Chapter 2

Representative Carbon Compounds

2.1 Hydrocarbons
H H C H
saturated
H H C C C H C H C C H H

Methane An alkane

H C H C

H H

Ethene An alkene

Ethyne H An alkyne

Benzene An aromatic

unsaturated compounds (can react with H2)

2.1D Aromatics
In organic chemistry, aromatic has nothing to do with the

sense of smell. Compounds with benzene ring(s) are aromatic. There are other types of aromatics besides benzene derivatives (next semester). Bubblegum flavor is a mix of 3 aromatics:

cinnamon

vanilla

wintergreen

2.2 Polar Covalent Bonds

In a covalent bond, electronegativity differences often pull

bonding electrons closer to one atom. This effect polarizes the bond; each atom has a partial charge (one positive, one negative). There are three ways to represent polar covalent bonding:

Partial

CO

charges Bond polarity Electrostatic potential map

2.2A 2.3 Polar Maps Covalent of Electrostatic Bonds Potential

The surface + of the- molecule is colored to show the

and negative charge. of positive distribution Blue = positive; red = negative The spherical shape of the map around the nuclei represents electron density.

2.3 Polar vs Nonpolar Molecules

Polar molecules have nonzero dipole moments.
Dipole moment the vector sum of individual bond

polarities.
The 4 bond polaritiesc cancel out.
The CCl bond polarity gives rise to the dipole moment. The CH bond dipole is minor and insignficant.

2.3 Dipole Moment

+ + + + + + + + + + + + +

Dipole moment is measured by

placing a sample between 2 oppositely charged plates. Samples with non-zero dipole moments conduct a current because their positive and negative sides line up along the plates.

2.3 Dipole Moment

Which of the following has a dipole moment of zero?

There is no way to orient this ion between two

charged plates so that one side of the molecule is positive and one is negative.

2.4 Functional Groups

Functional groups arrangements of atoms that

indicate how a molecule reacts; e.g., the alcohol FG has a C-O-H linkage and all alcohols react similarly.
ALCOHOLS
H H C H H C H
HO

OH
OH

ethanol

cholesterol

menthol

2.4 Functional Groups

Functional groups arrangements of atoms that

indicate how a molecule reacts; e.g., the alcohol FG has a C-O-H linkage and all alcohols react similarly.
ALCOHOLS ALCOHOL in oxidation strong acid base
H H H C H H C C
H H H

H H H

H
+-

C O O C O OH
H H

H
H
H O+ O O O
-

2.4A More Alkyl Groups

Alkyl groups = alkane H atom Named by replacing the ane suffix of the parent alkane

with yl The H atom that is removed is substituted with another atom or group. H H
H H C H

H C H

H C H

H C OH H

Cl

C H

NH2

methane methyl methyl alcohol methyl chloride group methylamine

2.4A Alkyl Groups

H H C H H C H H H H C H H C H

ethane
H H C H H C H H C H H H

ethyl group
H C H H C H H C H H H C H H C H C H H

propane

propyl group

isopropyl group

2.4A Alkyl Group Abbreviations

R is general for any alkyl group.
For example, ROH = any alcohol. Alkyl groups of 4 carbons or fewer have symbols:
Condensed Formula CH3 CH3CH2 CH3CH2CH2 (CH3)2CH Alkyl Group Methyl Ethyl Propyl Isopropyl Symbol Me Et Pr i-Pr

2.4B Phenyl and Benzyl Groups

A phenyl group is a benzene ring minus a hydrogen. A benzyl group is methylbenzene minus a hydrogen.
HH H H H C H H C H C H

H
C C

H C

CC C C HH C C C C CH H 2

C
C C

CH2 ? ? C

Bn Ph ??

CC C C HH H H

C
H

methylbenzene benzene

benzyl phenylgroup group

methyl : alkane :: phenyl : aromatic

2.5 Alkyl Halides (Haloalkanes)

Alkyl halides have an alkyl group attached to:

F, Cl, Br or I (halogens or X)
Alkyl halides are classified as methyl, primary (1),

secondary (2) or tertiary (3). Consider the C atom directly attached to the halogen (CX) and determine how many C atoms are attached to CX.

2.5 Alkyl Halides

What is the degree of substitution (methyl, 1, 2 or 3)

for the following alkyl halides?

H F C H C H C H H H

H H C H

H C H

H C Cl

H C H

2
H H

I C H H

C H H

H Br C H

H C H

H C H

H C H H

2.6 Alcohols
The alcohol functional group is a hydroxyl (OH) group

attached to an sp3-hybridized carbon. Just like alkyl halides, alcohols are classified as methyl, primary (1), secondary (2) or tertiary (3).

2.6 Alcohols
What is the degree of substitution (methyl, 1, 2 or 3)

for the following alcohols?

1 H
OH

H C H

H C H OH

H H C H

F C

H
HO

OH H

2.7 Ethers
Ethers have oxygen atoms bound to two carbons. The groups bound to oxygen can be alkyl or phenyl. Since they are so unreactive, ethers make good

solvents.

2.8 Amines
Amines have one or more alkyl groups attached to

nitrogen. Amines are classified as 1, 2 or 3 based on the number of carbons attached to N.

C N H
1 amine

N C

N C

2 amine

3 amine

2.8 Amine Geometry

Amines, like ammonia, have trigonal pyramidal

molecular geometry. The amine N is sp3-hybridized; most amine chemistry occurs at the lone pair.

trimethylamine

2.9 The Carbonyl Subgroup

The carbonyl group is a carbon-oxygen double bond. Its not a functional group itself, but a part of other FGs. The two atoms or groups on C dictate the FG.

O C
carbonyl subgroup

2.9 The Carbonyl Subgroup

O O C C C C H/C OH H/C O C H/C N O C O C

O C
carbonyl subgroup

2.9 Aldehydes and Ketones

Aldehydes always have a H bound to the carbonyl group;

the other atom can be H (formaldehyde) or C. Ketones have two carbons bound to the carbonyl group. Aldehydes and ketones are grouped together because they have similar reactivity.

O C H H/C

O C C
ketone

aldehyde

2.10 Carboxylic Acids, Esters and Amides

Carboxylic acids, esters and amides are

grouped together because they are all interconvertible by simple chemical reactions.
O C H/C O H H/C O C O C
H/C O C N

carboxylic acid

ester

amide

2.10A Carboxylic Acids, RCO2H

Carboxylic acids are so named because the H atom on

oxygen is acidic. They range in acid strength from weak to strong.

O F C F F C O H O

O
O
-

F C F F

F C F F

C O

+ H+

The pKa of trifluoroacetic acid (above) is 0.23. pKa (H3PO4) = 2.15; pKa (HCl) = -2.2.

2.10B Esters, RCO2R

Esters are typically formed by reaction of

carboxylic acids and alcohols:

O C R OH O

+ ROH
R

C OR'

+ H2O

carboxylic acid

ester

2.10C Amides
Amides are commonly formed by reaction of

carboxylic acids and amines:

O C R O H
O

+ NHRR
amine

C R N R'

R"

carboxylic acid

amide

2.11 Nitriles, RCN

Nitriles have a CCN bond linkage. The CN bond in nitriles resembles the CC bond in

alkynes.
H H C H C N

CN
O

CN

ethanenitrile

benzonitrile

cyanoacrylate

Identifying Functional Groups

H H H H H H O O O O H H
H C C H H H H H H H C C C C CC C NH C Cl H2 N

CH NH OH H3 H H H H H H H H OCH 23

ester alkyl carboxylic halide aromatic aldehyde ketone alkane alkene amine alkyne amide nitrile or haloalkane acid

2.13 Physical Properties and Molecular Structure

By analyzing molecular structure, you can predict

physical properties such as:

Melting point

Boiling point

Solubility

2.13B Intermolecular Forces

What are the three intermolecular forces?
1. Dipole-dipole forces

2. Hydrogen bonding
3. Dispersion forces (instantaneous dipole)

2.13B Attractive Electric Forces

2.13B Dipole-dipole Forces

Dipole-dipole forces cause molecules with dipole

moments to approach each other at opposite poles.

Blue = d+ Red = d-

2.13B Hydrogen Bonds

Hydrogen Bonds

molecules with HX bonds (X = N, O, F). N, O and F only because they are:

strong dipole-dipole forces in

Small; molecules can approach closely Very electronegative; strong partial charges on H and X

O C H N H H H

O C N H CH3

O C H N CH3

CH3

Which of these has the highest153 boiling point? 210 C compounds 198

H Bonds:

2.13B Dispersion Forces

Present in all atoms, molecules

and ions Caused by temporary buildup of charge at one part of a particle (instantaneous dipole) that in turn induces a dipole in its neighbor. Responsible for liquid and solid phases of nonpolar molecules.

2.13D Solubility
Will solute A dissolve in solvent B? Like dissolves like If A is ionic, YES if strong ion(A) - dipole(B) interactions If A is polar covalent, YES if strong dipole(A) - dipole(B) interactions If A is nonpolar covalent, YES if B is nonpolar.
O HO CH3

oleic acid (olive oil)

O C CH3

HO

acetic acid (vinegar)

2.14E Water Solubility

In general, for compounds with one very polar group:

Number of Carbons 1-3

Water Solubility High

4-5 6+
O

Moderate Low
HO
O

OH OH
H H C H F

O
CH3

HO

Cl

CH3

HO HO O H

Yes

No

Kind of

Yes

No

Are these soluble in water?

2.15 Infrared (IR) Spectroscopy

IR spectroscopy reveals a molecules functional

groups, not its entire structure. Most organic molecules absorb IR radiation. IR absorptions produce transitions from low to high vibrational levels within molecules. DE(Absorption of an IR photon) 1 10 kcal/mol It takes < 1 min to acquire an IR spectra.

2.15 An Infrared (IR) Spectra

The most diagnostic IR region 1 is 4000 - 1300 cm1; here you will find peaks

x-axis: 4000 - 400 cm

corresponding to FGs. percent transmittance ( absorbance). y-axis: The fingerprint region is 1300 - 400 cm1 and is unique to every compound.

(mid-IR region)

wavenumber, =1/l units are cm-1

H H C H OH

This is the IR spectra of methanol.

C H

OH

2.15 IR Absorptions

DE = hn

Wavenumber (1/l) is proportional to frequency, frequency, increasing increasing

wavenumber (increasing, decreasing) energy. A (triple, double, single) bond is the strongest bond. The highest wavenumbers are required to vibrate a (triple, double, single) bond.

2.15 Frequency of IR Absorptions

Single bonds (except for H-X) appear on the right side of the

spectrum since they are generally weaker bonds. H-X bonds appear on the left because hydrogen has the smallest mass.

2.15 Frequency of IR Absorptions

This molecule has carbon-carbon single, double and triple bonds.

Which highlighted peak corresponds to each bond?

Stronger bond, higher frequency

CC

C=C

CC

2.15 Frequency of IR Absorptions

The wavenumber of absorption of a CH bond is dependent on

the hybridization state of the carbon atom.

CH3 H CH3

CCH

C=CH

CCH

2.15 Interpreting IR Spectra

You cant figure out a compounds entire structure by IR,

only its functional groups. Most of the peaks on an IR spectrum are not useful. To interpret an IR, consider what FGs may be present in the molecule (based on molecular formula) and look for their characteristic peaks.

2.15A IRs of Alkenes

The fingerprint region is useful

for determining alkene substitution.

2.15B IR Spectra of Carbonyls

A C=O bond appears as a very strong, sharp peak between

1630 1780 cm-1. The peak usually dominates the spectra.

carboxylic ketone aldehyde acid (CH [CH (CH (CH CHO) ) ) CO ester amide (CH [HCON(CH CCO CH )2 ]) 2H] 3COCH 3 3 2CH 34 2 2CH 2 3 3

Rings and Multiple Bonds

H H C H H C H H

H C C H H C H

propane C3H8

C H

cyclopropane C3H6

propene C3H6

propyne C3H4

4.17 Index of Hydrogen Deficiency

IHD = multiple bonds and/or rings in a molecule.

The formula is:

O, S: just ignore them. Halogens: convert them to H. N: subtract 1 H, then ignore them

general alkane formula: CnH2n+2

4.17 Index of Hydrogen Deficiency

If the molecular formula of Prozac is C17H18F3NO, what

is its IHD?

C17H18F3NO C17H18H3NO C17H17H3NO C17H20

IHD = (C17H36 - C17H20)/2 = 8

4.17 Index of Hydrogen Deficiency

If the molecular formula of paclitaxel (a chemotheraputic

drug) is C47H51NO14, what is its IHD?

C47H51NO14 C47H51N C47H50

IHD = (C47H96 - C47H50)/2 = 23

4.17 Index of Hydrogen Deficiency

If digitoxin (shown below) has 41 carbons, how many

hydrogens does it have?

IHD 10 = (C41H96 84 - C41Hx)/2 x = 64

O C H

2.16 IR
following IR. What is the compound?

C H

A compound with molecular formula C2H4O has the

amide c. acid aldehyde ketone ester

C=O

# rings/multiple bonds = 1

2.16 IR

CH3(CH2)3CCH

What is a possible structure for a compound with

molecular formula C6H10 and the following IR?

CCH stretch CC stretch CCH bend

# rings/multiple bonds = 2

2.15B IR Spectra of Alcohols and Phenols

A phenol is an OH group attached to a benzene ring:
OH

OH

alcohol

phenol

In IR, the OH bond of an alcohol or phenol has two

possible appearances depending on whether the IR sample was concentrated or dilute:

Concentration Dilute Concentrated Frequency 3200 3550 2500 3000 Intensity Sharp Broad, strong

2.15B IR Spectra of Alcohols and Phenols

phenol PhOH2CH2CH3] alcohol [CH 3CH(OH)CH

2.16B IR Spectra of Carboxylic Acids

In IR, carboxylic acids have a very strong C=O peak and a

broad OH at 2500 3000 cm-1.

carboxylic acid, CH3CH2C(CH3)2CO2H

2.15B IR Spectra of Carboxylic Acids

When concentrated, carboxylic acids can hydrogen bond to

themselves:

R H O C R O H O C O

2.15B IR Spectra of Amines

The substitution of amines can be determined by IR by

counting the number of (medium-sized) peaks in the 3300 3500 cm-1 region.

H 2 H-bonds 2 peaks

C 1 H-bonds 1 peaks

C 0 H-bonds 0 peaks

2.15B IR Spectra of Amines

Amine N-H peaks are usually stubby. For 1 amines, the two

N-H peaks have the same %T.

CH3(CH2)9NH2 NH2CH2CH2CH2NH2

2.15B IR
What is a possible structure for a compound with

molecular formula C7H13N and the following IR?

amine amide nitrile

# rings/multiple bonds = 2

What functional groups have N?