`
S
S
N
S
S
N
S
S
N
S
S
R`
Z9
E9
9a, R` = CH3
b, R` = C2H5
Abstract 2-Thioxo—3-allyl-4-thiazolidinone 1a reacts with Lawesson’s reagent (LR, 2) to
give the ethylenic product 5 through a coupling reaction along with the dithioxo compound 6.
Coupling reaction products of types 8 and 9 are also produced upon reacting thiazolidinones
1 and with the appropriate tris(diallkylamino) phosphine reagent (3 a,b). Reaction of the
thiazolidinone 1a with the ylidenetriphenylphosphorane reagents 4 a–c proceeds according to
the Wittig mechanism yielding ethylenes 10a–c, respectively. Structural elucidations for the
new products were based upon compatible analytical and spectroscopic measurements as well
a confirmatory single crystal X-ray structure for 5.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the related elements to view the free supplemental file.
Keywords 2-Thioxo-4-thiazolidinones; Lawesson’s reagent; P4S10; tris(dialkylamino)phos
phines and phosphonium ylides
Received 17 July 2011; accepted 25 September 2011.
Address correspondence to Hoda A. Abdel-Malek, Department of Organometallic and Organometalloid
Chemistry, National Research Centre, Giza, 12622, Egypt. E-mail: hodanwar@yahoo.com
506

REACTION OF 2-THIOXO-4-THIAZOLIDINONES TOWARD LAWESSON’S REAGENT 507
INTRODUCTION
Thiazolidinone 1 derivatives1–3 are reported to possess a varity of biological ac-
tivities such as anticonvulsant, tuberculostatic, anti-inflammatory, and antithyroidal ac-
tivities. They are also used as bactericidal, fungicidal, and insecticidal agents.3,4 In line
with our growing interest5–13 in the chemistry of organophosphorous compounds, we
have now studied the reaction of thiazolidinone 1 a–d with Lawesson’s reagent (LR,
2), tris(dialkylamino)phosphines (3 a,b), and ylidenetriphenyl-phosphoranes (4 a–c).
O
S
S
S
R
N
H3CO
OCH3
P
P
S
S
S
2
1a, R = CH2CH=CH2
b, R = C2H5
c, R = CH3
d, R = H
(C6H5)3P=CHR
P(NR2)3
3a, R = CH3
b, R = C2H5
4a, R = COOCH3
b, R = COOC2H5
c, R = COCH3
Scheme 1
RESULTS AND DISCUSSION
When one mole of 1a was allowed to react with half mole equivalent of 2,4-bis-
(4-methoxy phenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson’s reagent LR,
2),11 a mixture of 3-(prop-2-en-1-yl)-5-[3-(prop-2-en-1-yl)-2,4-dithioxo-1,3-thiazolidine-
5-ylidene]-1,3-thiazolidine-2,4-dithione (5), 3-allylthiazolidine-2,4-dithione (6), and 2,4,6-
tris(4-methoxyphenyl)-2,4,6-trisulfanylene-1,3,5,2,4,6-trioxatriphosphinane (7) were ob-
tained. Compounds 5, 6, and 7 are chromatographically pure and possess sharp melting
points. The structure of compound 5 was confirmed mainly based upon X-ray crystallogra-
phy14–18 (Figure 1, Tables S1 and S2). Correct analytical and mass spectral measurements
for 5 (m/z 374, M+, 100%) corresponding to C12H10N2S6. Its IR spectrum (KBr, cm−1
)
revealed the absence of the amide –carbonyl band (shown in the IR spectrum of 1a at
1680 cm−1) and presence of a thiocarbonyl absorption band at 1175 cm−1 together with a
band at 1625 (C C). The 1H NMR spectrum of 5 (CDCl3, δ ppm) reveals the absence of
the signal due to the methylene protons that appeared in the spectrum of 1a at δ = 3.76
ppm (s, 2H). Moreover, the 13C NMR spectrum of 5 (CDCl3, δ ppm) showed the presence
of a signals at δ = 198.1 (C S), 196.6 (C S), and the absence of the signal due to the
C O group that is shown in the spectrum of 1a at 169.5. Compound 6 was unequivocally
prepared and identified (m.p, mixed m.p, and comparative IR spectra) through thiation of
1a with P4S10. Apparently, oxidative dehydrodimerization of 6 occurred to give 5. The
structure of compound 7 was proven by comparing its melting point as its IR and 1H NMR
spectrum with those of an authentic specimen.19 Formation of 7 is frequently observed
during the thiation processes initiated by LR, 2.20

508
H. A. ABDEL-MALEK
Figure 1 X-ray structure of compound 5 (shown at 30% probability).
Moreover, compound 7 was isolated from the reaction mixture as a colorless crys-
talline phosphorus-containing product and proved to be trimer by comparing its melting
1
point as well as IR and H NMR spectra with those of an authentic sample.19 Forma-
tion of compound 7 is frequently observed during the thiation processes initiated by LR
(Scheme 2).
S
O
S
S
+
CH CH2
H3CO
CH2
S
OCH3
N
P
P
S
S
2
1a
S
S
N
S
R
O
P
R
S
P4S10
P
P
S
S
O
O
N
CH CH2
CH2
N
S
S
S
R
S
6
S
S
5
7, R = C6H4OCH3p
Scheme 2
Product 6 is also obtained and identified (m.p, mixed m.ps, and comparative IR spec-
tra) by reacting 1a with phosphorus pentasulfide21 in refluxing toluene (cf. Experimental,
Scheme 2).
Next, the reaction of 2-thioxo-3-methyl-4-thiazolidinone 1a–c with tris(dimethyla
mino)phosphine 3a has been investigated under solvent free conditions. The yellow
crystalline products, so formed were assigned structures 8a–c, respectively that can exist
either in the Z or E conformations (Scheme 3). Structural reasoning for N[2-[4-
[(dimethylamino)oxy]-3-(prop-2-en-1-yl)-1,3-thiazol-2(3H)ylidene]-3-(prop-2-en-1-yl)-2,
3-dihydro-1,3-thiazol-4-yl]oxy-N-methylmethan- amine 8a, taken as examples are:
(a) correct analytical and molecular weight measurements (Ms: m/z 368, M+, 100%)
corresponded to C16H24N4O2S2. (b) The amide carbonyl absorption band present in the
IR spectrum of 1a at 1680 cm−1 was absent in the spectrum of 8a. (c) Similarly, the C O

REACTION OF 2-THIOXO-4-THIAZOLIDINONES TOWARD LAWESSON’S REAGENT 509
signal present at δ = 169.6 in the 13C NMR spectrum of 1a was absent in the spectrum of
8a.
O
R
N
P(NR`2)3
+
S
S
3a, R` = CH3
1a, R = CH2CH=CH2
b, R = C2H5
c, R = CH3
CH3
CH3
R
N
R
R
N
H3C
H3C
H3C
O
N
N
N
O
N
O
S
H3C
CH3
CH3
S
S
S
O
N
R
N
Z8
8a, R = CH2CH=CH2
b, R = C2H5
E8
c, R = CH3
O
NH
P(NR`2)3
+
S
S
3a, R` = CH3
b, R` = C2H5
1d
R`
R`
N
R`
N
S
S
N
S
S
S
S
N
S
S
R`
Z9
E9
9a, R` = CH3
b, R` = C2H5
Scheme 3
In a similar manner 1b and 1c react under identical conditions to form 8b and 8c
respectively.
On the other hand, the reaction of compound 1d with excess tris(dimethyl
amino)phosphine 3a without solvent, gave mainly the coupling product 9a. The structural
assignment for compound 9a is based upon elemental and spectroscopic analyses. The IR
spectrum of 9a reveals the absence of absorption bands of C O and NH that recorded at
δ = 1680 and 3235 cm−1 respectively, in the starting thiazolidinone 1d. The 13C NMR of
compound 9a lacks the C O signal recorded in the compound 1d at δ = 169.6 (C O,
thiazolidinone) (cf. Experimental, Scheme 3).
Similarly, the reaction of 2-thioxo-4-thiazolidinone 1d with tris(diethyl-
amino)phosphine 3b proceeds without solvent to give 9b (Scheme 3).
Reaction of thiazolidinone 1a with one mole equivalent of the ylidenetriphenylphos-
phoranes 4a–c in refluxing toluene proceeded according to the Wittig mechanism yielding
the ethylenic products 10a–c, respectively (Scheme 4). Triphenylphosphine sulfide was also
isolated and identified (m.p., mixed m.p., and comparative IR spectra) in each case. The
main features of the IR spectrum of 10a–c (in KBr, cm−1) were the absence of thiocarbonyl
band (shown in the IR spectrum of 1a at 1175 cm−1) and the appearance of absorption bands

510
H. A. ABDEL-MALEK
at 1680 cm−1 (C O, amide) and at 1623 cm−1 (C C, ethylenic). Moreover, compatible
analytical as well as spectroscopic measurements were gained for 10a–c (Experimental).
O
- (C6H5)3P=S
+
CH2
CH
N
CH2
S
(C6H5)3P=CHR
4a, R = COOCH3
b, R = COOC2H5
c, R = COCH3
S
1a
O
CH CH2
N
CH2
S
CHR
10a, R = COOCH3
b, R = COOC2H5
c, R = COCH3
Scheme 4
CONCLUSION
From the present study, it is evident that 2-thioxo-4-thiazolidinones 1a–d react with
the phosphorus reagents 2, 3, and 4 to give products whose structures vary according
to the nature of reactants in each case. Thus, thiation of 1a with LR, 2 in the usual
manner20 to give 6 also leads to the new ethylernic product 5 through a coupling reaction.
Meanwhile, coupling products of type 8 or 9 are essentially produced upon reacting 1a–d
with tris(dialkylamino)phosphines 3a,b. On the other hand, the 2-thioxo-4-thiazolidinone
derivative 1a reacts with the ylidenetriphenyl- phosphoranes 4 according to the Wittig
mechanism to yield ethylenic products of type 10a–c.
EXPERIMENTAL
Melting points were determined in open glass capillaries using Electrothermal IA
9000 series digital melting points apparatus (Electrothermal, Essex, UK) and are un-
corrected. The IR spectra were measured in KBr pellets with Perkin–Elmer Infracord
1
spectrophotometer model 157 (Grating). The H and 13C NMR spectra were recorded in
CDCl3/ and DMSO as solvent on Joel-500 MHz spectrometer, and the chemical shifts were
recorded in δ values relative to TMS. The mass spectra were performed at 70 eV on a
Shimadzu GCS-OP 1000 Ex spectrometer provided with data system. Elemental analysis
was performed using Elmenter Varu EL Germany Instrument.
Reaction of 2-Thioxo-4-thiazolidione (1a) with LR (2)
A mixture of 1a (0.34 g, 0.002 mole) and LR 2 (0.4 g, 0.001 mole) was refluxed
in boiling toluene (30 mL) for 5 h. The reaction mixture was evaporated under reduced
pressure and the residue was applied to a silica gel column chromatography, using

REACTION OF 2-THIOXO-4-THIAZOLIDINONES TOWARD LAWESSON’S REAGENT 511
acetone/petroleum ether as eluent to give products 5, 6, and the trimer 7, respectively.
The product 5 3-(prop-2-en-1-yl)-5[3-(prop-2-en-1-yl)-2,4-dithioxo-1,3-thiazolidine-5-
ylidene]-1,3-thiazolidine-2,4-dithione (5, C12H10N2S6). Eluent: petroleum ether/acetone
(98.2, v/v). It was separated as dark green needles yield (55%), m.p. 183–184 ◦C
(acetone/petroleum ether). IR [ν, cm−1, KBr]: 1175 cm−1 (C S), 1625 (C C). 1H NMR
(500 MHz, δ ppm, CDCl3): 3.87 (d, 4H, JHH = 10 Hz, 2(N-CH2)), 5.15, 5.17 (t, 4H,
2[CH2 CH)], 5.83 [m, 2H, 2( CH CH2)]. 13C NMR (125 MHz, δ ppm, CDCl3): 49.8
(N CH2, allyl), 119.6 (CH2 CH-allyl), 134.3 (CH CH2-allyl), 149.4 (C C), 198.1
(C S), 196.6 (C S). MS m/z (%): 374 [M+] (100), corresponding to the molecular
formula C12H10N2S6. Anal. Calcd for C12H10N2S6 (373.92): C, 38.47; H, 2.69; N, 7.48;
S; 51.36. Found: C, 38.45; H, 2.66; N, 7.44; S, 51.39.
X-Ray crystallographic study:14–18 A single crystal was separated by careful evap-
oration of petroleum ether/acetone (98/2, v/v) solution. The crystal structure was solved
and refined, using maxus (Nonius Delft and Mac science, Japan). MoKα (λ = 0.71073 Å)
and graphite monochromator were used for data collection. A summary of the crystal
analysis parameters is given in Table S2 (Supplemental Materials). CCDC 830679 con-
tains the supplemental crystallographic data for this paper. These data can be obtained
free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.com.ac.
uk/datarequest/cif.
3-Allylthiazolidine-2,4-dithione (6, C6H7NS3). Eluent petroleum ether/ace◦tone (95/5
v/v) product 6 was separated as orange crystals, yield 20% and m.p. 228–229 C. IR [ν,
1
cm−1, KBr]: 1175 (C S). H NMR (500 MHz, δ ppm, CDCl3): 3.66 (s, 2H, CH2), 3.87
(d, 2H, N CH2), 5.15, 5.17 (d, 2H, CH CH2), 5.83 (m, 1H, CH CH2). MS m/z (%)
189 (100) corresponding to the molecular formula C6H7NS3. Anal. Calcd for C6H7NS3
(188.97): C, 38.06; H, 3.73; N, 7.40; S, 50.81. Found: C, 38.09; H, 3.71; N, 7.42; S, 50.84.
The trimer 7 was isolated as colorless crystals and identified.
Reaction of Thiazolidinone (1a) with Phosphorus Pentasulfide
Thiazolidinone 1a reacts with P4S10 according to the general procedure described
before, to give product 6 as orange, crystals, and identified.
Reactions of 2-Thioxo-4-thiazolidinone (1a) with
Tris(methylamino)-phosphine (3a) in Solvent Free Conditions
An excess of aminophosphine 3a (≈3 mL) was added to 1a (0.17 g, mmol)
and was heated for 15 h. The reaction mixture was evaporated under reduced pres-
sure and the residue was chromatographed on a silica gel column to give product
8a N[2-[4-[(dimethylamino)oxy]-3-(prop-2-en-1-yl)-1,3-thiazol-2(3H)ylidene]-3-(prop-2-
en-1-yl)-2,3-dihydro-1,3-thiazol-4-yl]oxy-N-methyl methanamine (8a, C16H24N4O2S2).
Eluent: petroleum ether/acetone (85/15, v/v) product 8a was separated as yellow crystals,
◦
yield 65% and m.p. 39-4 C (petroleum ether/acetone). IR [ν, cm−1, KBr]: 1625 (C C).
1H NMR (500 MHz, δ ppm, CDCl3): 2.76 [s, 12H, 2(N(CH3)2], 3.80 [d, 4H, 2(N-CH2)],
5.15, 5.17 [d, 4H, 2(CH2 CH )], 5.35 [s, 2H, 2(HC C)], 5.83 [m, 2H, 2( CH CH2)].
13C NMR (125 MHz, δ ppm, CDCl3): 49.6 (CH2-N, allyl), 50.8 [N(CH3)2], 69.7 (HC C),
119.6 (CH2 CH, allyl), 134.3 (CH CH2, allyl), 106.9 (C C), 182.9 (C C O). MS m/z
(%): 368 (100) corresponding to the molecular formula C16H24N4O2S2. Anal. Calcd for

512
H. A. ABDEL-MALEK
C16H24N4O2S2 (368.13): C, 52.15; H, 6.56; N, 15.20; S, 17.40. Found: C, 52.17; H, 6.59;
N, 15.24; S, 17.39. MS, m/z (%): 368 (100) [M+].
Reaction of Thiazolidinone 1b with Tris(dimethylamino) Phosphine 3a
The same method described for 8a to give adduct 8b N-[-2-4-[(dimethylamino)oxy]-
3-ethyl-1,3-thiazol-2(3H)-ylidene)-3-ethyl-2,3-dihydro-1,3-thiazol-4-yl]oxy-N-methylme
thanamine(8b,C14H24N4O2S2). Eluent: petroleum ether/ acetone (85/15, v/v). Product 8b
was separated as yellow crystals, yield (67%) and m.p. 47–48 ◦C (petroleum ether/acetone).
1
IR [ν, cm−1, KBr]: 1625 (C C). H NMR (500 MHz, δ ppm, CDCl3): 1.20 [t, 6H,
2(CH3)2], 3.24 [q, 4H, 2(CH2)], 5.25 [s, 2H, 2(CH C)]. MS (%) 344 [M+] (90),
corresponding to the molecular formula C14H24N4O2S2. Anal. Calcd for C14H24N4O2S2
(344.13): C, 48.81; H, 7.02; N, 16.26; S, 18.62. Found: C, 48.83; H, 7.05; N, 16.23; S,
18.64%.
Similarly, thiazolidinone 1c reacted with aminophosphine 3a to give 8c N-[-2-4-
[(dimethylamino)oxy]-3-methyl-1,3-thiazol-2(3H)-ylidene-3-methyl-2,3-dihydro-1,3-4-yl]
oxy-N-methylmethanamine
(8c, C13H20N4O2S2). Eluent: petroleum ether/acetone (85/15, v/v) product 8c was
◦
separated as yellow crystals, yield 63% and m.p. 44–45 C (petroleum ether/acetone).
IR [ν, cm−1, KBr]: 1625 (C C). H NMR (500 MHz, δ ppm, CDCl3): 2.79 [s, 12H,
1
2(NCH3)2], 3.11 [s, 3.11, 6H, 2(NCH3)], 5.52 [s, 2H, 2(CH C)]. [t, 6H, 2(CH3)2], 3.24
[q, 4H, 2(CH2)[, 5.25 [s, 2H, 2(CH C)]. 13C NMR (125 MHz, δ ppm, CDCl3): 29.7
(NCH3), 50.8 [N(CH3)2], 69.7 (CH C), 106.9 (C C), 182.9 ( O C C). MS m/z (%)
316 [M+] (100), corresponding to the molecular formula C13H20N4O2S2. Anal. Calcd. for
C13H20N4O2S2 (316.10), C, 45.55; H, 6.37; N, 17.71; S, 20.27. Found: C, 45.52; H, 6.39;
N, 17.73; S, 20.24%.
Reaction of Thiazolidinone 1d with Tris(dimethylamino) Phosphine 3a
The same method described before was applied to give product 9a 3-(dimethylamino)-
4-[3-(dimethylamino)-2-thioxo-1,3-thiazolidin-4-ylid-ene]-1,3-thiazolidine-2-thione (9a,
C10H16N4S4). Eluent: acetone: petroleum ether (◦30: 70) product 9a was separated as
colorless crystals, yield 65% and m.p. 195–196 C. IR [ν, cm−1, KBr]: 1175 (C S),
1
1625 (C C). H NMR (500 MHz, δ ppm, CDCl3): 2.79 [s, 12H, 2(NCH3)2)] 3.54 [s,
4H, 2(CH2)]. 13C NMR (125 MHz, δ ppm, CDCl3): 35.1 (CH2), 39.9 [N(CH3)2)] 117.9
(C C), 198.1 (C S), MS m/z (%) 320 [M+] (60), corresponding to the molecular formula
C10H16N4S4. Anal. Calcd. for C10H16N4S4 (320.03): C, 37.47; H, 5.03; N, 17.48; S, 40.02.
Found: C, 37.45; H, 5.07; N, 17.45; S, 40.01%.
Similarly thiazolidinone 1d reacted with tris(dimethylamino) phosphine 3b to
give product 9b (4Z)-3-(diethylamino)-4-[3-(diethylamino)-2-thioxo-1,3-thiazolidin-4-
ylidene]-1,3-thiazolidine-2-thione (9b, C14H24N4S4). Eluent: petroleum ether/acetone (70:
30, v/v), product 9b separated as orange crystals, yield 55% and m.p. 270–271 ◦C. IR [ν,
1
cm−1, KBr]: 1175 (C S), 1625 (C C). H NMR (500 MHz, δ ppm, CDCl3): 1.01 [t,
12H, 2(NCH2CH3)2)] 2.59 [q, 8H, 2(NCH2CH3)2], 3.54 [s, 4H, 2(CH2)]. 13C NMR (125
MHz, δ ppm, CDCl3): 10.9 [2(N(CH2CH3)2)] 35.3 [2(CH2), 53.2 (2N(CH2CH3)2], 118.3
(C C), 198.6 (C S). MS m/z (%) 376 [M+] (70), corresponding to the molecular formula

REACTION OF 2-THIOXO-4-THIAZOLIDINONES TOWARD LAWESSON’S REAGENT 513
C14H24N4S4. Anal. Calcd. for C14H24N4S4 (376.09): C, 44.65; H, 6.42; N, 14.88; S, 34.05.
Found: C, 44.69; H, 6.41; N, 14.85; S, 34.08%.
Reaction of 2-Thioxo-4-thiazolidine 1a with Carbmethoxymethylene
Triphenylphosphorane 4a
A mixture of thiazolidine 0.17 g 1a (1 mmol) and 0.34 g (1 mmol) of ylide 4a in 30 mL
dry toluene. The reaction mixture was refluxed for 5 h. The volatile material was evaporated
under reduced pressure. The residue was subjected to silica gel column chromatography
to give methyl-2-(3-allyl(4-oxothiazolidin-2-ylidene)acetate (10a, C9H11NO3S). Eluent:
petroleum/acetone (95/5, v/v) product 10a was separated as yellow compound, yield 55%
◦
1
and m.p. 29–30 C. IR [ν, cm−1, KBr]: 1680 (C O), 1710 (C O, ester). H NMR (500
MHz, δ ppm, CDCl3): 3.75 (s, 2H, CH2), 3.87 (d, 2H NCH2), 5.15, 5.17 (d, 2H, CH CH2),
5.83 (m, 1H, CH CH2). MS m/z (%) 213 [M+] (65), corresponding to the molecular
formula C9H11NO3S. Anal. Cacld. for C9H11NO3S (213.05): C, 50.69; H, 5.20; N, 6.57; S,
15.04. Found: C, 50.65; H, 5.21; N, 6.55; S, 15.06%. Triphenylphosphine sulfide was also
isolated.
Similarly, the reaction of thiazolidinone 1a with carbethoxymethylene triphenylphos-
phorane 4b was performed in boiling toluene for 5 h to give product ethyl-2-(3-allyl(4-
oxthiazolidin-2-ylidene)acetate (10b, C10H13NO3S). Eluent: petroleum ether (95/5, v/v).
Product 10b was separated as yellow crystals, yield 63% and m.p. 34–35 ◦C. IR [ν, cm−1
,
1
KBr]: 1679 (C O, amide), 1710 (C O, ester). H NMR (500 MHz, δ ppm, CDCl3):
1.36 (t, 3H, CH3), 4.2 (q, 2H, CH2), 3.76 (s, 2H, CH2), 3.87 (d, 2H, N-CH2), 5.15, 5.17
(d, 2H, CH CH2), 5.83 (m, H, CH CH2). 13C NMR (125 MHz, δ ppm, CDCl3): 14.3
(C CH3), 62.9 (OCH2), 34.9 (CH2), 86.1 (C CH), 109.2 ( CH), 49.8 (N CH2, allyl),
119.6 (CH2 CH, allyl), 134.3 (CH CH2, allyl), 166.3 (C O, ester), 169.9 (C O, amid).
MS m/z (%) 227 [M+] (50), corresponding for C10H13NO3S (227.06). Anal. Cacld for
C10H13NO3S (227.06): C, 52.85; H, 5.77; N, 6.16; S, 14.11. Found: C, 52.87; H, 5.72; N,
6.14; S, 14.13. Triphenylphosphine sulfide was also isolated.
Similarly, thiazolidinone 1a was reacted with phosphorane 4c to give product
(Z)-3-allyl-2-(2-oxopropylidine) thiazoildin-4-one (10c, C9H11NO2S). Eluent: petroleum
ether/acetone (95: 5, v/v). Product 10c was separated as yellow crystals, yield 57% and m.p.
41–42 ◦C. IR [ν, cm−1, KBr]: 1660 (C O, acyl), 1679 (C O, amide). 1H NMR (500 MHz,
δ ppm, CDCl3): 2.22 (s, 3H, CH3), 3.75 (s, 2H, CH2), 3.87 (d, 2H, N CH2), 5.15, 5.17 (d,
2H, CH CH2), 5.83 (m, H, CH CH2), 6.03 (s, 1H, CH). MS m/z (%) 197 [M+] (50),
corresponding for molecular formula C9H11NO2S (197.25). Anal. Calcd. for C9H11NO2S
(197.25): C, 54.80; H, 5.62; N, 7.10; S, 16.26. Found: C, 54.83; H, 5.65; N, 7.11; S, 16.26.
Found: C, 54.83; H, 5.65; N, 7.11; S, 16.21. Triphenylphosphine sulfide was also isolated.
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