Doc Brown's Chemistry Revising Advanced Level Organic Chemistry

Revision Notes PART 3 HALOGENOALKANES (haloalkanes, alkyl halides)

3.1 The molecular structure and naming-nomenclature of halogenoalkanes once know
n as 'haloalkanes' ('alkyl halides') - 3.1.1 The homologous series of HALOGENOAL
KANES
of general formula CnH2n+1X (X = F, Cl, Br or I, initially n = 1, 2 or 3)
How do we name haloalkanes? What is the molecular structure of halogenoalkanes?
This page describes the molecular structure and how to name halogenoalkanes of t
he simplest monosubstituted halogenoalkanes and some polysubstituted haloalkanes
of the C1, C2 and C3 carbon chains. Examples of displayed formula of halogenoal
kane molecules (fluoro, chloro, bromo and iodo alkane derivatives), graphic form
ula, molecular formula, skeletal formula, structural formula of these homologous
series, including isomers of halogenoalkane molecules and some of the further h
alogen substitution products including CFCs, HFCs and HCFCs. Some 'old' trivial
and commercial names of the fluoroalkanes, chloroalkanes, bromoalkanes, and iodo
alkanes are quoted in () though their use should be avoided if possible.
See also 3.1.2 more haloalkanes of C4 * 3.1.3 more haloalkanes >C4_and cyclohalo
alkanes
A brief guide to halogenoalkane nomenclature
The generic suffix name (..ane) is based on the longest carbon chain. 1 carb
on, methane; 2 carbons, ethane; 3 carbons, propane; 4 carbons, butane. After the
se 4 preserved 'old trivial' names, the name is 'numerically' systematic eg 5 ca
rbons, pentane; 6 hexane, 7 heptane etc.
The halogenoalkane structures are based on replacing one or more hydrogen at
oms in the alkane structure with a halogen atom X (X = F, Cl, Br or I).
The positions of the substituent(s), denoted with a prefix eg halo or alkyl gr
oups, are denoted by using the lowest possible numbers for the associated carbon
atoms in the main chain.
If there is more than one 'type' of substituent eg using the prefixes: bromo ,
chloro , methyl etc., they are written out in alphabetical order irrespective of c
arbon atom number (note: di, tri are ignored in using this rule).
The examples on this page are based on 1 to 3 carbon atoms
Some 'old' and commercial names are quoted in () though their use should be
avoided if possible [but many still used - just put one into GOOGLE!].
A sub-CLASSIFICATION based on structural differences, which can have chemica
l consequences on e.g. rate of reaction or products formed in a reaction.
Halogenoalkanes are classified according to the atoms/groups attached to
the carbon of the halogen atom X.
Primary halogenoalkanes have the structure R-CH2-X, R = H, alkyl, aryl e
tc. i.e. apart from chloromethane they have one alkyl/aryl group attached to the
C of the C-X group.
e.g. chloroethane CH3CH2Cl
Secondary halogenoalkanes have the structure R2CH-X, R = alkyl or aryl e
tc. i.e. they have two alkyl/aryl groups attached to the C of the C-X group.
e.g. 2-bromobutane CH3CHBrCH2CH3
Tertiary halogenoalkanes have the structure R3C-X, R = alkyl or aryl etc
. i.e. they have three alkyl/aryl groups attached to the C of the C-X group.
e.g. 2-iodo-2-methylpropane (CH3)3CI
NOTE: Some 'old' and commercial names are quoted in () though their use shou
ld be avoided if possible.
AND some abbreviations:
CFC = chlorofluorocarbon (molecule consists of C, Cl, F atoms)
HFC = hydrofluorocarbon (molecule consists of C, H, F atoms)

HCFC = hydrochlorofluorocarbon (molecule consists of C, H, Cl, F atoms)

The shapes and bond angles of simple molecules - section on bond angles in o
rganic molecules
Virtually all the bond angles for the molecules on this page are ~109o e
.g. the H-C-H, H-C-Cl, H-C-Br, Cl-C-F etc. bond angles will be ~109o
Examples of non-cyclo C1-3 HALOGENOALKANES
1. The simplest halogenoalkane is exemplified by chloromethane (methyl chloride)
, whose formula and structured are shown in 4 styles. (a)(c) doc bmolecular form
ula, (b)(c) doc b abbreviated structural formula,
(c)(c) doc b, full structural formula, (d)(c) doc b '3D' representation of the s
tructural formula. The H-C-H and H-C-Cl bond angles will be ~109o

2. to 7. Are examples of multi-substituted halogenoalkanes based on methane

(c) doc b 2. (a) trichlorofluoromethane, (CFC-11, a chlorofluorocarbon or CFC).
The Cl-C-Cl and F-C-Cl bond angles will be ~109o
(b)(c) doc b, chlorotrifluoromethane (a CFC)

3. (c) doc b (a) dichlorodifluoromethane, (CFC-12),

(b)(c) doc b, dichlorofluoromethane (a HCFC)

4. (c) doc bdifluoromethane (a hydrofluorocarbon or HFC, methylene difluoride)

5. (c) doc btribromomethane
6. (c) doc btetrachloromethane, (carbon tetrachloride)
7. (c) doc bchlorodifluoromethane, (HCFC-22 a hydrochlorofluorocarbon or HCFC)

8. Bromoethane (ethyl bromide) exemplifies the simplest mono-substituted alkane

with 2 carbon atoms.
(a)(c) doc b molecular formula, (b)(c) doc b abbreviated structural formula,
(c)(c) doc b more expanded structural formula, (d)(c) doc b full graphic structu
ral formula. The H-C-H and H-C-Br bond angles will be ~109o
(e)(c) doc b '3D' structural formula, (f)(c) doc b skeletal formula

9. to 14., show a series of multi-substituted halogenoethane molecules (with the

possibility of positional isomerism with only 2 carbon atoms) ...
9. (a) (c) doc b, 1-chloro-1,1,2-trifluoroethane

(b) (c) doc b2-chloro-1,1,1-trifluoromethane (a HCFC)

(c) (c) doc b, 1-chloro-1,2-difluoroethane
(d) (c) doc b, 2-chloro-1,1-difluoroethane
(e) (c) doc b, 1-chloro-1,2,2-trifluoroethane

10. (a) (c) doc b, 1-chloro-1-fluoroethane

(b) (c) doc b, 1-chloro-2-fluoroethane
(c) (c) doc b, 1-chloro-1,1-difluoroethane
(d) (c) doc b, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113)

11. (c) doc b2,2-dichloro-1,1,1-trifluoroethane (HCFC-123)

12. (a) (c) doc b, 1,1-difluoroethane (HFC-152a)

(b) (c) doc b, 1,2-difluoroethane

13. (a) (c) doc b, 1,1-dichloro-1-fluoroethane (HCFC-141b)

(b) (c) doc b, 1,1-dichloro-2,2-difluoroethane

14.(a)(c) doc b 1,1,1-trifluoroethane

(b) (c) doc b, 1,1,2-trifluoroethane
(c) (c) doc b1,1,1,2-tetrafluoroethane (HFC-134a)
(d) (c) doc b, 1,1,2,2-tetrafluoroethane

with 3 carbon atoms you get positional isomerism with only 1 halogen atom (1- or
2- )
15. (a)(c) doc b, (b)(c) doc b , (c)(c) doc b, 1-bromopropane (propyl bromide)

16. (a)(c) doc b, (b)(c) doc b, (c) (c) doc b, (d)(c) doc b, 2-bromopropane (iso
propyl bromide)

17.(a)(c) doc b, (b)(c) doc b, (c)(c) doc b , 2-chloropropane (isopropyl chlorid

e)
18.(a)(c) doc b, (b)(c) doc b, (c)(c) doc b, (d)(c) doc b , 1-iodopropane (propy
l iodide)

19. (c) doc bWith 2 like halogen atoms there are four positional isomers
(a)(c) doc b , (c) doc b, (c) doc b, 1,1-dichloropropane
(b)(c) doc b , (c) doc b, (c) doc b, 1,2-dichloropropane
(c)(c) doc b , (c) doc b, (c) doc b, 1,3-dichloropropane
(d)(c) doc b , (c) doc b, (c) doc b, 2,2-dichloropropane

20.(c) doc b with 3 like halogen atoms there are 5 positional isomers
(a)(c) doc b , (c) doc b, (c) doc b, 1,1,1-trifluoropropane
(b)(c) doc b , (c) doc b, (c) doc b, 1,1,2-trifluoropropane
(c)(c) doc b , (c) doc b, (c) doc b, 1,1,3-trifluoropropane
(d)(c) doc b , (c) doc b, (c) doc b, 1,2,2-trifluoropropane
(e)(c) doc b , (c) doc b, (c) doc b, 1,2,3-trifluoropropane