Chem Factsheet

April 2001 Number 17

Organic Chemistry III - Reactions II

To succeed with this topic you need to e.g. Solid P with solid I2 to make PI3 ,
• Be able to name and draw organic molecules (Factsheet 15) 3C2H5OH + PI3 → 3C2H5I + H3PO3
• Know the reactions of alkanes, alkenes and halogenoalkanes reaction type: substitution
(Factsheet 16) mechanism: nucleophilic

After working through this Factsheet you will

halogenating Halogenalkane
Alcohol
• Know the reactions of alcohols agent
• Know some of the reactions of aldehydes, ketones and carboxylic
acids
• Know the ways in which the organic compounds of this Factsheet
and Factsheet 16 can be converted from one to another (i.e. Exam Hint - test for alcohols (i.e. the – OH group).
synthetic pathways) Add solid PCl5 in dry conditions. It is an alcohol if white ‘steamy’
fumes (of HCl) are seen. This is a very important test and, like the
bromine water test for a alkene, is a common examination question
Important
The question at the end of this Factsheet test not only the information in
it, but also the information in Factsheet 16. Factsheets 16 and 17 make up
the complete work on organic reactions. 2. Dehydration (i.e. the removal of H2O)
Add concentrated H2SO4 and heat to 170 0C,
Exam Hint - The secret to answering questions on organic chemistry
is not to be put off by the unfamiliar compounds used in the question. e.g. H OH
Always look for the functional groups / families of the compounds conc. H2SO4
Functional groups always react in the same way! H C C H H C C H + H2 O
heat to 170 oC
H H H H
Alcohols
dehydrating Alkene
Alcohols have the general formula, Cn H2n + 1OH, and the functional group Alcohol agent
is –OH. The ending of the name in –ol shows the presence of the –OH
group. If two –OH groups are present it is called a diol. The position of the
–OH group on the carbon chain of a molecule affects its properties, so you
need to be able to identify the three types of alcohols: 3. Oxidation (only primary and secondary not tertiary)
Potassium dichromate(VI), K2Cr2O7, in dilute H2SO4 with heating. This is
the oxidising agent and it is orange in colour, but changes to green as it is
Primary Secondary Tertiary reduced. N.B. remember this colour change !
H OH OH
C (i) Primary alcohols
OH C C C C C C
H H C e.g. Cr2O72-/ O
C2H5OH + [O] + CH 3 C + H2O
H
-OH on the 2 carbon atoms 3 carbon atoms H
end of the attached to the attached to the
carbon chain OH- carrying C atom OH- carrying C atom Then – if left, the aldehyde is oxidised further to the carboxylic acid ,

e.g. O O
Reactions
CH 3 C + [O] CH 3 C
1. Halogenation
Primay, secondary, tertiary alcohols behave the same way. The – OH H OH
groups is replaced by Cl , Br or I.
[O]
e.g. PCl5 in dry conditions. Alcohol Aldehyde
C2H5OH + PCl5 → C2H5Cl + HCl + POCl3
reaction type: substitution
mechanism: nucleophilic [O]
Aldehyde Carboxylic acid
e.g. Solid NaBr with concentrated H2SO4 are used to produce HBr,
C2H5OH + HBr → C2H5Br + H2O
reaction type: substitution
mechanism: nucleophilic

1
Organic chemistry III - reactions II Chem Factsheet

(ii) Secondary alcohols

N.B. In the A2 course these oxidation processes are shown to be
e.g. OH O capable of being reversed by a reduction process,

CH 3 C CH3 + [O] CH3 C CH 3 + H2O i.e. Carboxylic [H] [H] Primary

acid Aldehyde alcohol
H
Ketones cannot be oxidised further.
[H] Secondary
Ketone
alcohol
[O]
Secondary alcohol Ketone

Synthetic Pathways
Summary Of Reactions From Factsheet 16 & 17

Primary KOH(aq) K2Cr2O7 K2Cr2O7 Carboxylic

Primary Aldehyde
Halogenalkanes Alcohol H+ H+ Acid

KOH / ethanol HX

X2 Dihalogeno KOH(aq)
Alkene Diol
Alkanes

KOH / ethanol HX

Secondary KOH(aq) Secondary K2Cr2O7

Halogenalkanes Alcohol H+ Ketone

Practice Questions 3. An unknown liquid gives the following test results:

1. The molecule contains the – OH group in various positions: (a) Produces white steaming fumes with dry PCl5
(b) changes potassium dichromate(VI) in dilute sulphuric acid from
H
6 yellow to green when heated.
H C OH What family could the liquid belong to?
H H OH H
1 2 3 4 5 4. For each of the steps A – D give the regents and the conditions necessary
HO C C C C C H
to bring about the conversion:
H H OH H H OH
step A
CH 3 C CH3 CH2 C CH 3
Is the –OH in a primary, secondary or tertiary position in the carbon
atom numbered 1, 3, 4 and 6? H H
step B
2. Propan -1– ol is reacted with the following reagents under the conditions
shown. In each case give: Br
(i) The balanced chemical equation.
(ii) The systematic name of the organic product. CH 3 C CH 3
H
(a) Solid NaBr and concentrated sulphuric acid.
(b) Heating to 170 oC with concentrated sulphuric acid. step C
(c) Heating with potassium dichromate (VI) in dilute sulphuric acid.
O OH
step D
CH3 C CH 3 CH3 C CH 3
H
2