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Prepared by V. Aditya vardhan -- [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com ADICHEMISTRY Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com ACiONLINE COACHING FOR CSIR NET & GATE through hem stry SELF LEARNING MODULES DAY-1Prepared by V. Aditya Vardhan 1) Daily Question - detailed step by step explanation of solution is offered along with extra informatiown. ww.adichemistry.com 2) Quick Facts - Know few important points, extra information which help you in attempting knowledge/information based questions. 3) Assessment - Test yourself - How far you can apply the knowledge gained. Revise the ACiwhere the time management is important. subject - through these practicing questions. Improve your skills and get ready for the final exam hem stry READ --------- GET THE CONCEPT -------- REVISE THEN PRACTICE ------- PRACTICE ------P--r-ePpRaArCeTdICbEy ------- PRACTICE ------- PRACTICE V. AUNdTILiYtOyU RaEACVH YaOUrR dGOAhL an P.T.O www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan -- [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com 1) DAILY QUESTION Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com ACiIn the reaction shown below, identify the correct combination of the intermediate, P and the product, Q. (GATE 2004) hem stry H NN excess Ts BuLi Ph-CHO PQ Prepared by (Ts = 4-methylphenylsulfonyl) V. Aditya Vardhan Li OH .adiNcNPhh Tes mBi)stry.Lcianod m Ph A) wN wwH Li N and Ts OH PQ PQ C) and Ph Li ACiOHPh Li OH D) and Q hem stry P PQ P.T.O Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan - - [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com STEP BY STEP SOLUTION Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com ACiFirst of all, few questions............. hem stry 1) What type of compound is the starting molecule? * It is a tosyl hydrazone. 2) What is the nature of reagent usedPinrethpeafrirestdstbepy? V. Aditya Vardhan* BuLi is a very strong base. It can abstract a proton very quickly. 3) Guess the name of reaction in the first step. * It is calledwShawpirowreac.tioan.dichemistry.com * In this reaction, a tosyl hydrazone is converted into a less substituted alkene when treated with strong bases like alkyl lithium or Grignard reagents. * It is a kinetically controlled reaction. P.T.O ACihem stry Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan -- [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com ACihem stry SHAPIRO REACTION Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com H Li N N 2 moles of Ts BuLi Prepared by P V. AdityaP.T.VO ardhan www.adichemistry.com ACihem stry Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan - - [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com MECHANISM Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com ACiAgain, few questions.............. 1) How many moles of BuLi are consumed in this reaction? * 2 moles. That is why in the question it is mentioned that excess of BuLi was used. hem stry 2) How many protons are going to be abstracted? * Obviously, 2 protons. 3) Where are the protons that are goiPngretopbaeraebdstbraycted? * Most acidic protons are abstracted. i.e. the proton on nitrogen. V. Aditya Vardhan 4) What about second proton? Where is it? * Keep guessing. It will be clear in few minutes. www.adichPe.T.mO istry.com ACihem stry Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan - - [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com MECHANISM - CONTINUED.......... See which two protons are abstracted. Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com ACihem stry Bu - Li H NN Ts Prepared by V. Aditya Vardhan Abstraction of first proton www.adichemistry.com NN Ts H Bu - Li ACihem stry Abstration of second proton. A dianion is formed. NN PrTes pared by V. Aditya Vardhan www.adichPe.T.mO istry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan - - [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com MECHANISM - CONTINUED.......... The dianion will lose a tosyl group and finally dinitrogen. Note that removal of very stable Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com ACinitrogen is the driving force for this reaction. N N hem stry NN Li Ts -Ts- -N2 Li+ Prepared by P V. Aditya VardhanJust tilt your head sidewise to the right and find P in the given options (see the question). www.adichemistry.com P.T.O ACihem stry Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan - - [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com WHAT ABOUT SECOND REACTION? Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com ACiIt is a simple step. The doubly bonded carbon with negative charge is nucleophilic. Thus the aldehyde, Ph-CHO undergoes nucleophilic addition with ‘P’. hem stry Ph O- Ph OH H H Li Ph O protic workup H Prepared by V. Aditya VardhanQ That is all. Tilt your head once again. www.adichemistry.com P.T.O ACihem stry Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan -- [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com EXTRA INFORMATION ACi* In the Bamford-Stevens reaction, the tosyl hydrazones (p-Toluenesulfonyl hydrazones) of Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com aliphatic aldehydes or ketones furnish more substituted alkenes as thermodynamic product when treated with strong bases like NaOMe, NaH, LiH, NaNH2 etc. hem stry * It is highly stereoselective, when compared to Shapiro reaction, especially in aprotic solvents in which Z-alkene is formed predominantly. * More information can be found at: http://www.adichemistry.com/organic/namedreactions/ bamfordstevens/bamford-stevens-1.html Prepared by P.T.O V. Aditya Vardhan www.adichemistry.com ACihem stry Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan - - [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com EXTRA INFORMATION Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com ACi SPECTRAL DATA FOR ‘Q’ IR Spectrum: * Absorptihoenm fosrtryO-H bond expected at 3550 - 3200 cm-1 as a broad peak. 1H NMR: * Expecting 10 signals. Homework: Guess the chemical shift vaPlureesp. ared by V. Aditya1H, triplet Vardhan 2H, doublet 2H, doublet www.adichemOiHstry1H,.scingloet m 2H, triplet H 1H, singlet 2H, triplet 1H, triplet ACihem stry 6H, singlet 2H, doublet GO TO NEXT PAGE FOR QUICK FACTS SECTION P.T.O Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan - - [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com QUICK FACTS Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com ACi SUPER CONDUCTIVITY hem stry * A superconductor loses its electrical resistance and exhibits perfect diamagnetic behaviour when it is cooled below its critical temperature, T . c * The Meissner effect: If an external magnetic field is applied to a superconductor, the applied magnetic field is completely excluded. Experimentally it is found that a permanent magnet rises to become suspended in mid-air when placPedreovpear raesdupberyconductor at the critical temperature, T of c the superconducting material. V. Aditya Vardhan* YBa Cu O is a high temperature superconductor. Its unit cell of can be considered in terms 2 37 of three stacked perovskite unit cells. www.adichemistry.com ACihem stry Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan - - [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com ACi QUICK FACTS Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com hem stry CARBOXY PEPTIDASE * It is a hydrolase enzyme. It removes C-terminal aminoacid from a protein. Helps in degradation of peptides in biological systems. The active site in carboxy peptidase contains tetrahedrally coordinated Zn2+, which is coordinated to two histidine residues, one glutamate residue and one water molecule. Prepared by OH2 V. Aditya ZVn2+ ardhan His(N) O(Glu) His(N) Mechanism:www.adichemistry.com i) Zn2+ activates water molecule for nucleophilic attack. ii) H2O is polarized by a nucleophile (base). iii) polarization of carbonyl bond which is to be cleaved. ACihem stry Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com

Prepared by V. Aditya vardhan - - [email protected] lesson is part of Online coaching for CSIR NET & GATE by V. Aditya vardhan - www.adichemistry.com ASSESSMENT Get study material for CSIR NET & GATE by V. Aditya vardhan at www.adichemistry.com ACi True or False Statements 1) The Shapirhoemreascttryion is a kinetically controlled reaction. 2) In Shapiro reaction, a tosylhydrazone is converted into aldehyde. 3) Two moles of BuLi are consumed in Shapiro reaction. 4) In Bamford-Steven’s reaction, an E-alkene is formed in aprotic solvents predominantly. 5) The IR spectrum of product, Q shows a broad absorption peak due to C-O bond stretching in between 3550 - 3200 cm-1. Prepared by 6) YBa Cu O has perovskite unit cell structure. 2 37 V. Aditya Vardhan7) A superconductor exhibits perfect paramagnetic behaviour below its critical temperature,Tc. 8) The active site in carboxy peptidase contains octaahedrally coordinated Zn2+. 9) Zn2+ in carboxy peptidase is coordinated to two histidine, one glutamate and three water molecules. 10) Carboxy pewptidawse rewmov.esaa dC-teircminhal aeminmo aciidsfrotmrpyoly.saccchoaridmes. ACihem stry Prepared by V. Aditya Vardhan www.adichemistry.com Learn Rajayoga meditation to awaken your inner divine powers to lead a successful and happy life - Visit www.brahmakumaris.com