Shrichakradhar.com 10 2 B ‘Tutor Marked Assignment 9958947060 BCHCET-147: ORGANOMETALLICS, BIOINORGANIC CHEMISTRY, POLYNUCLEAR HYDROCARBONS AND UV, IR SPECTROSCOPY ‘oarse Code: BCHCET-147 Assignment Code: BCHET-147/TMA2024 ‘Maximum Marks: 100 The muri for each sre indicated PART A: ORGANOMETALLICS, BIOINORGANIC CHEMISTRY, Give the reactions where sodium nitroprusside is used forthe qualitative analysis for the deterction of S* and S in organic compounds. Give the differences between organometallic compounds and organic compounds. ‘What is the structure of ferrocene in the solid state? What happens to the structure at cexmernly low terpernure? Explain the structure of Ni(CO). based on valence bond approach. With suitable reactions (any two) explain reductive carbonylation. How are binuclear carbonyls charscterized? Give the stature of Fe {CO}, and explain the diferent rypes of bond present init. Give the following reactions forthe formation of: (i) carbonylate anion by addition of alkali or reduction (any two) (i) casbonyl hydrides (any oe) (i cathy by displacement of CO by ater ligands (sy to). Discus the clasification ofthe elements on the bass of mechanism of action. ‘Discuss the importance of cadmium of biological system. Why they cannot harm new ‘bond babies? Whats the effect of long term cadmium exposure in animals and ‘human? ‘What are the reactions involved in photosystem I and IL Give the Z-scheme of ‘photosynthesis also. PART B: POLYNUCLEAR HYDROCARBONS AND UV, IR SPECTROSCOPY [Discuss the preparation ofthe following compounds starting from ethy! 3 ‘oxobutanaate? 1) 2-Butenoic acid (crotonic acid) {i) 4-ketwpentanoie acid Why I-position (a-position) of naphthalene is more reactive than the 2-postion (B- position}. Explain. Give IUPAC name ofthe following compounds: 6 6 6 “ 6 6 o o “ 6 o “ 6)Shrichakradhar.com 9958947060 i oe on} ity 14 (@) The amsck of the clecteophile in fursn occurs at the C-2 (ora) position. Explain with the (3) help of a suitable exansple. (@ Write the preparation of pyridine. 15. Give the sehematic diagram of the order of molecular orbital energies and give the 8 possible electronic transitions in them. 16 Explain bathochromic shift with 2 suitable example. 6 17 Explain the electronic spectra of the acetylene and benzenoid chromophore. 6 18 Explain the degrees of freedom for polyatomic molecules. o 19 i) List different factors which gover the position and intensity of hands appearing in the IR (5) spectrum of an organic compound ii) The C-C stretching vibration is infrared inactive (or neatly inactive). Give reason. In which region, C-H stretching absorptions of alkanes are exhibited? 20 Give the characteristics bands observed ia the IR spectra of carboxylic acids and 3 carboxylic acid anhyilrides.Shrichakradhar.com 9958947060 Disclaimer/Special Note: These are just the sample of the Answers/Solutions to some of the Questions given in the Assignments. These Sample Answers/Solutions are prepared by Private Teacher/Tutors/Authors Meenakshi Sharma for the help and guidance of the student to get an idea of how he/she can answer the Questions given the Assignments. We do not claim 100% accuracy of these sample answers as these are based on the knowledge and capability of Private Teacher/Tutor Meenakshi Sharma. Saniple answers may be seen as the Guide/Help for the reference to prepare the answers of the Questions given in the assignment. As these solutions and answers are prepared by the private Teacher/Tutor so the chances of error or mistake carmot be denied. Any Omission or Error is highly regretted though every care has been taken while preparing these Sample Answers/ Solutions. Please consult your own Teacher/Tutor before you prepare a Particular Answer and for up-to-date and exact information, data and solution, Student should must read and refer the official study material provided by the university PART A: ORGANOMETALLICS, BIOINORGANIC CHEMISTRY 1 Give the reactions where sodium nitroprusside is used for the qualitative analysis for the deteretion of S2- and § in organic compounds. (5) ‘ANS: Sodium nitroprusside (Na2[Fe(CN)SNO)) is commionly’used to detect the presence of sulfide ions (S2-) and sulfur in organic compounds through specific chemical reactions. Here are the reactions involved: Detection of Sulfide Ions (S2-): Sulfide ions react with sodium nitroprusside in an acidic-medium to form a deep violet coloration due to the formation of a complex ion,This reaction is highly sensitive and specific to sulfide ions. The reaction can be represented as follows Sulfide ion (S2-)+Sodium nitroprusside—Purple color complexSulfide ion (S2-)*Sodium ni troprusside—Purple color complex Detection of Elemental Sulfur (S) Sulfur in organic compounds can also be detected tising sodium nitroprusside. When sulfur is present, it forms a purple coloration with sodium nitroprusside under similar conditions (acidic medium). The sulfur is oxidized to a higher oxidation state, fonming a complex with the sodium nitroprusside The reaction equation —is-—_similar_ to that-—of_— sulfide ions Sulfir+ Sodium nitroprusside—»Purple color eomplexSulfiar+ Sodium nitroprusside—»Purple ¢ olor complex These reactions are useful for qualitative analysis, particularly in identifying the presence of sulfide ions and sulfursin organic compounds based on the distinctive color changes or formations of complexes. Topof Form 2 Give the differences between organometallic compounds and organic compounds. (5) ‘ANS; Organometalli¢ compounds and organic compounds share similatities due to their carbon-containing nature, but they differ significantly in their composition, bonding, and reactivity. Here are the key differences Metal Presence: Organometallic Compounds: These compounds contain at least one metal-carbon (M-C) bond. Metals like lithium, sodium, potassium, transition metals, and lanthanides form bonds with carbon in these compounds. Organic Compounds: Organic compounds primarily consist of carbon atoms bonded to hydrogen, oxygen, nitrogen, sulfur, and other non-metallic elements. They lack metal-carbon bonds Reactivity:Shrichakradhar.com 9958947060 Organometallic Compounds: These compounds often display unique reactivity due to the presence of metal atoms, which can participate in a wide range of reactions, including oxidative addition, reductive elimination, and coordination reactions. Organic Compounds: Organic compounds exhibit a diverse range of reactions typically involving covalent bonds such as substitution, addition, elimination, and rearrangement reactions, Nature of Bonds: Organometallic Compounds: They contain polarized M-C bonds with varying degrees of ionic and covalent character depending on the metal and ligands attached. Metal atoms contribute their d-orbitals to form bonds. Organic Compounds: Organic compounds primarily consist of covalent bonds between carbon and other non-metallic elements, resulting in molecules with varying polarities and functional groups Role and Applications: Organometallic Compounds: These compounds find applications in catalysis, synthesis of pharmaceuticals, materials science, and various industrial processes due to their unique reactivity and catalytic properties. Organic Compounds: Organic compounds are fundamental to life, serving as the basis for biological molecules such as carbohydrates, proteins, lipids, and nucleic acids. They are also erucial in industries ranging from medicine to polymers and agriculture Complexity and Structure: Organometallic Compounds: Often exhibit complex structures due to the coordination of metal atoms with various ligands, leading to diverse geometries and electronic properties. Organic Compounds: While organic compounds can be complex, their structures are typically based on carbon skeletons with funetional groups that determine their properties and reactivity 3 What is the structure of ferrocene in the solid state? What happens to the structure at extremely low temperature? (5) ANS: In the solid state, ferrocene adopts a sandiich-like structure, which is one of its most notable features. This structure consists of two parallel cyclopentadienyl rings (CSHS) acting as "sandwich bread," with an irou (Fe) afom situated between them. The iron atom fous bonds with each of the five carbon atoms, from the.cyclopentadienyl rings, creating a stable and symmetric structure At extremely low temperatures}ifertocene undergoes a phase transition known as a "phase change." As the temperature decreases significantly, typically below -20°C (-4°F), ferrocene experiences a structural change from its standard arrangement to a more ordered state This transition is often referred o as a solid-state phase transition, and in the case of ferrocene, it involves a change in the molecular orientation within the crystal lattice. At very low temperatures, the molecules in the crystal lattice arrange themselves in a more ordered fashion, resulting in a different Solid-state structure compared to the higher temperature phase. This change in structure at extremely low temperatures can be studied using techniques like X- ray crystallography, which reveals the differences in molecular arrangements between the two phases of ferrocene in the structure of Ni(CO)4 based on valence bond approach. (5 ANS: Ni(CO)4, known as tetracarbonyl nickel, is a classic example of a transition metal complex. In the valence bond approach, the structure of Ni(CO)4 can be explained using molecular orbital theory, considering the valence electrons of nickel and carbon monoxide ligandsShrichakradhar.com 9958947060 nico) [4|4|4]1|1 1 3d 4s 4p Ni under the influence of strong Co ligand [nicco,] [t]e[a[o]a ; [Te] co cococo u___ Sp? hybrid orbital Nickel (Nd: Nickel has a valence electron configuration of 3d°8 48*2..In Ni(CO)4, the nickel atom undergoes hybridization to foun four sp3 hybrid orbitals. The four CO ligands donate their lone pairs (from the oxygen atoms) to the empty 4d orbitals of nickel through a process called back-donation, Carbon Monoxide (CO) Ligands: Each carbon monoxide ligand (CO) is a strong a-acceptor ligatid, It donates its lone pair from the oxygen atom to form a sigma (0) bond with the nickel atom and accepts electron density via its 2* orbital. This a-back-donation from the nickels d orbitals ("the x* antibonding orbitals of CO strengthens the Ni-CO bond. The bonding in Ni(CO)4 can be described as @’combination of o-donation from CO to Ni and x-back-donation from Ni to CO. It results in the formation of four strong Ni-CO o bonds and an overall tetrahedral geometry. The molecular orbital diagram for Ni(CO)4 diivolves the overlap of the Ni ds, 4p, and 4d orbitals with the ligand orbitals of the CO molecules, resulting in the formation of bonding and antibonding molecular orbitals. The & bonds form from the overlap of the Ni 4s/4p/4d orbitals with the CO ¢ orbitals, while the s:back-donation occurs ftom Ni's d orbitals to the CO x* antibonding orbitals. 5 With suitable reactions (any two) éxplain reductive carbonylation. (5) ANS: Reductive carbonylation involves the introduction of a carbonyl group (CO) into an organic substrate via a reaction that employs carbon monoxide (CO) and a reducing agent. Two classical reactions that illustrate reductive carbonylation are the hydroformylation and the Koch-Haaf reaction: Hydroformylation (Oxo Process): Reaction: In hydroformylation, an alkene reacts with carbon monoxide and hydrogen in the presence of a transition metal catalyst, typically chodium or cobalt, to form an aldehyde. R-CH=CH2 + CO 4 H2 PY, R_CHO Mechanism: The transition metal catalyst coordinates with both CO and H2, facilitating the insertion of CO and H2 into the metal-carbou bonds of the alkene. This results in the formation of an aldehyde group adjacent to the original carbon-carbon double bond. Koch-Haaf Reaction: Reaction: The Koch-Haaf reaction involves the reductive carbonylation of aryl halides (e.g., aryl iodides) using CO and a redncing agent like zinc in the presence of a catalyst (e.g., copper),Shrichakradhar.com 9958947060 Ar-I+ CO + Zn *, Ar-CO-R Mechanism: The reaction proceeds through the generation of an arylzinc intermediate by the reaction of the aryl halide with zine metal. Subsequently, the arylzine intermediate reacts with carbon monoxide in the presence of the copper catalyst, leading to the formation of the aryl ketone (Ar-CO-R). In both reactions, the carbon monoxide acts as a carbonyl source, adding a carbonyl group to the organic substrate. The reducing agent, whether hydrogen in hydroformylation or a metal (like zinc) in the Koch-Haaf reaction, participates in reducing the intermediate species formed during the reaction, allowing for the insertion of the carbonyl group into the organic compound. These reactions exemplify reductive carbonylation processes, showcasing the introduction of carbonyl groups into organic compounds using CO and reducing agetits with the aid of specifie catalysts. 6 How are binuclear carbonyls characterized? Give the structure of Fe2(CO)9 and ex] the different types of bond present (5) ANS: Binuclear carbonyls, like Fe2(CO)9, are characterized’by the presence of two metal atoms (in this case, iron) bridged by multiple CO ligands; These compounds are often characterized using various spectroscopic and crystallographic techniques. ‘Structure of Fe2(CO)9: Fe2(CO)9 consists of two iron atoms bridged by nine carbon monoxide ligands. The structure can be visualized as two iron atoins connected by three bridging CO ligands and six terminal CO ligands. Types of Bonds Present: Metal-Metal Bond (Fe-Fe): Fe2(CO)9 exhibits a direct metal-metal bond between the two iron atoms. This bond is often described as a dative or coordinative bond, where electrons are shared between the iron atoms. The Fe-Fe bond in Fe2(CO)9 is relatively;weak compared to typical covalent bonds but is important for stabilizing the structure. Fe-CO Bonds: Terminal CO Ligands: Each iron atom in Fe2(CO)9 is coordinated to six terminal CO ligands, forming Fe-CO bonds. Bridging CO Ligands: Three CO ligands bridge the two iron atoms, connecting them in the binuclear complex. These bridging CO ligands are shared between the two iron atoms, contributing to the overall structure and stability. x-Bonding: There is extensive x-back bonding between the metal (iron) and the CO ligands. The CO ligands act as x-acceptor ligands, donating electron density from their x* antibonding orbitals to the d orbitals of iron. This x-back bonding strengthens the Fe-CO bonds and is essential for the stability of the binuclear carbonyl complex. Characterization of binuclear carbonyls like Fe2(CO)9 involves techniques such as X-ray crystallography, infrared spectroscopy (for CO stretching frequencies), and nuclear magnetic resonance (NMR) spectroscopy, which provide valuable structural and bonding information about these compounds. The distinctive spectroscopic features, such as IR stretching frequencies of CO ligands and the nature of metal-metal and metal-ligand bonds, aid in characterizing and understanding these complexes. 7 Give the following reactions for the formation of: (i) carbonylate anion by addition of alkali or reduction (any two) (i) carbonyl hydrides (any one) (iii) carbonyls by displacement of CO by other ligands {any two). (5) ANS: (i) Formation of Carbonylate Anion:Shrichakradhar.com 9958947060 Addition of Alkali: Reaction: Formation of the acetate (carbonylate) anion by the addition of sodium hydroxide to acetic acid, CH3COOH+NaOH-+CH3COONa+H20CH3COOH+NaOH-+CH3COONa+H20 Acetic acid*Sodium hydroxide—Sodium acetate (Carbonylate anion)*WaterAcetic acid+Sod ium hydroxide>Sodium acetate (Carbonylate anion)+Water Reduction: Reaction: Electrochemical reduction of carbon dioxide to generate the carbonylate anion C02+2e° + 2H'+CO+H20C02+2e° + 2H-+CO+H20 Carbon dioxide+Electrons + Protons~»Carbonylate anion (COO")+WaterCarbon dioxide+Ele etrons + Protons—>Carbonylate anion (COO™)+Water i) Formation of Carbonyl Hydride: Reduction of Carboxylic Acid: Reaction: Reduction of a carboxylic acid to form a carbonyl hydride, such as an aldehyde or an alcohol. RCOOH+LiAIH4—RCHO (Aldehyde or ketone)+LiOH+Al(OH)3RCOOH*LiAIH4 RCH 0 (Aldehyde or ketone)+LiOH+Al(OH)3 Carboxylic acid+Lithium aluminum hydride—-Aldehyde (or ketone)+By- productsCarboxylie acid+Lithium aluminum hydride Aldehyde (or ketone) +By-products Formation of Carbonyls by Displacement of CO by Other Ligands: Substitution of CO in Metal Carbony! Reaction: Replacement of one or more CO ligands in a metal carbonyl complex by other ligands, such as phosphines or halides. Fe(CO)5+PPh3—>Fe(CO)4(PPh3)+COFe(CO)S+PPh3—>Fe(CO)4(PPh3)+CO Iron pentacarbonyl+Triphenylphosphine—Tetracarbony|(phosphine) iron*Carbon monoxidel ron pentacarbonyl+Triphenylphosphine—Tetracarbony|(phosphine) iron+Carbon monoxide Formation of Acyl Chlorides from Metal Carbonyls: Reaction: Conversion of metal carbonyls into acyl chlorides by treatment with a chlorinating agent, such as thionyl chloride (soc2) Fe(CO)5+SOCI2Fe( CO)4C12+COFe(CO)S+SOCL2—Fe(CO)ACL2+CO Iron pentacarbonyl+Thionyl chloride—>Tetracarbonyl dichloride iron+Carbon monoxidelron pentacarbonyi+Thionyl chloride—>-Tetracarbony] dichloride iron+Carbon monoxide 8B ‘uss the clas: of at ANS: The classification of elements based on their mechanism of action involves categorizing elements according to their interactions and roles in various chemical reactions. Elements can be broadly classified into different groups based on how they participate in reactions or their mechanisms of action. Here'¥a general overview of such classifications: Metals vs. Non-Metals: Metals: Metals typically exhibit metallic bonding, have a tendeney to lose electrons, and form cations in reactions. Non-Metals: Nousmetals tend to gain or share electrons, forming anions or covalent bonds in reactions, They often display electronegativity and can be found in various molecular forms. Electropositive vs. Electronegative Elements: Electropositive Elements: These elements have a tendency to lose electrons and form positive ions (cations). Alkali metals and alkaline earth metals are examples of electropositive elements, Electronegative Elements: These elements have a higher affinity for electrons, tending to gain or share electrons to achieve a stable electron configuration. Halogens and some non-metals like oxygen and nitrogen are examples of electronegative elements. Transition Metals:Shrichakradhar.com 9958947060 Transition metals occupy the central block in the periodic table and often exhibit variable oxidation states. They are known for their ability to form colorful complexes, display catalytic properties, and participate in redox reactions. Halogens: Halogens are a group of highly reactive non-metals (Fluorine, Chlorine, Bromine, Iodine, Astatine) that have a tendency to form diatomic molecules and show high electronegativity. Metalloids: Metalloids exhibit properties of both metals and non-metals. They have intermediate conductivity and can behave either as semiconductors or insulators Noble Gases: Noble gases are chemically inert elements due to their stable electron configuration. They rarely participate in chemical reactions. Actinides and Lanthanides: Actinides and lanthanides are part of the inner transition metals. Actinides are generally radioactive and exhibit a wide range of oxidation states, P-block, S-block, and D-block Elements: Elements in the p-block, s-block, and d-block of the petiodié table have distinct properties based on their electron configurations and orbital filling, leading to variations in their reactivity and chemical behavior. This classification based on mechanism of action highlights the diverse roles and behaviors of elements in chemical reactions, based on their electronic configurations, tendencies to gain or lose electrons, and participation in various bonding mechanisms. 9 Discuss the importance of cadmium of biological system. Why they cannot harm new bond babies? What is the effect of long term cadmium exposure in animals and human? 5 as Cadmium is a toxic heavy metal thatyWhile not having a known biological role, can have significant detrimental effects on living organisms. Here's an overview of its importance and potential effects: Importance of Cadmium in Biological Systems: Cadmium does not have any known/essential biological function in organisms. Instead, it is considered a pollutant and a health hazard dne to its toxicity. Its presence in the environment primarily stems from industrial activities, including mining, smelting, and manufacturing processes, leading to contamination of air, water, and soil Effects on Newborn Babies: Newbom babies are less likely to be directly affected by cadmium toxicity because they receive their nutrients primarily from their mothers during pregnancy and breastfeeding. However, cadmium exposure in pregnant women can lead to the accumulation of cadmium in the mother's body, potentially affecting the fetus. Minimizing exposure during pregnancy is crucial to avoid detrimental effects on the developing baby, Effects of Long-Term Cadmium Exposure: ‘Animals: Long-tefmwexposure to cadmium in animals can lead to various adverse effects. It accumulates in tissues, particularly in the kidneys, liver, and bones, causing organ damage, impaired Kidney function, osteoporosis, reproductive system disorders, and potential carcinogenic effects. Humans: Chronic exposure to cadmium in humans can lead to similar health issues, including kidney damage, bone fractures, respiratory problems, cardiovascular diseases, and an increased risk of certain cancers (such as lung cancer). Cadmium exposure can also interfere with essential minerals like calcium and zine, disrupting their metabolic functions in the body.Shrichakradhar.com 9958947060 Cadmium's long-term exposure, even at low levels, poses serious health risks to both animals and humans. Its toxie effects can accumulate over time and cause severe damage to various organ systems, Limiting exposure to cadmium by minimizing contact with contaminated environments, avoiding smoking (as cigarettes are a source of cadmium), and adhering to food safety regulations can help mitigate its adverse effects on health, Efforts to reduce cadmium exposure and pollution are crucial to safeguarding human health and preserving the environment. Regular monitoring and regulation of cadmium in industrial processes and products are necessary to minimize its harmful impacts on living organisms. 10 What are the reactions involved in photosystem I and II. Give the Z-scheme of photosynthe: (5) ANS: Photosystem I (PSI) and Photosystem II (PSI) are key components of the photosynthetic electron transport chain in plants and algae. These photosystems work in tandem to hamess light energy and drive the synthesis of ATP and NADPH, crucial for the Calvin cycle Photosystem II (PSII): PSII absorbs light energy and initiates the photosynthetic electron transport chain. Reaction involved: Photolysis of water: Light energy is used to split water molecules into oxygen, protons (H+), and electrons (¢") The electrons released from water are used to replace the electrons lost by the chlorophyll molecule in PSI, maintaining its electron flow. Photosystem I (PSI): PSI receives electrons from PSII via the electrom transport'ehain and further energizes them using light energy. Reaction involved: Absorption of light: PSI absorbs light energy, excititig electrons to a higher energy state. Electron transfer: Excited electrons from PSL are tised to reduce NADP* to NADPH, which is, an energy carrier molecule used in the Calvin cycle! Z-Scheme of Photosynthesis: The Z-scheme illustrates the flow of electrons through PSII and PSI in photosynthesis, forming a pattern resembling the letter'Z' when graphically represented, Here are the key steps: Photon Absorption in PSI: PSII absorbs light energy, exciting electrons to a higher energy state Photolysis of water occurs, releasing electrons, protons, and oxygen. Electron Transport in PSH Excited electrons from PSII move through an electron transport chain, releasing energy as they move. Plastoquinone (PQ) and Cytochrome b6f Complex: Electrons pass through carriers, including plastoquinone (PQ) and the cytocuome b6f complex, pumping protons across the thylakoid membrane and contributing to the proton gradient. Photon Absorption in PSI: PSI absorbs more light energy, further energizing electrons. Electron Transport in PSI: The energized electrons from PSI reduce NADP+ to NADPH ATP Synthesis: As electrons move through the electron transport chain, energy released is used to pump protons into the thylakoid lumen, creating a proton gradient. ATP synthase utilizes this gradient to produce ATP through chemiosmosis.Shrichakradhar.com 9958947060 The Z-scheme highlights the cyclic flow of electrons from water through PSII, the electron transport chain, PST, and NADP+ reduction, driving the production of ATP and NADPH, essential for the subsequent dark reactions (Calvin cycle) of photosynthesis, PART B: POLYNUCLEAR HYDROCARBONS AND UV, IR SPECTROSCOPY 11 Discuss the preparation of the following compounds starting from ethyl 3- oxobutanoate? i) 2-Butenoic acid (crotonic acid) il) 4-ketopentanole acid (5) ANS: Starting Compound: Ethyl 3-Oxobutanoate Preparation of 2-Butenoic Acid (Crotonic Acid): Reaction: Ethyl 3-oxobutanoate undergoes a base-catalyzed decarboxylation reaction to form 2-butenoic acid (Crotonic acid). Procedure: Ethyl 3-oxobutanoate is treated with a strong base (¢.g., sodium of potassium hydroxide) in an alcoholic solvent (e-g., ethanol) This reaction induces decarboxylation, leading to the removal of the carboxyl group (-COOEX), resulting in the formation of 2-butenoic acid Reaction Equation: Ethyl 3-oxobutandate—+BaseAlcoholic solvent2- Butenoic acid (Crotonic acid)+EthanolEthyl 3-oxobutanoateAleoholic solventBase2- Butenoic acid (Crotonic acid)~Fthanol Preparation of 4 Ketopentanoie Acid: Reaction: Ethyl 3-oxobutanoate undergoes an oxidative Cleavage of the carbon-carbon bond and subsequent rearrangement to form 4-ketopentanoic acid, Procedure: Ethyl 3-oxobutanoate undergoes a Perkin reaction, which involves the base-catalyzed reaction of the starting material with an aromatic aldehyde, followed by an acidic work-up. The reaction initially yields a B-Keto acid intermediate, which undergoes decarboxylation and rearrangement to form 4-ketopentanoic acid; Reaction Equation: Acidic work-up Base Ethyl 3-oxobutanoate + Aromatic aldehyde 4-Ketopentanoic acid ‘These reactions demonstrate synthetic pathways to gonvert ethyl 3-oxobutanoate into 2-butenoie acid (crotouic acid) and 4-ketopentanoic acid’ by employing suitable chemical transformations involving decarboxylation and rearrangement reactions, 12 Why 1-position (a-position) of naphthalene is more reactive than the 2-position (B- position). Explai ANS: The reactivity of different positions on a molecule like naphthalene can be influenced by factors such as steric hindrance, resonance stabilization, and the availability of electrons. In the case of naphthalene, the»1-position (a-position) tends to be more reactive than the 2-position (B-position) due to several reasons: Steric Hindrance: The 1-position of naphthalene is less hindered compared to the 2-position. At the 2-position, the neighboring hydrogen atoms can cause steric hindrance, making it relatively more difficult, for reagents to approach and react. Resonance Stabilization: The 1-position of naphthalene has a greater potential for resonance stabilization of the resulting intermediate or transition state after a reaction occurs. The a-carbon in naphthalene, when undergoing a reaction, can form a resonance-stabilized intermediate that involves delocalization of the x-electrons across the aromatic ring system, providing additional stability to the intermediate.Shrichakradhar.com 9958947060 Electron Density: The 1-position tends to have higher electron density compared to the 2-position in naphthalene This higher electron density makes the I-position more nucleophilic and therefore more reactive toward electrophiles. Effect of Substituents: The presence of substituents on naphthalene can also affect the reactivity of different positions, Substituents can alter the electronic distribution within the ring system, potentially enhancing or reducing the reactivity of specific positions. Due to these combined effects, the 1-position of naphthalene is generally more reaetive than the 2-position. This higher reactivity can influence the regioselectivity of reactions and dictate which position is more favored for certain chemical transformations, such as electrophilic aromatic substitution or micleophilic addition reactions. 13 Give IUPAC name of the following co: yunds: a or a ANS: 1,2-Dichloronaphthalene a Br li) NO, Ans: L-nitro-3-bromo-4-chloronaplithalene cl | CH, Ans: I-mnethyl-4-chloroanthraceneShrichakradhar.com 9958947060 cl NO; CH, iv) Ans: 1-chloro-3-methyl-8-nitroanthracene v) cl Ans: chloroanthracene 14 (i) The attack of the electrophile in furan occurs atthe C-2 (ora) position. Explain with the help of a suitable example, Ans: Furan isa five-membered heterocyclic aromiati¢ compotifid containing an oxygen atom in its ring structure. Due to the presence of this oxygen atom atid the ring's electronic structure, electrophilic attack typically occurs at the C-2 position (a-position) of furan. One example that illustrates this phenomenon is the Friedel-Crafts acylation of furan, Friedel-Crafts Acylation of Furan: Reaction Setup: Furan reacts with an acylating agent (such as acetyl chloride or acetic anhydride) in the presence of a Lewis acid catalyst, usually aluatinum chloride (AIC). The Lewis acid facilitates the generation of the acylium ion, which serves as the electrophile in the reaction. Mechanism: The Lewis acid (AICI3) reacts with the aeylating agent to form an acylium ion (R-C+) Attack at C-2 (a-position) of Furan: The acylium ion acts as an electrophileyand furan’s a-carbon (C-2 position) has higher electron density due to the electrouwithdrawing effect of the oxygen atom, The nucleophilic attack occurs at the C-2 position of furan by the acylinm ion, resulting in the fonnation of a resonauce-stabilized carbocation intermediate, Formation of Acylated Product: The intermediate undergoes a reamangement via resonance stabilization, leading to the formation of the aeylated product. The acyl group gets attached to the C-2 position of furan, yielding the acylated furan product. This reaction exemplifies the preference for electrophilic attack at the C-2 position (a-position) of furan due to the higher electron density at this location caused by the oxygen atoms electron- withdrawing effect. The resulting product confirms the attack of the eleetrophile at the C-2 position, consistent with furan’s reactivity pattern. (ii) Write the preparation of pyridine Ans: Pyridine, a six-membered aromatic heterocycle containing one nitrogen atom, can be prepared by various methods. One common approach involves the Hantzsch pytidine synthesis,Shrichakradhar.com 9958947060 which utilizes the condensation of -ketoester, an aldehyde, and ammonia. Here's the general process. Hantzsch Pyri Reagent B-ketoester (such as ethyl acetoacetate) Aldehyde (such as formaldehyde or acetaldehyde) Ammonia (NH3) Acidie catalyst (such as ammonium acetate or piperidine) Steps: Formation of Intermediate: Condensation of the B-ketoester and aldehyde in the presence of ammonia Ina suitable solvent and under reflux conditions, the -Ketoester reacts with the aldehyde and ammonia to form an intermediate, typically a dihydropyridine Cyclization and Oxidation: Cyclization and oxidation of the dihydropyridine intermediate The cyclic intermediate undergoes oxidation, often using an acidic catalyst like ammonium acetate or piperidine under reflux conditions. This step leads t0 the formation of pyridine. e Synthesis: Reaction Equation: B-ketoester + Aldehyde + NH3 Cyclization, oxidation, dine ‘The Hantzsch pyridine synthesis provides a Straightforward route to synthesize pyridine from readily available starting materials. Pyridine, is an important compound used in various chemical applications, pharmaceuticals, audias a solvent in organic synthesis. This method is just one of several approaches to prepare pyridine, and. alternative synthetic rontes also exist for its production, 15 Give the schematic diagram of the order of molecular orbital energies and give the possible electronic transitions in them. (5) Ans: The schematic diagram of molecular otbital energies typically follows a pattem based on the qualitative molecular orbital theory. In atypical molecular orbital diagram for a diatomic molecule, the molecular orbitals‘are arranged in the following order of increasing energy. ¢ Molecular Orbitals (s MOs): ols c*2p transition to a Transitions:*Shrichakradhar.com 9958947060 Absorption of light can cause an electron to transition from a lower-energy bonding x orbital toa higher-energy antibonding x* orbital. Example: x2p — 2p transition These transitions involve the excitation of electrons from lower-energy orbitals to higher- energy antibonding orbitals due to the absorption of photons of specific energies (corresponding to the energy gap between the orbitals) 16 Explain bathochromie shift with a suitable example. (3) ‘Aus: The bathochromic shift, also known as a red shifl, refers to the phenomenon where the absorption maximum ofa molecule's electronic transition shifts to a longer wavelength (toward the red end of the spectrum) compared to a reference compound. This shift occurs due to changes in the molecular structure or environment of the molecule, leading to altered electronic transitions and absorption spectra. One common example of a bathochromic shift is observed itt the)case of certain dyes or molecules called cyanine dyes. These dyes are known for their sensitivity to solvent polarity and their absorption in the visible range. For instance, consider a cyanine dye molecule in two different solvents: a non-polar solvent (ike hexane) and a polar solvent (like ethanol). In a non-polar solvent (e.g., hexane), the cyanine dye molecule might exhibit an absorption maximum at a certain wavelength due to the molecular arrangement and environment within the non-polar solvent When the same cyanine dye molecule is dissolved ini aypolar solvent (e.g., ethanol), its absorption maximum might shift to a longer wavelength (bathochromic shift) compared to the non-polar solvent. The bathochromic shift in this case could bélattributed to-the interaction between the dye molecule and the polar solvent molecules. In a polar solvent, the interactions between the dye molecule and the solvent cause changes)in the) molecule's electronic distribution or conformation. This alters the energy levels of the molecular orbitals involved in the electronic transitions, resulting in a shift of the absorption maximum to a longer wavelength. The bathochromic shift is significant in various fields, including materials science, organic chemistry, and biochemistry, as it provides insights into the electronic properties and behavior of molecules in different environments. Tt helps in understanding how changes in structure or extemal factors influence the absorption spectra of compounds, which is crucial in various applications, such as designing dyes, sensors, and optical materials 17 Explain the electronic spectra of the acetvlenic and benzenoid chromophore. (5) Ans. The electronic spectra of acetylenic and benzenoid chromophores are associated with specific molecular structures that exhibit distinet patterns of absorption in the ultraviolet-visible (UV-Vis) region due to their conjugated m-electron systems. Acetylenie Chromophore: Structure: Acetylenic’¢lromophores coutain triple bonds (-C=C-) with conjugated a-electron systems, Compounds like alkynes and polyynes fall into this category. Electronic Spectra: Acetylenic chromophores typically absorb light at higher energies (shorter wavelengths) compared to benzenoid systems due to the presence of triple bonds and extended conjugation. Absorption Bands: Acetylenic compounds exhibit UV-Vis absorption bands in the higher energy ultraviolet region. Their spectra often display more intense and higher-energy absorption peaks compared to benzenoid compounds Conjugation Effects: The absorption bands are a result of x — 7* transitions within the conjugated system. The energy gaps between the a and 1* orbitals are relatively smaller due to the extended conjugation, leading to absorption at shorter wavelengths,Shrichakradhar.com 9958947060 Example: Compounds like ethyne (acetylene) or extended acetylenic systems in organic molecules exhibit characteristic absorption bands in the UV region Benzenoid Chromophore: Structure: Benzenoid chromophores contain benzene rings (or other aromatic rings) with a planar, cyclic, and conjugated x-electron system. Electronic Spectra: Benzenoid compounds absorb light at lower energies (longer wavelengths) compared to acetylenic systems due to their extended m-electron delocalization within the aromatic ring. Absorption Bands: Benzenoid compounds exhibit UV-Vis absorption bands in the lower energy UV or visible region. The absorption peaks appear at longer wavelengths compared to acetylenic compounds Conjugation Effects: t —+ n* transitions within the conjugated system lead to absorption in the UV-Vis spectrum. The larger energy gaps between 1 and n* orbitals compared to acetylenic systems result in absorption at longer wavelengths. Example: Benzene, substituted benzene derivatives, and other aromatic compounds display characteristic absorption peaks in the UV or visible range. The differences in absorption spectra between acetylenic aud)benzenoid chromophores arise from their structural differences, conjugation lengths, and the nature of their a-clectron systems, leading to distinctive patterns of absorption in the UV-Vis region. 18 Explain the degrees of freedom for polyatomic molecules. (5) Ans: In the context of polyatomic molecules, degrees of freedom refer to the different ways in which a molecule can move or store energy based on its)stmctural characteristics. For a molecule consisting of N atoms, the total degrees of freedom (DOF) are determined by its molecular structure, bonding, and overall geometry The degrees of freedom for a polyatomic molecule can be categorized into three main types: Translational Degrees of Freedom (3 DOF): Polyatomic molecules, like all molecules, have thtee translational degrees of freedom corresponding to motion along the three spatial dimensions (x, y, z). These involve the molecule’s movement through space as a whole, Rotational Degrees of Freedom (3 DOF for linear, 3 DOF for nonlinear): Linear Molecules: Linear molecules. possess. three rotational degrees of freedom - rotation about the molecule's axes (x, y, 2). Nonlinear Molecules: Nonlinear molecules have three rotational degrees of freedom around the axes perpendicular to each other, known as Eulerian angles (6, 0, y). However, due to the constraint of the bond angles, only two out of these three rotational modes are independent. Vibrational Degrees of Ereedom (3N - 6 for nonlinear, 3N - 5 for linear): Vibrational degrees of freedom involve the vibration of atoms within the molecule. For a molecule with N atoms, the total vibrational degrees of freedom can be calculated using the fonnula 3N - 6 for nonlinear molecules and 3N - 5 for linear molecules. These vibrations comespond to the stretching, bending, and rotational-vibrational motions of bonds and angles between atoms within the molecule. Each type of bond (e.g., stretching of bonds, bending of angles) contributes to the overall vibrational degrees of freedom. The total degrees of freedom (DOF) for a polyatomic molecule can be summarized as the sum of its translational, rotational, and vibrational degrees of freedom: Total DOF = Translational DOF + Rotational DOF + Vibrational DOF Understanding the degrees of freedom of a polyatomic molecule is crucial in various areas of chemistry and physics, as it provides insights into the molecule's behavior, its energy distribution, and its interactions with other molecules in different states (solid, liquid, gas). Additionally, it helps in stdying molecular spectroscopy, reaction dynamics, and thermodynamic properties of chemical systems.Shrichakradhar.com 9958947060 19 i) List different factors which govern the position and intensity of bands appearing in the IR spectrum of an organic compoun Ans: The position and intensity of bands in the infrared (IR) spectrum of an organic compound are influenced by various factors related to molecular structure, chemical environment, and vibrational motions. Here are the different factors that govern the position and intensity of bands in an IR spectrum: Functional Groups: Different functional groups present in a molecule exhibit characteristic IR absorption bands due to specific vibrational modes associated with those groups. For example, C=O stretching in carbonyl groups, C-H stretching in alkyl groups, N-H stretching in amines, ete, Bond Strength: The strength of a bond affects the wavenumber (frequency) at which it absorbs infrared radiation. Stronger bonds generally absorb at higher wavemtumbers. Mass of Atoms: The masses of the atoms involved in a bond influence the frequency at which they vibrate. Lighter atoms vibrate at higher frequencies compared to heavier atoms, Bond Length: Longer bonds typically have lower frequencies of vibration and absorb at lower wavenumbers, while shorter bonds absorb at higher wavenumbers, Conjugation and Resonance: Conjugation and resonance in/A molecule can alter the bond strengtiis and result in shifts in absorption bands. For example, conjugation in a molecule containing double bouds or aromatic rings can cause a bathochromic (red) shift in the absorption bands. Hydrogen Bonding: Hydrogen bonding affects the vibrational frequencies of functional groups involved in hydrogen bonding interactions. It can/eanse shifis and broadening of absorption bands, particularly in O-H and N-H stretching regions. Steric Effects: The spatial arrangement of atoms and groups within a molecule can influence bond angles and strengths, thereby affecting the position and intensity of absorption bands Substituent Effects: Substituents attached)to. funetional groups can alter the electronic environment and affect the IR spectra of neighboring functional groups. Solvent Effects: Solvents with hydrogen bonding capabilities can influence the intensity and position of IR absorption bands, particularly those involving hydrogen bonding functional groups. ii) The C-C stretching vibratiomis infrared inactive (or nearly inactive). Give reason. In which region, C-H stretching absorptions of alkanes are exhibited? (5 ans: The C-C stretching vibration.is generally considered to be infrared inactive or weakly active in most simple, saturated hydrocarbons (like alkanes) due to the symmetric nature of this, vibration and the way it behaves in terms of the change in dipole moment. The reason behind the infiared inactivity of the C-C stretching vibration lies in the molecular symmetry and the way this vibration affects the dipole moment Symmetry: In a molecule like an alkane (¢.¢., methane, ethane), the C-C stretching vibration involves both carbon atoms moving toward and away fiom each other syaunettically. This symmetrical movement, results in no net change in the molecule’s dipole moment during the vibration. Change in Dipole Moment: Infrared spectroscopy relies on the interaction between the electromagnetic radiation and the changing dipole moment of a molecule during a vibration Since the C-C stretching vibration in alkanes does not cause a significant change in the dipole moment due to its symmetric nature, it results in weak or negligible absorption of infrared radiation, Regarding the C-H stretching absorptions of alkanes, these absorptions typically occur in the region of the IR spectrum between approximately 2800 to 3000 cm-I. The exact position within this range depends on factors like the nature of the C-H bond (e.g., sp3, sp2, sp hybridization) and the chemical environment of the hydrogen atoms. For saturatedShrichakradhar.com 9958947060 hydrocarbons (alkanes), the C-H stretching bands appear as sharp, intense peaks in this spectral region 20 Give the characteristics bands observed in the IR spectra of carboxylic acids and carboxyl id anhyd: Ans: Inthe IR spectra of carboxylic acids and carboxylic acid anhydrides, certain characteristic bands appear due to specific vibrational modes associated with their functional groups. These bands help in the identification and differentiation of these compounds. Here are the characteristic bands observed in their IR spectra: Carboxylic Acids: Carbonyl Stretching (C=O): Strong and broad band around 1700-1725 eny*-1 (usually appears as.a broad peak), This band arises from the stretching vibration of the C=O bond in the carboxylic acid functional group. O-H Stretching: Broad and strong band in the region of 2500-3300 cm*-1 (usually appearing as a broad peak ora shoulder), Due to the O-H stretching vibration of the carboxylic acid grdp. This band can overlap with the stretching vibrations of hydrogen-bonded carboxylic acid dimers, leading to a broadening of the peak C-H Stretching: Weak to medium intensity bands around 2800-3000 enr*1 (aliphatic C-H stretching bands). O-H Bending: Medium intensity band around 1400-1500 m1 due to O-H bending vibrations Carboxylic Acid Anhydrides: Anhydride Carbonyl Stretching (C=O): ‘Two distinct strong bands around 1770-1800\cm*-1 (two peaks due to two carbonyl groups in the anhydride) These bands correspond to the stretching vibratioits/of the carbonyl groups in the anhydride functional group C-O-C Stretching (Anhydride Group); A band around 1250-1300 em1 (medinm intensity) due to the stretching vibration of the C- O-C bond in the anhydride group O-H Stretching (If Present): Similar to carboxylic acids, ifthere are fiee -OH groups present (e-g., acetic anhydride), a broad band appears around 2500-3300. cm-l due to O-H stretching. These characteristic bands in the IR spectra of carboxylic acids and carboxylic acid anhydrides arise from the specific vibrational modes associated with their fmctional groups. Analyzing these bands aids in the identification and differentiation of these compounds in organic synthesis and analysis.