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Home > Synthesis and Characterization of Novel Heterocycles: Pyrazoles, Dihydropyrimidinones, Iminothiazolidinones, Quinolinyloxy Oxa/Thiadiazolamines and Triazolones /Thiones and Study of Palladium 0 -Catalyzed Cross- Coupling Reactions

Synthesis and Characterization of Novel Heterocycles: Pyrazoles, Dihydropyrimidinones, Iminothiazolidinones, Quinolinyloxy Oxa/Thiadiazolamines and Triazolones /Thiones and Study of Palladium 0 -Catalyzed Cross- Coupling Reactions

Thesis Info

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Author

Naeem Abbas

Program

PhD

Institute

Quaid-I-Azam University

City

Islamabad

Province

Islamabad.

Country

Pakistan

Thesis Completing Year

2012

Thesis Completion Status

Completed

Subject

Chemistry

Language

English

Link

http://prr.hec.gov.pk/jspui/handle/123456789/2177

Added

2021-02-17 19:49:13

Modified

2024-03-24 20:25:49

ARI ID

1676727457119

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This thesis describes the synthesis of various classes of heterocyclic compounds like, pyrazoles, dihydropyrimidinones, iminothiazolidinones, quinolinyloxy oxa/thiadiazol amines and triazolones/thiones and in addition study of palladium(0)-catalyzed cross- coupling reactions. Michael addition of some substituted anilines to methyl acrylate in acidic medium afforded the methyl 3-(substituted anilino)propionates (96-104), which on treatment with hydrazine hydrate in methanol were converted into corresponding 3-(substituted anilino) propionohydrazides (105-113) in good yields. Microwave irradiation of the latter with pentane-2,4-dione afforded 1-(3,5-dimethyl-1H-pyrazol-1-yl)-3-(substituted anilino) propan-1-ones (114-122) under solventless conditions. A series of new 5-substituted thiobarbituric acid derivatives 5-acetyl-3-aryl-2-thioxo- dihydropyrimidine-4,6(1H,5H)-diones (133-140) were synthesized by cyclocondensation of 1-aroyl-3-arylthioureas with malonic acid in the presence of acetic anhydride. These compounds exist in equilibrium with their enolic tautomeric form 5-(1-hydroxy ethylidene)-3-aryl-2-thioxo-dihydropyrimidine-4,6-(1H,5H)-diones. Plausible mechanism for the formation of products was proposed. Compounds (133-140) were evaluated for their preliminary antibacterial activity against a representative panel of Gram positive and Gram negative bacteria and were found to exhibit promising activity towards the tested microorganisms using levofloxacin as the reference drug. Of these compounds, the derivative (134) having methoxy group at ortho position of phenyl ring showed the highest effect on pathogenic bacteria and was identified as the lead molecule for further structural modifications. An efficient, synthesis of some 1-aroyl-3-aryl thioureas (123-132) was carried out. Substituted aroyl chlorides were treated with an equimolar quantity of potassium thiocyanate in acetone to afford the corresponding isothiocyantes which were not separated followed by reaction with an equimolar amount of substituted anilines to furnish the 1-aroyl-3-arylthiourea derivatives (123-132) which were assayed in vitro for their antimicrobial activity against Gram positive and Gram negative bacteria and were found to exhibit moderate to potent activity towards the tested microorganisms, compared to the standard drugs Tetracycline, Penicillin and Metronidazole.An efficient, regioselective synthesis of some 2-aroylimino-3-aryl-thiazolidin-4-ones (141-150) involving base-catalyzed cyclization of 1-aroyl-3-aryl thioureas with chloroacetyl chloride in dioxane is reported. Compounds (141-150) were assayed in vitro for their antimicrobial activity against Gram positive and Gram negative bacteria and were found to exhibit promising activity towards the tested microorganisms, comparable to and in some cases better than those of the standard drugs. The cyclic condensation of 1-aroyl-3-aryl thioureas with dimethyl acetylene dicarboxylate (DMAD) in methanolic solution at room temperature resulted in the formation of methyl [4-oxo-2-(substituted benzoylimino)-3-(substituted phenyl) thiazolidin-5-ylidene] acetates (151-164) in good to excellent yield. The synthesis of bis(thioureas) was carried out by treatment of aroyl/alkyl chloride with potassium thiocyanate and as a result corresponding isothiocyanates were obtained using acetone as solvent. These isothiocyanates were treated with 1,2-phenylene diamine and 1,2-bis(thioureas) (165-172) were obtained in good yield. Similarly, these isothiocyanates were treated with 1,4-phenylene diamine and resulted in 1,4-bis(thioureas) (173-180) synthesis. These bis-(thioureas) were also treated with dimethyl acetylene dicarboxylate (DMAD) and corresponding 1,2-bis(iminothiazolidinone) acetates (181-188) and 1,4- bis(iminothiazolidinone) acetates (189-196) were synthesized in good yield. A series of quinolinyloxy oxa/thiasemicarbazide derivatives (200-207) were synthesized. Intramolecular cyclization of these quinolinyloxy oxa/thiasemicarbazide derivatives in the acidic medium of poly phosphoric acid (PPA) resulted in synthesis of quinolinyloxy 1,3,4-oxa/thiadiazolamine derivatives (208-215) while in basic medium of sodium hydroxide intramolecular cyclization of these quinolinyloxy oxa/thiasemicarbazide derivatives resulted in synthesis of quinolinyloxy 1,2,4- triazolones/thiones derivatives (216-223). A series of 1,2-difluoro-3,4,5,6-tetra substituted phenylbenzene derivatives (226-228) was reported through Suzuki-Miyaura coupling-reaction of 1,2-difluoro-3,4,5,6- tetraiodobenzene with various boronic acid derivatives using tetrakis(triphenyl phosphine) palladium(0) as catalyst. The substrate 1,2-difluoro-3,4,5,6-tetraiodobenzene (225) was also synthesized by treatment of 1,2-difluoro-benzene with molecular iodine in the presence of K2S2O8, trifluoro acetic acid and sulphuric acid.
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اقبال کا تصور مردِمومن

اقبال کا تصور مردِمومن
نحمدہ ونصلی علی رسولہ الکریم امّا بعد فاعوذ بااللہ من الشیطن الرجیم
بسم اللہ الرحمن الرحیم
صاحب صدر معزز اساتذہ کرام اور میرے ہم مکتب شاہینو! آج مجھے جس موضوع پر لب کشائی کی سعادت نصیب ہورہی ہے وہ ہے:’’اقبال کا تصور مرد مومن ‘‘
معزز سامعین!
علامہ اقبال رحمۃ اللہ علیہ کا تصور مردمومن کوئی نیا تصورنہیں ہے۔ یہ وہی تصور ہے جو حضرت جنید بغدادی رحمۃ اللہ علیہ نے پیش کیا۔ یہ وہی تصور ہے جو بایزید بسطامی رحمۃ اللہ علیہ نے پیش کیا۔ یہ وہی تصور ہے جو فرید الدین گنج شکر رحمۃ اللہ علیہ نے پیش کیا۔ یہ وہی تصور ہے جوخواجہ معین الدین چشتی اجمیری رحمۃ اللہ علیہ نے نوے لا کھ کو کلمہ پڑھا کر پیش کیا۔ یہ وہی تصور ہے جو داتا گنج بخش علی ہجویری رحمۃ اللہ علیہ نے لاہور کی مسجد میں کعبہ دکھا کر پیش کیا۔ یہ وہی تصور ہے جو بہاؤ الدین زکریا ملتانی رحمۃ اللہ علیہ نے معاصرین میں اپنا لوہا منوا کر پیش کیا۔ یہ وہی تصور ہے جو غوث پاک رحمۃ اللہ علیہ نے ہر چاند کی گیارہ کو میلادُالنبی ؐ کی محفل سجا کر پیش کیا۔ یہ وہی تصور ہے جو حضرت امام حسینؑ نے سر نیزے پر چڑھا کر پیش کیا۔ یہ وہی تصور ہے جو حضرت صدیق اکبر ؓ نے غار میں سانپ سے ڈسوا کر پیش کیا۔ یہ وہی تصور ہے جومحسنِ کائنات نے طا ئف کے میدان میں تبلیغ کے دوران پتھر کھا کر پیش کیا۔ یہ وہی تصور ہے جو اللہ تعالیٰ نے مرد مومن کو اپنا خلیفہ بنا کر پیش کیا۔
صاحبِ صدر!
علامہ اقبالؒ نے اپنی ساری زندگی اس مساعی جمیلہ میں گزاری کہ انسان جس مقصد کے لیے تخلیق ہوا ہے اسے پورا کرے اور...

فن حدیث میں مولانا عبد الرحمن مبارک پوری کی خدمات کا جائزہ

Sūnan-ul-Tirmizi is an encyclopedia of Ahādith-ul-Ahkām. Imam Tirmizi is the Mohadith who divided hadiths into Sahih and Zaeef for the first time. He accepts or rejects a hadith on the base of Taāmul-e-Ummah. He is only the Mohadith who established the terminology of “Filbāb” in which he gives the words of hadith from a Sahabi and mentions the names of all other sahabies who are rawi of the same hadith. There are many sharh of Tirmizi written by Muhadiseen. Among them Tuhfat ul Ahwazi is famously written by Molana Abdul Rahman Mubarakpuri. He explores the terminologies of Sonan-e-Tirmizi. He discussed uloom ul hadith, books of hadith, Shoroh-ul-hadith, Asma-ul-rejal and ilm ul ansab etc. He mentions tafsiri aqwal, fiqhi problems and usool-e-hadith. He also solved the Tasaholat-e-Tirmizi in validity (sihat) and unvalidity (zouf). He is the first mohadith who tried to find the words of hadith from other sahabies whose names are given in “Filbab”. He did it but could not find the words of 87 ahadith for which he used the term “Lam aqif alaih” and 417 ahadith for which he used the term “Le Yonzar man akhraja haza ul hadith”. This thing makes it distinct from other shoroh of Sūnan-e-Tirmizi. He depends on the usool-e-hadith of forefather Muhadiseen and he did not establish his own usool hadith.

Phytotoxicity of Lead on Leguminous Plants Phaseolus Mungo and Lens Culinaris

Heavy metal is a major source of the edaphic pollution which is extensive incidence as consequences of modernity in industries and agriculture. Lead is a probable contaminant among all heavy metal that eagerly gathers in edaphic factors. In plant Lead is not a vital constituent but it enters and accumulates easily in various parts of the plant. Absorption of Lead in root is controlled by different physico-chemical parameters.Such as cation exchangeability of the soils, pH and particle size, as well as by root exudation. Lead is a predominantly hazardous element, as it can accumulate in individual organisms, but also in entire food chains. Rising in the uses of Lead made stuffs in our environment, lead to significant elevation of its toxicity in the atmosphere. This thesis examined the effect of toxic metal Lead on seedlings of two important crops widely used in Pakistan i.e., Phaseolus mungo L. and Lens culinaris Medik. those were cultivated in natural environment in nutrient medium in which Lead salt was added. Analysis revealed that Lens culinaris Medik. distinctly influence by Lead stress as compared to Phaseolus mungo L. Both leguminous species showed the prominent effect of Lead absorption in roots through the inhibition in seed and seedling germination, alteration in morphology of root and reduction in root elongation. Histomorphological revolution in vascular bundles of root in both pulses showed a rapid response of reduction in the ascent of sap which ultimately influences the other physiological and morphological attributes. Seed and seedling germination index, fresh and dry weight of root and shoot adversely affected by Lead toxicity. The degree of affection of Lead is mostly based upon the nature of the plant species. Lead effect the plant multidimensionality way, photosynthesis is one of the most familiar and sensitive phenomenon. UV/Visible double beam Schimadzo Spectrophotometer was used for examined the absorption spectrum of photosynthetic pigments. The alteration in absorption spectrum in response to elevation of Lead stress related to reduction in synthesis of chlorophyll with values of 1.415 to 0.426 for Lens culinaris Medik. and 1.004 to 0.023 for Phaseolus mungo L. viiAbstract The spectral change in photosynthetic pigments is the signal of the Lead acumulation. The uptake of Lead in root was higher than the other essential nutrients. Decline in Magnesium concentration related with the replacement of this essential ion by Lead. This was linked to the conversion of light green colors leaves to the dark green colors of leaves in both leguminous plants. It was also observed that these leaves remain dark green color after facing the demise. It was the indication of less concentration of real Mg chlorophyll. Total protein contents in the seedlings of Phaseolus mungo L.were found to be increased in shoot as compared to roots whereas it is significantly reduced in root and shoots of Lens culinaris. Amino acids in the roots of both species were found to be increased and decreased in the shoots of Lens culinaris while higher concentration of amino acids was observed in shoots of Phaseolus mungo L. Higher proline content and phenol contents in both species showed adaptation of self defense bio- chemical system to manage the toxicity of Lead while peroxidase and lignin activity were Lead dose depended. The reduced leaves sizes were correlated with an increase in Lead levels, and activities of peroxidase and lignin deposition in it. The intensification of activities of peroxidase and phenol in the Lead treated plants were accompanied by an increase in the biosynthesis of lignin content which perform function of scavenging reactive oxgen species (ROS radical). A strong correlation (r 2 =0.8570) was observed between Lead and lignin deposition in Lens culinaris Medik. whereas it was non- significant relation in Phaseolus mungo L.(r 2 =0.466). Increase in the lignin contents of Lens culinaris Medik. as a chemical adaptation of the cell walls of various leaves tissues for endurance while decreased in the lignin contents in Phaseolus mungo L. at high dose of Lead may be attributed with the decline in the peroxidase activity. Investigations revealed that although plants adopt several bio-physicomorphological and biochemical strategies for their survival but toxicity of Lead was considerably high due to which plant failed to continue to exist. viiiAbstract Bio-physico morphological deviation in anatomy of leaf under the Lead toxicity revealed that the most important immunological strategy. Presence of the trichomes or leave hairs on the margin of the leaves is the self protective phenomenon to neutralize the harmful effect of Lead. It was examined in both Phaseolus mungo L. and Lens culinaris Medik. by using the photo-camera microscope. Enhancement in number of trichome and stomata in the upper surface of the leaf is very important modification for defensive mechanism followed to conduct the normal photosynthesis process or to regulate the light reaction under the exposure of Lead toxicity. Leave morphological modification in Phaseolus mungo L. and Lens culinaris Medik. may be sign of defensive strategy that enables leaves to maintain their physiology in an environment marked by strong variations of Lead toxicity with light, temperature ,wind and relative humidity. Trichom play a role of a bioindicator of atmospheric pollution and biogeochemical signal of Lead contamination in soil. Tricome also act as the protective shield or defensive obstacle against the Lead toxicity. Trichom production increase with an increasing concentration of Lead.This led to reduction in transpiration and stimulation in conservation of water in leaves. Leaves hairs are responsible for protection in response to anxiety circumstance particularly in leave succession.Enhancement in the quantity of stomata is very important attribute in realtion with the gaseous exchange particularly emission of oxygen and absorption of carbondioxide. Elevation in creatinine, CK enzymatic activity, reducing sugar and glucose (p<.001) with the smaller size of stomata were observed in both leguminous plant in response to Lead toxicification. Decrease in mineral ions (Na, K, Ca, Mg, Fe, Mn and Zn) uptake in both species due to Lead accumulation indicates that Lead absorption more frequently as compared to essential mineral ion. The accumulation trend of Lead and Calcium showed a linear relation in between applied dose and accumulation of Lead in Phaseolus mungo L. and Lens culinaris Medik. which inversely related with Calcium content of both members of Fabaceae family. ixAbstract The reduction in Calcium content was due to chemical similarities in between the oxidation states of two ions but smaller ionic radius and high density of Lead helps in accumulation of it in tissues of both species. These interactions may occur at the cellular and molecular level and are the abilities of Lead to displace Calcium during specific physiological process. It is likely that the higher density and smaller ionic radii of heavy metal plays an integral role to block the access of essential mineral ions in plants and alter physiological processes of both species. Results obtained by atomic absorption Spectrophotometry from measurements of different essential macronutrient and micronutrient with Lead content both in roots and shoots showed that Lead accumulation was more pronounced in root than shoot.