Synthesis and fluorescence studies of novel ...Draft 3 Introduction 1 Aldol condensation reaction is...

Draft

Synthesis and fluorescence studies of novel

bisarylmethylidene derivatives of 2-methoxy-2-methyl-1,3-

dioxan-5-one

Journal: Canadian Journal of Chemistry

Manuscript ID cjc-2017-0099.R1

Manuscript Type: Article

Date Submitted by the Author: 12-Apr-2017

Complete List of Authors: Mojtahedi, Mohammad; Chemistry and Chemical Engineering Research

Center of Iran, Darvishi, Kiana; Chemistry and Chemical Engineering Research Center of Iran Abaee, Mohammad Saeed; Chemistry and Chemical Engineering Research Center of Iran, Organic Chemistry, Organic Chemistry Halvagar , Mohammad R. ; Chemistry and Chemical Engineering Research Center of Iran

Is the invited manuscript for consideration in a Special

Issue?: N/A

Keyword: Bisarylmethylidene derivatives, dioxanone, fluorescent, chalcones, aldol condensation

https://mc06.manuscriptcentral.com/cjc-pubs

Canadian Journal of Chemistry

Draft

1

Synthesis and fluorescence studies of novel bisarylmethylidene derivatives of 2-methoxy- 1

2-methyl-1,3-dioxan-5-one 2

3

Mohammad M. Mojtahedi, Kiana Darvishi, M. Saeed Abaee, Mohammad R. Halvagar 4

Department of Organic Chemistry and Natural Products, Chemistry and Chemical 5

Engineering Research Center of Iran, Pajohesh Blvrd., 17th km of Tehran-Karaj Highway, 6

P.O.Box 14335-186, Tehran, Iran 7

Tel: (+98)21-44787749 8

Fax: (+98)21-44787785 9

Corresponding author's e-mail: [email protected] 10

11

Page 1 of 21



Draft

2

Abstract: The first general procedure is described for the synthesis of novel 1

bisarylmethylidenes of 2-methoxy-2-methyl-1,3-dioxan-5-one 1. Thus, several derivatives of 2

3 are obtained rapidly in high yields by reacting 1 with different aldehydes in the presence of 3

catalytic quantities of pyrrolidine in EtOH at rt. Upon completion of the reactions, products 4

are obtained directly by spontaneous precipitation avoiding time consuming and expensive 5

chromatographic separations. All products were characterized by proton and carbon NMR 6

spectroscopy methods, and in one case, the proposed structure was elucidated by X-ray 7

crystallography, confirming the Z stereochemistry for the olefinic C=C bonds. Due to showing 8

different colors in solid and solution states, products were studied for their photophysical 9

properties as well. 10

11

Key words: Bisarylmethylidene derivatives, dioxanone, fluorescent, chalcones, aldol 12

condensation. 13

14

Resume: 15

16

Page 2 of 21



Draft

3

Introduction 1

Aldol condensation reaction is arguably the most important route for the preparation of C=C 2

bonds conjugated with carbonyl groups.1 The two unsaturated sites together constitute the 3

chalcone entities2 which occur in many natural products3 and biologically important 4

structures.4 In addition, molecules containing the C=C─C=O functionalities are reactive 5

moieties and act as useful intermediates for further synthetic manipulations to access more 6

complex structures,5 polymers,6 and other compounds of interest.7 7

A well-studied group of chalcones are the bisarylmethylidene derivatives of cyclic ketones.8 8

These compounds are mainly synthesized through various aldol condensation reactions9 and 9

possess interesting biological,10 medicinal,11 and industrial12 properties. Alternatively, they 10

are studied for their optical,13 dye,14 or liquid crystal15 features. In the framework of our 11

investigations on the aldol condensation reaction,16 we have published several reports on the 12

synthesis of bisarylmethylidene derivatives of homocyclic17 and heterocyclic18 ketones. In 13

continuation, we were persuaded to extend this chemistry to 2-methoxy-2-methyl-1,3-dioxan- 14

5-one 1 system, which in reaction with various aldehydes efficiently produce the 15

corresponding products 3 under very mild conditions (Fig. 1). 16

17 Fig. 1. Synthesis of 3. 18

19

The ketone 1 was selected for this study due to the importance this type of heterocycles has 20

found in the synthesis of many useful target structures.19 As far as we know, no paper is 21

available in the literature on the synthesis of 3 and there is only one patent20 dealing with this 22

chemistry without presenting a general procedure or reporting the characterization data of the 23

products, although this patent illustrates the use of the target compounds as dyes, fluorescent 24

Page 3 of 21



Draft

4

compounds, and candidates for electronic devices. In the present work, we offer the first 1

practical method for the synthesis of the target products along with their full spectroscopic 2

analyses and one example of X-ray crystallography. The products are also explored for their 3

photophysical properties. 4

5

Experimental 6

General 7

Melting points are uncorrected. FT-IR spectra were recorded using KBr disks on a Bruker 8

Vector-22 spectrometer. NMR spectra were obtained on a FT-NMR Bruker Ultra ShieldTM 9

(500 MHz for 1H and 125 MHz for 13C) or Bruker DRX-400 AVANCE (400 MHz for 1H and 10

100 MHz for 13C) as CDCl3 or DMSO-d6 solutions using TMS as internal standard reference. 11

Elemental analyses were performed using a Thermo Finnigan Flash EA 1112 instrument. MS 12

spectra were obtained on a Finnigan Mat 8430 instrument at ionization potential of 70 eV. All 13

fluorescence measurements were carried out on a Jasco (Japan) FP-6500 spectrofluorimeter 14

equipped with 1.00 cm quartz cells and a 150 W Xe lamp. TLC experiments were carried out 15

on pre-coated silica gel plates using petroleum ether/EtOAc as the eluent. Chemicals and 16

starting materials were purchased from commercial sources. Aldehydes were redistilled or 17

recrystallized before being used. 18

Synthesis of ketone 1 19

A mixture of dimer of dihydroxyacetone (8.08 g, 44.8 mmol) and camphor-10-sulfonic acid 20

(105 mg, 452 µmol) in dioxane (300 mL) was heated at 60 °C under argon. After 10 minutes, 21

trimethyl orthoacetate (120 mL, 948 mmol) was added to the mixture. The solution was 22

stirred overnight at 60 °C. The mixture was concentrated under reduced pressure and the 23

residue was distilled (170 °C/200 torr) to obtain 8.9 g of 1 as a clear and colorless liquid.21 24

Typical procedure for the synthesis of 3 25

Page 4 of 21



Draft

5

A mixture of ketone 1 (1.0 mmol), an aldehyde (2.0 mmol), and pyrrolidine (25 µl, 30 mol%) 1

in ethanol (1 mL) was stirred at room temperature for the time indicated in Table 2. The 2

completion of the reaction was monitored with TLC (petroleum ether/EtOAc:10:1). The 3

product precipitated in the mixture. The crude solid product was purified by recrystallization 4

from EtOH. Solid products 3a-k were obtained in 75-97% yields. 5

Characterization data of new products 6

(4Z,6Z)-4,6-Bis(4-methylbenzylidene)-2-methoxy-2-methyl-1,3-dioxan-5-one (3a) 7

Yellow solid; mp 130-132 oC; 1H NMR (500 MHz, CDCl3) 1.99 (s, 3H, Me), 2.39 (s, 6H, 8

Me), 3.37 (s, 3H, OMe), 6.94 (s, 2H, =CH), 7.22 (d, J = 8.0 Hz, 4H), 7.70 (d, J = 8.0 Hz, 4H) 9

ppm; 13C NMR (125 MHz, CDCl3) 21.5, 22.0, 52.4, 113.3, 116.4, 129.8, 130.9, 131.2, 139.8, 10

144.0, 177.7 ppm; IR (KBr, cm-1) 2967, 1686, 1590, 1280; MS (70 eV) m/z 350 (M+), 318, 11

274, 260; Anal. Calcd for C22H22O4: C, 75.41; H, 6.33. Found: C, 75.37; H, 6.25. 12

(4Z,6Z)-4,6-Bis(4-methoxybenzylidene)-2-methoxy-2-methyl-1,3-dioxan-5-one (3b) 13


OMe), 3.84 (s, 6H, OMe), 6.91 (s, 2H, =CH), 6.93 (d, J = 8.5 Hz, 4H), 7.76 (d, J = 8.5 Hz, 15

4H) ppm; 13C NMR (125 MHz, CDCl3) 21.6, 52.4, 55.7, 113.3, 114.6, 116.2, 126.6, 132.9, 16

143.2, 160.7, 177.5 ppm; IR (KBr, cm-1) 2940, 1685, 1590, 1252; MS (70 eV): m/z 382, 353, 17

306, 148; Anal. Calcd for C22H22O6: C, 69.10; H, 5.80. Found: C, 68.92; H, 5.45. 18

(4Z,6Z)-4,6-Bis(4-(methylthio)benzylidene)-2-methoxy-2-methyl-1,3-dioxan-5-one (3c) 19


SMe), 3.35 (s, 3H, OMe), 6.90 (s, 2H, =CH), 7.25 (d J = 8.5 Hz, 4H), 7.70 (4H, d, J = 8.5 Hz) 21

ppm; 13C NMR (125 MHz, CDCl3) 15.6, 21.5, 52.5, 113.4, 116.0, 126.3, 130.2, 131.5, 140.9, 22

144.1, 177.2 ppm; IR (KBr, cm-1): 2922, 1681, 1281; MS (70 eV) m/z 414, 373, 220, 194, 23

164; Anal. Calcd for C22H22O4S2: C, 63.74; H, 5.35. Found: C, 63.16; H, 5.22. 24

Page 5 of 21



Draft

6

(4Z,6Z)-4,6-Bis(4-(dimethylamino)benzylidene)-2-methoxy-2-methyl-1,3-dioxan-5-one 1

(3d) 2

Red solid; mp 219-220 oC; 1H NMR (500 MHz, CDCl3) 1.95 (s, 3H, Me), 3.05 (s, 12H, 3

NMe), 3.37 (s, 3H, OMe), 6.70 (d, J = 9.0 Hz, 4H), 6.93 (2H, s, =CH), 7.72 (4H, d, J = 9.0 4

Hz) ppm; 13C NMR (125 MHz, CDCl3) 21.8, 40.5, 52.2, 112.3, 113.0, 117.2, 122.1, 132.9, 5

142.4, 151.0, 177.0 ppm; IR (KBr, cm-1) 2895, 1592, 1298, 1158; MS (70 eV) m/z 408 (M+), 6

334, 306, 191, 161; Anal. Calcd for C24H28N2O4: C, 70.57; H, 6.91. Found: C, 70.19; H, 6.57. 7

(4Z,6Z)-4,6-Bis(2,4,5-trimethoxybenzylidene)-2-methoxy-2-methyl-1,3-dioxan-5-one (3e) 8

Orange solid; mp 180-182 oC; 1H NMR (500 MHz, CDCl3) δ 1.92 (s, 3H, Me), 3.37 (s, 3H, 9

Me), 3.77 (s, 6H) 3.80 (s, 6H), 3.93 (s, 6H), 6.51 (s, 2H), 7.43 (s, 2H), 7.83 (s, 2H) ppm; 13C 10

NMR (125 MHz, CDCl3) δ 21.6, 52.3, 56.4, 56.6, 56.9, 97.0, 110.1, 112.9, 113.9, 114.7, 11

143.1, 143.2, 151.4, 154.6, 177.0 ppm; IR (KBr, cm-1) 2942, 1672, 1594, 1256; MS (70 eV): 12

m/z 502 (M+), 484, 454, 428, 195; Anal. Calcd for C26H30O10: C, 62.14; H, 6.02. Found: C, 13

62.33; H, 5.91. 14

(4Z,6Z)-4,6-Bis(3,4-dimethoxybenzylidene)-2-methoxy-2-methyl-1,3-dioxan-5-one (3f) 15

Orange solid; mp 134-135 oC; 1HNMR (500 MHz, CDCl3) 1.95 (s, 3H, Me), 3.36 (s, 3H, 16

OMe), 3.89 (s, 12H, OMe), 6.88 (d, J = 10.0 Hz, 2H), 6.90 (s, 2H, =CH), 7.36 (d, J = 10.0 Hz, 17

2H), 7.45 (s, 2H) ppm; 13C NMR (125 MHz, CDCl3) 21.6, 52.4, 56.1, 56.3, 111.4, 113.1, 18

113.6, 116.5, 125.3, 126.7, 143.3, 149.1, 150.4, 177.2 ppm; IR (KBr, cm-1) 2933, 1685, 1596, 19

1251; MS (70 eV) m/z 442 (M+), 409, 367, 208, 178; Anal. Calcd for C24H26O8: C, 65.15; H, 20

5.92. Found: C, 65.01; H, 5.81. 21

(4Z,6Z)-4,6-Bis(3,4,5-trimethoxybenzylidene)-2-methoxy-2-methyl-1,3-dioxan-5-one (3g) 22


OMe), 3.89 (s, 18H, OMe), 6.88 (s, 2H, =CH), 7.09 (s, 4H) ppm; 13C NMR (125 MHz, 24

CDCl3) 21.4, 52.5, 56.4, 61.4, 108.5, 113.2, 116.6, 129.0, 139.7, 143.8, 153.5, 177.1 ppm; IR 25

Page 6 of 21



Draft

7

(KBr, cm-1) 2941, 1605, 1255; MS (70 eV) m/z 502 (M+), 428, 372, 195; Anal. Calcd for 1

C26H30O10: C, 62.14; H, 6.02. Found: C, 62.32; H, 5.88. 2

(4Z,6Z)-2-Methoxy-2-methyl-4,6-bis((E)-3-phenylallylidene)-1,3-dioxan-5-one (3h) 3


OMe), 6.82 (d, J = 11.5 Hz, 2H, =CH), 6.91 (d, J = 16.0 Hz, 2H, =CH), 7.17 (dd, J = 11.5, 5

16.0, 2H, =CH), 7.26-7.40 (m, 6H), 7.51(d, J = 7.5, 4H) ppm; 13C NMR (125 MHz, CDCl3) 6

21.4, 52.3, 113.5, 118.0, 120.9, 129.1, 127.6, 139.4, 137.2, 144.1, 176.3 ppm; IR (KBr, cm-1): 7

2950, 1674, 1584, 1254; MS (70 eV) m/z 374 (M+), 299, 271, 195; Anal. Calcd for C24H22O4: 8

C, 76.99; H, 5.92. Found: C, 77.15; H, 5.99. 9

(4Z,6Z)-4,6-Bis(4-fluorobenzylidene)-2-methoxy-2-methyl-1,3-dioxan-5-one (3i) 10


OMe), 6.90 (s, 2H, =CH), 7.09 (dd, J = 8.5, 12.0 Hz, 4H, Ar), 7.78 (dd, J = 5.0, 8.5 Hz, 4H, 12

Ar) ppm; 13C NMR (125 MHz, CDCl3) 21.5, 52.5, 113.4, 115.2, 116.2 (d J = 21.5 Hz), 129.8, 13

133.1 (d, J = 8.0 Hz), 143.9. 164 (d, J = 250 Hz), 177.4 ppm; IR (KBr, cm-1) 2947, 1694, 14

1630, 1275; MS (70 eV) m/z 358 (M+), 326, 283, 193; Anal. Calcd for C20H16F2O4: C, 67.04; 15

H, 4.50. Found: C, 67.21; H, 4.60. 16

(4Z,6Z)-4,6-Bis(4-chlorobenzylidene)-2-methoxy-2-methyl-1,3-dioxan-5-one (3j) 17

Yellow solid; mp 165-166 oC; 1H NMR (400 MHz, DMSO-d6): 1.99 (s, 3H, Me), 3.31 (s, 3H, 18

OMe), 6.90 (s, 2H, =CH), 7.50 (d, J = 8.0 Hz, Ar), 7.87 (4H, d, J = 8.0 Hz, Ar) ppm; 13C 19

NMR (100 MHz, DMSO-d6): 20.9, 52.5, 113.6, 114.0, 129.3, 131.9, 132.7, 134.3, 144.2, 20

176.5 ppm; IR (KBr, cm-1) 2944, 1695, 1607, 1274; MS (70 eV) m/z 391 (M+), 360, 314, 280, 21

209; Anal. Calcd for C20H16Cl2O4: C, 61.40; H, 4.12. Found: C, 61.55; H, 4.21. 22

(4Z,6Z)-2-Methoxy-2-methyl-4,6-bis((thiophen-2-yl)methylene)-1,3-dioxan-5-one (3k) 23

Yellow solid; mp 120-122 oC: 1HNMR (500 MHz, CDCl3) δ 2.03 (s, 3H, Me), 3.39 (s, 3H, 24

OMe), 7.10 (dd, J = 4.0, 5.0 Hz, 2H), 7.27 (s, 2H, =CH), 7.38 (d, J = 4.0 Hz, 2H), 7.51 (d, J = 25

Page 7 of 21



Draft

8

5.0 Hz, 2H) ppm; 13C NMR (125 MHz, CDCl3) 21.4, 52.7, 111.3, 114.0, 127.8, 130.8, 132.1, 1

136.4, 142.4, 176.0 ppm; IR (KBr, cm-1) 2968, 1679, 1608, 1269; MS (70 eV) m/z 334 (M+), 2

302, 258, 231, 203; Anal. Calcd for C16H14O4S: C, 57.47; H, 4.22. Found: C, 57.55; H, 4.34. 3

X-ray crystal structure analysis of 3a 4

Suitable single crystals for 3a were obtained by slow evaporation of a water/methanol 5

mixture. The single crystal X-ray diffraction measurement was carried out on STOE IPDS-2T 6

diffractometer with graphite-monochromated Mo Kα (λ = 0.71073 Å) at 293.15 K. radiation. 7

The crystal was placed onto the tip of an about 0.1 mm diameter glass capillary. Cell 8

constants and an orientation matrix for data collection were obtained by least-square 9

refinement of the diffraction data from 3227 reflections with 3.03° < θ < 25.00°. Diffraction 10

data were collected in a series of ω scans in 1° oscillations and integrated using the Stoe X- 11

AREA software package. The structure was solved by direct methods and subsequent 12

difference Fourier analyses and then refined on F2 by a full-matrix least-squares procedure 13

using anisotropic displacement parameters. The crystals were formed in Triclinic crystal 14

system and P-1 space group. Atomic factors are from the International Tables for X-ray 15

Crystallography. All non-hydrogen atoms were refined with anisotropic displacement 16

parameters. Hydrogen atoms were placed in ideal positions and refined as riding atoms with 17

relative isotropic displacement parameters as follows: Uiso(H) = 1.2Ueq(C) aromatic protons 18

and Uiso(H) = 1.5Ueq(C) for CH3 protons, where Ueq = 1/3(U11+U22+U33). A view of the 19

structure is depicted in Fig. 2. A key structural feature of 3a is that the aromatic wings of the 20

motif are rotated by about 10˚ relative to each other. Packing diagram of the structure is 21

presented in Fig. 3. Refinement was performed using the SHELXL-2014 and WinGX-2013.3 22

programs.22 CCDC-1522108 contains the supplementary crystallographic data for this paper. 23

These data can be obtained free of charge from the Cambridge Crystallographic Data Centre 24

via www.ccdc.cam.ac.uk/data_request/cif. 25

Page 8 of 21



Draft

9

Results and discussion 1

After we prepared the ketone 1 by using a known procedure,21 we optimized the conditions 2

for the reaction of 1 with 4-MeC6H4CHO (Table 1). In the presence of catalytic amounts of 3

pyrrolidine, an ethanolic solution of 1 reacted with 2a within 2 h to efficiently give 3a in high 4

yield (entry 1). Use of other solvents (entries 2-5) proved that EtOH is the optimum medium 5

for the reactions in terms of yield and safety. The outcome did not improve by using other 6

bases (entries 6-7), Lewis acids (entries 8-9), or organocatalysts (entries 10-12). Similarly, 7

variation of the amounts of pyrrolidine could not lead to better results (entries 13-15). 8

9

Table 1. Optimization of the synthesis of 3a. 10

Entry Solvent Catalyst Catalyst mol% Yield (%)a

1 EtOH pyrrolidine 30 96

2 MeOH pyrrolidine 30 94

3 CH3CN pyrrolidine 30 68

4 H2O pyrrolidine 30 14

5 CH2Cl2 pyrrolidine 30 67

6 EtOH NaOH 30 82

7 EtOH K2CO3 30 41

8 EtOH LiClO4 30 55

9 EtOH MgBr2.OEt2 30 27

10 EtOH NHEt2 30 27

11 EtOH NEt3 30 41

12 EtOH morpholine 30 48



Page 9 of 21



Draft

10


aIsolated yields. 1 2

The optimum conditions were then used to evaluate the generality of the process (Table 2). 3

Therefore, in addition to the model reaction (entry 1), other aldehydes bearing electron 4

donating (entries 2-5) or electron withdrawing groups (entries 6-10) reacted equally well 5

under the optimized conditions to give 3b-3j in high yields. Similar behavior was observed 6

for a heterocyclic aromatic aldehyde to give the corresponding product 3k (entry 11). At the 7

end of reactions, products precipitated in the mixtures. This allowed us to easily separate the 8

products by filtration and purify them by recrystallization from EtOH and avoid cumbersome 9

and expensive chromatographic separations. 10

11

Table 2. Synthesis of various derivatives of 3. 12

Entry Aldehyde Product Time

(h)

Yield

(%)a

1 4-MeC6H4CHO

(2a)

2 96

2

4-MeOC6H4CHO

(2b)

3 89

3 4-MeSC6H4CHO

(2c)

2 95

Page 10 of 21



Draft

11

4 4-Me2NC6H4CHO

(2d)

4 75

5

2,4,5-

(MeO)3C6H2CHO

(2e)

3 90

6 3,4-(MeO)2C6H3CHO

(2f)

3 94

7

3,4,5-

(MeO)3C6H2CHO

(2g)

3 87

8 C6H5CH=CHCHO

(2h)

2 95

9 4-FC6H4CHO

(2i)

2 85

10 4-ClC6H4CHO

(2j)

2 97

11 2-ThienylCHO

(2k)

3 96

Page 11 of 21



Draft

12

aIsolated yields. 1 The structures of the products 3a-k were elucidated based on their spectroscopic analyses. In 2

the 1H NMR spectra, the presence of two singlet signals corresponding to the Me-C-OMe 3

fragment was the indication of the incorporation of 1 in the structure of the final products, 4

while low field aromatic hydrogens and a singlet at about 7.0 ppm for two olefinic protons 5

proved the presence of the two reacting aldehydes in the target compounds. Similar trend was 6

observed for 13C NMR spectra of the products. Alternatively, FT-IR spectroscopy strongly 7

supported the formation of the α,β-unsaturated C=C─C=O moieties. Although assignment of 8

the Z stereochemistry for the olefinic bonds in 4a-k can be assumed from the previous results 9

in other analogous heterocyclic23 and homocyclic systems,24 X-ray crystallography 10

experiments were conducted to confirm the suggested structure for the products (Fig.2 and 11

Fig. 3). 12

13 Fig. 2. Crystal structure of 3a. Displacement ellipsoids at 50% probability level. 14

Page 12 of 21



Draft

13

1

Fig. 3. Packing diagram of 3a viewed along the crystallographic a axis. 2

3

The fluorescence properties of bisarylmethylidene derivatives of various cyclic systems have 4

been studied extensively.25 However, search in the literature shows that there are very limited 5

reports on photophysical properties of the 1,3-dioxan-5-one counterpart.20 Thus, we decided 6

to study the photophysical behavior of our series of synthesized products. The UV-Vis 7

absorption spectra of the products in CH2Cl2 solutions are given in Fig. 4a, exhibiting a 8

significant absorption band at 360-475 nm in the visible region. Table 3 shows the data for the 9

products when they are excited at their respective λmax, while relatively strong red-shifted 10

emissions are observed for the products (Fig. 4b). Among the products, 3d behaved more 11

promising since it is a ketocyanine dye due to having an electron donor amino group in the 12

para position and an electron acceptor carbonyl group on the chromophore fragment.26 13

Consequently, when different solutions of 3d were analyzed, maximum fluorescence activity 14

was observed in CH2Cl2, while the λmax remained almost constant at 566 nm for all solvents 15

Page 13 of 21



Draft

14

(Fig. 4c). Some illustrations of various colors of the samples in solid and dissolved forms are 1

also given in Fig. 4d-4h and these properties are currently under further detailed studies. 2

(a) (b)

(c) (d) (e) (f) (g) (h) Fig. 4. (a) The absorption spectra of 3a-3k in CH2Cl2 (3×10-5 M). (b) Fluorescence spectra of 3

3a-3k in CH2Cl2. (c). Fluorescence spectra of 3d in various solvents. (d) A solution of 3c in 4

CH2Cl2 at 366 nm. (e) A solution of 3c in CH2Cl2 at room light. (f) A solution of 3d in 5

CH2Cl2 at room light. (g) Solid 3c at room light. (h) Solid 3d at room light. 6

7

Table 3. Selected photophysical properties of componds 3a-3k in CH2Cl2. 8

Entry Compounds Absorption Emission

ʎabs(nm) ɛ (104 M-1cm-

1) λex (nm)

λem

(nm) Stokes’ shift (nm)

Qfa

1 3a 376 247

41735 3.05

376 467 91 0.016

2 3b 400 255

3.10 2.31

400 507 107 0.060

3 3c

413 271 231

4.78 3.92 5.71

413 522 109 0.077

Page 14 of 21



Draft

15

4 3d 476 285

5.36 2.58

476 572 96 0.636

5 3e 448 259

3.90. 2.08

448 557 109 0.333

6 3f 417 263

4.33 3.01

417 527 110 0.141

7 3g

402 261 229

3.47 1.96 3.23

402 547 145 0.115

8 3h 417 282

5.27 2.46

417 537 120 0.394

9 3i 367 241

3.49 2.37

367 472 105 0.010

10 3j 370 248

3.57 2.81

370 467 97 0.012

11 3k 415 268

4.20 1.78

415 507 92 0.028

aThe fluorescence quantum-yield measurments were done in EtOH using 9,10- 1 diphenylanthracene as a standard. 2 3

Conclusion 4

In summary, we have presented the first general method for the synthesis of 5

bisarylmethylidene derivatives of ketone 1. The reaction takes place for various aldehydes and 6

the respective products are formed as crystals under very mild reaction conditions at room 7

temperature. Primary studies were also carried out on the fluorescence and dye properties of 8

the products. Further studies on these aspects and the extension of the results to other 9

heterocyclic analogues are also under study. 10

11

Supplementary material 12

Supplementary data are available with the article through the journal Web site at 13

http://nrcresearchpress.com/doi/suppl/10.1139/cjc-2017-xxxx. 14

Acknowledgments 15

Omid Hazrati from the Public Affairs Department is acknowledged for photography of the 16

samples. 17

18

Page 15 of 21



Draft

16

References 1

1. (a) Nielsen, A. T.; Houlihan, W. J. The Aldol Condensation: John Wiley: New York, 2004; 2

(b) Mandal, S.; Mandal, S.; Ghosh, S. K.; Ghosh, A.; Saha, R.; Banerjee, S.; Saha, B. Synth. 3

Commun. 2016, 46 (16), 1327. doi:10.1080/00397911.2016.1206938; (c) Hutchinson, J. H.; 4

Li, D. L. F.; Money, T.; Palme, M.; Agharahimi, M. R.; Albizati, K. F. Can. J. Chem. 1991, 5

69 (3), 558. doi:10.1139/v91-084. 6

2. (a) Palleros, D. R. J. Chem. Edu. 2004, 81 (9), 1345. doi:10.1021/ed081p1345; (b) Ngaini, 7

Z.; Abdul Rahman, N. I. Can. J. Chem. 2010, 88 (7), 654. doi:abs/10.1139/V10-057. 8

3. (a) Ghosh, S.; Banerjee, S.; Sil, P. C. Food Chem. Toxicol. 2015, 83, 111. 9

doi:10.1016/j.fct.2015.05.022; (b) Zheng, Y.; Wang, X.; Gao, S.; Ma, M.; Ren, G.; Liu, H.; 10

Chen, X. Nat. Prod. Res. 2015, 29 (19), 1804. doi:10.1080/14786419.2015.1007973. 11

4. Singh, P.; Anand, A.; Kumar, V. Eur. J. Med. Chem. 2014, 85, 758. 12

doi:10.1016/j.ejmech.2014.08.033. 13

5. (a) Rajakumar, P.; Satheeshkumar, C.; Ravivarma, M. Arkivoc 2014, iv, 67. 14

doi:10.3998/ark.5550190.p008.375; (b) Matvieiev, Y.; Karpenko, I.; Kulinich, A.; Ryabitskii, 15

A.; Pivovarenko, V.; Shishkina, S.; Shishkin, O.; Kalchenko, V. Tetrahedron Lett. 2011, 52 16

(30), 3922. doi:10.1016/j.tetlet.2011.05.094. 17

6. (a) Li, Z.; Pucher, N.; Cicha, K.; Torgersen, J.; Ligon, S. C.; Ajami, A.; Husinsky, W.; 18

Rosspeintner, A.; Vauthey, E.; Naumov, S.; Scherzer, T.; Stampfl, J.; Liska, R. 19

Macromolecules 2013, 46 (2), 352. doi:10.1021/ma301770a; (b) Wu, J.; Zhao, Y.; Li, X.; Shi, 20

M.; Wu, F.; Fang, X. New J. Chem. 2006, 30 (7), 1098. doi:10.1039/B604695A. 21

7. (a) Zhao, Y.; Wang, W.; Wu, F.; Zhou, Y.; Huang, N.; Gu, Y.; Zou, Q.; Yang, W. Org. 22

Biomol. Chem. 2011, 9 (11), 4168. doi:10.1039/C0OB01278E; (b) Pana, A.-M.; Badea, V.; 23

Bănică, R.; Bora, A.; Dudas, Z.; Cseh, L.; Costisor, O. J. Photochem. Photobiol. A 2014, 283, 24

22. doi:10.1016/j.jphotochem.2014.03.008. 25

Page 16 of 21



Draft

17

8. (a) Wu, Y.; Hou, J.; Liu, Y.; Zhang, M.; Tung, C.-H.; Wang, Y. Tetrahedron 2016, 72 (12), 1

1511. doi:10.1016/j.tet.2016.01.055; (b) Pan, J.; Xu, T.; Xu, F.; Zhang, Y.; Liu, Z.; Chen, W.; 2

Fu, W.; Dai, Y.; Zhao, Y.; Feng, J.; Liang, G. Eur. J. Med. Chem. 2017, 125, 478. 3

doi:10.1016/j.ejmech.2016.09.033 4

9. Xu, L.; Yue, F.; Shi, W.; Hui, Y.; Mi, H.; Ma, F.; Tian, Y.; Xie, Z. Dyes Pigments 2013, 99 5

(3), 822. doi:10.1016/j.dyepig.2013.07.010. 6

10. (a) Fang, Y.; Liu, T.; Zou, Q.; Zhao, Y.; Wu, F. RSC Adv. 2015, 5 (69), 56067. 7

doi:10.1039/C5RA06143A; (b) Yamakoshi, H.; Ohori, H.; Kudo, C.; Sato, A.; Kanoh, N.; 8

Ishioka, C.; Shibata, H.; Iwabuchi, Y. Bioorg. Med. Chem. 2010, 18 (3), 1083. 9

doi:10.1016/j.bmc.2009.12.045; (c) Szarek, W. A.; Pinto, B. M.; Grindley, T. B. Can. J. 10

Chem. 1983, 61 (3), 461. doi:10.1139/v83-082. 11

11. (a) Sun, J.; Zhang, S.; Yu, C.; Hou, G.; Zhang, X.; Li, K.; Zhao, F. Chem. Biol. Drug Des. 12

2014, 83 (4), 392. doi:10.1111/cbdd.12254; (b) Qiu, C.; Hu, Y.; Wu, K.; Yang, K.; Wang, N.; 13

Ma, Y.; Zhu, H.; Zhang, Y.; Zhou, Y.; Chen, C.; Li, S.; Fu, L.; Zhang, X.; Liu, Z. Bioorg. 14

Med. Chem. Lett. 2016, 26 (24), 5971. doi:10.1016/j.bmcl.2016.10.080. 15

12. (a) Hu, J.; Lu, Z.; Yin, H.; Xue, W.; Wang, A.; Shen, L.; Liu, S. J. Ind. Eng. Chem. 2016, 16

40, 145. doi:10.1016/j.jiec.2016.06.018; (b) King, F.; Kelly, G. J. Catal. Today 2002, 73 17

(1─2), 75. doi:10.1016/S0920-5861(01)00520-X; (c) Mahmood, K.; Zia, K. M.; Zuber, M.; 18

Salman, M.; Anjum, M. N. Int. J. Biol. Macromol. 2015, 81, 877. 19

doi:10.1016/j.ijbiomac.2015.09.026. 20

13. (a) Zou, Q.; , H.; Zhao, Y.; Fang, Y.; Chen, D.; Ren, J.; Wang, X.; Wang, Y.; Gu, Y.; Wu, 21

F. J. Med. Chem. 2015, 58 (20), 7949. doi:10.1021/acs.jmedchem.5b00731; (b) Zoto, C. A.; 22

Ucak-Astarlioglu, M. G.; MacDonald, J. C.; Connors, R. E. J. Mol. Struct. 2016, 1112, 97. 23

doi:10.1016/j.molstruc.2016.02.009; (c) Yang, W.; Zou, Q.; Zhou, Y.; Zhao, Y.; Huang, N.; 24

Gu, Y.; Wu, F. J. Photochem. Photobiol. A 2011, 222 (1), 228. 25

Page 17 of 21



Draft

18

doi:10.1016/j.jphotochem.2011.06.002; (d) Zammit, R.; Pappova, M.; Zammit, E.; Gabarretta, 1

J.; Magri, D. C. Can. J. Chem. 2014, 93 (2), 199. doi:10.1139/cjc-2014-0266. 2

14. (a) Pivovarenko, V. G.; Klueva, A. V.; Doroshenko, A. O.; Demchenko, A. P. Chem. 3

Phys. Lett. 2000, 325 (4), 389. doi:10.1016/S0009-2614(00)00708-9; (b) Zou, Q.; Zhao, Y.; 4

Makarov, N. S.; Campo, J.; Yuan, H.; Fang, D.-C.; Perry, J. W.; Wu, F. Phys. Chem. Chem. 5

Phys. 2012, 14 (33), 11743. doi:10.1039/C2CP41952A; (c) Rudolph, T.; Buehle, P.; 6

Rosskopf, R. U.S. Patent 0234238, 2014. 7

15. Gangadhara, K. K. Polymer 1995, 36 (9), 1903. doi:10.1016/0032-3861(95)90938-X. 8

16. (a) Abaee, M. S.; Doustkhah, E.; Mohammadi, M.; Mojtahedi, M. M.; Harms, K. Can. J. 9

Chem. 2016, 94 (9),733. doi:10.1139/cjc-2016-0246; (b) Abaee, M. S.; Mojtahedi, M. M.; 10

Pasha, G. F.; Akbarzadeh, E.; Shockravi, A.; Mesbah, A. W.; Massa, W. Org. Lett. 2011, 13 11

(19), 5282. doi:10.1021/ol202145w. 12

17. Mojtahedi, M. M.; Abaee, M. S.; Samianifard, M.; Shamloo, A.; Padyab, M.; Mesbah, A. 13

W.; Harms, K. Ultrason. Sonochem. 2013, 20 (3), 924. doi:10.1016/j.ultsonch.2012.11.004. 14

18. (a) Abaee, M. S.; Mojtahedi, M. M.; Hamidi, V.; Mesbah, A. W.; Massa, W. Synthesis 15

2008, 40 (13), 2122. doi:10.1055/s-2008-1067114; (b) Mojtahedi, M. M.; Abaee, M. S.; 16

Samianifard, M.; Shamloo, A. Scientia Iran 2014, 21 (3), 719. (c) Mojtahedi, M. M.; Abaee, 17

M. S.; Khakbaz, M.; Alishiri, T.; Samianifard, M.; Mesbah, A. W.; Harms, K. Synthesis 2011, 18

43 (23), 3821. doi:10.1055/s-0031-1289571. 19

19. (a) Casey, T. C.; Carlisle, J.; Tisselli, P.; Male, L.; Spencer, N.; Grainger, R. S. J. Org. 20

Chem. 2010, 75 (21), 7461. doi:10.1021/jo101531b; (b) Müller, S. N.; Batra, R.; Senn, M.; 21

Giese, B.; Kisel, M.; Shadyro, O. J. Am. Chem. Soc. 1997, 119 (12), 2795. 22

doi:10.1021/ja9641416; (c) Harmata, M.; Sharma, U. Org. Lett. 2000, 2 (17), 2703. 23

doi:10.1021/ol006281x. 24

20. Rudolph, T.; Buehle, P.; Rosskopf, R. U. S. Patent 0309184, 2013. 25

Page 18 of 21



Draft

19

21. Kimura, M.; Ezoe, A.; Mori, M.; Iwata, K.; Tamaru, Y. J. Am. Chem. Soc. 2006, 128 (26), 1

8559. doi:10.1021/ja0608904. 2

22. (a) Farrugia L. J. J. Appl. Crystallogr. 1999, 32 (4), 837. 3

doi:10.1107/S0021889899006020; ( b) Allen, F. H.; Johnson, O.; Shields, G. P.; Smith, B. R.; 4

Towler, M. J. Appl. Crystallogr. 2004, 37 (2), 335. doi:10.1107/S0021889804003528; (c) 5

Macrae, C. F.; Edgington, P. R.; McCabe. P.; Pidcock, E.; Shields, G. P.; Taylor, R.; Towler, 6

M.; van de Streek, J. J. Appl. Crystallogr. 2006, 39 (3), 453. 7

doi:10.1107/S002188980600731X; (d) Burnett, M. N.; Johnson, C. K. ORTEP-III Report 8

ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA 1996. (e) Spek, A. L. J. Appl. 9

Crystallogr. 2003, 36 (1), 7. doi:10.1107/S0021889802022112; (f) Sheldrick, G. M. Acta 10

Crystallogr. 2008, A (64), 112. doi:10.1107/S0108767307043930; (g) Coppens, P.; 11

Leiserowitz, L.; Rabinovich, D. Acta Cryst. 1965, 18 (6), 1035. 12

doi:10.1107/S0365110X65002487. 13

23. (a) Santiago-Vazquez, Y.; Das, S.; Das, U.; Robles-Escajeda, E.; Ortega, N. M.; Lema, C.; 14

Varela-Ramírez, A.; Aguilera, R. J.; Balzarini, J.; De Clercq, E.; Dimmock, S. G.; Gorecki, D. 15

K. J.; Dimmock, J. R. Eur. J. Med. Chem. 2014, 77, 315. doi:10.1016/j.ejmech.2014.03.009; 16

(b) Mojtahedi, M. M.; Massa, W.; Abaee, M. S.; Mesbah, A. W. Acta Crystallogr. E 2012, 68 17

(2), o356. doi:10.1107/S1600536812000372. 18

24. (a) Dimmock, J. R.; Sidhu, K. K.; Quail, J. W.; Jia, Z.; Duffy, M. J.; Reid, R. S.; 19

Kirkpatrick, D. L.; Zhu, L.; Fletcher, S. M. J. Pharm. Sci. 1992, 81 (11), 1059. 20

doi:10.1002/jps.2600811103; (b) Zhao, C.-Y.; Liu, J.-Y.; Wang, Y.; Zhao, X.-J.; Yuan, B.; 21

Yue, M.-M. Synth. Commun. 2014, 44 (6), 827. doi:10.1080/00397911.2013.834362. 22

25. (a) Wan, Y.; Chen, X.-M.; Pang, L.-L.; Ma, R.; Yue, C.-H.; Yuan, R.; Lin, W.; Yin, 23

W.; Bo, R.-C.; Wu, H. Synth. Commun. 2010, 40 (15), 2320. 24

doi:10.1080/00397910903243781; (b) Makarov, M. V.; Rybalkina, E. Y.; Röschenthaler, 25

Page 19 of 21



Draft

20

G.-V.; Short, K. W.; Timofeeva, T. V.; Odinets, I. L. Eur. J. Med. Chem. 2009, 44 (5), 1

2135. doi:10.1016/j.ejmech.2008.10.019. 2

26. Sardar, S. K.; Srikanth, K.; Mandal, P. K.; Bagchi, S. Spectrochim. Acta, Part A 2012, 99 3

(#), 37. doi:10.1016/j.saa.2012.09.015. 4

5

Page 20 of 21



Draft

21

Graphical Abstract 1

Synthesis and fluorescence studies of novel bisarylmethylidene derivatives of 2-methoxy- 2

2-methyl-1,3-dioxan-5-one 3

Mohammad M. Mojtahedi, Kiana Darvishi, M. Saeed Abaee, and Mohammad R. Halvagar 4

5

6 7

8

Page 21 of 21



Date post:	17-Jul-2020
Category:	Documents
Upload:	others
View:	9 times
Download:	0 times

Synthesis and fluorescence studies of novel ...Draft 3 Introduction 1 Aldol condensation reaction is...

Documents