Synthesis and application of some novel fluorescent heterocyclic disperse dyestuffs based on phenothiazine on polyester

M. Hosseinnezhad; K. Gharanjig; S. Moradian; S. Tafaghodi

doi:10.1016/j.arabjc.2014.12.027

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Original article

12 (

); 2069-2076

doi:

10.1016/j.arabjc.2014.12.027

Synthesis and application of some novel fluorescent heterocyclic disperse dyestuffs based on phenothiazine on polyester

M. Hosseinnezhad^{^a}, K. Gharanjig^{^a,^c,⁎}, S. Moradian^{^b,^c}, S. Tafaghodi^{^a}

a Department of Organic Colorants, Institute for Color Science and Technology, P.O. Box 16656118481, Tehran, Iran

b Faculty of Polymer and Color Engineering, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran, Iran

c Center of Excellence for Color Science and Technology, Institute for Color Science and Technology, P.O. Box 16656118481, Tehran, Iran

⁎Corresponding author at: Department of Organic Colorants, Institute for Color Science and Technology, P.O. Box 16656118481, Tehran, Iran. gharanjig@icrc.ac.ir (K. Gharanjig)

Received: 2012-8-15, Accepted: 2014-12-31, Published: 2015-12-01

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Peer review under responsibility of King Saud University.

Abstract

A series of novel heterocyclic disperse dyestuffs derived from phenothiazine were prepared by standard reactions from phenothiazine as the starting material. Phenothiazine was nitrated and oxidized then reduced to obtain synthesized disperse dyestuffs. The reaction conditions were varied in order to obtain optimal yields for each stage of the preparation to obtain the corresponding derivative and final disperse dyestuffs. All intermediates and disperse dyestuffs were purified and characterized by DSC, FTIR, ¹H NMR, ¹³C NMR, elemental analysis and UV–Visible spectroscopic techniques. The molar extinction coefficients (ε), wavelengths of maximum absorption (λ_max) and solvatochromism effects were studied in solvents as toluene, acetone and N,N-dimethylformamide (DMF). Results represented that the dyestuffs had extinction coefficients of 2011–28189 L mol⁻¹ cm⁻¹, wavelengths of maximum absorption of 448–475 nm in acetone and positive solvatochromism by changing solvent from toluene to DMF. The disperse dyestuffs were applied to locally manufactured polyester fibers and their dyeing properties were investigated. Results showed that the buildup of dyestuffs was acceptable and dyed fibers had very good heat and wash fastness and medium light fastness on polyester fibers.

Keywords

Phenothiazine

Synthesis

Polyester

Disperse dyestuff

Fastness properties

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1 Introduction

Phenothiazine was first prepared by Bernthsen in 1883 in the course of proving the structures of violet and methylene blue through studies on Lauth’s methods. Since then it has played an important role in dye chemistry as the parent compound of the thiazine dyes. In the last twenty years phenothiazine and its derivatives have found numerous applications in other fields, and this has stimulated further research on these compounds (Pineroa et al., 2008; Msorrison and Boyd, 1992). Phenothiazines (PH) and their related derivatives are used in many applications including medicinal chemistry (Wainwright et al., 2007; Lacasse et al., 2006; Barra et al., 1991 ), polymer chemistry (Barra et al., 1991), dyes (Rizk et al., 2011), sensors (Bakhtiari et al., 2014), and material science (Nodiff and Hausman, 1964). The usefulness of the PH derivatives is determined by the type and position of the substituents because they strongly affect their redox, photophysical, and photochemical properties. The neuroleptic activity of the PH derivatives is greatly enhanced by substituting the heterocyclic nitrogen with a propylamino chain (Mitchell, 2006). Molecules bearing these properties are chlorpromazine, triflupromazine, and promethazine. Other molecules with similar pharmacological properties are derivatives having a propylpyrazine as the nitrogen side chain including thioridazine and trifluoperazine (Kurihara et al., 1999). Tests showed that the substitution at the C2-position apparently affects the tumor cell activity and the length of the aliphatic side chain at N10 contributes to the anti-tumor activity and the cytotoxicity of the resulted drugs (Nagy et al., 1996). 2-Trifluoromethyl phenothiazine, for instance, shows potent antitumor activity whereas the corresponding chlorine derivative has a relative weak effect (Eregowda et al., 2000). Biological relevant phenothiazine derivatives substituted at the C2-position are also known to induce photosensitization of the skin after systematic use or topical applications (Mitchell, 2006). Therefore, it is pertinent and relevant to search for new derivatives with fewer side effects and to acquire knowledge on their photophysical and photochemical properties that depend on the C2-substitutions (Lakowicz, 2006). Disperse dyes have experienced moderate patent activity over the last three year. The structures of the new example reflect a continuation of a 20-year-old trend in this area, namely the development of bright dyes containing heterocyclic especially phenothiazines rings. The most often patented dyes were based on heterocyclic amines and the combination of heterocyclic dyes. Other recently patented disperse dyes are based on phenothiazine derivatives. In this case the main aim is to enhance technical fastness degrees and buildup properties of these derivatives (Freeman and Sokolowska, 1999).

In the present study, a series of novel heterocyclic disperse dyestuffs have been synthesized and investigated for the first time. In this respect, phenothiazine was nitrated and oxidized and finally reduced to obtain the disperse dyestuffs (Fig. 1). All intermediates and final disperse dyestuff were purified in order to be in an unmixed form. The obtained pure dyestuffs and their corresponding intermediates were characterized by DSC, FTIR, ¹H NMR, ¹³C NMR, elemental analysis and UV–Visible spectroscopic techniques. Spectrophotometric investigations of the prepared dyestuffs in various solvents were carried out in order to obtain their wavelengths of maximum absorption and color intensities. Finally the disperse dyestuffs were applied on polyester fabrics and their dyeing properties and the obtainable color gamut were measured.

Synthesis of the dyestuffs and their intermediates; R = CH3 in 1, 3, 5, 7, 9 and 11 and R = C4H9 in 2, 4, 6, 8, 10 and 12.

2 Experimental

2.1

2.1 Materials and apparatus

All compounds used in this study were of analytical grade unless otherwise stated. Apparatuses utilized in this research were as follows: FTIR measurements were carried out on a Bomene Canada instrument. NMR measurements were carried out on a 500 MHz Joel instrument. DSC thermal analysis measurements were carried out on a Dupont 2000 DSC instrument. UV–Visible spectrophotometry was carried out on a Cecil 9200 double beam transmission spectrophotometer. Elemental analysis was carried out by a CHNO AnalyserFrossHerps machine.

2.2

2.2 Synthesis of intermediates

2.2.1

2.2.1 Synthesis of N-methyl (butyl) phenothiazine (1, 2)

A mixture of 10 mmol phenothiazine, 10 mmol methyl bromide (butyl bromide) and 75 mL DMF was added to a 50 mL two-necked glass reactor. The solution was heated to 60 °C and treated portionwise with 15 mmol potassium tert-butoxide and then refluxed for 18 h. After water (150 mL) was added, the mixture was extracted with chloroform (75 mL). Crude oils obtained by removing the remaining solvent were purified by column chromatography (silica gel, n-hexane: ethyl acetate; 20:1 as eluent) to give corresponding N-alkyl phenothiazine.

2.2.2

2.2.2 Synthesis of 3-nitro-N-methyl (butyl) phenothiazine (5, 6)

A mixture of N-alkyl phenothiazine (28 mmol) was dissolved in 1,2-dichloroethane (25 mL) and the solution cooled down in an ice–water bath to 10 °C. Concentrated nitric acid (31 mmol, 65–68%) was dropped in for 1 h with vigorous stirring. Stirring was continued for a further hour at 10 °C. The obtained liquor was steam distilled to remove 1,2-dichloroethane; the mixture was cooled and filtered and the product washed several times with water.

2.2.3

2.2.3 Synthesis of 3-formyl-N-methyl (butyl) phenothiazine (3, 4)

POCl₃ (8.31 mL) was added dropwise to freshly distilled DMF (10 mL) at 0 °C under nitrogen atmosphere. A solution of N-methyl (butyl) phenothiazine (10 mmol) in DMF (25 mL) was added dropwise to the POCl₃/DMF complex at 30 °C. The reaction mixture was stirred at 80 °C for 4 h. When the reaction was completed (TLC monitoring), the reaction mixture was cooled down to room temperature and poured into an ice–water mixture. The obtained mixture was neutralized with NaOH until pH 7–8 was obtained. The precipitates were separated by filtration and washed with methanol. The crude product was purified by column chromatography (ethylacetate:hexane; 1:6 as eluent).

2.2.4

2.2.4 Synthesis of 3-formyl-6-nitro-N-methyl (butyl) phenothiazine (7, 8)

3-Formyl-N-alkyl phenothiazine (35 mmol) was dissolved in 1,2-dichloroethane (25 mL) and the solution cooled in an ice–water bath to 10 °C. Concentrated nitric acid (31 mmol, 65–68%) was dropped in over 1 h with vigorous stirring. Stirring was continued for a further hour at 10 °C. The obtained liquor was steam distilled to remove 1,2-dichloroethane; the mixture was cooled and filtered and the product washed several times with water.

2.3

2.3 Synthesis of dyestuffs

2.3.1

2.3.1 Synthesis of 3-amino-N-methyl (butyl) phenothiazine (9, 10)

A mixture of 3-nitro-N-methyl (butyl) phenothiazine (15 mmol), SnCl₂ (20 g), ethanol (20 mL) and hydrochloric acid (5 mL) was added to a two-necked glass reactor. The solution was refluxed for 2 h. After water (150 mL) was added, the mixture was purified by column chromatography (silica gel, n-hexane: ethyl acetate; 15:1 as eluent) to give 3-amino-N-alkyl phenothiazine.

2.3.2

2.3.2 Synthesis of 3-formyl-6-amino-N-methyl (butyl) phenothiazine (11, 12)

A mixture of 3-formyl-7-nitro-N-methyl (butyl) phenothiazine (20 mmol), SnCl₂ (26 g), ethanol (25 mL) and hydrochloric acid (7 mL) was added to a two-necked glass reactor. The solution was refluxed for 3 h. After water (150 mL) was added, the mixture was purified by column chromatography (silica gel, n-hexane: ethyl acetate; 15:1 as eluent) to give 3-formyl-7-amino-N-butyl phenothiazine.

2.4

2.4 Dyeing polyester fabrics

Polyester fabrics (1 g) were pretreated with a nonionic detergent (5 g/L) at 80 °C for 20 min prior to dyeing. Dyeing was carried out using a liquor ratio (L:G) of 50:1.(pH4–5 adjusted by acetic acid). The concentrations of the dyestuff dispersions were 0.1%, 0.4%, 0.8%, 1.2%, 2%, 4% and 8% (owf). Dyeing was performed by raising the dye bath temperature from 30 °C to 90 °C at the rate of 2 °C/min followed by further raising the temperature from 90 °C to 130 °C at 1 °C/min. Staying at this temperature for 60 min and then cooling to 70 °C at 3 °C/min. The dyed fabrics were reduction cleared with sodium hydrosulfite (2 g/L), sodium hydroxide (3 g/L), detergent (1 g/L) for 20 min at 50 °C. The dyed fabrics were thoroughly rinsed by cold water at the end.

3 Results and discussions

3.1

3.1 Synthesis of intermediates and dyestuffs

In early work (Rizk et al., 2011), some heterocyclic dyestuffs were prepared by nucleophilic attach. However, in this work, phenothiazine was reacted with alkyl bromide in order to obtain N-alkyl phenothiazine. The aldehydes were prepared by a Vilsmeier reaction of N-alkyl phenothiazine with phosphoryl chloride (POCl₃) in DMF. The main products of the mono-nitration were 3-nitro-N-alkyl phenothiazine and 3-formyl-7-nitro-N-alkyl phenothiazine when using nitric acid (65–68%) as nitrating agent. The nitration of aromatic compounds using nitric acid in a neutral organic solvent mainly involves the attacking of nitronium ion to the aromatic ring.

The σ-complex intermediate is initially formed from the nitronium ion and phenothiazine during the nitration. The stability of this intermediate is the decisive factor influencing the position of the entering nitro group. The resonance structure for the ortho- or para-σ-complex in phenothiazine is stabilized by the effect of the unshared pair of electrons on the N-hetero atom; the para-σ-complex is much more stable than the ortho-analogue due to the spatial effect of the substituent on the nitrogen atom and also the field effect so that the 3- and 6-positions are the most reactive ones. The main product of mono-nitration is therefore the 3-nitro derivative; formation of the 1-nitro derivative and dinitro compounds is negligible (Mitchell, 2006; Lakowicz, 2006). The yields (Y%), melting points and the intermediate crystals’ forms and colors of are given in Table 1. The FTIR, ¹H NMR, ¹³C NMR spectra and elemental analysis data of all these intermediates are given in Table 2.

Table 1 Characterization of synthesized intermediates.

Intermediates	Y (%)	Form of crystals	Color	m.p. (°C)
1	82	Needle	White	103.4
2	85.3	Needle	White	112
3	82.5	Needle	Pale yellow	117.6
4	76.8	Needle	Pale yellow	123.4
5	84.6	Needle	Pale yellow	128.7
6	83.8	Needle	Pale yellow	131.2
7	86.7	Needle	Pale yellow	133.3
8	82.9	Needle	Pale yellow	139.9

Table 2 FTIR, ¹H NMR, ¹³C NMR spectra and elemental analysis of intermediates.

Intermediate	R	FTIR, ¹H NMR, ¹³C NMR spectra and elemental analysis
1	CH₃	FTIR (KBr) (cm⁻¹): 3120: C—H str. Ar., 1657, 1470: C⚌C str, 1298: C—N str; ¹H NMR (CDCl₃), δ (ppm): 3.73 (s, 3H, CH₃), 7.46–7.47 (d, 2H, J = 7.5 Hz), 7.57 (t, 2H, J = 7 Hz), 7.73 (t, 2H), 8.10–8.12 (d, 2H, J = 7.8 Hz); ¹³C NMR (CDCl₃) δ (ppm): 115.71, 118.45, 123.4, 127.2, 131.44, 133.49, 135.49, 140.38, 44.4; Elem. Anal. Calcd. for C₉H₁₁NS: C, 73.24%; H, 5.16%; N, 6.57%. Found: C, 73.2%; H, 5.11%; N, 6.61%
2	C₄H₉	FTIR (KBr) (cm⁻¹): 3117: C—H str. Ar., 1660, 1607: C⚌C str., 1486: C—N str;¹H NMR (CDCl₃), δ (ppm): 4.12 (2H, CH₂CH₂CH₂CH₃), 2.77 (2H, CH₂CH₂CH₂CH₃), 1.56 (2H, CH₂CH₂CH₂CH₃), 1.02 (3H, CH₂CH₂CH₂CH₃), 7.35–7.37 (d, 2H, J = 7 Hz), 7.69 (t, 2H, J = 7.5 Hz), 7.77 (t, 2H), 8.25–8.30 (d, 2H, J = 7.7 Hz); ¹³C NMR (CDCl₃) δ (ppm): 107.10, 111.15, 119.13, 120.7, 124.44, 132.73, 138.49, 146.1, 13.2, 27.6, 39.9; Elem. Anal. Calcd. for C₁₆H₁₇NS: C, 75.29%; H, 6.66%; N, 5.49%. Found: C, 75.33%; H, 6.69%; N, 5.43%
3	CH₃	FTIR (KBr) (cm⁻¹): 3117: C—H str. Ar., 2870: C—H str. Ald, 1720: C⚌O str, 1649, 1468: C⚌C str, 1288: C—N str; ¹H NMR (CDCl₃), δ (ppm): 3.78 (3H, CH₃), 7.04–7.07 (d, 2H, J = 7.4 Hz), 7.09 (t, 1H, J = 7.1 Hz), 7.16 (t, 1H), 7.33–7.36 (d, 1H, J = 7.9 Hz), 7.40 (t, 1H, J = 7.6 Hz), 7.45 (s, 1H), 9.32 (s, 1H, COH); ¹³C NMR (CDCl₃) δ (ppm): 264.65(C⚌O), 109.57, 112.49,119.53, 121.6, 128.56, 134.65, 21.84; Elem. Anal. Calcd. for C₁₄H₁₁NSO: C, 69.71%; H, 4.61%; N, 5.78%. Found: C, 69.69%; H, 4.56%; N, 5.81%
4	C₄H₉	FTIR (KBr) (cm⁻¹): 3114: C—H str Ar., 1736: C⚌O str., 1650, 1615: C⚌C str, 1479: C—N str; ¹H NMR (CDCl₃), δ (ppm): 3.72 (2H, CH₂CH₂CH₂CH₃), 2.81 (2H, CH₂CH₂CH₂CH₃), 2.16 (2H, CH₂CH₂CH₂CH₃), 1.77 (3H, CH₂CH₂CH₂CH₃), 6.93–6.96 (d, 2H, J = 7.1 Hz), 7.18 (t, 1H, J = 7.4 Hz), 7.31–7.34 (d, 1H, J = 7.8 Hz), 7.42–7.45 (d, 1H, J = 7.5 Hz), 7.47 (t, 1H), 7.50 (s, 1H,), 9.38 (s, 1H, COH); ¹³C NMR (CDCl₃) δ (ppm): 258.34 (C⚌O), 106.5, 112.32, 112.97, 121.9, 128.76, 130.14, 134.76 (Ar), 17.9, 21.54, 32.4 (Aliphatic); Elem. Anal. Calcd. for C₁₇H₁₇NSO: C, 72.08%; H, 6.00%; N, 4.94%. Found: C, 72.11%; H, 6.07%; N, 4.9%
5	CH₃	FTIR (KBr) (cm⁻¹): 3121: C—H str, 1545, 1330: NO₂ str, 1655, 1623: C⚌C str, 1491: C—N str; ¹H NMR (CDCl₃), δ (ppm): 3.02 (3H, CH₃), 7.10–7.12 (d, 2H, J = 7 Hz), 7.16–7.18 (d, 1H, J = 7.5 Hz), 7.24 (t, 1H, J = 7.7 Hz), 7.28–7.31 (d, 1H, J = 7.9 Hz), 7.34 (s, 1H), 7.37 (s, 1H); ¹³C NMR (CDCl₃) δ (ppm): 118.50, 119.38, 121.48, 123.58, 129.87, 130.58, 141.73(Ar), 19.87, 25.38, 43.17 (Aliphatic); Elem. Anal. Calcd. for C₁₃H₁₀N₂SO₂: C, 60.46%; H, 3.87%; N, 10.85%. Found: C, 60.49%; H, 3.85%; N, 10.86%
6	C₄H₉	FTIR (KBr) (cm⁻¹): 3117: C—H str, 1558, 1347: NO₂ str, 1647, 1623: C⚌C str, 1485: C—N str; ¹H NMR (CDCl₃), δ (ppm): 3.92(2H, CH₂CH₂CH₂CH₃), 3.46 (2H, CH₂CH₂CH₂CH₃), 2.74 (2H, CH₂CH₂CH₂CH₃), 0.84 (3H, CH₂CH₂CH₂CH₃), 6.84–6.88 (d, 2H, J = 7 Hz), 6.89–6.92 (d, 1H, J = 7.5 Hz), 6.94 (t, 1H, J = 7.7 Hz), 7.11–7.15 (d, 1H, J = 7.6 Hz), 7.19 (s, 1H), 7.25 (s, 1H); ¹³C NMR (CDCl₃) δ (ppm): 118.94, 119.48, 122.75, 128.37, 132.49, 139.58, 143.71 (Ar), 19.85, 25.9, 27.19, 32.58 (Aliphatic); Elem. Anal. Calcd. for C₁₆H₁₆N₂SO₂: C, 64.04%; H, 5.33%; N, 9.38%. Found: C, 64.00%; H, 5.33%; N, 9.33%
7	CH₃	FTIR (KBr) (cm⁻¹): 3122: C—H str, 1554, 1338: NO₂ str, 1758: C⚌O str., 1630, 1614: C⚌C str, 1478: C—N str; ¹H NMR (CDCl₃), δ (ppm): 1.28 (s, 3H, CH₃), 6.64–6.66 (d, 2H, J = 7.8 Hz), 6.71–6.73 (d, 1H, J = 7 Hz), 6.75–6.78 (d, 1H, J = 7.5 Hz), 6.83 (s, 1H), 7.16 (s, 1H), 9.55 (s, 1H, COH); ¹³C NMR (CDCl₃) δ (ppm): 188.39(C⚌O), 111.4, 112.28, 116.32, 125.48, 135.53, 143.83(Ar), 33.42 (Aliphatic); Elem. Anal. Calcd. for C₁₄H₁₀N₂SO₃: C, 58.74%; H, 3.49%; N, 9.79%. Found: C, 58.70%; H, 3.44%; N, 9.82%
8	C₄H₉	FTIR (KBr) (cm⁻¹): 3121: C—H str, 1549, 1327: NO₂ str, 1743: C⚌O str, 1626, 1619: C⚌C str, 1482: C—N str; ¹H NMR (CDCl₃), δ (ppm): 3.78 (2H, CH₂CH₂CH₂CH₃), 3.34 (2H, CH₂CH₂CH₂CH₃), 2.29 (2H, CH₂CH₂CH₂CH₃), 1.04 (3H, CH₂CH₂CH₂CH₃), 7.14–7.16 (d, 2H, J = 7 Hz), 7.21–7.23 (d, 1H, J = 7.7 Hz), 7.25–7.27 (d, 1H, J = 7.3 Hz), 7.33 (s, 1H), 7.39 (s, 1H), 9.48 (s, 1H, COH); ¹³C NMR (CDCl₃) δ (ppm): 215.72 (C⚌O), 117.36, 122.94, 124.71, 129.32, 137.54, 145.97 (Ar), 21.73, 36.86, 42.58 (Aliphatic); Elem. Anal. Calcd. for C₁₇H₁₆N₂SO₃: C, 62.19%; H, 4.87%; N, 8.53%. Found: C, 62.15%; H, 4.85%; N, 8.54%

The dyestuffs were synthesized by the reaction of intermediates containing nitro groups with stannous chloride (II) in hydrochloric acid as reducing agent and ethanol as solvent. Purification of products was carried out by column chromatography on silica gel G (60–120) using hexane and ethyl acetate (15:1) mixtures. However, four novel disperse dyestuffs have been prepared from phenothiazine as the starting material and investigated the influence of NO₂, NH₂, CHO and R (CH₃ and C₄H₉) substituents on dyeing and fastness properties from the first time. The melting points, FTIR, ¹H NMR, ¹³C NMR spectra and elemental analysis data of all the synthesized dyestuffs are given in Table 3.

Table 3 FTIR, ¹H NMR, ¹³C NMR spectra and elemental analysis of dyestuffs.

Dyestuff	R	FTIR, ¹H NMR, ¹³C NMR spectra and elemental analysis
9	CH₃	mp134.5 °C, FTIR (KBr) (cm⁻¹): 3125: C—H str, 3421: NH str, 1654, 1631: C⚌C str, 1454: C—N str; ¹H NMR (CDCl₃), δ (ppm): 3.14 (s, 3H, CH₃), 5.17 (2H, NH₂), 7.12–7.14 (d, 2H, J = 7.3 Hz), 7.16 (t, 1H, J = 7.5 Hz), 7.21 (t, 1H, J = 7.9 Hz), 7.27–7.29(d, 1H, J = 7 Hz), 7.37–7.39 (d, 1H, J = 7.6 Hz), 7.62 (s, 1H); ¹³C NMR (CDCl₃) δ (ppm): 113.72, 115.42, 118.24, 120.58, 123.76, 132.57, 134.52 (Ar), 21.4 (Aliphatic); Elem. Anal. Calcd. for C₁₃H₁₂N₂S: C, 68.42%; H, 5.26%; N, 12.28%. Found: C, 68.47%; H, 5.22%; N, 12.26%
10	C₄H₉	mp139.7 °C, FTIR (KBr) (cm⁻¹): 3121: C—H str, 3332: NH str., 1743: C⚌O str., 1655, 1627: C⚌C str, 1465: C—N str; ¹H NMR (CDCl₃), δ (ppm): 3.78 (2H, CH₂CH₂CH₂CH₃), 3.34 (2H, CH₂CH₂CH₂CH₃), 2.61 (2H, CH₂CH₂CH₂CH₃), 1.32 (3H, CH₂CH₂CH₂CH₃), 5.35 (2H, NH₂), 7.14–7.16 (d, 2H, J = 7.4 Hz), 7.17–7.19 (d, 1H, J = 7.9 Hz), 7.23–7.26 (d, 1H, J = 7 Hz), 7.29 (s, 1H), 7.35 (s, 1H), 9.27 (1H, COH); ¹³C NMR (CDCl₃) δ (ppm): 113.68, 115.32, 119.41, 124.76, 127.84, 138.42, 145.93(Ar), 17.48, 27.98, 32.54, 33.25 (Aliphatic); Elem. Anal. Calcd. for C₁₄H₁₂N₂SO: C, 65.62%; H, 4.68%; N, 10.93%. Found: C, 65.66%; H, 4.72%; N, 10.95%
11	CH₃	mp 152.3 °C, FTIR (KBr) (cm⁻¹): 3124: C—H str, 3426: NH str., 1725: C⚌O str, 1656, 1620: C⚌C str, 1475: C—N str; ¹H NMR (CDCl₃), δ (ppm): 3.32 (s, 3H, CH₃), 7.13–7.175 (d, 2H, J = 7.2 Hz), 7.19 (t, 1H, J = 7.5 Hz), 7.24 (t, 1H, J = 7.8 Hz), 7.29–7.31 (d, 1H, J = 7.12 Hz), 7.35–7.36 (d, 1H, J = 7.6 Hz), 7.39 (s, 1H); ¹³C NMR (CDCl₃) δ (ppm):214.25 (C⚌O), 112.39, 117.65, 119.04, 127.48, 129.83, 139.11, 143.15(Ar), 17.29 (Aliphatic); Elem. Anal. Calcd. for C₁₆H₁₆N₂S: C, 71.08%; H, 6.63%; N, 10.38%. Found: C, 71.11%; H, 6.66%; N, 10.37%
12	C₄H₉	mp161.3 °C, FTIR (KBr) (cm⁻¹): 3117: C—H str, 3475: NH str., 1737: C⚌O str, 1641, 1618: C⚌C str, 1476: C—N str; ¹H NMR (CDCl₃), δ (ppm): 3.85 (2H, CH₂CH₂CH₂CH₃), 3.48 (2H, CH₂CH₂CH₂CH₃), 2.71 (2H, CH₂CH₂CH₂CH₃), 1.26 (3H, CH₂CH₂CH₂CH₃), 7.13–7.16 (d, 2H, J = 7.5 Hz), 7.17–7.20 (d, 1H, J = 7.8 Hz), 7.22–7.26 (d, 1H, J = 7.18 Hz), 7.29 (s, 1H), 7.41 (s, 1H), 9.32 (s, 1H, COH); ¹³C NMR (CDCl₃) δ (ppm): 234.65(C⚌O), 116.6, 118.37, 123.45, 129.64, 135.12, 141.17, 146.95(Ar), 19.85,26.82, 32.34,45.76 (Aliphatic); Elem. Anal. Calcd. for C₁₇H₁₈N₂SO: C, 68.41%; H, 6.07%; N, 9.42%. Found: C, 68.45%; H, 6.04%; N, 9.39%

3.2

3.2 Electronic absorption and fluorescence spectra

It is a well-accepted fact that the constitution of dyestuffs has a fundamental role in producing the desired color over substrates. The correlation between the color and constitution is a highly interesting aspect of dyestuffs development and commercialization. Due to the abovementioned points, the subject has attracted the attention of the companies producing commercial disperse dyestuffs (Boschloo and Hagfeldt, 2005; Choi et al., 2000). The wavelengths of maximum absorption (λ_max) and molar extinction coefficients (ε_max) are all equally important for dyestuffs (Sing et al., 2003). The absorption spectra of the dyestuffs 9–12 were determined in toluene, acetone and DMF solvents and summarized in Table 4. In the present study, the carbonyl groups of aldehydes in dyestuffs 11 and 12 act as an acceptor group and amino group acts as a donor; therefore, these dyestuffs exhibit bathochromic effects. The measurement of maximum absorption of the dyestuff in toluene, acetone and DMF (Table 4) showed that all dyestuffs have positive solvatochromic effects which occur when polarity of the solvent increases. We found that the absorption maximum of dyestuffs generally indicated bathochromic shifts as the polarity of solvent was increased. Apparently these dyes exhibit a strong solvent dependence. The influence of solvents on dyes increases in the order of DMF > acetone > toluene. Heterocyclic based disperse dyestuffs tend to show larger solvatochromic effects than benzene based dyes because of increased polarity of the dye system especially in the excited state (Seferoglu et al., 2008). The presence of the N-butyl group in the imide system (N-C₄H₉) and CHO substituent of dyestuff 12 result in an increase in the dipolar and absorption maximum band. It was observed that in dyestuffs 9 and 10 the absorption is lower than dyestuffs 11 and 12. This is due to presence of the CHO group in molecular structures of the aforementioned dyestuffs. The presence of electron-acceptor and electron-donor substituents makes the largest bathochromic shifts in dyestuffs 11 and 12 (Philipova et al., 1995). The difference between the dyestuff 12’s absorption maxima in DMF and Toluene was 54 nm whereas for dyestuff 10 this difference was about 43 nm. This foundation showed that the presence of a NH₂ group and an aldehyde group on dyestuff molecules leads to an increase in the bathochromic effects.

Table 4 The absorption data of synthesized dyestuffs.

Dye	Toluene	Acetone	DMF
Dye	λ_max (nm)	λ_max (nm)	λ_max (nm)	ε (L mol⁻¹ cm⁻¹)
9	416.3	448.5	468.5	20,111
10	432.7	460	476.4	26,034
11	422.1	450	481.3	20,431
12	442.8	475	496.7	28,189

The fluorescent characteristics of all synthesized dyes were measured in DMF and are represented in Fig. 2 and Table 5. In DMF solutions, dyestuffs 9–12 show intense yellow–green fluorescence due to the charge transfer from the electron donating amino group to the accepting aldehyde group.

The emission spectra of synthesized dyes.

Table 5 The fluorescent characteristics of dyestuffs at concentration 10⁻⁴ mol L⁻¹ in DMF solution.

Dye	λ_F (nm)	Δυ_1/2 (cm⁻¹)	υ_A–υ_F (cm⁻¹)	f	Φ_F	E_F
9	524	4100	2261	0.356	0.38	0.34
10	532	4252	2194	0.478	0.41	0.37
11	527	4196	1802	0.371	0.66	0.60
12	539	4291	1608	0.522	0.91	0.84

The emission of dyestuffs is in the visible region at about 524–539 nm. It proves that dyestuffs 9 and 10 have similar fluorescent behaviors in DMF. This fact was also seen in dyestuffs 11 and 12. These results show that various substitutions on the imido group have no fluorescence-related effects on phenothiazine derivatives’ wavelengths.

This is because of the preserved planarity of the dyestuff’s molecular structure in excited state. The Stokes shift (υ_A−υ_F), oscillator strength (f) and quantum yield (Ф_F) are important properties for the fluorescent dyestuffs. The Stokes shift is a parameter that represents the differences in the properties and structure of the fluorescent compounds between the ground state and the first excited state. The Stokes shifts of all dyes were determined by Eq. (1) (Grabchev et al., 2001).

(1)

ϑ_{A} – ϑ_{F} = (\frac{1}{λ_{A}} - \frac{1}{λ_{F}}) \times 10^{- 7}

where υ_A−υ_F is Stokes shift, υ_A and υ_F are absorption and fluorescence maxima, respectively.

The Stokes shift values of the dyestuffs 9 and 10 (2261 and 2194 cm⁻¹) were higher than those of the dyestuffs 11 and 12 (1802 and 1608 cm⁻¹). As the dipole moment of the molecule is enhanced upon excitation due to electron density redistribution, the excited molecule is more stabilized in polar solvents, such as DMF because of stronger interaction with the solvent dipoles (Bojinov et al., 2009). This effect causes the red shift in the fluorescence maxima resulting in large scale addition of the Stokes shift values for dyestuffs.

The oscillator strength (f) demonstrates the effectiveness of the number of electrons which their transition from ground to excited state gives the absorption area in the electron spectrum. Values of oscillator strength were calculated by Eq. (2) (Shaki et al., 2010).

(2)

f = 4.32 \times 10^{- 9} \times ϑ_{1 / 2} \times ε_{max}

where υ_1/2 is the width of the absorption band at 1/2 (ε_max).

The oscillator strengths of all dyes in DMF solution were between 0.356 and 0.522. For the dyestuff 12 having NH₂ and CHO groups as substituents at the C4 and C7 position, the f value was the highest while dyestuff 9 containing only amino group had the lowest f value.

The fluorescence quantum yield of fluorescent compounds is measured by the capability of the molecules to emit the absorbed light energy. The quantum yield of fluorescent compound was calculated using fluoroscein (Ф_ref = 0.95) as a standard material according to Eq. (3) (Shaki et al., 2010).

(3)

Φ_{F} = Φ_{ref} (\frac{S_{sample}}{S_{ref}}) (\frac{A_{ref}}{A_{sample}}) (\frac{n_{sample}^{2}}{n_{ref}^{2}})

where Ф_F is quantum yield of samples, Ф_ref is quantum yield of fluoroscein, A_ref, S_ref, n_ref and A_sample, S_sample, n_sample are the absorbance at the excited wavelengths, the integrated emission band area and the solvent refractive index of the standard and the sample, respectively. Comparison of the fluorescence quantum yields of the dyestuffs containing CHO group in C3 position (dyes 11 and 12) has quantum yield higher than dyestuffs 9 and 10 containing only NH₂ group in DMF solutions. The energy yield of fluorescence is obtained using Eq. (4) (Shaki et al., 2010; Bojinov et al., 2008).

(4)

E_{F} = Φ_{F} (\frac{λ_{A}}{λ_{F}})

As can be seen from the data shown in Table 5, the quantum yield of fluorescence of dye 12, possessing CHO group in phenothiazine ring has the most of quantum yield compared to other dyes. This finding may be related to the polarity of dye 12 due to having aldehyde group and a primary amino substituted in C7 position. Therefore dye 12 could have stronger interaction with DMF which is a polar solvent. This interaction between dye molecules and DMF can increase the rigidity of dye molecules and therefore the quantum yield increases (Zhang et al., 2003). The comparison of quantum yields of these compounds with the synthesized dyes showed that quantum yield values of all dyes are in the range of the dyes which have been synthesized by the other researchers (Nodiff and Hausman, 1964; Mitchell, 2006; Kurihara et al., 1999; Eregowda et al., 2000 ).

3.3

3.3 Dyeing and fastness properties of dyestuffs

The dyestuffs 9–12 were applied on polyester fabrics under high temperature dyeing conditions at concentration of 0.1%, 0.4%, 0.8%, 1.2%, 2%, 4% and 8% of dyestuffs on the weight of fabrics (owf) and acetic acid was added (pH = 4.5–5). The dyeing was carried out according to Fig. 3. The reduction cleared samples were then rinsed with hot and cold water.

Diagram of dyeing fabrics with the synthesized dyestuffs.

For elaborating on the building of the synthesized dyestuff, the K/S was calculated by using the Kubelka-Munk Eq. (5).

(5)

\frac{K}{S} = \frac{{(1 - R)}^{2}}{2 R}

where K, S and R are absorption coefficient, scattering coefficient and reflectance of dyed samples, respectively.

According to the results of buildup curves of polyester fabrics (Fig. 4) the synthesized dyestuffs have good buildups on polyester fabrics. As it is seen vividly from Fig. 4, they generally reached saturation at concentration of 1.2–2%. The spectrophotometric properties of polyester dyeing treatments in terms of the CIE Lab system are shown in Table 6. The chromaticity curve of the synthesized dyestuffs in concentration of 2% on polyester fabrics showed that synthesized dyestuffs have the almost same hue.

Table 6 The spectrophotometric data of the synthesized dyestuffs on polyester fabrics (2% owf).

Dye	L^∗	a^∗	b^∗	c^∗	h°	K/S
9	84.12	−24.36	72.87	55.22	110.60	22.58
10	82.08	−24.79	67.49	69.09	102.36	20.45
11	83.64	−26.25	71.41	82.17	105.79	19.97
12	80.99	−27.43	51.69	73.24	102.82	17.28

The wash fastness of dyed polyester fabrics was tested according to ISO 105-C02:1989(E). The data represented that washing fastness of all samples was very good (4–5 to 5) (Table 7). For testing light fastness, the samples of fabric standards were mounted on a frame partly covered on opaque sheet, leaving the other half exposed in Xenone lamp ISO105-B02:1994(E). The dyestuffs showed medium light fastness on polyester fabrics. The sublimation, rubbing and perspiration fastnesses of dyed fabrics were tested according to ISO 105-X11:1994(E), ISO 105-X12 and ISO 105-E04:1994(E), respectively. All dyed fabrics showed good sublimation fastness, rubbing fastness and perspiration fastness properties due to the ability of the molecules of the dyestuffs to self-associate through intermolecular hydrogen bonding because of the presence of primary amino grouping dyestuff molecules (Table 8).

Table 7 Wash fastness properties of the synthesized dyestuffs on polyester fabrics (2% owf).

Dye	Staining						Change
Dye	Wool	Cotton	Cellulose acetate	Nylon	Polyester	Acrylic	Change
9	4–5	4–5	4–5	5	5	4–5	5
10	4–5	5	4–5	5	5	5	5
11	4–5	5	4–5	5	5	5	5
12	4–5	4–5	4–5	5	5	5	5

Table 8 Light, sublimation, rubbing and perspiration fastnesses of the dyestuffs on polyester fabrics (2% owf).

Dye	Light fastness	Sublimation fastness (180 °C)	Rubbing fastness		Perspiration fastnesses
Dye	Light fastness	Sublimation fastness (180 °C)	Staining	Change	Staining	Change
9	4–5	4–5	4–5	4–5	4–5	4–5
10	4–5	4–5	4–5	4–5	4–5	4–5
11	4–5	4–5	4–5	4–5	4–5	4–5
12	4–5	4–5	4–5	4–5	4–5	4–5

3 Conclusions

A series of novel fluorescent heterocyclic disperse dyestuffs derived from phenothiazine were prepared by standard reactions from phenothiazine as the starting material for the first time. Phenothiazine was nitrated and oxidized then reduced to obtain disperse dyestuffs. The chemical structures of all purified dyestuffs and their intermediates were confirmed by DSC, FTIR, ¹H NMR, ¹³C NMR, elemental analysis and UV–Visible spectroscopy. The spectrophotometric data of the prepared dyestuffs showed that they have acceptable color strength and positive solvatochromism by changing solvents from toluene to DMF. The fluorescent characteristics of all dyes were measured in DMF and all dyestuffs showed an intense yellow–green fluorescence. Dyestuffs containing both electron acceptor and electron donor groups showed the highest quantum yields. The synthesized disperse dyestuffs were applied on polyester fabrics at high temperature and their dyeing properties were investigated. The synthesized dyestuffs represented good buildups, acceptable colorfastness properties and give orange color gamuts on polyester fabrics.

References

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Introduction

Experimental

Materials and apparatus
Synthesis of intermediates
Synthesis of dyestuffs
Dyeing polyester fabrics

Results and discussions

Synthesis of intermediates and dyestuffs
Electronic absorption and fluorescence spectra
Dyeing and fastness properties of dyestuffs

Conclusions

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[1] Bakhtiari, G., Moradi, S., Soltanali, 2014. A novel method for the synthesis of dyes derived 3-(1H-benzoimidazol-2-yl) comarin-2-one under microwave irradiation. Arab. J. Chem. 7, 972–975.

[2] Barra M., Redmond R.W., Allen M.T., Calabrese G.S., Sinta R.J., . Spectroscopic and electrochemical properties of 2-aminophenothiazine Scaiano. Macromolecules. 1991;24:4972.
[Google Scholar]

[3] Bojinov V.B., Georgiev N.I., Nikolov P.S., . Design and synthesis of core and peripherally functionalized with 1,8-naphthalimide units fluorescent PAMAM dendron as light harvesting antenna. J. Photo. Photobiol A: Chem.. 2008;197:281.
[Google Scholar]

[4] Bojinov V., Georgiev N., Bosch P., Design, . Design and synthesis of highly photostable yellow–green emitting 1,8-Naphthalimides as fluorescent sensors for metal cations and protons. J. Fluoresc.. 2009;19:127.
[Google Scholar]

[5] Boschloo G., Hagfeldt A., . Activation energy of electron transport in dye-sensitized TiO₂ solar cells. J. Phys. Chem. B.. 2005;109:12093.
[Google Scholar]

[6] Choi J.H., Hong H.H., Lee E.J., Towns A.D., . Structure-wet fastness relationships of some blue disperse dyes for polyester. J. Soc. Dyers. Colour.. 2000;116:273-280.
[Google Scholar]

[7] Eregowda G., Kalpana H., Hedge R., Thimmaiah K., . Synthesis of novel azo dyes derived from 4-phenylurazole. Indian J. Chem.. 2000;39B:243-259.
[Google Scholar]

[8] Freeman H.S., Sokolowska, . Developments in dyestuff chemistry. J. Rev. Progc. Coloratio.. 1999;29:7-22.
[Google Scholar]

[9] Grabchev I., Bojinov V., Petkov H., . Synthesis and photophysical properties of polymerizable 1,8-naphthalimide dyes and their copolymers with styrene. Dyes Pigm.. 2001;51:1-8.
[Google Scholar]

[10] Kurihara T., Motohashi N., Sakagami H., Molnar J., . Relationship between cytotoxic activity and dipole moment for phthalimido and chloroethyl phenithiazine. Anticancer Res.. 1999;19:4081-4083.
[Google Scholar]

[11] Lacasse H., Perreault M.M., Williamson D.R., . Systematic review of antipsychotics for the treatment of hospital-associated delirium in medically or surgically III patients. Ann. Pharmacother.. 2006;40:1966-1972.
[Google Scholar]

[12] Lakowicz J.R., . Principles of Fluorescence Spectroscopy (3rd ed.). New York, USA: Springer Science; 2006.

[13] Mitchell S.C., . A novel and specific NADPH oxidase-1 (Nox1) small-molecule inhibitor blocks the formation of functional invadopodia in human colon cancer cells. Curr. Drug Targets. 2006;7:1181-1189.
[Google Scholar]

[14] Msorrison R.T., Boyd R.N., . Organic Chemistry. New York: John Wiley & Sons pub; 1992. p. 985

[15] Nagy S., Argyelan G., Molnar J., Kawase M., Motohashi N., . Anticancer activity of newly synthesized azaphenothiazines from NCI’s anticancer screening bank. Anticancer Res.. 1996;16:1915-1918.
[Google Scholar]

[16] Nodiff E.A., Hausman M., . Oxidative radical cyclization of (omega.-Iodoalkyl)indoles and Pyrroles. Synthesis of Monomorine and three diastereomers. J. Org. Chem.. 1964;29:2453-2455.
[Google Scholar]

[17] Philipova T., Karamancheva I., Grabchev I., . Absorption spectra of some N-substituted-1,8-naphthalimides. Dyes Pigm.. 1995;28:91-98.
[Google Scholar]

[18] Pineroa L., Calderona X., Rodrıgueza J., Nieves I., Arceb R., Garcıaa C., Oyolaa R., . Spectroscopic and electrochemical properties of 2-aminophenothiazine. J. Photo. Photobiolo A: Chem.. 2008;198:85-91.
[Google Scholar]

[19] Rizk H.F., El-Badawi M.A., Ibrahim S.A., El-Borai M.A., . Synthesis of some novel heterocyclic dyes derived from pyrazole derivatives. Arab. J. Chem.. 2011;4:37-44.
[Google Scholar]

[20] Seferoglu Z., Ertan N., Hokelek T., Sxahin A., . The synthesis, spectroscopic properties and crystal structure of novel, bis-hetarylazo disperse dyes. Dyes Pigm.. 2008;77:614-623.
[Google Scholar]

[21] Shaki H., Gharanjig K., Rouhani S., Khosravi A., . Synthesis and photophysical properties of some novel fluorescent dyes based on naphthalimide derivatives. J. Photo. Photobiol A: Chem.. 2010;216:44-53.
[Google Scholar]

[22] Sing K., Sing S., Taylor J.A., . Monoazo disperse dyes. Part 2; colour constitution relationships of some novel blue disperse dyes. Color. Technol.. 2003;119:158.
[Google Scholar]

[23] Wainwright M., Mohr H., Walker W.H., . Phenothiazinium derivatives for pathogen inactivation in blood products. J. Photochem. Photobiol. B.. 2007;86:45-58.
[Google Scholar]

[24] Zhang W., Wang Y., Xu Y., Qianm X., . Photochemistry of a cyanine dye in reversed micelles. Monatshefte for Chemie Chemical Monthly. 2003;134:393.
[Google Scholar]

Synthesis and application of some novel fluorescent heterocyclic disperse dyestuffs based on phenothiazine on polyester

Abstract

Keywords

Phenothiazine

Synthesis

Polyester

Disperse dyestuff

Fastness properties

1 Introduction

2 Experimental

2.1 Materials and apparatus

2.2 Synthesis of intermediates

2.2.1 Synthesis of N-methyl (butyl) phenothiazine (1, 2)

2.2.2 Synthesis of 3-nitro-N-methyl (butyl) phenothiazine (5, 6)

2.2.3 Synthesis of 3-formyl-N-methyl (butyl) phenothiazine (3, 4)

2.2.4 Synthesis of 3-formyl-6-nitro-N-methyl (butyl) phenothiazine (7, 8)

2.3 Synthesis of dyestuffs

2.3.1 Synthesis of 3-amino-N-methyl (butyl) phenothiazine (9, 10)

2.3.2 Synthesis of 3-formyl-6-amino-N-methyl (butyl) phenothiazine (11, 12)

2.4 Dyeing polyester fabrics

3 Results and discussions

3.1 Synthesis of intermediates and dyestuffs

3.2 Electronic absorption and fluorescence spectra

3.3 Dyeing and fastness properties of dyestuffs

3 Conclusions

References

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