STD: 12*" CHEMISTRY SWERN OXIDATIO! In this method, dimethyl sulfoxide (DMSO) is used as the oxidising agent, which converts alcohols to ketones / aldehydes. In this method an alcohol is treated with DMSO and oxalyl chloride followed by the addition of triethylamine. oH ° oo ° i Won EWN i (CH,— CH—CH; + Ce so CH, + Cl-C—C—cl ——> CHy—C—CH; + (CHy),S + CO) + CO+2HCI Propan - 2-ol MSO Oxalylchloride propanone DOWS PROCESS: When Chlorobenzene is hydrolysed with 6-8% NaOH at 300 bar and 633K in a closed vessel, sodium phenoxide is formed which on treatment with dilute HCI gives phenol. i: Na oH 633K + NaOH = ———————> “men + NaCl 300 bar Chlorobenzene Sodium pftenoxide Phenol SCHOTTEN-BAUMANN REACTION: Phenol on treatment with acid chlorides gives esters. The acetylation and benzoylation of phenol are called Schotten-Baumann reaction. C,HOH + CH,COC] “> CH,-COOC,H, + HCI “el wciilrde phen ehnet CH,OH + C,H,COC] —S#> C,H,-COOC,H, + HCl phenl beoy chloe Peng enante Aniline reacts with benzoylchloride (CcHsCOCI) in the presence of NaOH to give N —phenyl benzamide. This reaction is known as Schotten — Baumann reaction. The acylation and benzoylation are nucleophilic substitutions. i I Pyridine CcHs—-NH + CH C- cl —=SEY cg, — NH C—CcHs + HCI Aniline Benzoylchloride N.- phenyl benzamide WILLIAMSON ETHER SYNTHESIS: An alkaline solution of phenol reacts with alkyl halide to form phenyl ethers. The alkyl halide undergoes nucleopilic substution by the phenoxde ion in the presence of alkali OH OCH, eon a + Nal ee Phenol Sodium Phenoxide _Anisole (methoxybenzene)KOLBE’S (OR) KOLBE’S SCHMIT REACTION: In this reaction, phenol is first converted into sodium phenoxide which is more reactive than phenol towards electrophilic substitution reaction with CO». Treatment of sodium phenoxide with CO2 at 400K, 4-7 bar pressure followed by acid hydrolysis gives salicylic acid. on oN 400K a aot Wao 160, — {00 | phenol sodium phenoxide sodium salicylate Salicylic ai RIEMER — TIEMANN REACTION: On treating phenol with CHCI;/NaOH, a ~CHO group is introduced at ortho position. This reaction proceeds through the formation of substituted benzal chloride intermediate. on na" on oO cucl, an" “Neon oa we er ew sage PHTHALEIN REACTION: On heating phenol with phthalic anhydride in presence of con.H»SOs, phenolphthalein is obtained. oH OQ J Con H,SO, 2 + aya Phenolphthalein é phthalic Phenol Enhydride ‘oH COUPLING REACTION: Phenol couples with benzene diazonium chloride in an alkaline solution to form p-hydroxy azobenzene (a red orange dye). C)-s+ () on 0 (Vg Ts-278K {po Baste — Phenol p-hydroxy azobenzene Benzene diazonium chloride reacts with electron rich aromatic compounds like phenol, aniline to form brightly coloured azo compounds. Coupling generally occurs at the para position. If para position is occupied then coupling occurs at the ortho position. Coupling tendency is enhanced if an electron donating group is present at the para — position to -Np“CI' group. This is an electrophilic substitution. = 3H (9-10) = — 1-{ on e. O- n-n-{)—on 273-278K _p-hydroxy azobenzene . ste (orange dye) —N =Ncl a H(4-5) = a : ee Oe a enzene AWA dizzonium 273-278K —__p- amino azobenzene chloride ulna) Ae (Yellow dye) ela PY 2- phenylazo - 4 cu,-€")—on ———> cu, + on 2zpheny! ae {_Z— OH “Methyl phenol p-cresol N=N-CeHFRIEDEL CRAFT’S REACTION: Anisole/Benzene undergoes Fridel Craft’s reaction in presence of anhydrous AICI; as a catalyst. Friedel Craft’s Alkylation oct, oct ae oH ca-o{ ct, ie os eo ean Friedel Craft’s Acylation OCH, cH, COCH, Hy. COCK, Anhyd. AIC, aa +CH,COCl —————_» y acetophenone — 4-methoxy Acetophenone (major) (minor) It is the best method for preparing alkyl aryl ketones or diary ketones. This reaction succeeds only with benzene and activated benzene derivatives. caren, (yA GOGH Caiy-C-Cl , AlCl, £O—CoHHs "OQ acetophenone I one acetylchloride benzene benzene ROSENMUND REDUCTION: Aldehydes can be prepared by the hydrogenation of acid chloride, in the presence of palladium supported by barium sulphate. This reaction is called Rosenmund reduction. oO benzoylchloride' W Il —C-cl+H, PUBS, cH,-C—H+HCI Acetyl chloride Acetaldehyde In this reaction, barium sulphate act as a catalytic poison to palladium catalyst, so that aldehyde cannot be further reduced to alcohol. Formaldehyde and ketones cannot be prepared by this method. STEPHEN'S REACTION: When alkylcyanides are reduced using SnCl/ HCl, imines are formed, which on hydrolysis gives corresponding aldehyde. CHC = N28 5 CH;- CH-NH —®°> CH- CHO + NH SELECTIVE REDUCTION ¢ OF CYANIDES: Diisobutyl aluminium hydride (DIBAL-H) selectively reduces the alkyl cyanides to form imines which on hydrolysis gives aldehydes. i) ALH(iso-butyD, — CH = CH—CH,—CH;- CN» CH; CH= CH— CH, — CH; CHO hex - 4- ennitrile ii) H,0 hex - 4- enal ETARD REACTION: Side chain oxidation of toluene and its derivatives by strong oxidising agents such as KMnOs gives benzoic acid. When chromylchloride is used as an oxidising agent, toluene gives benzaldehyde. This reaction is called Etard reaction. Acetic anhydride and CrOs can also be used for this reaction. CH(OCIOHCI); CHO cH, L cS: OL ‘ethylbenzene +CrO,Cl; ——> benzaldehydeOxidation of toluene by chromic oxide gives benzylidine diacetate which on hydrolysis gives benzaldehyde. GATTERMANN ~ KOCH REACTION: This reaction is a variant of Friedel — Crafts acylation reaction. In this method, reaction of carbon monoxide and HCl generate an intermediate which reacts like formyl chloride. CO, HCL (> ‘AIC CuCl (CLEMMENSEN REDUCTION: Aldehydes and Ketones when heated with zine amalgam and concentrated hydrochloric acid gives hydrocarbons, : + cH - H+ 4H) 20-8 oy cH, + H,0 | CH,—G— CH, * (4, %n-Hg. CH,CH,CH, + 1,0 oO HO ‘Con HCl — Propane joe Ethane WOLF KISHNER REDUCTION: Aldehydes and Ketones when heated with hydrazine (NH:NH2) and sodium ethoxide, hydrocarbons are formed Hydrazine acts as a reducing agent and sodium ethoxide as a catalyst. CH,-c-H+4(@) ‘NH, NH), CH,—CH,+ H,0 +N, | CHy-C-CH,+ 4() NN, CH,CH,CH, + H,0 +N, 4 GHONa Ethane I GHLONs Propane Acealdehyde Acetone Aldehyde (or) ketones is first converted to its hydrazone which on heating with strong base gives hydrocarbons. HALOFORM REACTION: Acetaldehyde and methyl ketones, containing -C(O)CHs group, when treated with halogen and alkali give the corresponding haloform. This is known as Haloform reaction. CH,-G-CH, 23, CCl-C-CH, wou, CHCI, + CH,-C-ONa oO Acetone — NOH 5 Sy ALDOL CONDENSATION: The carbon attached to carbonyl carbon is called a - carbon and the hydrogen atom attached to «@.- carbon is called a - hydrogen. In presence of dilute base NaOH, or KOH, two molecules of an aldehyde or ketone having a - hydrogen add together to give B- hydroxyl aldehyde (aldol) or B - hydroxyl ketone (ketol). The reaction is called aldol condensation reaction. The aldol or ketol readily loses water to give 4,8 — unsaturated compounds which are aldol condensation products. Acetaldchyde when warmed with dil NaOH gives B - hydroxyl butyraldehyde (acetaldol) H i ~¢ + H-CH)~ CHO MOH Chay CH CHO 6 OH Acetaldol Acetaldehyde (3 - Hydroxy butanal) Mechanism The mechanism of aldol condensation of acetaldehyde takes place in three steps. Step 1 : The carbanion is formed as the a - hydrogen atom is removed as a proton by the base. ° HO TH* CH, - CHO ——+> CH, -CHO+H,0 Page | 6Step 2 : The carbanion attacks the carbonyl carbon of another unionized aldehyde to form an alkoxide ion. H I~ CH, - C + @CH, - CHO ——+ CH, - CH- CH, - CHO b b, Step 3: The alkoxide ion formed is protonated by water to form aldol. CH - CH- CH - cHo AHO, cH, - CH-CHl,-CHO + OH- b bu 3-Hydroxy butanal The aldol rapidly undergoes dehydration on heating with acid to form a - B unsaturated aldehyde. CH, — CH-CH- CHO a CH;~ CH = CH- CHO + H,0 ae ‘ous aeend) CROSSED ALDOL CONDENSATION: Aldol condensation can also take place between two different aldehydes or ketones or between one aldehyde and one ketone such an aldol condensation is called crossed or mixed aldol condensation. This reaction is not very useful as the product is usually a mixture of all possible condensation products and cannot be separated easily. dil NaOH HCHO + CH,CHO ————»HO-CH,-CH,-CHO formaldehyde acetaldehyde 3-hydroxy propanal dil. NaOH HCHO + CH; -C-CH, S08 = Ho-cu,-cH,-c-CH, formaldehyde acetone 4-hydroxybutan-2-one CLAISEN — SCHMIDT CONDENSATION: Benzaldehye condenses with aliphatic aldehyde or methyl ketone in the presence of dil. alkali at room temperature to form unsaturated aldehyde or ketone. This type of reaction is called Claisen — Schmidt condensation. C,H, CH £0 + H]CH— CHO aiNoH, C,H, CH=CH—CHO +H,0 Benzaléehyde _Acetaldehyde Cinmamaldehyde cots cHfo + af —e-emy BOF Calls CH= CH-C— CH, + 11,0 é Benzaldehyde ° Benzylidene acetone mt ‘Acetone (Benzal acetone) CANNIZARO REACTION: In the presence of concentrated aqueous or alcoholic alkali, aldehydes which do not have a - hydrogen atom undergo self oxidation and reduction (disproportionation) to give a mixture of alcohol and a salt of carboxylic acid. This reaction is called Cannizaro reaction. Benzaldehyde ‘on treatment with concentrated NaOH (50%) gives benzyl alcohol and sodium benzoate. C,H,CHO + C,H,CHO 50%NsoH C,H,CH,OH , C,HsCOONa Benzaldehyde Benzylalcohol " Sodiumbenzoate This reaction is an example disproportionation reactionMechanism of Cannizaro reaction Cannizaro reaction involves three steps. Step 1 : Attack of OH’ on the carbonyl carbon. ° o- Il es ee on Step 2 : Hydride ion transfer oO ° i i. i ° Cols —G CH CQHg=C-H Pm Cals — E+ ColiCHO on OH Benzaldehyde Step 3 : Acid ~ base reaction. ° cgi,— bon + cgi, cuyo- P% ou b-8 “dy gH, CHO” Cy é + C,H,CH,OH benzoate Benylaleohol Cannizaro reaction is a characteristic of aldehyde having no a — hydrogen. CROSSED CANNIZARO REACTION: When Cannizaro reaction takes place between two different aldehydes (neither containing an a hydrogen atom), the reaction is called as crossed cannizaro reaction. CéH;CHO + HCHO NaOH, CsHsCH,OH + HCOONa Benzaldehyde Formaldehyde Benzyl alcohol sodium formate In crossed cannizaro reaction more reactive aldehyde is oxidized and less reactive aldehyde is reduced. BENZOIN CONDENSATION: The Benzoin condensation involves the treatment of an aromatic aldehyde with aqueous alcoholic KCN. The products are a hydroxy ketone. Benzaldehyde reacts with alcoholic KCN to form benzoin. i Hane + HOGG “ CsH, —CH—C—C,H, ° ° OH O Benzaldehyde Benzoin 2-hydrory = 1,2 = iphenylethanone PERKINS’ REACTION: When an aromatic aldehyde is heated with an aliphatic acid anhydride in the presence of the sodium salt of the acid corresponding to the anhydride, condensation takes place and an a, B unsaturated acid is obtained. This reaction is known as Perkin’s reaction. f Oo =) ‘ I CéHs—C 40 +HACH-CL COONS Cats CH= are (CcHsCH = CH-COOH + CH;COOH H CH fe noe Acetic acid acid ne eee ce i oO Benzaldehyde Acetic anhydrideKNOEVENAGAL REACTION: COOH [coon — riding (C6Hs-CH o+ne —Paidine CgHs CH= C. —A__» (Hs CH = CH- COOH =H20 ~COr ‘COOH COOH Benzaldehyde —Malonic acid Cinnamic acid Benzaldehyde condenses with malonic acid in presence of pyridine forming cinnamic acid, Pyridine act as the basic catalyst. ESTERIFICATION: When carboxylic acids are heated with alcohols in the presence of conc. H2SO, or dry HCI gas, esters are formed. The reaction is reversible and is called esterification. 9 9 ll Ht Il C6Hs—C— OH + CH,OH ——> H.-C — OCH, + H,0 Bemzoic acid ethyl benzoate Mechanism of esterification: The Mechanism of esterification involves the following steps. _ a" 2 | | c. Gm, He on Hac (on eA 6. cae 2 u 4 Hye. eo 6 Hee. ° 4 “E cation ri ©. — City“ O~H + Ocal 0P~CaHs KOLBE’S ELECTROLYTIC DECARBOXYLATION: The aqueous solutions of sodium or potassium salts of carboxylic acid on electrolysis gives alkanes at anode. This reaction is called kolbes electrolysis. CH;COONa Electrolysis. CH = ——— CH3;COONa Sodium acetate Anode Cathode Sodium formate solution on electrolysis gives hydrogen HELL — VOLHARD — ZELINSKY REACTION (HVZ Reaction): Carboxylic acids having an a - hydrogen are halogenated at the a. - position on treatment with chlorine or bromine in the presence of small amount of red phosphorus to form « halo carboxylic acids. This reaction is known as Hell — Volhard — Zelinsky reaction (HVZ reaction) The a - Halogenated acids are convenient starting materials for preparing a - substituted acids. + 2CO, + 2Na CH,Ch,/red Py CH;- coon "4 cH, -cooH #20 I a Acetic acid Mono Chloro acetic acid TRANSESTERIFICATION: Esters of an alcohol can react with another alcohol in the presence of a mineral acid to give the ester of second alcohol. The interchange of alcohol portions of the esters is termed transesterification. 9° 9 ll Ht Il CH3—C [ OCoHs + rbcath CH3—C — OC3Hy+ C)HsOH Ethyl acetate Propyl alcohol Propyl acetate Ethyl alcohol The reaction is generally used for the preparation of the esters of a higher alcohol from that of a lower alcohol. AMMONOLYSIS: Esters react slowly with ammonia to form amides and alcohol. i Il CH3—C — OC)Hs + H-NH, ——> CH3;—C — NH, + C;HsOH Ethyl acetate Acetamide Ethyl alcohol CLAISEN CONDENSATION: Esters containing at least one «- hydrogen atom undergo self condensation in the presence of a strong base such as sodium ethoxide to form B- keto ester. Oo 9 9 Il Il (CsHsONa I] Il CH3— C + OC;Hs + HT CHy~ C— OC;Hs ===> CH— C — CH~ C—00 3H + C2HsOH Ethyl acetate Ethyl acetate Ethyl aceto acetate Ethyl alcohol HOFFMANN’S DEGRADATION: Amides reacts with bromine in the presence of caustic alkali to form a primary amine carrying one carbon less than the parent amide. ° A NE} + Br; +4 KOH ——> CH NE + K2CO3 + 2KBr + 2H20 ide Methyl amine TAUTOMERISM: Primary and secondary nitroalkanes, having a-H , also show an equilibrium mixture of two tautomers namely nitro — and aci — form. H 1 > con CH,=N Xo . ‘No (Aci form) Nitromethane (Nitro form) NEF CARBONYL SYNTHESIS: = 7? s9fx CH,CH,NO,“"» CH,—CH=N_ ——» CH.— CHO+HNO ‘OH Nitroxyl azanone Page 110GABRIEL PHTHALIMIDE SYNTHESIS: Gabriel synthesis is used for the preparation of Aliphatic primary amines. Phthalimide on treatment with ethanolic KOH forms potassium salt of phthalimide which on. heating with alkyl halide followed by alkaline hydrolysis gives primary amine. Aniline cannot be prepared by this method because the arylhalides do not undergo nucleophilic substitution with the anion i by phthalimide. — alcoholic aqueces od oy aoc a Le NK N-R (oe +R— NH, i ‘HO oar — OK = i « N- Ba Jeeta) Ser Potassium phthalimide phthalimide tet pthalati HOFFMANN’S AMMONOLYSIS: When Alkyl halides (or) benzylhalides are heated with alcoholic ammonia in a sealed tube, mixtures of 1°, 2° and 3° amines and quaternary ammonium salts are obtained. N - CH, - Br «CH; Br .. CH, Br tp CH; Br Nes cH, NB 3 (CH) — > (CH,)3N ——> (CH3),N BF A ae oO + NaCl + 2H,0 Aniline Benzenediazonium chloride CARBYLAMINE REACTION: Aliphatic (or) aromatic primary amines react with chloroform and alcoholic KOH to give isocyanides (carbylamines), which has an unpleasant smell. This reaction is known as carbylamine test. This test used to identify the primary amines. CoH; - NH, + CHCl, + 3KOH —* CyH, -NC +3KCl+3H,0 Ethylamine Chloroform Ethylisocyanide Pave 114MUSTARD OIL REACTION: When primary amines are treated with carbon disulphide (CS,), N - alkyldithio carbomic acid is formed which on subsequent treatment with HgCh, give an alkyl isothiocyanate. s s i | Hgcl, CH; -N-H+C=S ——> CH, - NH-C-SH ——> CH3-N=-C-S +HgS +2HCI | H N- methyl Methyl dithiocarbamic acid isothiocyanate Methylamine (Mustard oil smell) When aniline is treated with carbon disulphide, or heated together, S- diphenylthio urea is formed, which on boiling with strong HCI , phenyl isothiocyanate (phenyl mustard oil), is formed, Op Na it O-N q/ a Neos CM ©) neces Orme oo 8 - diphenyl Aniline thiourea Phenyl isothiocyanate These reactions are known as Hofmann — Mustard oil reaction. This test is used to identify the primary amines. SANDMEYER REACTION: On mixing freshly prepared solution of benzene diazonium chloride with cuprous halides (chlorides and bromides), ary! halides are obtained. This reaction is called Sandmeyer reaction. When diazonium salts are treated with cuprous cyanide, cyanobenzene is obtained. CuCl SHC cgi, -Cl+N, Chlorobenzene oe CoHs -N:Cl CoHs-Br+N Bromobenzene Benzene diazonium “hloride C Cols -N,BF; ———> CoH -F + BF; +N, Benzenediazonium _Fluorobenzene ee fluoroborate acidGOMBERG REACTION: Benzene diazonium chloride reacts with benzene in the presence of sodium hydroxide to give biphenyl. This reaction in known as the os reaction. ‘NaOH ye Racist fy“. {) + %af +H Benzene on THORPE NITRILE CONDENSATION: Self condensation of two molecules of alkyl nitrile (containing a—H atom) in the presence of sodium to form iminonitrile. NH CH, | fa CH;CH;-C == N + CH)-CN Sipe Cosas Propanenitrile CH, 3 - imino - 2- methyl pentanenitrile LEVINE AND HAUSER ACETYLATION: The nitriles containing a- hydrogen also undergo condensation with esters in the presence of sodamide in ether to form ketonitriles. This reaction is known as “Levine and Hauser” acetylation. This reaction involves replacement of ethoxy (OC2Hs) group by methylnitrile (-CH»CN) group and is called as cyanomethylation reaction. T i) NaNH, ii) H* g ———> CH; CH; —C—CH,—CN ll CH,CH, — c = Oc, + HCH, -CN Ethane : Ethyl Propionate nitrile Sieh ems GRIGNARD REAGENT REACTION: Nucleophilic addition of Grignard reagent to aldehydes/ketones in presence of dry ether followed by the acid hydrolysis gives alcohols. Formaldehyde gives primary alcohol and other aldehydes give secondary alcohols. Ketones give tertiary alcohols. H Ether I 1,0 CgHsMgBr + HCHO ao OMgBr Se” CoHSCHLOH + Mg(OH) Br Phenyl Methanal H Phenyl methanol magnesium — (Formaldehyde) bromide CL. 5 Ether I HO CHIsCH:MgBr + CH,CHO > _|CH,CHh,- €- OMgBs] > » CH,CH,CHICH, + Mg(OE) Br Ethyl perner u a i cet aor Butan-2-o1 bromide Ether Fs CH; (CH,(CH,),MgBr + CH,COCH, re | HO. (CH), Mg COCH; —*"|CH,CH,), ¢ OME ayer) “4-1-+ Mao Be n-butyl magnesium Propsnone cH, Brome est Reto) : oi 2-methylhexan-2-olFormate ester is used to prepare a secondary alcohol with identical alkyl groups 9° OH i 3) ether solvent | Br 2CH,MgBr + H- C- O-CH)-CH, —————> CH;—-CH—CH, +Mg< i) HO" OCH - CH; ethylmethanoate ss propan - 2- ol BBBBHSDHDHH PRODUCT NAME REACTIONS PREPARATION OF GLYCOL: We have already learnt that the hydroxylation of ethylene using cold alkaline solution of potassium permanganate (Baeyer’s reagent) gives ethylene glycol. Cold alkaline KMnO, CH, — CH, CH; = CH; +H,0 ————+—> | |” ethane-1,2-diol ethene [o] OH OH PREPARATION OF GLYCEROL: Glycerol occurs in many natural fats and it is also found in long chain fatty acids in the form of glyceryl esters (Triglycerides). The alkaline hydrolysis of these fats gives glycerol and the reaction is known as saponification. oO CH, — O- é- (CH,)\,— CH CH, —OH [ie | ° CH — O—C— (CH,)yy— CH; + 3NaOH —A_~ cH —on + 3Na0- C — (CH), — CH, | ° | Sodium palmitate cH, - o- b- Cu CH CH,—OH —_Sodiumhexadeconoate Glycerylpalmitate Glycerol (a triglyceride) (propane-1,2,3-triol) PREPARATION OF EPOXIDE: Ethyleneglycol undergoes dehydration reaction under heated to 73K, it forms epoxides. i — 0H TBK ie i a CH, — OH . a CH, a ethane-1,2-diol ——— (Oxirane) NITRATION OF GLYCEROL: Glycerol reacts with concentrated nitric acid in the presence of concentrated sulphuric acid to form TNG (trinitroglycerine). ae OH CH, — 0 — NO, ConH,s0, | CH — OH + 3HONO, Son SO4, CH —O—NO, I -3H,0 I CH, — OH CH, — 0 — NO, Propan - 1,2,3 - triol 1,2,3 - trinitroxy propane glycerolPREPARATION OF ACROLEIN: When glycerol is heated with dehydrating agents such as Con H:SOs, KHSO, etc., it undergoes dehydration to form Acrolein. CH, — OH CH 1 KHSO, II fe CH) ~ OH CHO Propane - 1,2,3 -triol Prop - 2- enal (acrolein) NITRATION OF PHENOL: Phenol can be nitrated using Conc,HNO;+con.H:SO, gives pierie acid even at room temperature. 1H SH cone. 80, ON NO} Cone. HNO; 298K +310 phenol NO, 2,4,6-trinitrophenol (picric acid) PREPARATION OF SALICYCLIC ACID: N Kolbe’s (or) Kolbe’s Schmit reaction PREPARATION OF SALICYLALDEHYDE | Riemer — Tiemann Reaction HC cH, cH, PREPARATION OF PHENOLPHTHALEIN: | Phthalein reaction N PREPARATION OF UROTROPINE: ace Formaldehyde reacts with ammonia to form hexa methylene a 2 Ne tetramine, which is also known as Urotropine. N N 6HCHO + 4 NH, ————» (CHg3)sNq + 6 H20 ~ a Formaldehyde Hexamethylene tetramine CHY PREPARATION OF PINACOLS: Ketones, on reduction with magnesium amalgam and water, are reduced to symmetrical diols known as pinacol. CH, CH, 1 Mg—Hg 1 CH, -¢=0 +0=¢-CH, +20) “Hg CH, - C-C- CH, cH, cH, _ OHOH i Acetone Acetone 2,3 dimethyl! butane 2,3 - diol (pinacol) PREPARATION OF CINNAMIC ACID: Perkins’ reaction (or) Knoevenagal reaction PREPARATION OF SCHIFF ’S BASE: Aromatic aldehydes react with primary amines (aliphatic or aromatic) in the presence of an acid to form schiff’s base. CoHs— CH £0 +H N- Cos CoHs —CH= N- CH + H20 ae Benzaldehyde Aniline edPREPARATION OF MALACHITE GREEN DYE: Benzaldehyde condenses with tertiary aromatic amines like N, N — dimethyl aniline in the presence of strong acids to form triphenyl methane dye. a) oS { > N (CH3)2 i AD (-b4o 4 susan, (4 ; u-< S—ncmy \Cp vec N,N - Dimethyl aniline Malachite green dye PREPARATION - OIL OF MIRBANE: When benzene is heated at 330K with a nitrating mixture (Con.HNO3 + Con.H2SO,), electrophilic substitution takes place to form nitro benzene. (Oil of mirbane). H NO, oO + HNO, —_COmHSOs O +H,0 PREPARATION OF BENZENEDIAZONIUM CHLORIDE: Aniline reacts with nitrous acid at low temperature (273-278 K) to give benzene diazonium chloride which is stable for a short time and slowly decomposes even at low temperatures. This reaction is known as diazotization. Benzaldehyde Ge ie 273 - 278K i + NaNO, + 2Ho1 —=—=ER, (Cy + Nacl + 21,0 aie Benzenediazonium chloride LIBERMANN’S NITROSO TEST: Alkyl and aryl secondary amines react with nitrous acid to give N — nitroso amine as yellow oily liquid which is insoluble in water. This reaction is known as Libermann’s nitroso test. CH, CH; a Nye N-o N-Nitroso methyl | NaNO, | canteen roll) CO +HON=O CO a Cone HCI - H,0 N- methylaniline HOFMANN - MUSTARD OIL REACTION: When aniline is treated with carbon disulphide, or heated together, S- diphenylthio urea is formed, which on boiling with strong HCI , phenyl isothiocyanate (phenyl mustard oil), is formed. These reactions are known as Hofmann — Mustard oil reaction. This test is used to identify the primary amines. )- iH ex Aniline S- diphenyl thiourea ConHCl = c-s SS CO en-c-s A Phenyl isothiocyanatePREPARATION OF ZWITTER ION: Aniline reacts with Cone. H2SO, to form anilinium hydrogen sulphate which on heating with H)SOs at 453 — 473K gives p- aminobenzene sulphonic acid, commonly known as sulphanilic acid, as the major product. But, its delocalse itself to from unstable Zwitter ion, NH) NHHSO;, iH, in Cone. HINOs =—_—_ —_ — Pyridine a S803 hydt sulphat pee it \ydrogensulphate Sulphanilic acid Zwitter ion. PREPARATION OF BIPHENYL: Gomberg reaction PREPARATION OF PHENYL HYDRAZINE: Certain reducing agents like SnCl / HCl; Zn dust / CHyCOOH, sodium hydrosulphite, sodium sulphite etc. reduce benzene diazonium chloride to phenyl hydrazine, O- ker _SnCly + HCL O- iain, yn 80, PREPARATION OF NYLON - 6,6: Nylon — 6,6 can be prepared by mixing equimolar adipic acid and hexamethylene — diamine to form a nylon salt which on heating eliminate a water molecule to form amide bonds. It is used in textiles, manufacture of cards etc... ° ° HO- lett + HjN—(CH.9> NH, —> OCH F-6—0 @ hexan - 1,6-dioicacid —_ihexan - 1,6- diamine NHj—{CHy- Hy a ‘Nylon salt =o CCH) CF NH CH2 9 NHC (CHC NACH IN, 4 Poly (hexamethyleneadipamide) Nylon 6,6 PREPARATION OF TEFLON (PTFE): The monomer is tetrafluroethylene. When the monomer is heated with oxygen (or) ammonium persulphate under high pressure, Teflon is obtained. It is used for coating articles and preparing non — stick utensils. nCF;=CF, —& EOF) OF Ie PREPARATION OF ORLON (POLYACRYLONITRILE — PAN): It is prepared by the addition polymerisation of vinylcyanide (acrylonitrile) using a peroxide initiator. It is used as a substitute of wool for making blankets, sweaters etc... Peroxides n (CH, = CH) ———> i a I A cN PAN CN Prop - 2-enenitrile Page 117PREPARATION OF NYLON - 6: Capro lactam (monomer) on heating at 533K in an inert atmosphere with traces of water gives €-v amino carproic acid which polymerises to give nylon — 6. It is used in the manufacture of tyrecards fabrics etc. HW 0 533K cao —c113-coon feel Nylon -6 2 PREPARATION OF TERYLENE (DACRON): The monomers are ethylene glycol and terepathalic acid (or) dimethylterephthalate. When these monomers are mixed and heated at 50K in the presence of zine acetate and antimony trioxide catalyst, terylene is formed. It is used in blending with cotton or wool fibres and as glass reinforcing materials in safety helmets. /HO-CHy-CH-OH| 4 eee Eo hen —— ee are | g 4 iy CHy ethan-1,2-diol Za(OOCCH): +Sb;05 a benzene-1,4-dicarboxylic acid Terylene (an polyester) PREPARATION OF BAKELITE: The monomers are phenol and formaldehyde. The polymer is obtained by the condensation polymerization of these monomers in presence of either an acid or a base catalyst. Phenol reacts with methanal to form ortho or para hydroxyl methylphenols which on further reaction with phenol gives linear polymer called novolac. Novalac on further heating with formaldehyde undergo cross linkages to form backelite, OH OH 9 CH,-OH Gri on & gre oe Ny ye wer A cH, 7 s. Nott Toe MELAMINE (FORMALDEHYDE MELAMINE): The monomers are melamine and formaldehyde. These monomers undergo condensation polymerisation to form melamine formaldehyde resin. OH Ae Gi HAN NS_NH, 4H i nN b (ae NN UNH ee g HN, nl clon “yey NaN + H-C—H —————> ——_- i condensation = Nx_N Polymerisation N ‘Melamine Methanal ° He dy ‘Melamine-formaldehyde polymerPREPARATION OF NEOPRENE: The free radical polymeristion of the monomer, 2-chloro buta-1,3-diene(chloroprene) gives neoprene, It is superior to rubber and resistant to chemical action. free radical NCH, = C— CH = CH, = —__> =CH-CH, CHa = F— CH= CHa “Poiymerisation 2 u : cl a PREPARATION OF BUNA-N: Itis a co-polymer of acrylonitrile and buta-1,3-diene. nCi~CH~ CH=CH, + CH= ¢H —_Na__ fon ca= ce —CHiy-CH-CHy} cN Vinyl cyanide PREPARATION OF BUNA-S: Iisa co-polymer. Its obtained by the polymerisation of buta-1,3-diene and styrene in the ratio 3:1 in the presence of sodium. CH=CH, Na CHaxce - CH—CH,; HH cu nCH,=CH— CH=CH, +2 = ISS Vinyi benzene 7 SB a (tyrene) C;* PREPARATION OF PHBV: : Itis the co— polymer of the monomers 3 — hydroxybutanoic acid and 3-hydroxypentanoic acid. In PHB, the monomer units are joined by ester linkages. on : On I Pi I 20 nCH;—CH—CH;— COOH +n CH;~ CH;~CH—CH,— CooH > / fo —CH-CH,— on ECF | CH; ° Ci -CHs 0 PREPARATION OF NYLON- 2-NYLON -6: It is a co — polymer which contains polyamide linkages. It is obtained by the condensation polymersiation of the monomers, glycine and E - amino caproic acid. an HN-CH,- OOH + nHj=N— (CH},COOH, —> + un-cu,- c-NH- (CHL ie -1) HO Glycine Aminocaproic acid I ° q Nylon -2-nylon - 6 POPOFF’S RULE: The oxidation of unsymmetrical ketones is governed by Popoff ’s rule. It states that during the oxidation of an unsymmetrical ketone, a (C-CO) bond is cleaved in such a way that the keto group stays with the smaller alkyl group. ~ CH, CH, C-CH, aS CH,CH,- COOH + CH, COOH ° pentan—2~one Propanoic acid ethanoic acidIUPAC NOMENCLATURE RULES FOR ORGANIC COMPOUNDS [Prefix(es) +[infix|+[ Root word }+(1° suffix] +[2° suffix Prefix: a Side chain or . Prefix Root word: eovians Substituent = | -CHs methyl- No. of | Root No: of | Root | | -cHsCHs (or) -CaHs_| ethyl- rs carbon | word | | carbon| we Ghetietts aropyl 1 Meth 11 Undec isoy - - CH= propyl: 2 | Eth 12) Dodec_| | iio 3_| Prop 13 | Tridec | | -CH2CHaCHaCHs Buty! 4 But 14 __| Tetradec I sec-butyl (or) (1- 5 | Pent 15 | Pentadec aot a methyl)propyl__ — O 6 Hex 16 | Hexadec | |. 40 on, — isobutyl (or) (2-methyl)propy! 7 Hept 17__| Heptadec CH Aint i tert-butyl (or) (1,1- 8 Oct 18 | Octadee | | Hc-¢-cHy dimethyljethy! 9 Non 19 Nonadec | |__| - 10 | Dec 20 Icos x haloz~ 2% 1° suffix: -OR alkoxy- i as lel -NO2 -nitro = Primary | we Type of carbon chain suftie — Bet “gi fea CH3 Saturated (all C-C bonds) -ane 3Methyl + but + ane + 201 Unsaturated: one C=C -ene prefix root word _1°suffix 2°suffix Unsaturated: two -diene wie me eee) Unsaturated: one -yne Unsaturated: two -diyne Unsaturated: one C=C | nye 2° suffix & prefi : 7 “Suffix Suffix Name of "When carbon of _ | When carbon of the Functional | Representation | the functional functional group Prefix group | group is part of the is NOT part of the parent chain parent chain carboxylic acid -oic acid -carboxylic acid carboxy- Acid anhydride -oicanyhydride —_| -carboxylic anhydride : Ester alkyl -oate alkyl -carboxylate alkoxycarbonyl- Acid halide -oyl halide -carbonyl halide halocarbonyl- Acid amide -amide -carboxamide carbamoyl- Nitrile nitrile -carbonitrile eyano- Aldehyde -al -carbaldehyde oxo- Ketone -one : oxo- Alcohol -ol : hydroxy | Thiol -thiol - mercapto Amine -amine : amino- Imine -imine : imino- | Alkene -ene : e Alkyne ~yne 3 = %&%% WISH YOU ALL THE BEST sps5 es