Hydrocarbon Part 1 PDF

# Manzil 2.0 - Hydrocarbon ## IIT/NIT - Rohit Agrawal Sir - Produced Many ICHO & KVPY Selected Students - Air - 10, 12, 18, 19, 27, 61 - Joint Director & HOD, Kota - Author of more than 4 books - Experience of more than 10 Years & Mentored many JEE & NEET students ## MOP - ✓ Alkanes - ✓...

# Manzil 2.0 - Hydrocarbon ## IIT/NIT - Rohit Agrawal Sir - Produced Many ICHO & KVPY Selected Students - Air - 10, 12, 18, 19, 27, 61 - Joint Director & HOD, Kota - Author of more than 4 books - Experience of more than 10 Years & Mentored many JEE & NEET students ## MOP - ✓ Alkanes - ✓ Alkene - $C-H = 1.124°A°$ - ✓ Alkyne - $C-C \equiv 1.54A°$ - ✓ Benzene ## Free Radical - Paramagnetic - $CH_3$ - Octet Incomplete - Highly unstable - $O$ activation energy - Reaction - combination - disproportionation - rearrangement (not in Jee & NEET) ## Combination 1. $CH_3-CH_3 \rightarrow H_3C-CH_3$ 2. $CH_3-CH_2 \rightarrow CH_3-CH_2-CH_2-CH_3$ 3. $\rightarrow$ ## Disproportionation - $R-R \rightarrow R + R$ ## Wurtz Family - 2R- - $Na \rightarrow$ R-R $Et_2O$ - R-X $Na \rightarrow$ X-R $2$ - Mechanism - (i) $R *X$ - (ii) $R * + Na \rightarrow R + NaX$ - (iii) $R + R \rightarrow R-R$ - Alkane + Alkene ## Wurtz Family (RA Points) - Free Radical Intermediate - $R \rightarrow R>R-Br\rightarrow R-I\rightarrow RX$ - Symmetrical hydrocarbon obtained - Even carbon hydrocation - CH4 Can never be obtained - Carbanion (-) also obtained ## Wurtz - Fittig - R-X + $Ph-X \rightarrow R-Ph$ - $Na$ - R - PH - major - R-R $Ph-Ph $ ## Wurtz - Fittig (RA points) - Wurtz (R-X + Na $\rightarrow$ R-R) - (Alkyl) - Fittig ($Ph-X + Na \rightarrow$ R-Ph) - (Aryl) - $Ph$ ## Ulmann - ($Ph-X + Cu \rightarrow$ Ph-Ph) ## FrankLand - $R-X \rightarrow$ $Zn \rightarrow$ R-R ## Jugad 1. ${CH_3}_3C-Br \rightarrow $ ${CH_3}_2-CH_2-{CH_3} $ - $Na$ 2. ${CH_3}_2-{CH_2}-{Br} \rightarrow $ ${CH_3}_2-CH_2-{CH_2}-{CH_2}-{CH_3} $ 3. ## Jugad (RA points) 4. - ${CH_2}=CH_2 \rightarrow CH_2\equiv{CH_2}$ - $\downarrow $ 5. - ${CH} \equiv{CH} \rightarrow HC\equiv{CH}$ - $\downarrow$ - ${CH_2}\equiv{CH_2}$ 6. - $\rightarrow $ - Br - $\downarrow$ - $\rightarrow$ ## Corey House Reaction - R-X $ (i) Li \rightarrow R-R$ $ (ii) Cu-X \rightarrow$ $ (iii) R-X \rightarrow$ - CH3-Br (i) Li $\rightarrow CH_3-CH_2-CH_3 $ (ii) Cu-X $\rightarrow$ (iii) {CH_3}3C-O $\rightarrow$ ## Corey House Reaction (Mechanism) - (i) R-X + 2Li - (ii) RLi + Cu-X - (iii) R₂CuLi + R'X - Gillmann's Rep - R-R', ## Kolbe Electrolysis - R-C-O- $Na \rightarrow$ R-R - *free radical - Anode: $CO_2$ - Cathode: $H_2$ - $CH_4$ - *R-R can be gas - *pH will increase. ## Kolbe Electrolysis (RA points) 1. ${CH_3}_2-COONa \rightarrow{CH_3}_2-CH_2-{CH_3}$ - K.E 2. ${CH_3}-{C_2}H_5-COONa \rightarrow {CH_2}={CH_2}$ - ${CH_3}-{C_2}H_5- $COONa, 3. - ${CH_3}-{CH_2}-{COONa} \rightarrow $ HC=CH - ${CH_3}-{CH_2}-{COONa}$ ## Decarboxylation - RC-O-Na $\rightarrow$ R-H - NaOH - CaO - R-O - $CO_2$ - ${Na_2}{CO_3}$ ## Decarboxylation (RA Points) - * Soda lime decarboxylation - * Oakwood degradation - * Carbanion intermediate - * NaOH: CaO 13:1 - * Rate of $R^-$ \ Stability of (Carbanion) ## Decarboxylation (RA points) 1. $CH_3-COONa \rightarrow CH_4 $ - $NaOH $ - $CaO, \Delta$ 2. 3. $CH_3-CH_2-COONa < {CH_2}_2-COONa < HC=C-COONa$ - (Compare the rate) - $SP^3$ ## Reaction With Grignard - RMgX+ $En-H \rightarrow R-H$ - $S^+$ - $S^-$ - Alkane - $(R+ X + RMgX) \rightarrow$ R-R ## Reaction With Grignard (RA points) - ${RO}_2CH_3$ - $CH_3$MgBr - RSH - ${R-COO}_2$ - ${RN}_2$ ## Adsorption Hydrogenation - Ni-Al/Naou - $CH_2=CH_2 \rightarrow CH_3-CH_3$ - $H_2$ - $Pd/Pt \rightarrow $ - $H_2$ - $Ni$ - $Pd/Pt$ - HC≡CH $ \rightarrow$ $CH_3-CH_3$ - $H_2$ - $Ni$ - $Pd/Pt$ - $CH_3-CH_2$ ## Hydrogenation (RA points) - Hydrogen atoms bound to metal atoms on catalyst surface - First hydrogen transfers to carbon of surface-bound alkene - Catalyst surface - Ni. Pd, Pt - Syn = Same side - Alkane product released from surface - Second hydrogen transfers, completing hydrogenation - H-H has added syn ## Hydrogenation (RA Points) 1. $\rightarrow $ - $H_2/Ni $ - $B_2/Ni$ - $\rightarrow$ - D - D 2. $\rightarrow $ - $H_2/Ni$ - $D_2/Ni \rightarrow $ ## Stereochemistry of Hydrogenation |Type of Alkene | Type of Addition | Type of product | | :--: | :--: | :--: | | +(Cis) | + (Syn) | +(Same Side) | | +(Cis) | - (Anti) | - | | -(Trans) | +(Syn) | - | | -(Trans) | - (Anti) | + | - RA Table ## Lindlar's Catalyst - HCECH $H_2/Ni \rightarrow$ $CH_2=CH_2$ - HCECH $H_2 \rightarrow $ $CH_2=CH_2$ - $Pd/BasO_4$ - $CalO3$ - Lindlar's catalyst - *Quinoline is added as poison ## Reactions of Alkane - Substitution - isomerization - aromatization - combustion - pyrolysis - *Halogenation* - nitration - sulphonation - Reed's reaction ## Halogenation <start_of_image> - $R-H + X_2 \rightarrow R- X + H-X $ - $h\nu$ or - $UV$ rays - *size* - Termination - R + R $\rightarrow$ R-R - X + X $\rightarrow$ X-X - R + X $\rightarrow$ R-X - Initiaton - X + X $h\nu \rightarrow 2X$ - Propagation - (i) $R-H + X \rightarrow $ - (ads) $ R * + H-X$ - (ii) $R * $ - $X \rightarrow R-X + X$ ## Halogenation (RA points) - F - Highly unstable - Most reactive - Highly exothermic (Explosive) - Cl - Highly stable - Least reacting - R-H + Cl₂ $h\nu \rightarrow$ R-Cl + HCl - Reversible - Oxidisimmel - $(TIO_2, KNO_3)$ ## Halogenation (RA points) - Cl - Less stable - More reactive - Less selective - Br - More stable - Less reactive - More selective - $ \rightarrow$ FR Stability - $RCl \rightarrow$ 1:3.8:45. - $\downarrow$ - 10, 20, 30 - $RBr \rightarrow$ 1:80:1600 - $\downarrow$ - 10, 20, 30 ## Halogenation (RA points) 1. $\rightarrow$ - $ {Cl_2} /h\nu$ - (1) $\rightarrow$ - (1) = $\rightarrow$ (2) - u - u - (1) = $\rightarrow$ (2) - * 2. $\rightarrow $ - ${Cl_2} /h\nu $ - (1) $\rightarrow$ - (2) = $\rightarrow$ (3) - u - u - * - (1) 3. $\rightarrow $ - ${Cl_2} /h\nu$ - (1) $\rightarrow$ - (1) - * ## Halogenation (RA points) - 3 - ${Cl_2} /h\nu $ - $\rightarrow $ - (Major) - 3.8 : 4.5 - $1°H\rightarrow$ 9 x 1 $\rightarrow$ 9/13.5 - $2° H \rightarrow $ 0 x 3.8 $\rightarrow$ 0 - $ 3°H\rightarrow $ 1 x 4.5 $\rightarrow$ 4.5/13.5 - (Minor) ## Halogenation (RA points) - 1°H = 6 x 1 - $\downarrow$ - $\frac{6}{23}$ - $3°H =1 x 6$ - $2° = 2x4$ - $\downarrow$ - $\frac{6}{23}$ - $\downarrow$ - $\frac{8}{23}$ - $1°H = 3 x 1$ - $\downarrow$ - $\frac{3}{23}$ - (1:4:6) - u - u - u - u - (2) - All possible ## Reaction With $Al_2O_3, (Cr_2O_3, M_2O_3/V_2O_5, A$ 1. $ \rightarrow$ 2. $\rightarrow$ - (o-luene) 3. $\rightarrow$ ## Reaction With Pd/C - (1) $\rightarrow$ - $Pd/C $ - Se, $\Delta$ - (2) $\rightarrow$ - (3) $\rightarrow$ ## Isomerism - $AlCl_3/HCL$ - ${(x+HY + (x+y/4) O_2}$ - $\downarrow$ - $xCO_2 + y/2 H_2O$ ## Incomplete Combustion - ${CH_4} + {O_2} \rightarrow $ $C_{(S)} + {H_2}O$ ## Controlled Oxidation - Cu - ${CH_4} + {O_2} \rightarrow {CH_3}OH$ - $\Delta (523K)$ - $1H\rightarrow DH$ - ${CH_4} + {O_2} \rightarrow HCHO$ - ${Mo_2}O_3$ - $2H \rightarrow OH$ - $CH_3-CH_2-CH_3 + O_2 \rightarrow CH_3-C-O$ - $Mn (MnO_2)$ - $\Delta$ - $H_2C=C=O$ - $BH\rightarrow OH$ - With $KMnO_4$ ## Reaction With Steam - $CH_4 + H_2O \rightarrow CO + 3H_2$ ## Pyrolysis (Cracking) - $C_6H_{14} \rightarrow C_6H_{12} + H_2$ - 773K - $C_6H_{14} \rightarrow C_4H_8 + C_2H_6$ - $\rightarrow$ - $C_6H_{14} \rightarrow C_3H_6 + C_2H_4 + CH_4$ - $\rightarrow$ - $C_{12}H_{26}\rightarrow C_7HI_6 + C_5H_{10} + other$ - $\rightarrow$ - $\rightarrow$ ## Nitration - ${CH_3}-{CH_3 } \rightarrow {CH_3}-{CH_2}-{NO_2}$ - ${HNO_3}$ - $\Delta$ - $\rightarrow$ - ${NO_2 } + {N_2}+ H_2O$ ## Sulphonation - $\rightarrow$ - ${H_2}SO_4$ - $SO_3H$ - $SO_4^{2-}$ - $SO_3H$ - $SO_3H$ - $SO_3H$ - $H_2O$ - $Hcl$ - $K_2Cr_2O_7$ - Reed's Reaction ## Properties of Alkane - * $C_1-C_4 \rightarrow $ Gas - * ${C_5} - {C_{17}} \rightarrow$ Liquid - * ${C_{18}} \rightarrow$ Solid - ** - B.P $\propto $ M.wt - $\propto$ Branching - R-X-C-X - R-X-X - R-X - R-X ## RA conversion 1. $Na/Et_2O$ 2. ${O_2}/h\nu$ 3. $Zn/\Delta$ - $COONa$ - Kolbe electrolysis - $NaOH$ - $CaO, \Delta$ - $R$ - ${H_2}/Ni$ - (leq.) ## Rearrangement of Carbocation - $H_3C-CH-CH_3 \rightarrow H_3C-CH-CH3$ - $R-X$ - $2KH$ - Hydride Shift - $ * \rightarrow R-X, {6H_4}$ - * Backbonding - $\rightarrow$ - $^+$ - $Me$ - Shift - $8H_4$ - BB - Reso - $C^+$ ## Rearrangement of Carbocation (RA points) - $3x1$ - $\rightarrow$ - $\rightarrow$ - $ 4x1$ - $ \rightarrow$ - $ \rightarrow$ - no shifting - $ 7xH$ - $\rightarrow$ - $\rightarrow$ - BB - Ring Expansion - $ 3 \rightarrow 2$ - $ 5 \rightarrow 3 $ - $4 \rightarrow 5 $ - $4 \rightarrow 2 $ - $3 \rightarrow 4$ - $\rightarrow$ - ⊕ - $48x$ - $47x$ ## Rearrangement of Carbocation( RA Points) - * If backbonding is possible then $H>Ph>3°>2° >1°$ ## Dehydration of Alcohol - $R-OH \rightarrow Alkene $ - con.$ H_2SO_4, \Delta$ - $H_3PO_4$ - $K_2SO_4$ - $R-OH \rightarrow R^+OH_2 $ - $R-OH$ - $(ads) R^+$ - $R-OH \rightarrow$ Stable alkene - $\Delta$ ## Dehydration of Alcohol (RA points) 1. Carbocation 2. Stability of $CC^+ \rightarrow Rate $ 3. Elimination (E1) 4. Stable alkene is major 5. Rearrangement is possible ## Dehydration of Alcohol (RA points) 1. $\rightarrow $ - ${H_2}SO_4$ - $\rightarrow$ - $\rightarrow$ - $9H_4$ - $6H_4$ - (Ma),(Mi) 2. $\rightarrow$ - ${H_2}SO_4$ - $\rightarrow$ - $\rightarrow$ - $\rightarrow$ - $\rightarrow$ - $\rightarrow$ 3. $\rightarrow$ - ${H_2}SO_4$ - $\rightarrow$ - $\rightarrow$ - $\rightarrow$ - TODM ## Bimolecular Elimination - $X$ - Base - Moderate - Alk. KOH, poor - RO$^-$ - V. Strong - ${(C_2H_2})_2N $ - $RO^-$ - V. good, Moderated - Alkene Stability decides major product - -F, ${-CH_2}$-OR, ${-NR_2}$ , -SR, $-B \rightarrow$ (Stability decides major ) ## Bimolecular Elimination (RA points) - ${EtO^-}$ - $5^-$ - $\rightarrow$ - $1(AgF) $ - F - $EtO, \Delta$ - $ (AgF) \rightarrow $ ## Bimolecular Elimination (RA points) - $CH_3-CH=CH_2 \rightarrow {CH_2}=CH-CH_3$ - (Partial double bond) - $Alc. KOH$ - (i) $Alc.KOH$ - $CH_3-CH-CH_2 \rightarrow CH_2=CH-CH_2$ - (ii) $NaNH_2$ - $H_2C\equiv{CH} \rightarrow$ ## Bimolecular Elimination (RA points) - $H_2C\equiv{CH} $ - $+NaNH_2 \rightarrow $ - $ \rightarrow$ - $HC \equiv{CH}$ - ${H_3}C-C \equiv CH_3$ - $E1CB$ takes place in case of EWG & poorly - EWG - $\rightarrow$ - ${EtO^-}$ - $\rightarrow$ - $OH$ - E1CB ## Dehalogenation - $\rightarrow$ - $Na_2/H_2$ - $Zn, \Delta$ - $\rightarrow$ ## Electrophilic Addition - 1. HBr - U - + - 2. $H_2{O}$ - $NO$ - $H_2{SO}_4$ - $OAC$ - $ E, C=C$ - ${H_2}SO_4$ - $\rightarrow$ - *Carbocation* - *Can rearrange* - *Both Syn & Anti* - *Non-classical carbonium ion (NCC)* - *No rearrangement* - *Anti add* ## Hydrohalogenation (Addth of HX) - 1. $\rightarrow $ - $HBr $ - $H_2O$ - $\rightarrow$ - 2. $\rightarrow$ - $H_2O$ - $H_2SO_4$ - $\rightarrow$ - $\rightarrow $ - **( ads)** - $H_2SO_4$ - ⊕ - K+ $HSO_4^-$ - white ppt - 4. $\rightarrow $ - $dil. H_2O$ - $H_2SO_4$ ## Hydrohalogenation (Addth of HX) (RA points) <start_of_image>- 5. $CH_3-C=CH \rightarrow$ $CH_3-C-CH_3$ - $(i) HBr$ - $D_2C, C^-_H_3$ - (ii) $H_2O$ - $CH_3-C=CH_2 \rightarrow CH_3-C=CH_2$ - $CH_3-C=CH_2 \rightarrow CH_3-C=CH_2$ - 6. $CH_3-C\equiv CH \rightarrow$ $CH_3-C-CH_3$ - $H_2O$ - ${CH_3}=CH_2 \rightarrow CH_3-CH_2$ - 7. $CH_3-CH=CH-CH_2 \rightarrow CH_3-C-CH-CH_2$ - $Br_2/CH_2Cl_2$ - Brown ## Hydrohalogenation (Addth of HX) (RA points) - 8. $\rightarrow $ - - Me - Br - $CH_3-CH-CH_2$ - $Br$ - Anti - + - $CH_3-CH-CH-CH_2 $ - Me - Me - 9. $\rightarrow $ - Me - Br - Br - Me - $ CH_3-CH-CH_2$ - + - $CH_3-CH-CH-CH_2 $ - Me - Me - Br - 10. ${CH_3}-{C} \equiv{CH}\rightarrow$ - $Br_2$ - $Br$ - $Br$ - ${H_3}C-C-CH_3$ ## Markovnikoffs Rule (RA points) - $H_2O$ - $OMDM$ - $HBO$ - $H_2OAC$ - $OMDM$ - (i) Hg(OAC)₂/H₂O - (ii) $NaBH_4/NaoH $ - $OMDM$ - HBO - $(i)$ $B_2H_6/THF \rightarrow$ - $(ii) H_2O_2/NaoH \rightarrow$ - $OMDM$ ## KCP & TCP - $HBr/CCl_4 $ - $(1 eq.) \rightarrow$ - $Br$ - $Br$ - (KCP) - $Br$ - (TCP) - $ \downarrow $ - High Temp - (RT. 80℃) ## KCP & TCP (RA points) - * If Temp is not mentioned, assume it is RT & TCP will be major. - Low temp (-80℃) ## Kuchrov's Reaction - ${CH_3}C=CH $ $ \frac{1}{2}H_2SO_4 \rightarrow$ - $H_2O$ - $H_2C=CH$ - $CH_2$ - $ * good yield$ ## Hydroxylation - $Mn^+7+2$ - $Mn^+7+4 $ - Alkaline $KMnO_4$ - $(Sun) \rightarrow$ - H - Me - OH - $OH$ - Me - $H_2O\rightarrow$ - $KMnO_4$ - $(+)$ - $OH$ - $O$ - Mn - $O_2\rightarrow$ - Weak $O_2 \rightarrow$ - $OK$ - $O_3SO_4$ - $(+)$ - $Na_2SO_3$ - $\rightarrow$ - $O_3\rightarrow$ - $O_3$ - (i) $m-CPBA$ - (ii) $H_2O_2$ - $H_2O\rightarrow$ - $Me$ - $OH$ - $MnO_2$ ## Hydroxylation (RA Points) - * Baeyer's reagent - * Glycolisation - * Test for unsaturation ## Hydroxylation (RA Points) - $OH + MnO_2$ - (Brown) - $0_3$ - $O_3$ - $O \rightarrow O$ - $O$ - $OH $ - $O$ - $O$ - $O$ - *1,2 add* - $Me$ - OH - $OH $ - $Me$ - $Anti$ - $ Me$ - $Me$ - $ OH$ - $OH$ - $Me$ - $Anti$ ## Kharash Effect - Peroxide effect - $HBr/Cl$ - $HBr$ - $(CH_3COO)_2 $ - (Peroxide) - $Br$ - (Electrophilic addition) - $(Free Radical Addition) $ ## Kharash Effect (Mechanism) - $Mech$ - initiation - (i) - $Ph-C-O-C-O-Ph \rightarrow PhCOO \rightarrow Ph$ - $||$ - $||$ - $O$ - O - $h\nu$ - (ii) $Ph + HBr \rightarrow $ $Ph-H * Br $ - $Propagation$ - (iii) $ \rightarrow $ - *Br* - $Br$ - $H_2C-CH_2$ - (iv) $\rightarrow $ - Br - $HBr$ - $HBr$ ## Kharash Effect (Mechanism) - * $CH_2-CH + Br \rightarrow CH_2-CH_2 + Br$ - $H_2C-CH_2$ - $Br$ - $Br$ - $H_2C-CH_2$ - $Br $ - $H_2C-CH_2$ - Br - $HBr$ - $HBr$ - $H_2C-CH_2$ - $ Br$ - $Br$ - - st - endo - $Br$ - $H_2C-CH_2 $ ## NBS - $N-Br$ - - $N-Bromo Succinimide $ - Allyl & Benzylic ## NBS (RA Points) - Br substitute (free radical) - ${CH_3} \rightarrow$ - $Br$ - ${CH_3}{Br}$ - NBS ## Ozonolysis - $Zn, PPh_3, {SMe}_2 \rightarrow$ - $Zn$ - $PPh_3$ - $ {SMe}_2$ - *Breaking* - $O_3 \rightarrow $ - $O=C=O$ - *Reductive* - ${O_3} \rightarrow $ - (i) ${O_3}$ - (ii) $Zn/H_2O$ - $CH_2=CH_2 \rightarrow $ - $O$ - $C$ - $O$ - $C$ - $H$ - $C$ - $c$ - $H$ - $O=C=O$ - (Oxidative) - (i) ${O_3}$ - $H_2O$ - $PPh_3$ - $O$ - $C$ - $OH$ - $C$ - $O$ - ${O_2}$ - $\rightarrow$ - $ O$ - $NO$ - $C$ - $OH$ - $O$ - $C$ - $O_2$ ## Ozonolysis (RA points) - R.O ${HC \equiv CH} \rightarrow {HC}={CH}-{O}-{CH}=O $ - $O_3$ - $D.O \rightarrow {H_2}C=CH-OH +{CO_2}$ - $O_3$ - $O_3 \rightarrow$ - $O_3 \rightarrow$ ## Ozonolysis (RA points) 1. $\rightarrow$ - $D_2$ - $ Zn/H_2O$ - CHO - CHO - ${CH_3}$ 2. $HC-CH=C-CH_3 \rightarrow$ - $CH_3$ - $O_3$ - Zn/H_2O - $ \rightarrow $ - $CH_3$ - $O $ - $CH_3$ - $O$ - $CH_3$ - $O$ - $CH_3$ - $ O$ - $CH_3$ - $O$ 3. $ ?? \rightarrow $ - $O_3$ - $Zn/H_2O$ - $ CHO$ - $1,3,5$ - $1,2,4 $ - $H_3C-CH=CH_2$ - $ CH_3-CH_2-CH_2-CH_3$ - $HC=CH$ - $CH_2=CH-CH_2$ - Propenal & acetone ## Ozonolysis (Mechanism) - $Mech$ - $B$ - $Br$ - St - $CH_2=CH_2$ - $O$ - $B$ - $Br$ - $Br$ - $O$ - $ \rightarrow CH_2- \equiv CH_2$