One-pot synthesis of 2-acylimino-3-aryl-thiazoline derivatives in aqueous media

Article abstract of DOI:10.1080/00397910600781208

A one-pot, two-step synthesis for acyliminothiazolines by treated N,N′-substituted thioureas with α-bromocarbonyl compounds under aqueous media was described. Compared to the classical reaction in organic solvents, this method consistently has the advanta

Full text of DOI:10.1080/00397910600781208

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One‐Pot Synthesis of
2‐Acylimino‐3‐aryl‐thiazoline Derivatives in
Aqueous Media
Xicun Wang a , Fang Wang a , Zhengjun Quan a , Zhang Zhang a & Mangang
Wang a
a Gansu Key Laboratory of Polymer Materials, College of Chemistry and
Chemical Engineering, Northwest Normal University, Lanzhou, Gansu, China
Version of record first published: 27 Oct 2006.
To cite this article: Xicun Wang, Fang Wang, Zhengjun Quan, Zhang Zhang & Mangang Wang (2006): One‐Pot
Synthesis of 2‐Acylimino‐3‐aryl‐thiazoline Derivatives in Aqueous Media, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:17, 2453-2460
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Synthetic Communicationsw, 36: 2453–2460, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600781208
One-Pot Synthesis of 2-Acylimino-3-aryl-
thiazoline Derivatives in Aqueous Media
Xicun Wang, Fang Wang, Zhengjun Quan, Zhang Zhang, and
Mangang Wang
Gansu Key Laboratory of Polymer Materials, College of Chemistry and
Chemical Engineering, Northwest Normal University, Lanzhou,
Gansu, China
Abstract: A one-pot, two-step synthesis for acyliminothiazolines by treated N,N0-sub-
stituted thioureas with a-bromocarbonyl compounds under aqueous media was
described. Compared to the classical reaction in organic solvents, this method consist-
ently has the advantage of short reaction times, convenient procedures, and mild
reaction conditions.
Keywords: Aqueous media, 2-iminothiazolines, one-pot procedure, thioureas
INTRODUCTION
The use of water as a medium in organic reactions has received considerable
attention because of its advantages: it is inexpensive, not hazardous to the
environment, and nontoxic, and isolation of the organic products can be
performed by simple phase separation. Also, there are beneficial effects of
aqueous solvents on rates and selectivity of important organic transformations,
for example, Diels–Alder reaction, aldol reaction, and Michael addition.[1–3]
Iminothiazoline derivatives have been reported to exhibit significant bio-
logical activities such as bactericidal, analgesicidal, fungicidal, and insecti-
cidal activities.[4–6] Some thiazoline derivatives show interesting anti-HIV
or anticancer activities and can inhibit cell division.[7–9] The classical
Received in Japan December 12, 2005
Address correspondence to Xicun Wang, Gansu Key Laboratory of Polymer
Materials, College of Chemistry and Chemical Engineering, Northwest Normal
University, Lanzhou 730070, Gansu, China. E-mail: wangxicun@nwnu.edu.cn
2453

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X. Wang et al.
synthesis of these compounds involve the Hantzsch condensation reactions of
disymmetric thioureas and chloroacetone in organic solvent or under
microwave irradiation supported by alumina in solvent-free conditions.[10,11]
More recently, one-pot, three-component condensation of aroylthiourea,
primary amine, and a-halocarnony derivatives for the synthesis for the 2-acy-
liminothiazoline derivatives in alcohol has been reported.[12] However, all
these methods need the preparation and isolation of the intermediates isothio-
cyanate in a toxic organic solvent such as dichloromethane or acetonitrile and
longer reaction times.
In continuation of our ongoing program to synthesize biologically active
compounds and develop benign and rapid strategy for organic transform-
ation,[13] we have explored an expeditious one-pot route for the synthesis of
2-acylimino-3-phenyl-1,3-thiazoline under aqueous media (Scheme 1).
As described in Scheme 1, treatment of equimolar proportions of benzoyl
chloride 1a with ammonium thiocyanate and arylamines 2 in the presence of
triethylbenzylammonium chloride (TEBA) as catalyst in H2O at room temp-
erature for 30 min afforded thioureas 3a–b. Without isolation of the inter-
mediate thiourea, one equimolar amount of bromoacetone was added to the
reaction mixture, and the mixture was stirred under refluxing for another
45 min, affording 2-benzoylimino-3-aryl-4-methyl-1,3-thiazolines 4a, b in
73 and 71% yield, respectively (Table 1, entries 1 and 2). 2-Benzoylimino-
3-aryl-4-phenyl-1,3-thiazolines 4c, d, can also be obtained by extending
bromoacetone to phenacyl bromide by this procedure; however, these
reactions need a longer time (50 min) with moderate total yields (Table 1,
entries 3 and 4).
To further demonstrate the scope of the reaction, this reaction was
extended to the preparation of 2-(2-benzofuroylimino)-3-aryl-1,3-thiazolines
4e–h (Table 1, entries 5–8) and 2-[(5-aryl)-2-furoylimino]-3-aryl-1,3-thiaz-
olines 4i–l (Table 1, entries 9–12). The preparation of compounds 4e–h
and 4i–l were carried out as previously described. 2-Benzofuroyl chloride
1b and 5-(3-nitrophenyl)-2-furoyl chloride 1c were treated in water with
ammonium thiocyanate and arylamines 2 in one pot to afford the correspond-
ing N-aryl-N0-(2-benzofuroyl)thioureas 3c–d and N-aryl-N0-[5-(3-nitrophe-
nyl)-2-furoyl]thioureas 3e–f, respectively. Subsequent condensation with
Scheme 1.

2-Acylimino-3-aryl-thiazoline
2455
Table 1. Synthesis of 2-acylimino-3-aryl-thiazolines 4a–l
Entry
Compound
Ar1
Ar2
R
Yield (%)a
1
2
4a
4b
4c
4d
4e
4f
1a
1a
1a
1a
1b
1b
1b
1b
1c
1c
1c
1c
C6H5
4-ClC6H4
C6H5
CH3
CH3
73
71
60
61
63
67
68
59
71
71
62
69
3
C6H5
C6H5
CH3
4
4-ClC6H4
C6H5
5
6
3-BrC6H4
4-ClC6H4
4-BrC6H4
C6H5
CH3
7
4g
4h
4i
C6H5
C6H5
CH3
8
9
10
11
12
4j
4-ClC6H4
C6H5
4-ClC6H4
CH3
C6H5
C6H5
4k
4l
aOverall isolated total yield based on benzoyl chloride.
a-bromocarbonyl compounds in water gave the corresponding 2-acylimino-
1,3-thiazolines 4c–l in acceptable total yields (59–71%).
All the product structures were characterized by IR, 1H NMR, 13C NMR,
and element analysis. The X-ray crystallography of 4a identified the structure
of the desired products (Figure 1).[12]
In order to compare this procedure with the conventional method in
organic solvent, we carried out the reaction for 4a with the previously
Figure 1. X-ray structure of compound 4a.

2456
X. Wang et al.
mentioned materials in acetone; however, it did not give the desired. The
reason is that the reaction of acyl chloride with arylamine affording amide
was dominant over those of acyl chlorides with ammonium thiocyanate.
In summary, this approach constitutes a novel and efficient synthesis of
2-aroylimino-3-substituted-4-methyl (or phenyl)-1,3-thiazolines using a one-
pot, two-step reaction by thioureas, which derived simultaneously from
aroyl chloride, ammonium thiocyanate, and arylamines, with bromoace-
tone/phenacyl bromide in aqueous media under mild reaction conditions.
Finally, this reaction sequence could conveniently be performed in water in
one pot without isolation of the intermediates, allowing the development of
a straightfoward, simple, green chemical, and efficient procedure for the gen-
eration of libraries of 2-imino-1,3-thiazolines.
EXPERIMENTAL
All reagents were obtained commercially and used without further purifi-
cation. Melting points were determined on an XT-4 electrothermal micromelt-
ing-point apparatus and are uncorrected. IR spectra were recorded using KBr
pellets on Nicolet Avatar 36 FT-IR spectrophotometer. NMR spectra were
recorded at 400 (1H) and 100 (13C) MHz, respectively, on a Varian
Mercury plus 400 instrument using CDCl3 or DMSO-d6 as solvent and
TMS as internal standard. Mass spectra were recorded on a ZAB-HS spec-
trometer. Elemental analyses were performed on a Carlo-Erba 1106
elemental analysis instrument.
General Procedure for Preparation of 2-Acylimino-3-phenyl-1,3-
thiazolines (4)
Ammonium thiocyanate (1.5mmol) and triethylbenzylammonium chloride
(TEBA) (0.1mmol) were added to water (3 mL). At the same time, acyl
chloride (1.0mmol) and arylamine (1.0mmol) were added. The suspension
was stirred at rt for 45min until the products were fully precipitated. Then bro-
moacetone/phenacyl bromide (1.0mmol) was added to the suspension of
thiourea, and the mixture was heated under refluxing for 30min (50min for
phenacyl bromide). After the reaction was completed (monitored by TLC),
crude product was obtained by filtering and recrystallization from EtOH-H2O
(4: 1), affording pure product (Table 1).
Data
2-Benzoylimino-3-phenyl-4-methyl-1,3-thiazoline 4a: Mp 156–157 8C.
IR (KBr): 1597, 1564, 1492 cm21
.
1H NMR (CDCl3): d ¼ 8.10–7.20
(m, 10H, ArH), 6.38 (s, 1H, CH55C), 2.05 (s, 3H, CH3). 13C NMR

2-Acylimino-3-aryl-thiazoline
2457
(CDCl3): d ¼ 170.5, 174.7, 137.8, 137.3, 134.8, 131.7, 129.9, 129.6, 128.5,
128.3, 104.9, 15.5. Anal. calcd. for C17H14N2OS: C, 69.35; H, 4.79; N,
9.51. Found: C, 69.55; H, 4.74; N, 9.54.
Crystal structure of 4a: C17H14N2OS, space group P-1, T ¼ 293 (2) K,
˚
˚
˚
a ¼ 9.635(3) A, b ¼ 9.962(3) A, c ¼ 16.258(4) A, a ¼ 97.177(4)8, b ¼
3
3
˚
92.595(4)8, g ¼ 97.864(4)8, V ¼ 1530.7(7) A , Z ¼ 4, Dc ¼ 1.277 Mg/m .
Crystal size: 0.47 ꢀ 0.34 ꢀ 0.11 mm; u range for data collection 2.08 to
26.038. Limiting indices 25 , h , 11, 212 , k , 12, 220 , I , 19.
Reflections collected: 8491; independent reflections: 5845 (Rint ¼ 0.0135);
refinement method: Full-matrix least-squares on F2; goodness-of-fit on F2:
0.981; final R indices [I . 2s(I)]: R1 ¼ 0.0490, wR2 ¼ 0.1404; R indices
(all data): R1 ¼ 0.0603, wR2 ¼ 0.1539. Largest diff. peak and hole: 0.615
23
˚
˚
and 20.275 e A . Selected bond lengths (A) and angles (0): S(1)-C(3):
1.734(3), S(1)-C(1): 1.7452(19), O(1)-C(11): 1.234(2), N(1)-C(1): 1.358(3),
N(1)-C(2): 1.405(3), N(1)-C(5): 1.448(3), N(2)-C(1): 1.310(2), N(2)-C(11):
1.366(3), C(2)-C(3): 1.329(4), C(2)-C(4): 1.491(4), C(5)-C(10): 1.368(3),
C(5)-C(6): 1.373(3), C(6)-C(7): 1.377(3), C(7)-C(8): 1.369(4), C(8)-C(9):
1.377(4), C(9)-C(10): 1.381(4), C(11)-C(12): 1.491(3), C(12)-C(17):
1.373(3), C(12)-C(13): 1.388(3), C(13)-C(14): 1.378(3), C(14)-C(15):
1.353(4), C(15)-C(16): 1.365(4), C(16)-C(17): 1.382(3), C(3)-S(1)-C(1):
90.53(11), C(1)-N(1)-C(2): 114.87(18), C(1)-N(1)-C(5): 121.45(16), C(2)-
N(1)-C(5): 123.39(18), C(1)-N(2)-C(11): 116.60(16), N(2)-C(1)-N(1):
121.43(17), N(2)-C(1)-S(1): 128.87(16), N(1)-C(1)-S(1): 109.70(14),
C(3)-C(2)-N(1): 111.9(2), C(3)-C(2)-C(4): 128.5(2), N(1)-C(2)-C(4):
119.6(2), C(2)-C(3)-S(1): 112.99(18), O(1)-C(11)-N(2): 124.89(19),
O(1)-C(11)-C(12): 120.56(18), N(2)-C(11)-C(12): 114.55(16). (Crystallo-
graphic data for the structure analysis have been deposited at the
Cambridge Crystallographic Data Centre as supplementary publication,
CCDC no. 281801, for 4a. Copies of this information can be obtained free
of charge upon application to CCDC, 12 Union Road, Cambridge CB2
1EZ, UK, fax: (44) 01223 336033 or e-mail: deposit@ccdc.cam.ac.uk.)
2-Benzoylimino-3-(4-chlorophenyl)-4-methyl-1,3-thiazoline 4b: Mp 210–
1
211 8C. IR (KBr): 1597, 1565, 1492 cm21. H NMR (CDCl3): d ¼ 8.05–
7.26 (m, 9H, ArH), 6.40 (s, 1H, CH55C), 2.07 (s, 3H, CH3). 13C NMR
(CDCl3): d ¼ 174.6, 170.2, 136.6, 135.7, 133.8, 131.9, 129.6, 129.5, 127.8,
104.8, 15.1. Anal. calcd. for C17H13ClN2OS: C, 62.09; H, 3.98; N, 8.52.
Found: C, 62.15; H, 4.04; N, 8.54.
2-Benzoylimino-3-phenyl-4-phenyl-1,3-thiazoline 4c: Mp 209–210 8C. IR
1
(KBr): 1598, 1565, 1472 cm21. H NMR (CDCl3): d ¼8.10–8.06 (m, 2H,
ArH), 7.43–7.20 (m, 13H, ArH), 6.66 (s, 1H, CH55C). 13C NMR (CDCl3):
d ¼174.5, 169.7, 137.3, 136.8, 136.4, 134.4, 131.3, 130.1, 129.6, 129.4,
129.3, 128.8, 128.4, 128.3, 106.9. Anal. calcd. for C22H16N2OS: C, 74.13;
H, 4.52; N, 7.86. Found: C, 74.20; H, 4.56; N, 7.80.

2458
X. Wang et al.
2-Benzoylimino-3-(4-methylphenyl)-4-phenyl-1,3-thiazoline 4d: Mp 276–
277 8C. IR (KBr): 1597, 1564, 1473 cm21. 1H NMR (CDCl3): d ¼ 8.13–8.11
(m, 2H, ArH), 7.44–7.12 (m, 12H, ArH), 6.69 (s, 1H, CH55C), 2.39 (s, 3H,
CH3). 13C NMR (CDCl3): d ¼174.5, 169.8, 139.2, 138.4, 136.8, 134.9,
131.4, 130.7, 129.4, 129.3, 128.9, 128.7, 128.4, 128.1, 127.9, 107.4, 21.3.
Anal. calcd. for C23H18N2OS: C, 74.57; H, 4.90; N, 7.56. Found: C, 74.51;
H, 4.94; N, 7.52.
2-(2-Benzofuroylimino)-3-phenyl-4-methyl-1,3-thiazoline 4e: Mp 190–
191 8C. IR (KBr): 3093, 1605, 1557, 1469, 1369, 1257, 1227 cm21 1H
.
NMR (CDCl3): d ¼ 7.56–7.48 (m, 2H, ArH), 7.44–7.31 (m, 4H, ArH),
7.30–7.21 (m, 4H, ArH), 6.41 (d, 1H, J ¼ 1.2 Hz, C55CH), 2.06 (d, 3H,
J ¼ 0.8 Hz, CH3). 13C NMR (CDCl3): d ¼ 169.6, 167.4, 154.9, 152.2,
137.3, 134.8, 130.0, 129.9, 129.6, 127.5, 126.9, 123.6, 122.9, 111.9, 111.2,
104.9, 15.5. Anal. calcd. for C19H14N2O2S: C, 68.25; H, 4.22; N, 8.38.
Found: C, 68.34; H, 4.13; N, 8.33.
2-(2-Benzofuroylimino)-3-(3-bromophenyl)-4-methyl-1,3-thiazoline 4f:
Mp 230–231 8C. IR (KBr): 3104, 1605, 1557, 1469, 1369, 1256,
1
1227 cm21. H NMR (CDCl3): d ¼ 7.73 (d, 1H, J ¼ 1.6 Hz, ArH), 7.71–
7.48 (m, 4H, ArH), 7.35–7.20 (m, 4H, ArH), 6.42 (d, 1H, J ¼ 1.2 Hz,
C55CH), 2.08 (d, 3H, J ¼ 1.2 Hz, CH3). 13C NMR (CDCl3): d ¼ 169.6,
166.7, 155.7, 152.5, 138.0, 133.9, 132.5, 131.2, 130.7, 127.0, 126.4, 123.1,
122.7, 123.4, 112.3, 111.3, 105.1, 15.0. Anal. calcd. for C19H13BrN2O2S: C,
55.22; H, 3.17; N, 6.78. Found: C, 55.15; H, 3.23; N, 6.73.
2-(2-Benzofuroylimino)-3-(4-chlorophenyl)-4-phenyl-1,3-thiazoline 4 g:
1
Mp 250–2518C. IR (KBr): 3098, 1600, 1557, 1467, 1442 cm21. H NMR
(DMSO-d6): d ¼7.74–7.72 (m, 1H, ArH), 7.65–7.63 (m, 1H, ArH), 7.45–
7.41 (m, 1H, ArH), 7.38–7.25 (m, 11H, ArH), 7.15 (s, 1H, C55CH). 13C
NMR (DMSO-d6): d ¼169.3, 165.7, 155.2, 152.5, 140.5, 138.4, 134.8,
130.3, 129.5, 129.2, 129.0, 128.5, 128.4, 127.3, 126.9, 123.7, 122.9, 111.9,
111.1, 108.3. Anal. calcd. for C24H15ClN2O2S: C, 66.90; H, 3.51; N, 6.50.
Found: C, 66.81; H, 3.55; N, 6.46.
2-(2-Benzofuroylimino)-3-(4-bromophenyl)-4-phenyl-1,3-thiazoline 4 h:
1
Mp 252–253 8C. IR (KBr): 3100, 1601, 1557, 1461, 1446 cm21. H NMR
(DMSO-d6): d ¼ 7.76–7.73 (dd, 1H, J ¼ 8.0 and 0.8 Hz, ArH), 7.67–7.64
(dd, 1H, J ¼ 8.0 and 0.8 Hz, ArH), 7.46–7.40 (m, 1H, ArH), 7.38–7.22
(m, 11H, ArH), 7.20 (d, 1H, J ¼ 1.2 Hz, C55CH). 13C NMR (DMSO-d6): d
¼169.4, 165.6, 155.0, 152.5, 141.1, 138.4, 134.5, 131.0, 129.9, 129.4,
129.1, 128.8, 128.6, 127.5, 126.7, 123.7, 123.2, 120.1, 111.3, 108.4. Anal.
calcd. for C24H15BrN2O2S: C, 60.64; H, 3.18; N, 5.89. Found: C, 60.69; H,
3.15; N, 5.84.

2-Acylimino-3-aryl-thiazoline
2459
2-[5-(3-Nitrophenyl)-2-furoylimino]-3-phenyl-4-methyl-1,3-thiazoline 4i:
Mp 235–236 8C. IR (KBr): 3106, 1611, 1512, 1476, 1344, 1272,
1
1221 cm21. H NMR (CDCl3): d ¼ 8.45 (d, 2H, J ¼ 2.0 Hz, ArH), 8.09–
8.06 (m, 1H, ArH), 8.00–7.98 (m, 1H, ArH), 7.62–7.48 (m, 6H, ArH),
6.94–6.93 (m, 1H, FuH), 6.76–6.75 (m, 1H, FuH), 6.40 (s, 1H, C55CH),
2.07 (d, 3H, J ¼ 0.8 Hz, CH3). 13C NMR (CDCl3): d ¼ 169.6, 165.5, 153.1,
151.9, 148.6, 136.9, 134.5, 131.7, 129.9, 129.6, 129.5, 129.4, 127.9, 122.3,
119.1, 117.3, 108.8, 104.8, 15.0. Anal. calcd. for C21H15N3O4S: C, 62.21;
H, 3.73; N, 10.36. Found: C, 62.29; H, 3.70; N, 10.41.
2-[5-(3-Nitrophenyl)-2-furoylimino]-3-(4-chlorophenyl)-4-methyl-1,3-
thia-zoline 4j: Mp 217–218 8C. IR (KBr): 3106, 1620, 1533, 1461, 1353,
1
1260 cm21. H NMR (CDCl3): d ¼ 8.46 (s, 1H, ArH), 8.10–8.00 (m, 2H,
ArH), 7.55–7.38 (m, 4H, ArH), 7.30–7.24 (m, 1H, ArH), 6.92–6.88
(m, 1H, FuH), 6.77–6.74 (m, 1H, FuH), 6.40 (d, 1H, J ¼ 0.8 Hz, C55CH),
2.07 (d, 3H, J ¼ 0.8 Hz, CH3). 13C NMR (CDCl3): d ¼ 169.3, 165.6, 153.1,
151.8, 148.6, 136.9, 136.7, 134.5, 131.7, 131.4, 129.6, 129.5, 129.4, 127.9,
127.4, 122.3, 119.3, 117.3, 109.1, 104.9, 15.0. Anal. calcd. for
C21H14ClN3O4S: C, 57.34; H, 3.21; N, 9.55. Found: C, 57.40; H, 3.16; N,
10.01.
2-[5-(3-Nitrophenyl)-2-furoylimino]-3-phenyl-4-phenyl-1,3-thiazoline 4 k:
The previous described method for the reaction of 2-benzofuroyl chloride
(1b) with ammonium thiocyanate (1.5 mmol), aniline (1.0 mmol), and
phenacyl bromide (1.0 mmol) was used to prepare the product. It was
purified by recrystallization from DMF-EtOH. Mp 194–195 8C. IR (KBr):
1
3088, 1599, 1521, 1452, 1344 cm21. H NMR (CDCl3): d ¼8.53 (d, 1H,
J ¼ 2.0 Hz, ArH), 8.13–8.05 (m, 2H, ArH), 7.57–7.53 (m, 1H, ArH),
7.33–7.24 (m, 10H, ArH), 7.07 (d, 1H, J ¼ 3.6 Hz, FuH), 6.80 (d, 1H,
J ¼ 3.2 Hz, FuH), 6.70 (d, 1H, J ¼ 2.0 Hz, C55CH). 13C NMR (CDCl3):
d ¼169.6, 165.6, 153.2, 151.9, 148.6, 137.4, 136.8, 134.6, 131.7, 130.1,
129.8, 129.6, 129.5, 128.8, 128.6, 128.3, 128.1, 122.4, 119.0, 117.4, 108.8,
107.6. Anal. calcd. for C26H17N3O4S: C, 66.80; H, 3.67; N, 8.99. Found: C,
66.72; H, 3.73; N, 8.93.
2-[5-(3-Nitrophenyl)-2-furoylimino]-3-(4-chlorophenyl)-4-phenyl-1,3-thi-
azoline 4l: Mp 236–2378C. IR (KBr): 3100, 1584, 1521, 1461, 1338 cm21. 1H
NMR (CDCl3): d ¼ 8.53 (d, 1H, J ¼ 2.0 Hz, ArH), 8.16–8.07 (m, 2H, ArH),
7.59–7.54 (m, 1H, ArH), 7.32–7.19 (m, 9H, ArH), 6.95 (d, 1H, J ¼ 3.6 Hz,
FuH), 6.81 (d, 1H, J ¼ 3.2 Hz, FuH), 6.72 (d, 1H, J ¼ 2.0 Hz, C55CH). 13C
NMR (CDCl3): d ¼169.4, 165.7, 153.3, 152.0, 148.5, 139.2, 138.8, 134.9,
131.5, 130.4, 129.7, 129.4, 128.7, 128.5, 128.2, 122.5, 120.2, 117.8, 109.2,
108.1. Anal. calcd. for C26H16ClN3O4S: C, 62.21; H, 3.21; N, 8.37. Found:
C, 62.14; H, 3.19; N, 8.34.

2460
X. Wang et al.
ACKNOWLEDGMENT
We thank the Natural Science Foundation of Gansu Province (ZS021-A25-
006-Z) and Gansu Key Laboratory of Polymer Materials for financial support.
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