O

HRCarboxylic O acid C . OH

Acyl OChloride C Cl . OH

Alkali, Cu2+

Nucleophilic Substitution Reflux KCN in alcohol

Warm withNaBH4 (H- source) in H2O or ethanol

Primary –OHDistil with acidified K2Cr2O7

Warm with NaBH4

in H2O or ethanol

Alkenes

C=C

Alkanes

C-C

Alcohols

Bases attack H atom Nucleophiles attack Alkyl O: attacks other, say H+

Diol (If hot acidified then further oxidised to two carboxylic acids unless C=C at end of chain then CO2 one of the products.

Dehydration/ Elimination –Hot Pumice & Al2O3 or conc

H2SO4

Alkaline KMnO4

cold

HaloalkanesC-X

Reactivity of-I > Br > Cl

Aldehyde O

C H

+ Ester O

R-C O-R

Heat with alcohol &

acid catalyst

Nitriles

R-CN

Amines

C-NH2

Heat under pressure with NH3 in alcohol Reduction with

LiAlH4

Nucleophilic SubstitutionHeat with dilute alkali solution (H2O)SN2 PriSN1 Ter

Distil from mix of alcohol & conc H2SO4 & KBr or H3PO4 & KI for iodo orPCl5 or SOCl2 for chloro

EliminationReflux with conc

alcoholic alkali, OH-

Attacks H on 2nd C at lower temp

Hydrolysis-Reflux with HCl(aq) or H2SO4 orAlkali

Electrophylic addition with HX(aq)

at room Temp & pressure. With X2

for dihaloIf H2O present = alcohol + halo

Reflux with excess acidified K2Cr2O7

Free radical substitution with halogen and UV, room Temp & P heated H3PO4 acid catalyst & High

Test for – OH I2 & NaOH(aq) for

ethanol only and 2nd alcohols =

CHI3 yellow ppt

Ketones O

c Secondary –OH

Distil with acidified K2Cr2O7

Carbon Atom Increases by 1

Cracking

Nucleophilic Addition NaCN, base catalyst

(H2O)

Warm with LiAlH4

producing secondary -OH

R-O-Na+ + H2

Key Oxidation add[O] or remove [H]Reduction remove [O] or add [H] Na

Nucleophilic Addition NaCN, base catalyst

(H2O)

Red brown ppt Cu2OAlkali, Cu2+Fehling’s

Silver mirrorAldehyde’s ease of

oxidation

[Ag(NH3)2]+Tollen’sTest with 2,4-DNPH

Test with 2,4-DNPH

TriiodomethaneAll CH3CO-

(methy ketones) react with NaOH & I2(aq) forming

CHI3 yellow ppt test

p288Maple

p285 MapleMelting Point

p284 Maple

IO‒ strong oxidizing agent

& Alkene

Test reaction with AgN

O3

Polymer

Initiation ROPropagationtermination

AdditionHeat under Pressure, H2, & with Ni catalyst

Hydration/electrophylic

addition

Pass alkene and steam (300oC) over heated H3PO4 acid

catalyst & SiO2 High Pressure

Nucleophile Cl-

addition then elimination = sub

1

2

3

+ +

2–

RO- good nucleophile Better than OH- as R grouppushes electrons away

Alcohol reactsas a nucleophile

Cl- better leaving Group than OH- of carboxylic acid

4

6

5

7

1

23

1) Markovnikov’s rule: When hydrogen halides add to asymmetrical alkenes the hydrogen goes on the carbon atom which already bears more hydrogen. Why? CH3CHCH3 + Br‒ and NOT CH3CH2CH2 + Br‒ Reason: Alkyl groups push electrons away from themselves stabilising carbocation.

2) Ziegler-Natta catalyst prevents side chain growth

3) SN2 is second order with respect to the rate of reaction. Rate is dependent on the alcohol and the alkali concentration. This is a 1 step reaction involving both reacting simultaneously. It takes place faster than the two step reaction where the slow step involves the breaking of the C–O bond.

4) Two factors influence the ionisation of an acid. Firstly, the strength of the bond being broken. Secondly, the stability of the ions being formed. Consider the following explanation as to why the H+ is acidic.

Methanoic acid, is stronger than ethanoic acid because it’s ion is more stable as it does not have an alkyl group pushing electrons into the already negative end. Diagram available at http://www.auburn.edu/~deruija/pda1_ acids 1.pdf accessed on 01/06

5) The reverse reaction where an ester is converted back into the alcohol and carboxylic acid is known as a hydrolysis reaction. The H+ catalyses the reaction by picking up the single-bonded oxygen of the ester forming a dative covalent bond. Under alkali conditions hydrolysis of an ester occurs without establishing an equilibrium. The OH - reacts as a nucleophile.

+ +

Greater polarization of bond (1) leads to less polarization of bond (2) which leads to greater polarization of bond (3). H+ therefore better leaving ‘group’

6) The following is extracted and modified from http://www.chemguide.co.uk/organicprops/carbonyls/addelim.html accessed on 01/06/2011

Hydrazine is:

In phenylhydrazine, one of the hydrogens is replaced by a phenyl group, C6H5. This is based on a benzene ring.

2,4-dinitrophenylhydrazine, there are two nitro groups, NO2, attached to the phenyl group in the 2- and 4- positions. The corner with the nitrogen attached is counted as the number 1 position, and you just number clockwise around the ring.

The overall reaction is given by the equation:

By measuring the boiling point of the yellow solid produced the identity of the ketone or reacting aldehyde is easy to establish7)