Classification of Amines Nomenclature: mt ‘Common name : Aliphatic amine is named Nha Se RN Sie Ral SE Rat by prefixing alkyl group to amine. In ‘where R= Alkyl group or aryl group ‘secondary and tertiary amines prefix di or trlisput before name of alkyl group. IUPAC name : Replacement of eof alkene by the word amine, Suffix ‘e’ of arene i replacedbyamine, eo Unshared electron pair Gees X ‘Trlangular Pyramidal shape of amines 422 © scanned with OKEN Scannervans | oer? ay a a) + SD — orm: acimectntait * R—NH}X? NaOH —+ RNH, + H,0 + ax RCN Ste RCN, + RCN HN ence ‘© Lower aliphatic amines are gases. Primary amines with three or more C atoms are. liquids andhigher onesare solids. « Arylamines ae colourless but gets coloured on storage due to atmospheric oxidation. ‘© Loweraliphaticaminesare soluble in water whilehigher onesare insoluble. ‘*Primaryand secondary amines form intermolecularassoclation of H-Bonding. ‘Bolling Points: rimary>Secondary>Tertiary © scanned with OKEN Scannerjm «= [ERAN CRACKER CHEMISTRY RTE (€BSE) = 2. Alkylation + ROH; + HK eet RONHX RNH: 2+ RNP RNB aN oon) wm) By ime NHS b--6 3. Acyation Cats Hit hc a ats —CHy+H#—0 Gis 8 ts N-Ethylethanamine NN-Diethylethanamide 4 Carbyfamine reaction: + Benzoylation : RN, + CHO, + 3KOH HES RNC + 3KCI+ CHsNH +CgHsCOCl_ = —+ CHsNHCOCGHs + HCL 30 fea ‘Methanamine Benzoyichloride _N-Methyibereamide sreing ‘6. Reaction with benzenesulphony| chloride (Hinsberg’s reagent) | Cyfempr— Of pre | [enemas us a + RONH, + HNO, MMOH [R-NYCT] Sy (1" amine) _N-Allytbenzenesulphonamide (soluble in KOH) ROH +N + HO + GH NH, MMOL, Canela nace Ofer — Of pe Par pce [ (2" amine) 1,N-Dialkybenzenesulphonamide (lnsolublein KOH) Of een mma ++ The reaction is used for the distinction of primary, secondary and tertiary amines and also for separation of mixture of amines, © scanned with OKEN Scanner Pe... —pecrtca a) 2%) (a) Alkanamines versus ammonia tn gaseous phase: Order of basic 3°>2°> 1°> NM, In aqueous phase: Order ofbaskity Spot" (Onthe basi of Inductive eect) 3°>293" (Onthe bai of Solvation Eft 315293" (Onthe basis of tere hindrance) Subtle interplay ofthese factors determines the basic strength of clan omnes in aqueous medivm. “SN UH > (69MM > Gg > (STP) on) me) (incase of ety substituted amines) {chy > Cy (CHM > NH SPT) Cat eC) {incase of meth! wbsttted amines) {b) Arylamine versus ammonia : Arylamines are less basic than ammonia due to Involvement of lone pair of electrons on nitrogen atom in resonance ‘s€- releasing groups Increase basic strength (~Cy, ~C, M4). 1 Electron withdrawing groups decrease basic strength (~NO,.—X). © scanned with OKEN Scanner426 ELAM CRACKER CHEMISTRY.I1 (CBSE) « Preparation of Bentenelatonhm chloride HC): ‘tis prepared by larotsation (the conversion of primary aromati arvines tt azo st Gpawpenanoye Ime LEW, cyyyyc + Mach + 24,0 Deveson ‘horse ‘+ Benzenediazonium chloride * Colourlesserystaline solid ‘© Benzenediazonum : + Readily soluble inwater SN Muorotorate: * Stableinice cold onty (273-278). ‘Insoluble in water. + Decomposes easilyin drystate. « Stableatroomtemperture, ‘Reacts with water when warmed, ‘Importance of Diaronlum salts: They are used In the synthesis of substituted aromatic compounds which cannot be prepared by direct substitution in benzene/substituted benzene. Na i © scanned with OKEN ScannerAns. (0) (ii) The structures and their IUPAC names of different isomeric amines corresponding to the ‘molecular form ula, C,H, N are tabulated below : AMINES | 429 Butan--amine Hy © enor bray Butan-2amine 2.Methylpropan.2-amine 1N-Methylropanamine N-Ethylethanamine = CHs i—NH—CH; ‘N-Methylpropane-2-amine (@) CH,—CH.—CH—CH,—NH, (©) CH,—CH,—CH,—NH—CH, CH,—CH,—NH—CH,—CH, Hy (i) CHy—CHy—N—CHy 3 Amine NN-Dimethyethnamine and vice-versa. (2° amine) (1° amine) [_ Metiod ofpreparation Reduction of nitro compounds 4, PREPARATION OF AMINES. Description Reagents that can reduce nitro compounds to amines are = ~ catalytic hydrogenation (HNi, Pt or Pd) ~metals in acidic medium (Fe/HCl, Sn/HCl) NO2 NH: ws NO} Ny i Reduction with Fe scraplH1Clis preferred because FeCl, Iydrochloric acid during the reaction, Therefore, om to initiate the reaction, ‘Ans, (9 Propan-2-amine(1° amine) (i), Propan-L-amine (1° amine) (id) N-Methylpropan-2-amine (2° amine) Rasta ()2-Methylpropan-2-amine(1° amine) () N-Methylbenzamine or N-methylaniline (if) The pairs (a) and (b) ; (e) and (g) exhibit position isomerism. The pairs (a) and (c); (a) and ( (B)and (a) exhibitchain isomerism. The pairs (e) and (fi, (and (g) exhibit metamerism. All primary amines exhibit functional isomerism with secondary and tertiary amines (b)and (c}, Q9. Write IUPAC namesof the following compounds and classify them into primary, secondary and tertiary 1° Amines amines. ( (CH),CHNH, @ CHYCH,NH, (ii) CH,NHCH(CH), —_(@») (CH,),CNH, () C,H,NHCH, (*) (CH,CH,,NCH, (i) m-BrCHNH, INCERT Chapter End Exercise] (09) N-Ethyl-N-methylethanamine(3° amine) (vi 3-Bromobenzenamine or 3-bromoaniline formed gets hydrolysed to release ‘small amount of HCL is required © scanned with OKEN ScannerDR 30 | cca coacrer cota ‘Ammonolysis of alty! halides ‘Hoffmann bromamide degradation reaction ASTANA (€88¢—)§ —$A A. “Ammonia reacts wth alkyl halides to form a mixture of three types of amines alongwith {quaternary ammonium salt. This reaction is known as ammonolyss. Ney -BXS RH: -BXs INH BSS RIN BMS RAN'X” ‘Ammonia I*Amie Amine Amine Quaternary | “The amines formed reacts with HX to form substituted ammonium salts and the free amine can be recovered from the ammonium salt by treatment with a strong base like NaOH << , Ly. a Nu, + RLX—> R-NHX Noelle Suet smmoniam st R-NHyxX™ + NiOH —? RNH, +H,0+ Std ‘Reagents that can reduce nitriles to amines are : ‘© catalytic hydrogenation (H,/Ni, Pt or Pd) © lithium aluminium hydride, LiAIH, © Nalig/C,H,0H R-CmN- i RCH, NH, HyNior RCaN hear’ BCH Nib Lithium aluminium hydride, LiAIH, also reduces amides to yield amines. 4H) R-C_NH, = R—CH,—NH, +2H,0 Amide “This method is used forthe preparation of pure aliphatic primary amines. Phthalimide is treated with alcoholic KOH to form potassium salt of phthalimide, which on heating with alkyl halide (R-X) followed by alkaline hydrolysis produces the corresponding primary amine. This reaction involves the S,,2 attack of the anion formed by phthalimide on R-X. Chapa Cp ote Phahalimide \N-Alkylphtalimide { Na" 4 RNH; yNa* (1* amine) Aromatic \° amines cannot be prepared by this method because ary! halides do not underge ‘nucleophilic substitution with the anion formed by phthalimide. ‘Amides on treating with bromine in an aqueous or ethanolic solution of NaOH or degradation reaction KOH yield primary amines with one carbon less than that present in the amide, This reaction is known as Hoffmann bromamide degradation reaction vi. IH, + Br, + 4N1OH——* R—-NH, + NayCO3 + 2NaBr + 2H;0 © scanned with OKEN ScannerAMINES | 435 5, PHYSICAL PROPERTIES Physical State ‘Solubility i CHEMICAL REACTIONS The lower aliphatic amines are gases with fishy odour. 1° amines with three or more carbon atoms are liquid and higher ones are solid. Arylamines are usually colourless but get coloured on storage due to atmospheric oxidation. Lower aliphatic amines are soluble in water because they ean form hydrogen bonds with water molecules. This solubility decreases with increase in size of the hydrophobic alkyl part. Higher amines are almost insoluble in water. The solubility of amines is lesser than that of alcohols of comparable molecular mass because alcohols are more polar than amines and form stronger hydrogen bonds. ‘The order of boiling points of isomeric amines is as follows : 1° Amines> 2° amines> 3° amines ‘The highest boiling point of 1° Amines is because of the maximum extent of hydrogen bonding in them. In 1° Amines, two hydrogens are linked to nitrogen atom whereas in 2° Amines only ‘one hydrogen is linked to nitrogen. 3° Amines do not have intermolecular hydrogen bonding as no hydrogen is atached to the nitrogen atom. Basic character T" “Amines are basic in nature and react with acids to form salts. ant Re RNH, +HX== RWH,X” ‘Nucleophile Substituted scmonium sat ‘The parent amine can be regenerated from these substituted ammonium salts by treating them with a strong base NaOH. RNH3X” + NaOH —> R—NH; + NaX +H,0 Order of basic character of amines in gaseous phase is as : 3° amines > 2° amines > 1° amines > NH, (According to + Ieffect) However, in aqueous phase, there is subtle interplay of Inductive effect, steric effect and solvation effect. As a result, following order of basic character of amines are observed : (CHyCH,),NH > (CHyCHy)N > CHCHyNH; > NHy 2 amine amine Vamine ammonia 6 © ® (CHy),NH > CHyNH; > (CHyN > NH amine Waning amine ammonia ” ® o ‘Arylamines are less basic than ammonia because the lone pair of electrons on N-atom of aryl ‘amines is involved in resonance and is less available for protonation, © scanned with OKEN Scanner456 EXAM CRACKER CHEMISTEY.AT1 (CBSE) + Amines react with alky! halides ane undergo alkylation as shown ‘Alkvintion RNH, Xs R,NH 1 Amine 2° Amine | Resction with nitrous ‘cid, HNO,(NaNO/HC) ‘Amines react with any acyl chloride in presence of base like pytidine or acid anhydride ang undergo acylation. For example, OHHH ele tess t-te + HAC y H dasamine (amine) N-Etyletanamide GHs—-N-n son ea twee, cag oy +H-Cl Hs GHs - . N-Ethylethanamie (2° amine) N,N-Diethylethanamide tH + CH;—C—O—C—CH; —> Cloth +CH;COOH H H Benzenamine Ethanoie anhydride N-Phenyletnamide ‘or Acetanilide The introduction of -COCH, group is known as acetylation whereas the introduction of -COC;H, group is known as benzoylation. For example, i & GHs—N-H+ ai ta Ervine, cathy +H—Cl h H Fthanamine Benzoyl ehloride Ne-EthyIbenzamide (1 amine) ‘All aliphatic and aromatic primary amines react with chloroform (CHCl, on beating in presence of ethanolic KOH to form foul smelling isocyanides or carbylamines R—NHy + CHCh + 3KOH—A—» R—NC + 3KCI+3thO 1 amine out smelting cyanle 1° aliphatic amines react with nitrous acid (1NO,) to form unstable diazonium salts as interes diate, which on hydrolysis from alcohols RN + HNO, MNOMEY (R_NECL)ILO ROH + Ny + HCL Unsble © scanned with OKEN ScannerReaction with arylsulphonyl chloride aromatic amines react with nitrous acid (IINO,) in ice cold conditions (273-278 Ky to form iazonium salts, Ni mcr Navoytic, Q + NaCl +2H)0 Auli vee Aromatic diazonium salts are stable due to resonance. Benzenesulphonyl chloride (C,H,SO,CI) is known as Hinsberg’s reagent. This reagent is ‘used to make distinction between three types of amines. For making distinction, the amine is shaken with benzenesulphonyl chloride (Hinsberg's reagent) in presence of excess of aqueous alkaline solution. (@) Primary amines give N-alkylbenzenesulphonamide, Form O-f ane \N-Alky| benzenesulphonamide {soluble in alkali) soluble in alkali. (@) Secondary amines give N, N-dialkylbenzenesulphonamide which is insoluble in alkali. Ofeves,— O-be eaeeeeeeys (insoluble in alkali) (©) Tertiary amines do not react with benzenesulphonyl chloride. Ote + BP ‘These days benzenesulphonyl chloride has been replaced by p-toluene sulphonyl chloride. Bectrophitic substitution + NH, group on benzene ring is ortho and para directing and is a This is because of +R effect. NH Ni NH NH, —o—h— 6 sto the powerful activating group. Ortho- and para-posi NIL, group become centres of high electron density due to +Reffect. AMINES | 437 eee © scanned with OKEN Scanner438 ERAN CRACKER CHEMISTRY-IHT (CBSE) (@) Bromination “Aniline reacts with bromine water (B/11,0) at room temperature to form a white precipitate of 2.4, 6-tibromoaniline nn, NH, onto, lad + 3Br, > +3HBe rite ir 2,4, 6-Tribromosniline + To prepare monosubstituted aniline derivatives, the activating effect of -NH, group is controlled by acetylation before carrying out the desired substitution. For example, aniline | «can be converted into p-bromoaniline as follows : | ryt sa Ba 8 Asitine N-Phenyletanamide (Acetnilide) © Nitration + Direct nitration of aniline is never carried out because it forms tarry oxidation products, along with nitro derivatives in which significant amount of meta derivative is also formed. This is because inthe strongly acidic medium, aniline is protonated to form the anilinium ion which is a meta directing group. b NH, iH NO; a> + + NO, 1%) «nm em e can be converted into:p-nitroaniline as follows : E NH, ICOCH, NHCOCH, (CH,C0),0. NO, ome. CaO) ae rae Axilne (Acetanilide) NO, p-Nitoacetanitie pi (©)Sulphonation |+ Aniline being basic, reacts with concentrated sulphuric acid to form om anlian ‘on further heating with sulphuric acid at 453-473 K produces sulphanilic acid (p-aminobenzene sulphonic acid) that exists as Zwitter ion, iin, Ru,us0, NH, 1,804 a. Oa a - Asie Anilisim SOyH hydrogensulphate Sulpanlic cid _ © scanned with OKEN ScannerII. DIAZONIUM SALTS The diazonium salts are generally represented by the formula At-N3X”, where Aris any aryl group and X~ is an anion| like Cl, Br, HSO4 or BF, . Examples of Diazonium salts : nycr N}BFy Benzenediazonium —_ Benzenediazonium chloride fluoroborate © scanned with OKEN Scanner450 | EAM CRACKER CHEMISTRY-XIL (CBSE) ——— 7. METHOD OF PREPARATION OF DIAZONIUM SALTS ‘Benzene diazonium chloride can be prepared by treating aniline with NaNO /HCI (nitrous acid, HINO, in ice cold conditions ARIK. Njcr NaNO, Bre 8 ncrme ke & PHYSICAL PROPERTIES ‘The important physical properties of Benzenediazonium chloride and Benzenediazonium fluoroborate are as follows : + Itis.a colourless crystalline solid. + Ttis insoluble in water. + Itis readily soluble in water, + It is stable at room temperature. + This stable only at low temperature (273K-278 K). + It easily decomposes in dry state. + Rereacts with water on warming. The conversion of -N,CI group into different groups like ~Cl, -Br and ~CN groups using Brand -CN groups | Cu(Y)saltsis called Sandmeyer reaction. ene evn wer C5 Lae. Sone Loomer, oe fcopper powder is used instead of Cu(/) salts, the reaction is called Gattermann reaction. igor san, J enroe 0 com L m2 Sona Yield obtained from Sandmeyer reaction is better than Gattermann reaction. © scanned with OKEN ScannerReplacement by -1, -Fand-OH groups =N,Cl group is converted into -1, -F and ~OH groups a follows Njcr O- Replacement by-NO, | -N,Cl group is converted into -NO, groups as follows : | ad Nier NBR NO, +HBF, ——>| Sad +N) +NaBF, y nese " Replacement by-H/ —_ | -N, Cl group can be removed from benzene ring as follows : removal of-N,Cl group : Nycr + CH,CH,OH yaaa? Co + Nyt HCl+ CHyCHO Benzene Nycr -iyrastno—o (Jensen Benzene Coupling reaction ‘Benzene diazonium chloride reacts wit phenol in alkaline medium to form an orange coloured dye, p-hydroxyazobenzene. Similarly, with aniline, a yellow coloured dye, paminoazcbenzene is formed. ‘These reactions are referred as coupling reaction, (prwrenersi-{ on.) -wan-{)-ont+ cr +0 p-Ulydroxyarobcazene (orange dye) (wena HC )-n tC )-vanK a +r +H,0. ‘PrAminoazobeazene (gellow dye) © scanned with OKEN Scanner |(ORR sz ex crate CHEMISTRN SR (BSE) 10, IMPORTANCE OF DIAZONIUM SALTS IN SYNTHESIS OF AROMATIC COMPOUNDS ‘The diazonium salts are very good intermediates for the preparation of many organic compounds. For example, + Aryl fluorides and iodides cannot be prepared by ditect halogenation but these can be prepared through the formation of diazonium salts as intermediate. ceasily obtained from diazonium salt, + The cyano group cannot be introduced by nucleophilic substitution of halogen in haloarene but benzonitrile can be g SSSA Co” NO cancnon (CBSE. All India 2018] NCI “OM oma oe Benzene Q.76. Give the structure of ‘A”in the following reaction, a +HCL273-278K, . GHGPOs, HO [Exemplar NCERT] Ans. Nno, Q.77. Why is benzenediazonium chloride not stored and is used immediately after its preparation ? [Exemplar NCERT] ‘Ans. Benzenediazonium chloride is not stable at room temperature, therefore, it is not stored and is used immediately after its preparation Q.78. Under what reaction conditions (acidic/basie), the coupling reaction of aryldiazonium chloride with aniline |s carried out ? [Exemplar NCERT] ‘Ans. Coupling reaction of aryldiazonium chloride with aniline is carried out in mild acidic condition (p11 4-5), Fy £ g > re r By ce} rS oe s o a 2 e tr) Q.79. Complete the following reaction, Acker, Ow Q.80. Give the structures of A, B and C in the following reaction : [Exemplar NCERT] Ces, C12 5 a HOM", p_ NILA [CBSE Sample Paper 2016] ‘Ans. A=C,H,CN ; B=C,H,COOH ; C=C,H,CONH, Q81. Writea chemical test to distinguish between aniline and methylamine. [CBSE Sample Paper 2017] ‘Ans. These can be distinguished by azo dye test. Aniline being an aromatic primary halide, when reacts with HNO, (273-278 K) to form diazonium salt which on treatment with alkaline solution of phenol gives an organe coloured azo dye while methylamine does not give this test. NaNoyict x Cee > ‘Ne=NCr ‘ailing OmO-n pellydroxyavobenzene orange dye) © scanned with OKEN Scannervi ‘* Monosaccharides: Simplest units of polyhydroxy aldehydes and ketones that cannot be hydrolysed further. Aldoses (Containing Aldehyde group) —__—_ Biomolecules Carbohydrates are optically active polyhydroxy ‘aldehydes or Ketones or compounds which produce such units on hydrolysis. Due to sweet taste they are also called saccharides. ‘¢ Oligosaccharides : On hydrolysis, \ ( » Polysaccharides : On hydrolysis, these yield two to ten units of }| these yield a large number of monosaccharides. ‘monosaccharide units. © scanned with OKEN Scannersroxouecuus | «71 Preparation {a)From sucrose (cane sugar: C_aHi20ys +0 = CeM204 + CyHs205 (Sucrose) nee (Fractose) {(b)Fromstarch or cellulose :(CqMyoOs)n# nH: pyr aem™ noe (starch or cellulose) ‘CHy—CHy—CH,—CH,—CH,—CHy [Six C-atoms of glucose) n-Hexane ‘are in straight chain) 0H Fest, oo [tucose contains Crmohyein | carbonyl group] Gi=n—on (Hom, H,0H (oxime) “00H (GHOH), [Carbony| group HoH ——_—Presentin glucose ug acid {s aldetnyde.) ny ooH (EHOW, —[Gtucose contains primary alcholic coon Saccharicacd —6"UP Hale (Glucose contains five-OM groups} Hy Glucose pentacetate © scanned with OKEN Scanner472 | GRAM CRACKER CHEMISTRY.KH (CASE) + Cytlestructure Glucose: g pt): ose 12241) Genpyanon 8.0.4)-Georrna%e, -shcgtrin eens dion HOM’ on HH EPO Fretuanene pes )-frectturanoss Haworth retures {) Disaccharides : Two monosaccharides are joined by glycosidic linkage. © Sucrose : Non reducting sugar, dextrorotatory, is hydrolysis is. called inversion of cane sugarandproductiscalled invert sugar. ‘ Maltose:Reducing sugar. + Lactose:Commonly called miksugar.itis2reducing sugar. (1) Polysaccharides: Large number of monosaccharide units are |" pinedbyehcoticnages, © Starch : Polymer of a-glucose with two components amylose {water soluble) and amylopectin (water insoluble). ‘Cellulose : Consists of f-O-glucose units joined by glycosidic | inkages. '* Glylogen : ts a storage saccharide in animal body (animal starch). + Importance :» Maltose: Major dletry source. «Storage moleculesasstarchinplants&gycogen nanimals. Raw material for industries ike textiles, pape, lacquers an breweries. © Scanned with OKEN ScannerBromovecutes | «73 SNA ‘Amino acids © Amino acids contain —NH2 and —COOH groups, Except glycine,allather naturally occurring -amino acidsare optically active. # On the basts of relative number of ‘© Onthe basis ofplaceof synthesis: —NH,and—COOH group, (i Essential amino acids : Cannot be { Neutral : Equal number of —NH, and synthesizedinthe body. COOH groups. , Examples: Valine, Leucine. ~ (il) Basle : More number of —NH groups (i) Non-essential amino acids : Can be than—COOH groups. synthesized inthe boo. (til) Acidic : More number of —COoH Examples: Giycine and Alanine. groups than —NH groups. (770 proteins, amino acids are linked with peptidelinkage Ho1-E—irfon-coom * Onthebasisofshape: gas (i) Fibrous proteins : Fibre like structure, Peptide linkage | insoluble in water. Example :Keratin and myosin. (i) Globular proteins Spherical structure, ‘water soluble. Examples : Insulin and Structure : Primary (square of amino albumin acids), secondary (shape of long. = polypeptide chain), tertiary (overall folding of polypeptide chain) and quaternary (special arrangement of sub Denaturation of Proteins: units.) «The loss of biological activity of proteins, when a protein n ts native form, is subjected to physical change like change In temperature or chemical ‘change like change in pH is called denaturation of Proteins. ‘© During denaturation of proteins, 2° and 3* structures get destroyed but 1° structure Ita © scanned with OKEN Scanner4474) EXAM CRACKER CHEMISTS (BS) Organic compounds required in det in small amounts to perform specie biological functions {or growth and maintenance, *Clasincation {WFatsoluble : Soluble in fats and ols but insoluble in water. Vitamins A, O,€ and Kare examples, (i) Water-soluble: 8 group vitamins and vitamin Care soluble in water, + Cannotbe storedin body (excep Vitamine 8} andare excretedthroughurine. + Needs toberegulartysuppledin diet. Importance: Different vitaminsare supplied by various oodresources. + Excess aswellasdefcieneyofvitaminsisharmful * Deficiency of vitamins ead todlfferent diseases. i : ‘Composition: in ON sugar These ae long chen polymers of | etl Ona ucleotides which are joined by niacin feo-rese : tongs ane sinenliee gi] tases in DNA are Adenine (A), zoe nf spentosesngar: Thymine (T), Guanine (6) and £ + Two types: Deorybonucleic acd ° ytosine(c) {ONY Ribonucleic acd (ANA) Bases in RNA are Adenine (A), Guanine (G); Cytosine (C) and Uraci(U). ‘+ Nucleoside : Formed by attachment of a baseto1'of sugar. I + Nucleotide: Formed by linking phosphoric acid at5‘of sugar presentina nucleoside, ‘© DNA: Double helical structures in which ‘and are linked by two and G and C by threehydrogen bonds. + RNAs Single stranded a-helixstructue, tis of three types:m-RNA,P-RNA, CRNA, Biological Functions: ‘* DNAIsthechemicalbasisofheredity ‘+ RNAis responsible for protein synthesis in the cell, Bes s © scanned with OKEN ScannerSynopsis | 1, CARBOHYDRATES wowocecuues | «7s SI ‘© Most of the carbohydrates have a general formula, C,(H,0),, Thus, these were considered as hydrates of carbon. © The carbohydrates are defined as optically active polyhydroxy aldehydes or ketones or the compounds that produce such units on hydrolysis. 1.1 Classification of Carbohydrates ‘On the basis of their behaviour on hydrolysis, carbohydrates are classified as : © Monosaccharides : Acarbohydrate that cannot be hydrolysed further to give simpler unit of polyhydroxy aldehyde or ketone is called a monosaccharide. For example, glucose and fructose. © Oligosaccharides : Carbohydrates that yield two to ten monosaccharide units, on hydrolysis, are called oligosaccharides. These are further classified as disaccharides, trisaccharides ete. For example, sucrose, maltose and lactose are disaccharides. polysaccharides. For example, starch, cellulose and glycogen. 1.2 Monosaccharides Polysaccharides : Carbohydrates that yield a large number of monosaccharide units on hydrolysis are called Monosaccharides are further classified on the basis of number of cafbon atoms and the functional group present in them. Aldehyde Aldotriose Aldotetrose ‘Aldopentose 1.3 Preparation of Glucose From sucrose (Cane sugar): (Gucross) Fromstarch or cellulose: (Commercial method) (Starch or celsise) 1.4 Structure of Glucose Giucose (also known as dextrose) is an aldohexose Ithas molecular formula C,H,,O, and was assigned the open chain structure based on various evidences. ‘After studying many other properties, the exact spatial arrangement of different -OH. CiHa.01,+ H0 "+ Cyt,204+ Cy (Giacue CeliaOs)y_ +180 rsa NCH, aa) HHO 4— Ore aldehyde group byoin¢— ee Tare toth oma pee © scanned with OKEN ScannerBREE 76 exam concen coemste cn (688¢) $$ i a i cHO eich HT (ten) I (Hom, M4 cH, — ct, — CH, — CH — CH, — CH; This reaction suggests that all the six carbon atoms are linked in a straight chain, Reaction with i Tone —OH (ro1, aa, Horn, CH;OH CH,OH Odee Se CN ‘These reactions confirm Reaction win #CN | CHO en the presence of a ca carbonyl group in Grom, > (cut, y CH.OH cH,OH cycle Reaction with Br, CHO ‘COOH This indicates thatthe jester I Beene, | carbonyl group is (Hor, > (Cot, present as an aldeby- di . CH,OH CH,OH ic group. Cheatin I ton, in cH01, a (ios. — (cHot, HOH coon CH,OH Giocne Saccarie cit (consid s0ups in glucose was given by Fischer, “Correct Configuration CHO ufo OH+H HOW HOW CHO DA rglecure Glyceraldehyde, \Reaction with acetic | CHO CHO ° This confirms the |entordrides(CH,00),0 «ci, pete rintstes by g— é Ch oe a CH, a Score pence [Reaction with HNO, | ca 1H COOH This indicates the Significance of name presence of a primary alcoholic (-OH) ‘group in glucose. “(4Y' represents dextrorotatory nature of the molecule whereas ‘D' before the name of glucose represents that the —OH group on the last asymmetric carbon is on the fight side ie., its configuration resembles (+) © scanned with OKEN ScannerHionotecutes | 477 SE U DG Glucore 1.5 Cyclic Structure of Glucose + The open chain structure of glucose could not explain the following reaction and facts: (9 Glucose does not give 2, 4 ~-DNP test, Schiff's test and sodium hydrogensulphite test. (ti) The pentaacetate of glucose does not react with NH,OH indicating absence of free —CHO group. (iii) Glucose exists in two different crystalline forms, which are named as a-glucose and -glucose, ‘Tewas found that glucose forms a ‘six-membered ring in which —OH at C-5 is involved in| ‘ring formation. This explains the absence of free —CHO group and also the existence of glucose in two forms as shown below : u—c-Fon) no—é— H2-OH 0 H+ On H2-0H 0. HOH = Ho-H ) == Holy He-H H4-OH, H4-H H Hy H ‘CH,oH ‘con ‘CH,OH e-D4+}uleoe PD-+}-Guleose «The stereoisomers ofa monosaccharide which differ onl inthe orientation ofthe -OH group at anomeric carbon e.C,) are called anomers. e.g., a~ glucose and B- glucose ure the anomers of glucose, where a-glucose contains ~ OH on right side of C, and f-glucose contains -OH on the left side ofthe Cy. ‘@ The cyclic structure of glucose is more correctly represented by its Haworth structure : ‘ ‘ CH,OH CH,OH H, H H on 4 G 4 e HONE Won Ho H H OH H OH os 22-)-Gneommneee __BDv}Oheonynnone, ‘©. The six membered cyclic structure of glucose is analogous to pyra hence it is also called pyranose structure O Pyran © scanned with OKEN ScannerI «re | exam ceaceer cuemister.an (cast) 1.6 Structure of Fructose Haworth structure Hon, 10H HOHE HH Wy oon orffcr,01 OH OH a-D-{-}-Fructofuranose ‘#-D-4-)-Fructofuranose Tes eft en ing sag [compe Ta ed - faranose structure. Fern 1.7 Disaccharides In disaccharides, two monosaccharide units are joined together by an oxide linkage formed by loss of water molecule. Such «linkage between two monosaccharide units through oxygen atom is called glycosidic linkage. Nature Structure (reducing or non-reducing) yo] non-reducing HOW PD-Gatactove © scanned with OKEN ScannerHiowoecuLes | 479 1.8 Polysaccharides: Cellulose Starch Starch is the main. storage polysaccharide of plants. 2 Itisa polymer of a-glucose. 3. Ithas two components ie. amylose and amylopectin. Cellulose is a predominant constituent of cell wall of plant cells. 2. Itisa straight chain polysaccharide composed only of B-D-glucose Itis a storage saccharide in animal body. 2. Itis also ‘known as animal starch because its structure is similar to 4. Amylose is water soluble component units which are joined by glycosidic | amylopectin and is rather mote ‘which constitutes about 15-20% of | linkage between C, of one glucose | highly branched. sarch Chemically amyloseisalong | unitand C, ofthe next glucose unit. unbranched chain with a-D-(+)- glucose units held together by C—C, glycosidic linkages. 5. Amylopectin is insoluble in water. It constitutes about 80-85% of starch Itisa branched chain polymer of a-D-glucose units in which chain isfomedbyC,-C, ghvosidic linkage and branching occurs by C.-C, elycosidic linkage. It is present in liver, muscles and brain, When the body needs Blucose, the glycogen is converted into glucose by the enzymes present in the body. Glycogen is also found in yeast and fungi. CH,OH 7 recta 1.9 Importance of Carbohydrates 1. Carbohydrates are essential for life in both plants and animals. 2 They are the major dietary source. 3. Carbohydrates are used as storage molecules as starch in plants and glycogen in animals, 4, They provide raw materials for many important industries like textiles, paper, lacquers and breweries. 5. Carbohydrates are found in biosystem in combination with many proteins and lipids. © scanned with OKEN ScannerGRRDUEEBENY 24 | xan cence coewistey-tu (casey (iti) Gtucose exists in two different crystalline forms, which are named as a-ghicose and -glucose. AA, Caution : Above reactions and facts can be explained on the basis of cyclic structure of glucose. Q446, How will you distinguish 1° and 2° hydroxyl groups Present in glucose ? Explain with reactions, (Exemplar NCERT] Ans, On oxidation with HNO,, glucose as well as gluconic acid, both give a dicarboxylic acid, saccharic acid. This indicates the presence of a primary alcoholic (— OH) ‘group in glucose. The other — (OH) groups are secondary. 0 HH 1H Oridation (GHOH), 7 dion a dio 0H 00H L0H Grove Seecharc aid Gconic aid (9.47. How doyou explain the presence of an aldehydic groupin aghacose molecule? [Exemplar NCERT] ‘Ans. Glucose reacts with hydroxylamine to form oxime and adds one molecule of hydrogen cyanide to give cyanohydrin. This confirms the presence of carbonyl ‘group which can be an aldehyde or a ketone. 0 HH 1H), NILOW, (CHOH), CH,OH ‘0H 0 on (HOH), EX, (CHOH), OH L0H Cyanobydrin ‘On mild oxidation with bromine water, glucose is ‘oxidised to gluconic acid. This indicates that carbonyl ‘group present in glucose is an aldehydic group. “HO cooH (CHOW), > (Gorn, CH,OH Chon coment 0.48, How do you explain the absence of aldehyde group In the pentaacetate of D-glucose 7 INCERT Intext Question Glucose pentaacetate cannot be converted into the ‘open chain form because its anomeric -OH group is, acetylated and hence does not form the oxime. This, confirms the absence of aldehyde group in the pentaacetate of D-glucose. Ans. ‘CHOcOCH, H-}—OCOCH; CH,CO0. qc H-4}—OCOCH; 9 np ‘CH,OCOCH, Giacospetacete Q.49, Whatis the basic structural difference between starch and cellulose? INCERT Chapter End Exercise, CBSE 2023] Starch consists of two components - amylose and amylopectin. Amylose is a long linear chain of a-D-glucose units joined by C,-C, glycosidic linkage (ac-link). Amylopectin is a branched-chain polymer of a-D-glucose units, in which the chain is formed by C,-C, glycosidic linkage and the branching occurs by C,~C, glycosidic linkage On the other hand, cellulose is a straight-chain polysaccharide of B - D - glucose units joined by C,-Cyglycosidic linkage (B — link). Give any one property of glucose that cannot be explained by the open chain structure. [CBSE AN! India 2019) Pentaacetate of glucose does not react with hydroxyl amine to form oxime. Compare amylose with amylopectin in terms of constituting structure, (CBSE All India 2019] ‘Ans. Refer to Ans. Q.14. Sarge? No oxime Ans. Q.50. Ans. Qs. 2. PROTEINS Proteins are the most abundant biomolecules of the living system, Chief sources of proteins are milk, cheese, pulses, peanuts, fish, meat, etc, 2.1 Amino Acids ‘© Amino acids contain amino (-NH,) and carboxyl (~COOH) functional groups, ‘© Depending on the relative position of amino group with respect to carboxyl group, the amino acids can be classified as @, B, 7, and s0.0n. © scanned with OKEN Scannerstearton R—CI=COOH oxo ‘Amino gp —> NI camino eld ‘9 Except glycine, all other naturally occurring a- amino acids are optically active because the a-carbon atom is asymmetric in nature. ‘9 Most naturally occurring amino acids have L-configuratfon, L-Aminoackds are represented by writing the -NH, group ‘on left hand side, + Inaqueous solution, the carboxyl group can lose a proton and amino group can accept a proton, giving rise toa dipolar ion known as zwitter ion. This is neutral but contains both positive and negative charges. rato ties rato 2NH, “NH, 7 (2witer oo) 49 The pH st which amino acid exists completely as zwitter ion is known as isoelectric point. Each amino acid has a characteristic isoelectric point, 2.2 Classification of Amino Acids @ Depending upon the: relative number of amino and carboxyl groups : ‘Neutral Basic | ‘Acidic Number ofamino and carboxyl groups] Number of amino groups is more than | More earboxyl groups as compared to is equal. the number of carboxyl groups amino groups. 9 Asessential and non-essential amino acids : Non-essential amino acids Essential amino acids The amino acids that ean be synthesized inthe body are known|| Those amino acids that cannot be synthesized in the body as non-essential amino acids. For example, Glycine and| and must be obtained through diet are known as essential Alanine. amino acids, For example, Valine and Leucine. 2.3 Structure of Proteins 9 Proteins are the polymers of a-amino acids joined together by peptide linkage. 9 A polypeptide with more than bundred amino acid residues having molecular mass higher than 10,000 wu is called a prot 9 Peptide linkage is an amide linkage formed by condensation reaction between —COOH group of one amino acid and —NH, group of the other amino acid. H.N—CH_CooH + alt hes —H,.N. R ‘9 A product formed by the condensation of two amino acids is known as dipeptide, For example, when carboxyl group of ‘glycine combines with the amino group of alanine we get a dipeptide, glycylalanine, H,N—CH,—COOH + H.N- Toon Nii (SOS F-c0oe yeas Hy Peptide linkage n Alanine ‘Glyeylatanin (Gly-AL) © scanned with OKEN Scanner* Terefers to sequence ‘of amino acid in each polypeptide chain, Structure of Protelns Tertiary Structure © Terepresents the overall folding of the polypeptide chain i. further folding of 2° structure. @) Fibrous i) Globular 2.4 Denaturation of Proteins ‘© A protein found in a biological system with a unique three-dimensional structure and biological activity is called asa native protein. © When protein in its native form, is subjected to physical change like change in temperature or chemical change like ‘unfold and helix get uncoiled and protein loses, change in pH, the hydrogen bonds are disturbed due to which globules its biological activity. This is called denaturation of protein. RRR ne | xan ceancnee coremastnr.a (e880) —$ $a é i i mma ‘© On the basis of their molecular shape, proteins can be classified into two types 1. Fibrous and globular proteins, © Structure and shape of proteins is studied at four different levels, Ke. primary, secondary, tertiary and quaternary Becondary Structure © It refers to shape in which polypeptide chain exist, (i) achelix, Gi) B-pleated ‘Quaternary Structure « Itrefers to spatial ‘arrangement of subunits with respect to each other. © During denaturation, 2° and 3° structures are destroyed but 1° structure remains intact. © The coagulation of egg white on boiling and curdling of milk are common examples of denaturation. 3. ENZYMES @ Enzymes are the proteins that act like biological catalysts and catalyse most of the biochemical reactions. For example, invertase, zymase, urease etc. ‘© Enzymes are very specific fora particular reaction and for a particular substrate. 3.1 Mechanism of Enzyme Action ‘The enzyme-catalysed reactions proceed in two steps. ‘Step 1 : Binding of enzyme to substrate to form an activated complex. E+S—Es* ‘Step 2 : Decomposition ofthe activated complex to form product. ES*—>E+P @ EIT Q52. Name a protein that s insoluble In water, ‘Ans. Keratin ‘What type of linkage is responsible for the formation Or Q53, Write the name of linkage Joining two amino acids. of protein? ICDSE AU India 2013} | pus, Peptide linkage © scanned with OKEN Scanneri MR cme xen concert cormster an cease) — eS Ans. (0 Peptide inkage : Peptide linkage ie an ide Hnkage ; formed ty condensation reaction hetween COOH. Primary atructare of a protein is the sequence of Aero of one amino Reid and —NH, group of the other amino acids in etch polypeptide bain in protein, aio wei. . ‘The sequence in which amino acid are arrange, ferent in each protein. A change in the sequenc H:N—CH—COOH + H;N- ¢it-cool different in each pt < un Primary structure: creates a different protein. & & (if Denaturation: When a protein in its native form, is subjected t ‘eal change like change in temperature of 0 hysi : é rimieal change like change in pH, the hydrogen HaNegtt 2 -NH+ Ci COOH bonds are disturbed due to which globules unfold ~T and helix get uncoifed and protein loses its biological ‘ Peptide linkage a activity. This is called denaturation of protein. 4. VITAMINS, ‘© Vitamins are organic compounds required in the diet in small amounts to perform specific biological functions for ‘maintenance of optimum growth and health ofthe organism. ‘© Although vitamin deficiency causes specific diseases but excess of vitamins is also harmful. Thus, vitamin pills should not be taken without the advice of doctor. 4.1 Classification of Vitamins . Depending upon their solubility in water or fat, vitamins are classified into two groups. © Water soluble vitamins Fat soluble vitamins 1. These vitamins are soluble in fat and oils but insoluble | 1. These vitamins are soluble in water but insoluble in fa in water. and oils. 2 Vitamins A, D, E and K are fat-soluble vitamins. 2. Bgroup vitamins and vitamin C are water-soluble vitamins, Some Important Vitamins, their Sources and their deficiency disea: [_—Nemeorvitamin [source Defclency disease Vitamin A Carrots, Butter, Milk and Liver ‘Night blindness, Xerophthalmia (hardening of comes ofeye) Vitamin B, (thiamine) | Green vegetables, Cereals and Milk | Beri-beri |. Vitamin B, (Riboflavin) | Milk, Li Vitamin B,(Pyridoxine) | Yeast, Milk, Cabbage and Cereals | Convulsions Vitamin Byy Meat, Fish, Cheese and Curd Pemicious anaemia +, Egg and Almonds Digestive disorders and burning sensation of skin. Vitaonin D Exposure to Sunlight, Fish, Potatoes, | Rickets and Osteomalacia Kivi fruit 1. Vitamin C Citrus fruits, Amla and Green Leafy | Scurvy, (Ascorbic acid) Vegetables Vitaenin E Vegetable Oils like Wheat germ oil, } Muscular weakness Sunflower Oil and Meat Green leafy vegetables, Tomatoes, | Increased blood clotting time Green tea © scanned with OKEN Scanner