Scholarly article on topic ' Thioxopyrimidine in Heterocyclic Synthesis III: Synthesis and Properties of Some Novel Heterocyclic Chalcone Derivatives Containing a Thieno[2,3- d ]pyrimidine-Based Chromophore '

Thioxopyrimidine in Heterocyclic Synthesis III: Synthesis and Properties of Some Novel Heterocyclic Chalcone Derivatives Containing a Thieno[2,3- d ]pyrimidine-Based Chromophore Academic research paper on "Chemical sciences"

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Academic research paper on topic " Thioxopyrimidine in Heterocyclic Synthesis III: Synthesis and Properties of Some Novel Heterocyclic Chalcone Derivatives Containing a Thieno[2,3- d ]pyrimidine-Based Chromophore "

Hindawi Publishing Corporation

Journal of Chemistry

Volume 2013, Article ID 649576, 11 pages

http://dx.doi.org/10.1155/2013/649576

Research Article

Thioxopyrimidine in Heterocyclic Synthesis III: Synthesis and Properties of Some Novel Heterocyclic Chalcone Derivatives Containing a Thieno[2,3-d]pyrimidine-Based Chromophore

Yuh Wen Ho1 and Wei Hua Yao2

1 Department of Creative Fashion Design, Taoyuan Institute of Innovation Technology, Jhongli, 32091, Taiwan Department of Materials and Textiles, Oriental Institute of Technology, Pan-Chiao 22064, Taiwan

Correspondence should be addressed to Yuh Wen Ho; wen@tiit.edu.tw

Received 29 June 2012; Accepted 26 November 2012

Academic Editor: Jacques Lalevee

Copyright © 2013 Y. W. Ho and W. H. Yao. "His is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Cyclization of 4-methyl-2-phenyl-6-thioxo-1,6-dihydropyrimidine-5-carbonitrile 1 with chloroacetone in DMF in the presence of excess potassium carbonate anhydrous gave the 1-(5-amino-4-methyl-2-phenylthieno[2,3-d]pyrimidin-6-yl)ethanone 3, which can react with 2,5-dimethoxytetrahydrofuran in glacial acetic acid producing the 1-[4-methyl-2-phenyl-5-(1H-pyrrol-1-yl)thieno[2,3-d]pyrimidin-6-yl]ethanone 4. On the other hand, a series of novel 3-aryl-1-[4-methyl-2-phenyl-5-(1H-pyrrol-1-yl)-thieno[2,3-d]pyrimidin-6-yl]prop-2-en-1-one chalcone dyes 6a—n were obtained by the condensation reaction of 1-[4-methyl-2-phenyl-5(1H-pyrrol-1-yl)thieno[2,3-d]-pyrimidin-6-yl]ethanone 4 with appropriate aldehydes. "Hie structures of chalcone dyes were characterized by IR, 'HNMR, mass, elemental analysis, and UV-Vis spectroscopy. He dyes were applied to polyester fibers for creating hues ranging from greenish-yellow to orange; their spectral characteristics, substituent effect in DMF solution, fastness properties, and colorimetric assessment are also discussed.

1. Introduction

He considerable biological and medicinal activity caused by fused thienopyrimidines has stimulated much research in this field [1-5]. Moreover, several series of heterocyclic compounds possessing a bridgehead pyrrolic moiety play a vital role in many biological activities [6-10]. Likewise, compounds with a chalcone-based structure have showed an array of pharmacological activities [11-16]. However, chalcones, the bichromophoric molecules separated by vinyl chains and the carbonyl group, are found being effective photosensitive materials and exhibit promising nonlinear optical properties [17]. On the other hand, molecular two-photon absorption (TPA) has attracted a lot of interest recently for its applications in the field of both biological imaging and materials science; TPA materials have recently received considerable attention [18-20]. A number of organic molecules have been studied for TPA activity [21-24]. Among these TPA systems, the heterocycle-based chromophores are particularly interesting due to their easily

polarizable heteroaromatic rings which can help to improve their degree of intramolecular charge transfer (ICT) [2527]. Recently the synthesis and characterization of chro-mophores have been reported in which the donor moiety is represented by a ^-excessive five-membered heterocycle (pyrrole or thiophene) and the acceptor group is a deficient heterocyclic azine ring (pyridine, pyrazine, pyrimidine, and pyridazine), which exhibit solvatochromic, electrochromic, photochromic, fluorescent, and nonlinear optical properties [28, 29]. Further developments involve the stretch of the charge transfer and the length of the ^-bridge, such as multibranched octupoles or dendrimers [30].

Beyond these very important applications in biological chemistry, the chalcones are also found being used in the production of nematic liquid crystals [31], photosensitive polymers [32], antioxidants [33, 34], and as dyes [35, 36]. Although a number of papers concerning the synthesis of chalcone compounds have been published, those containing a new heterocyclic system of thieno[2,3-d]-pyrimidine-based chromophores and application have not yet been

reported. tterefore, based on our previous works [37-39], we aim to report herein the preparation of a series of chalcone derivatives containing a thieno[2,3-d]-pyrimidine-based chromophore, and there was application to polyester fibers as disperse dyes. tte spectral characteristics, dyeing properties, and colorimetric assessment of the dyes are also discussed.

2. Experimental

2.1. General. All melting points are uncorrected and in °C. IR spectra were recorded on a JASCO FTIR-3 spectrometer (KBr); 'HNMR spectra were obtained on a Bruker AM-300 WB FI-NMR spectrometer, and chemical shifts are expressed in S ppm using TMS as an internal standard. Electron impact mass spectra were obtained at 70 eV using a Finnigan Mat TSQ-46C spectrometer. Elemental analyses were performed on a Perkin-Elmer 240 elemental Analyzer. Electronic spectra were recorded on a Shimadzu UV 240 from dye solutions in DMF at a concentration of 2 x 10-5 mol L-1. Aldehydes 5a-n were purchased from Aldrich and were used without further purification.

2.2. Synthesis of 1-(5-Amino-4-methyl-2-phenylthieno[2,3-d]pyrimidin-6-yl)ethanone (3). To a solution of 4-methyl-2-phenyl-6-thioxo-1,6-dihydropyrimidine-5-carbo-nitrile 1 (2.27 g, 0.01 mol) in DMF (50 mL), potassium carbonate anhydrous (2.76 g, 0.02 mol) and chloroacetone 2 (0.93 g, 0.01 mol) were added. tte reaction mixture was stirred at room temperature for 4 h and then diluted with cold water (50 mL). tte resulting solid product was collected by filtration, washed with water, and recrystallized from ethyl acetate/ethanol to give 2.66 g of yellow needles (94% yield), m.p. 210°C; IR: v 3424, 3295 (NH2), 1663 (C=O) cm-1; 1HNMR (CDCl3): 5 2.47 (3H, s, COCH3), 3.07 (3H, s, CH3), 3.76 (2H, br, NH2), 8.58-8.55, 7.60-7.55 (5H, m, phenyl-H); MS: 283 (M+, 100), 268 (95), 240 (20), 212 (2), 165 (5), 160 (10), 137 (34), 110 (18), 77 (9). Anal. Calcd. for C15H13N3OS: C, 63.60; H, 4.59; N, 14.84. Found: C, 63.63; H, 4.50; N, 14.77%.

2.3. Synthesis of 1-[4-Methyl-2-phenyl-5-(1H-pyrrol-1-yl) thieno[2,3-d]pyrimidin-6-yl]ethanone (4). A mixture of 1-(5-amino-4-methyl-2-phenylthieno[2,3-d]pyrimidin-6-yl)eth-an-one 3 (2.83 g, 0.01 mol), 2,5-dimethoxytetrahydrofuran (1.26 g, 0.01 mol), in glacial acetic acid (20 mL) was refluxed for 12 h. After cooling, the resulting solid product was collected by filtration, washed with water, and the crude product recrystallized from ethanol/glacial acetic acid to give 2.96 g of gray white needles (89% yield), m.p. 204°C; IR: v 1660 (C=O) cm-1; 1HNMR (CDCl3): 5 2.09 (3H, s, COCH3), 2.20 (3H, s, CH3), 6.50 (2H, t, 3,4-H of pyrrolyl), 6.87 (2H, t, 2,5-H of pyrrolyl), 8.56-8.54, 7.51-7.49 (5H, m, phenyl-H); MS: 333 (M+, 100), 318 (35), 290 (36), 277 (4), 223 (4), 185 (8), 166 (10), 160 (14), 116 (10), 103 (20), 77 (19), 51 (5). Anal. Calcd. for C19H15N3OS: C, 68.46; H, 4.50; N, 12.61. Found: C, 68.33; H, 4.52; N, 12.59%.

Table 1: Physical and analytical data of 6-(3-substituted-acryloyl)-5-(1-pyrrolyl)-4-methyl-2-phenylthieno[2,3-d]pyrimidine derivatives 6a-n.

Dye M.P. (°C)a Yield (%) Molecular formula Elemental analysis (%) Calcd/Found C H N

C26H18ClN3OS 68.49 3.95 9.22

6a 184 88

68.55 4.02 9.33

6b 282 96 C28H24N4OS 72.41 5.17 12.06

72.58 5.21 12.12

C27H21 N3 OS 74.48 4.82 9.65

6c 170 96

74.44 4.92 9.55

6d C27H21N3O2S 71.84 4.65 9.31

262 95

71.80 4.71 9.45

C30H28N4OS 73.17 5.69 11.38

6e 230 93

73.22 5.74 11.24

6f C32H23N3OS 77.26 4.62 8.45

148 95

77.23 4.77 8.56

C24H17N3 O2S 70.07 4.13 10.21

6g 130 92

70.15 4.22 10.36

6h C24H17N3 OS2 67.44 3.98 9.83

262 98

67.39 4.06 9.89

6i C36H23N3OS 79.26 4.22 7.70

278 95

79.58 4.56 7.98

6j C34H26N4OS 75.83 4.83 10.40

178 98

75.88 4.73 10.33

6k C29H25N3 OS 75.16 5.40 9.07

152 93

75.18 5.42 9.24

61 C28H22N4O2S 70.29 4.60 11.71

210 84

70.32 4.56 11.55

c34h23n3os 78.31 4.41 8.06

6m 228 90

78.29 7.48 7.97

C38H28N4OS 77.55 4.76 9.52

6n 286 94

77.68 4.82 9.52

Recrystallization from DMF/ethanol.

2.4. Synthesis of 3-Aryl-1-[4-methyl-2-phenyl-5(1H-pyrrol-1-yl)thieno[2,3-d]pyrimidin-6-yl]prop-2-en-1-ones (6a-n) General Procedure. A mixture of compound 4 (0.33 g, 1.0mmol), appropriate aldehydes 5a-n (1.0mmol) and NaOH (2.2mmol) in absolute ethanol (10 mL) was stirred at room temperature for 24 h. tte mixture was stirred at room temperature for 24 h. tte mixture was acidified with dilute acetic acid, and the precipitated product was collected by filtration, washed with water, and the crude product recrystallized from THF/ethanol. tte physical constants and spectral data of compounds 6a-n are recorded in Tables 1 and 2.

2.5. Dyeing Procedure [40]. Polyester fabrics were dyed in a laboratory dyeing machine at a liquor ratio of 30: 1. Dyebath

Table 2: Spectra data of 6-(3-substituted-acryloyl)-5-(1-pyrrolyl)-4-methyl-2-phenyl-thieno[2,3-d]pyrimidine derivatives 6a-n.

MS IR 'H-NMRa

Dye (m/e M+) (KBr) (CF3COOD)

v (cm- 8 (ppm)

2.20 (3H, s, CH3), 5.80 (1H, d, 7 = 3.1 Hz, COCH=), 6.62 (2H, m, 3,4-H of

6a 455.5 1667 (C= O) pyrrolyl), 6.87 (2H, m, 2,5-H of pyrrolyl), 6.75 (2H, d, / = 1.00 Hz, 3,5-H of phenyl), 7.33 (2H, d, 7 = 1.00 Hz, 2,6-H of phenyl), 7.82 (1H, d, / = 3.1 Hz, =CH-), 8.57-8.55, 7.55-7.21 (5H, m, phenyl-H)

2.27 (3H, s, CH3), 3.06 (6H, s, N(CH3)2), 5.70 (1H, d, 7 = 3.1 Hz, COCH=),

6b 464 1628 (C= O) 6.59-6.50 (2H, m, 3,4-H ofpyrrolyl), 6.98-6.87 (2H, m, 2,5-H ofpyrrolyl), 6.70 (2H, d, / = 1.0 Hz, 3,5-H of phenyl), 7.25 (2H, d, 7 = 1.5 Hz, 2,6-H of phenyl), 7.75 (1H, d, 7 = 3.1 Hz, =CH-), 8.57-8.54, 7.51-7.50 (5H, m, phenyl-H).

2.27 (3H, s, CH3), 2.39 (3H, s, CH3), 6.02 (1H, d, 7 = 3.0 Hz, COCH=), 6.61-6.51

6c 435 1663 (C= O) (2H, m, 3,4-H of pyrrolyl), 7.09-6.87 (2H, m, 2,5-H of pyrrolyl), 7.79 (1H, d, 7 = 3.0 Hz, =CH-), 8.59-8.58, 7.81-7.33 (9H, m, phenyl-H).

2.33 (3H, s, CH3), 3.84 (3H, s, OCH3), 5.75 (1H, d, 7 = 3.1 Hz, COCH=), 6.60 (2H,

6d 451 1668 (C= O) t, 3,4-H of pyrrolyl), 6.87 (2H, d, 7 = 1.0 Hz, 3,5-H of phenyl), 6.99 (2H, t, 2,5-H of pyrrolyl), 7.28 (2H, d, 7 = 1.0 Hz, 2,6-H of phenyl), 7.76 (1H, d, 7 = 3.0 Hz, =CH-), 8.59-8.55, 7.52-7.51 (5H, m, phenyl-H).

1.21 (6H, t, 7 = 1.4 Hz, CH3), 2.27 (3H, s, CH3), 3.41 (4H, q, 7 = 1.4 Hz, CH2), 5.68

6e 492 1628 (C= O) (1H, d, 7 = 3.1 Hz, COCH=), 6.59-6.49 (4H, m, 3,4-H of pyrrolyl and 3,5-H of phenyl), 6.98-6.87 (2H, m, 2,5-H of pyrrolyl), 7.24 (2H, d, 7 = 1.0 Hz, 2,6-H of phenyl), 7.74 (1H, d, 7 = 3.0 Hz, =CH-), 8.56-8.53, 7.50-7.49 (5H, m, phenyl-H).

6f 497 1667 (C= O) 2.18 (3H, s, CH3), 5.75 (1H, d, 7 = 3.0 Hz, COCH=), 6.50 (2H, t, 3,4-H of pyrrolyl), 6.86 (2H, t, 2,5-H of pyrrolyl), 8.65-8.54, 7.63-7.38 (15H, m, =CH- and phenyl-H).

2.28 (3H, s, CH3), 5.88 (1H, d, 7 = 3.1 Hz, COCH=), 6.59-6.48 (3H, m, 3,4-H of

6g 411 1667 (C= O) pyrrolyl and 4-H of furyl), 6.87 (2H, m, 2,5-H of pyrrolyl), 7.00 (1H, d, 7 = 2.0 Hz, 3-H of furyl), 8.15 (1H, d, 7 = 3.0 Hz, =CH-), 8.63-8.54, 7.58-7.48 (6H, m, 5-H of furyl and phenyl-H).

2.11 (3H, s, CH3), 5.47 (1H, d, 7 = 3.2 Hz, COCH=), 6.63-6.39 (3H, m, 3,4-H of

6h 427 1641 (C= O) pyrrolyl and 4-H of thienyl), 7.06-7.03 (2H, m, 2,5-H of pyrrolyl), 7.13 (1H, d, 7 = 1.0 Hz, 3-H ofthienyl), 7.80 (1H, d, 7 = 3.0 Hz, =CH-), 8.48-8.45, 7.54-7.44 (6H, m, 5-H of thienyl and phenyl-H).

2.06 (3H, s, CH3), 5.79 (1H, d, 7 = 3.1 Hz, COCH=), 6.51 (2H, m, 3,4-H of

6i 545 1623 (C= O) pyrrolyl), 6.90 (2H, m, 2,5-H of pyrrolyl), 8.62-8.42, 8.32-8.05 (15H, m, =CH-, phenyl-H and pyrenyl-H).

1.77 (3H, t, 7 = 1.2 Hz, CH3), 2.52 (3H, s, CH3), 4.03 (2H, d, 7 = 1.0 Hz, CH2), 5.79

6j 538 1633 (C= O) (1H, d, 7 = 3.0 Hz, COCH=), 6.51 (2H, m, 3,4-H of pyrrolyl), 6.90 (2H, m, 2,5-H of pyrrolyl), 8.72-7.61, (13H, m, =CH-, phenyl-H and carbazolyl-H).

2.10 (3H, s, CH3), 2.22 (6H, s, CH3), 2.28 (3H, s, CH3), 5.88 (1H, d, 7 = 4.0 Hz,

6k 463 1643 (C= O) COCH=), 6.51-6.45 (2H, m, 3,4-H of pyrrolyl), 6.88-6.84 (2H, m, 2,5-H of pyrrolyl), 7.39 (1H, d, 7 = 1.2 Hz, =CH-), 8.58-8.53, 7.54-7.51 (7H, m, phenyl-H).

2.06 (3H, s, CH3), 2.16 (3H, s, COCH3), 5.78 (1H, d, 7 = 3.0 Hz, COCH=), 6.49

61 478 3324 (NH), 1622 (C=O) (2H, m, 3,4-H of pyrrolyl), 6.97 (2H, m, 2,5-H of pyrrolyl), 6.87 (2H, d, 7 = 1.00 Hz, 3,5-H of phenyl), 7.57 (1H, d, 7 = 1.5 Hz, =CH-), 8.50-8.29, 7.47-7.41 (7H, m,

phenyl-H), 8.29 (1H, br, NH).

2.22 (3H, s, CH3), 6.13 (1H, d, 7 = 3.0 Hz, COCH=), 6.24 (2H, m, 3,4-H of

6m 521 1679 (C= O) pyrrolyl), 6.91 (2H, m, 2,5-H of pyrrolyl), 8.93-7.99, 7.54-7.26 (15H, m, =CH-, phenyl-H and anthracenyl-H).

2.30 (3H, s, CH3), 5.71 (1H, d, 7 = 3.0 Hz, COCH=), 6.55 (2H, t, 3,4-H of pyrrolyl),

6n 588 1631 (C= O) 6.98-6.94 (4H, m, 3,5-H of phenyl and 2,5-H of pyrrolyl), 7.74 (1H, d, 7 = 3.0 Hz, =CH-), 8.59-8.57, 7.53-7.13 (17H, m, phenyl-H).

s: Singlet; d: doublet; t: triplet; m: multiplet; br: broad.

(60 mL) was prepared with formulated dye and a dispersing agent (Diwatex 40, 0.5 gL-1) and adjusted to pH 4.0. tte polyester fabric (2.0 g) was immersed in the dyebath and dyed for 60min at 130°C. After dyeing, the dyed fabric was reduction cleared (Na2S2O4 2.0 gL-1, NaOH 2.0 gL-1, soaping agent 2.0 g L- ) for 20 min at 75°C.

2.6. Fastness Test. tte light fastness was determined using standard procedures [41]. For sublimation fastness determinations, the dyed polyester fibers were stitched between two pieces of undyed polyester fibers (stain cloth) and treated at 200° C for 1 min. Any staining on the undyed piece, change in tone, or loss in depth was assessed on 1 (poor) to 5 (very good) rating.

2.7. Colorimetric Analysis. tte color parameters of the dyed polyester fabrics were measured using the Applied Color System, CS-5 chroma-sensor, model 502 using D65 source and ultraviolet radiation [42]. Each fabric sample was folded twice so as to realize a total of four thicknesses of fabric. tte assessment of color-dyed fabrics was made in terms of tristimulus colorimetry [43]. tte CIE attributes of lightness (L *), chroma (C *), and hue (a* value represents the degree of redness (positive) and greenness (negative) and fc* represents the degree of yellowness (positive) and blueness (negative)) were calculated in the present work.

3. Results and Discussion

3.1. Synthesis and Spectral Characteristics. All relevant reactions are depicted in Schemes 1 and 2. 4-Methyl-2-phenyl-6-thioxo-1,6-dihydropyrimidine-5-carbonitrile 1, which is required as a starting material, was prepared in our previously reported [44]. Cyclization of thioxopyrimidine 1 with chloroacetone 2 in DMF in the presence of excess anhydrous potassium carbonate at room temperature gave the 1-(5-amino- 4-methyl-2-phenylthieno[2,3-d]pyrimidin-6-yl)ethanone 3 in good yields (Scheme 1). tte possible mechanism for formation of compound 3 can be explained by the reaction pathway depicted in Scheme 1. tte IR spectrum of the compound 3 indicated the absence of the C=N and C=S groups, and the amino group appears at 3424-3259 cm-1 in the form of two bands due to intramolecular association between the 5-NH2 and 6-COCH3 groups of compound 3 and the characteristic absorption band at 1663 cm-1 for the carbonyl group (C=O). In addition, the 1 H NMR spectra (CDCl3) of compound 3 showing a singlet at S 2.47 (3H, s) assigned for the acetyl group, a broad singlet at 3.76 (2H, br) assigned to the NH2 protons, and a multiplet at S 8.58-7.55 (5H, m) assigned to the phenyl protons were also confirmed by the mass spectra m/z 283 (M+, 100).

Moreover, treatment of compound 3 with 2,5-dimethoxytetrahydrofuran in glacial acetic acid produced the 1-[4-methyl-2-phenyl-5-(1H-pyrrol-1-yl)thieno[2,3-d]-pyrimidin-6-yl]ethanone 4 (Scheme 1). tte IR spectrum of the compound 4 indicates the absence of the NH2 group. tte HNMR spectra (CDCl3) of the compound 4 show a

singlet at S 2.09 (3H, s) assigned for the acetyl group and two triplets at S 6.50 (2H, t) and 6.87 (2H, t), which were readily assigned to the hydrogen attached at C3, C4 and C2, and C5 of the pyrrolyl ring, respectively. On the other hand, the 3-aryl-1-[4-methyl-2-phenyl-5-(1H-pyrrol-1-yl)thieno[2,3-d]pyrimidin-6-yl]prop-2-en-1-one chalcone dyes 6a-n were obtained in good yields (84-98%) based on Claisen-Schmidt condensation of compound 4 with appropriate aldehydes 5a-n (Scheme 2). tte formation of compounds 6a-n can be explained by the reaction pathway depicted in Scheme 2. tte mechanism [44] involves base (OH-) removes a C-H proton of CH3CO group in compound 4 to give carbanion 4 , which then adds to C=O group in aldehydes 5, followed then undergoes condensation via dehydration affording the final products 6a-n. tte structures of dyes 6a-n were established by examining spectral data and elemental analysis. tte IR spectrum of dyes 6a-n indicates the characteristic absorption bands at 1679-1622 cm-1 for the C=O group. Physical and spectral data of dyes 6a-n are given in Tables 1 and 2.

3.2. Absorption Spectral Characteristics. tte absorption maxima (Amax) of the dyes 6a-n were measured in DMF solution and are listed in Table 3. tte absorption maxima of the dyes 6a-n ranged from 412 to 488 nm, with dye 6e showing the highest Amax (488 nm) and 6a the lowest (412 nm). Color shifts are in accord with variations resultant from changes in substituents in these dyes. As seen from Table 3, structural modification occurs only in one terminal moiety, where a p-chlorophenyl donor 6a was replaced by a dialkyl(aryl)aminophenyl or heteroaryl or polycyclic groups. Such a modification could be expected to result in notable changes in the ^-conjugated and red shifts in the absorption spectra. tte Amax of dyes 6a-n is related to intramolecular charge transfer (ICT) chromophoric system in which these molecules consist of a typical A-rc-D structure, where 6-carbonyl-pyrrolythieno[2,3-d]pyrimidinyl, vinyl, and substituent moieties (R) are employed as acceptor (A), rc-conjugated center (rc), and donor (D) moieties, respectively. tte absorption maxima are mainly dominated by the nature of the excited state ^-electron system. As well known, a strong electron donor could help to stabilize the charge-separated excited state of the molecule; the red-shift could be explained by the electron-donating strength of donor group [35, 46].

Compound 6a, as a standard, absorbed at 412 nm and substituent effects on the absorption maxima were evaluated compared with this value. As is apparent in Table 3, introduction of electron-donating substituents into the 6-carbonyl-pyrroly-thieno[2,3-d]pyrimidinyl-based chromophore produces a significant bathochromic shifts of the absorption maxima. tte differences of these values are shown by AAmax. As a result, the dyes 6b-n were bathochromic shift of 11-76 nm. It can be seen from Table 3 that dyes 6b, 6e, 6l, and 6n selected in this case produced bathochromic shifts of 41 to 76 nm caused by introduction of the stronger electron-donating substituents (dialkyl(aryl)aminophenyl) into 6-carbonyl-pyrrolythieno[2,3-d]pyrimidinyl-based chromo-phore at which there is an electron density decrease

that should produce a bathochromic shift of Amax [46]. In general, with respect to the substituents R of dyes 6b, 6e, 6l, and 6n, the dyes were bathochromically shifted in the following order: diethylaminophenyl (6e) (AAmax 76 nm)>diphenylaminophenyl (6n) (AAmax 58nm)>dimethylaminophenyl (6b) (AAmax 43nm)>4-acetamidophenyl (6l) (AAmax 41 nm). Furthermore, the spectroscopic data also demonstrate that the dye 6e (Amax 488 nm) containing the diethylaminophenyl group showed a largest bathochromic shift of 76 nm.

On the other hand, Amax value in the case of selected dyes 6c, 6f, 6i, 6j, 6k, and 6m indicates that replacement of the p-chlorophenyl group of dye 6a for appropriate heteroaryl or polycyclic substituents, such as tolyl (6c), biphenylyl (6f), pyrenyl (6i), carbazolyl (6j), 2,4,6-trimethylphenyl (6k), and anthryl (6m), leads to a significant bathochromic shift of 11 to 69 nm. tte differences of these values are shown by AAmax. For instance, dye 6a was absorbed at 412 nm, with increasing donor ability from the p-chlorophenyl (6a) to the carbazolyl (6j), pyrenyl (6i), and anthryl (6m); their AAmax values show large bathochromic shifts to 442 nm (AAmax = 30 nm), 478 nm (AAmax = 66 nm), and 481 nm (AAmax = 69 nm), respectively. In general, with respect to the substituents R of dyes 6c, 6f, 6i, 6j, 6k, and 6m, the dyes were bathochromically shifted in the following order: anthryl (6m) (AAmax 69 nm)>pyrenyl (6i) (AAmax 66 nm)>biphenylyl (6f) (AAmax 44 nm)>carbazolyl (6j) (AAmax 30nm)>2,4,6-trimethylphenyl (6k) (AAmax 28nm)>tolyl (6c) (AAmax

11 nm). Moreover, the spectroscopic data also demonstrate that the dye 6g (Amax 442 nm) containing the furyl moiety shows a bathochromic shift of 18 nm in comparison with the dye 6h (Amax 424 nm) containing the thienyl moiety.

In brief, dyes derived from dialkyl(arkyl)aminophenyl substituents exhibited significantly larger bathochromic shift compared with those derived from heteroaryl or polycyclic substituents. Furthermore, it is well known that molar extinction coefficients e values reflect the molecular planarity and enlargement of ^-conjugation. tte dyes 6c, 6f, 6k, and 6m have bigger e values than those of other dyes which indicates that dyes 6c, 6f, 6k, and 6m have much more planar and rigid ^-conjugation system than that of other dyes [47].

3.3. Dyeing and Fastness Properties. For imparting greenish-yellow to orange hues, the dyes 6a-n were applied to polyester fiber at 1% shade by high-temperature-pressure techniques. tte fastness properties of the dyes are shown in Table 3. Table 3 shows that the light fastness of these dyes varied from 1-5; thus the dyes 6b, 6e, 6g, 6j, 6k, and 6l had poor light fastness (1-2), dyes 6c, 6d, 6f, 6h, 6i, and 6m had fair light fastness (3-4), and dyes 6a and 6n had good light fastness (4-5). In general, the dyes in the range of 3-5 show good sublimation fastness properties on polyester fibers.

3.4. Colorimetric Assessment. ttree important attributes of color that must be considered in the development of new colorants are lightness, chroma, and hue. ttese attributes can

5,6 a b c d e

R Oci <^^N(CH3)2 \J>~ -OCH3 ^^-N(C2HS)2

5,6 f g h i j

R u O r S^ [1 1 T 1) I lj CnD 1 C2H5

5,6 k l m n

R CH3 ^ NHCOCH3 \j) \w)

CH3 \J) u

Scheme 2: Synthesis of chalcone dyes 6(a-n).

be determined by colorimetric assessment using the prototype dye. He CIE attributes of lightness (L*), chroma (C*), and hue (a* = redness/greenness; b* = yellowness/blueness) were calaulated in the present work. He values of the CIE coordinate (L*, a*, b*, h°, and C*) are listed in Table 4. According to Richter [48] and McLaren et al. [49] the position of the color is distributed in the red-green area with hue angle hh 33.07-116.83° and radial chroma C* of length 8.35-48.08. Figure 1 shows a graph of CIE coordinates a* versus b* for selected dyes 6b, 6e, 6l, and 6n (an increasing a* value represents an increase in redness, while a decrease in a* represents a green hue shift). Dyes 6l and 6n provided a reference point for the color attributes of each dye, since 6l is

a yellow and 6n is a strong orange. He dye based on dimethy-laminophenyl (6b) was yellow-orange, and thus the a* b* graph shows the dye to be bathochromic compared with 6l and hypsochromic relative to 6n. Apart from 6e and 6n, dyes displayed similar hues both to each other and to 6l. Hence, the presence of stronger electron-donating substituents in the 6-carbonyl-pyrrolythieno[2,3-d]pyrimidinyl-based chro-mophore linkage produced the desired colorimetric effect.

Furthermore, Figures 2 and 3 show a graph of CIE C* versus L* for selected dyes (6b, 6e, 6l and 6n) and (6a, 6c, 6d, 6f-6k, and 6m), respectively. In general, dyes derived from dialkyl(arkyl)aminophenyl substituents exhibited significantly higher chroma compared with those derived from

Table 3: Absorption spectra and dyeing properties of 6-(3-substituted-acryloyl)-5-(1-pyrrolyl)-4-methyl-2-phenyl-thieno[2,3-d]pyrimidine derivatives 6a-n.

I y—COCH=CHR S

Colour on dyed polyester fibers

(DMF)(nm)

£X 1CT

_j _j AAmax Light fastness Sublimation fastness (mol cm )

6a 6b 6c 6d

N(CH3)2

\\ // N(CH 3

6e ^N(C2H5)2

II .1 L II

" N ' I

<^CH CH3

NHCOCH3

f « o-v

Light yellow Orange Greenish yellow Yellow Orange Yellow

Yellow

Yellow

Yellow Light yellow

Greenish yellow Yellow

Orange yellow

Orange

424 488

442 424

418 442

440 453

6.02 1.83 8.43 6.24 3.81 9.34

43 11 12 16

4.39 30

1.13 41

5 1-2 3-4 3-4 2

6.64 30 2-3

6.23 12

3.04 66 3-4

1.11 69

4.09 58 4-5

3-4 3-4 3

Table 4: CIE of dyes 6a-n on polyester.

Dye L' a' b' C' h" K/S

6a 88.40 0.09 9.52 9.52 90.56 0.1789

6b 91.32 17.34 37.98 41.76 65.46 0.9125

6c 84.29 -3.77 7.45 8.35 116.83 0.3417

6d 91.06 -6.12 21.90 22.74 105.60 0.4236

6e 85.84 33.35 34.63 25.55 46.06 1.3319

6f 89.61 -0.79 15.38 15.40 92.96 0.2368

6g 73.24 6.04 15.97 17.07 69.27 0.7793

6h 88.41 -3.80 24.22 24.52 98.92 0.5565

6i 89.52 -0.10 11.27 11.27 90.50 0.3050

6j 90.60 -6.69 33.96 34.61 101.14 0.8942

6k 82.53 -2.94 12.51 12.85 103.22 0.6437

61 85.06 5.34 24.99 48.08 46.08 0.4600

6m 83.41 9.27 20.99 22.95 66.18 0.3820

6n 76.37 35.23 22.94 42.04 33.07 0.5334

40 -| 38 -36 -34 -32 -30 -28 -26 -24 -22 -

• 6l

• 6b

• 6n

5 10 15 20 25 30 35 40

Figure 1: Graph of CIE a* versus b* for selected dyes.

92 -90 -88 -86 -L* 84 -82 -80 -78 -76 -

• 6e

Figure 2: Graph of CIE C* versus L* for selected dyes.

heteroaryl or polychlic substituents. Figure 2 shows that the dyes 6b, 6e, and 6l were lighter than 6n. Similar results are observed in Figure 3; the lightness of 6a, 6c, 6d, 6f, 6h-k, and 6m were all high except for dye 6g.

On the other hand, Figure 4 shows a graph of CIE coordinates a* versus b* for selected dyes 6a, 6c, 6d, 6f-6k and 6m. As the b* scale represents yellowness (increasing b* value) versus blueness (decreasing b* value), it is evident that most of the new dyes were significantly yellower than 6c. He dye 6f based on biphenylyl possessed approximately the same yellowness but was redder than dye 6j. However, the dyes 6c, 6d, 6h, and 6k were green hue shift relative to the dye 6f, although not as green as 6j, and were similar in hue to 6d. Also, the dyes based on p-chlorophenyl (6a) and tolyl (6c) were bluer than biphenylyl (6f) and 2,4,6-trimethylphenyl (6k). In the case of 6a and 6c, the hypsochromic shift due to the presence of weak electron-donating substituents in the 6-carbonyl-pyrrolythieno[2,3-d]pyrimidinyl-based chro-mophore linkage is significant. In addition, dyes based on

furyl (6g) and anthryl (6m) were bathochromic relative to when p-chlorophenyl (6a) was employed.

4. Conclusions

Fourteen novel heterocyclic chalcone derivatives containing a thieno-[2,3-d]pyrimidine-based chromophore were obtained from thioxopyrimidine 1. He chalcone derivatives were applied to polyester fibers as disperse dyes for creating hues ranging from greenish-yellow to orange. He substituent effect in DMF solution was also discussed. He results indicate that the novel chalcone dyes derived from dialkyl(arkyl)aminophenyl substituents exhibited significantly larger bathochromic shift compared with those derived from heteroaryl or polycyclic substituents. On the other hand, color shifts are in accord with variations resultant from changes in substituents in these dyes. In general, the presence of dialkyl(aryl)aminophenyl substituents in the thieno[2,3-d]pyrimidinyl-based chromophore linkage produced the red hue shift, while the heteroaryl or polychlic

6a 0 6c*

5 10 15 20 25 30 35

Figure 3: Graph of CIE C* versus L* for selected dyes.

40 35 30 25

20 6f 1»

6i »6a

—.—i—0--4 -2 0 a*

Figure 4: Graph of CIE a* versus b* for selected dyes.

substituents produced the green hue shift. In addition, these dyes showed good sublimation fastness and poor- to good-light fastness on polyester fibers.

Acknowledgments

tte authors are grateful to the high valued instrument Center of National Taiwan Normal University for measuring the data of spectroscopy. ttey also want to thank National Science Council of Taiwan (NSC 97-2113-M-253-001) for their financial support.

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