Spectroscopy

IR
Infrared Spectroscopy (IR) measures the frequency at which covalent bonds bend, stretch, and rotate when the molecule is irradiated with light in the infrared region.

IR spectroscopy is primarily used on the MCAT to identify the specific functional groups that a molecule contains.

What you need to know: - 3200 3600 cm-1: OH (broad) and NH (sharp) - 1680 1750 cm-1: C=O (strong)

IR defined

p. 248

Spectroscopy
NMR
Nuclear Magnetic Resonance (NMR) exploits the inherent spin of odd-numbered nuclei. When such a sample is placed in an applied magnetic field, nuclei in the lower energy state are promoted to a higher energy state. NMR measures the frequency of this energy difference. What you need to know about proton NMR: sp2
C C O C H 10 8 H 6 ppm downfield (deshielded) C H 4.5 O C H H C H 0
~2.5 ppm sp

sp3

p. 249

Spectroscopy
NMR
sp3

0 - 4.5 ppm peaks; hydrogen retains almost full electron cloud. 2 - 4 ppm peaks; shielded hydrogens share some electron cloud.

sp

sp2

4.5 -10 ppm peaks; deshielded hydrogens have smaller electron cloud. 6 - 8 ppm peaks; from hydrogen electron clouds on aromatic sp2 carbons .

aromatic

ewgs

1-2 shift in ppm; electron withdrawing groups pull downfield.

aldehydic

9-10 ppm peaks; carboxylic groups further shifted (10-12 ppm).

p. 249

Aldehydes and Ketones

Naming Convention
Aldehyde/Ketone common names

IUPAC name: 2-propanone Common name: acetone

IUPAC name: benzaldehyde Common name: benzaldehyde

IUPAC name: ethanal Common name: acetaldehyde

IUPAC name: methanal Common name: formaldehyde

Directed Practice Organic Chemistry Review Notes: Chapter 8 (Aldehydes and Ketones)

p. 250

Aldehydes and Ketones

Key Reaction
Because the carbonyl carbon is an electrophile, a key reaction of aldehydes and ketones involves nucleophilic addition by a strong nucleophile.

a tetrahedral intermediate a strong nucleophile! strong nucleophiles: - OH, OR, CN, H, RMgX (R) weak nucleophiles: - H2O, ROH, NH3 (neutral!) - need an acid catalyst (usually H+)

p. 252

Aldehydes and Ketones

Critical Thinking Exercise
What question should you always ask yourself after an attack on a carbonyl?

Ask, Do I have a leaving group? (Can I re-form the carbonyl?) Question: How do you recognize a leaving group? Answer: By what it is not! - a hydrogen never leaves. - a carbon never leaves. - everything else can. Usual LGs are . . . (a) -S
CTE: reform the carbonyl

best LG of the three decent LG lousy LG

(b) -O (c) -N

The takeaway: - only aldehydes and ketones undergo addition to the carbonyl. - all other carbonyl-containing compounds undergo substitution.

Restoring the carbonyl group gives a more stable (favored) final state. Adding an external H+ is still possible, but a carbonyl will always be preferred.

p. 252

Aldehydes and Ketones

Acid-catalyzed formation of a Hemiketal from a ketone
(II) Td

(I)

(III)

(IV)

a weak nucleophile!

p. 252

Aldehydes and Ketones

Acid-catalyzed reaction of hemiacetals to make acetals
(III)

(I)

(IV) (II) H+

H (IIIa)

Directed Practice Organic Chemistry Review Notes: Chapter 8 (Aldehydes and Ketones)

p. 252

Aldehydes and Ketones

Wolff-Kishner Reduction of a carbonyl to make an alkane

in base Also:
Zn(Hg) conc. HCl

in acid

This is the Clemmenson reduction.

Wittig Reaction of carbonyl with phosphonium ylide to make an alkene

+

Wolf-Kishner and Wittig Reaction

Note: your Lesson Book should have this!

R1
:

R1 R3 R2

R3

R2

R4

R4

p. 253

Carboxylic Acids
Nomenclature
Common Examples

2-hydroxypropanoic acid (lactic acid)

2-methylpropenoic acid

ethanedioic acid (oxalic acid)

cyclohexanecarboxylic acid
Carboxylic Acid common names

2-butyl-heptanoic acid
*

p. 255

Carboxylic Acids
Critical Thinking Exercise
Which is more acidic, Cl3CCOOH or ClCH2COOH?

More Cl groups => better induction. This is a # effect.

Which is more acidic, FCH2COOH or CH3OCH2COOH?

F is more electronegative than O => better induction. This is an EN effect.

Which is more acidic, FCH2CH2COOH or CH3CHFCOOH?

Closer F group => better induction. This is a proximity effect.

The mantra: electron-density withdrawing groups make acids stronger.

Question:
CTE: induction effects

How do you recognize an electron withdrawing group? - it is an EAS deactivator (halogen / nitro / carbonyl / cyano). *

p. 256

Carboxylic Acids
Synthesis
Oxidative cleavage of alkenes
The oxidative cleavage of alkenes also produces carboxylic acids.

KMnO4

KMnO4,

p. 258

Oxidative cleavage, alkenes

Carboxylic Acid Derivatives

*

Nomenclature
Derivative

Naming chart/rules

Structure

Name of Derivative

Acid chloride

ethanoyl chloride

Acid anhydride

benzoic anhydride

Ester

isopropyl propanoate

Amide

N-benzyl ethanamide

Directed Practice

p. 259

Organic Chemistry Review Notes: Chapter 10 (Carboxylic Acid Derivatives)

Carboxylic Acid Derivatives

*

Order of Reactivity
Rank the following carboxylic acid derivatives in order of reactivity. LG Conjugate Acid: pKa HX : 6

Most reactive Acyl halide

3b

3a
Acid anhydride RCOOH: ~5

2
Ester Carboxylic acid ROH/HOH : ~16

Amide

R2N-H : ~33 Takeaway: The stronger the conjugate acid of the LG {the more () the pKa}, the more reactive the acyl derivative!

Least reactive
Reactivity of derivatives

p. 261

Carbonyl Compounds as Nucleophiles

Aldol Condensation Step 1: aldehyde enolate

Stop here with aldol, unless . . .

Step 2: enolate attacks a second aldehyde molecule

Td

. . . if heat, then Step 4: dehydration

Step 3: protonation . . . because theres no LG

p. 263

Aldol Condensation

Carbonyl Compounds as Nucleophiles

The Claisen condensation reaction

Td, with LG

Similar mechanism: enolate attacks a carbonyl carbon, but different reaction. Aldol rxn = net addition. Claisen rxn = net substitution. p. 264
Claisen condensation