Facile synthesis of 5-benzylidene rhodamine derivatives under microwave irradiation

Article abstract of DOI:10.1080/00397910600941166

A series of 5-benzylidenerhodamine derivatives were synthesized by the cross-aldol condensation of an aromatic aldehyde with rhodamine or rhodamine acetic acid in sodium acetate/acetic acid under microwave irradiation. The reaction was completed in 8-20 min with 63-94% yields and was environmentally benign with easy workup. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910600941166

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Facile Synthesis of 5‐Benzylidene Rhodamine
Derivatives under Microwave Irradiation
Jian‐Feng Zhou a b , Yuan‐Zhi Song a , Feng‐Xia Zhu a & Yu‐Lan Zhu a b
a Department of Chemistry , Huaiyin Teachers College , Huaian, China
b Jiangsu Key Laboratory for Chemistry of Low‐Dimensional Materials ,
Huaian, China
Published online: 23 Nov 2006.
To cite this article: Jian‐Feng Zhou , Yuan‐Zhi Song , Feng‐Xia Zhu & Yu‐Lan Zhu (2006) Facile Synthesis
of 5‐Benzylidene Rhodamine Derivatives under Microwave Irradiation, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:22, 3297-3303, DOI:
10.1080/00397910600941166
To link to this article: http://dx.doi.org/10.1080/00397910600941166
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Synthetic Communicationsw, 36: 3297–3303, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600941166
Facile Synthesis of 5-Benzylidene
Rhodamine Derivatives under Microwave
Irradiation
Jian-Feng Zhou
Department of Chemistry, Huaiyin Teachers College, Huaian, China and
Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials,
Huaian, China
Yuan-Zhi Song and Feng-Xia Zhu
Department of Chemistry, Huaiyin Teachers College, Huaian, China
Yu-Lan Zhu
Department of Chemistry, Huaiyin Teachers College, Huaian, China and
Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials,
Huaian, China
Abstract: A series of 5-benzylidenerhodamine derivatives were synthesized by the
cross-aldol condensation of an aromatic aldehyde with rhodamine or rhodamine
acetic acid in sodium acetate/acetic acid under microwave irradiation. The reaction
was completed in 8–20 min with 63–94% yields and was environmentally benign
with easy workup.
Keywords: Aromatic aldehyde, benzylidenerhodamine, microwave irradiation,
rhodamine, rhodamine acetic acid
Rhodamine derivatives have been proven to be attractive compounds because
of their outstanding biological activities. They have undergone rapid develop-
ment as anticonvulsant, antibacterial, antiviral, and antidiabetic materials.[1,2]
At the same time, rhodamine-based molecules have been popular as small
molecule inhibitors of numerous targets such as HCV protease,[3] HCV NS3
Received in Japan March 23, 2006
Address correspondence to Jian-Feng Zhou, Department of Chemistry, Huaiyin
Teachers College, Huaian 223300, China. E-mail: jfchow@sohu.com
3297

3298
J.-F. Zhou et al.
protease,[4] aldose reductase,[5,6] b-lactamase,[7] UDP-N-acetylmuramate/L-
alanine ligase,[8] cathepsin D,[9] histidine decarboxylase,[10] fungal protein
mannosyl transferase 1 (PMT1),[11] anthrax lethal factor protease,[12] and
JNK-stimulating phosphatase-1 (JSP-1).[13] Some derivatives of rhodamine
were found to have higher sensitivity and selectivity for the spectrophoto-
metric analysis of some noble metal ions and heavy metal ions.[14]
Therefore, the synthesis of these compounds are of considerable interest.
Herein, we report an efficient synthesis of 5-benzylidenerhodamines by the
aldol condensation of aromatic aldehyde with rhodamine or rhodamine
acetic acid in sodium acetate/acetic acid under microwave irradiation
(Scheme 1). The reactions were generally completed in 8–20 min with
63–94% yield and were environmentally benign with easy workup.
The synthetic route is shown in Scheme 1.
RESULTS AND DISCUSSION
In the 5-position of rhodamine, the methylene group is active. Therefore, they
were rapidly reacted with several aromatic aldehydes when subjected to
microwave irradiation in the presence of sodium acetate in acetic acid
solvent. Conventional approaches for the synthesis of these compounds
often involves long reaction times, harsh reaction conditions, unsatisfactory
yields, and environmentally unfavorable solvents. For example, the conden-
sation of aromatic aldehydes with rhodamine has been performed using piper-
idinium benzoate in refluxing toluene,[15,16] sodium acetate in refluxing glacial
acetic acid,[9] the synthesis of 5-benzylidenerhodamine in 60–82% yields by
heating the reactants suspended in toluene heated at 1108C for 3 days,[17] the
condensation of aromatic aldehyde with rhodamine by heating in anhydrous
EtOH for 6 h at 808C,[4] and so on. The results as summarized in Table 1
clearly reveal the scope and generality of the reaction with respect to
various substituted aromatic aldehydes and that reasonable yields (63–94%)
of the products were achieved after only 8–20 min of microwave irradiation.
In conclusion we have described a rapid and environmentally friendly
procedure for the synthesis of 5-benzylidenerhodamine derivatives from the
corresponding aromatic aldehyde with rhodamine or rhodamine acetic acid
under microwave irradiation.
Scheme 1.

5-Benzylidene Rhodamine Derivatives
3299
Table 1. Microwave irradiation synthesis of 3a–m and 3a0 –j0
Yields
(%)a
Compound
Ar
R
Time (min)
3a
3b
3c
3d
3e
3f
C6H5
2-ClC6H4
4-ClC6H4
H
H
H
H
H
H
H
H
H
H
H
H
H
8
10
10
10
10
15
10
10
10
10
15
20
15
86
75
81
89
94
73
70
70
74
63
71
74
71
4-NO2C6H4
3-NO2C6H4
4-CH3C6H4
4-CH3OC6H4
4-(CH3)2NC6H4
2-Furyl
3g
3h
3i
3j
4-HOC6H4
2-HOC6H4
2,4-(HO)2C6H3
3,4-(OCH2O)
C6H3
3k
3l
3m
3a0
3b0
3c0
3d0
3e0
3f0
C6H5
2-ClC6H4
4-ClC6H4
CH2CO2H
CH2CO2H
CH2CO2H
CH2CO2H
CH2CO2H
CH2CO2H
CH2CO2H
CH2CO2H
CH2CO2H
CH2CO2H
16
20
18
10
8
83
82
86
88
85
71
75
71
73
76
4-NO2C6H4
3-NO2C6H4
4-CH3C6H4
4-CH3OC6H4
4-(CH3)2NC6H4
4-HOC6H4
3,4-(CH3O)2C6H3
10
10
10
20
10
3g0
3h0
3i0
3j0
aYields of the isolated products.
EXPERIMENTAL
Melting points were determined in an XT-5 digital melting-point instrument
and are uncorrected. IR spectra were recorded on a Nicolet Avatar 360 FT-
1
IR instrument. H NMR were measured on a Burke 400-MHz spectrometer
in CDCl3 with TMS as internal standard. MS spectra were recorded on a
LCQ Advantage instrument. Elemental analyses were determined using a
Perkin-Elmer 240C elemental analyzer. The reactions were carried out with
a modified commercial microwave oven (Sanle WP650D 650 W) under
atmospheric pressure. All the reagents are commercially available.
General Procedure for the 5-Benzylidenerhodanine Derivatives
(3a–3m and 3a0 –3j0)
A mixture of the aromatic aldehyde (1 mmol), rhodamine (1 mmol) or
rhodamine acetic acid, sodium acetate (1.5 mmol), and acetic acid (5 mL)

3300
J.-F. Zhou et al.
in an Erlenmeyer flask (25 mL) equipped with reflux condenser were
irradiated in a microwave oven for 8–20 min (as indicated by thin layer
chromatography, TLC). The reaction mixture was allowed to stand at room
temperature to solidify. The crude product was collected, washed with
water, and recrystallized from DMF-H2O.
Data
3a: Yellow solid. Mp 205–2068C (204.5–2068C).[18]
3b: Yellow solid. Mp 177–1788C (179.5–180.58C).[18]
3c: Yellow solid. Mp 242–2438C (224–2308C).[19]
3d: Yellow solid. Mp 255–2568C (180.5–181.58C).[18]
3e: Yellow solid. Mp 269–2708C (263–2648C).[18]
3f: Yellow solid. Mp 233–2348C (219–2238C).[19]
3g: Yellow solid. Mp 261–2628C (240–2468C).[19]
3h: Yellow solid. Mp 283–2848C (266–2708C).[19]
3i: Yellow solid. Mp 228–2298C (228–2298C).[18]
3j: Yellow solid. Mp 184–1858C; 1H NMR (400 MHz, DMSO-d6):
d 10.43 (s, 1H, OH), 7.94 (s, 1H, CH55), 7.55 (s, 1H, NH), 7.46 (d, 2H,
J ¼ 8.0 Hz, Ar-H), 6.91 (d, 2H, J ¼ 8.0 Hz, Ar-H); IR (KBr): 3397, 3369,
3092, 1687, 1566, 1186 cm21; LC/MS (ESI): m/z: 236 (M-H)2. Anal.
calcd. for C10H7NO2S2: C, 50.63; H, 2.95; N, 5.91. Found: C, 50.49; H,
2.90; N, 5.82.
1
3k: Yellow solid. Mp 221–2228C. H NMR (400 MHz, DMSO-d6): d 10.66
(s, 1H, OH), 7.84 (s, 1H, CH55), 7.31 (s, 1H, NH), 7.28–6.96 (m, 4H, Ar-
H); IR (KBr): 3145, 1693, 1588, 1186 cm21; LC/MS (ESI): m/z: 236 (M-
H)2. Anal. calcd. for C10H7NO2S2: C, 50.63; H, 2.95; N, 5.91. Found: C,
50.44; H, 2.90; N, 5.78.
1
3l: Yellow solid. Mp 162–1638C. H NMR (400 MHz, DMSO-d6): d 10.65
(s, 1H, OH), 7.91 (s, 1H, CH55), 7.78 (s, 1H, NH), 7.25–6.92 (m, 3H, Ar-
H); IR (KBr): 3164, 3093, 1709, 1442, 1187 cm21; LC/MS (ESI): m/z: 252
(M-H)2. Anal. calcd. for C10H7NO3S2: C, 47.43; H, 2.77; N, 5.53. Found:
C, 47.29; H, 2.70; N, 5.38.

5-Benzylidene Rhodamine Derivatives
3301
1
3m: Yellow solid. Mp 278–2798C. H NMR (400 MHz, DMSO-d6): d 7.59
(s, 1H, CH55), 7.39 (1H, s, NH), 7.25–7.11 (m, 3H, Ar-H), 6.13 (s, 2H,
OCH2O); IR (KBr): 3145, 3006, 1686, 1581, 1190 cm21; LC/MS (ESI): m/
z: 264 (M-H)2. Anal. Calcd for C11H7NO3S2: C, 49.81; H, 2.64; N, 5.28.
Found: C, 49.67; H, 2.58; N, 5.17.
1
3a0: Yellow solid. Mp 202–2058C; H NMR (400 MHz, DMSO-d6) d 7.81
(s, 1H, CH55), 7.49 (s, 5H, Ar-H), 4.95 (s, 2H, CH2); IR (KBr): 1734,
1491, 1191 cm21; LC/MS (ESI): m/e ¼ 278(M-H)2; Anal. calcd. for
C12H9NO3S2: C 51.61; H 3.23; N 5.02. Found: C, 51.34; H, 3.19; N, 4.94.
1
3b0: Yellow solid. Mp 242–2438C; H NMR (400 MHz, DMSO-d6) d 7.75
(s, 1H, CH55), 7.52–7.39 (m, 4H, Ar-H), 4.94 (s, 2H, CH2); IR (KBr):
1708, 1488, 1183 cm21; LC/MS (ESI): m/e ¼ 312 (M-H)2. Anal. calcd.
for C12H8ClNO3S2: C, 46.01; H, 2.56; N, 4.47. Found: C, 45.79; H, 2.51;
N, 4.41.
1
3c0: Yellow solid. Mp 250–2538C; H NMR (400 MHz, DMSO-d6) d 8.17
(s, 1H, CH55), 7.96 (d, 2H, J ¼ 7.6 Hz, Ar-H), 7.42 (d, 2H, J ¼ 7.6 Hz, Ar-
H), 4.95 (s, 2H, CH2); IR (KBr): 1718, 1467, 1197 cm21; LC/MS (ESI):
m/e ¼ 312 (M-H)2. Anal. calcd. for C12H8ClNO3S2: C, 46.01; H, 2.56; N,
4.47. Found: C, 45.80; H, 2.51; N, 4.40.
3d0: Orange yellow solid. Mp 240–2438C; 1H NMR (400 MHz, DMSO-d6) d
8.35 (d, 2H, J ¼ 8.8 Hz, Ar-H), 7.81 (s, 1H, CH55), 7.67 (d, 2H, J ¼ 8.8 Hz,
Ar-H), 4.96 (s, 2H, CH2); IR (KBr): 1713, 1515, 1186 cm21; LC/MS (ESI):
m/e ¼ 323 (M-H)2. Anal. calcd. for C12H8N2O5S2: C, 44.44; H, 2.47; N,
8.64. Found: C, 44.23; H, 2.43; N, 8.59.
3e0: Yellow solid. Mp 280–2838C; 1H NMR (400 MHz, DMSO-d6) d
8.30(s, 1H, CH55), 7.93–7.71 (m, 4H, Ar-H), 4.96 (s, 2H, CH2); IR (KBr):
1702, 1533, 1205 cm21, LC/MS (ESI): m/e ¼ 323(M-H)2. Anal. calcd. for
C12H8N2O5S2: C, 44.44; H, 2.47; N, 8.64. Found: C, 44.22; H, 2.43; N, 8.60.
3f0: Yellow solid. Mp .3008C; 1H NMR (400 MHz, DMSO-d6) d 7.94 (s, 1H,
CH55), 7.79 (d, 2H, J ¼ 8.0 Hz, ArH), 7.31 (d, 2H, J ¼ 8.0 Hz, ArH), 4.94
(s, 2H, CH2); IR (KBr): 1718, 1507, 1191 cm21; LC/MS (ESI): m/e ¼ 292
(M-H)2. Anal. calcd. for C13H11NO3S2: C, 53.24; H, 3.75; N, 4.78. Found:
C, 53.01; H, 3.69; N, 4.71.
1
3g0: Yellow solid. Mp 190–1938C; H NMR (400 MHz, DMSO-d6) d 7.77
(s, 1H, CH55), 7.49 (d, 2H, J ¼ 8.0 Hz, Ar-H), 7.05 (d, 2H, J ¼ 8.0 Hz, Ar-
H), 3.86 (s, 3H, CH3), 4.94 (s, 2H, CH2); IR (KBr): 1715, 1510,
;
1204 cm21
C13H11NO4S2: C, 50.49; H, 3.56; N, 4.53. Found: C, 50.24; H, 3.52; N, 4.47.
LC/MS (ESI): m/e ¼ 308 (M-H)2. Anal. calcd. for

3302
J.-F. Zhou et al.
3h0: Orange red solid. Mp 276–2798C; 1H NMR (400 MHz, DMSO-d6) d 7.74
(s, 1H, CH55), 7.42 (d, 2H, J ¼ 9.2 Hz), 6.68 (d, 2H, J ¼ 9.2 Hz), 4.94 (s, 2H,
CH2), 3.10 (s, 6H, 2CH3); IR (KBr): 1698, 1523, 1177 cm21; LC/MS (ESI):
m/e ¼ 320 (M-H)2. Anal. calcd. for C14H13N2O3S2: C, 52.33; H, 4.05; N,
8.72. Found: C, 52.08; H, 3.98; N, 8.60.
3i0: Yellow solid. Mp .3008C; 1H NMR (400 MHz, DMSO-d6) d 7.81 (s, 1H,
CH55), 7.45 (d, 2H, J ¼ 8.4 Hz), 6.95 (d, 2H, J ¼ 8.4 Hz), 4.95 (s, 2H, CH2);
IR (KBr): 1691, 1514, 1188 cm21; LC/MS (ESI): m/e ¼ 294 (M-H)2. Anal.
calcd. for C12H9NO4S2: C, 48.81; H, 3.05; N, 4.75. Found: C, 48.55; H, 3.00;
N, 4.68.
1
3j0: Bright yellow solid. Mp 290–2938C; H NMR (400 MHz, DMSO-d6) d
7.76 (s, 1H, CH55), 7.50 (s, 1H, Ar-H), 7.42 (d, 1H, J ¼ 8.4 Hz), 6.90
(d, 1H, J ¼ 8.4 Hz), 4.94 (2H, s, CH2); IR (KBr): 1701, 1514, 1194 cm21
;
LC/MS (ESI): m/e ¼ 338 (M-H)2. Anal. calcd. for C14H13NO5S2: C,
49.58; H, 4.3.83; N, 4.13. Found: C, 49.32; H, 3.77; N, 4.07.
ACKNOWLEDGMENT
We thank the National Natural Science Foundation of China (No. 20571029)
and Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials for
financial support.
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