(Chemistry , Paper-I ) ORGANIC SYNTHESIS B ( कार्बनिक संश्लेषण ) U.P B.Sc 6th Semester book

Unit

Topics

No. of

Lectures

I

Reagents in Organic Synthesis

A detailed study of the following reagents in organic transformations Oxidation with DDQ, CAN and SeO₂, mCPBA, Jones Oxidation, PCC, PDC, PFC, Collin’s reagent and ruthenium tetraoxide. Reduction with NaBH₄, LiAlH₄, Meerwein-Ponndorf-Verley (MPV) reduction, Wilkinson's catalyst, Birch reduction, DIBAL-H

dkcZfud la'ys"k.k esa vfHkdeZd

dkcZfud :ikarj.kksa esa fuEufyf[kr vfHkdeZdksa dk foLr`r v/;;u] DDQ, CAN vkSj SeO2, mCPBA v‚Dlhdj.k] PCC, PDC, PFC, dksfyu vfHkdeZd vkSj :Fksfu;e VsVªkv‚DlkbM ds lkFk v‚Dlhdj.kA NaBH4, LiAlH4, ehjohu&iksaMkWQZ&osysZ (MPV) ds lkFk vip;u] fofYdalu mRçsjd] cpZ vip;u] DIBAL-H

6

II

Organometallic Compounds: Organomagnesium compounds: the Grignard reagents, formation, structure and chemical reactions. Organozinc compounds: formation and chemical reactions. Organolithium compounds: formation and chemical reactions.

dkcZ/kkfRod ;kSfxd& v‚xsZukseSXuhf'k;e ;kSfxd& fxzXukMZ vfHkdeZd] xBu] lajpuk vkSj jklk;fud vfHkfØ;k,¡A v‚xsZuksftad ;kSfxd& xBu vkSj jklk;fud vfHkfØ;k,¡A v‚xsZuksfyfFk;e ;kSfxd& xBu vkSj jklk;fud vfHkfØ;k,¡A

4

III

Chemistry of Aldehydes and Ketones: Nomenclature and structure of the carbonyl groups, synthesis of aldehydes and ketones with particular reference to the synthesis of aldehydes from acid chlorides, synthesis of aldehydes and ketones uses 1, 3-dithianes, synthesis of ketones from nitrites and from carboxylic acids, Physical properties. Mechanism of nucleophillic additions to carbonyl group with particular emphasis on benzoin, aldol, Perkin and Knoevenagel condensations, Condensation with ammonia and its derivatives. Wittig reaction, Mannich reaction.  Oxidation of Aldehydes, Cannizzaro reaction, MPV, Clemmensen, Wolff-Kishner, LiAlH₄ and NaBH₄ reductions. Halogenation of enolizable ketones. An introduction to α, β unsaturated aldehydes and Ketones.

,fYMgkbM vkSj dhVksu dk jlk;u& dkcksZfuy lewgksa dk ukedj.k vkSj lajpuk] vEy DyksjkbM ls ,fYMgkbM ds la'ys"k.k ds fo'ks"k lanHkZ esa ,fYMgkbM vkSj dhVksu dk la'ys"k.k] ,fYMgkbM vkSj dhVksu ds la'ys"k.k ds mi;ksx] 1] 3&MkbfFk,u  ukbVªkbV ls dhVksu dk la'ys"k.k vkSj dkcksZfDlfyd vEy] HkkSfrd xq.kA csatksbu] ,YMksy] ifdZu vkSj uksosustsy la?kuu] veksfu;k vkSj blds O;qRiUu ds lkFk la?kuu ij fo'ks"k tksj nsus ds lkFk dkcksZfuy lewg esa UkkfHkdLusgh ;ksxkRed dh fØ;kfof/kA fofVx vfHkfØ;k] ekfu’k vfHkfØ;kA ,fYMgkbM dk v‚Dlhdj.k] dSfutkjks vfHkfØ;k] MPV] Dysesalsu] oksYQ&fd'kuj] LiAlH₄ vkSj NaBH₄ vip;uA ,uksykbtscy dhVksUk dk gSykstuhdj.k]  a, b-vlar`Ir ,fYMgkbM vkSj dhVksu dk ifjp;A

10

IV

Carboxylic Acids and their Functional Derivatives

Nomenclature and classification of aliphatic and aromatic carboxylic acids. Preparation and reactions. Acidity (effect of substituents on acidity) and salt formation. Reactions: Mechanism of reduction, substitution in alkyl or aryl group. Preparation and properties of dicarboxylic acids such as oxalic, malonic, succinic, glutaric, adipic and phthalic acids and unsaturated carboxylic acids such as acrylic, crotonic and cinnamic acids. Reactions. Action of heat on hydroxy and amino acids, and saturated dicarboxylic acids, stereospecific addition to maleic and fumaric acids. Preparation and reactions of acid chlorides, acid anhydrides, amides and esters, acid and alkaline hydrolysis of esters, trans-esterification.

dkcksZfDlfyd vEy vkSj muds fØ;kRed O;qRiUu

,sfyQSfVd ;k ,sjkseSfVd dkcksZfDlfyd vEy dk ukedj.k vkSj oxhZdj.kA rS;kjh vkSj vfHkfØ;k,¡A vEyrk ¼vEyrk ij izfrLFkkfi;ksa dk çHkko½ vkSj yo.k dk fuekZ.kA vfHkfØ;k,¡& ,sfYdy ;k ,sfjy lewg esa vip;u] çfrLFkkiu dh fØ;kfof/kA MkbdkcksZfDlfyd vEy tSls v‚DtSfyd] eSyksfud] LkfDlfud] XywVsfjd] ,fMfid vkSj FkSfyd vEy vkSj vlar`Ir dkcksZfDlfyd vEy tSls ,sØsfyd] ØksVksfud vkSj fluSfed vEy dh rS;kjh vkSj xq.kA vfHkfØ;k,¡ gkbMª‚Dlh vkSj vehuks vEy vkSj lar`Ir MkbdkcksZfDlfyd vEy ij Å"ek dh fØ;k] eSysbd vkSj ¶;wesfjd vEy ds fy, f=foefof'k"V ;ksxA vEy DyksjkbM] vEy ,ugkbMªkbM] ,ekbM~l vkSj ,LVj dh rS;kjh vkSj vfHkfØ;k,¡] ,LVj ds vEy vkSj {kkjh; tyvi?kVu] Vªkal&,LVjhdj.kA

8

V

Organic Synthesis via Enolates

Acidity of α-hydrogens, alkylation of diethyl malonate and ethyl acetoacetate, Synthesis of ethyl acetoacetate: the claisen condensation, Keto-enol tautomerism of ethyl acetoacetate. Alkylation of 1, 3-dithianes, Alkylation and acylation of enamines.

buksysV~l ds ek/;e ls dkcZfud la'ys"k.k

α&gkbMªkstu dh vEyrk] Mkb,fFky eSyksusV vkSj ,fFky ,flVks,lhVsV dk {kkjhdj.k] ,fFky ,lhVks,lhVsV dk la'ys"k.k& Dyslsu la?kuu] ,fFky ,lhVks,lhVsV dk dhVks&bukWy pyko;orkA  1]3&MkbfFk,Ul dk ,sfYdyhdj.k] busehu dk ,sfYdyhdj.k vkSj ,sflyhdj.kA

5

VI

Organic Compounds of Nitrogen: Preparation of nitroalkanes and nitroarenes, Chemical reactions of nitroalkanes. Mechanisms of nucleophilic substitution in nitroarenes and their reductions in acidic, neutral and alkaline media, Picric acid. Halonitroarenes: reactivity, Structure and nomenclature of amines, physical properties, Stereochemistry of amines, Separation of a mixture of primary, secondary and tertiary amines. Structural features effecting basicity of amines.

Amine salts as phase-transfer catalysts, Preparation of alkyl and aryl amines (reduction of nitro compounds, nitrities), reductive amination of aldehydic and ketonic compounds, Gabrielphthalimide reaction, Hofmann bromamide reaction. Reactions of amines, electrophilic aromatic substituton in aryl amines, reactions of amines with nitrous acid. Synthetic transformations of aryl diazonium salts, azo coupling

ukbVªkstu ds dkcZfud ;kSfxd& ukbVªks,sYdsu vkSj ukbVªks,sjhu dks cukuk] ukbVªks,sYdsu dh jklk;fud vfHkfØ;k,¡A ukbVªks,sjhu esa ukfHkdLusgh çfrLFkkiu dh fØ;kfof/k vkSj vEyh;] mnklhu vkSj {kkjh; ek/;e] fifØd vEy esa mudk vip;uA gsyksukbVªks,sjhUl& vfHkfØ;k'khyrk] ,sehu dh lajpuk vkSj ukedj.k] HkkSfrd xq.k] ,sehu dk f=foejlk;u] çkFkfed] f}rh;d vkSj r`rh;d ,sehu ds feJ.k dk i`FkDdj.kA ,sehuksa dh {kkjdrk dks çHkkfor djus okyh lajpukRed fo'ks"krk,aA

pj.k&LFkkukarj.k mRçsjd ds :i esa ,sehu yo.k] ,sfYdy vkSj ,sfjy ,sehu dks cukuk ¼ukbVªks ;kSfxdksa] ukbVªsV~l dk vip;u½] ,YMhgkbfMd vkSj dhVksfud ;kSfxdksa dk vipk;d ,sehuhdj.k] xsfcz;yFkSfyekbM vfHkfØ;k] g‚QeSu czksekekbM vfHkfØ;kA ,sehu dh vfHkfØ;k,¡] ,sfjy ,sehuksa esa bysDVªkWuLusgh ,sjkseSfVd çfrLFkkiu] ukbVªl vEy ds lkFk ,sehu dh vfHkfØ;k,¡A Mkb,stksfu;e yo.k dk la’ysf"kr ifjorZu] ,tks ;qXeu

10

VII

Heterocyclic Chemistry

Molecular orbital picture and aromatic characteristics of pyrrole, furan, thiophene and pyridine, Methods of synthesis and chemical reactions with particular emphasis on the mechanism of electrophilic substitution, Mechanism of nucleophilic substitution reaction in pyridine derivatives, Comparison of basicity of pyridine, piperidine and pyrrole.

Introduction to condensed five and six membered heterocycles, Preparation and reactions of indole, quinoline and isoquinoline with special reference to Fisher indole synthesis, Skraup synthesis and Bischler-Nepieralski synthesis, Mechanism of electrophilc substitution reactions of indole, quinoline and isoquinoline

fo"kepØh; jlk;u

ikbjksy] ¶;wjku] fFk;ksQhu vkSj ikbjhMhu dh vk.kfod vkfcZVy vkjs[k vkSj ,jkseSfVd fo'ks"krk,a] bysDVªkWuLusgh çfrLFkkiu dh fØ;kfof/k ij fo'ks"k tksj nsus ds lkFk la'ys"k.k vkSj jklk;fud vfHkfØ;kvksa dh fof/k;k¡] ikbjhMhu O;qRiUu esa ukfHkdLusgh çfrLFkkiu vfHkfØ;k dh fØ;kfof/k] ikbjhMhu] ikbisjhMhu vkSj ikbjksy dh {kkjdrk dh rqyukA

la?kfur ikap vkSj Ng lnL;h; fo"kepØh; dk ifjp;] fQ'kj baMksy la'ys"k.k] LØSi la'ys"k.k vkSj fcLDyj&usfi,jYLdh la'ys"k.k ds fo'ks"k lanHkZ esa baMksy] fDouksfyu vkSj vkblksfDouksfyu dks cukuk vkSj vfHkfØ;k,a] baMksy] fDouksfyu vkSj vkblksfDouksfyu dh bysDVªkWuLusgh çfrLFkkiu dh fØ;kfof/kA

10

VIII

Natural Products

Alkaloids & Terpenes: Natural occurrence, General structural features, their physiological action, Hoffmann’s exhaustive methylation, Emde’s modification. Medicinal importance of Nicotine, Hygrine, Quinine, Morphine, Cocaine, and Reserpine. Natural Occurrence and classification of terpenes, isoprene rule.

çk—frd mRikn

,Ydsy‚bM vkSj VihZu& çk—frd çkfIr LFkku] lkekU; lajpukRed fo'ks"krk,a] mudh dkf;Zdh; fØ;k,¡] g‚QeSu dk lEiw.kZ feFkkbys'ku] ,EMs dk la'kks/kuA fudksVhu] gkbZxzhu] fDofuu] e‚fQZu] dksdhu vkSj jslihZu dk vkS"k/kh; egRoA VihZu dh çk—frd izkfIr LFkku vkSj oxhZdj.k] vkblksçhu fu;eA

7

Unit

Topics

No of

Lectures

I

Gravimetric Analysis

1)      Analysis of Cu as CuSCN

2)      Analysis of Ni as Ni (Dimethylgloxime)

3)      Analysis of Ba as BaSO₄

HkkjkRed fo'ys"k.k

1)       Cu dk CuSCN ds :i esa fo'ys"k.k

2)       Ni dk Ni ¼MkbZesfFkyXy‚fDle½ ds :i esa fo'ys"k.k

3)       BaSO₄ ds :i esa Ba dk fo'ys"k.k

30

II

Paper Chromatography

1)      Ascending and Circular.

2)      Determination of R_f values and identification of organic compounds:

3)      Separation of a mixture of phenylalanine and glycine. Alanine and aspartic acid Leucine and glutamic acid. Spray reagent – ninhydrin.

4)      Separation of a mixture of D, L – alanine, glycine, and L-leucine using n-butanol: acetic acid: water (4:1:5). Spray reagent–ninhydrin. Separation of monosaccharaides – a mixture of D- galactose and D – fructose using n- butanol: acetone: water (4:5:1). Spray reagent – aniline hydrogen phthalate

dkxt o.kZysf[kdh

1)       vkjksgh vkSj xksykdkjA

2)       R_f eku dk fu/kkZj.k vkSj dkcZfud ;kSfxdksa dh igpku&

3)       Qsfuy,ysfuu vkSj Xykbflu ds feJ.k dks vyx djukA ,ysfuu vkSj ,LikfVZd vEy Y;wlhu vkSj XywVkfed vEyA Lçs vfHkdeZd & fuugkbfMªuA

4)       n&C;wVsu‚y % ,flfVd vEy % ty (4:1:5) dk mi;ksx djds D, L& ,ysfuu] Xykbflu vkSj L&Y;wlhu ds feJ.k dks vyx djukA Lçs vfHkdeZd&fuugkbfMªuA D&xSysDVkst vkSj D&ÝDVkst] vkSj n&C;wVsu‚y % ,lhVksu % ty (4:5:1) ds feJ.k dk mi;ksx djds eksukslSdsjkbM~l dk i`FkDdj.kA Lçs vfHkdeZd& ,fufyu gkbMªkstu FkSysVA

8

III

Thin Layer Chromatography

1)      Determination of R_f values and identification of organic compounds:Separation of green leaf pigments (spinach leaves may be used)

2)      Preparation of separation of 2,4-dinitrophenylhydrazones of acetone, 2-butanone, hexan-2, and 3-one using toluene and light petroleum (40:60)

3)      Separation of a mixture of dyes using cyclohexane and ethyl acetate (8.5:1.5)

iryh ijr o.kZysf[kdh

1)       R_f ekuksa dk fu/kkZj.k vkSj dkcZfud ;kSfxdksa dh igpku& gjh iÙkh ds jaxæO; dks vyx djuk ¼ikyd dh ifÙk;ksa dk mi;ksx fd;k tk ldrk gS½

2)       VkWYkqbu vkSj gYds isVªksfy;e ¼40%60½ dk mi;ksx djds ,lhVksu] 2&C;wVsuksu] gsDlsu&2 vkSj 3&vksu ds 2]4&MkbZukbVªksQsfuygkbMªktksu dks vyx djus dh rS;kjh

3)       lkbDyksgsDlsu vkSj ,fFky ,lhVsV dk mi;ksx djds jatdksa ds feJ.k dks vyx djuk ¼8-5%1-5½

8

IV

Thermochemistry

1)       To determine the solubility of benzoic acid at different temperatures and to determineΔH of the dissolution process

2)       To determine the enthalpy of neutralization of a weak acid/weak base versus strong base/strong acid and determine the enthalpy of ionization of the weak acid/weak base

3)       To determine the enthalpy of solution of solid calcium chloride and calculate the lattice energy of calcium chloride from its enthalpy data using Born-Haber cycle.

Å"ekjlk;u

1)       fofHkUu rkiekuksa ij csatksbd vEy dh ?kqyu'khyrk fu/kkZfjr djus vkSj fo?kVu çfØ;k dk ΔH fu/kkZfjr djukA

2)       nqcZy vEy@ nqcZy {kkj vkSj izcy {kkj@ izcy vEy ds mnklhuhdj.k dh ,UFkSYih dk fu/kkZj.k djuk vkSj nqcZy vEy@nqcZy {kkj ds vk;uu ,UFkSYih dk fu/kkZj.k djukA

3)       Bksl dSfY'k;e DyksjkbM ds foy;u dh ,UFkSYih fu/kkZfjr djuk vkSj cksuZ&gScj pØ dk mi;ksx djds blds ,UFkSYih MsVk ls dSfY'k;e DyksjkbM dh tkyd ÅtkZ dh x.kuk djukA

14