Production of New Monomers from Cyclic derivatives and study of their (Chemical, Physical, Thermal Characterizations and Biological Effects)

 

Noor Dia Jaffer

Chemistry Department, Education Faculty, University of Kufa, Iraq

 

ABSTRACT:

Five Monomers have been synthesized in our paper through chemical reactions including (condensation reaction, cyclization and reaction of sulphone compound with Schiff base) leads to form the new monomers which contain (hydroxyl and carboxyl) groups with thiadiazole and triazole compounds. (TLC) and many other techniques like ((FT.IR,¹ H.NMR, DSC-Measurement)) were used to investigate  the monomers. The thermal measurements were also used to find out the stability for the monomers. The physical characterizations study and Analytical studies like solubility in different solvents and the Biological  Effect study have taken place in this study also.

 

 

 

INTRODUCTION:

The term (Polymer) means a huge and bulky molecule that can be built up from smaller units linked together by chemical bonds in a process called Polymerization. Polymerization is induced by irradiation and heat, the small units are known as (Monomers), mostly chemical  organic  compounds joining together to form polymers, the word  (mono) means  (one) and (mer) means (part) while poly  means (many), monomers have one or more functional or polymerizable groups, if the monomer has more than one polymerizable group it called multifunctional monomer^(1-4).

 

Scheme 1  Monomers  include  two  functional groups in  their  terminal:

 

Polymers could have an aliphatic or aromatic structure. The aromatic polymers have more interest in different fields of industry^(5,6).

 

The combination of inorganic and organic components gives the desired properties for the final products like chemical, physical, electrical, antibacterial, catalytic, thermal, mechanical and optical properties and thus make it suitable for many new appliances^(7,8). Polymers are widely used in industrial applications to meet the basics of our life, this back to their excellent specifications, low production cost, and lightweight^(9,10).

 

So, chemists have recently gone to design and prepare monomers, and polymers fit medical and pharma fields⁽¹¹⁾.   

 

In this paper, five Monomers were produced by means of the condensation reaction, cyclization and reaction of sulphone compound with Schiff base to form the new monomers which contain  (hydroxyl and carboxyl)  groups with thiadiazole and triazole compounds.

 

EXPERIMENTAL  AND  MATERIALS:

FT-IR 8300 Shimadzu was used in the range of (400-4000) cm^-1 as potassium bromide discs to obtain FT-IR spectra. 

 

¹H.NMR spectra in (DMSO) solvent, DSC – Thermal Analysis, physical and analytical studies and on some types of bacteria.

 

 

 

Preparation  Methods   of  Monomers:

Production   of  Monomer {1}:

Para- hydroxyl benzoic acid (0.01mole)  was refluxed for (5hrs) with  (0.01 mole) of thiosemicarbazide with the presence of phosphoryl chloride in the solvent ( absolute ethanol) according to procedures of^(12,13). The resulting compound precipitated, filtered and dried then recrystallized to give  Monomer  {1}.   

 

Production  of  Monomer {2}:

(0.01mole) of monomer {1} reacted with (0.01 mole ) benzene sulphonyl chloride according to papers^(12,13). The resulting compound has precipitated, filtered and dried then recrystallized to give  Monomer{2}.

 

 

Scheme 2: Monomer {2}

 

Production  of  Monomer {3 }:

Para- hydroxyl benzoic acid (0.01mole)  was refluxed for (5hrs) with  (0.01 mole) of thiosemicarbazide with the presence of 5% sodium hydroxide in the solvent (absolute ethanol) according to procedures of^(12,13). The resulting  was compound precipitated, filtered and dried then recrystallized to give  Monomer{3}.

 

 

Scheme 3: Monomer {3}

 

Production  of  Monomer {4 }:

Thiadiazole derivative  (0.01mole) and triazole derivative were refluxed with (0.01mole) diethyl malonate for (7hrs) in the solvent (absolute ethanol) according to procedures of^(12,13). The resultant compound precipitated, filtered, dried and then recrystallized to give  Monomer {4}.

 

 

Scheme 4: Monomer {4}

 

Production  of  Monomer { 5 }:

Thiadiazole derivative (0.01mole) was refluxed with (0.01 mole) of para- hydroxyl benzoyl chloride for (4hrs) in the solvent (absolute ethanol) according to procedures of^(12,13). The consequential compound has been precipitated, filtered and dried then recrystallized to give  Monomer {5}.

 

 

Scheme 5: Monomer {5}

 

Results  and  Discussion :

In  the  present  study,  synthesis of  five  Monomers  with much chemical   identification  was  through  spectral  methods  such as (FT.IR, H.NMR ) spectra  and   studying   some of the thermal  and  analytical  measurements  with chemical  measurements  like (DSC – Analysis, Solubility in different solvents, biological  effect ) :

 

Spectral    Characterization:

The   FT.IR-  Chemical  Characterization:

The  data  of  spectra  gave   bands: (CH=N) Schiff base: 1622, (-OH-) Phenol: (3446), (OH) hydroxyl of carboxyl  group: (3164 - 2734), (CO-O-) Carbonyl  of  carboxyl: 1743, (C=N) Endocycle: 1665 in the compound (1), while  the other bands  were (-OH^-) Phenol: (3350), (OH^-) hydroxyl of carboxyl  group: (3029 - 2574),

(CO-O-) Carbonyl  of  carboxyl: 1735, (C=N) Endocycle: 1654, (SO₂) Sulphone: (1486, 1371), (C- Cl ):  750,   in  the compound (2), the  spectra  gave  bands  (C=N) Endocycle: 1650, (CO-O-) Carbonyl  of  carboxyl: 1750, (-OH) Phenol: 3450, (NH ) Triazole: 3240   in  compound (3), (CO-N-) Carbonyl  of  Amide: 1690, (-OH) Phenol: 3427, (NH ) Triazole: 3230, (NH) Amide: 3137   in   compound (4), bands  (CO-N-) Carbonyl  of  Amide: 1680, (-OH) Phenol: 3446, (CO-O-) Carbonyl of carboxyl: 1742, (NH) Amide: 3229 in compound (5). Other bands are in figures  (1- 5).

 

 

Fig (1): FT.IR  spectra of  Monomer 1

 

                                          

Fig (2): FT.IR spectra of   Monomer 2

 

Fig (3): FT.IR spectra of  Monomer 3

 

Fig (4): FT.IR  of   Monomer 4

 

Fig (5): FT.IR spectra of  Monomer 5

 

The ¹H.NMR-  Chemical  Characterization gave   signals  at the DMSO-d6 (solvent ): 2.50, Protons  of  the  Aromatic  ring: (7.52 -7.88), (CH=N) proton  of  Imine group: 8.13,  (OH) Phenol: 11.03, (COOH) Proton of carboxyl: 13.15    in  compound (1), but   compound (2) had  peaks for Protons  of   Aromatic  ring: (7.52 -8.01), (CH-N-Cl) proton: 3.40,  (OH) Phenol: 11.11, (COOH) Proton of carboxyl: 13.15, compound (3) gave  signals  for Protons  of  Protons  of   Aromatic  ring: (7.52 -8.02) , (NH-) proton: 5.43,  (OH) Phenol: 11.05,  and  signals  of  other  protons  in figures  (6- 8) .

 

 

Fig (6): H.NMR  of  Monomer 1

 

Fig (7): H.NMR  of   Monomer 2

 

Fig (8): H.NMR  of  Monomer 3

 

Thermal – Analysis of   Monomers:

Thermo – measurements of  monomers were analyzed  to  give information about the stability  of  compounds  as showed in  figures (9-13), Thermal  analysis  gave   high  stability  compared  with  other papers^(14-16)  toward  series of  temperature degrees :

 

 

Fig (9): The Thermal  Analysis   of   Monomers  1

 

Fig (10): The Thermal  Analysis    of    Monomers  2

 

 

Fig (11): The Thermal  Analysis    of    Monomers  3

 

 

Fig (12): The Thermal  Analysis    of    Monomers  4

 

Fig (13): The Thermal  Analysis of  Monomers   5

 

Effect   of   Monomers  on  Bacteria:

The  new   monomers  were  studied   against  types  of  bacteria  through   microbial  assay  procedures^(17-20)  at   Three  concentrations ((0.1  X 10^-3 ,  0.5 X 10^-3 , 1 X 10^-3  M) in (DMSO) as a solvent  with  two  kinds of  bacteria (bacteria- B. subtilis) and (bacteria-  Staphylococcus. Aureu) which   incubated  at  37^oC   for  48 hrs.

 

Picture. 1: Staphylococcus. Aureu

 

Picture. 2: B. subtilis

 

The study of the new monomers {1- 5} with two kinds of bacteria were summarized in table (1). It was noted that in the presence of each thiadiazole, triazole , sulfur or sulphone groups, the antibacterial activity of the monomers against bacteria was increased.

 

Results    in the table (1)  gave the best  concentration (1 X  10^-3  M ) for monomers (2, 4 )which    have a high    activity  to  presence  active  groups  in their  structures^(18-20)

 

Table(1): The anti-bacterial  Activity of  the  New Compounds (Inhibition  Zone  in (mm)) as an average of   three Concentrations (1X10^-3 ) M

Monomers	(average) B. subtilis	(average) Staphylococcus. Aureu
{ 1 }	6	6
{ 2 }	12	14
{ 3 }	10	8
{ 4 }	10	14
{ 5 }	4<	6

 

Picture. 3: Inhibition of  Monomers   on B. subtilis

 

Picture. 4: Inhibition of the Monomers on  Staphylococcus. Aureus

 

Analytical  Studying  -  Effect  of  Solvent:

The solubility of the new monomers was studied in different solvents according to the polarity, and the results are shown in table (2).

 

Table (2): Solubility of Monomers in Different  Solvents.

Monomers	Solvents
	CH3OH	Eth-OH	Dioxane	Hexane	CH2Cl2	C6H6
{[M1}	+	+	-	-	-	-
{M2}	+	+	-	-	-	-
{M3}	+	+	-	-	-	-
{M4}	+	+	-	-	-	-
{M5}	+	+	-	-	-	-

 

The solubility of new Monomers depends on the polarity of groups in the terminal of monomers which give interaction with solvents.    

 

CONCLUSIONS:

In this paper, 5 Monomers are synthesized through by means of the condensation reaction, cyclization and reaction of sulphone compound with Schiff base form the new monomers which contain  (hydroxyl and carboxyl)  groups with thiadiazole and triazole compounds. TLC and FT. IR, ¹H.NMR and DSC-Measurement have been employed to the monomers. The thermal measurements were also used to find out the stability for the monomers. The physical characterizations study and Analytical solubility in different solvents and the Biological  Effect study have taken place in this study as well. The solubility of suggested on the polarity of groups in the terminal of monomers that give interaction with solvents. The proposed Monomers are advantageous in modern industry of medical and pharmaceutical applications.

 

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Accepted on 23.05.2019          © RJPT All right reserved

Research J. Pharm. and Tech 2019; 12(9):4149-4154.