Introduction

Plant oils offer many advantages apart from their renewability .Their world -wide availability and relatively low prices make them industrially attractive and feasible .as daily demonstrated with industrial oleo chemistry. Furthermore diverse chemistry can be applied on them .Leading to a large variety of monomers and polymers [1]. Most importantly, the synthetic potential of nature is very high with this renewable feedstock and consequently .Only a few minor modification reactions (if any at all) have to be performed in order to obtain suitable monomers for many different applications [2]. The double bonds present in fatty acids [FA] make them ideal starting materials for such transformations .Moreover olefin metathesis can not only be used for monomer synthesis but also as polymerization technique [3]. The possibility of polymerization of FA is feasible since in their structure many double bonds are found and available .Therefore, there is favored radical polymerization reaction through the hydrogen in the allyl position, duo to the higher reactivity of this hydrogen creating a distinct monomer [4]. A large number of polymers applications results from their early properties and the way they are processed. In order to increase these applications and also to improve some properties, it is common in polymer industry to under go by synthesis modification [4]. In a recent studies fatty acids demonstrated biological activity [5-18] and some physical properties [19-28] and its polymers [29-41].

Materials and Methods

All chemicals had been used as supplied by (Alfa Assar and Aldrich).

Devices instrument

The melting points were determined by Electro thermal Melting Apparatus 9300 in open capillary tubes that were uncorrected. Thin layer chromatography (TLC) was used for monitory the reaction and check purity.The FT-IR spectra were recorded using FT-IR 8400s shimadzu spectro photometer scale (400-4000 cm^-1). The UV-Vis spectra was measured in ethanol using shimadzu 800UV in rang (200-400) nm. ¹H-NMR and ¹³C-NMR spectrum was recorded on Varianoperaing at 400 MHz instrument using DMSO-d⁶ and CDCl₃ as a solvent.Thermal analysis Tgwas recorded on instrument SDT Q600 V20.9 Build 20 under Nitrogen.

Synthesis methods.

Synthesis of semicarbazide derivatives [E₁-E₅]

Semicarbazide (0.0l mol, 0.75 g) was dissolved in (50 mL) of DMF. After complete dissolving, 0.0l mol of  one of different fatty acid was add .After adding (3 drops) of diluted H₂SO₄ (1:1), the mixture was then refluxed for 4-5 hours and cooled to room temperature .Filtered, dried and recrystallized physical properties are given in Table 1 [42].

Table 1: Physical properties of prepared compounds [E₁-E₅]

Synthesis of polymer [EP₁-EP₅]

In dry polymerization bottle (0.0l mol) of semicarbzide derivatives [E₁-E₅] and equivalent moles of malic anhydride was dissolved in (10 mL) of DMF then (0.1 L of H₂O₂ was add and bottle was flushed with nitrogen and fimly stoppered.The mixture was maintained at 80 °C for 3 h. then the resulted solution was poured into 25 mL of ethanol and precipitated polymer was filtered  washed with ethanol and dried physical properties of polymer [EP₁-EP₅] are listed in Table 2 [43].

Table 2: Physical properties of prepared polymer [EP₁-EP₅]

Scheme 1: Synthesis of polymer [EP₁-EP₅]

Results and Discussion

Characterization of seiecarbazide derivatives [E₁-E₅]

The semicarbazide derivatives [E₁-E₅] were prepared by the reaction semicarbazide with (1mol) of fatty acids (olic, lenolic, lenolinic, recenolic and cinnamic acid) in DMF.

 The UV spectra gave absorption band at different wave lengthe for the resulted semicarbazide derivatives (in %99 EtOH) due to π π* and n π* transition and all these transition are listed in Table 3.

The FT-IR spectrum for semicarbazide derivatives showed to appear two band due to primary amid group (3595-3392), (3394-3300) cm^-1, beside secondary amid group which appear (3433-3249) cm^-1, ν(=CH) alken appear (3086-3010) cm^-1, (ν C-H) aliphatic appear to band (2962-2926), (2860-2818) cm^-1, also (C=O) amid group appear (1695-1646) cm^-1 and (1600-1608) cm^-1 due to (ν C=C) alken, (CH₂ and CH₃) group appear (1492-1402) cm^-1, and (769-750), (754-715) cm^-1 attributed to ν (C-C)_asy., _sym .In addition, a band at (3222) cm^-1 attributed to (ν OH) alcohol in [E₄] also appearance of bands (3190) cm^-1 due toν (C-H)_arom., and (1616, 1525) cm^-1 due to ν (C=C)_arom. in [E₅],These results are in agreement with recent literature[14]. As shown in Figure S1 E₁. UV and FT-IR spectrum are given in Table 3.

Moreover the ¹H-NMR spectra of [E₁] Figure S2 shows a clear singlet signal at δ=10.66ppm attributed to –CO-NH and δ =10.37 ppm attributed  to NH- C=O, triplet signal at δ = 7.23, 7.10,6.97 attributed to NH₂, triplet signal at δ =5.03, 5.02, 4.93, 4.74 ppm attributed to -CH=CH-, triplet signal at δ =4.74, 4.34, 4.33 ppm attributed to CH₂-C=O, multiple signal at arrange δ =4.33-2.01 ppm for CH₂ and singlet signal at δ = 2.01 to CH₃. As well as signal of DMS0-d₆ appear at δ = 2.50, 2.51, 2.52 ppm.

The ¹³C-NMR spectrum of [E₁] Figure S3 shows a clear singlet signal at δ =178.89 ppm attributed to-C=O-NH, singlet signal at δ =152.12 ppm attributed to- C=O-NH₂, doublet signal at δ =131.94, 119.34 ppm attributed to- CH=CH-, multiple signal at rang δ=25.50-18.02 ppm due to CH₂ and singlet signal at δ =15.87 ppm attributed to CH₃.

The ¹H-NMR spectra of [E₂] Figure S4 shows singlet signal at δ =10.66 ppm attributed to C=O-NH, singlet signal at δ =10.37 ppm attributed to HNC=O, triplet signal at δ =7.23, 7.10, 6.97 ppm attributed to NH₂, multiple signal  an the rang 5.03-4.74 ppm attributed to-CH=CH, triplet signal at δ =4.34, 4.33, 3.98 ppm attributed to -CH=CH-CH₂*-CH=CH-, also multiple signal at δ =3.58-2.01 ppm attributed ta CH₂ group and singlet signal at δ =2.01 ppm attributed to CH₃ as well as signal of DMSO-d₆ appear at δ =2.52, 2.51, 2.50 ppm.

The ¹³C-NMR spectrum of [E₂] shows singlet signal at δ =167.37 ppm attributed to C=O-NH and singlet signal at δ =155.21ppm attributed to C=ONH₂, Doublet signal at δ =132.17, 129.12 ppm attributed to -CH₌CH-, singlet signal at δ =61.78 ppm due to CH₂, multiple signal an the rang δ =17.90-16.62 ppm attributed CH₂, singlet signal at δ =14.35ppm due to CH_3.

The ¹H-NMR spectra of [E₃] Figure S5 shows a clear singlet signal at δ =11.12 ppm attributed to amin group in CH₂-CO-NH and singlet single at 10.58 ppm attributed to -CO-NH troubled signal appear at δ =7.26, 7.14, 7.01 ppm attributed to NH₂, triplet signal at δ =6.25, 5.83, 4.53 ppm attributed to CH=CH, triplet signal at δ =2.51, 2.44, 2.28 ppm attributed to CH₂ and singlet signal at δ =1.24 ppm attributed to CH₃. DMSO-d₆ signal appear at δ =2.51 ppm.

The ¹³C-NMR spectra of [E₃] Figure S6 shows doublet signal at δ =169.76, 163.40 ppm attributed to -CO-NH, and triplet signal at δ =150.45, 147.28, 145.34 ppm attributed to -CO-NH₂ singlet signal at δ =130.11ppm due to HC=CH, triplet signal at δ=79.77,79.44, 79.11 ppm attributed to CH=CHCH₂*CH=CH, multiple signals at rang δ=31.15 -16.66ppm due to CH₂ and singlet signal at δ =16.41 attributed to CH₃ group.

The ¹H-NMR spectra of [E₄] Figure S7 shows doublet signal to NH group at δ =9.90, 9.71 ppm and doublet signal for NH₂ group at δ=8.70, 8.58 ppm multiple signal at ring δ =7.90-7.01ppm attributed to -HC=CH-doublet signal at δ =3.39, 3.37 ppm duo to OH alcohol. Singlet signal at δ =2.29 ppm attributed to CH. multiple signal at rang δ =2.10-1.39 ppm duo to CH₂ and singlet signal at δ=0.85 ppm attributed to CH₃ as well as signal of DMSO-d₆ appear at δ =2.51 ppm.

The ¹³C-NMR  spectrum of [E₄] shows singlet signal at δ =163.02 ppm attributed to C=O-NH and singlet signal at δ =154.17ppm attributed to C=ONH₂, Doublet signal at δ =1143.46, 135.41 ppm attributed to -CH₌CH-, singlet signal at δ =60.92 ppm due to C-OH, singlet signal at δ =53.21ppm due to CH₂, multiple signal  an the rang δ =25.08-16.62 ppm attributed CH₂, and singlet signal at δ =16.41ppm due to CH_3.

The ¹H-NMR spectra of [E₅] shows doublet signal at δ =10.91, 10.73 ppm attributed to C=O-NH, δ =10.37 ppm attributed to C=ONH, multiple signal at δ =7.75 -7.61 ppm attributed to CH aromatic, doublet signal at δ =7.68, 7.67 ppm due to NH₂ and multiple signal at 6.67 -7.63ppm attributed to -CH=CH- aleph. As well as signal of DMSO-d⁶ appear at δ =2.57, 2.50 ppm.

The ¹³C-NMR spectrum of [E₅] shows singlet signal at δ =169.15 ppm attributed to C=O-NH and singlet signal at δ =159.08ppm attributed to C=ONH₂, multiple signal at δ =133.28-128.80ppm attributed to CH aromatic, doublet signal at δ =127.63, 125.60 ppm due to -CH=CH-_.

Characterization of polymers [Ep₁-Ep₅]

Semicarbazid derivatives copolymers [Ep₁-Ep₅] were prepared from the reaction semicarbazide derivatives [E₁-E₅] and malice hydride in DMF with H₂O₂ as initiator. The FT-IR spectrum showed to appear two band due to primary amid group (3450-3393), (3496-3340) cm^-1, beside secondary amid group which appear (3327-3192) cm^-1. Beside new bands appear at 1728-1701 cm^-1 attributed to the (C=O) of malice anhydride as well as the appearance of the bond at 1116-1105 cm^-1 due to (C-O) malic anhydride. The rest of the packages kept their positions as shown in Figure S8 and S9, Ep₁, Ep₅ and FT-IR spectrum are given in Table 3.

Table 3: FT-IR & UV-Vis data of prepared compounds and Copolymers

Thermal characterization of copolymers [Ep₂-Ep₅]

The thermal behavior data of copolymers [Ep₂-Ep₅] is summarized in Table 5. Thermogram of [Ep₃] show a broad single stage weight loss because of linkages in its structure. Is higher than other copolymers that may emanate from higher cross linking in copolymer backbond (Figure S11). Thermogram of [Ep₄] show a double stage weight loss because of double bond and OH alcohol in its structure that come from cross linking in copolymer bacbbond (Figure S12). Thermograms of [Ep₂] and [Ep₃] have three and four stage decomposition straight in the rate of 97.33%, 89.57%. Char yield of Ep₂ is higher than other copolymers (Figure S10 and S13).

Also the prepared copolymers showed good thermal stability through their thermal analysis, softening points and this due to the presence of semicarbazide and fatty acids and malic anhydride in their repeating units since insertion of these components in copolymeric chains exhibit the copolymer good thermal and chemical stability.

Table 4: ¹H&¹³C data of prepared compounds [E₁-E₅]

Table 5: Thermal properties of copolymers [Ep₂-Ep₅]

Antibacterial activity

The effect of the prepared compounds [Ep₁-Ep₅] on the growth of bacterla, namely Staphylococcus auras, Staphylococcus staprophyticus gram (+ve), Proteus gram (-ve). Antibacterial activity of the prepared compounds were studied and the results showed that some of the prepared compounds possess good antibacterial activity .The results of in hibition zone diameter (IZD) in millimeter are shown in Table 5 [16].

Table 6: Growth inhibition zone diameter (mm) of seven heterocyclic compounds against two pathogenic bacteria species

Conclusion

The aim of the research was to preparation of some new compounds and polymers for some fatty acids and study of their thermal stability, which showed high stability. The antibacterial activity of all of the synthesized compounds [E1-EP5] was tested in vitro. It showed good activity against selected gram-negative and gram-positive bacteria.

Funding

This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.

Authors' contributions

All authors contributed toward data analysis, drafting and revising the paper and agreed to responsible for all the aspects of this work.

Conflict of Interest

Authors have declared that they have no known competing financial interests or non-financial

ORCID:

Iman Aywob Yass

https://orcid.org/0000-0002-9796-3983

HOW TO CITE THIS ARTICLE

Iman Aywob Yass. Preparation and Characterization and Thermal Study of New Copolymers of Semicarbazide and Fatty Acids Derivatives with Malic Anhydride and Assess their Biological Activity, J. Med. Chem. Sci., 2022, 5(7) 1347-1356

https://doi.org/10.26655/JMCHEMSCI.2022.7.23

URL: http://www.jmchemsci.com/article_155761.html