Thiol–Yne Coupling of Propargylamine under Solvent-Free Conditions by Bond Anion Relay Chemistry: An Efficient Synthesis of Thiazolidin-2-ylideneamine

Article abstract of DOI:10.1002/ejoc.201700603

Thiol–yne coupling of propargylamine with isothiocyanate has been developed under metal- and solvent-free conditions. The addition of propargylamine to isothiocyanate gives propargylthiourea. This intermediate in situ undergoes intramolecular 5-exo-dig cyclization to give thiazolidin-2-ylideneamine. A through-bond anion relay reaction occurs by attack of the sulfur (not the nitrogen) atom on the alkyne in a highly regioselective manner at ambient temperature. Wide varieties of thiazolidin-2-ylideneamine derivatives were formed in excellent yields.

Full text of DOI:10.1002/ejoc.201700603

A Journal of
Accepted Article
Title: Thiol-yne coupling of propargylamine under solvent free condition
via through bond anion relay chemistry: An efficient synthesis of
thiazolidin-2-ylideneamine
Authors: Dattatraya Hanumant Dethe, Alok Ranjan, Abhijit S. Deore,
and Swapnil Yerande
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201700603
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10.1002/ejoc.201700603
European Journal of Organic Chemistry
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Thiol-yne coupling of propargylamine under solvent free
condition via through bond anion relay chemistry: An efficient
synthesis of thiazolidin-2-ylideneamine
Alok Ranjan,[a] Abhijit S. Deore,[b] Swapnil G. Yerande,[b] and Dattatraya H. Dethe*[a]
Abstract: Thiol-yne coupling of propargylamine with isothiocyanate
mechanistic background behind this late transition metal
catalyzed hydrothiolation is reviewed.13
has been developed under metal and solvent free condition. The
addition
of
propargylamine
on
isothiocyanate
gives
Most recently, some improvements on selective hydrothiolation
of alkyne for the preparation of vinyl sulfides have been
described. These comprise the use of catalytic phenylselenenyl
bromide,14 nickel,15 gold16 or native silica nanoparticle17 under
solvent-free conditions, β-cyclodextrin in the presence of
water/acetone18 or under catalyst-free conditions in water.19
Silica gel promoted, solvent free, tandem addition-cyclization
propargylthiourea. This intermediate in situ undergoes intramolecular
5-exo-dig cyclization to give thiazolidin-2-ylideneamine. This through
bond anion relay reaction occurs by attack of sulphur (not nitrogen)
on alkyne in highly regioselective manner at ambient temperature.
Wide varieties of thiazolidin-2-ylideneamine derivatives were formed
in excellent yields.
reaction of
a
series of 2-alkynylbenzenamines with
isothiocyanates for the synthesis of 2,4-dihydro-1-H-
benzo[d][1,3]thiazines is also reported in the literature.20 In
absence of the silica gel the reaction was sluggish with low
isolated yields.
Introduction
In 2012, Guchhait et. al.21 reported the copper iodide catalyzed
synthesis of thiazolidin-2-ylideneamine from propargylamine
and isothiocyanate in moderate yield. In 2013, Fokin et. al.22
efficiently converted 1-mesyl-1,2,3-triazoles into a variety of
thiazole derivatives by Rh(II)-catalyzed denitrogenative reactions
with isothiocyanates. Recently, we have reported chiral Cu(I)OTf
and pybox complex catalyzed enantioselective synthesis of
Discovered by Posner in 1905, direct addition of sulphur and
hydrogen on carbon-carbon multiple bonds is universally
referred as hydrothiolation.1 Alkyne hydrothiolation reaction is
popularly known as thiol-yne coupling reaction. This over
century old reaction which forms the sulphur carbon bond in an
atom economical way is still an active area of research today
and work in this area is recently reviewed.2 Sulfur-carbon bond
is found in many pharmaceutical,3 material,4 synthetic reagents,5
as well as natural products.6 Hydrothiolation is often judged as a
part of “click chemistry” and a process of high atom-economy.7
Hydrothiolation can be promoted by free radicals,8 strong acids,9
or bases.10
thiazolidine-2-imines
from
imines,
acetylenes
and
isothiocyanates by an asymmetric alkynylation/hydrothiolation
cascade reaction.23 During this work, we observed that the
hydrothiolation reaction was proceeding without any catalyst
under solvent free condition.
In contrast to the popular belief that sulfur compounds are potent
poisons for metal catalysts,11 several excellent catalytic systems
have been found for C-S bond formation, leading to the
development of practical procedures for organic synthesis. The
first transition-metal-catalyzed alkyne hydrothiolation was
reported in 1976 using a molybdenum catalyst.12 Afterwards
increased attention in homogeneous, catalytic alkyne
hydrothiolation has afforded a number of metal complexes
proficient to achieve this transformation using late transition
metal catalysts, even though control of the stereo and
regioselectivity remains an important challenge. Recently, the
This work summarizes our efforts for the development of a metal
and
solvent
free,
environmentally
benign
5-exo-dig
hydrothiolation of propargylthiourea for the one pot synthesis of
diversely substituted thiazolidin-2-ylideneamine.
Results and Discussion
24
We started our investigation by reacting propargylamine
1a
(1.0 mmol) with phenyl isothiocyanate 2a (1.0 mmol), in
presence of 20 mol Cu(OTf)2. This reaction gave
%
a
chromatographically separable mixture of 4a and 5a (Table 1,
entry 1). Changing the catalyst to Rh(OAc)2 did not improve the
selectivity of this reaction (Table 1, entry 2). To our delight, when
this reaction was carried out without any catalyst in
dichloromethane at 25 °C 4a formed exclusively via 5 exo dig
hydrothiolation (Table 1, entry 3). When toluene was used as a
solvent, reaction took 12 h for completion and 4a was formed in
81% yield (Table 1, entry 4). In order to reduce the reaction time,
we carried out this transformation at elevated temperature in
dichlorobenzene, xylene and toluene. In all these conditions,
reaction went to completion and desired product 4a was formed
in 2 h (Table 1 entries 5-7). Later, we decided to check the
[a]
Alok Ranjan, Dattatraya H. Dethe
Department of Chemistry
Indian Institute of Technology Kanpur
Kanpur-208016, Uttar Pradesh, India.
E-mail: ddethe@iitk.ac.in
http://home.iitk.ac.in/~ddethe/index.html
Abhijit S. Deore, Swapnil G. Yerande
Acoris Research (A Division of Hikal Ltd).
International Biotech Park, Hinjewadi, Pune 411 057, Maharashtra,
India.
[b]
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/ejoc.201700603
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4a in excellent yield. Notably, propargylamine prepared from
aliphatic alkynes reacted well with both aliphatic and aromatic
isothiocyanate to give 4b, 4e, 4f, and 4g-l in excellent yields.
These reactions were found to be sluggish at 35 °C and
preceded to completion with snail’s pace. Raising the reaction
temperature to 50-55 °C enhanced the reaction rate; as a result
reaction went to completion in less than 1 h.
Temp.
(°C)
Time
(h)
Yieldb
(%)
Yieldb
(%)
Catalyst
Entrya
1
Solvent
(20 mol %)
Cu(OTf)2
In case of aromatic isothiocyanates bearing electron
donating group, desired products 4e and 4n were obtained
in high yields. Aromatic isothiocyanate having electron
withdrawing group also reacted to generate 4o and 4q in
excellent yields.
4a
5a
CH2Cl2
CH2Cl2
25
12
70
25
30
Rh(OAc)2
25
25
12
12
12
2
2
3
4
60
85
81
NA
NA
CH2Cl2
25
toluene
dichloro
benzene
160
5
NA
90
140
110
35
2
2
2
6
7
8
NA
NA
NA
xylene
toluene
NA
93
95
98
aAll the reactions were performed with propargylamine (1.0 mmol), PhNCS
(1.0 mmol), solvent (5 mL); bIsolated yield after column chromatography.
Table 1 Optimization of Reaction Conditions for the One Pot Formation of
Thiazolidin-2-ylideneamine.a
feasibility of this transformation under solvent free condition. It is
advantageous to try solvent-free reactions which are
environmentally benign. Solvent-free reactions not only reduce
the burden of organic solvent disposal, but also enhance the
rate of many organic reactions. To our delight when this reaction
was carried out at 35 °C under solvent free condition, reaction
went to completion in 2 h and desired product 4a was obtained
in 98% yield (Table 1, entry 8).
Earlier, we have reported that in presence of base
propargylamine
reacts
with
isothiocyanate
and
the
hydroamination product imidazolidine-2-thione 5a was
exclusively formed.25 But under the current optimized solvent
free condition, hydrothiolation product thiazolidine 4a, was
exclusively formed through the un-isolated propargylthiourea
intermediate 3a. The exclusive formation of 4a over 5a could be
explained by hard-soft nucleophile concept. In presence of base
5a is formed as base generates hard nucleophile N which
quickly reacts with triple bond to generated 5a, while in absence
of base, soft nucleophile reacts with triple bond to generated 4a
exclusively.
aReaction conditions: All of the reactions were performed with propargylamine
(0.5 mmol), R4NCS (0.5 mmol), at room temperature(35-50 °C).
After we optimized the reaction conditions, the scope of this
process was evaluated for other propargylamines and
isothiocyanates (Table 2). We found that
propargylamines participated effectively in this solvent free
hydrothiolation reaction with range of isothiocyanates to yield the
a variety of
Table 2. One Pot Formation of Thiazolidin-2-ylideneamine from Functionalized
Isothiocyanates and Propargylamine Precursora
corresponding
thiazolidin-2-ylideneamine
products
with
Next, we decided to use benzoyl isothiocyanate in this reaction.
Benzoyl isothiocyanate reacted proficiently with a variety of
propargylamines to give thiazolidin-2-ylideneamine 4r-4w in
complete chemo- and regioselectivity. Phenyl isothiocyanate
reacted smoothly with propargylamine to furnish desired product
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aReaction conditions: All of the reactions were performed with propargylamine
(1.0 mmol), R4NCO (1.0 mmol), at room temperature 35 °C.
Table 4. Synthesis of Propargylurea under Solvent Free Conditiona
We used different propargylamines 1 and isocyanates 10 in this
reaction, all of those stopped at the propargylurea stage 11a-
11d. The outcome of this reaction can be rationalized on the
basis of inferior nucleophilicity of oxygen as compared to sulphur.
This might have resulted in the halting of the reaction at
propargylurea stage. We did not observe any hydroamination
product imidazole derivative under this reaction condition. We
believe that this hydrothiolation reaction proceeds through bond
anion relay chemistry (ARC) principle.28 Through bond ARC
involves transfer of a negative charge from one atom to another
via bonding system of a molecule. In this case, propargylamine
1 reacts with isothiocyanate 2 to give propargylthiourea 3. Under
the reaction conditions negative charge present in the π system
aReaction conditions: All of the reactions were performed with propargylamine
(1.0 mmol), R4NCS (1.0 mmol), at room temperature (35-50 °C).
Table 3. Scope of the Solvent Free Hydrothiolation Reactiona
near quantitative yields. Van der Eycken et. al. have reported an
elegant approach for the synthesis of propargylamine 6 from
alkyne, ketone and amine.26 We imagined that spirocyclic
thiazole derivative 9 can be efficiently synthesized by solvent
free hydrothiolation reaction. Propargylamine 6 participates
proficiently in the solvent free hydrothiolation reaction with a
array of isothiocyanates to give thiazolidin-2-ylideneamine 9a-9f
in excellent yields (Table 3).
The structures of 4s and 9e were unambiguously determined by
single crystal X-ray crystallography and the stereochemistry of
the exocyclic double bond was found to be “Z” (figure 1).27
Next we decided to extend this protocol for the synthesis of
oxazole derivatives. To check the feasibility of synthesis of
oxazole derivative, we treated propargylamine 1 (1.0 mmol) with
isothiocyanate 10 (1.0 mmol), under solvent free condition. The
isolated product of this reaction was found to be propargylurea
11 (Table 4).
Scheme 1. Proposed Mechanism for the Anion Relay Chemistry Reaction of
propargylthiourea
of un-isolated propargylthiourea 3 is transferred on sulphur 4’,
which in turn attacks the alkyne carbon of propargylthiourea 4’ to
give thiazolidin-2-ylideneamine 4 (Scheme 1) by hydrothiolation
reaction. The observed chemoselectivity (“N” vs “S” attack)
under the solvent free condition can be attributed to the thiol
tautomeric form 4’ of un-isolated propargylthiourea intermediate
3. A previously reported work by our group shows that under
basic condition nitrogen present in the propargylthiourea attacks
the alkyne to give hydroamination product imidazole-2-thione 5.
Figure 1. X-ray Structure of Compound 4s and 9e
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10.1002/ejoc.201700603
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20.8, 13.5; HRMS (ESI) m/z calcd. for C19H21N [M+H]+ 264.1752; found
264.1760.
Conclusions
In summary, we have developed thiol-yne coupling of
propargylamine for the synthesis of thiazolidin-2-
ylideneamine. The present metal and solvent free protocol
gave superior yields than the already reported metal
catalyzed reaction. The atom economy of this reaction
combined with ecological and economical benefits of the
solvent-free methodology are in well agreement with green
chemistry requirements. The importance of the chemistry
described here lies in the established new synthetic method
to prepare a wide variety of thiazolidin-2-ylideneamine
derivatives in a short reaction time, using mild reaction
conditions, in the absence of base, solvent, additive and
N-benzyl-1,3-diphenylprop-2-yn-1-amine (1d): Viscous oil; Yield 268
mg (90%); IR (neat): νmax/cm-1 3061, 3028, 2841, 1598, 1570, 1490,
1452, 1328, 1098, 1071, 1027, 914, 755, 696; 1H NMR (500 MHz,
CDCl3) δ 7.64 (d, J = 8.0 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.46 - 7.24 (m,
11H), 4.83 (s, 1H), 4.02 (s, 2H); 13C NMR (125 MHz, CDCl3) δ 140.2,
139.6, 131.7, 128.5, 128.4, 128.4, 128.3, 128.2, 127.8, 127.7, 127.1,
123.1, 89.0, 85.8, 53.6, 51.1; HRMS (ESI) m/z calcd. for C22H19N [M+H]+
298.1596; found 298.1599.
N-benzyl-1-cyclohexyloct-2-yn-1-amine (1e): Colourless oil; Yield 184
mg (62%); IR (neat): νmax/cm-1 3062, 3027, 2926, 2852, 1604, 1495,
1451, 1327, 1107, 1028, 732, 697; 1H NMR (400 MHz, CDCl3) δ 7.39 -
7.28 (m, 4H), 7.26 - 7.20 (m, 1H), 4.02 (d, J = 12.8 Hz, 1H), 3.79 (d, J =
12.8 Hz, 1H), 3.15 (td, J = 2.1, 5.5 Hz, 1H), 2.23 (dt, J = 2.1, 7.0 Hz, 2H),
1.84 - 1.69 (m, 4H), 1.66 - 1.64 (m, 1H), 1.58 - 1.47 (m, 3H), 1.44 - 1.30
(m, 4H), 1.26 - 1.09 (m, 5H), 0.91 (t, J = 6.9 Hz, 3H); 13C NMR (125 MHz,
CDCl3) δ 140.4, 128.2, 128.2, 126.7, 84.5, 80.2, 55.0, 51.5, 42.6, 31.0,
30.1, 28.7, 28.5, 26.5, 26.2, 26.0, 22.1, 18.6, 14.0; HRMS (ESI) m/z
calcd. for C21H31N [M+H]+ 298.2535; found 298.2530.
metals
.
Experimental Section
General Procedure for Preparation of Secondary Propargylamines:
A magnetically stirred solution of aldehyde (1.0 mmol), amine (1.5 mmol),
acetylene (1.5 mmol) and copper bromide (0.2 mmol) in toluene (2.0 ml)
N-benzyl-1-(pent-1-ynyl)cyclohexanamine (1f): Colourless oil; Yield
153 mg (60%); IR (neat): νmax/cm-1 3433, 3027, 2930, 2854, 1662,
1604, 1518, 1453, 1270, 1210, 1115, 698; 1H NMR (500 MHz, CDCl3) δ
7.41 - 7.21 (m, 6H), 3.90 (s, 2 H), 2.25 (t, J = 7.2 Hz, 2H), 1.89 - 1.84 (m,
was refluxed for
2 h. The reaction mixture was cooled to room
temperature and quenched with saturated aq. NH4Cl solution. Reaction
was continued for further 2 h at room temperature and then resulting dark
blue solution was extracted with Toluene. Further organic layer was
washed three times with saturated aq. NH4Cl solution, brine and dried
over sodium sulphate. Evaporation of the solvent and purification of the
residue on a silica gel column using ethyl acetate-petroleum ether (1:19)
as eluent furnished the propargylamine (1) as a light yellow oil, in 60 -
90% isolated Yield, Rf = 0.40 (EtOAc - petroleum ether, 1:19).
2H), 1.72 - 1.52 (m, 8H), 1.48 - 1.39 (m, 2H), 1.04 (t, J = 7.4 Hz, 3H); 13
C
NMR (125 MHz, CDCl3) δ 141.2, 128.4, 128.3, 126.7, 84.3, 83.9, 54.8,
47.9, 38.4 (2 Carbon), 25.9, 23.0 (2 Carbon), 22.6, 20.7, 13.5; HRMS
(ESI) m/z calcd. for C18H25N [M+H]+ 256.2065; found 256.2064.
N-benzyl-1-phenyloct-2-yn-1-amine (1g): Light yellow oil; Yield 178 mg
(61%); IR (neat): νmax/cm-1 3080, 3010, 2931, 2869, 1639, 1489, 1459,
1377, 1135, 1025, 748, 692; 1H NMR (500 MHz, CDCl3) δ 7.68 (d, J =
7.6 Hz, 2H), 7.55 - 7.33 (m, 9H), 4.69 (s, 1H), 4.08 - 3.97 (m, 2H), 2.42
(td, J = 1.8, 7.2 Hz, 2H), 1.72 - 1.68 (m, 2H), 1.60 - 1.46 (m, 4H), 1.06 (t,
J = 7.3 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 140.9, 139.9, 128.2, 128.1
(2 Carbon), 127.4, 127.3, 126.8, 85.8, 79.7, 53.1, 50.9, 31.0, 28.5, 22.1,
18.7, 13.9; HRMS (ESI) m/z calcd. for C21H25N [M+H]+ 292.2065; found
292.2060.
N-benzyl-5-methyl-1-phenylhex-1-yn-3-amine (1a): Viscous oil; Yield
197 mg (71%); IR (neat): νmax/cm-1 3062, 3028, 2955, 2927, 2868,
1
1671, 1598, 1489, 1453, 1384, 1070, 1027, 912, 755, 691; H NMR (500
MHz, CDCl3) δ 7.54 - 7.50 (m, 2H), 7.46 (d, J = 7.4 Hz, 2H), 7.42 - 7.33
(m, 5H), 7.33 - 7.29 (m, 1H), 4.17 (d, J = 12.6 Hz, 1H), 3.97 (d, J = 12.6
Hz, 1H), 3.71 (dd, J = 7.4, 7.6 Hz, 1H), 2.12 - 1.99 (m, 1H), 1.73 - 1.64
(m, 2H), 1.59 (br. s., 1H), 1.01 (d, J = 6.9 Hz, 6H); 13C NMR (125 MHz,
CDCl3) δ 140.0, 131.6, 128.3 (2 Carbon), 128.2, 127.8, 126.9, 123.4,
91.1, 83.8, 51.4, 48.3, 45.2, 25.2, 22.8, 22.2; HRMS (ESI) m/z calcd. for
C20H23N [M+H]+ 278.1909; found 278.1904.
1-benzyl-1-(5-methyl-1-phenylhex-1-yn-3-yl)-3-phenylthiourea(3a):
Viscous oil; Yield 392 mg (95%); IR (neat): νmax/cm-1 3076, 3060, 3028,
2955, 2924, 1639, 1618, 1589, 1597, 1492, 1462, 1453, 1251, 1052, 982,
868, 755, 694; 1H NMR (400 MHz, CDCl3) δ 7.48 - 7.39 7 (m, 3H), 7.38 -
7.20 (m, 10H), 7.17 - 7.09 (m, 2H), 5.15 (d, J = 17.2 Hz, 1H), 4.85 (d, J =
17.2 Hz, 1H), 2.01 - 1.90 (m, 1H), 1.87 - 1.75 (m, 2H), 1.05 (d, J = 6.6 Hz,
3H), 1.07 (d, J = 6.4 Hz, 3H), 0.98 - 0.88 (m, 1H); 13C NMR (125 MHz,
CDCl3) δ 181.8, 139.4, 135.7, 131.5, 129.5, 129.3, 128.5, 128.3, 128.2,
126.6, 125.9, 125.6, 122.4, 87.0, 86.0, 53.2, 50.8, 42.4, 25.5, 23.6, 21.5;
HRMS (ESI) m/z calcd for C27H28N2S [M + H]+ 413.2051, found 413.2052.
N-benzyl-1-phenylnon-2-yn-1-amine (1b): Yellow oil; Yield 198 mg
(65%); IR (neat): νmax/cm-1 3085, 3062, 2931, 2871, 1644, 1494, 1452,
1378, 1130, 1027, 751, 697; 1H NMR (500 MHz, CDCl3) δ 7.70 (d, J =
7.3 Hz, 2H), 7.57 - 7.33 (m, 8H), 4.71 (s, 1H), 4.10 - 3.98 (m, 2H), 2.44
(td, J =1.8, 7.0 Hz, 2H), 1.75 - 1.68 (m, 2H), 1.64 - 1.55 (m, 2H), 1.52 -
1.43 (m, 4H), 1.07 (t, J = 6.9 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ
140.9, 139.9, 128.1 (2 Carbon), 128.2, 127.4, 127.3, 126.8, 85.8, 79.7,
53.1, 50.9, 31.2, 28.7, 28.4, 22.5, 18.7, 13.9; HRMS (ESI) m/z calcd. for
C22H27N [M+H]+ 306.2222; found 306.2226.
General Procedure for Preparation of Thiazolidin-2-ylideneamine: To
a round bottom (25 mL) flask was charged with Propargylamine (0.5
mmol) and isothiocyanate (0.5 mmol). The reaction mixture was stirred at
35 °C (Aliphatic propargylamine derived from aliphatic alkynes required
high temperature 35-50 °C) for 2 h under solvent-free conditions in argon
atmosphere. After completion of the reaction (monitoring by TLC), the
mixture was purified over silica gel column chromatography (1-9 %
EtOAc in Petrolium ether) yielded pure thiazolidin-2-ylideneamine 4 in 90
- 98% isolated yield Rf = 0.40 (EtOAc - petroleum ether, 1:9). [If both
N-benzyl-3-methyl-1-phenylpent-1-yn-3-amine (1c): Viscous oil; Yield
158 mg (60%); IR (neat): νmax/cm-1 3060, 3030, 2955, 2929, 2869,
1603, 1510, 1450, 1351, 1201, 1130, 1031, 750, 691; 1H NMR (500 MHz,
CDCl3) δ 7.59 (d, J = 7.3 Hz, 2H), 7.48 - 7.26 (m, 8H), 4.61 (s, 1H), 4.00 -
3.87 (m, 2H), 2.32 (td, J = 2.1, 7.0 Hz, 2H), 1.72 (s, 1H), 1.69 - 1.59 (m,
2H), 1.08 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 141.0, 139.9,
128.3 ,128.3 (2 carbon), 127.5, 127.4, 126.9, 85.8, 79.9, 53.2, 51.0, 22.3,
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starting materials are solid then we can use minimum amount of solvent
to dissolve it (Toluene, CHCl3 etc.)]
(Z)-N-((Z)-3-benzyl-4-cyclohexyl-5-hexylidenethiazolidin-2-ylidene)-
4-chloroaniline (4f): Viscous oil; Yield 219 mg (94%); IR (neat):
νmax/cm-1 3029, 2926, 2853, 1619, 1584, 1486, 1452, 1409, 1355, 1292,
1230, 1149, 1089, 1029, 1010, 833, 699; 1H NMR (400 MHz, CDCl3) δ
7.40 - 7.18 (m, 7 H), 6.95 10 - 6.84 (m, 2 H), 5.40 (d, J = 15.4 Hz, 1 H),
5.37 - 5.32 (m, 1 H), 4.25 (d, J = 15.4 Hz, 1 H), 4.05 - 3.96 (m, 1 H), 2.09
- 1.86 (m, 2 H), 1.84 - 1.72 (m, 4 H), 1.68 – 1.62 (m, 1 H), 1.48 - 1.21 (m,
9 H), 1.18 - 1.01 (m, 3 H), 0.88 (t, J = 7.0 Hz, 3 H); 13C NMR (100 MHz,
CDCl3) δ 157.8, 150.40, 137.2, 130.0, 128.9, 128.7, 128.2, 127.9, 127.5,
123.8, 123.7, 69.5, 47.9, 41.7, 31.5, 31.25, 29.0, 28.7, 26.7, 26.6, 26.5,
26.4, 22.5, 14.2; HRMS (ESI) m/z calcd. for C28H35 35ClN2S [M + H]+
467.2288, found 467.2283, m/z calcd. for C28H35 37ClN2S [M + H]+
469.2258, found 467.2274.
(Z)-N-((Z)-3-benzyl-5-benzylidene-4-phenylthiazolidin-2-ylidene)
aniline (4a): White solid; Yield 211 mg (98%); mp 90 - 100 °C
(recrystallized in methanol); IR (neat): νmax/cm-1 3060, 3028, 2953,
2925, 2866, 1639, 1617, 1589, 1491, 1454, 1400, 1356, 1273, 1216,
1193, 1072, 1028, 772, 696; 1H NMR (400 MHz, CDCl3) δ 7.52 - 7.25 (m,
14 H), 7.19 - 7.15 (m, 6 H), 6.25 (s, 1 H), 5.59 (d, J = 15.1 Hz, 1 H), 5.37
(s, 1 H), 3.81 (d, J = 15.1 Hz, 1 H); 13C NMR 8 (125 MHz, CDCl3) 155.8,
151.3, 140.0, 136.6, 135.8, 133.7, 129.2, 129.2, 128.8, 128.7, 128.6 (2C),
128.5, 128.0, 127.7, 127.1, 123.4, 122.6, 122.3, 70.3, 47.5; HRMS (ESI)
m/z calcd. for C29H24N2S [M + H]+ 433.1738, found 433.1731.
(Z)-N-((Z)-3-benzyl-4-cyclohexyl-5-hexylidenethiazolidin-2-ylidene)-
1-phenylmethanamine (4g): Viscous oil; Yield 206 mg (93%); IR (neat):
νmax/cm-1 3062, 3027, 2926, 2853, 1632, 1583, 1494, 1451, 1401, 1347,
(Z)-N-((Z)-3-benzyl-5-heptylidene-4-phenylthiazolidin-2-ylidene)cyc
lopropanamine (4b): Viscous oil; Yield 189 mg (94%); IR (neat):
νmax/cm-1 3085, 3063, 3028, 3005, 2955, 2926, 2855, 1697, 16331494,
1454, 1385, 1265, 1192, 1076, 974, 700; 1H NMR (500 MHz, CDCl3) δ
7.38 - 7.19 (m, 8 H), 7.12 (d, J = 6.8 Hz, 2 H), 5.24 (d, J = 15.2 Hz, 1 H),
5.14 (td, J = 7.2, 1.7 Hz, 1 H) 4.98 (s, 1 H), 3.53 (d, J = 15.2 Hz, 1 H),
2.72 (dt, J = 7.1, 3.5 Hz, 1 H), 2.05 - 1.92 (m, 2 H), 1.30 - 1.18 (m, 8 H),
0.85 (t, J = 7.0 Hz, 3 H), 0.78 (dd, J = 7.2, 2.8 Hz, 2 H), 0.72 -0.63 (m, 2
H); 13C NMR (125 MHz, CDCl3) δ 157.9, 140.5, 137.1, 133.7, 128.9,
128.6, 128.5, 128.3, 127.6, 127.3, 123.0, 68.2, 47.2, 35.6, 31.7, 31.4,
28.9, 28.7, 22.6, 14.1, 7.6, 7.5; HRMS (ESI) m/z calcd. for C26H33N2S [M
+ H]+ 405.2364, found 405.2361.
1
1296, 1193, 1077, 1028, 952, 892, 728, 697; H NMR (400 MHz, CDCl3)
δ 7.41 -7.17 (m, 10 H), 5.48 - 5.32 (m, 2 H), 4.62 - 4.42 (m, 2 H), 4.21 (d,
J = 15.8 Hz, 1 H), 4.05 - 3.93 (m, 1 H), 2.23 - 1.98 (m, 2 H), 1.88 - 1.66
(m, 5 H), 1.53 - 1.42 (m, 3 H), 1.41 - 1.30 (m, 5 H), 1.26 (t, J = 9.5 Hz, 2
H), 1.19 - 1.08 (m, 3 H), 0.94 (t, J = 6.8 Hz, 3 H); 13C NMR (100 MHz,
CDCl3) δ 157.5, 141.4, 137.9, 130.5, 128.5, 128.2, 127.8, 127.3, 127.1,
126.3, 123.1, 69.1, 58.2, 47.9, 41.8, 31.5, 31.3, 29.0, 28.7, 26.7, 26.7,
26.6, 26.4, 22.6, 14.2; HRMS (ESI) m/z calcd. for C29H38N2S [M + H]+
447.2834, found 447.2831.
(Z)-N-((Z)-3-benzyl-4-cyclohexyl-5-hexylidenethiazolidin-2-ylidene)
prop-2-en-1-amine (4h): Viscous oil; Yield 177 mg (90%); IR (neat):
νmax/cm-1 3027, 2926, 2854, 1629, 1494, 1452, 1400, 1324, 1231, 1077,
1029, 993, 699; 1H NMR (500 MHz, CDCl3) δ 7.36 - 7.15 (m, 5 H), 6.02 -
5.88 (m, 1 H), 5.39 - 5.28 (m, 2 H), 5.21 (d, J = 17.1 Hz, 1 H), 5.05 (d, J =
10.3 Hz, 1 H), 4.15 (d, J = 16.0 Hz, 1 H), 3.97 - 3.83 (m, 3 H), 2.17 - 1.95
(m, 3 H), 1.82 -1.59 (m, 6 H), 1.43 (br. s., 3 H), 1.33 (br. s., 5 H), 1.21 (t,
J = 9.1 Hz, 2 H) 1.14 – 0.98 (m, 3 H) 0.91 (t, J = 6.3 Hz, 3 H); 13C NMR
(125 MHz, CDCl3) δ 157.3, 137.7, 136.9, 130.5, 128.40, 127.6, 127.0,
122.8, 114.2, 68.9, 56.7, 47.7, 41.6, 31.4, 31.15, 28.9, 28.6, 26.56, 26.4,
26.3, 22.4, 14.1; HRMS (ESI) m/z calcd. for C25H36N2S [M + H]+ 397.2677,
found 397.2670.
(E)-N-((Z)-3-benzyl-5-benzylidene-4-phenylthiazolidin-2-ylidene)-1-
phenylmethanamine (4c): White solid; Yield 216 mg (97%); mp 100 -
110 °C (recrystallized in methanol); IR (neat): νmax/cm-1 3059, 3026,
2921, 1647, 1619, 1582, 1492, 1452, 1390, 1345, 1270, 1192, 1076,
1
1027, 817, 729, 695; H NMR (500 MHz, CDCl3) δ 7.53 - 7.24 (m, 20 H),
6.29 (s, 1 H), 5.52 (d, J = 15.1 Hz, 1 H), 5.32 (s, 1 H), 4.82 - 4.67 (m, 2
H), 3.75 (d, J = 15.1 Hz, 1 H); 13C NMR (125 MHz, CDCl3) δ 155.9, 141.1,
140.3, 137.0, 136.0, 133.8, 131.8 (2C), 129.1 (2C), 128.6, 128.5, 128.3,
128.1, 127.6, 127.4, 127.1, 126.6, 122.4, 70.2, 58.2, 47.4; HRMS (ESI)
m/z calcd. for C30H26N2S [M + H]+ 447.1895, found 447.1893.
(Z)-N-((Z)-3-benzyl-5-benzylidene-4-phenylthiazolidin-2-ylidene)prop-
2-en-1-amine (4d): Viscous oil; Yield 184 mg (93%); IR (neat): νmax/cm-
1 3060, 3027, 2919, 1648, 1636, 1618, 1542, 1492, 1454, 1389, 1326,
(Z)-N-((Z)-3-benzyl-4-cyclohexyl-5-hexylidenethiazolidin-2-ylidene)
cyclopropanamine (4i): Viscous oil; Yield 178 mg (90%); IR (neat):
νmax/cm-1 3085, 3004, 2926, 2853, 1698, 1631, 1494, 1451, 1402, 1354,
1290, 1233, 1192, 1030, 721, 699; 1H NMR (500 MHz, CDCl3) δ 7.32 -
7.26 (m, 2 H), 7.25 - 7.19 (m, 3 H), 5.32 (t, J = 7.2 Hz, 1 H), 5.22 (d, J =
15.2 Hz, 1 H), 4.06 (d, J = 15.3 Hz, 1 H), 3.89 (br. s., 1 H), 2.63 - 2.58 (m,
1 H), 2.17 - 2.00 (m, 2 H), 1.74 (br. s., 2 H), 1.67 – 1.60 (m, J = 11.6 Hz,
3 H), 1.42 - 140 (m, 3 H), 1.35 - 1.28 (m, 4 H), 1.20 (t, J = 9.4 Hz, 2 H),
1.12 - 1.03 (m, 3 H), 0.91 (t, J = 6.9 Hz, 3 H), 0.72 - 0.65 (m, 2 H), 0.59 -
0.54 (m, 2 H); 13C NMR (100 MHz, CDCl3) δ 159.2, 137.6, 130.9, 128.4
(2C), 127.7 (2C), 127.1 (2C), 122.7, 68.9, 47.7, 41.6, 35.2, 31.4, 31.2,
28.8, 28.7, 26.6, 26.6, 26.5, 26.3, 22.5, 14.1, 7.4, 7.3; HRMS (ESI) m/z
calcd. for C25H36N2S [M + H]+ 397.2677, found 397.2672.
1
1194, 1076, 999, 697; H NMR (400 MHz, CDCl3) δ 7.47 -7.39 (m, 3 H),
7.38 -7.28 (m, 9 H), 7.24 – 7.19 (m, 3 H), 6.27 (s, 1 H), 6.20 - 6.08 (m, 1
H), 5.47 (d, J = 15.1 Hz, 1 H), 5.41 (d, J = 17.4 Hz, 1 H), 5.27 (s, 1 H),
5.21 (d, J = 10.5 Hz, 1 H), 4.24 - 4.07 (m, 2 H), 3.72 (d, J = 15.1 Hz, 1 H);
13C NMR (125 MHz, CDCl3) δ 155.9, 140.2, 136.9, 136.7, 135.9, 133.7,
129.0, 128.6 (2C), 128.5, 128.5, 128.4, 128.0, 127.5, 127.4, 127.1, 122.2,
114.7, 70.2, 56.8, 47.2; HRMS (ESI) m/z calcd. for C26H24N2S [M + H]+
397; 1738, found 397.1733.
(Z)-N-((Z)-3-benzyl-4-cyclohexyl-5-hexylidenethiazolidin-2-ylidene)-
4-ethylaniline (4e): Viscous oil; Yield 209 mg (91%); IR (neat):
νmax/cm-1 3029, 2927, 2854, 1685, 1496, 1435, 1354, 1029, 710; 1H
NMR (500 MHz, CDCl3) δ 7.38 - 7.30 (m, 4 H), 7.28 -7.26 (m, 1 H), 7.11
– 7.01 (m, 2 H), 6.95 - 6.85 (m, 2 H), 5.43 (d, J = 15.4 Hz, 1 H), 5.32 (td,
J = 7.2, 1.7 Hz, 1 H), 4.23 (d, J = 15.4 Hz, 1 H), 3.99 (br. s., 1 H), 2.62 (q,
J = 7.7 Hz, 2 H), 2.07 - 1.88 (m, 2 H), 1.76 (br. s., 4 H), 1.68 (br. s., 1 H),
1.40 -1.18 (m, 11 H) 1.11 (d, J = 9.5 Hz, 2 H), 0.93 -0.81 (m, 3 H); 13C
NMR (100 MHz, CDCl3) δ 157.4, 149.4, 138.9, 137.5, 130.5, 128.7,
128.3, 128.0, 127.4, 123.3, 122.2, 69.4, 48.0, 41.8, 31.5, 31.2, 29.0, 28.8,
28.4, 26.7, 26.6, 26.6, 26.5, 22.6, 15.7, 14.2; HRMS (ESI) m/z calcd. for
C30H40N2S [M + H]+ 461.2990, found 461.2982.
(Z)-N-((Z)-3-benzyl-5-hexylidene-4-phenylthiazolidin-2ylidene)aniline
(4j): Viscous oil; Yield 200 mg (94%); IR (neat): νmax/cm-1 3062, 2955,
2930, 2858, 1602, 1493, 1453, 1072, 732, 698; 1H NMR (500 MHz,
CDCl3) δ 7.46 - 7.22 (m, 12H), 7.18 - 6.99 (m, 3H), 5.47 (d, J = 14.9 Hz,
1H), 5.15 (td, J = 7.0, 1.8 Hz, 1H), 5.10 (d, J = 1.8 Hz, 1H), 3.68 (d, J =
15.3 Hz, 1H), 1.95 - 1.77 (m, 2H), 1.29 - 1.06 (m, 6H), 0.80 (t, J = 7.2 Hz,
3H); 13C NMR (125 MHz, CDCl3) δ 156.4, 151.7, 140.2, 136.6, 133.1,
128.9 (2C), 128.5, 128.5, 128.4, 127.5, 127.4, 123.4, 123.2, 122.3, 68.3,
47.3, 31.2, 31.2, 26.3, 22.3, 13.9; HRMS (ESI) m/z calcd. for C28H30N2S
(M+H) 427.2208; found 427.2200.
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201700603
European Journal of Organic Chemistry
FULL PAPER
(Z)-N-((Z)-3-benzyl-5-butylidene-4-phenylthiazolidin-2-ylidene)aniline
(4k): Viscous oil; Yield 183 mg (92%); IR (neat): νmax/cm-1 3029, 2925,
2854, 1743, 1625, 1589, 1492, 1455, 1389, 799, 697; 1H NMR (500 MHz,
CDCl3) δ 7.52 - 7.33 (m, 12 H), 7.24 - 7.16 (m, 3 H), 5.60 (d, J = 15.2 Hz,
1 H), 5.25 (dt, J = 7.3, 1.7 Hz, 1 H), 5.23 (d, J = 1.7 Hz, H), 3.80 (d, J =
15.2 Hz, 1 H), 2.04 - 1.87 (m, 2 H), 1.41 - 1.26 (m, 2 H), 0.84 (t, J = 7.3
Hz, 3 H); 13C NMR (125 MHz, CDCl3) δ 156.4, 151.7, 140.2, 136.6, 133.4,
128.9 (2C), 128.5, 128.5, 128.4, 127.5, 127.4, 123.2, 123.1, 122.2, 68.3,
47.3, 33.2, 21.9, 13.6; HRMS (ESI) m/z calcd. for C26H26N2S (M+H)+
399.1895, found 399.1892.
1314, 1288, 1175, 1102, 1068, 877, 780, 716, 699; 1H NMR (400 MHz,
CDCl3) δ 7.53 -7.47 (m, 2 H), 7.46 -7.21 (m, 13 H), 5.49 (d, J = 14.9 Hz,
1 H), 5.25 (td, J = 7.2, 1.8 Hz, 1 H), 5.14 (d, J = 1.7 Hz, 1 H), 4.75 - 4.63
(m, 2 H), 3.71 (d, J = 14.9 Hz, 1 H), 2.13 - 1.95 (m, 2 H), 1.38 -1.24 (m, 8
H), 0.92 (t, J = 7.0 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 156.5, 141.2,
140.5, 137.1, 133.3, 128.9, 128.6, 128.5, 128.4, 128.3, 127.6, 127.5,
127.3, 126.5, 123.3, 68.3, 58.4, 47.4, 31.6, 31.4, 28.8, 28.7, 22.6, 14.1;
HRMS (ESI) m/z calcd. for C30H34N2S [M+H]+ 455.2521, found 455.2523.
(Z)-N-((Z)-3-benzyl-5-benzylidene-4-phenylthiazolidin-2-ylidene)-4-
chloroaniline (4q): White solid; Yield 223 mg (97%); mp 120 - 130 °C
(recrystallized in methanol); IR (neat): νmax/cm-1 3029, 2924, 1637,
1615, 1585, 1486, 1455, 1356, 1273, 1216, 1147, 1028, 614, 834, 772,
697; 1H NMR (500 MHz, CDCl3) δ 7.50 - 7.26 (m, 14 H), 7.24 - 7.12 (m, 3
H), 7.13 - 7.06 (m, 2 H), 6.26 (d, J = 1.7 Hz, 1 H), 5.55 (d, J = 15.1 Hz, 1
H), 5.37 (d, J = 1.7 Hz, 1H), 3.80 (d, J = 15.1 Hz, 1 H); 13C NMR (125
MHz, CDCl3) δ 156.3, 150.0, 139.8, 136.4, 135.6, 133.3, 129.2, 129.2
(2C), 128.9, 128.7, 128.6, 128.6, 128.0, 127.7, 127.6, 127.3, 123.7,
122.9, 70.4, 47.5; HRMS (ESI) m/z calcd. for C29H23N2SCl [M + H]+
467.1349, found 467.1349.
(Z)-N-((Z)-3-benzyl-5-heptylidene-4-phenylthiazolidin-2-ylidene)
aniline (4l): Viscous oil; Yield 199 mg (90%); IR (neat): νmax/cm-1 3028,
2954, 2925, 2853, 1624, 1589, 1491, 1454, 1396, 1355, 1194, 1071, 770,
696; 1H NMR (400 MHz, CDCl3) δ 7.46 – 7.16 (m, 12 H), 7.18 – 7.05 (m,
3 H), 5.51 (d, J = 15.1 Hz, 1 H), 5.18 (td, J = 7.2, 2.1 Hz, 1 H), 5.14 (d, J
= 2.0 Hz, 1 H), 3.73 (d, J = 15.1 Hz, 1 H), 1.97 - 1.84 (m, 2 H), 1.30 -
1.11 (m, 8 H), 0.85 (t, J = 7.1 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ
156.5, 151.8, 140.3, 136.7, 133.3, 129.0 (2C), 129.0, 128.6, 128.6, 127.6,
127.5, 123.4, 123.3, 122.4, 68.4, 47.4, 31.6, 31.3, 28.8, 28.7, 22.6, 14.1;
HRMS (ESI) m/z calcd. for C29H32N2S [M
441.2360.
+
H]+ 441.2364, found
(Z)-N-((Z)-3-benzyl-5-heptylidene-4-phenylthiazolidin-2-ylidene)
prop-2-en-1-amine (4r): Viscous oil; Yield 181 mg (90%); IR (neat):
νmax/cm-1 3063, 3029, 2955, 2926, 2855, 1631, 1494, 1455, 1325, 1195,
(Z)-N-((Z)-3-benzyl-5-benzylidene-4-isobutylthiazolidin-2-ylidene)
aniline (4m): White solid; Yield 190 mg (92%); mp 90 - 110 °C
(recrystallized in methanol); IR (neat): νmax/cm-1 3059, 3026, 2921,
1647, 1619, 1492, 1452, 1345, 1270, 1192, 1027, 729, 695; 1H NMR
(500 MHz, CDCl3) δ 7.44 - 7.28 (m, 9 H), 7.27 - 7.17 (m, 3 H), 7.13 - 7.06
(m, 1 H), 7.02 (d, J = 7.4 Hz, 2 H), 6.42 (s, 1 H), 5.53 (d, J = 14.9 Hz, 1
H), 4.40 (dd, J = 7.7, 3.2 Hz, 1 H), 4.20 (d, J = 15.5 Hz, 1 H), 1.90 - 13
1.77 (m, 2 H), 1.71 - 1.61 (m, 1 H), 0.98 (d, J = 6.9 Hz, 3 H), 0.91 (d, J =
6.3 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 156.2, 150.7, 136.7, 135.6,
133.4, 129.0, 128.7, 128.5, 128.1, 128.0, 127.6, 127.2, 123.3, 122.4,
121.2, 65.2, 47.5, 42.3, 23.8, 23.7, 22.5; HRMS (ESI) m/z calcd. for
C27H28N2S [M + H]+ 413.2051, found 413.2053.
1
1077, 914, 776, 699; H NMR (400 MHz, CDCl3) δ 7.38 - 7.12 (m, 11 H),
6.12 - 5.97 (m, 1 H), 5.39 - 5.26 (m, 2 H), 5.20 - 5.09 (m, 2 H), 5.00 (s, 1
H), 4.11 - 3.93 15 (m, 2 H), 3.59 (d, J = 15.1 Hz, 1 H), 1.96 (dquin, J =
13.8, 7.2, 7.2, 7.2, 7.2 Hz, 2 H), 1.29 - 1.15 (m, 8 H), 0.84 (t, J = 6.9 Hz, 3
H); 13C NMR (125 MHz, CDCl3) δ 156.7, 140.6, 137.1, 136.9, 133.3,
128.9, 128.5, 128.5, 128.4, 127.6, 127.3, 123.3, 114.7, 68.3, 57.1, 47.4,
31.6, 31.4, 28.8, 28.7, 22.6, 14.1; HRMS (ESI) m/z calcd. for C26H32N2S
[M + H]+ 405.2365, found 405.2365.
(Z)-N-((Z)-5-benzylidene-4-(4-chlorophenyl)-3-p-tolylthiazolidin-2-
ylidene)benzamide (4s): White solid; Yield 242 mg (98%); mp 200 -
215 °C (recrystallized in methanol); IR (neat): νmax/cm-1 3465, 3028,
2951, 1613, 1574, 1510, 1489, 1462, 1389, 1305, 1285, 1168, 1059,
1015, 826, 717; 1H NMR (500 MHz, CDCl3) δ 8.18 - 8.09 (m, 2 H), 7.48 -
7.43 (m, 1 H), 7.42 - 7.32 (m, 6 H), 7.28 - 7.22 (m, 5 H), 7.18 - 7.12 (m, 4
H), 6.36 (s, 1 H), 5.91 (s, 1 H), 2.33 (s, 3 H); 13C NMR (125 MHz, CDCl3)
δ 176.0, 168.1, 138.0, 137.3, 135.9, 135.1, 134.5, 132.2, 129.7, 129.5,
129.1, 128.8, 128.5, 128.3, 128.0, 127.5, 126.5, 124.3, 71.5, 21.0; HRMS
(ESI) m/z calcd. for C30H23 35ClN2OS [M + H]+ 495.1298, found 495.1281,
m/z calcd. for C30H23 37ClN2OS [M + H]+ 496.1331, found 496.1335.
(Z)-N-((Z)-3-benzyl-5-benzylidene-4-phenylthiazolidin-2-ylidene)-4-
ethylaniline (4n): White solid; Yield 209 mg (96%); mp 110 - 130 °C
(recrystallized in methanol); IR (neat): vmax/cm-1 3453, 3027, 2963, 2929,
1641, 1454, 1398, 1273, 1147, 774, 699; 1H NMR (500 MHz, CDCl3) δ
7.49 - 7.42 (m, 3 H), 7.41 - 7.30 (m, 7 H), 7.30 - 7.22 (m, 4 H), 7.21 - 7.14
(m, 3 H), 7.08 – 7.04 (m, 2 H), 6.23 (s, 1 H), 5.57 (d, J = 15.0 Hz, 1 H),
5.33 (s, 1 H), 3.77 (d, J = 15.0 Hz, 1 H), 2.72 (q, J = 7.6 Hz, 2 H), 1.32 (t,
J = 7.6 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 155.7, 148.8, 140.1,
139.2, 136.7, 135.8, 134.0, 129.2, 128.8, 128.7 (2C), 128.5 (2C), 128.0,
127.7, 127.6, 127.1, 122.5, 122.1, 70.3, 47.5, 28.5, 15.7; HRMS (ESI)
m/z calcd. for C31H28N2S [M + H]+ 461.2051, found 461.2057.
(Z)-N-((S,Z)-5-benzylidene-3-(4-chlorophenyl)-4-p-tolylthiazolidin-2-
ylidene)benzamide (4t): White solid; Yield 244 mg (96%); mp 180 -
210 °C (recrystallized in methanol); IR (neat): νmax/cm-1 3018, 2924,
1637, 1587, 1515, 1465, 1338, 1241, 1135, 1068, 1017, 848, 684; 1H
NMR (500 MHz, CDCl3) δ 8.17 - 8.01 (m, 2 H), 7.46 (d, J = 7.4 Hz, 1 H),
7.39 - 7.34 (m, 2 H), 7.33 - 7.27 (m, 4 H), 7.24 - 7.19 (m, 4 H), 7.17 - 7.09
(m, 4 H), 6.37 (d, J = 2.3 Hz, 1 H), 5.86 (d, J = 1.7 Hz, 1 H), 2.31 (s, 4 H),
2.34 (s, 3 H); 13C NMR (125 MHz, CDCl3) δ 176.0, 168.6, 138.8, 137.6,
137.5, 136.2, 136.0, 133.5, 132.8, 1 132.5, 132.3, 129.8, 129.3, 129.0,
128.3, 128.2, 128.1, 127.3, 124.3, 72.0, 21.2, 21.2; HRMS (ESI) m/z
calcd. for C31H25 35ClN2OS [M + H]+ 509.1454, found 509.1451.
(Z)-N-((Z)-3-benzyl-5-benzylidene-4-isobutylthiazolidin-2-ylidene)-4-
chloroaniline (4o): White solid; Yield 207 mg (93%); mp 135 - 150 °C
(recrystallized in methanol); IR (neat): νmax/cm-1 2955, 2925, 1637,
1616, 1585, 1486, 1217, 1192, 1010, 833; 1H NMR (500 MHz, CDCl3) δ
7.37 - 7.29 (m, 6 H), 7.26 - 7.19 (m, 6 H), 6.94 - 6.86 (m, 2 H), 6.41 (s, 1
H), 5.43 (d, J = 15.0 Hz, 1 H), 4.42 - 4.33 (m, 1 H), 4.15 (d, J = 15.4 Hz, 1
H), 1.87 - 1.74 (m, 2 H), 1.69 - 1.61 (m, 1 H), 0.96 (d, J = 6.3 Hz, 3 H),
0.90 (d, J = 6.3 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 156.2, 149.8,
136.6, 135.5, 133.1, 128.9, 128.7, 128.5, 128.2, 128.0 (2C), 127.6, 127.2,
123.6, 121.3, 65.1, 47.3, 42.3, 23.8, 23.7, 22.4. HRMS (ESI) m/z calcd.
for C27H2735ClN2S [M + H]+ 447.1662, found 447.1660; C27H27 37ClN2S [M
+ H]+ 449.1632, found 449.1645.
(Z)-N-((S,Z)-5-benzylidene-3-(4-chlorophenyl)-4-p-tolylthiazolidin-2-
ylidene)benzamide (4u): White solid; Yield 240 mg (97%); mp 175 -
200 °C (recrystallized in methanol); IR (neat): νmax/cm-1 3020, 2914,
1637, 1589, 1500, 1480, 1340, 1247, 1128, 1088, 1019, 849, 688; 1H
NMR (500 MHz, CDCl3) δ 8.09 (m, 2 H), 7.41 - 7.29 (m, 9 H), 7.26 - 7.20
(m, 5 H), 7.12 (d, J = 8.0 Hz, 2 H), 6.40 (d, J = 1.7 Hz, 1 H), 5.88 (d, J =
2.3 Hz, 1 H), 2.31 (s, 3 H); 13C NMR (125 MHz, CDCl3) δ 176.0, 168.4,
(Z)-N-((Z)-3-benzyl-5-heptylidene-4-phenylthiazolidin-2-ylidene)-1-
phenylmethanamine (4p): Viscous oil; Yield 215 mg (95%); IR (neat):
νmax/cm-1 3062, 3029, 2927, 2855, 1719, 1632, 1603, 1524, 1384, 1356,
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10.1002/ejoc.201700603
European Journal of Organic Chemistry
FULL PAPER
138.9, 137.5, 136.1, 135.3, 134.8, 132.9, 132.3, 129.8, 129.8, 129.0,
128.6, 128.4, 128.2, 128.1, 127.5, 127.3, 125.3, 124.3, 72.0, 21.2; HRMS
(ESI) m/z calcd. for C30H23 35ClN2OS [M + H]+ 495.1298, found 495.1297.
(Z)-N-((Z)-3-benzyl-5-benzylidene-4-ethyl-4-methylthiazolidin-2-
ylidene)-1-phenylmeth anamine (9d): Viscous oil; Yield 196 mg (95%);
IR (neat): νmax/cm-1 3083, 3060, 3025, 2970, 2876, 1802, 1643, 1614,
1583, 1494, 1344, 1255, 1077, 1029, 751, 731, 695; 1H NMR (500 MHz,
CDCl3) δ 7.55 - 7.39 (m, 6 H), 7.39 - 7.15 (m, 9 H), 6.49 (s, 1 H), 5.08 (d,
J = 16.0 Hz, 1 H), 4.59 (q, J = 15.5 Hz, 2 H), 4.43 (d, J = 16.0 Hz, 1 H),
2.06 (qd, J = 14.5, 7.2 Hz, 1 H), 1.78 (qd, J = 14.5, 7.2 Hz, 1 H), 1.49 (s,
4 H), 0.87 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, CDCl3) δ 155.8, 141.2,
139.4, 138.4, 136.4, 128.5, 128.1, 128.1, 128.0, 127.3, 127.1, 126.9,
126.6, 126.2, 118.4, 71.9, 57.6, 46.1, 34.0, 28.1, 8.1; HRMS (ESI) m/z
calcd. for C27H28N2S [M + H]+ 413.2051, found 413.2055
(Z)-N-((Z)-5-benzylidene-4-(4-methoxyphenyl)-3-phenylthiazolidin-2-
ylidene)-4-bromo benzamide (4v): White solid; Yield 258 mg (94%); mp
195 - 220 °C (recrystallized in methanol); IR (neat): νmax/cm-1 3336,
3015, 2926, 1726, 1310, 1587, 1510, 1452, 1396, 1306, 1251, 1166,
1067, 1029, 1009, 891, 762; 1H NMR (400 MHz, CDCl3) δ 7.96 - 7.83 (m,
2 H), 7.49 - 7.43 (m, 2 H), 7.42 - 7.31 (m, 6 H), 7.29 - 7.17 (m, 7 H), 6.88
- 6.70 (m, 2 H), 6.40 (d, J = 2.1 Hz, 1 H), 5.89 (d, J = 2.1 Hz, 1 H), 3.76 (s,
3 H); 13C NMR (125 MHz, CDCl3) δ 175.2, 168.6, 159.9, 138.9, 135.3,
135.1, 135.0, 131.3, 131.3, 131.3, 128.9, 128.6, 128.3, 127.6, 127.5,
127.1, 127.1, 124.3, 114.4, 72.2, 55.2; HRMS (ESI) m/z calcd. for C30H23
79BrN2O2S [M + H]+ 555.0743, found 555.0731, m/z calcd. for C30H23
81BrN2O2S [M + H]+ 557.0721, found 557.0731.
(Z)-N-((Z)-1-benzyl-4-benzylidene-3-thia-1-azaspiro[4.5]decan-2-
ylidene)-4-chloroanili ne (9e): White solid; Yield 212 mg (93%); mp 140
- 150 °C (recrystallized in methanol); IR (neat): νmax/cm-1 3030, 3027,
2927, 2854, 1633, 1611, 1583, 1485, 1450, 1380, 1345, 1261, 1234,
1089, 1028, 1010, 833, 802, 739, 695; 1H NMR (500 MHz, CDCl3) δ 7.39
- 7.16 (m, 12 H), 6.99 (s, 1 H), 6.86 - 6.80 (m, 2 H), 4.85 (s, 2 H), 2.06 -
2.00 (m, 2 H), 1.77 - 1.92 (m, 6 H), 1.66 - 1.77 (m, 2 H); 13C NMR (100
MHz, CDCl3) δ 156.7, 149.2, 139.1, 138.8, 136.1, 129.0 (2C), 128.7,
128.6, 128.5 (2C), 127.6, 126.9, 126.6, 123.9, 123.0, 70.8, 46.3, 33.5,
24.8, 23.0; HRMS (ESI) m/z calcd. for C28H35N2SCl [M + H]+ 459.1662,
found 459.1661.
(Z)-N-((S,Z)-5-benzylidene-4-(4-methoxyphenyl)-3-phenylthiazolidin-
2-ylidene)-4-meth oxybenzamide (4w): White solid; Yield 248 mg
(92%); mp 190 - 230 °C (recrystallized in methanol); IR (neat): νmax/cm-
1 3003, 2928, 2837, 1599, 1572, 1515, 1453, 1388, 1318, 1252, 1159,
1
1064, 1029, 892, 777, 696; H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.6
Hz, 2 H), 7.43 - 7.38 (m, 2 H), 7.37 - 7.30 (m, 4 H), 7.28 - 7.21 (m, 6 H),
6.82 (dd, J = 8.7, 6.2 Hz, 4 H), 6.38 (d, J = 1.8 Hz, 1 H), 5.88 (d, J = 1.8
Hz, 1 H), 3.80 (s, 3 H), 3.75 (s, 3 H); 13C NMR (125 MHz, CDCl3) δ 175.5,
167.6, 162.9, 159.8, 139.2, 135.6, 135.4, 131.9, 131.6, 128.9, 128.8,
128.8, 128.6, 128.4, 127.3, 127.3, 127.1, 123.9, 114.3, 113.3, 72.0, 55.3,
55.2; HRMS (ESI) m/z calcd. for C31H26N2O3S [M + H]+ 507.1742, found
507.1745.
(Z)-N-((Z)-1-benzyl-4-benzylidene-3-thia-1-azaspiro[4.5]decan-2-
ylidene)aniline (9f): White solid; Yield 220 mg (98%); mp 110 - 120 °C
(recrystallized in methanol); IR (neat): νmax/cm-1 3029, 2932, 2850,
1640, 1480, 1446, 1370, 1275, 1250, 1130, 1070, 830, 690; 1H NMR
(500 MHz, CDCl3) δ 7.44 - 7.25 ( m, 12 H), 7.12 - 6.95 (m, 4 H), 4.90 (br.
s., 2 H), 2.12 (d, J = 13.1 Hz, 2 H), 1.96 - 1.73 (m, 8 H); 13C NMR (100
MHz, CDCl3) δ 155.6, 151.3, 139.7, 139.2, 136.2, 128.9, 128.5, 128.4,
127.3, 126.7, 126.6, 123.0, 122.4, 122.3, 70.3, 46.1, 33.4, 24.8, 22.9;
(Z)-N-((Z)-3-benzyl-5-benzylidene-4-ethyl-4-methylthiazolidin-2-
ylidene)benzamide (9a): Viscous oil; Yield 202 mg (95%); IR (neat):
νmax/cm-1 2925, 2914,1613, 1575, 1521, 1453, 1395, 1313, 1272, 1165,
1065, 718; 1H NMR (500 MHz, CDCl3) δ 8.22 (d, J = 7.3 Hz, 2 H), 7.5 -
7.4 (m, 5 H), 7.4 - 7.3 (m, 8 H), 5.44 (d, J = 15.3 Hz, 1 H), 4.69 (d, J =
15.3 Hz, 1 H), 2.13 (dd, J = 14.7, 7.3, Hz, 1 H), 1.77 (dd, J = 14.7, 7.3,
Hz, 1 H), 1.46 (s, 3 H), 0.77 (t, J = 7.3 Hz, 3 H); 13C NMR (125 MHz,
CDCl3) δ 175.6, 168.8, 139.6, 137.8, 136.4, 135.8, 132.0, 129.7 (2C),
128.7, 128.6, 128.4, 128.0, 127.5, 127.2, 120.1, 71.7, 47.8, 34.5, 28.6,
7.8; HRMS (ESI) m/z calcd. for C27H26N2OS (M+H)+ 427.1844, found
427.1842.
HRMS (ESI) m/z calcd. for C28H29N2S [M
425.2052.
+
H]+ 425.2051, found
1-benzyl-1-(1,3-diphenylprop-2-ynyl)-3-phenylurea (11a): White solid;
Yield 201 mg (96%); mp 195 - 220 °C (recrystallized in methanol); IR
(neat): νmax/cm-1 3355, 3062, 3029, 2928, 2853, 1630, 1531, 149995,
1452, 1390, 1358, 1263, 1222, 1077, 1028, 965, 729, 697; 1H NMR (400
MHz, CDCl3) δ 7.81 - 7.68 (m, 2 H), 7.47 - 7.29 (m, 13 H), 7.27 - 7.19 (m,
2 H), 7.19 - 7.11 (m, 2 H), 7.06 - 6.97 (m, 2 H), 6.44 (s, 1 H), 4.68 (d, J =
17.4 Hz, 1 H), 4.48 (d, J = 16.9 Hz, 1 H); 13C NMR (125 MHz, CDCl3) δ
155.4, 138.6, 137.9, 137.0, 131.6, 129.1 (2C), 128.7, 128.5, 128.2, 20
128.2, 128.0, 127.7, 127.0, 123.1, 122.3, 119.7, 86.8, 85.9, 51.2, 48.5;
HRMS (ESI) m/z calcd. for C29H24N2O [M + H]+ 417.1964, found
417.1961.
(Z)-N-((Z)-1-benzyl-4-heptylidene-3-thia-1-azaspiro[4.5]decan-2-
ylidene)aniline (9b): Viscous oil; Yield 203 mg (94%); IR (neat):
νmax/cm-1 3028, 2927, 2854, 1618, 1589, 1490, 1451, 1260, 1164, 1071,
695; 1H NMR (500 MHz, CDCl3) δ 7.40 - 7.17 (m, 8H), 7.03 - 6.94 (m,
2H), 5.87 (t, J = 6.9 Hz, 18 1H), 4.77 (s, 2H), 2.02 (q, J = 7.0 Hz, 2H),
1.90 (d, J = 12.5 Hz, 2H), 1.75 - 1.58 (m, 8H), 1.42 - 1.17 (m, 9H), 0.88 (t,
J = 13.1 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 156.0, 151.8, 139.4,
138.0, 128.7, 128.2, 126.6, 126.5, 123.0, 122.8, 122.3, 68.7, 45.9, 33.2,
31.6, 31.5, 29.0, 28.8, 24.7, 22.7, 22.5, 14.0; HRMS (ESI) m/z calcd. for
C28H36N2S (M+H)+ 433.2677, found 433.2678.
1-benzyl-3-tert-butyl-1-(1,3-diphenylprop-2-ynyl)urea (11b): White
solid; Yield 194 mg (94%); mp 195 - 220 °C (recrystallized in methanol);
IR (neat): νmax/cm-1 3431, 3061, 3030, 2962, 2925, 1657, 1519, 1491,
1453, 1390, 1362, 1269, 1211, 962, 756, 698; 1H NMR (500 MHz, CDCl3)
δ 7.68 (d, J = 7.4 Hz, 2 H), 7.44 - 7.37 (m, 4 H), 7.37 - 7.24 (m, 9 H), 6.96
(s, 1 H), 4.51 (d, J = 16.6 Hz, 1 H), 4.33 (s, 1 H), 4.26 (d, J = 17.2 Hz, 1
H), 1.19 (s, 9 H); 13C NMR (125 MHz, CDCl3) δ 156.8, 138.5, 137.8,
131.5, 128.7, 128.4, 128.2, 128.1, 127.7 (2C), 127.4, 126.9, 122.5, 86.5,
86.3, 50.8, 50.6, 48.3, 29.0.; HRMS (ESI) m/z calcd. for C27H28N2O [M +
H]+ 397.2280, found 397.2281.
(Z)-N-((Z)-3-benzyl-5-benzylidene-4-ethyl-4-methylthiazolidin-2-
ylidene)aniline (9c): Viscous oil; Yield 189 mg (96%); IR (neat):
νmax/cm-1 30226, 2970, 2931, 1633, 2876, 1633, 1612, 1588, 1445,
1158, 695; 1H NMR (400 MHz, CDCl3) δ 7.56 - 7.46 (m, 2 H), 7.42 - 7.32
(m, 8 H), 7.32 - 7.20 (m, 2 H), 7.15 - 7.03 (m, 3 H), 6.47 (s, 1 H), 5.19 (d,
J = 16.0 Hz, 1 H), 4.50 (d, J = 16.0 Hz, 1 H), 2.11 (qd, J = 14.5, 7.2 Hz, 1
H), 1.80 (qd, J = 14.5, 7.3 Hz, 1 H), 1.51 (s, 3 H), 0.91 (t, J = 7.2 Hz, 3
H); 13C NMR (125 MHz, CDCl3) δ 155.5, 151.4, 139.0, 138.4, 136.1,
128.8, 128.5, 128.2, 127.9, 127.3, 126.8, 126.8, 122.9, 122.2, 118.4,
72.4, 46.0, 34.2, 28.2, 8.0; HRMS (ESI) m/z calcd. for C26H26N2S [M +
H]+ 399.1895, found 399.1890.
1-benzyl-1-(1-cyclohexyloct-2-ynyl)-3-phenylurea (11c): Viscous oil;
Yield 186 mg (92%); IR (neat): νmax/cm-1 3362, 3061, 3028, 2928, 2853,
1651, 1597, 1531, 1499, 1443, 1387, 1310, 1239, 1218, 965, 751, 697;
1H NMR (500 MHz, CDCl3) δ 7.46 – 7.40 (m, 2 H), 7.38 – 7.36 (m, 2 H),
7.35 - 7.27 (m, 1 H), 7.19 – 7.15 (m, 2 H), 7.13 – 7.10 (m, 2 H), 7.02 -
6.87 (m, 1 H), 6.57 (br. s., 1 H), 4.94 (d, J = 17.1 Hz, 1 H), 4.88 (br. s., 1
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10.1002/ejoc.201700603
European Journal of Organic Chemistry
FULL PAPER
H), 4.32 (d, J = 17.1 Hz, 1 H), 2.16 (dt, J = 7.0, 1.8 Hz, 2 H), 2.01 (d, J =
12.2 Hz, 1 H), 1.84 - 1.62 (m, 5 H), 1.47 - 1.38 (m, 2 H), 1.33 - 1.09 (m, 9
H), 0.90 - 0.80 (m, 3 H); 13C NMR (125 MHz, CDCl3) δ 155.1, 138.9,
137.7, 128.7, 128.5, 127.6, 126.9, 122.6, 119.4, 86.4, 77.7, 54.1, 49.1,
42.3, 30.8, 29.8, 29.6, 28.1, 26.1, 25.8, 25.7, 22.0, 18.4, 13.8; HRMS
(ESI) m/z calcd. for C30H34N2O [M - H]- 415.2748, found 415.2740
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10.1002/ejoc.201700603
European Journal of Organic Chemistry
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Entry for the Table of Contents
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Anion relay chemistry *
Alok Ranjan,[a] Abhijit S. Deore,[b]
Swapnil G. Yerande,[b] and Dattatraya H.
Dethe*[a]
Page No. – Page No.
Thiol-yne coupling of propargylamine with isothiocyanate has been developed
under metal and solvent free conditions. The addition of propargylamine on
isothiocyanate gives propargylthiourea. This intermediate in situ undergoes
intramolecular 5-exo-dig cyclization to give thiazolidin-2-ylideneamine. Wide
varieties of thiazolidin-2-ylideneamine derivatives were formed in excellent yields.
Thiol-yne coupling of propargylamine
under solvent free condition via
through bond anion relay chemistry:
An efficient synthesis of thiazolidin-2-
ylideneamine
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