Synthesis and Spectral Properties of Some bis-Subtituted Formazans

Submitted To: Dr. Khurram Shahzad Munawar Submitted By: Shakeel Ahmad Khan (14003140007)

Program: MS (Chemistry) 3rd

Department of Chemistry, University of Management and Technology Lahore

H. Tezcan / Spectrochimica Acta Part A 69 (2008) 971–979

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Introduction about FormazansImportance of workAim of the StudResearch Methodologya. Chemicals Used b. Formation outline for Formazansc. Scheme for the Synthesis of Formazansd. Instrument UsedResult and Discussiona. Elemental Analysisb. Spectral Analysis (1HNMR 400MHz, Mass Spectrometer, UV-Visible Spectrometer, FTIR).Conclusion and Future AspectsReferences

List of Contents

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Formazans:Formazans and their derived Metal complexes are colored. They impart color due to π-π* transitions of π electrons in formazan skeleton (-N=N–C=N–NH-). [1]

a. TPF b. p-SCSPF

Introduction

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Formazans:Formazans dyes are ranging from Red to Orange as well as Blue color. Its color Depending upon the structure [2, 3].

Color Range For Formazan DyesFormazans are Polydentate Ligands with donor atoms [4,5].

Introduction

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Formazans:Formazans dyes have more light fastness, wash fastness, bleach fastness, and rub fastness.These properties make them Unique for Industrial dyes sector as compared to other dyes such as Acid dyes, Mordant dyes, etc.[2, 3].

Wash fastness Light Fastness of dyes

Importance of work

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Objective of this study involve to synthesize Water soluble macromolecule bis-formazans with various structures [2].

Objective of this study also involve to investigate their spectral properties [2].

Aim of this Study

1H NMR Spectra

IR Spectra

Mass Spectra

UV-vis Spectra 6

Following Chemicals (Sigma Aldrich) are used in this study

Anthranilic acid Benzaldehyde O-OH Benzaldehyde

m-OH Benzaldehyde p-OH Benzaldehyde p-PDSA

Research Methodology

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Following Chemicals (Sigma Aldrich) are used in this study

CH3OH DMSO NaNO2

HCl Sodium acetate CDCl3

Research Methodology

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Formation outline for Formazans [6]. a. b. c.

d. e. F.

Research Methodology

Diazotization Hydrazine Hydrazone

s

Diazotization

Coupling Reaction

Formazan Dyes

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Research Methodology Scheme for the Synthesis of Formazans [2].

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Research Methodology Scheme for the Synthesis of Formazans [2].

The structure of the formazans synthesized11

Following Instruments are used in Study [2].a. 1HNMR (400MHz) c. Mass Spectrometer

b. UV-visible Spectrophotometer

Research Methodology

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Following Instruments are used in Study [2].d. Elemental analyzer. e. FTIR

Research Methodology

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Result and DiscussionTable 1 Experimental data and elemental analysis of the formazans synthesized

Comp. mp (◦ C) (lit.) Yield (%) (lit.) Color Elemental analysis

Calculated Found

C H N S C H N S

1 172–173 (172–174)6 7 5 (5 4 )6 ,(6 3 ) 2 4 Cherry red 76.00 5.33 18.66 – 75.97 5.29 18.69 – 2 255–256 55 Salmon 59.13 3.76 16.23 4 .6 3 59.01 3.67 16.12 4 .6 8 3 213 46 Cyclamen 56.51 3.60 15.51 4 .4 3 56.48 3.54 15.47 4 .5 5 4 >300 53 Yellow-brown 56.51 3.60 15.51 4 .4 3 56.48 3.54 15.47 4 .5 5 5 207 54 Light brown 56.51 3.60 15.51 4 .4 3 56.48 3.54 15.47 4 .5 5

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Table 2. The 1H NMR data of formazans (1–5) (400 MHz, in CDCl3).

Result and Discussion

Comp. A r H N H A r OH COOH SO3H

1 7.55–6.70(m,15H) 1.14 (s,1H) – – –

2 8.55–6.90(m,21H) 2.50–2.25(s,2H) – 10.90(s,2H) 11.28(s,1H)

3 7.92–6.85(m,19H) 2.75–2.60(s,2H) 3.10(s,2H) 10.80(s,2H) 11.27(s, 1H)

4 8.50–6.65(m,19H) 2.55–2.20(s,2H) 3.40(s,2H) 10.85(s,2H) 10.85(s,1H)

5 7.98–6.65(m,19H) 2.05–1.70(s,2H) 3.20(s,2H) 10.85(s,2H) 10.85(s,1H)

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Figure 1. 1H NMR spectra of CSPF, o-HCSPF, p-HCSPF measured in CDCl3 at 25◦C.

Result and Discussion

Ar-H (8.50-6.90 m, 21H)

Ar-H (7.92-6.85 m, 19H)

Ar-H (7.98-6.65 m, 19H) N-H (2.05-1.70 s, 2H)

N-H (2.75-2.60 s, 2H)

N-H (2.50-2.25 s, 2H)

Ar-OH (3.20 s, 2H)

Ar-OH (3.10 s, 2H)

SO3H (11.28 s, 1H), COOH (10.90 s, 2H)

SO3H (11.27 s, 1H), COOH (10.80 s, 2H)

SO3H (10.85 s, 1H), COOH (10.85 s, 2H)

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Table 3. IR spectral data of formazans (1–5) (in KBr, cm−1)Result and Discussion

mp. C N stretching N N stretching A ro m a tic C C CNNC Skeletal N H + A r OH COOH stretching S O 3 H stre tch in g

stretching vibration stretching

1500 1358 1600 800–600 3050–3000 – –

1540–1580 1455–1335 1629 930–600 3600 3 4 0 0 – 3 3 0 0 1 4 2 0 – 1 3 3 0

1590–1520 1418–1330 1620 850–620 3480–3300 3 3 9 0 – 3 3 0 0 1 3 8 5 – 1 2 2 0

1635–1580 1450–1335 1630 920–610 3600–3200 3 4 2 0 – 3 2 1 0 1 4 1 0 – 1 3 4 0

1600–1530 1420–1335 1622 850–620 3400–3220 3 3 9 5 – 3 3 0 0 1 3 8 0 – 1 2 2 0

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Fig. 2. IR spectra of: (A) TPF; (B) CSPF; (C) o-HCSPF; (D) m-HCSPF; (E) p-HCSPF.

Result and Discussion

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Fig. 3. Mass spectrum of the formazan (p-HCSPF, 5).Result and Discussion

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Scheme 4. Proposed fragmentation pattern of p-HCSPF (5).

Result and Discussion

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Table 4 UV–vis absorption λmax values of formazans (1–5) (CH3OH, 10−4 mol l−1)

Result and Discussion

Comp. λmax1 (nm) (Abs) λmax2 (nm) (Abs) _λmax1 according to TPF (nm) _λmax1 according to CSPF (nm)

1 483 (0.370) 335 (0.614) – – 2 352 (0.912) 233 (0.565) 131 – 3 356 (1.590) 218 (1.714) 127 4 4 353 (0.912) 218 (1.714) 130 1 5 354 (1.222) 219 (1.282) 129 2 Column 4: _λmax1 = λmax1 (TPF) − λmax1 (substituted formazans). Column 5:

_λmax1 = λmax1 (CSPF) − λmax1 (HCSPF).

Fig. 4. The electronic absorption of formazans in CH3OH, 10−4 mol/l.21

Fig. 5. The electronic absorption in CH3OH, DMSO, DMF, 1,4-Dioxane, CH2Cl2·10−4 mol/l: (A) compound 1; (B) 2; (C) 3; (D) 5.

Result and Discussion

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From the present study it is evident that the lowest yield was obtained by the o-hydroxy carboxy sulfo phenyl formazans (o-HCSPF) in 2–5 formazans.

The relative increase in yield obtained with both m-hydroxy carboxy sulfo phenyl formazans (m-HCSPF)and p-hydroxy carboxy sulfo phenyl formazans (p-HCSPF).

Future Aspects To evaluation and characterization of synthesized formazans in medical applications.

Conclusion

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1. H. Tezcan / Spectrochimica Acta, Part A 70 (2008) 973–982

2. H. Tezcan / Spectrochimica Acta, Part A 69 (2008) 971–979

3. A.M. Mattson, C.O. Jensen, R.A. Dutcher, J. Am. Chem. Soc. 70 (1948) 1284.

4. G. Arnold, V.C. Schiele, Spectrochim. Acta 25 (1966) 685.

5. G.M. Abou-Elenien, J. Electroanal. Chem. 375 (1994) 301.

6. H. Tezcan, S. Can, R. Tezcan, Dyes Pigments 52 (2002) 121.

References

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