Reactions of ALKENE | | - C = C - ALKANE | | - C - C - | | HALOHYDRIN | | - C - C - | | X OH VICINAL DIHALIDE | | - C - C - | | X x SATURATED MONOHALIDE// HALOALKANE// ALKYLHALIDE | | - C - C - | | H x ALCOHOL | | - C - C - | | H OH DIOL | | - C - C - | | OH OH CARBONYL | | - C =O @ O= C –H Ketone @ aldehyde METHANAL ; other ALDEHYDE// KETONE ↓ ↓ ↓ HCOOH - COOH does not oxidized ↓ remain ketone CO2 + H2O Halohydrin: X attached to C=C with C more H atoms Markovnikov’s rule: H attached to C=C with C more H atoms *Type of alkene reaction: (a) electrophilic addition reaction: chemical reaction of all alkene (b) elimination: formation of alkene from alcohol or haloalkane (follow Saytzeff’s rule) MIND MAP OF ALKENE: CHEMICAL REACTIONS
MIND MAP OF ALKENE: CH2=CH2 CH2=CH2 E F CH3CH3 I A B C D H H2O, H3O+ Conc H2SO4, ∆ KMnO4, H3O+ , ∆ Cl2, H2O
MIND MAP OF BENZENE: CHEMICAL REACTION Topic preparation of amine X2, FeX3// AlCl3 (X = Cl @ Br) Zn, H+ // SnCl2, H+ // Fe,H+ // Sn/,HCl RCl AlCl3 (*Pay attention on type of carbocation formed*) KMnO4, H3O+ , ∆ *must have benzylic H* X2, uv (X= Cl@ Br) Conc HNO3, conc H2SO4 50-55oC *halobenzene and alkybenzene: ortho-para director; Nitrobenzene and acylbenzene: meta director. If monosubstituted benzene is deactivator group (-NO2 and -COR); nitration of benzene need to carry out at 100oC. Nitro benzene and acyl benzene unable to carry out Friedal-Crafts Alkylation RCOCl, AlCl3 RCOCl, AlCl3 RCl AlCl3 (*Pay attention on type of carbocation formed*)
A Topic preparation of amine Cl2, FeCl3 B Zn, H+ // SnCl2 ,H+ // Fe, H+ // Sn, HCl F AlCl3 KMnO4, H3O+ , ∆ *must have benzylic H* C E Br2, uv D MIND MAP OF BENZENE G H J K L M CH3COCl, AlCl3 O (CH3)3CCl AlCl3 S T Q R
Topic preparation of amine Br2, FeBr3 B A Zn, H+ // SnCl2, H+ // Fe, H+ // Sn, HCl F AlCl3 (*Pay attention on type of C KMnO4, H3O+ D , ∆ Cl2, uv E Conc HNO3, conc H2SO4 50-55oC MIND MAP OF BENZENE (CH3)2CHCO2Cl, AlCl3 H I J K L M N O (CH3)3CCl AlCl3 S T R Q
MIND MAP OF HALOALKANE: CHEMICAL REACTION + Grignard Reagent R-MgX Mg, dry ether R-C≡ N H3O+ 1 o alcohol 2 o alcohol 3 o alcohol Alkane (i) Ether (ii) H3O+ R-COOH HALOALKANE R-X RCOOCH3 ETHER (C-O-C) Alkoxide ion, -OR// alcohol ALKANE ALKENE NaOH//KOH, CH3CH2OH, ∆ (elimination) ALCOHOL RCH2NH2 (topic preparation of amine) RCOOH (Topic preparation of COOH) R-NH2 (1o amine) (Topic preparation of amine) (Topic preparation of amine)
MIND MAP OF HALOALKANE: CH3CHClCH3 Mg, dry ether D H3O+ L K J I (i) Ether (ii) H3O+ (CH3)2CHCOOH CH3CHClCH3 C P CH3CH2CH3 B NaOH CH3CH2OH, ∆ M E F G (Topic preparation of amine) (Topic preparation of amine) N +
MIND MAP OF ALCOHOL: CHEMICAL REACTION PHENOL 1 O ALCOHOL R-OH ALKYL CHLORIDE R-Cl ALKYL BROMIDE R-Br R-O-Na+ ALKENE Conc HCl, ZnCl2//HCl//PCl3// PCl5// SOCl2 in pyridine 2 O 3 O R-COOH ALDEHYDE PCC, CH2Cl2 + Grignard reagent + O3 (i) ether (ii) H KETONE HALOALKANE R-X NaOH// H O2
MIND MAP OF ALCOHOL: CH3CH2OH CH3CH2OH A B C E Conc HCl, ZnCl2 H G PCC, CH2Cl2 CH3CH2Br F PHENOL I
MIND MAP OF CARBONYL COMPOUNDS: CHEMICAL REACTION CARBONYL COMPOUND BENZENE ALKENE ALCOHOL CYNOHYDRIN One equivalent of ROH, H+ Na +HSO3 - i) LiAlH4 (ii) H3O+ @ H2O// NaBH4 in methanol// H2, Ni@Pd@Pt // + Grignard Reagent (i)ether (ii) H3O+ Aldehyde to COOH Ketone no reaction Using mild oxidizing agent: 1o OH to aldehyde Using strong oxidizing agent: 2 OH to ketone o
CH3 C NNH2 H MIND MAP OF CARBONYL COMPOUND: CH3 C O H H: I: J: C: CH3CH2OH E: One equivalent of CH3OH, H+ F: D: G: K: B:
A: MIND MAP OF CARBONYL COMPOUND: CH2 CCH3 O CH3 F: I: J C: D: One equivalent of CH3CH2OH, H+ Na +HSO3 - NaBH4 in methanol G: CH3 NH2
MIND MAP OF CARBOXYLIC ACID: CHEMICAL REACTION CARBOXYLIC ACID RCOOH AMIDE +H2O +H2 1 o ALCOHOL R-MgX(i) CO2 (ii) H3O+ R-CN ESTER R must contain at least one H KMnO4, H3O+ , ∆
(CH3)2CHCOOH A: B: (CH3)2CHCH2OH E: F: (CH3)2CH-MgBr G: H: K: J: (CH3)2NH MIND MAP OF CARBOXYLIC ACID: (CH3)2CHCOOH
MIND MAP OF AMINE: CHEMICAL REACTION AMINE Zn/H +// SnCl2/ H +// Fe/ H + NITRILE COMPOUNDS Amide (i) LiAlH4 (ii)H3O + H2O Hoffmann’s Degradation of amides form 1º alkyl and aryl amine will shortening the length of carbon chain by one carbon atom Br2 , NaOH R C NH2 H2O O amide amine RNH2 HINSBERG TEST To distinguish 1o , 2o and 3o amines [benzene sulphony chloride, excess KOH, HCl] Amine Add KOH Add HCl 1 o Clear solution Precipitate 2 o Precipitate No change(precipitate) 3 o No change Clear solution NITROUS ACID TEST [NaNO2, HCl; 0-5 oC] Amine Aliphatic Aromatic 1 o Bubble gas ↑ Clear solution 2 o Yellow oil Yellow oil 3 o No observation Green precipitate Identification test of aniline using bromine water Observation: reddish brown colour of bromine water decolorized and white precipitate formed Formation of dye by coupling reaction of diazonium salt and phenol Aryl diazonium ions react with phenols and 3o arylamines to yield azo compound
A: Hoffmann’s degradation: Br2, NaOH, H2O B: C: HINSBERG TEST (Write complete reaction): D: E: MIND MAP OF AMINE: CH2 CH2 NH2 (i) LiAlH4 (ii)H3O + H2O
MIND MAP OF AMINO ACID: CHEMICAL REACTION AMINO ACID ACT AS BASE HCl ACT AS ACID ESTER One peptide bond is made by 2 peptide molecules hence dipeptide.
MIND MAP OF AMINO ACID A: HCl B: E: D: C:
Halohydrin: X attached to C=C with C more H atoms; Markovnikov’s rule: H attached to C=C with C more H atoms *Type of alkene reaction: (a) electrophilic addition reaction: chemical reaction of all alkene (b) elimination: formation of alkene from alcohol or haloalkane (follow Saytzeff’s rule) ALKENE: CH3CH=CH2 CH3CH=CH2 E F G H A B C D H2, Pt H2O, H3O+ Conc H2SO4, ∆ KMnO4, H3O+ , ∆ Br2, H2O
G BENZENE Topic preparation of amine Cl2, FeBr3 B A Zn, H+ // SnCl2 ,H+ // Fe, H+ // Sn, HCl F CH3CH2CH2Cl, AlCl3 C KMnO4, H3O+ , ∆ D Br2, uv E Conc HNO3, conc H2SO4 50-55oC CH3CH2CH2COCl, AlCl3 H K N (CH3)2CHCOCl, AlCl3 O P AlCl3 T S Q R
A KOH F G D C L +H2O J + H3PO3 +POCl3 + HCl H +SO2 + HCl ALCOHOL
A KOH F G E D C +H2O K J I +SO2 + HCl B ALCOHOL
A: CARBONYL F: I: J C: D: One equivalent of CH3CH2OH, H+ Na +HSO3 - NaBH4 in methanol G: CH3 NH2
C O OH A B H E C +H2O J G N M cyclopentanecarboxylic acid +H2 +H2O + CO2 CARBOXYLIC ACIDS