ORGANIC CHEMISTRY CONCEPT BASED QUESTION &ANSWER Bondenthalpy decreasesas:(CH,-F>CH,-Cl>CH,-Br>CH,| BecauseC-Xbond length increasesttom Ftol duetogreatersize Phenolcannotbeconvertedinto chlorobenzene by usingHCl Because C-O bondinphenol has partial double bond character and- OH gris attached to sp’ carbon Thionylchlorideis preferred to convert ROHinto RCI Because the side products are gases and the product can be obtained as pure 2 alcohol easly canbe converted ino aly halide Because3' carbocations arestable Benzene|sconverted intoiodobenzene in presence of oxidizing agent ike HNO,or HIO, CH,+1JFe —_,_C,H,| +HI Because HNO, orHIO,oxidises Hl andprevent backward reaction ROHisconvertedintORIbyusing Klin presenceof H,PO,not H.S0, H.SO, converts Klinto Hland thaninto I, B.pt Of alky/halides (RX) is higher than hydrocarbons Because R-X is polar so there is dipole-dipole attraction Bopt: RIPRB> RC RF Because molecular mass decreases so Van der Waals force decreases from RI to RF Bypt:CH,-CH,-CH,-CH,Br> CH,-CH,-CH(Br)-CH.> (CH,)CBr Becauseas the branching increases surface area decreases so Van der Waals force of attraction decreases 10 P-dichlorobenzenehas higherm.ptthanorthoand metaisomer Because p-dichloro benzene has symmetrical structure soit ts wel in the crystal latice 11 Alkyl halide (RX) with KCN gives alkyl cyanide (RCN) where as with AgCN it gives isocyanide(RNC) KCNisionicandCN isambidentnucleopile butitinkthrough becauseC-C bondismore stable thanC-N. In theotherhand AgCNiscovalentandlinksthrough Nonly. 12S 2reactivity: (1'>2'>3') Due to stearic hindrance nucleophile can not approach easly. In S,2 path release of X and linking of Nu® take place simultaneously 13 Sy reactivity:( 1"<2"<3') Because S,1 path involves formation of carbocation intermediate. And stabilty of Carbocation isin theorder: (1‘<2°<3") 14 S,treactivity: RA>R-Br >R-Cl> RF Because as the size of halogen increases C-X bond becomes weaker 15 Aryl halides ( C,H,OX) are less reactive than alkyl halides(RX) towards nucleophilic substitution BecauseinarylhalideC-X bondhas patialdoublebondcharacterandXisattachedtosp’C, thereisalsotherepulsion between Nurand benzene ringwhichis electron rich 16 Chloroformisstoredin darkcoloured botteasclosedandcompletelyfiled, becausein airandlight itconverts into poisonous phosgenegas(COC!,).0 a B a 5 a B Inmany countries DOT has been banned now, because ofits slow metabolism and it has toxic effect on aquatic animals. Cyclohexylchloridehasgreaterdipolemomentthan chlorobenzene. Alkylhalides areimmiscibleinwater although they are polar, inwaterthereisintermolecularHUbonding butthereislessattraction beweenR-XandH,0. Grignard reagent (RMgX} should be prepared in anhydrous conction becauseRMgXreacts with waterand ives corresponding alkane, Alkyt halides undergo substitution when treated with aq KOH but in presence of ale KOH elimination takes place Alootol +KOH produces RO” whichisastrong base soitextract H’ andelimination takes place. C-O-H bond angle in alcohols less than regular tetrahedral angle due tol-Ip repulsion. Inphenolthe C- bond engthis less Due toi) partial double bond character i) O is attached to sp’ carbon InethertheR-O-R bondangleisgreater, duetorepulsion between twobulkier R-group To convertacid intoalochol LiAIH, isnotused, becauseitis expensive so: RCOOH-+RCOOR 'thenester isteducedintoRCH,CHby Hyd. b.ptof alcohol(ROH) is higher than alkane(RH), ether(R-O-R), alkyl halide(R-X) and aryl halide(Ar- X), due to inter molecular H-bonding in R-O-H. b.pt: n-butylalcohol> sec. butylalcohol>tert. Butylalcohol, because asthebranchingincreases surfacearea decreases so Van der Waals orce of attraction decreases. Alcohols are highly miscblein weter, duetoH-bondingwith water.9 30 3 32 8 35 36 37 38 39 40 4 2 8 Acidity ofalcohol : R-CH,-OH>R,CH-OH>R,C-OH Becauseas the Rgr increases +leffectincreasessoalkoxideion becomes less stable. Alcoholisweakeracidthan water, becauseR-O" is less stablethanHO™ Phenol (Ph-OH)is acidicin nature Because phenoxide ion( Ph-O') is resonance stabilized. Acidity: nitrophenol>phenol>methylphenol. Because -NO, group is electron withdrawingit further increases the stability of phenoxide ionwhereas - CH, groupiselectron donating it destabilizes phenoxideion, Esterificationis carriedoutin presenceofsmall amount ofconc.H,SO, because it absorbs the water produced and accelerate the forward reaction. RICOCI+R-OH ~R'COOR+HCI. Pyridineis usedinthisreaction. It is toremoveHCl produced andto prevent the backward reaction. Tert. Alcohols are easierto dehydrate Because the intermediate tert. carbo cation is stable. -OHgroupin benzene ring is orthoand para directing for electrophilicsubstitution, due to+ R effect it increases the electron density at orthoandpara positions. O-nitro phenolis steam volatile( low b.pt) but p-nitro phenolis not In o-nitro phenol there is intra molecular H-bonding. But in p-nitro phenol there is inter molecular H bonding so molecules get associated and hence ithas comparatively higher b.pt. Phenol with aq bromine gives 2,4,6-tribromophenol but in non polar medium mono -substitution takes place. CuSO,andpyridinearemixedwithethanol used for industrial purpose, toprevent its misuse.CuSO, gives colourpyridine givessmell Ethers (R-O-R) are polar. Ethers are solublein water, due to H-bond with water and ether. ‘Aldehydes (R-CHO) and ketones (R-CO-R) have higher b.ptthan hydrocarbon and ether, because they are polar so thereis dipole-dipoleattractionin aldehyde andketones. Lower aldehydes and ketones are miscible with water, becausetheyform hydrogen bond withwater Aldehydes(R-CHO)aremorereactivethanketones(R-CO-R)innucleophilicaddition, in ketonethe two alkyl groups(R)have+leffect so theyreducetheelectrophilicitycarbonyl carbon. Also there is stearic hindrance in ketone. 45 46 a7 48 49 50 5 52 53 55 56 ST 58 59 60 Benzaldehyde (C,H,CHO) isless reactive than propanal (CH,CH,CHO) due to resonance the electrophility of carbonyl carbon is less in benzaldehyde. NaHSO, is used for separation of aldehydes. Itforms a soluble compound with aldehyde which on hydrolysis gives backthealdehyde. A-Hofaldehyde and ketones acidic nature, because the corresponding carbanion is resonance stabilized, Carboxylic acids ( R-COOH ) do not give nucleophilic addition reaction like RCHO & RCOR althoughit has >C=0 duetoresonancethecarbony carbonloosesitselecrophilty. Carboxylicacidshave higherb.pt thanaldehyde, ketonesandeventhanalcohols. ‘There is extensive inter molecular H-bonding in carboxylic acid (RCOOH). Even in vapour phaseiit exists as dimer. Carboxylic acids are miscible inwater, due to H-bonding with water, R-COOHis acidic in nature, because the conjugate base R-COO’ (carboxylate ion) is stable due to resonance Acidic Strength: Cl-CH-COOH> CH,-COOH > CH,CH-COOH BecauseC! has -| effect which stabiizes the conjugate baseandethy|grhas +! effec. InaminestheC-N-HIC bondangleislessthan 109.5’ due to Ip-bp repulsion. Forreduction ofnittocompoundsinto amines Fe/HClis preferredinstead of Sn/HCI, becauseFe+HCI—» FeCl,.Chhydrolysis FeCl, givesHCI, s just smallquantityof HCI is required to initiate the reaction. To convert alkyl halide(R-X)into amines (R-NH,) ammonolysisisnotsuitable, because on ammonolysis amixture of pri sec, tetand quaternary amine willbe produced. Anilineon exposure air and ightturnsintocoloured, due tto atmospheric oxidation. Lower amines are soluble in water, duetoH-bondingwithwater, Incaseofhigher amine alky! group islarger whichis hydrophobic. Amines (R-NH,)areless soluble than alcohols (R-OH), inacoholtheHbondingith water istronger because OismoreelectronegativethanN. Amines (R-NH,)arelowerboiling than alcohols (R-OH), in alcohol he intermolecular H-bonding is stronger because O is more electronegative than N. Order of b.pt: primary amine > sec. amine> tert. amine The no. of N-H bond decreases so extent of H-bonding also decreases.«: In gaseous phase theorder of basicstrength:3'-amine>2'-amine> 1'-amine> NH; Due to +leffectofalkylgroupstheelectron densityonN increases.So3*isstrongestasit has 3 alkyl ‘groups. 62 Inaqueous statethebase strengthorder: (2°>3°>1"> NH) (2 1" 3°> NHs) Inaqueous state eect stericeffectandsolvation effectinterplay.Sotheorderisnot regular 63 R-NH, is stronger base than NH, Due to +1 effect of alkyl group electron density on N increases in R-NH, 64 Aniline (C,H,-NH,)is weaker base than NH, and R-NH, Inanilinethe one pairofelectronofNisinvolvedin resonance. Soitislessavailable. 65. Base strength : p-methoxy aniline > aniline > p-nitro aniline Methoxy group -OCH,)has +Reffectwhereas-NO, grouphas-Reffectsoelectrondensiy inthefirstcase increases butin the secondcase it decreases. 66 Acylationof aniline is carried out in presence of pyridine .PyridineremovesHC! producedand favours forwardreaction. 67 -NH, groupinbenzenerrngis ortho -para directing forelectrphilicsubstitution Dueto+Reeffectitincreasesthe electron density atortho and para position. 68 Bromination of aniline gives 2,4,6-tribromo aniline Because-NH,groupactvatesbenzeneringby-+Reffect.Soformonosubsttution-NH, group is acylated. 69 Nitrationofaniline gives un usual meta‘ initroanilineathough-NH, groupis orthotipara directing In presence of acid -NH is converted into -NH “which is meta directing 70 Aniline does not undergo Friedel Craftreaction Anilineis base andreactswith anhydrous AICI, so N becomes positive which deactivates benzene ring.