A convenient one-pot synthesis of arene-centered tris(thiazoline) compounds

Article abstract of DOI:10.3987/COM-08-11586

A simple and practical one-pot synthesis of novel enantiopure tris(thiazoline) compounds was documented. The desired products were obtained in moderate to good yields through three steps from commercially available 1,3, 5-benzenetricarboxylic acid or 2, 4, 6-pyridinetricarboxylic acid, and chiral amino alcohols. Only one column chromatographic purification was needed for the three steps.

Full text of DOI:10.3987/COM-08-11586

HETEROCYCLES, Vol. 78, No. 4, 2009
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HETEROCYCLES, Vol. 78, No. 4, 2009, pp. 1031 - 1039. © The Japan Institute of Heterocyclic Chemistry
Received, 24th October, 2008, Accepted, 8th December, 2008, Published online, 9th December, 2008
DOI: 10.3987/COM-08-11586
A CONVENIENT ONE-POT SYNTHESIS OF ARENE-CENTERED
TRIS(THIAZOLINE) COMPOUNDS
Xuhong Lu, Qingqing Qi, Yumei Xiao, Nan Li, and Bin Fu*
Department of Applied Chemistry, China Agricultural University, Beijing
100094, P. R. China
*Corresponding author: fubinchem@cau.edu.cn
Abstract – A simple and practical one-pot synthesis of novel enantiopure
tris(thiazoline) compounds was documented. The desired products were obtained
in moderate to good yields through three steps from commercially available 1, 3,
5-benzenetricarboxylic acid or 2, 4, 6-pyridinetricarboxylic acid, and chiral amino
alcohols. Only one column chromatographic purification was needed for the three
steps.
Thiazoline rings have been found in a large number of biological active natural products, such as
thiangazole,1 curacin A,2 and lissoclinamides.3 Moreover, thiazoline compounds have been widely applied
as food additives,4 agrochemicals,5 chiral ligands,6 and so on. In view of the versatile properties of
thiazoline compounds, their synthesis attracts the attention from many researchers. To date, many
methods have been developed for the construction of thiazoline ring system. One major type of the
methods is the condensation of 2-aminoethanethiol with carboxylic acids or their derivatives, such as
nitriles, esters, and iminoesters.7 Another type is the cyclization of β-hydroxythioamides.8 Besides of the
two types of methods, some other methods have also been developed with both advantages and
deficients.9 In recent years, direct cyclization of β-hydroxyamide has been employed as one convenient
method for its simplicity and practicability. Some mono- and bis-thiazoline compounds have been
synthesized with Lawesson reagent or phosphorus pentasulfide (P2S5) as reagent.10 However, the
generality of this method has not been comfirmed. Thus, our effort was focused on the development of
efficient and general route towards arene-centered tris(thiazoline) compounds, analogue of arene-centered
tris(oxazoline) compounds with versatile properties.11 Herein, we would like to document the efficient
one-pot preparation of tris(thiazoline) compounds 1 and 2 with potent applications in molecular

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HETEROCYCLES, Vol. 78, No. 4, 2009
recognition and self-assembly.
R
*
N
R
*
N
S
S
a R = L-Bn
b R = L-Me
c R = L-i-Pr
d R = L-i-Bu
e R = L-Ph
f R = D-Ph
a R = L-Bn
b R = L-Me
c R = D-Me
d R = L- i-Pr
S
S
*
S
S
*
N
N
N
N
N
*
*
R
R
R
R
1
2
The synthetic route is illustrated in Scheme 1. The starting material benzenetricarboxylic acid was
refluxed in SOCl2 for 12 h, and the excess SOCl2 was removed in vacuo. The crude triacyl chlorides were
dissolved in CH2Cl2 and added dropwise to the solution of amino alcohols and Et3N in CH2Cl2 at 0 °C.
After being stirring for 4 h, the solvent was removed in vacuo, and the crude intermediate
tris(β-hydroxyamides) were used in the cyclization step without further purification. The mixture of P2S5
with tris(β-hydroxyamides) was refluxed in toluene for 6~8 h in the presence of Et3N. The desired
tris(thiazoline) compounds were obtained in 58~82%.yield after purification, as listed in Table 1. During
the whole synthetic course, only one column chromatographic purification was needed. The addition of
Et3N and high temperature were crucial, while refluxing only in toluene or Et3N gave no product (Entries
2 and 3). Alternatively, pyridine can be used instead of toluene/Et3N in this reaction, though the yield
decreased significantly (Entry 4). The cheap reagent P2S5 was quite effective in the cyclization step. On
the contrary, using Lawesson reagent12 in the final step the tris(thiazoline) 1a was only obtained in 20%
yield. For different chiral amino alcohols, the corresponding tris(thiazoline) compounds was afforded in
moderate to good yields (Entries 5~9). The structure of the novel tris(thiazoline) compounds were
thoroughly characterized by spectroscopic methods. In addition, the single crystal of tris(thiazoline)
(S)-1e was cultivated and detected by X-Ray crystal diffraction analysis, as illustrated in Figure 1.13
R
*
H
S
N
O
N
OH
CO H
2
a R = L-Bn
b R = L-Me
c R = L-i-Pr
d R = L-i-Bu
e R = L-Ph
f R = D-Ph
*
R
1), 2)
3)
H
H
S
N
N
S
HO C
CO H
2
HO
OH
2
*
R
*
R
N
N
O
O
*
*
R
3
1
R
Scheme 1
2) amino alcohol, Et N, CH Cl
3) P S , Et N, toluene
1) SOCl
3
2
2
2
5
3
2

HETEROCYCLES, Vol. 78, No. 4, 2009
1033
Table 1. Synthesis of benzene-centered tris(thiazoline) compounds.
Entry
R
Reaction conditiona
toluene/Et3N
toluene
Refluxing time (h) Yield b (%)
1
2
3
4
5
6
7
8
9
L-Bn
L-Bn
L-Bn
L-Bn
L-Me
L-i-Pr
L-i-Bu
L-Ph
D-Ph
6
82
10
10
6
no reaction
Et3N
no reaction
pyridine
60
78
72
58
68
73
toluene/ Et3 N
toluene/Et3N
toluene/Et3N
toluene/Et3N
toluene/Et3N
6
6
6
8
8
aAll reactions were performed using P2S5 as cyclizing reagent.
bIsolated Yield by Column Chromatography.
Figure 1. The molecular structure of (S)-1e shown from different view
With the optimized reaction conditions in hand, we further investigated the synthesis of pyridine-centered
tris(thiazoline) compounds starting from 2,4,6-pyridinetricarboxylic acid14 (Scheme 2). The reaction
results were listed in Table 2. Generally, the yields in these cases were lower than corresponding
benzene-centered tris(thiazoline) compounds 1 (Entries 10~13). When R was phenyl, no expected
tris(thiazoline) compound was obtained (Entries 14 and 15), but complex mixture indicated by TLC
analysis. Similar result was obtained when purified tris(β-hydroxyamide) was used. Such a phenomenon
can be attributed to the nucleophilic nitrogen atom in the pyridine unit, which may react with the
intermediates in the ring-closing step.

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HETEROCYCLES, Vol. 78, No. 4, 2009
R
*
N
S
CO2H
N
a R = L-Bn
b R = L-Me
c R = D-Me
d R = L-i-Pr
1), 2), 3)
S
S
*
HO2C
CO2H
N
N
N
*
2
R
R
2) amino alcohol, Et3N, CH2Cl2
3) P2S5, Et3N, toluene
1) SOCl2
Scheme 2
Table 2. Synthesis of pyridine-centered tris(thiazoline) compounds.
Entry
R
Reaction condition Refluxing Time (h)
Yield (%)a
10
L-Bn
L-Me
D-Me
L-i-Pr
L-Ph
L-Ph
toluene/Et3N
toluene/Et3N
toluene/Et3N
toluene/Et3N
toluene/Et3N
pyridine
6
42
30
38
33
0
11
8
12
8
13
8
14
8
15
12
0
aIsolated yield by Column Chromatography.
On the basis of our experimental results and relevant reports,10, 12 we deduced that the simple reagent
combination of P2S5 and Et3N is not only suitable for the synthesis of mono- and bis(thiazoline)
compounds, but also suitable for complex tris(thiazoline) compounds. The thiazolines with aryl or tertiary
alkyl group at 2-position can be synthesized efficiently, while those with α-hydrogen at 2-position are not
suitable target, an alternative route to those complex thiazoline compounds was developed by our group.15
The mechanism of the cyclization step is not clear now, it is hypothesized that the carbonyl group is
thionated, and the hydroxyl group is transformed to a leaving group by P2S5 before the intramolecular
nucleophilic substitution is occurred.
In conclusion, two series of chiral tris(thiazoline) compounds with benzene and pyridine centers were
synthesized in one pot through a continuous 3-step sequence with P2S5/Et3N mediated cyclization of
corresponding tris(β-hydroxyamides) as key step. The desired products can be obtained in moderate to
good overall yields with only one column chromatographic purification. The mild condition and easy
purification indicate the possibility of its application in large scale synthesis of fine chemicals.
Although bis(thiazoline) with benzene and pyridine skeleton have been synthesized, this paper afford
further extension for the synthesis of complex thiazoline compounds based on previous report.16, 6d The

HETEROCYCLES, Vol. 78, No. 4, 2009
1035
application of the products in molecular recognition and self-assembly are under going in our laboratory.
EXPERIMENTAL
General. Melting points were measured on an XT-4 melting point apparatus without correction. NMR
spectra were recorded on a Bruker Avance DPX300 spectrometer with tetramethylsilane as internal
standard. Infrared spectra were obtained on a Nicolet AVATAR 330 FT-IR spectrometer. Optical
rotations were measured on a Perkin–Elmer 341 LC polarimeter. Mass spectra were carried out using a
VG Autospec instrument. Elemental analyses were carried out on an Elementar Vario EL instrument.
Solvents were purified and dried following standard procedures.
General procedure for the synthesis of tris(thiazoline) 1a~f
The 1, 3, 5-benzenetricarboxylic acid (0.42 g, 2.0 mmol) was refluxed with SOCl2 (3.0 mL) for 12 h, then
the excess SOCl2 was removed in vacuo. Benzene (5 mL) was added and the solvent was removed again
to dryness to remove the trace amount of SOCl2 and afford the triacyl trichloride. The triacyl trichloride
in CH2Cl2 (20 mL) was added dropwise to a solution of amino alcohol (6.40 mmol) and Et3N (4 mL, 28.9
mmol) in CH2Cl2 (20 mL) at 0 °C and stirred at rt for 4~6 h. The reaction mixture was evaporated to
remove the solvent in vacuo, and toluene (20 mL) and Et3N (6 mL, 43.4 mmol) were added to the crude
trihydroxyl triamide, P2S5 (2.0 g, 9.0 mmol) was added under refluxing in 3 portions within 1 h, and the
suspension was continued to reflux for another 6~8 h. After being cooled to room temperature, the
solution was washed with H2O (5 mL×2), dried over anhydrous Na2SO4 and concentrated to give the
crude product. Column chromatographic purification on silica gel (40% ethyl acetate in petroleum ether)
afforded the tris(thiazoline) compounds 1a~f.
1, 3, 5-Tris[2-(4S)-4-benzyl-1, 3-thiazolin-2-yl]benzene (1a)
25
1
Pale oil, [α]D -84.4 (c 0.15 in CH2Cl2). IR (cm-1): 3025, 2923, 1610, 1584, 1494, 1189, 741, 699. H
NMR (CDCl3): δ 8.37 (s, 3H，ArH), 7.29 (m, 15H, ArH), 5.00~4.91 (m, 3H, CHN=), 3.41~3.31 (m, 6H,
13
CH2S), 3.20 (dd, J = 6.90, 11.4 Hz, 3H), 2.84 (dd, J = 9.30, 13.5 Hz 3H). C NMR (CDCl3): δ 165.9,
138.3, 134.1, 130.4, 129.3, 128.5, 126.5, 78.8, 40.1, 37.6. MS: m/z 604 (M+1). Anal. Calcd for
C36H33N3S3: C, 71.60; H, 5.53; N, 6.96. Found: C, 71.85; H, 5.41; N, 6.78.
1, 3, 5-Tris[2-(4S)-4-methyl-1, 3-thiazolin-2-yl]benzene (1b)
25
Mp 155~157 °C. [α]D -64.0 (c 0.15 in CH2Cl2). IR (cm-1): 2971, 2927, 1610, 1587, 1433, 1372, 1188,
923, 715. 1H NMR (CDCl3): δ 8.47 (s, 3H, ArH), 4.80~4.77 (m, CHN=, 3H), 3.57 (dd, J = 8.10, 10.50 Hz,
13
3H), 3.08 (dd, J = 8.10, 10.50 Hz, 3H). C NMR (CDCl3): δ 165.0, 134.1, 130.2, 73.1, 40.3, 20.3. MS:

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HETEROCYCLES, Vol. 78, No. 4, 2009
m/z 376 (M+1). Anal. Calcd for C18H21N3S3: C, 57.58; H, 5.64; N, 11.19. Found: C, 57.85; H, 5.61; N,
11.28.
1, 3, 5-Tris[2-(4S)-4-i-propyl-1, 3-thiazolin-2-yl]benzene (1c)
25
Mp 159~161 °C. [α]D -49.7 (c 0.10 in CH2Cl2). IR (cm-1): 2958, 2870, 1613, 1588, 1384, 1366, 1192,
1019, 722. 1H NMR (CDCl3): δ 8.31 (s, 3H, ArH), 4.49~4.08 (m, 3H, CHN=), 3.43 (dd, J = 8.70, 11.1Hz
3H), 3.18 (dd, J = 9.6, 11.1 Hz, 3H), 2.14~2.08 (m, 3H, CH), 1.13 (d, J = 6.60 Hz, 9H), 1.02 (d, J = 6.60
Hz, 9H). 13C NMR (CDCl3): δ 164.8, 134.1, 130.2, 84.3, 35.7, 33.2, 19.8, 18.9. MS: m/z 460 (M+1). Anal.
Calcd for C27H39N3S3: C, 62.70; H, 7.34; N, 9.14. Found: C, 62.85; H, 7.41; N, 9.05.
1, 3, 5-Tris[2-(4S)-iso-butyl-1, 3-thiazolin-2-yl]benzene (1d)
Pale oil, [α]D25 -55.4 (c 0.10 in CH2Cl2). IR (cm-1): 2954, 2868, 1612, 1587, 1433, 1384, 1366, 1186, 718.
1H NMR (CDCl3): δ 8.30 (s, 3H, ArH), 4.75~4.65 (m, 3H, CHN=), 3.52 (dd, J = 8.10, 10.8 Hz, 3H,
CH2S), 3.08 (dd, J = 8.1, 10.8 Hz, 3H, CH2S), 1.94~1.80 (m, 6H, CH2), 1.53~1.44 (m, 3H, CH), 1.01 (d, J
= 6.60 Hz, 9H), 1.00(d, J = 6.60 Hz, 9H); 13C NMR (CDCl3): δ 164.8, 134.2, 130.2, 44.1, 38.9, 25.8, 22.9,
22.5. MS: m/z; 502 (M+1). Anal. Calcd for C27H39N3S3: C, 64.62; H, 7.83; N, 8.37. Found: C, 64.82; H,
7.60; N, 8.28.
1, 3, 5-Tris[2-(4S)-4-phenyl-1, 3-thiazolin-2-yl]benzene (1e)
Mp 139~140 °C. [α]D25 -80.8 (c 0.15 in CH2Cl2). IR (cm-1)：3026, 1610, 1580, 1492, 1179, 738, 697. 1H
NMR (CDCl3): δ 8.55 (s, 3H), 7.42~7.25 (m, 15H, ArH), 5.73 (t, J = 9.0 Hz, 3H, CHN=), 3.86 (dd, J =
13
8.7, 11.40 Hz, 3H), 3.37 (dd, J = 9.30, 11.1 Hz, 3H). C NMR (CDCl3): δ 167.1, 141.7, 134.1, 130.9,
128.7, 127.7, 126.6, 80.9, 41.4. MS: m/z 562 (M+1). Anal. Calcd for C33H27N3S3: C, 70.55; H, 4.84; N,
9.14. Found: C, 70.43; H, 5.11; N, 9.02.
1, 3, 5-Tris[2-(4R)-4-phenyl-1, 3-thiazolin-2-yl]benzene (1f)
Mp 139~140 °C. [α]D25 +81.4 (c 0.15 in CH2Cl2). IR (cm-1): 3029, 1610, 1580, 1492, 1179, 737, 697. 1H
NMR (CDCl3): δ 8.55 (s, 3H), 7.36 (m, 15H), 5.73 (t, 3H), 3.86 (dd, 3H), 3.37 (dd, 3H). 13C NMR
(CDCl3): δ 167.1, 141.7, 134.1, 130.9, 128.7, 127.7, 126.6, 80.9, 41.4. MS: m/z 562 (M+1). Anal. Calcd
for C33H27N3S3: C, 70.55; H, 4.84; N, 9.14. Found: C, 70.65; H, 4.98; N, 9.00.
General procedure for the synthesis of tris(thiazoline) 2a~d
The 2, 4, 6-pyridinetricarboxylic acid (0.422 g, 2.0 mmol) was refluxed with SOCl2 (3.0 mL) for 8 h, then
the excess SOCl2 was removed in vacuo. Benzene (5 mL) was added and the solvent was removed again

HETEROCYCLES, Vol. 78, No. 4, 2009
1037
to dryness to remove the trace amount of SOCl2 and afforded the triacyl trichloride. The triacyl trichloride
in CH2Cl2 (20 mL) was added dropwise to a solution of amino alcohol (6.40 mmol) and Et3N (4 mL, 28.9
mmol) in CH2Cl2 (20 mL) at 0 °C and stirred at rt for 4~6 h. The reaction mixture was evaporated to
remove the solvent in vacuo, and toluene (20 mL) and Et3N (6 mL, 43.4 mmol) were added to the crude
trihydroxyl triamide, P2S5 (2.0 g, 9.0 mmol) was added under refluxing in three portions within 1 h, and
the suspension was continued to reflux for another 6~8 h. After being cooled to rt, the solution was
washed with H2O (5 mL×2), dried over anhydrous Na2SO4 and concentrated to give the crude product.
Column chromatographic purification on silica gel (50% EtOAc in petroleum ether) afforded the
tris(thiazoline) compounds 2a~d.
2, 4, 6-Tris[2-(4S)-4-benzyl-1, 3-thiazolin-2-yl]pyridine (2a)
Mp 152~154 °C. [α]D25 -76.4 (c 0.10 in CH2Cl2). MS: m/z 605(M+1); IR (cm-1): 3026, 2937, 1601, 1494,
1
1185, 722, 700; H NMR (CDCl3): δ 8.53 (s, 2 H, ArH), 7.63~7.25 (m, 15 H, ArH), 5.08~4.93 (m, 3 H,
CHN=), 3.45~3.30 (m, 6 H, CH2S), 3.16~3.10 (m, 3 H, CH2Ph), 2.84 (m, 3 H, CH2Ph). 13C NMR
(CDCl3): δ 168.9, 165.0, 151.3, 141.9, 138.3, 138.0, 129.7, 129.3, 128.6, 128.5, 126.6, 126.5, 121.3, 79.5,
79.0, 40.3, 40.9, 37.8, 36.2. Anal. Calcd for C35H327N4S3: C, 69.50; H, 5.33; N, 9.26. Found: C, 69.63; H,
5.21; N, 9.21.
2, 4, 6-Tris[2-(4S)-4-methyl-1, 3-thiazolin-2-yl]pyridine (2b)
25
Mp 162~163 °C. [α]D -42.6 (c 0.10 in CH2Cl2). IR (cm-1): 2967, 2925, 1603, 1450, 1374, 1183, 1025,
1
923, 715. H NMR (CDCl3): δ 8.47(s, 2H), 4.90~4.77 (m, 3H), 3.63~3.47 (m, 3H), 3.14~2.98 (m, 3H),
13
1.46 (t, J = 6.6 Hz, 9H). C NMR (CDCl3): δ 168.0, 164.0, 151.3, 141.9, 121.2, 73.7, 73.2, 40.4, 38.8,
20.5, 20.2. MS: m/z 377 (M+1). Anal. Calcd for C17H20N4S3: C, 54.22; H, 3.50; N, 14.88. Found: C,
54.29; H, 3.61; N, 14.94.
2, 4, 6-Tris[2-(4R)-4-methyl-1, 3-thiazolin-2-yl]pyridine (2c)
25
Mp 162~163 °C. [α]D +44.1 (c 0.10 in CH2Cl2). IR (cm-1): 2966, 2926, 1603, 1552, 1185 1022, 923,
1
713; H NMR (CDCl3): δ 8.48 (s, 2H), 4.91~4.77 (m, 3H, CHN=), 3.63~3.48 (m, 3H, CH2S), 3.14~2.98
13
(m, 3H, CH2S), 1.46 (t, J = 6.6 Hz, 9H). C NMR (CDCl3): δ 168.0, 164.0, 151.3, 141.9, 121.2, 73.7,
73.2, 40.4, 38.8, 20.5, 20.2. Anal. Calcd for C17H20N4S3: C, 54.22; H, 3.50; N, 14.88. Found: C, 54.37; H,
3.57; N, 14.80.
2, 4, 6-Tris[2-(4S)-4-iso-propyl-1, 3-thiazolin-2-yl] pyridine (2d)
25
Mp 132~134 °C. [α]D -48.2 (c 0.10 in CH2Cl2). IR (cm-1): 2958, 2870, 1609, 1552, 1175, 1018, 932,

1038
HETEROCYCLES, Vol. 78, No. 4, 2009
1
723. H NMR (CDCl3): δ 8.47 (s, 2H, ArH), 4.59~4.47 (m, 3H, CHN=), 3.50~3.37 (m, 3H, CH2),
3.25~3.08 (m, 3H, CH2), 2.16~2.09 (m, 3H, CH), 1.13~1.01 (m, 18 H, CH3). 13C NMR (CDCl3): δ 168.0,
164.0, 151.2, 141.8, 121.1, 84.9, 84.5, 35.7, 34.1, 33.4, 33.2, 19.7, 18.9. MS: m/z 461(M+1). Anal. Calcd
for C23H32N4S3: C, 59.96; H, 7.00; N, 12.16. Found: C, 59.83; H, 7.16; N, 12.21.
ACKNOWLEDGEMENTS
This work was financially supported by the Ministry of Science and Technology of China (No.
2006BAE01A01) and China Agricultural University.
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13. Intensity data for the title complex were collected at 293(2)K on a Rigaku AFC6S diffractometerr.
Crystallographic data: C33H27N3S3, M = 561.76, monoclinic, space group C2, a = 30.595(6) Å, b =
6.0296(12)Å, c = 19.425(4) Å, α = 90.00°, β = 126.86 (3)°, γ = 90.00°, V = 2867.0(10)Å3, Z = 4, D =
1.301 g.cm-3; MoKα (λ = 0.71073 Å), T = 293(2)K, µ = 0.286 mm-1, crystal size (mm)
0.50×0.18.×0.18. Area detector data collected on a Rigaku AFC6S diffractometer. A total of 6187
reflections were collected (2.10< θ <25.03). Structure solution by direct method (SHELXS-97),
refinement by full-matrix least-squares using all reflections, R1 = 0.0793, wR2 = 0.0812, GOF =
0.913. Crystallographic data for the structure have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no. CCDC-701494. Copies of the data
can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(fax: +44 1223 336033 or e-mail: deposit@ccdc.cam.ac.uk).
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