CLEA ENGINEERING | MEDICAL | FOUNDATION Aldehydes & Ketones Aldol condensation : Carbonyl compounds having acidic sp* a-H shows this reaction in presence of dil. NaOH or dil. acid. H on 2CHg -C =O CH bch, = CHO" 3 >CHsCH = CHCHO “Hy | H Crossed aldol condensation () CH,CHO + HCHO 28204, HOCH,-CH,-CHO ™°_ CH,=CH-CHO Ht /H,O A CH,CO-CH=CH, (ii) ~CH,COCH, + HCHO" _, CH. CO-CH,CH,OH Cannizzaro reaction : Carbonyl compounds not having sp*a-H shows following disproportion reaction ° Ih 2H-C-H + NaOH ——> CH3;-OH + HCOONa (50%) 2CgHsCHO + NaOH ——> CgHsCH,OH + CgHsCOONa (50%) Crossed Cannizzaro reaction : cHo{O)-cHoe HCHO +NaOH —+cHo-{O)-chon + HCOONa (50%) Formation of hydrzones and azines NHNH, Neo Sc-0 +NH.NH, —> NC HONG. NNH, 2 = N-N = fo a“ 7 Non 7 7 Perkin reaction : When benzaldehyde (or any other aromatic aldehyde) is heated with theCLEA ENGINEERING | MEDICAL | FOUNDATION anhydride of an aliphatic acid (containing two a-hydrogen atoms) in the presence of its sodium salt, condensation takes place to form a B-arylacrylic acid ; e.g., with acetic anhydride and sodium acetate, cinnamic acid is formed. C,H,CHO + (CH,CO),O —_cH:CO:Ne_, C,H,CH = CHCO,H Mechanism : CH,COOCOCH, + CH,CO,, ——* CH,COOCOGCH, + CH,CO;H 5 Il. | HY CAH + CH.COOCOCH, ——= C.HGECH.COOCOCH, =— H H OH ex¢cH.coococe, —H:2_, C,H,CH=CHCOOCOCH, —#° > H C,H_CH = CHCO,H + CH,CO,H Haloform reaction : Acetaldehyde and methylalkyl ketones react rapidly with halogen (Cl,, Br, or I,) in the presence of alkali to give haloform and acid salt. ° ° ll ll R-C-CH, —B2/ NAOH | _G_oNa+CHBr, (Bromoform) O° ll In this reaction - CH, of CH, -C — group is converted into haloform as it contains acidic hydrogen atom and rest-part of alkyl methyl ketone give acid salt having carbon atom corresponding to alkyl ketone. Preparation of haloform from methylketone involves two steps. (a) Halogenation 9 ° Il R-C-CH, 82 , p ft ~cBr, (Halogenation)CLEA ENGINEERING | MEDICAL | FOUNDATION (b) Alkalihydrolysis ° oO I NaOH I , | R-C-CBr, —N804 , CHBr,+ R-C-ONa (Alkalihydrolysis) oO ll Note : This reaction is used to distinguish the presence of CH, —C — group. Other reactions : NH, >> Hexamethylene tetramine (urotropine) Evaporated CH, = 0 Todrynes (1) _ (Formaldehyde) ~CH,OCH,OCH,O~ Paraformaldehyde Kept at room “™ —— tempt for a | | longtime ©. } are cH, Trioxane (metaformaldehyde) NH, NH, CH,-CH- 0H (Acetaldehyde ammonia) _H,80, ¢ CH, = CH= 0 — teu drops) Cyclic trimer (paraldehyde) cetaldehyde} LDVHC! _, Cyclic tetramer (Metaldehyde) NH, vot [> 0, 0-H, C0, (Diacetone amine) | (3) cH,-C=0 —f HS 5 resiyiene (Acetone) CH, oO cH, I I I LODIHC! oy Cech -G-cHed-on, (Phorone) ° I + CH. G=CH-C- cH, cH, (Mesityioxide)CLEAR EXAM ENGINEERING | MEDICAL | FOUNDATION ° il 2 0-C-cH, (CH,CO),O C,H,-CH=0. OHH oy by onc cn, SO asc, (Genzeldehyde) _n ~ HCOOH) ¢ s cil of bitter almond on o (i) CO,C1, CCL, (i) HO NH. (HON + HOI AICI, WHO oO (4) on-cH-n-on- | CO +HeI/AICl, CH Hycrobenzamide ° : I H1Pd-B680, gy Hh gy boling xylene CHNH, C,H. — CH = N-C,H, Sch base or ais cl p— + > ¢,H,-C-CH,-cl in absence of i catalyst i C,H, - C - CH, ———J Phenacylehlonde (Lacrymater) (5) “Acccohenone cH. cH, Jon cocivaic, — | Zn—Hg HCl ° (6) i CH,-C-CH, ‘Benzophenone} oncoojfac \ goons excess