LECTURE

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Functional Groups Carbonyl

O C R O C R O H R

Ketone

O wants e-, making carbon electrophilic

Aldehyde

H attached adjacent to carbon is acidic (resonance)

Ester

R O C R O C R

OR

Acid Halide X= halogen

Of all Carbonyl derivatives acid halide most reactive

Carboxylic Acid

The proton on the OH is acidic

Nitro
R NH2
O C R

OH

Amine Amide

we see these in Amino Acids They are stable (we want proteins stable) Resonance, double bond character
O C R NH2

NH2

O H2C CH2

epoxide

Ring strain, not stable

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Alkyl Fragments
CH3

Commonly seen on MCAT Methyl Ethyl

CH2CH3

CH2CH2CH3

N-propyl (normal) Iso-propyl

H3C CH H3C

CH2CH2CH2CH3

N-butyl Tert-butyl

CH3 H3C C CH3

O H3C C

Acetyl (Ac)

Hydrocarbons Boiling point Increase MW

Increase BP

Branching

Increase Branching

Decrease BP

*Shorter alkanes usually are seen in the form of gas (think methane/ethane) *Hexane/octane usually liquid (think gasoline in your car) *20+ are solids In mixture low branching will react closer harder to separate.
vs

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Degrees unsaturation *formula to know* -usually seen in rings & alkenes -Saturated= fully bonded, reduced. Units of unsat= (2n+2)-x n= # carbons, X= # hydrogens + mono val atoms (N, Hal) 2 Hybridization -Count # grps around atom & put into orbital TRUE sp3 vs not true sp3 True sp3 is 4 single bonds Not True sp3 is when you have long pairs Inductive Effect -used to spread out charge and stabilize molecules Radicals Carbocation (also referred to on MCAT as carbonium ion) Carbanion Which is most stable is important to know for MCAT Carbocation Series formed by heterolytic cleavage one atoms takes off with both e-, the other is left deficient
>

>

>>>

Radical Series: Formed by homolytic cleavage one atom takes one electron Carbocation and radicals behave the same due to inductive effect more substituted (3o) the more stable

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Carbanion Series
<

<

<

3o least stable anion

CH3

too many electrons!!! Via inductive effect Resonance - share e- via double bond - delocalize into system= conjugation example:
NO2
NO2 NO2 NO2

H3C

CH3

Br

MCAT likes to ask how MANY of something - resonance= #db in conjugated system +1 - =3

only non sp2 carbon

Br

Br

Br

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Terms to point out on MCAT H Allylic

H2C C CH2

Benzylic
CH2

Carbocation is one step away from double bond allowing delocalization Even though the carbocation series just said 1o is less stable than 3o, this one is more stable than 3o carbocation. This particular arrangement has resonance! Ring form of allylic

Steric hindrance

Torsional Strain

Ring strain Stability

most strain < 60o 90o <

Happiest

e- clouds form non- covalent bond of atoms interacting Larger groups have larger clouds making it harder for something to come in and bond *Think of enzyme and active site that is phosphorolyated e- clouds on same molecule colliding. i.e. protein folding certain residues dont like to interact

109.5o

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Isomers & Chirality Isomer: Same molecular formula Structural Isomer: Do not have same connectivity Another name on MCAT: constitutional isomers (different constit)
CH3 Cl Cl CH3 Br

Br Confirmational Isomers: Same connectivity - different in rotation around single bond

H H

H CH3

H3C

Take grp rotate forward into board Left out of board Right With Carb in front

Newman Projection

rotate 60o

rotate 60o Eclipsed

Anti/Staggered

Guache

MCAT loves stability questions, in general. Which is most stable confirmation? -ANTI/STAGGERED -biggest groups furthers apart -think e- cloud

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Configurational Isomers: same form, same connectivity but different spatial arrangement of atoms chiral (cant superimpose) 4 different substituent groups attached rotate light (polarized light) *If you have a chiral center, you can assign absolute configuration CH2OH C H CH2CH3 determine that you have 4 different grps OH
2
CH2OH C OH

3
CH2CH3

Rank according to atomic number

1
H H3CH2C C OH

CH2OH

Lowest priority grp in back ** if not, just reverse configuration

To note for Absolute Configuration: *Double bond counts as if attached to two atoms *H vs D atomic mass
1

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Enantiomers: non superimposable mirror images - look for chiral centers

O

2
C

OH

HO

2
C

O H

4H 1 Br

3
CH2CH3

3
H3CH2C

C Br

Due to chiral centers the molecules will have opposite configuration! -50/50 mix racemate/racemic mixture Unless optical activity value is given, you dont know any information This is the only time on MCAT know about optical activity 0- they counter-act. Equal and opposite Diasteriomers: stereoisomers that are not enantiomers. two or more stereoisomers of a compound have different configurations at one or more (but not all) of the equivalent stereocenters (see in sugars a lot) MCAT tries to confuse you with these!
S
CHO H HO H H OH H OH OH CH2OH H H H H CHO OH OH OH OH CH2OH

All carbons not on end are chiral centers

1 stereocenter differs so we have diastereomers Can separate Enantiomers? do differ in any physical properties? NO polarimitry is not a separation tech Can you separate Diastereomers? YES slightly different properties fractional distillation is viable (intramolecular forces differ slightly)
D-Glucose D-Allose

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Meso Compound: plane of symmetry Mirror image of self

CH3 H H CH3 OH OH

Fischer Projection up= back side= out

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Lab Techniques -always show up in organic section -most common is H1 NMR and TLC -others show up commonly as answer choices - so just know what they are and property it is assessing We can break Lab techniques into 2 categories 1) Ways to identify 2) Ways to separate (different lecture) 1) Identification -Most Common on MCAT a) Infrared Spectroscopy: IR -Identify fnal groups on molecule -Essentially covalent bonds, vibrating- generating dipoles picked up by transmittance/absorbance - if group has no dipole (diatomic molecule such as N2) IR will not pick up anything -used when running reaction to see if it has gone to completion or any change - MCAT focuses on did I get a new bond or group does the test taker know what is going on here? IR Frequencies (cm-1) Single bonds to H 3700-2500 Double Bonds Triple Bonds *OH *C=O C=C C=C C=N 10 1900-1500 2300-2000 3600-3200 1760-1670 1680-1640 2260-2100 2260-2220

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

-ranges b/c type of molecule can change the properties of frequency *two most common- you would be safe to go into MCAT knowing just these two and knowing properties to gauge others

11

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

correlates to fn'al groups

Plot
broad peak

sm (% ittan ) ce

tra n

sharp peak

4,000

wave numbers (cm-1)

400

For MCAT know: carbonyl 1760-1670 sharp band OH 3600-3200 broad band If the MCAT gets nitty gritty they give a table one in a HW passage b) Nuclear Magnetic Resonance: H1 NMR -4 properties to be familiar with and be able to asses -chemical equivalency -integration (how many contribute to particular peak) -splitting (H on neighboring atom?) -chemical shift (how far move peak down spectrum) -Protons spinning- hit with radio-waves to spin synchronously -towards TMS = more shielded (upfield) -TMS is standard usually ~1 -shield surrounded by e- clouds (such as R groups) -deshielded e- hogged (e- neg atoms) (such as aldehyde ~10)
CH3 H3C C CH3 CH3

completely shielded Chemical Shifts ( ) -CH3 have lower shift than CH2 -Protons attached to C=C ~5-7.5 -Protons on benzene ring ~6-9 -Protons attached to aldehyde or carboxylic acids ~10-13

12

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Plot
downeld deshielded upeld shielded

ity ns e t n
TMS Tetramethyl siline

5 14

3 PPM

Example 1:
Hb Hb C Hb Cl C Cl Ha Cl H C H H C H Cl

1,1 dichloroethane #1

Sometimes MCAT asks how many different peaks will you get? -how many different H? Equivalency: #1- 2 different H all 3Hb rotate around C single bond #2- 1 H symmetry Integration: #1- Ha 1H contributes Hb 3H contribute #2- 4H contribute - more area under curve since more H contribute Splitting: Spin-spin coupling uses n+1 rule # H on neighboring atom + 1= how many peaks split #1- Ha how many H on neighboring atoms? 3 3+1= 4 Quartet Hb how many H on neighboring atoms? 1 1+1= 2 Doublet #2- 2+1= 2 Triplet

1,2 dichloroethane #2

13

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Overall: Shift:

#1- Ha 1H Quartet Hb 3H Doublet #2- 4H Triplet #1- Ha shift further b/c attached to C attached to electroneg atom -Cl pulls e- away from C deshielding H Ha downfield Hb upfield

Example 2 (if time):

Ha Cl C Ha

Hb C Hb

Ha C Ha Cl

Do we have symmetry? Yes chemical equivalence How many peaks do we expect? 2 Types of peaks: Ha: 4H Triplet downfield Integration= 4H splitting= triplet (2 neighbors) shift= downfield (attached to C attached to electroneg atom) Hb: 2H Quintet upfield Integration= 2H Splitting= quintet (4 neighbors) Shift= upfield
TMS 4H Quartet 2H Quintet

Upfield/downfield is fair game on MCAT- has been seen - which is more desheilded? A closest to electroneg atoms More often questions arise such as: -how many different peaks -what is the integration -how many H contribute to splitting 14

10ppm

0ppm

LECTURE 1

CHAPTER 3 & 7; ICC 1, 2 ,3, 13 & 14 OCHEM

Examples:

c) Nuclear Magnetic Resonance: C13NMR -measure how many non equivalent carbons -seen 1 question on practice ask about shifting - not very likely so dont waste time on memorizing shifts

CH3 O

1 peak

5 peaks symmetry

usually see the following as answer choices: d) Mass Spectrum -Measures Mass/charge ratio e) UV Spec -used for molecules that are conjugated -lot of resonance e- movement -similar to Infrared f) Visible Light Spectrum -transition metal ions utilizing color rays

4 peaks no symmetry

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