2.

5 Nomenclature of Alkanes

in Chinese
 CH3CH2CH2CH CH3
Common CH3
nomenclature:
Isohexane

IUPAC P. 46, Internatinal Union of

Nomenclature: Pure and Applied Chemistry
 Names of Small Hydrocarbons
Greek numbers-ane

No. of Carbons Formula Name (CnH2n+2)

1 Methane CH4
2 Ethane C2H6
3 Propane C3H8
4 Butane C4H10
5 Pentane C5H12
6 Hexane C6H14
7 Heptane C7H16
8 Octane C8H18
9 Nonane C9H20
 Alkyl Groups
• Alkyl group – remove one H from an
alkane (a part of a structure)
• General abbreviation “R”
• Name: replace -ane ending of alkane
with -yl ending (See Eng. P. 44 and 45
for lists)
Alkanes Alkyl group Abbreviation
CH4 CH3
Me
Methane Methyl

CH3CH2CH3 CH3CH2CH2 Pr
Propane Propyl

CH3CH3 CH3CH2 Et
Ethane Ethyl

CH3CH2CH2CH3 CH3CH2CH2CH2
Bu
Butane Butyl
 Types of Alkyl groups
Classified by the connection site
a carbon at the end of a chain (primary alkyl
group)
a carbon in the middle of a chain (secondary alk
group)
a carbon with three carbons attached to it (terti
alkylH group) H
C
C C C C
C C
H C C
Alkyl groups Name
CH3 CH
Isopropyl
CH3
CH3 CH2 CH
sec-butyl (or sec-Bu)
CH3

CH3 CH CH2 Isobutyl

CH3
CH3 tert-butyl
H3C C or t-Butyl, t-Bu)
CH3
Naming Branched chain Alkanes -IUPAC

Prefix Parent Suffix

Where are How many What

the substituents? Carbons? Family?

P 47,
2.3
Step1 Find the parent
hydrocarbon

Find the longest continuous chain of

carbon atoms
 CH3 CH CH CH CH2 CH2 CH3
CH3 CH3 CH CH3
CH2
CH3
To equal long chains, choose the chain containing the
most branched chain.
CH3 CH CH CH CH2 CH2 CH3
CH3 CH3 CH CH3
CH2
Heptane
CH3
Step 2 Number the atoms in the main chain

Beginning at the end nearer the first branch point, number each C
atom in the parent chain.

1 CH3 7 CH3

2 CH2 NOT 6 CH2

4 4
H3C CHCH CH2CH3 H3C CHCH CH2CH3
3
5
CH2CH2CH3 CH2CH2CH3
5 6 7 3 2 1
3. Designate the location of the substituents
CH2CH2CH3
1 2 3 4
CH3 CH2 CH2 CH CH CH2 CH2 CH2 CH3
5 6 7 8 9
CH CH3
CH3
4-Isopropyl-5-propylnonane

• List the substituents in alphabetical order.

• When the same substituents appears more
than once, use the multiplying prefixes:
di-, tri-, tetra- and so on .
 CH3 CH3
CH3 C CH2 CH CH3
CH3

2,2,4-Trimethylpentane
 CH2CH3
CH3CH2CHCHCHCH2CH2CH3
CH3 CH3

4-Ethyl-3,5-dimethyloctane
2.6 Properties of Alkanes

P49 self-study after class

2.7 Conformation 构象 of Alkanes Eng.
p50
2.5

Conformation:
Different spatial arrangements of atoms
or atomic groups in a molecule that are
generated by rotation about C － C single
bond.
1. Conformational Analysis of Ethane
H H
H
HH
H
HH H
H H H
Eclipsed conformation
Newman
Sawhorse Projection
representation H H
H H
HH H
H H H
H H

Staggered conformation
3.1 Nomenclature of Alkenes

IUPAC Names: suffix-ene

1. Give the parent name by selecting

the longest continuous carbon chain
including the double bond .
Ethylene, propylene, butene, pentene…
i i: [ 英 ] [‵prəupili:n]
[ 美 ] [‵propə lin]  
﹐
2. Number:
Give the double- bond carbons
the lower number.
3. locate the substituents like alkanes.

CH3CH2
H CH3
C C
CH3CH2CH2 H
CH3
2-Ethyl-1-pentene
2- 乙基 -1- 戊烯 4,4-Dimethylcycloheptene
4. Before the parent name, list the
position of double bond

CH3CH2
H
C C
CH3CH2CH2 H

2-Ethyl-1-pentene

1 可以不标出来
Alkenyl groups:

CH2 CH Vinyl

CH2 CH CH2 Allyl (Allylic group)

烯丙基
CH3 CH CH Propenyl 丙烯基
e i
CH2 C
Isopropenyl
CH3
3.2 Structure of Alkenes
P13, 1.9
Ethylene: sp2 Hybrid orbitals
sp2-hybridized
Ground state Exited state state
2p
2p 2p
sp2
2s 2s
1s 1s 1s
Promotion Hybri-
of electron
dization
An sp2 orbital
1/3 s orbital
2/3 p orbital
 Three equivalent sp2
hybrid orbitals lie in a
plane at angle of 120°
to one another.

Geometric structure of
C atom with sp2-hybrid:
Planar triangle

A single unhybridized p orbital

perpendicular to the sp2 plane.
 In the molecule of Ethylene :
The formation of C- Cσbond:
sp2 _ sp2 overlap
The formation of C-C πbond:
2p-2p side by side overlap.
The formation of C-H σbond :
sp2-1s overlap.
One C-C σbond and 4 C-H σbond are coplanar.
The formation of C-C πbond:
2p-2p side by side overlap.
 p orbital overlap

H
H

H
H

σ- bond

p orbital
overlap
 Carbon-carbon double bond

σbond

πbond C C
Models of Ethylene
 3.3 Isomerism in Alkenes P79, 3.3
H CH2CH3 H CH3 H3C CH3 H3C H
C C C C C C C C
H H H CH3 H H H CH3
2-Methyl
propylene
1-Butene Isobutene cis-2-Butene trans-2-Butene

(I) (II) (III) (IV)

(I)
Constitutional
isomers (II) (III) (IV)
构造异构 : 原子连接顺序

(III)
Stereoisomers Cis-trans isomers
立体异构 : 空间 (IV)
 Configuration

cis-2-Butene
Rotation about
C-C double bond
is restricted
trans-2-Butene
 Naming Stereoisomeric Alkenes
1. Naming by term Cis-trans P79, 3.3
To disubstituted
Alkenes:

on the Prefix
The same atoms same sides cis-
or of the double
atomic groups on the bond.
trans-
opposite sides
2. Naming by the E, Z system

H3C CH2CH2CH3 Cl CH2CH3

C C C C
H CH3 Br H
Reading text:
key point

from P 81, 3.4

till P.83 practice problem 3.3
10 min
 E, Z system P81 3.4
base on an Sequence Rule
－ Cahn-Ingold-Prelog priority Rule
1. Considering each of the double-bonded carbon,
identify the two atoms directly attached and
rank them according to atomic number.
Low CH2CH3 High
priority Cl priority
C C
High Br H
Low Br > Cl, C > H
priority priority
(E)-1-Bromo-1-chloro-1-butene
E configuration: the high-priority groups
are on the opposite sides of the double-bond

Z configuration: the high-priority groups

are on the same sides of the double-bond
2. When two atoms directly attached to
the double bond are identical, look at
the second, third,or fourth atoms away
from the double-bonded carbons until the
first difference is found.

H3C CH2CH2CH3
C C
H CH3
(Z)-3-methyl-2-hexene
H H H
C H < C C H
H H H

CH3 H
C H > C CH3
CH3 H
H

O H < O C H
H
 3. Multiple-bonded atoms are equivalent to
the same number of single-bonded atoms.

H H O
C O C
O
The carbon is
The carbon is bonded to H, C, C
bonded to H, O, O H C
H H C C
C C C
H H H
 4.13 Alkynes Eng. P128

Hydrocarbons containing a carbon-carbon

triple bond.

R'C CR
 Nomenclature
Numbering starts from the end near triple bond.

• Suffix: ane yne HC CCH2CH3

1-Butyne
ai

1- 丁炔
Structure of Alkynes P18, 1.10
Acetylene (ethyne):
sp Hybrid orbitals
C: sp-hybridized
Ground state Exited state state
2p
2p 2p
sp
2s 2s
Promotion Hybri-
1s of electron 1s dization 1s
An sp-hybridized carbon atom:

180°

The two sp hybride orbitals

are oriented 180°away from each other,
perpendicular to the two remaining
p orbitals.
Acetylene:
formation of C-Cσbond : sp-sp overlap
formation C-H σbonds: sp-1s overlap

formation of two C-Cπbonds:

2py-2py overlap and 2pz-2pz overlap
 H

πbond H

σbond

πbond Carbon-carbon
triple bonds
Reactions of alkynes
1. Acidity of Terminal Alkynes
Acetylene: Ka
’ H C C H H C C + H
Carbanion
Conjugate base
Acidity:
HC CH H2C CH2 CH3 CH3
pKa: 25 44 50
HF > H OH > H OR > H C CR > H NH2
pKa:
3.2 15.8 16-17 26 38
2. Application of the Acidity of
Terminal Alkynes in Organic Synthesis
a. Preparation of Metal Alkynides P.131
Liq. NH3
HC C H + Na NH2 H C C Na + NH3
Stronger Stronger Weaker Weaker
acid base base acid

Acid-base reaction NaNH2 / Liq.NH3

Na C C Na + NH3
b. Formation of C-C Bonds
(Synthesis of Alkynes)
Sodium alkynides are useful intermediates
as nucleophile.

R X: Primary halides RCH2Cl

3. Hydrogenation of Alkynes

Pt, Pd, Ni or Rh
RC CR' + H2 RCH CHR'

Pt, Pd, Ni or Rh
RCH CHR' + H2 RCH2 CH2R'
cis-addition of H2:
Synthesis of cis-Alkenes

CH3(CH2)3 (CH2)3CH3
H2
CH3(CH2)3C C(CH2)3CH3 Lindlar C C
catalyst
H H
(96%)
4. Electrophilic Addition of Alkynes

• Regioselectivity: Follow Markov.’s Rule

• Reactivity: Chin. P81, paragraph 1
a. Addition of HX

HX
R'C CH R'C CH2
X
Alkenyl halide
b. Hydration of Alkynes OH
HgSO4
CH3(CH2)3C CH + H2O H2SO4
CH3(CH2)3C CH
H
1-Hexyne An-enol
Not-stabe
O
CH3(CH2)3C CH3
rearrange
2-Hexanone
stable
c. Addition of X2

P. 130, trans-additon
5.2 Nomenclature of Benzene
Derivatives P146, 5.3
1. Monosubstituted benzenes
a. Benzene as the parent name.
Cl
CH3
Chlorobenzene
Toluene
NO2
CH3
CHCH3
Nitrobenzene
Isopropylbenzene
 CH3 NO2 CH(CH3)2 COOH NH2 OH

¼×±½ Ïõ »ù±½ Òì±û±½ ±½¼×Ëá ±½°· ±½·Ó

当取代基为烷烃， 硝基和卤素时， 以苯为母体，

其它都以苯为取代基
b. Benzene as a substituent
C6H5–, Ph–: phenyl.
CH2
PhC CH
Phenylacetylene Diphenylmethane

CH3
PhC CHCH3 CH2 Cl
2-Phenyl-2-butene
Benzylchloride
 2. Disubstituted benzenes
1) 两基团相同 有三种异构体：邻 (o) 、间 (m) 、对 (p

Three isomers: Br
Br
Br
Br
1,2-Dibromobenzene Br Br
o-Dibromobenzene 1,3- 1,4-
m- p-
o-
ortho- meta- para-
2) 两基团不同 主官能团 ( Chin. P.197) 与苯环一
起作母体，另 一个作取代基。

OH CH3 CHO
NH2

Cl
SO3H

间氯苯酚 对甲苯磺酸 邻
氨基苯甲醛
3. Polysubstituted Benzenes

CH3

H3C CH3
1,3,5-Trimethylbezene

Parent name: P. 147, table 5.1, diff.

 1) 三基团相同 1,2,3-( 连 ) 1,2,4-( 偏 ) 1,3,5-(
三 均)
取
代 2) 三基团不同 (P.197)
苯
① 先定主官能团并编号为 1 ；

② 取代基位号尽可能小；
③ 写名称 , 次序规则小的基团优先。

NO2
CHO Cl
NH2

SO3H
HO

2- 氨基 -5- 羟基苯甲 3- 硝基 -2- 氯苯磺酸

醛

±½»ù: C6H5- ph- Üлù»ò±½¼×»ù: CH2-

 Rules for the nomenclature of
some organic compounds

1. Long chain alkanes

2. Cycloalkanes
3.Aromatic rings (benezene rings)

When the above compounds contain on

ly alkyl, halogen, nitro, nitroso and som
etimes alkoxy groups
A. loswest number for the substituents, and if there a
re more than one ways for numbering, then,

B. for English nomenclature, begin numbering at

the group that has alphabetical priority
For Chinese nomenclature, begin numbering at
the group that is lowest priority (smallest group)
 1 2
6
1,4- 二甲基 -2- 乙基环己烷
5 3 2-ethyl-1,4-dimethylcyclohexane
4 loswest number for the substituents

1 1 3
6 6
2 2 4 2
3 5 3 5
5
4 4 6 1
I II III
1 as smallest group 1 as alphabetical priority

I, II: 1,3- 二甲基 -5- 乙基环己烷

III: 1-ethyl-3,5-dimethylcyclohexane
 Br

3- 甲基 -5- 溴庚烷 --------------1 as the smallest group

3-bromo-5-methylheptane--1 as alphabetical priority

NO2

CH3

1- 甲基 -3- 硝基环己烷 ----------- 1 as the smallest group

1-methyl-3-nitrocyclohexane-- 1 as alphabetical priority
 6
1
5
2
4
3

4- 甲基 -2- 乙基 -1- 丙基苯

2-ethyl-4-methyl-1-propylbenzene
loswest number for the substituents

1- 甲基 -3,5- 二乙基苯 -------------1 as smallest group

1,3-diethyl-5-methylbenzene-- 1 as alphabetical priority
NO2
Cl
2-Chloro-1,4-dinitrobezene
NO2
Lowest possible numbers
Chapter 7 Alkyl Halides
 : Halogen-substiuted
X compounds.
R H organic

F
Cl Cl Cl C F
Cl H Cl
Dichlorodifluoro-
Trichloro-ethylene methane
(solvent) a refrigerant( 氟里昂 )

H F Cl
Br C H F C C H
H F Br

Bromomethane Halothane
a fumigant 熏蒸消毒剂 (an anesthetic 麻醉剂 )
7.1 Naming Alkyl Halides

Common name For simple alkyl groups

Halogen: as a functional group

Alkyl + halide
H
CH3F Cl I
Methyl fluoride Pentyl chloride Cyclohexyl
iodide
IUPAC Nomenclature Halogen as a substituent

Name is based on longest carbon chain

– (Contains double or triple bond if present)
– Number from end nearest any substituent (alkyl or
halogen)
Naming if Two Halides or Alkyl Are
Equally Distant from Ends of Chain
• Begin at the end nearer the substituent
whose name comes first in the alphabet
• 中文命名在此不同 :
• 给最小基团最小编号
Classes of Alkyl Halides
According to the type of the carbon
that bears the functional group.

RCH2X Primary alkyl halides

CH3
CH3CCH2Br 1-Bromo-2,2-dimethyl
propane
CH3
RCHR'
Secondary Alkyl halides
X
CH3CHCH2CH3
2-Bromobutane
Br

R3CX Tertiary alkyl halides

CH3
cis-1,4-Dimethyl
H3C Cl chlorocyclohexane
Models of 1,2-
dibromoethane
 8.1 Naming Alcohols
• General classifications of alcohols based on
substitution on C to which OH is attached
• Methyl (C has 3 H’s),
• Primary (1°) (C has two H’s, one R), secondary (2°) (C
has one H, two R’s), tertiary (3°) (C has no H, 3 R’s)
 IUPAC Rules for Naming
Alcohols
• Select the longest carbon chain containing the hydroxyl
group, and derive the parent name by replacing the -e
ending of the corresponding alkane with -ol
• Number the chain from the end nearer the hydroxyl group
• Number substituents according to position on chain, listing
the substituents in alphabetical order
 Many Alcohols Have Common
Names
• These are accepted by IUPAC
 Naming Phenols
• Use phenol as the family name
• Name substituents on aromatic ring by
their position from OH
 Common names

COOH COOH

OH O COCH3
Salicylic acid acetylsalicylic acis
reducing fevers, Aspirin
analgesic same potent
anti-inflammatory
but too acidic, less cotrrosive to stomach
corrosive to stomach
 Naming Ethers
• Simple ethers are named by identifying
the two organic substituents and adding
the word ether
 11.2 Naming Aldehydes and
Ketones
• Aldehydes are named by replacing the terminal
-e of the corresponding alkane name with –al
• The parent chain must contain the CHO group
– The CHO carbon is numbered as C1
• Table 9.2, P. 280 for common names
 Naming Ketones
• Replace the terminal -e of the alkane name with –
one
• Parent chain is the longest one that contains the
ketone group
– Numbering begins at the end nearer the carbonyl
carbon
 Ketones with Common Names
• IUPAC retains well-used but unsystematic names for
a few ketones
 Ketones and Aldehydes as
Substituents
• The R–C=O as a substituent is an acyl group
is used with the suffix -yl from the root of the
carboxylic acid
– CH3CO: acetyl; CHO: formyl; C6H5CO: benzoyl
 10.1 Naming Carboxylic Acids
and
• Derivatives
Carboxylic Acids, RCO H 2
• If derived from open-chain alkanes, replace
the terminal -e of the alkane name with -oic
acid
• The carboxyl carbon atom is C1
 Alternative Names
• Compounds with CO2H bonded to a ring are
named using the suffix -carboxylic acid
• The CO2H carbon is not itself numbered in this
system
• Use common names for formic acid (HCOOH) and
acetic acid (CH3COOH)
Acid Halides, RCOX

– Derived from the carboxylic acid name by

replacing the -ic acid ending with -yl or the
-carboxylic acid ending with –carbonyl
and specifying the halide
• 酰卤
O O
CH3CH2CHCBr HOOC CCl
Br
2- 溴丁酰溴 4-( 氯甲
酰 ) 苯甲酸
 Naming Acid Anhydrides,
RCO2COR'
• If symnmetrical replace “acid” with
“anhydride” based on the related carboxylic
acid (for symmetrical anhydrides)
• 酸酐

O
O O O O C O
HOOC C O
COC CH3COCCH2CH3

HOOC
苯甲 ( 酸 ) 酐
乙丙酐 1,2,3,4- 环己烷四羧酸

-1,2- 酐
 Naming Amides, RCONH2
• With unsubstituted NH2 group. replace -oic acid or -ic acid
with -amide, or by replacing the -carboxylic acid ending with
–carboxamide
• If the N is further substituted, identify the substituent groups
(preceded by “N”) and then the parent amide
 • 酰胺

CH3 O O COOH

CH3CH2CHCH2CNHCH3 HCN-CH3
CH3
NHCOCH3

N,3- 二甲基戊酰胺 N,N- 二甲基

4- 乙酰氨基 -1-
甲酰胺
(DMF) 萘羧酸

氮原子上有取代基 , 在取代基名称前加 N
标出。
 O O
R-C-NH CH3
S
NH
N CH3 R=C6H5CH2-
R O COOH (penicillin G)

γ- 内酰胺 青霉素 ( p
enicillin )
 Naming Esters, RCO2R
• Name R’ and then, after a space, the carboxylic acid
(RCOOH), with the “-ic acid” ending replaced by “-
ate”
• 酯
ClCH2CH2COOC6H5
- 氯丙酸苯酯

H3C

O O

- 甲基 -γ- 丁内
酯
(3- 甲基 -4- 丁内
酯内酯需标明羟基的位次。
)
 O
H3C CH3

H3C CH3
OH N(CH3)2
HO OH
H3CH2C HO CH3
H O O O
OCH3
Erythromycin A
O CH3
O
CH3 O OH ( 红霉素 ) A
CH3

O
HO HC O

HOH2C
OH Vitamin C
OH
 Nitriles, RCN
• Closely related to carboxylic acids named by
adding -nitrile as a suffix to the alkane name,
with the nitrile carbon numbered C1
 11.2 Structure and Physical
Properties of Carboxylic Acids
• Carboxyl carbon sp2 hybridized: carboxylic
acid groups are planar with C–C=O and O=C–O
bond angles of approximately 120°

• Carboxylic acids form hydrogen bonds,

existing as cyclic dimers held together by two
hydrogen bonds

• Strong hydrogen bonding causes much higher

boiling points than the corresponding alcohols
 15.1 Naming Amines
• Alkyl-substituted (alkylamines) or aryl-substituted
(arylamines)
• Classified: 1° (RNH2), methyl (CH3NH2), 2° (R2NH), 3°
(R3N)
 Quaternary Ammonium Iions
铵
• A nitrogen atom with four attached groups is
positively charged
• Compounds are quaternary ammonium salts
IUPAC Names – Simple Amines
• For simple amines, the suffix -amine is added
to the name of the alkyl substituent
 IUPAC Names – “-amine” Suffix
胺
• The suffix -amine can be used in place of the
final -e in the name of the parent compound
IUPAC Names – Amines With More
Than One Functional Group
• Consider the NH2 as an amino substituent on the
parent molecule
 IUPAC Names – Multiple Alkyl
Groups
• Symmetrical secondary and tertiary amines are
named by adding the prefix di- or tri- to the alkyl
group
 IUPAC Names – Multiple,
Different Alkyl Groups
• Named as N-substituted primary amines
• Largest alkyl group is the parent name, and other
alkyl groups are considered N-substituents
 Common Names
• Alkylamines do not have common names
unless they are biological molecules
• Simple arylamines have common names
Common Names of Heterocyclic
Amines
• If the nitrogen atom occurs as part of a ring, the
compound is designated as being heterocyclic
• Each ring system has its own parent name
 15.2 Structure and Bonding in
Amines
• Bonding to N is similar to that in ammonia
– N is sp3-hybridized
– C–N–C bond angles are close to 109° tetrahedral
value