Solvent Free Green Synthesis f 4-Substituted Thiocarbamido- Naphthols

Introduction

The literature survey reveals that several modern theories and concept concerning to the physical as well as chemical study of benzenoid, nonbenzenoid, heterocycles and heterocycles these compounds have their own individuality^1-5. These compounds showed remarkable  medicinal, biochemical, industrial, agricultural and pharmaceutical sciences. Thiocarbamido nucleus showed antimicrobial property as well as it acts as a versatile reagent in organic synthesis. Now-a-days thiocarbamido nucleus containg molecules showed great significances and scientific interest due their biological reactivity and biological features^6-13. Various derivatives of this group have useful applications, some of these showed anti-tuberculosis, anti-tumor, anti-cancer, and anti-pyretic activities^14-22. Considering all these things present research work is carried out solvent free green synthesis to synthesized new series of substitutedthiocarbamidonaphthols by the interaction of 4-amino-1-naphthol with phenylisothiocynate,  p-chlorophenylisothiocynate, p-tolylisothiocynate,  o-tolylisothiocynate and m-tolylisothiocynate in presence of lemon juice, sweet lemon juice and orange juice respectively which are hither to unknown. Scheme of synthesis is given in Scheme-I.

Figure 1: Scheme-I (Synthesis of Substituted Thiocarbamido Naphthols). Click here to View Figure

Experimental Part

Glassware

All glassware used throughout the research work is of Borosil make.

Chemicals

India make all chemicals were used of AR grade of Merck and Aldrich. Perkin-Elmer spectrum RXI FTIR was used for IR Spectra and Bruker DRX-300 spectrometer operating at 300 MHz was used for ¹H NMR spectra and solvent used CDCl_3.  Characterization was done at SAIF, Chandigarh, Punjab.

Method, Result and Discussion

4-(p-Methyl)phenylthiocarbamido-1-naphthol

Solvent freeinteraction of 4-amino -1-naphthol (0.1 M) and p-tolylisothiocynate (0.1 M) was carried out in sun light in presence of lemon juice (15 ml) which gave ivory colour needle shaped crystalline product. It was recrystallized by ethanol. Yield is 92.00% and melting point is 187-188^ºC. Same interactions were carried out in sweet lemon juice as well as orange juice to check the percentage of yields and purity.

Properties

Compound is ivory colour crystalline solid. Compound having melting point 187-188^ºC. Test for nitrogen and sulphur was positive.  Presence of C=S group conform on the basis of positive alkaline plumbite test. Product was soluble in acetone, ethanol, benzene, dioxane, DMSO, DMSOd₆ and water insoluble.

IR spectrum (cm^-1)

KBr pallets was used for  IR spectrum of compound. The essential absorptions are correlated as: N-H stretching at 3295.52cm^-1, Phenolic-OH stretching at 1282.82 cm-¹, Aromatic C-H stretching at 3059.54 cm-¹, Aliphatic C-H stretching at 2969.54 cm-¹, N-C-N stretching at 1605.81 cm-¹, C-N stretching at 1520.94 cm-¹, C-C stretching at 1390.74 cm-¹, C-O stretching at 1282.72 cm-¹, N-C=S stretching at 1520.94 cm-¹, C=S stretching at 912.37 cm-¹.

PMR spectrum

DMSO was used for the PMR spectrum of a compound. Due to presence of naphthol ring this spectrum distinctly displayed the signals six protons at δ 8.2072- 7.0867 ppm, Ar-H protons at δ 6.9071- 6.6549 ppm, phenolic –OH proton at δ 5.4632-5.2534 ppm, NH protons at δ 3.3706 ppm, and CH₃ protons at 1.4823-1.2406.

Figure 2: 4-(p-Methyl)phenylthiocarbamido-1-naphthol Click here to View Figure

Synthesis of 4-phenylthiocarbamido-1-naphthol

Solvent free interaction of 4-amino-1-naphthol (0.1 M) and phenylisothiocynate (0.1 M) was carried out in lemon juice (15 ml) in presence of sun light which gave yellow colour needle shaped crystalline product. It was recrystallized by ethanol. Yield is 91.41% and melting point is 203-204^ºC. Same reactions were carried out in sweet lemon juice as well as orange juice to check the percentage of yields and purity.

Properties

Compound isyellow needle shaped crystalline solid. It having melting point 203-204^ºC. Test for nitrogen and sulphur was positive.  Presence of C=S group conform on the basis of positive alkaline plumbite test. Product was soluble in acetone, ethanol, benzene, dioxane, DMSO, DMSOd₆ and water insoluble. 

IR spectrum (cm^-1)

KBr pallets was used for IR spectrum of compound. The essential absorptions are correlated as: N-H stretching at 3171.11 cm-¹, phenolic–OH stretching at 1598.09 cm-¹, aromatic C-H stretching at 2971.47 cm-¹, aliphatic C-H stretching at 2745.79 cm-¹, N-C-N stretching at 1598.09 cm-¹, C-N stretching at 1368.88 cm-¹, C-C stretching at 1598.09 cm-¹, C-O stretching at 1275.97 cm-¹, N-C=S stretching at 1275.97 cm-¹, C=S stretching at 1159.27 cm-¹.

PMR spectrum

DMSO was used for the PMR spectrum of a compound. This spectrum distinctly displayed the signals due to Ar-H protons at δ 6.9071- 6.6549 ppm, naphthol ring six protons at δ 8.2072- 7.0867 ppm, phenolic –OH proton at δ 5.4632-5.2534 ppm, NH protons at δ 3.3706 ppm, and CH₃ protons at 1.2406.

The compound was assigned the structure as 4-phenylthiocarbamido-1-naphthol, from the above chemical characteristics, elemental and spectral analysis.

Figure 3: 4-phenylthiocarbamido-1-napthol Click here to View Figure

Similarly, solvent free interactions of 4-amino-1-naphthol with p-chlorophenyl- isothiocynate,  p-tolylisothiocynate, o-tolylisothiocynate and m-tolylisothiocynate in presence of sweet lemon juice, sweet lemon juice  and orange juice were carried out in sun light respectively and results are listed in following.

Table 1

Sr. No.	4-Substituted thiocarbamido-1-naphthol	Melting Point (ºC)	Yield in lemon Juice (%)	Yield in Sweet lemon Juice (%)	Yield in orange Juice (%)
1	4-(p-Methyl)phenyl–	187-188	92.00	———	———
2	4-(p-Methyl)phenyl–	187-188	———	91.50	———
3	4-(p-Methyl)phenyl–	187-188	———	———	91.50
4	4-Phenyl——–	203-204	91.41	———-	———
5	4-Phenyl——–	203-204	———-	90.20	———-
6	4-Phenyl——–	203-204	———-	———-	89.90
7	4-(p-Chloro)phenyl–	217-218	90.00	———-	———
8	4-(p-Chloro)phenyl–	217-218	———-	87.53	———-
9	4-(p-Chloro)phenyl–	217-218	———-	———-	87.00
10	4-(o-Methyl)phenyl–	167-168	92.68	———-	———
11	4-(o-Methyl)phenyl–	167-168	———-	90.00	———-
12	4-(o-Methyl)phenyl–	167-168	———-	———-	90.00
13	4-(m-Methyl)phenyl-	175-176	91.50	———-	———
14	4-(m-Methyl)phenyl-	175-176	———-	89.88	———-
15	4-(m-Methyl)phenyl-	175-176	———-	———-	89.80

 

Conclusion

It is observed from the literature survey, in our research group different type of thiocarbamide were synthesized by using acetone^23-24 and acetone-ethanol (1:1) medium. It is also observed from the literature survey 5-thiocarbamide naphthol were synthesized in acetone medium²⁵, but green synthetic methods are not investigated yet.  The beauty of this research work and article said that in our synthetic method green synthesis parameter were maintain. It means that we didn’t use any type hazardous organic solvent as medium as well as we don’t use artificial heating condition means in our synthesis acetone-ethanol medium are not used and refluxion of the reaction mixture steps is also removed. Means all these reaction as well as synthesis as eco-friendly and protect the environment. It is again observed from the literature survey that the particular product yield are increase also purity of product was maintained. These molecules often have interesting biological activities.

Acknowledgement

The authors extend their heartful thanks to Dr. D.T. Tayade, Professor, Department of Chemistry, Government Vidarbha Institute of Science and Humanites, Amravati (M.S.) 444 604, India for moral support, guidance and valuable suggestions. Also thanks to SAIF, Chandigarh, Punjab for characterization.

Conflicts of Interest

The publication of this research article authors declare that have no conflict of interest.

References

1. Panpalia.R.C, Ph.D. Thesis.S.G.B. Amravati University Amravati, 2007.
2. Shedlovsky.T, J.Am.Chem.Soc., 1930, 52, 1793-1805.
   CrossRef
3. Shedlovsky.T., J.Am.Chem.Soc., 1930, 52, 1806-1811.
   CrossRef
4.  Kohlrausch.F, Das.Malty and M.E, “Elektrische Leitvermogenwassriger, Losungevon, Alkali-Chloriden and Nitraten. Wiss. Abh. Phys. Tech.  Reichsanst, 1900, 3, 155-228.
5.  Debye.P and Huckel.E, Theory of Electrolyte.11, The limiting law of electrical conductivity. Phys. Z., 1923, 24,305-325.
6. Murshid.G and Garg.S.Initial solubility and density evaluation of Non Aqueous System of amino acid salts for CO₂ capture: potassium prolinate blended with ethanol and ethylene glycol. IOP Conference Series: Earth and Environmental Science, 2018, 154(1), 12020.
   CrossRef
7. Bian.Yand Shen.S. CO₂ absorption into a phase change absorbent: Water-lean potassium prolinate/ethanol solution. Chinese Journal of Chemical Engineering, 2018, 26(11), 2318-2326.
   CrossRef
8. Shen.S, Yang.Y.N, Bian.Y and Zhao.Y, Kinetics of CO₂ absorption into aqueous basic amino acid salt: potassium salt of lysine solution. Environmental science and technology, 2016, 50(4), 2054-2063.
   CrossRef
9. Mazinani.S, Ramazani.R, Samsami.A, Jahanmiri.A, Van der Bruggen.B and Darvishmanesh, S.Equilibrium solubility, density, viscosity and corrosion rate of carbon dioxide in potassium lysinate solution. Fluid Phase Equilibria, 2015, 396, 28-34.
   CrossRef
10. Kumar.P.S, Hogendoorn.J.A, Feron.P.H.M and Versteeg.G.F Density, viscosity, solubility, and diffusivity of N₂O in aqueous amino acid salt solutions. Journal of chemical & engineering data, 2001, 46(6), 1357-1361.
    CrossRef
11. Wei, S. C. C., Puxty, G., and Feron, P. Amino acid salts for CO₂ capture at flue gas temperatures. Energy Procedia, 2013, 37, 485-493.
    CrossRef
12. Harris.F, Kurnia.K.A, Mutalib, M.I.A and Thanapalan.M, Solubilities of carbon dioxide and densities of aqueous sodium glycinate solutions before and after CO₂ absorption. Journal of Chemical & Engineering Data, 2009, 54(1), 144-147.
    CrossRef
13. Aronu.U.E, Hartono.A and Svendsen.H.F, Density, viscosity and N₂O solubility of aqueous amino acid salt and amine amino acid salt solutions. The Journal of chemical thermodynamics, 2012, 45(1), 90-99.
    CrossRef
14. Seyyed H.S. and Leila M., Solvent free synthesis of amidoalkyl derivatives under green and convenient conditions, Journal of Heterocyclic Chemistry. 2021, 59(4), 695-703.
    CrossRef
15. Zhang, Z.; Gao, X.; Wan, Y.; Huang, Y.; Huang, G.; Zhang, G. Ammonium Acetate-Promoted One-Pot Tandem Aldol Condensation/Aza-Addition Reactions: Synthesis of 2,3,6,7-Tetrahydro-1H-pyrrolo [3,2-c]pyridin-4(5H)-ones. ACS Omega, 2017, 2, 6844–6851.
    CrossRef
16. Ahmadzadeh, M.; Zarnegar, Z.; Safari, J. Sonochemical synthesis of methyl-4-(hetero)arylmethylene isoxazole-5(4H)-ones using SnII-montmorillonite. Green Chem. Lett. Rev. 2018, 11, 78–85.
    CrossRef
17. Dommaraju, Y.; Borthakura, S.; Prajapati, D. L-Proline-Catalysed One-Pot aza-Diels–Alder Reaction in Water: Regioselective Synthesis of Spiro (isoxazolo[5,4-b]pyridine-5,50 -pyrimidine) Derivatives. Synlett, 2018, 29, 1195–1198.
    CrossRef
18. Bhagat, S.B.; Telvekar, V.N. NBS mediated protocol for the synthesis of N-bridged fused heterocycles in water. Tetrahedron Lett., 2017, 58, 3662–3666.
    CrossRef
19. Bhat, P.; Shridhar, G.; Ladage, S.; Ravishankar, L. An eco-friendly synthesis of 2-pyrazoline derivatives catalyzed by CeCl3 ·7H2O. J. Chem. Sci., 2017, 129, 1441–1448.
    CrossRef
20. Bakherad, M.; Keivanloo, A.; Gholizadeh, M.; Doosti, R.; Javanmardi, M. Using magnetized water as a solvent for a green, catalyst-free, and efficient protocol for the synthesis of pyrano[2,3-c]pyrazoles and pyrano[40,30:5,6]pyrazolo[2,3-d]pyrimidines. Res. Chem. Intermed., 2017, 43, 1013–1029.
    CrossRef
21. Campos, J.F.; Scherrmann, M.-C.; Berteina-Raboin, S. Eucalyptol: A new solvent for the synthesis of heterocycles containing oxygen, sulfur and nitrogen. Green Chem. 2019, 21, 1531–1539.
    CrossRef
22. Hülsey, M.J.; Yang, H.; Yan, N. Sustainable Routes for the Synthesis of Renewable Heteroatom-Containing Chemicals. ACS Sustain. Chem. Eng., 2018, 65, 5694–5707.
    CrossRef
23. Tayade D.T., Ph.D. Thesis.S.G.B. Amravati University Amravati, 1996.
24. Bhagwatkar R.A., Ph.D. Thesis.S.G.B. Amravati University Amravati, 2012.
25. Wadekar A.B., Ph.D. Thesis.S.G.B. Amravati University Amravati, 2017.

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