EEA NNN \ oa, x Aldehydes, Ketones any . Carboxylic Acids | CHAPTER 4) wil help you prepare in CUET E [SEAN NOS. A ‘ALDEHYDES AND KETONES TUPAC Name Structural, Structures Physical Properties wemical Properties sag oo Physical state pe Preparation i Souiity Od6ur * Onidation of alcohols + Dehydrogenation + Nuclephiic addition reactions + Reactivity (Inductive and Stearic ees) * Hyrocarbon + Hyaton of ayes THN, RMX, NaHS, Acetl formation. + Dry distilation of calcium salts of fatty acids + Aion of Ay, NH,OH, + Ozonolysis of alkenes + Rosenmund reaction G tient, NH, —NH,, CcH,NHNH,, 2,4-DNP pace ac ota an DAL A) « Cleamensen Reduction, Woltt-Kishner Reduction, Reduction to alcohals are + Toluene wth C10, 5 oxidation with Tolns’,Fehling’s, Benedicts reagent in chlorination followed by hydrolysis iodotorm test + Aldo, Claisen, Gross aldol condensation 2 a S ee “= Cannizzaro’s Reaction + Aromatic electrophilic substitution : iu + Gyanides using CARBOXYLIC ‘ACIDS y 7 ¥ ¥ Y 7 IUPAC Name iu Preparation from Physical Properties Chemical Properties Uses of r : ae P carboxylic | Primary alcohols Physical state il Siu Ot aacaians aa anes) Mokena | CaN ae Crapenss 5 : : Mating point ' ‘Acetyl chloride Dimethyl cadmium Acctaldehyde (Esha) g 1,0. 1150, cue | AOE. ‘Acetaldehyde i cnt Acaleyae ‘ea CH,CHO Acetaldchyde (Ethanal) "than ° cu—l_en, (@-propanone) alia, | sti i co eo — St — cn,cnon cn Cn 35 c i, (ensh-ams. 2m Taso, HOH (Ethanal) (Acetylene) xO Caycuict i cocyene cut | oom yo a wir ~H-C=N on K,Cr,0, 1 eae. chien, go,is, CH=CH Propyne (@-propanone) HC CH, (OCH ,MeBe i oo, in C=N —Gyinonr?| Cy CH; | cysTo pentanone Cyclopsntanonoxime Sad cyemicraol, —_Cyetneninone H Zn Gu—cu, Hala | CoH, cast? SH.CH, {Dathi 2019, 161 |1-Phenyl ethanol Acetophenone Ethyl benzene Phenyl eteanooe, Icnse 2022(¢)) i H, docu, i (ocnsese Kc«0, CH, —CH, <——__} a + He one Hrsoccass CiH,COOH +CO, + H,0 A Beale acid 2henyl propanol j CH,—C=NOH nai) CH,CH, yout Nuit, KOM = ia ty be AcetopbeSeenine Aestphenone doen, cocn, pwoHt C,H,COONa + CHI, Be sm Bromeestoptenone Sodium benzoate Tofu y = Dein 20161 (yellow pri) Acetophenone274 egether week® Chemistry—12 a Natt ¢, E11 CH, —COOC,H, oe “oes chy i (Crem ay wo aeons. CI coon = Claisen condensati jensation ; » 7 I| om x oe ca davai 2 ont bs =i oo or te g Shyony- met pe ap cn —6—E crrcocsy, “ wt H—CH,—C—CH, eS ba, | | f l I AIcl, i sont A, Hal a ae Reactivity towards Nulephille addon restons (stents hndanc inercases, rect decreases) tatag HCHO > CH,CHO > C,H,CHO > CH,COCH, > C,H,COCH, > C,H,COC.H, Hyp 0? 5-6 —H Eleetrophilic substitution reactions will take place at m-position. There is positive charge on o- and p-positions, therefor, Hi¢z0 electron density is maximum at m-position. (CH,CH,CH,CH,OH > CH,CH,CH,CHO > C,H,OC;H, > CH,CH,CH,CH, is decreasing order of boiling point. + 2,2, 6-Trimethyl cyclohexanone does not form cyanchydrin in good yield due to stearic hindrance (crowding), ° + ntn—vn—davn, involved in reaction with C=O group to form semicarbazone. hhas double bond character, therefore, itis not second NH group is atached to —E In preparation of ammonia derivatives, pH should be carefully controlled. In strongly acidic medium, ammonia deti~ atives will get protonated. In strongly basic medium, OH” will be nucleophile and attack dc=o ‘group instead of ammonia derivatives. Uses of Aldehydes and Ketones. @ 40% aqueous solution of formaldehyde is called formalin which is used in preserving zoological specimens. (Gi) Urea formaldehyde resin and phenol formaldehyde resin (Bakelite) are thermosetting polymers. (ii) Acetaldehyde is used for manufacture of acetic acid, ethyl acetate, vinyl acetate, polymers and drugs.+ — Preparation and Properties of Carboxylic Acid Carboxylic acids Preparatio Knoy sO, : cu,cron SS) | eae om" c,cooc,tt, ae Ethanoic acid Ethyl ethanoate ° KMno,/ ° ° ° 1,80, cH SO cu—tion | — cu, —b_ot_cu, a iy r. ly — Ethanoie acid “a Acetic anhydride ° Ho culo "9 cHcoon | MXC. cy cH, +0, Ethanoyl chloride a Ethanoic acid - i i i so, CH,—C—NH, ——*} cu,—c—on |, cu,—C—cn, Ethanamide ‘hanoie acid conc. F350, “Aeetone 40 R Ke, i cl —F |S CH -C—OH_ | =. CH, —C—CH,—CH, te lhanoie eid HESOq(Goney CUS use: 2020 CHMgBr+€=0 for Blind . ! C: H CH, d ‘OH i ‘CH, ae cHcan +40 —" 4] cu—C_on |S —cu, ane ite hen ed coon Malone {a1 2016; Datni 20171 (Propane dik i)286 Fagecher eich? Chemistry —12 Physical Properties 1» form hydrogen bonds and exist as dimers. Carhoxylic Acids. 1. Carboxylic acids are polar in nature and cat ss ; 2. Lower members are soluble in water but higher members ate insoluble: Aromatic acids lke benzoic aig insoluble in water. Carboxylic acids are soluble in ether, alcohol and benzene »| 3. Carboxylic acids have higher boiling points than alcohols. They form dimers due to hydrogen bonding | 4. Their acidity decreases with increase in molecul 'S. Melting point of even ones are higher than odd ones i.e. hexanoi weight. ic acid has higher melting point than hepans Acidic character Electron releasing group will destabilise carboxylate ions, therefore, aide character decreases, Whereas eecton withdrawing a. stabilise earboxylate ions, therefore, acidic character increases. CF,COON > CC1,COOH > CHC,COOH > ON CH,COOH > NC - COOH » FCH,COOH > CICH,COOH > BICHCOOI > yee, > CICH,CH,COOH > C,H,COOH > C,4,CH,COOH > CH,COOH > CH,CH,COOH oct, coon coon on coon Benzoie acid NO; [cana hontaars noe aio beni ockd (hyo bene ald) loon pemeteny om ald Tepe (Benue ney ‘Chemical roperties f os i ba,—coon pe] cxcoon LP cn, o1+ pocy +101 COOH azmeia | Seo nen 2017 _ {cust 2020 or a ee scr,coon |“ _,3c,€_c1 + #,Po0, " eee Got ca ° i, H;—COOH «_5*—-——| CH,COOH soci, 2 COOH azresetor | GENCOOH | S08 a so, + HT (CH,CH,OH LAI (CH,COOH NA, heat Ena Ear oe aoe mle coon oa a | cicoon I H+ CH,COON: Bninicsed [40H | CHS—L—ON yoy dec — cH, —C—0 7 tates H,0 + CH,COONa 82" | cu,coon Sodium ethanoate thao acid cate sete [case 2051 NaHCO, C,H,OH CO, + H,0 + CH,COONa | _ccoon | 24" cH cooc,ti, + 1,0 CO, + H,O + 2CH,COON: dacs 2c! .+#,0+2cH,c00N8 | aen,coon |" ,cn,0, Ethanoie acid cH,co 70 * H:0 Ace ade roan OA, g_eyg eaamin, ug, (CH,CH,CH=CH—CcH,cn. ener, toc, 0m, ane CHy—CH=CH—cH,cN onan “uo (WVZ reaction) cxcH,coon oly mei fe © HC HC ‘CH,—CH,—CH=Cl—CH, CHy—CH—coon 2-Bromopropanoie acid Aldehydes, Ketones and Carboxylic Acids. 287 CHO 1At 2016) ae io Hy —CH=CH—CH,CHO [Dok Pre-Hoard 2023; Delhi 2016 Icnse, 2020) Hy 3 1, 4 a Ernie CMs ae =o Ge ye tense: 2023 COOH CH, cujcocr | [__kMaO. Benzoyl chloride * KOH, 4 bene id mime oan {cust 023) now a C,H,CONH, 90 cage pM Ce Benzamide = a Hon Phenyl Stier Brome benzene Si TE Si rem coon cu,cn, 2023-24 m0, cwu.conn, —™2:_ | a0 Bonime Boneole acid’ Ethyl benzene a tevst. 2023.24) CH,COX,, 4 K,Cr,0,/H,80, +n,0 —* J cuH,co 7° oo beusl cnie Ee ait Cost o35, ‘coon cuon " cai,coocn, + 1,0 —"—| Ney beneowe Soe coon ° i CHs HOE SO, (il) Decade288 Fagecher eee? Chemistry —12 Decarboxylation: Oss Beni [at 2017] = Benzamide & [Uttarakhand 2019}, ©OOCH, Methyl benzoate penvoie acid ‘cool 9 i C(t —C—C1 + Poca, 5 Tens cherie? HCL “00H ° so¢l, i + Gilly -E—C1 +80, +16) coon menitrobenzoie acid coon €,H,CON, ceca cave so+ 0 equcooxs 1,0 "| econ | Hi cacuot Uses of Carboxylic Acids. (@ Methanoic acid is used as reducing agent in rubber, Gi) Itis used in electroplating. (iif) Ethanoic acid is present (iv) Ethanoie acid is used as solvent. textile, dyeing and leather industry. in vinegar (5-10% acetic acid).