Chapter 2

Introduction to
organic compounds

Nomenclature
Physical properties
Conformation
Organic compounds Ch 2 #2

 in Organic Chemistry 1
 hydrocarbons [RH]
 alkanes
 alkenes
 alkynes
 alkyl halides [RX]
 ethers [ROR’]
 alcohols [ROH]
 amines [RNH2]
 in Org Chem 2
 aromatic comp’ds
 carbonyl comp’ds
Alkanes Ch 2 #3

 saturated hydrocarbons
 saturated ~ all single bonds; no multiple bond [= or ≡]
 hydrocarbon [HC] ~ contains only C and H <cf> carbohydrate

 homologs
 general formula ~ CnH2n+2
 differs by CH2 (methylene)
 paraffins
 non-polar, hydrophobic
Ch 2 #4
Constitutional isomers Ch 2 #5

 isomers [異性質體]
 same composition, different structure (and shape)
 constitutional isomer = structural isomer = skeletal isomer
 two or more compounds with
 the same molecular formula [composition]
 different structural formula [connectivity]
 e.g. C2H6O H H H H
H C C O H H C O C H
H H H H

 eg C4H10
Constitutional isomers in alkanes Ch 2 #6

 straight-chain vs branched alkanes

‘iso’ ~ C bonded to 1 H and 2 methyls [CH3]

neopentane
 Ch 2 #7

 # of possible isomers  as # of atoms 

 C20H42 has 366,319 isomers!
 drawn? calculated?
 nomenclature ~ naming
 common name = trivial name
 systematic name = IUPAC name
Alkyl substituents [groups] Ch 2 #8

 R ~ alkyl R with =, alkenyl; R with ≡, alkynyl

 RH is alkane, and If R covers alkyl, alkenyl, and alkynyl, RH is HC.

Isomeric alkyls Ch 2 #9

 propyl
 (n-)propyl ~ CH3CH2CH2- n ~ normal, commonly omitted

 isopropyl ~ (CH3)2CH-
 butyl CH3

sec- (or s-) tert- or t-

 Degree of substitution of carbon
CH3 H3C CH3

H3C CH C
C C CH3
primary [1°] H2 H2
carbon
secondary [2°] tertiary [3°] quaternary [4°]
carbon carbon carbon
 Ch 2 #10

 primary hydrogen?

 pentyl

pentyl isopentyl tert-pentyl

IUPAC name
perferred

sec-? sec-? neopentyl

 Ch 2 #11

 commonly used alkyl groups

OH

isobutyl alcohol NH2 sec-butylamine

(Systematic) nomenclature of alkanesCh 2 #12
1. Determine the number of carbons in the longest
continuous chain.

 longest continuous chain = parent HC = root chain

 ‘root+ane’
 Ch 2 #13

2. Number the chain so that the substituent gets the lowest

number.

 #-[substituent][parent]
iso, sec-, tert- are common names;
but accepted to IUPAC system when
 no # in common name used as part of substituent
 Ch 2 #14

3. Number the substituents to yield the lowest possible

number.

 Substituents are listed in alphabetical order.

 If two or more same subs, use di, tri, tetra, penta, ---

 ‘di, tri, ---’ and ‘sec-, tert-’ are ignored in alphabetizing

 ‘iso’ and ‘cyclo’ are not ignored
 Ch 2 #15

4. Assign the lowest possible numbers to all of the

substituents

5. If the same numbers in both directions, the first group

cited receives the lower number
 Ch 2 #16

6. If two or more longest chains of the same length, the

parent is the chain with the greatest number of subs.
 Ch 2 #17

7. For branched substituent,

5-(2-methylpropan-1-yl)decane

 may use common name; iso, sec-, tert-

 much simpler
 systematic
1. Find the longest chain beginning at the branch.
2. Number from the branching point.
3. Put (#-name) in parentheses.
* ‘di, tri, ---’ are not ignored in alphabetizing.
Skeletal structure Ch 2 #18

 skeletal structure = bond-line structure

 draw by line(-bond) structure
 drawing a line for a (C-C) bond = Kekule structure
 not showing C and H bonded to C
H H
H H H H
CH3 H3C CH3 H H C H C H

H3C CH C H C C C C C C H

C C CH3
H2 H2 H H H H C H

H H
H
O

H H O
H H C
O
H C O H
CH3
C C OH OH
H H
C C
H H OCH3
H H
Cycloalkanes Ch 2 #19

 cycloalkane ~ cyclic alkane ~ alkane in a ring, CnH2n

 acyclic ~ open-chain

 Nomenclature
1. (subs)cycloalkane
 If subs has more C than ring, cycloalkylalkane

2. Name two subs’ in alphabetical order; Give 1- to the first.

 Ch 2 #20

3. If more than 2 subs’: i) List alphabetically, ii) Give 1- to the

subs letting the second subs the lowest #, iii) So on.

4-ethyl-1,2-dimethylcyclohexane
Alkyl halides Ch 2 #21

 RX
 types

 nomenclature
alkyl halide (common) or haloalkane (IUPAC)
Ethers Ch 2 #22

 ROR (symmetrical) or ROR’ (unsymmetrical)

 nomenclature
 common name ~ alkyl alkyl ether

( )

 Common name is common [preferred] for simple ethers.

 IUPAC name ~ alkoxyalkane
Alcohols Ch 2 #23

 ROH ~ with hydroxy [OH] group

 types

 nomenclature
 common name ~ alkyl alcohol

 IUPAC name ~ alkanol

 ‘ol’ for hydroxy ‘functional group’
Functional group Ch 2 #24

 center of reactivity in molecules

site where reaction takes place
 priority of functional groups

alkoxyalkane
haloalkane
 Ch 2 #25

 IUPAC nomenclature for comp’d with functional group

 # just before ‘ol’ or before name

 Find the longest chain containing functional group [FG]

 Give lowest # to C with FG
 diol, triol, ---
 Ch 2 #26

 For FG and subs, FG gets lowest #.  priority of FG

 If # the same for FG, then lowest # for subs

 If more than 2 subs, alphabetical order

Amines Ch 2 #27

 RNH2, RR’NH, RR’R”N

 types ~ depends on # of alkyls not on DS of C

 nomenclature
 common name ~ alkylamine, alkylalkylamine, -- (one word)
 Ch 2 #28

 IUPAC name ~ alkanamine

 rules the same as for alcohols
 lowest # for amine; then for subs; subs alphabetical
 N- for 2° and 3° amines
 Ch 2 #29

NH2

triethylamine
N
OH
N,N-diethylethanamine
5-aminohexan-2-ol

 quaternary ammonium salt

Structure of RX, ROR’, ROH, and RNHCh2 2 #30
 all sp3 C, O, and N
Intermolecular interactions [forces] Ch 2 #31

(1) instantaneous dipole-induced dipole interaction

 betw non-polar molecules
 (London) dispersion force
 weak
(2) dipole-dipole interaction
 betw polar molecules
[permanent dipoles]
 stronger than (1)

 van der Waals force

 usually, (1) + (2) ~ 0.5 – 5 kcal/mol
 in a narrow sense, (1) only
 Ch 2 #32

(3) hydrogen bonding

 dipole-dipole interaction δ+
betw H on EN atom [N, O, F] and δ–
EN atom [N, O, F]
 fairly strong (3 – 8 kcal/mol)
 due to high ∆EN and H(2.1) C(2.5)
 short distance (small H) N(3.0) O(3.5) F(4.0)
Cl(3.0)
 H on C? H on Cl?
 strength the same?
 O-H is a better H-bond donor
 larger ∆EN
 -N: is a better accepter
 more loose e pair
Physical properties of RY Ch 2 #33

 boiling point
 liquid to gas ~ separation ~ depends on intermol force
 bp  with size [molecular weight]  larger contact area
 RH ~ low bp  (1) only
 ROR’ ~ bp higher than RH  (2)
 ROH ~ much higher bp  (3)
 amines
 lower bp than ROH
 relative H-bond strength
 bp ~ 1° > 2° > 3°
 RX
 bp ~ RF < RCl < RBr < RI
 larger µ  larger polarizability  larger X
 Ch 2 #34

 melting point
 solid to liquid ~ mobility ~ also dep on intermol forces
 trend the same to bp
 except for the effect of molecular shape
 symmetric, compact  close packing  high mp

mp bp

 even-odd effect p95

 Ch 2 #35

 solubility
 dissolution = mixing solvent [1] and solute [2]
 ∆Gmix = ∆Hmix – T ∆Smix
 ∆Smix > 0 always
 As Temp up, T∆S up
 ∆Hmix depends on 1-2 interaction
 intermolecular interaction betw 1 and 2
 ‘like dissolves like’
 {polar, hydrophilic, water-soluble} vs
{nonpolar, hydrophobic, oil-soluble [organic]}
 RH ~ nonpolar ~ water-insoluble
 floats on water ~ density of C30 < 1
 Ch 2 #36

 ROH ~ water-solubility depends on size and shape of R

 propanol soluble with water; butanol not
 butyl alcohol less soluble than t-butyl alcohol

OH
OH

 ROR’ ~ less water-soluble than ROH

 Ether is a good choice of solvent for organic reactions.
 not very reactive [stable], not very polar [dissolves organics]
Lewis base [dissolves salts (cations)], not protonic [useful for base]
 amine ~ 1° > 2° > 3° more water-soluble
 RX ~ R-F more water-soluble  polarity and H-bonding
Conformation and configuration Ch 2 #37

 conformation
 spatial arrangements formed by rotation around single bond

 2 conformers ~ 1 compound ~ not separable

 configuration
 spatial arrangements formed with breaking (double) bond

 2 isomers ~ 2 comp’ds ~ different properties ~ separable

Conformations of ethane Ch 2 #38

 Rotation around C-C bond gives 2 conformations.

staggered conformer eclipsed conformer

 conformer = conformational isomer? = rotational isomer?

= configurational isomer? ~ NOT isomer, but one compound
 Staggered conformer is of lower energy.
 due to hyperconjugation?
 C-H σ and C-H σ*

 due to (the absence of) repulsion between C-H bonding

electrons ~ torsional strain ~ 1 kcal/mol x 3
 Ch 2 #39

 Newman projection and potential energy map

 Actually, numerous conformations.
 3 max’s (eclipsed) and 3 min’s (staggered)

front carbon (C1)

rear carbon (C2)

rotate C2 60°

dihedral
angle
[二面角]
 Ch 2 #40

RT

RT

 ∆G = – RT ln K  K = exp [– ∆G/RT]
 K = exp [– 2.9/(.002)(300)] = .008 at 300 K
 Prob(eclipsed) = .008/1.008 = .8% at 300 K
 Most of ethane molecule is in staggered conformation.
= Ethane is in staggered conformation most of times.
Conformations of butane Ch 2 #41

 3 max (syn, eclipsed) and 3 min (anti, gauche)

(syn) gauche eclipsed anti eclipsed gauche

 Ch 2 #42

 anti
 of the lowest energy
(most stable)

 gauche
H3C CH3

 higher energy than anti due to

steric strain ~ repulsion between (non-bonded) groups ~ 0.87
 eclipsed
 torsional + steric strain
 1 x 3 + 0.4 x 2 = 3.8
 Ch 2 #43

 (syn)

 of the highest energy

 torsional + steric strain
 1 x 3 + 1.5 = 4.5
 higher alkanes

 all-anti  planar zigzag ~ most stable, but not most probable

Conformations of cycloalkanes Ch 2 #44

 6- (and 5-)membered rings are most popular.

 Cyclic comp’ds are strained. (angle+torsional+steric strain)
 strain ~ 6, 12 or larger < 5, 7-11 < 4 < 3

equivalent to Table 2.9 p104

 Ch 2 #45

 cyclopropane
 (has to be) planar
 high angle strain
 high torsional strain (planar)
 most highly strained
 cyclobutane
 if planar, 90° bond angle and fully eclipsed
 by puckering, angle strain , torsional strain 
 slightly nonplanar [puckered] ~ butterfly
 still, (highly) strained
 Ch 2 #46

 cyclopentane
 If planar, 108° bond angle (no angle strain) and eclipsed
 puckered to relieve torsional strain
 envelope
 little strained

 cyclohexane
 If planar, 120° and fully eclipsed
 puckered to reduce angle and torsional strain
 chair comformation
 virtually strain free (110° and staggered)
 Ch 2 #47

 cycloheptane
 nonplanar
 a little higher (angle and torsional) strain than cx, close to
cyclopentane
 rings betw C8 – C11
 very small angle and torsional strain
 transannular [cross-ring] strain (interior of the ring) arises
 similar total strain to those of C5 and C7, but not so popular
 rings larger than C12
 strain-free
 not popular
Drawing cx (chair) Ch 2 #48

 3 pairs of parallel ring bonds

 6 axial and 6 equatorial (subs) bonds

H
axial hydrogen

H
equatorial H

H
4
H
5
Conformations of cx Ch 2 #49

 chair and boat conformation

 Boat conformer is of higher strain

 torsional ~ 4 eclipsed
 steric ~ flagpole H
Ring flip of cx Ch 2 #50

 chair – boat – chair

 axial-equatorial change
 low E barrier ~ rapid equili of chairs

twist-boat
Monosubstituted cx Ch 2 #51

 methylcyclohexane CH3

CH3

 2 chair conformations are not identical (in energy)

 axial-Me-cx is of higher steric strain than equatorial-Me-cx.
 due to 1,3-diaxial interactions

H CH3
H
5 1 3 1
2
3

 Energy of 1,3-diaxial = E of 2 gauches = 2 x .87 = 1.74 kcal/mol

 Ch 2 #52

 Equili favored to equatorial CH3

 ∆G = –1.74 kcal/mol = –RT ln K K

CH3
 K = exp [1.74/.6] = 18 at 300 K
 Prob(equatorial) = 18/(1+18) = .95 at 300 K

H CH2CH3
CH3
H
H CH3
H

Me
Me
H Me
H

‘frozen’
Disubstituted cx Ch 2 #53

 1,2-dimethylcyclohexane

Me Me
Me
Me

Me
 cis-trans isomers [geometric isomers] Me

 not conformers
 Each has conformers.
 different configuration
 need breaking bonds to change
 different compounds with different mp, bp, ---
 Ch 2 #54

 trans-1,2-Me2cx is more stable.

cis-

.87 x 3 = 2.6 kcal/mol

trans-

.87 x 4 = 3.5 kcal/mol .87 kcal/mol

 Ch 2 #55

 1,4-Me2cx
 trans-isomer is more stable. ~ fully explained in the textbook
 1,3-Me2cx
 cis-isomer more stable ~ prove this by yourself
 1-tert-butyl-3-methylcyclohexane
Fused rings Ch 2 #56

 trans-fused rings are more stable.

 hormones, steroids, cholesterol