Efficient and novel synthesis of N-Aryl-N'-ethoxycarbonylthiourea and arene-bis-ethoxycarbonylthiourea derivatives catalyzed by TMEDA

Article abstract of DOI:10.1081/SCC-120038502

A series of N-aryl-N'-ethoxycarbonyl thioureas and arene-bis- ethoxycarbonylthiourea derivatives have been synthesized in good to excellent yields under the TMEDA catalyzed conditions at room temperature.

Full text of DOI:10.1081/SCC-120038502

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Efficient and Novel Synthesis of
N‐Aryl‐N′‐ethoxycarbonylthiourea and
Arene‐bis‐ethoxycarbonylthiourea Derivatives
Catalyzed by TMEDA
Tai‐Bao Wei a , Qi Lin a , You‐Ming Zhang a & Hai Wang a
a Department of Chemistry , Northwest Normal University , Lanzhou, Gansu, 730070, P.R.
China
Published online: 17 Aug 2006.
To cite this article: Tai‐Bao Wei , Qi Lin , You‐Ming Zhang & Hai Wang (2004) Efficient and Novel Synthesis of
N‐Aryl‐N′‐ethoxycarbonylthiourea and Arene‐bis‐ethoxycarbonylthiourea Derivatives Catalyzed by TMEDA, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 34:12, 2205-2213,
DOI: 10.1081/SCC-120038502
To link to this article: http://dx.doi.org/10.1081/SCC-120038502
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 12, pp. 2205–2213, 2004
Efficient and Novel Synthesis of
N-Aryl-N0-ethoxycarbonylthiourea and
Arene-bis-ethoxycarbonylthiourea
Derivatives Catalyzed by TMEDA
*
Tai-Bao Wei, Qi Lin, You-Ming Zhang, and
Hai Wang
Department of Chemistry, Northwest Normal University,
Lanzhou, Gansu, P.R. China
ABSTRACT
A series of N-aryl-N0-ethoxycarbonyl thioureas and arene-bis-ethoxy-
carbonylthiourea derivatives have been synthesized in good to excellent
yields under the TMEDA catalyzed conditions at room temperature.
Key Words: Ethyl chloroformate; Thiocyanate; Catalysts; TMEDA.
*
Correspondence: You-Ming Zhang, Department of Chemistry, Northwest Normal
University, Lanzhou, Gansu, 730070, P.R. China; Fax: þ086-931-7971216; E-mail:
kejichu@nwnu.edu.cn.
2205
DOI: 10.1081/SCC-120038502
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Wei et al.
INTRODUCTION
N-Aryl-N0-ethoxycarbonyl thioureas have attracted much attention due
to their strong coordination ability,[1] for example, many N-substituted-
N0-ethoxycarbonyl thioureas are commercially utilized as the collector for
copper sulfides and precious metals.[2] Moreover, N-aryl-N0-ethoxycarbonyl
thioureas exhibit high antibacterial activity.[3] It is also an important
intermediate for synthesis of heterocyclic compounds.[4] In view of these
and as a part of our work of the synthesis, biological activity, and coordination
behavior of thiourea derivatives,[5] herein we report an efficient method for
synthesis N-aryl-N0-ethoxycarbonyl thioureas (4a–1) and arene-bis-ethoxy-
carbonylthiourea derivatives (5a–e) catalyzed by N,N,N0,N0-tetramethylethyl-
enediamine (TMEDA) under mild conditions.
The common methods for the preparation of these compounds are via the
reaction of ethoxycarbonylthiocyanate (3) with corresponding aromatic
amines or arene diamines.[6] Obviously, the compound 3 is the key intermedi-
ate for 4 and 5. As early as 1908, Dixon and Taylor [7] repoted that potassium
thiocyanate (2) reacted with ethyl chloroformate (1) in acetone solutions to
give the compound 3, but this method gives 3 in very low yield and ethoxy-
carbonylthiocyanate as by-product.[8] Hence it is not a good method for prep-
aration 3. In our earlier work, we reported that acyl isothiocyanate could be
synthesized in high yield by the reaction of benzoyl chloride with potassium
thiocyanate under solid–liquid phase-transfer catalytic conditions,[5b] how-
ever, we have not obtained the compound 3 in high yield using similar method.
Recently, Sano et al.[9] reported that TMEDA could promote the acylation
of alcohols with benzoyl chloride. Kunz and Bechtolsheimor[10] reported that
pyridine could catalyze the reaction between 2-(triphenylphosphonio)ethyl
chloroformate and alcohols. In view of these, we think TMEDA and other
amine such as pyridine also can catalyze the reaction between 1 and 2 by
enhancing reactivity of 1. In order to select the best reaction condition and
the best catalyst for synthesis 3, we carried out a series of experiments. At
first, we estimated the reactivity of the model reaction (Sch. 1) between
1 (10 mmol) and 2 (12 mmol) with catalytic amount of TMEDA (0.1 mmol)
at room temperature in different solvents. Since the compound 3 is an oily
product, we did not separate it and added the aniline (10 mmol) slowly to
the reaction mixture with continuous stirring at room temperature for 5 hr
(Table 1). From these data, we concluded that ethyl acetate is the appropriate
solvent for this reaction.
In order to compare the catalytic effect of TMEDA, we examined the
similar reaction with different amines as catalysts, as well as, PEG-400 as a
solid–liquid phase-transfer catalyst (Table 2). From these data, we can find
the TMEDA is the best catalyst for this reaction. Finally, we explored the

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2207
Scheme 1.
general validity of the present methodology; different ethoxycarbonylthio-
ureas 4a–1 and 5a–e were synthesized in excellent yields (Table 3).
The details of the reaction mechanism are not clear at present but Sano
et al.[9] supposed that a benzoyl chloride–TMEDA complex plays a signi-
ficant role to enhance the reactivity of benzoyl chloride. Additionally, Kunz
and Bechtolsheimer[10] reported that the 2-(triphenylphosphonio)ethyl chloro-
formate–pyridine complex is the key intermediate to enhance the reactivity of
2-(triphenylphosphonio)ethyl chloroformate. Therefore, we think the forma-
tion of ethyl chloroformate–TMEDA complex (Sch. 2) is the key step of the
catalytic procedure.
In brief, TMEDA is an excellent catalyst for the synthesis of this kind
of isothiocyanate and thiourea. The use of TMEDA as the catalyst has many
Table 1. Yields of 4a in different solvents.
Yields of
4a (%)
Entry
Solvents
1
2
3
4
Acetone (8 mL)
CH2Cl2 (8 mL)
54
56
96
68
Ethyl acetate (8 mL)
Ethyl acetate (20 mL)

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Wei et al.
Table 2. Yields of 4a under the different catalysts catalyzed.
Yields of
4a (%)
Entry
Catalystsa
1
2
3
4
5
6
7
8
TPAb
TAAc
60
80
76
96
42
68
45
74
Pyridine
TMEDA
PEG-400d
PEG-400 þ TAA
PEG-400 þ Pyridine
PEG-400 þ TMEDA
aThe use of each catalyst is 0.1 mmol.
bTripropyl amine.
cTriamyl amine.
dPolyethylene glycol-400.
advantages such as excellent yields, high efficiency (10 mmol ethyl chlorofor-
mate only need 0.1 mmol TMEDA), mild reaction conditions (all reactions are
performed at room temperature), and simple operation. For these reasons, this
methodology represents an important improvement for the preparation of this
kind of products.
EXPERIMENTAL
Melting points were determined in open capillaries and are uncorrected.
IR spectra were recorded in KBr on a Nicolet NEXUS 670 FT-IR spectropho-
tometer and 1H-NMR spectra on a FT-80A instrument using TMS as internal
reference. Elemental analysis was determined on PE-2400 CHN instrument.
Typical Procedure for Preparation of 4a–1 and 5a–e
The synthesis of 4a–1 and 5a–e were carried out by adding powdered
2 (12 mmol), to an ethyl acetate solution of 1 (10 mmol) and TMEDA
(0.1 mmol). The reaction mixture was stirred at room temperature for 5 hr.
Then the aromatic amine (10 mmol) (to give 4a–1) or arene diamine
(5 mmol) (to give 5a–e) was slowly added to the reaction mixture with con-
stant stirring. The reaction mixture was stirred at room temperature for 5 hr
again. After evaporate the solvent in vacuum, the products were obtained
from washing the precipitation with 10 mL 75% ethanol three times and

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Novel Synthesis of Thiourea Derivatives
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Table 3. Compounds 4a–1 and 5a–e prepared.
Entry
Ar
Products
Yields (%)
1
2
C6H5
4a
4b
4c
4d
4e
4f
96
97
85
86
81
83
84
80
95
87
75
4-CH3C6H4
4-CH3COC6H4
4-ClC6H4
3
4
5
2,4,6-triClC6H2
3-BrC6H4
6
7
2,4,6-triBrC6H2
4-FC6H4
4g
4h
4i
8
9
1-Naphthyl
4-CH3OC6H4
10
11
4j
4k
12
4l
82
13
14
15
16
5a
5b
5c
5d
87
98
97
72
17
5e
94
15 mL H2O three times. If necessary, recrystallization 4a–1 from ethanol and
5a–e from DMF–EtOH–H2O gave the pure product.
N-Phenyl-N0-ethoxycarbonylthiourea (4a). Yield 96%, m.p. 125–1268C.
IR (KBr): n ¼ 3416 (NH), 3220 (NH), 1712 (C55O), 1596, 1534, 1449 (C55C),
1
1237 (C55S) cm21. H-NMR (CDCl3): dH ¼ 11.48 (s, 1H, NH), 8.29 (s, 1H,
Scheme 2.

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Wei et al.
NH), 7.50 (m, 5H, ArH), 4.361 (q, 2H, CH2), 1.368, (t, 3H, CH3). Anal. Cacld.
for C10H12N2O2S: C, 53.55; H, 5.39; N, 12.49. Found (%): C, 53.55; H, 5.40;
N, 12.54.
N-(4-Methylphenyl)-N0-ethoxycarbonylthiourea (4b). Yield 97%, m.p.
149–1508C. IR (KBr): n ¼ 3421 (NH), 3241 (NH), 1712 (C55O), 1529
(C55C), 1237 (C55S) cm21
.
1H-NMR (CDCl3): dH ¼ 11.38 (s, 1H, NH),
8.33 (s, 1H, NH), 7.45 (q, 4H, ArH), 4.34 (q, 2H, CH2), 2.37 (s, 3H, CH3),
1.36, (t, 3H, CH3). Anal. Cacld. for C11H14N2O2S: C, 55.44; H, 5.92; N,
11.76. Found: C, 55.47; H, 5.90; N, 11.75.
N-Acetylphenyl-N0-ethoxycarbonylthiourea (4c). Yield 85%, m.p.
177–1788C. IR (KBr): n ¼ 3174 (NH), 3061 (NH), 1728, 1681 (C55O),
1618, 1598, 1537 (C55C), 1249 (C55S) cm21
.
1H-NMR (CDCl3):
dH ¼ 11.76 (s, 1H, NH), 8.43 (s, 1H, NH), 7.96 (q, 4H, ArH), 4.35 (q, 2H,
CH2) 2.61 (s, 3H, CH3), 1.36 (t, 3H, CH3). Anal. Cacld. for C12H14N2O2S:
C, 55.44; H, 5.92; N, 11.76. Found: C, 54.04; H, 5.87; N, 10.80.
N-(4-Chlorophenyl)-N0-ethoxycarbonylthiourea (4d). Yield 86%, m.p.
120–1228C. IR (KBr): n ¼ 3424 (NH), 3259 (NH), 1725 (C55O), 1592, 1554,
1527 (C55C), 1249 (C55S) cm21. 1H-NMR (CDCl3): dH ¼ 11.48 (s, 1H, NH),
8.29 (s, 1H, NH), 7.50 (q, 4H, ArH), 4.35 (q, 2H, CH2) 1.36, (t, 3H, CH3).
Anal. Cacld. for C10H11N2O2SCl: C, 46.42; H, 4.29; N, 10.83. Found: C,
46.27; H, 4.64; N, 10.54.
N-(2,4,6-Trichlorophenyl)-N0-ethoxycarbonylthiourea (4e). Yield
81%, m.p. 177–1788C. IR (KBr): n ¼ 3432 (NH), 3194 (NH), 1728
(C55O), 1554, 1514 (C55C), 1242 (C55S) cm21
.
1H-NMR (CDCl3):
dH ¼ 10.92 (s, 1H, NH), 8.55 (s, 1H, NH), 7.45 (s, 2H, ArH), 4.369 (q, 2H,
CH2) 1.371 (t, 3H, CH3). Anal. Cacld. for C10H19N2O2SCl3: C, 36.57; H,
3.00; N, 9.24. Found: C, 36.66; H, 2.77; N, 9.24.
N-(3-Bromophenyl)-N0-ethoxycarbonylthiourea (4f). Yield 83%, m.p.
97–988C. IR (KBr): n ¼ 3415 (NH), 3179 (NH), 1711 (C55O), 1589, 1531,
1472 (C55C), 1237 (C55S) cm21
.
1H-NMR (CDCl3): dH ¼ 11.52 (s, 1H,
NH), 8.28 (s, 1H, NH), 7.48 (m, 4H, ArH), 4.358 (q, 2H, CH2) 1.370 (t, 3H,
CH3). Anal. Cacld. for C10H11N2O2SBr: C, 39.62; H, 3.66; N, 9.24. Found:
C, 39.55; H, 3.90; N, 9.24.
N-(2,4,6-Tribromophenyl)-N0-ethoxycarbonylthiourea (4g). Yield
84%, m.p. 196–1988C. IR (KBr): n ¼ 3430 (NH), 3175 (NH), 1724
(C55O), 1514, 1442 (C55C), 1247 (C55S) cm21
.
1H-NMR (CDCl3):
dH ¼ 10.95 (s, 1H, NH), 8.65 (s, 1H, NH), 7.80 (s, 2H, ArH), 4.37 (q, 2H,
CH2) 1.37 (t, 3H, CH3). Anal. Cacld. for C10H9N2O2SBr3: C, 26.06; H,
1.97; N, 6.08. Found: C, 26.07; H, 1.96; N, 6.11.
N-(4-Fluorophenyl)-N0-ethoxycarbonylthiourea (4h). Yield 90%, m.p.
187–1888C. IR (KBr): n ¼ 3424 (NH), 33168 (NH), 1726 (C55O), 1565,
1533, 1511 (C55C), 1252 (C55S) cm21
.
1H-NMR (CDCl3): dH ¼ 11.38

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Novel Synthesis of Thiourea Derivatives
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(s, 1H, NH), 8.26 (s, 1H, NH), 7.50 (m, 4H, ArH), 4.36 (q, 2H, CH2), 1.37
(t, 3H, CH3). Anal. Cacld. for C10H11N2O2SF: C, 49.57; H, 4.58; N, 11.56.
Found: C, 49.49; H, 4.58; N, 11.76.
N-(1-Naphthyl)-N0-ethoxycarbonylthiourea (4i). Yield 95%, m.p.
106–1088C. IR (KBr): n ¼ 3426 (NH), 3259 (NH), 1720 (C55O), 1597,
1521, 1478 (C55C), 1241 (C55S) cm21
.
1H-NMR (CDCl3): dH ¼ 11.65
(s, 1H, NH), 8.50 (s, 1H, NH), 7.64 (m, 7H, ArH), 4.39 (q, 2H, CH2) 1.39
(t, 3H, CH3). Anal. Cacld. for C14H14N2O2S: C, 61.29; H, 5.14; N, 10.21.
Found: C, 61.51; H, 5.20; N, 10.27.
N-(4-Methoxyphenyl)-N0-ethoxycarbonylthiourea (4j). Yield 87%,
m.p. 137–1388C. IR (KBr): n ¼ 3431 (NH), 3132 (NH), 1724 (C55O),
.
1564, 1538, 1492 (C55C), 1258 (C55S) cm21 1H-NMR (CDCl3):
dH ¼ 11.29 (s, 1H, NH), 8.26 (s, 1H, NH), 7.28 (m, 4H, ArH), 4.34 (q, 2H,
CH2), 3.83 (s, 3H, CH3) 1.36 (t, 3H, CH3). Anal. Cacld. for C11H14N2O2S:
C, 51.95; H, 5.55; N, 11.02. Found: C, 51.93; H, 5.49; N, 11.06.
N-(3-Pyridyl)-N0-ethoxycarbonylthiourea (4k). Yield 75%, m.p.
167–1688C. IR (KBr): n ¼ 3408 (NH), 3185 (NH), 1710 (C55O), 1555, 1533,
1479 (C55C, C55N), 1249 (C55S) cm21. 1H-NMR (CDCl3): dH ¼ 11.60 (s, 1H,
NH), 8.92 (s, 1H, NH), 8.50 (m, 2H, N55C–H), 8.25 (m, 1H, ArH), 7.40 (q, 1H,
ArH), 4.37 (q, 2H, CH2), 3.37 (s, 3H, CH3) 1.36 (t, 3H, CH3). Anal. Cacld. for
C9H11N3O2S: C, 47.99; H, 4.92; N, 18.65. Found: C, 47.60; H, 5.07; N, 18.56.
N-(2-Thiazolyl)-N0-ethoxycarbonylthiourea (4I). Yield 82%, m.p.
166–1678C. IR (KBr): n ¼ 3434 (NH), 3169 (NH), 1725 (C55O), 1568,
1510 (C55C, C55N), 1244 (C55S) cm21
(s, 1H, NH), 8.35 (s, 1H, NH), 7.28 (m, 2H, ArH), 4.39 (q, 2H, CH2), 1.37
(t, 3H, CH3). Anal. Cacld. for C7H9N3O2S2: C, 36.35; H, 3.92; N, 18.17.
Found: C, 36.55; H, 3.68; N, 18.39.
.
1H-NMR (CDCl3): dH ¼ 9.71
1,4-Phenylene-bis-ethoxycarbonylthiourea (5a). Yield 88%, m.p.
210–2118C. IR (KBr): n ¼ 3428 (NH), 3188 (NH), 1717 (C55O), 1590, 1522
1
(C55C), 1233 (C55S) cm21. H-NMR (DMSO-d6): dH ¼ 11.62 (s, 2H, NH),
10.86 (s, 2H, NH), 7.58 (s, 4H, ArH), 4.24 (q, 4H, CH2), 1.27 (t, 6H, CH3).
Anal. Cacld. for C14H18N4O4S2: C, 45.39; H, 4.90; N, 15.12. Found: C,
45.23; H, 5.06; N, 15.25.
4,40-(bis-Ethoxycarbonylthioureido)-diphenyloxide (5b). Yield 98%,
m.p. 187–1888C. IR (KBr): n ¼ 3414 (NH), 3263 (NH), 1711 (C55O), 1569,
1530, 1499 (C55C), 1282 (Ar–O–Ar), 1234 (C55S) cm21
.
1H-NMR
(CDCl3): dH ¼ 11.42 (s, 2H, NH), 8.31 (s, 2H, NH), 8.31 (s, 2H, NH), 7.28
(m, 8H, ArH), 4.35 (q, 4H, CH2), 1.39 (t, 6H, CH3). Anal. Cacld. for
C20H22N4O5S2: C, 51.93; H, 4.79; N, 12.11. Found: C, 52.07; H, 4.96; N, 12.17.
4,40-(bis-Ethoxycarbonylthioureido)-diphenyl (5c). Yield 97%,
m.p. . 2808C. IR (KBr): n ¼ 3425 (NH), 3172 (NH), 1718 (C55O), 1602,
1532, 1497 (C55C), 1239 (C55S) cm21
.
1H-NMR (CDCl3): dH ¼ 11.69

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Wei et al.
(s, 2H, NH), 10.93 (s, 2H, NH), 7.62 (m, 8H, ArH), 4.27 (q, 4H, CH2), 1.29
(t, 6H, CH3). Anal. Cacld. for C20H22N4O4S2: C, 53.79; H, 4.97; N, 12.55.
Found: C, 53.94; H, 5.11; N, 12.66.
4,40-(bis-Ethoxycarbonylthioureido)-(3,30-bis-methyl)diphenyl (5d).
Yield 72%, m.p. . 2808C. IR (KBr): n ¼ 3424 (NH), 3165 (NH), 1715
(C55O), 1531, 1443 (C55C), 1246 (C55S) cm21
.
1H-NMR (CDCl3):
dH ¼ 11.31 (s, 2H, NH), 10.44 (s, 2H, NH), 7.50 (q, 6H, ArH), 4.26 (q, 4H,
CH2), 2.27 (s, 6H, CH3), 1.28 (t, 6H, CH3). Anal. Cacld. for C22H26N4O4S2:
C, 55.68; H, 5.54; N, 11.80. Found: C, 55.68; H, 5.67; N, 11.98.
4,40-(bis-Ethoxycarbonylthioureido)-diphenylsulfone (5e). Yield 94%,
m.p. . 193–1948C. IR (KBr): n ¼ 3412 (NH), 3179 (NH), 1731 (C55O),
1
1591, 1531, 1497 (C55C), 1229 (C55S), 1149(O55S55O) cm21. H-NMR
(CDCl3): dH ¼ 11.90 (s, 2H, NH), 10.43 (s, 2H, NH), 7.83 (s, 8H, ArH),
4.23 (q, 4H, CH2), 1.24 (t, 6H, CH3). Anal. Cacld. for C20H22N4O6S3: C,
47.06; H, 4.43; N, 10.97. Found: C, 47.14; H, 4.62; N, 11.08.
ACKNOWLEDGMENTS
This work was supported by Natural Science Foundation (No. 20371040)
of China, the Foundation (031-A21-004) of Gansu province and the Found-
ation (No. 02-18) of Northwest Normal University, Which are gratefully
acknowledged.
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Received in Poland December 12, 2003

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