ChemInform Abstract: Ecofriendly Synthesis of Thieno[2,3-b]pyridines Derivatives

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Monatshefte für Chemie - ChemicalMonthlyAn International Journal of Chemistry ISSN 0026-9247Volume 144Number 5 Monatsh Chem (2013) 144:687-693DOI 10.1007/s00706-012-0850-1

Eco-friendly synthesis of highly substitutedfunctionalized oxazines by FeCl3/SiO2nanoparticles

Javad Safaei Ghomi & Safura Zahedi

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ORIGINAL PAPER

Eco-friendly synthesis of highly substituted functionalizedoxazines by FeCl3/SiO2 nanoparticles

Javad Safaei Ghomi • Safura Zahedi

Received: 21 December 2011 / Accepted: 23 August 2012 / Published online: 22 September 2012

� Springer-Verlag 2012

Abstract An efficient and modern method for the prep-

aration of amidoalkyl naphthols in the presence of silica

nanoparticle-supported ferric chloride under thermal sol-

vent-free conditions is explained. The prepared amidoalkyl

naphthols were converted to 1,3-oxazines by Vilsmeier

reagent in the presence of FeCl3/SiO2 nanoparticles. This

method provides a novel route to synthesis amidoalkyl

naphthol and 1,3-oxazine derivatives in terms of good

yields, short reaction times, and recyclable catalyst.

Keywords Amidoalkyl naphthol � Oxazine �Heterogeneous catalysis � One-pot synthesis � Solvent-free

Introduction

The synthesis of 1,3-oxazines has attracted attention in the

past because of their potential as antibiotics [1], antitumor

agents [2], analgesics [3], and anticonvulsants [4]. In

addition, benzo-1,3-oxazines are known to be biologically

active as anti-malarial [5], antianginal [6], anti-hyperten-

sive [7], and potent anti-rheumatic agents [8]. Hence, the

synthesis of these derivatives is of considerable interest.

Several methods for the preparations of 1,3-oxazine

derivatives have previously been reported [9]. The Vils-

meier-Haack reagent is an efficient, economical, and mild

reagent for the synthesis of highly functionalized oxazines

via different methods. However, some of the reported

methods suffer from disadvantages such as long reaction

times [10] and harsh reaction conditions [11]. Therefore, to

avoid these limitations, the discovery of a new, easily

available catalyst with high catalytic activity and short

reaction time for the preparation of 1,3-oxazines is still

desirable.

In a desired procedure, 1,3-oxazines were prepared by

amidoalkyl naphthols, which were synthesized by Lewis or

Brønsted acid catalysts such as p-toluenesulfonic acid [12],

H2NSO3H [13], oxalic acid [14], Fe(HSO4)3 [15], Sr(OTf)2

[16], I2 [17], K5CoW12O40�3H2O [18], HPMo [19],

Yb(OTf)3 in ionic liquid [20], indion-130 [21], montmoril-

lonite K10 [22], TMSCl/NaI [23], Al2O3–HClO4 [24], InCl3[25], 2,4,6-trichloro-1,3,5-triazine [26], CuPW and CuPMo

[27], FeCl3/SiO2[28], H4SiW12O40 [29], and CPTS [30].

We herein describe a new, convenient method for the

synthesis of amidoalkyl naphthols by multicomponent

reaction of 2-naphthol, aromatic aldehydes, and acetamide

catalyzed by FeCl3/SiO2 nanoparticles (NPs) under sol-

vent-free conditions. Then, the prepared amidoalkyl

naphthols were treated with Vilsmeier reagent in the

presence of FeCl3/SiO2 NPs to give oxazine derivatives

(Scheme 1; Table 1).

Results and discussion

It was of particular interest to us to study the application of

FeCl3/SiO2 NPs to the intramolecular cyclization of

amidoalkyl naphthols by Vilsmeier reagent. Hence, first we

prepared amidoalkyl naphthols as precursors to the prepa-

ration of oxazines. In order to select the best catalyst, the

reaction was carried out by treatment of benzaldehyde,

2-naphthol, and acetamide, and also the cyclization of

J. S. Ghomi (&)

Department of Chemistry, Qom Branch,

Islamic Azad University, Qom, Islamic Republic Iran

e-mail: [email protected]

S. Zahedi

Faculty of Chemistry, Department of Organic Chemistry,

University of Kashan, Kashan 51167, Islamic Republic Iran

123

Monatsh Chem (2013) 144:687–693

DOI 10.1007/s00706-012-0850-1

Author's personal copy

prepared amidoalkyl naphthols in the presence of FeCl3,

SiO2 NPs, and FeCl3/SiO2 NPs. The best yields were

obtained in the presence of FeCl3/SiO2 NPs. Notably,

amidoalkyl naphthols could not be obtained under similar Fig. 1 SEM image of FeCl3/SiO2 NPs

Table 1 Synthesis of amidoalkyl naphthols 4 and 1,3-oxazines 5 in the presence of FeCl3/SiO2 NPs (Scheme 1)

Entry Ar 4 Time/min Yielda/% M.p./�C (lit. m.p./�C) 5 Time/min Yielda/% M.p./�C

1 Ph 4a 10 88 245–246 (242–244) [30] 5a 30 88 235–237

2 4-NO2-Ph 4b 7 95 247–249 (248–250) [28] 5b 30 92 263-264

3 2-NO2-Ph 4c 8 92 178–180 (179–182) [28] 5c 30 92 255–257

4 4-Cl-Ph 4d 8 90 223–225 (223–225) [28] 5d 30 88 232–234

5 2,4-Cl2-Ph 4e 8 89 200–202 (202–204) [26] 5e 30 80 209–210

6 4-Me-Ph 4f 15 80 222–223 (220–222) [26] 5f 30 79 219–221

7 4-MeO-Ph 4g 17 84 183–185 (185–186) [26] 5g 30 79 205–206

8 4-i-Pr-Ph 4h 20 85 220–222 5h 30 82 228–229

9 4-Br-Ph 4j 8 90 227–229 (228–230) [22] 5j 30 88 237–239

10 4-OH-Ph 4k 15 80 226–227 5k 30 87 241–243

11 2,4-(MeO)2-Ph 4l 17 85 227–229 5l 30 85 250–252

12 1-Naphthyl 4m 15 82 210–220 5m 30 82 245–247

a Yields refer to isolated products

Table 2 Catalytic activity of various catalysts

Entry Catalysta Product 4 Product 5

Time Yieldb/% Time Yieldb/%

1 None 2 h 0 3 h 86 [10]

2 FeCl3 2 h 45 1.5 h 87

3 SiO2 NPs 2 h 40 1.5 h 87

4 FeCl3�SiO2 NPs 10 min 88 30 min 88

a The reaction was carried out under solvent-free conditionsb Isolated yield

Scheme 1

688 J. S. Ghomi, S. Zahedi

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reaction conditions, even after a long time (2 h) in the

absence of the catalyst (Table 2), while cyclization reac-

tions have been reported without using a catalyst for a long

time (3 h) [10].

Table 2 clearly illustrates that, among four mentioned

catalysts, nano-silica-supported ferric chloride is an effec-

tive catalyst in terms of reaction times and yields of

product, because the nano-SiO2 support increases the sur-

face area contact of materials. In order to investigate the

morphology and particle size of FeCl3/SiO2 NPs, a SEM

image of FeCl3/SiO2 NPs is shown in Fig. 1. As can be

seen, the sample shows a nanocrystalline structure.

To determine the best experimental conditions, the

reaction of benzaldehyde, 2-naphthol, and acetamide was

considered the model. The best results were obtained in the

presence of 0.1 mg (0.4 mol %) FeCl3/SiO2 NPs under

solvent-free conditions at 110 �C. We next investigated the

cyclization reaction of amidoalkyl naphthols, and for this

we selected the model reaction of N-[(2-hydroxy-1-naph-

thyl)(phenyl)methyl]acetamide, DMF, and POCl3. After

several attempts, reasonable results were obtained in the

presence of 0.1 mg (0.4 mol %) FeCl3/SiO2 NPs at 80 �C.

The results are summarized in Table 3.

In order to check the recyclability of the catalyst after

completion of the reaction, the reaction mixture was fil-

trated and the catalyst was recovered. Then the catalyst was

recycled five times without appreciable loss in catalytic

activity.

A plausible mechanism for the synthesis of substituted

oxazines 5 is presented in Scheme 2. In the suggested

mechanism, we have proposed that an acid–base interaction

between FeCl3–SiO2 NPs and a lone pair of oxygen polar-

izes the C=O bond of DMF for the in situ formation of the

chloromethyleniminium intermediate A, which is respon-

sible for the formylation. The enolizable ketone moiety of

the amidoalkyl naphthol derivative 4 readily reacts with the

chloromethylenedimethylammonium chloride intermediate

at the active methylene position of 6 to yield the interme-

diate 7, which undergoes dehydrochlorination to form

intermediate 8. The latter undergoes cyclization to inter-

mediate 9, which spontaneously undergoes dehydroxylation

to form the intermediate 10. Attack of another Vilsmeier

intermediate to 10 leads to the formation of intermediate 11,

the hydrolysis of which gives the product 5.

In summary, we have introduced novel ferric chloride-

supported silica nanoparticles (FeCl3/SiO2 NPs) as highly

efficient and green catalysts for organic transformations.

Currently, the synthesis of amidoalkyl naphthols and

oxazine derivatives was efficiently catalyzed by FeCl3/

SiO2 NPs. These applications are attractive because of the

considerable advantages such as simplicity of operation,

high product yields, short reaction times, solvent-free

conditions, and the use of an inexpensive and recyclable

catalyst.

Experimental

All reagents were purchased from Merck and Aldrich and

used without further purification. The reactions were

monitored by TLC using 0.2-mm Merck silica gel 60 F254

pre-coated plates, which were visualized with UV light.

Melting points were measured on an Electrothermal 9200

apparatus. The IR spectra were recorded on an FT-IR

Magna 550 apparatus using KBr discs. 1H NMR and 13C

NMR spectra were recorded on a Bruker Avance DRX-400

instrument using TMS as the internal standard. The ele-

mental analyses (C, H, N) were obtained from a Carlo

ERBA Model EA 1108 analyzer. Microscopic morphology

of products was examined by SEM (LEO 1455VP).

Preparation of nano-silica-supported ferric chloride

In a 100-cm3 flask, 25 g nano silica gel and 2 g

FeCl3�6H2O (8 % of the weight of nano-SiO2) were vig-

orously stirred under solvent-free conditions at room

temperature for 24 h to achieve homogeneous adsorption.

A pale yellowish-green product was obtained.

Table 3 The best experimental

conditions for preparation of

amidoalkyl naphthols 4 and

oxazines 5

a Isolated yield

Entry Catalyst/mg Product 4 Product 5

Temp/�C Time/min Yielda/% Temperature/�C Time/min Yielda/%

1 0.05 90 30 56 Room temperature 120 0

2 0.05 110 25 64 50 60 35

3 0.05 130 20 69 80 50 67

4 0.1 90 25 73 40 50 55

5 0.1 110 10 88 60 40 68

6 0.1 130 10 88 80 30 88

7 0.2 110 10 88 80 30 88

8 0.3 110 10 88 80 30 88

Eco-friendly synthesis of highly substituted functionalized oxazines 689

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General procedure for the synthesis of amidoalkyl

naphthols 4a–4m

A mixture of 0.14 g b-naphthol (1 mmol), aldehyde

(1 mmol), 0.07 g acetamide (1.2 mmol), and 0.1 mg

FeCl3/SiO2 NPs (0.4 mol %) was finely ground and heated

with stirring at 110 �C in an oil bath, and the reaction was

monitored by TLC. After cooling, the reaction mixture was

dissolved in hot ethanol, and the mixture was stirred for

5 min. The reaction mixture was filtered, and the hetero-

geneous catalyst was recovered. Then the crude product

was crystallized from EtOH (15 %) to afford the pure

product. The products were characterized by comparison of

their physical data with those of known compounds unless

otherwise mentioned.

N-[(2-Hydroxynaphthalen-1-yl)(4-isopropylphenyl)-

methyl]acetamide (4h, C22H24NO2)

White solid; IR (KBr): �m = 3,405, 3,168, 3,058, 1,633,

1,515, 1,438, 1,370, 1,330, 1,275, 1,168, 986, 816,

744 cm-1; 1H NMR (400 MHz, DMSO-d6): d = 1.14 (d,

6H), 1.95 (s, 3H), 2.81 (m, 1H), 7.06–7.11 (m, 5H), 7.19 (t,

J = 7.2 Hz, 1H), 7.27 (t, J = 7.6 Hz, 1H), 7.36 (t, 1H),

SiO2

Scheme 2


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7.75 (d, 1H), 7.80 (d, 1H), 7.88 (d, 1H), 8.43 (d,

J = 8.4 Hz, 1H), 9.96 (s, 1H) ppm; 13C NMR (100 MHz,

DMSO-d6): d = 23.1, 24.4, 33.4, 48.3, 119.0, 119.4, 122.8,

123.0, 123.6, 126.3, 126.6, 126.7, 128.0, 128.9, 129.0,

129.5, 132.8, 140.3, 146.6, 153.5, 169.5 ppm.

N-[(2-Hydroxynaphthalen-1-yl)(4-hydroxyphenyl)-

methyl]acetamide (4k, C19H17NO3)


1,514, 1,438, 1,370, 1,330, 1,275, 1,168, 986, 813,

738 cm-1; 1H NMR (400 MHz, DMSO-d6): d = 1.97 (s,

3H), 7.04–7.09 (m, 5H), 7.19 (t, J = 7.2 Hz, 1H), 7.25 (t,

J = 7.6 Hz, 1H), 7.36 (t, 1H), 7.77 (d, 1H), 7.80 (d, 1H),

7.88 (d, 1H), 8.55 (d, J = 8.4 Hz, 1H), 9.20 (s, 1H), 9.87

(s, 1H) ppm; 13C NMR (100 MHz, DMSO-d6): d = 23.4,

48.5, 119.3, 120.1, 122.8, 123.0, 123.6, 126.3, 126.6,

126.7, 128.0, 128.9, 129.0, 129.5, 132.8, 140.3, 146.8,

153.2, 168.9 ppm.

N-[(2,4-Dimethoxyphenyl)(2-hydroxynaphthalen-1-yl)-

methyl]acetamide (4l, C21H21NO4)

Yellow solid; IR (KBr): �m = 3,406, 3,139, 1,646, 1,521,

1,506, 1,442, 1,400, 1,374, 1,329, 1,264, 1,242, 1,091,

1,068, 818, 764, 659 cm-1; 1H NMR (400 MHz, DMSO-

d6): d = 1.90 (s, 3H), 3.72 (s, 6H), 6.89–7.01 (m, 2H), 7.17

(d, J = 8.4 Hz, 1H), 7.29 (t, J = 7.2 Hz, 1H), 7.33-7.39

(m, 2H), 7.46 (d, J = 8.4 Hz, 1H), 7.74–7.79 (m, 3H), 8.55

(d, J = 7.6 Hz, 1H), 9.98 (s, 1H) ppm; 13C NMR

(100 MHz, DMSO-d6): d = 23.3, 48.7, 55.2, 55.9, 110.4,

118.6, 118.8, 123.2, 126.9, 128.5, 129.1, 129.5, 129.7,

130.5, 131.6, 132.8, 144.9, 149.3, 153.7, 153.9, 170.2 ppm.

N-[(2-Hydroxynaphthalen-1-yl)(naphthalen-1-yl)-

methyl]acetamide (4m, C23H19NO2)


1,572, 1,514, 1,437, 1,400, 1,374, 1,332, 1,274, 1,224,

1,172, 932, 813, 745 cm-1; 1H NMR (400 MHz, DMSO-

d6): d = 1.90 (s, 3H), 7.22–7.29 (m, 3H), 7.39–7.44 (m,

4H), 7.61 (d, 1H), 7.70–7.80 (m, 3H), 7.91–8.03 (d, 3H),

8.70 (d, 1H), 10.01 (s, 1H) ppm; 13C NMR (100 MHz,

DMSO-d6): d = 22.9, 47.4, 117.6, 118.7, 119.3, 122.8,

123.5, 123.9, 125.5, 125.7, 125.9, 126.5, 126.7, 127.9,

129.0, 129.2, 129.7, 131.5, 133.3, 134.0, 137.8, 153.8,

168.9 ppm.

General procedure for the synthesis of 1,3-oxazines

5a–5m

To a solution of acetamidonaphthol 4 (1 mmol) and 0.1 mg

FeCl3/SiO2 NPs dissolved in DMF (1.2 equiv.), POCl3 (0.8

eqiuvalent) was added slowly dropwise (15 min) at 0 �C,

and the reaction mixture was allowed to reach room tem-

perature. Then the reaction mixture was stirred at 80 �C for

30 min. After completion of the reaction, it was allowed to

cool to room temperature. The reaction mixture was fil-

tered, and the heterogeneous catalyst was recovered. The

filtrate was poured into crushed ice and refrigerated over-

night. The solution was neutralized with sodium acetate,

and the crude compound was extracted with dichloro-

methane (3 9 10 cm3) and washed with water (3 9

5 cm3). The organic layer was dried over anhydrous

sodium sulfate and concentrated under reduced pressure.

The crude product was purified through crystallization

from EtOH to afford the pure product.

(1,2-Dihydro-1-phenyl-3H-naphtho[1,2-e][1,3]oxazine-3-

ylidene)malonaldehyde (5a, C21H15NO3)


1,221, 828 cm-1; 1H NMR (400 MHz, CDCl3): d = 6.24

(s, 1H), 7.13–7.15 (d, 2H), 7.17–7.21 (d, 2H), 7.48–7.49 (t,

3H), 7.76 (t, 2H), 7.90 (d, 1H), 7.97 (d, 1H), 10.04 (br s,

2H, CHO), 12.33 (s, 1H) ppm; 13C NMR (100 MHz,

CDCl3): d = 50.6, 101.1, 113.6, 118.3, 123.2, 124.7,

127.3, 128.8, 129.6, 130.4, 131.7, 132.9, 134.5, 143.6,

144.9, 148.4, 162.3, 186.9 ppm.

[1,2-Dihydro-1-(4-nitrophenyl)-3H-naphtho[1,2-e][1,3]-

oxazine-3-ylidene]malonaldehyde (5b, C21H14N2O5)


1,221, 828 cm-1; 1H NMR (400 MHz, CDCl3): d = 6.23

(s, 1H), 7.10–7.14 (d, 2H), 7.17–7.21 (d, 2H), 7.46–7.49 (t,

3H), 7.61 (d, 1H), 7.88 (d, 1H), 7.96 (d, 1H), 10.02 (br s,


CDCl3): d = 50.3, 101.3, 113.4, 117.9, 123.3, 125.7,

127.3, 128.5, 128.9, 129.6, 130.4, 131.7, 131.8, 132.9,

134.5, 143.6, 144.9, 148.4, 162.6, 187.0 ppm.

[1,2-Dihydro-1-(2-nitrophenyl)-3H-naphtho[1,2-e][1,3]-

oxazine-3-ylidene]malonaldehyde (5c, C21H14N2O5)


1,221, 825 cm-1; 1H NMR (400 MHz, CDCl3): d = 6.23

(s, 1H), 7.10–7.14 (d, 2H), 7.17–7.21 (t, 2H), 7.46–7.49 (t,

3H), 7.61 (d, 1H), 7.88 (d, 1H), 7.96 (d, 1H), 10.01 (br s,


CDCl3): d = 48.9, 101.1, 113.7, 118.4, 123.3, 125.7,

127.3, 128.5, 128.9, 129.6, 130.4, 131.7, 131.8, 132.9,

134.5, 143.2, 144.5, 148.2, 162.3, 186.8 ppm.

[1-(4-Chlorophenyl)-1,2-dihydro-3H-naphtho[1,2-e][1,3]-

oxazine-3-ylidene]malonaldehyde (5d, C21H14ClNO3)


1,221, 831 cm-1; 1H NMR (400 MHz, CDCl3): d = 6.21

(s, 1H), 7.12–7.14 (d, 2H), 7.19–7.25 (d, 2H), 7.46–7.49 (t,

3H), 7.61 (d, 1H), 7.88 (d, 1H), 7.96 (d, 1H), 10.01 (br s,


CDCl3): d = 50.4, 101.1, 113.4, 117.9, 123.3, 125.7,

127.3, 128.5, 128.9, 129.6, 130.4, 131.7, 131.8, 132.9,

134.5, 143.6, 144.9, 148.4, 163.1, 186.7 ppm.


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[1-(2,4-Dichlorophenyl)-1,2-dihydro-3H-naphtho[1,2-e][1,3]-

oxazine-3-ylidene]malonaldehyde (5e, C21H13Cl2NO3)


1,220, 826 cm-1; 1H NMR (400 MHz, CDCl3): d = 6.22

(s, 1H), 7.19–7.25 (d, 2H), 7.49–7.62 (d, 2H), 7.65–7.70 (d,

2H), 7.89–7.93 (d, 2H), 8.11 (s, 1H), 10.03 (br s, 2H,

CHO), 12.28 (s, 1H) ppm; 13C NMR (100 MHz, CDCl3):

d = 50.3, 101.3, 113.4, 117.2, 123.1, 124.3, 126.8, 128.8,

128.9, 129.6, 130.1, 131.7, 131.8, 131.9, 134.5, 143.0,

144.8, 148.6, 162.1, 186.7 ppm.

[1,2-Dihydro-1-(4-methylphenyl)-3H-naphtho[1,2-e][1,3]-

oxazine-3-ylidene]malonaldehyde (5f, C22H17NO3)


1,219, 821 cm-1; 1H NMR (400 MHz, CDCl3): d = 2.30

(s, 3H), 6.20 (s, 1H), 7.10–7.13 (d, 2H), 7.15–7.20 (d, 2H),

7.42–7.48 (t, 3H), 7.58 (d, 1H), 7.84 (d, 1H), 7.97 (d, 1H),

10.03 (br s, 2H, CHO), 12.26 (s, 1H) ppm; 13C NMR

(100 MHz, CDCl3): d = 23.3, 50.2, 101.1, 113.4, 117.9,

123.3, 125.7, 127.3, 128.5, 128.9, 129.6, 130.4, 131.7,

131.8, 132.9, 134.5, 142.9, 144.4, 147.8, 162.2, 186.8 ppm.

[1,2-Dihydro-1-(4-methoxyphenyl)-3H-naphtho[1,2-e][1,3]-

oxazine-3-ylidene]malonaldehyde (5g, C22H17NO4)


1,220, 819 cm-1; 1H NMR (400 MHz, CDCl3): d = 3.48

(s, 3H), 6.21 (s, 1H), 7.18-7.26 (d, 2H), 7.45-7.60 (d, 2H),

7.63-7.72 (d, 2H), 7.87–7.91 (d, 2H), 8.08 (s, 1H), 10.02

(br s, 2H, CHO), 12.24 (s, 1H) ppm; 13C NMR (100 MHz,

CDCl3): d = 33.5, 50.1, 101.1, 113.4, 117.2, 123.1, 124.3,

126.8, 128.8, 128.9, 129.6, 130.4, 131.7, 131.8, 131.9,

134.2, 143.5, 145.4, 148.4, 162.2, 187.2 ppm.

[1,2-Dihydro-1-(4-isopropylphenyl)-3H-naphtho[1,2-e][1,3]-

oxazine-3-ylidene]malonaldehyde (5h, C24H21NO3)


1,220, 834 cm-1; 1H NMR (400 MHz, CDCl3): d = 1.19

(d, 6H), 2.84 (m, 1H), 6.20 (s, 1H), 7.19–7.25 (d, 3H),

7.49–7.62 (t, 3H), 7.89–7.93 (t, 2H), 8.12 (m, 2H), 10.02


CDCl3): d = 23.2, 33.5, 50.3, 101.3, 113.4, 117.2, 123.1,

124.3, 126.8, 128.8, 128.9, 129.6, 130.1, 131.7, 131.8,

131.9, 134.5, 143.0, 144.8, 148.6, 162.1, 186.7 ppm.

[1-(4-Bromophenyl)-1,2-dihydro-3H-naphtho[1,2-e][1,3]-

oxazine-3-ylidene]malonaldehyde (5j, C21H14BrNO3)


1,220, 815 cm-1; 1H NMR (400 MHz, CDCl3): d = 6.20

(s, 1H), 7.13–7.15 (d, 2H), 7.18–7.20 (d, 2H), 7.46–7.49 (t,

3H), 7.61 (d, 1H), 7.88 (d, 1H), 7.96 (d, 1H), 10.01 (br s,


CDCl3): d = 50.5, 101.1, 113.3, 118.2, 123.5, 124.4,

127.3, 128.8, 128.9, 129.6, 130.2, 131.7, 131.8, 131.9,

134.5, 143.6, 145.4, 148.6, 162.4, 186.8 ppm.

[1,2-Dihydro-1-(4-hydroxyphenyl)-3H-naphtho[1,2-e][1,3]-

oxazine-3-ylidene]malonaldehyde (5k, C21H15NO4)


1,220, 822 cm-1; 1H NMR (400 MHz, CDCl3): d = 6.23

(s, 1H), 7.18–7.24 (d, 2H), 7.47–7.63 (d, 2H), 7.63–7.71 (d,

2H), 7.89–7.93 (d, 2H), 8.11 (s, 1H), 9.45 (s, 1H), 10.01 (br

s, 2H, CHO), 12.29 (s, 1H) ppm; 13C NMR (100 MHz,

CDCl3): d = 50.3, 101.3, 113.4, 117.2, 123.1, 124.3,

126.8, 128.8, 128.9, 129.6, 130.1, 131.7, 131.8, 131.9,

134.5, 143.0, 144.8, 148.6, 162.1, 186.7 ppm.

[1-(2,4-Dimethoxyphenyl)-1,2-dihydro-3H-naphtho[1,2-e]-

[1,3]oxazine-3-ylidene]malonaldehyde (5l, C23H19NO5)


1,220, 821 cm-1; 1H NMR (400 MHz, CDCl3): d = 3.72

(s, 6H), 6.22 (s, 1H), 7.19–7.25 (d, 2H), 7.49–7.62 (d, 2H),

7.65–7.70 (d, 2H), 7.89–7.93 (d, 2H), 8.11 (s, 1H), 10.03


CDCl3): d = 50.1, 53.5, 53.6, 101.2, 113.4, 117.2, 123.1,

124.3, 126.8, 128.8, 128.9, 129.6, 130.2, 131.7, 131.8,

131.9, 134.5, 143.0, 144.8, 148.4, 163.6, 186.9 ppm.

[1,2-Dihydro-1-(naphthalen-1-yl)-3H-naphtho[1,2-e][1,3]-

oxazine-3-ylidene]malonaldehyde (5m, C25H17NO3)


1,220, 826 cm-1; 1H NMR (400 MHz, CDCl3):

d = 7.20–7.27 (m, 3H), 7.36–7.42 (m, 4H), 7.61 (d, 1H),

7.70–7.82 (m, 3H), 7.89–8.01 (d, 3H), 8.77(d, 1H), 10.01


DMSO-d6): d = 53.4, 101.1, 118.7, 119.3, 122.8, 123.5,

123.9, 125.5, 125.7, 125.9, 126.5, 126.7, 127.9, 129.0,

129.2, 129.7, 131.5, 133.3, 134.0, 137.8, 144.8, 148.4,

163.6, 186.9 ppm.

Acknowledgments The authors are grateful to Islamic Azad Uni-

versity, Qom Branch, for financial support of this work.

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ChemInform Abstract: Ecofriendly Synthesis of Thieno[2,3-b]pyridines Derivatives

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