Mike's Videos - Organic Chemistry Lesson Outline

Dr.
Mike’s O-Chem Outline
Chapter 1: Bonding, Resonance, and Molecular

Geometry
Lesson 1 – Meet Dr. Mike Christiansen!
👋 -Dr. Mike
Lesson 2 – Molecular Bonding Geometry and Hybridization
Electron Bond
Geometry Hybridization
Domains Angle
2 Linear 180 sp
3 Trigonal planar 120 sp2
4 Tetrahedral 109.5 sp3
Lesson 3 – Condensed Formulas and Line-Bond Formulas
Lesson 4 – Sigma and Pi Bonds
Type of covalent bond Number of bonds
Single bond one sigma (σ)
Double bond one sigma (σ) + one pi (π)
Triple bond one sigma (σ) and two pi (π)
Lesson 5 – Orbital Hybridization
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Dr. Mike’s O-Chem Outline
Lesson 6 – Resonance Structures
Definition
There are some molecules that have pi electrons that can move around from one atom to another. For example, the
following molecules (A and B) are both different forms of acetate:
Structures A and B are called resonance structures (or resonance contributors). In reality, acetate actually exists
somewhere in-between A and B, with the – charge being shared equally by the two oxygens.
Resonance Rules
When drawing different resonance structures, remember:
1. Only electrons move. Specifically, only pi electrons, lone-pair electrons, or negative charges can move. Do
NOT move atoms.
2. You CAN move electrons toward or into an atom that does NOT have a full octet, such as carbocations.
3. If an atom already HAS a full octet, then you can move electrons into it ONLY IF you push electrons out the
opposite side (electrons in, electrons out).
4. Do not move or break sigma bonds, only pi bonds.
Determining Greatest Resonance Contributor

1. The most stable resonance structure will have a full octet on every atom.
2. The most stable resonance structure will have the smallest possible number of charges.
3. The most stable resonance structure will have negative charges on the most electronegative atoms and
positive charges on the least electronegative atoms.
Lesson 7 – Newman Projections
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Lesson 8 – Cycloalkanes and Ring Strain
Cycloalkanes are alkanes that are cyclic –in other words, ringed alkanes, or alkanes with rings in them.
Cyclohexane is the most stable cycloalkane.
How to draw chair conformations of cyclohexane (follow along!):
Axial vs. Equatorial
● Equatorial positions are more stable (lower energy) than axial positions for larger groups because of
1,3-diaxial interactions.
● Placing the largest substituents in the equatorial positions will usually achieve the greatest stability in
cyclohexane rings.
Trans vs. Cis cyclohexanes
Cis – two substituents going in same direction

Trans – two substituents going in opposite directions
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Chapter 2: Acids and Bases

Lesson 1 – Acid-Base Definitions
● A Lewis acid is a substance that accepts electrons.

● A Lewis base is a substance that donates electrons.
Lesson 2 – Conjugate Base-Acid Relationship and pH Scale

● The stronger the acid, the weaker its conjugate base.
● The stronger the base, the weaker its conjugate acid.
↑ KA = ↓ pKA = ↑ acid strength
● The more stable/weaker the conjugate base, the stronger the acid.
● The more stable/weaker the conjugate acid, the stronger the base.
pKas for Organic Compounds
Lesson 3 – Ranking Acids and Bases with CARDIO (Charge)
If all other factors are the same (or close to the same), then:
● The more positively-charged the compound = the more acidic

● The more negatively-charged the compound = the more basic
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Lesson 4 – Ranking Acids and Bases with CARDIO (Atom)
If all other factors are about the same, then hydrogen’s acidity increases as the atom that it’s bonded to:
● goes left-to-right across a row on the periodic table (increasing electronegativity)

● goes down a column on the periodic table (increasing size)
Lesson 5 – Ranking Acids and Bases with CARDIO (Resonance)
• The more stable the conjugate base, the stronger the acid
• The more stable the conjugate acid, the stronger the base
Resonance increases the stability of charges, therefore a resonance-stabilized conjugate base will be a stronger
acid.
Lesson 6 – Ranking Acids and Bases with CARDIO (Dipole Induction)
● Electron Withdrawing groups increase acidity

● Electron Donating groups decrease acidity
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Lesson 7 – Ranking Acids and Bases with CARDIO (Orbitals)
If all other factors are about the same, then acidity follows the below trend:
(less acidic) H–sp3 atom < H–sp2 atom < H–sp atom (more acidic)
● S-orbitals tend to be more electronegative, so the more “s-character” an atom has, the stronger the acid.
Lesson 8 – Acid and Base Review
How to Sort Acids and Bases by Strength
First, convert the acid to its conjugate base.
1. Charge – Positively charged compounds are typically more acidic, negatively charged compounds are typically
more basic.
2. Atom – The more electronegative/larger the atom with a negative charge, the more acidic the hydrogen is.
3. Resonance – The more resonance-stabilized the conjugate base, the stronger the acid.
4. Dipole Induction – Electron withdrawing groups increase acidity, electron donating groups decrease acidity.
5. Orbitals – The more s-character an atom has, the more electronegative it is, and the more acidic hydrogens
bonded to it will be. i.e. sp3 < sp2 < sp
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Lesson 9 – pH and Amino Acids
To determine the structure or charge of any amino acid:
● If the pH of the solution is LOWER than the pKa of the functional group, the functional group will be
protonated.
● If the pH of the solution is HIGHER than the pKa of the functional group, the functional group will be
deprotonated.
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Chapter 3: Nomenclature
Lesson 1 – IUPAC Basics and Naming Alkanes
Naming Alkanes
1. Find the parent chain, the longest carbon chain. If two possible parent chains have the same length, but
different substituent numberings, pick the one with the smaller substituent number at the first point of
difference.
2. Count the number of carbon atoms in the parent chain and match that number to the name from our
earlier chart (methane, ethane, propane, etc.)
3. Identify and number the substituents (appendage dangling off the parent chain) in whichever direction
gives them the lowest number.
4. Write the name as a single word with the substituents in alphabetical order.
Lesson 2 – Naming Cycloalkanes and Alkyl Halides
Naming Cycloalkanes
1. When there are two substituents on a cyclic molecule, their direction must be indicated with prefix “cis”,
meaning “same side”, or “trans”, meaning “opposite sides”.
2. If there are more than two substituents, “cis” and “trans” are no longer enough, and these substituents must
be named with their stereochemical configurations (R/S system).
Naming Alkyl Halides

When naming alkyl halides, we follow the same rules for naming alkanes, except that we use prefixes “fluoro-“,
“chloro-”, “bromo-”, or “iodo-”, to identify each halogen substituent. Alternatively, we may use suffixes “-yl fluoride”,
“-yl chloride”, “-yl bromide”, or “-yl iodide”.
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Lesson 3 – Naming Alkenes and Alkynes
Naming Alkenes
1. Use the suffix “-ene” instead of “-ane”.
2. Add a number at the start of the double bond.
3. Add prefixes “cis” or “trans” for alkenes with different priority substituents, and at least one hydrogen on
either side of the alkene.
4. If all substituents are different, use the E/Z naming system, where E = highest priority substituents on
opposite sides, and Z = highest priority substituents on the same side.
Determining Priority
1. Highest atomic number = highest priority.
2. If there’s a tie, keep going to adjacent carbons until you break the tie.
3. Multiple-bonded atoms are counted as the same number of single-bonded atoms:
Naming Alkynes
1. Use the suffix “-yne” instead of “-ane”.
2. Add a number at the start of the triple bond.
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Lesson 4 – Naming Alcohols, Ethers, and Amines
When naming alcohols, we follow the rules for naming alkanes, except:
1. The parent chain is now the longest chain that has the hydroxyl group, even if there are longer carbon
chains available.
2. Number the carbon chain in the direction that gives the smallest number to the carbon bonded to the
hydroxyl group.
3. Hydroxyl groups are higher priority than cycloalkanes, amines, alkenes, ethers, and alkyl halides, so they
must be numbered according to the lowest-number carbon that is bonded to the hydroxyl group.
4. Change the suffix “-e” to “-ol”.
When naming ethers:

1. Name the two alkyl groups as substituents with “ether” at the end:
2. Consider the longest carbon chain to be the parent chain and the alkoxy group to be a substituent:
When naming primary amines, add the suffix “amine” to the name of the organic substituent.
Symmetrical and secondary amines are named by adding “di-” or “tri-” to the alkyl group:
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Lesson 5 – Naming Aldehydes and Ketones
When naming aldehydes, we follow the rules for naming alkanes with the addition of two rules:
1. We number the parent chain in the direction that gives highest priority (lowest number) to the aldehyde
(carbonyl) carbon.
2. We replace “e” with “al”.
When naming ketones, we follow the same rules for naming alkanes, except:
1. Similar to aldehydes, the parent chain must be chosen with priority given to the ketone (carbonyl) carbon.
2. Replace the “e” with “one”.
3. The carbonyl carbon in a cyclic ketone is assumed to be the #1 carbon.
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Lesson 6 – Naming Carboxylic Acids and Derivatives
When naming carboxylic acids, we follow the rules for naming alkanes, except:
1. We number the parent chain in the direction that gives the highest priority (lowest number) to the carboxylic
acid group.
2. We replace “e” for “oic acid”.
When naming acid halides:

1. Follow the same rules as for carboxylic acids, and change the suffix to “oyl halide”.
When naming esters:

1. The alkyl group attached to the ester oxygen gets listed first with the suffix “yl”. The parent chain then
follows.
2. The parent chain starts at the carbonyl carbon and is counted moving away from the ester oxygen. Parent
chain’s suffix is replaced with “oate”.
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Lesson 6 – Naming Carboxylic Acids and Derivatives (Continued)
When naming amides, we follow the same pattern of naming for esters, except:
1. Any alkyl groups attached to the nitrogen gets listed as “N-methyl”, “N-ethyl”, “N-propyl” etc.
2. The parent chain starts at the carbonyl carbon and is counted moving away from the amide nitrogen.
3. In the name, the parent chain’s ending “e” is replaced with “amide”.
When naming acid anhydrides:

1. Determine the length of the chain on either side of the bridging oxygen.
2. List both lengths alphabetically, replacing each suffix “e” with “oic”.
3. Write “anhydride” at the end of the name.
When naming nitriles, follow the same rules for naming alkanes, except:
1. The parent chain is the longest carbon chain that involves the nitrile carbon.
2. Number the parent chain in the direction that gives the smallest number to the nitrile carbon.
3. Add the suffix “nitrile” to the parent name.
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Lesson 7 – Naming Aromatics
When naming substituted benzenes:

1. Identify the parent chain, which is the benzene containing the highest-priority functional group. That parent
chain is the parent chain name.
2. The carbon atom in the ring that is attached to the priority functional group is numbered as carbon #1.
3. Number around the ring in whichever direction (clockwise or counterclockwise) that gives the lowest
number at the first point of difference.
4. If the numbers are the same in both directions, pick the one that gives the lower number to the substituent
that is alphabetically first.
Lesson 8 – Naming Polyfunctional Compounds
When naming poly-functional compounds:

1. You must identify the highest-priority functional group. The parent chain containing this functional group is
the parent chain name.
2. Once you identify the parent chain and its functional group, follow the naming rules for that particular
functional group. All other functional groups in the molecule are considered and named as substituents.
Priority of Functional Groups
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Lesson 9 – Naming Spiro and Bicyclic Alkanes
Spiro Alkanes
IUPAC names for spiro alkanes have the format spiro[a.b]parent name.
1. Count the total number of carbons across the entire molecule. This tells you the alkane parent name that
goes at the end.
2. Count the number of carbons to the left, and to the right of your spiro-carbon center. These numbers are a
and b in your IUPAC name, listed from lowest to highest.
3. Write your final IUPAC name as spiro[a.b]parent name.
Bicyclic Alkanes
IUPAC names for bicyclic alkanes have the format bicyclo[a.b.c]parent name.
1. Count the total number of carbons across the entire molecule. This tells you the alkane parent name that
goes at the end.
2. Count the number of carbons to the left, and to the right, and above your bridgehead carbons. These
numbers are a, b, and c in your IUPAC name, listed from highest to lowest.
3. Write your final IUPAC name as bicyclo[a.b.c]parent name.
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Chapter 4: Stereochemistry
Lesson 1 – Isomers
Constitutional Isomers vs. Diastereomers vs. Enantiomers
● Molecules that have the same chemical formula, but a different arrangement of the atoms, are isomers.
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Lesson 2 – Chiral Centers
A chirality center is a carbon center that contains four unique substituents.
When using the R,S naming system:

1. Find your stereocenter atom.
2. Prioritize the four appendages coming off the stereocenter atom using the Cahn-Ingold-Prelog system.
a. Highest priority = highest atomic number.
b. If there’s a tie, keep going out in both directions, one by one, until the tie is broken.
3. Number your substituents 1, 2, 3, 4 (1 = highest priority, 4 = lowest priority)
4. Direct the lowest-priority substituent three-dimensionally away from you.
5. Make a circle from substituent 1 to 2 to 3.
a. Clockwise = R
b. Counterclockwise = S
Examples:
Chiral carbon Enantiomers
S S R
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Lesson 3 – Diastereomers
There are three types of diastereomers:
1. Cis/trans isomers of ringed compounds:
2. Cis/trans or E/Z isomers of alkenes:
3. Stereoisomers with multiple stereocenters that do NOT have exactly-opposite R,S configurations, and are
NOT mirror images of one-another. If stereoisomers are mirror images of one-another (have exact opposite
R,S assignments), they are considered enantiomers.
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Lesson 4 – Counting Stereoisomers
When counting how many stereoisomers one chiral molecule can possibly have, use the equation:
# of possible stereoisomers = 2n
Where “n” is the number of chiral centers.
Lesson 5 – Chirality and Physical Properties
● Chiral molecules have the ability to rotate plane-polarized light when they’re placed in a special machine
called a polarimeter.
● Molecules that don’t rotate plane-polarized light are called achiral or inactive. There are three kinds of
optically-inactive (or achiral) molecules or situations:
1. If you have a 50/50 mixture of two enantiomers, then that mixture (called a racemic mixture) is
achiral, despite all individual molecules being chiral!
2. Molecules that DON’T have stereochemistry in them (because they don’t have stereocenters, or they
don’t have cis/trans stereochemistry in them) are achiral.
3. Meso compounds are achiral.
● Enantiomers share extremely similar physical properties, and may only be distinguished by the direction
that they polarize light, and the way they interact with biological systems (some physiological enzymes may
react with R and not S of a particular molecule).
● Diastereomers have very different physical properties, and are separated easily, such as by boiling points.
Lesson 6 – Meso Compounds
A meso compound is any molecule with two or more chirality centers, and a line of symmetry. An enantiomer of a
meso compound is exactly the same as the original molecule (the two ARE superimposable).
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Lesson 7 – Fischer Projections
Fischer projections are flat representations of three-dimensional molecules. They are especially useful for
assessing chirality. Horizontal lines are used to represent atoms toward us, while vertical lines are used to represent
atoms away from us.
Example:
Lesson 8 – D vs. L Sugars
The “D” and “L” prefix refers to the direction in which a sugar rotates polarized light. Differences between the two
are outlined below:
● “D” and “L” assignments are made by looking at the bottommost OH (colored green) along the spine of a
sugar. If it points to the right, it is “D”, and if it points to the left, it is “L”. Most carbohydrates in nature are
“D”.
● Amino acids are assigned “D” or “L” based on the position of the amino group. Most amino acids in nature
are “L”.
Examples:
D-glyceraldehyde D-Fructose L-Ribose L-Glucose
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Chapter 5: Spectroscopy
Lesson 1 – IR Spectroscopy
IR Spectroscopy Peaks You Should Memorize
If you see the following on your IR spectrum: Then your compound has a:
A BIG point peak at 1700+/-50 cm-1 C=O (carbonyl)

A LARGE, broad trough far to the left for alcohols
OH
and on top of 3000 cm-1 for carboxylic acids
Big, pointy peaks coming straight down around

C-H’s
3000 cm-1
N-H
A sharp peak to the left of 3000 (around 3200-3500) (one peak for –NH, two peaks for
–NH2)
Medium-sized peak at ~2200 C≡N (a nitrile)
Vampire teeth at 1500-1600 and 1300-1400 NO2
● IR spectroscopy is used most often to determine a molecule's functional groups.

● For the DAT, you should also know that:
o Carbon-carbon double bonds (alkenes) are found in the 1600 cm-1 region.
o Carbon-nitrogen double bonds (imines) are also found in the 1600 cm-1 region.
Lesson 2 – UV Vis and Mass Spectrometry
● UV-Vis spectroscopy is used mostly to analyze compounds with conjugated double bonds.
● Mass spectrometry is a technique that lets you determine a compound’s mass.
Lesson 3 – Degrees of Unsaturation
Degrees of unsaturation:
# of degrees of unsaturation = # of double bonds or rings = (A – B)/2
Where A is the number of hydrogen atoms your compound would have if it didn’t have any double bonds or rings
(CnH2n+2), and B is the number of hydrogen atoms your compound in question actually has.
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Lesson 4 – Degrees of Unsaturation Molecular Formula
𝐷𝑒𝑔𝑟𝑒𝑒𝑠 𝑜𝑓 𝑢𝑛𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑖𝑜𝑛 = 𝐶 − ( )− ( )+ ( )+ 1
𝐻
2
𝑋
2
𝑁
2
Lesson 5 – 13C-NMR Spectroscopy
● The more positively-charged an individual carbon is, the further to the left it will appear on an 13C spectrum.
The more negatively-charged, the further to the right it will appear.
● If you don’t have a C=O bond in your compound, you can basically ignore this.
Kind of carbon in C-NMR: Where it shows up:

Carbonyl (C=O) carbons
• Esters, amides, and carboxylic acids 160-180 ppm
• Aldehydes and ketones >200 ppm
TMS (tetramethylsilane) – not part of your

0 ppm
compound!
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Lesson 6 – 1H-NMR Spectroscopy
• Each “different kind of” (or “non-equivalent”) hydrogen gives a different signal. The more positively-charged,
the further to the left it appears (downfield).
• The integral numbers above each peak tell you how many hydrogens are in that peak.
• Hydrogens get split by neighboring hydrogens. To figure out the splitting, count all the hydrogens next-door
in all directions and add 1 (n+1 rule).
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Chapter 6: IM Forces and Lab Techniques

Lesson 1 – Intermolecular Forces
Intra-molecular forces (forces WITHIN a molecule)

1. Covalent bonds: two non-metal atoms bond together and share electrons
2. Ionic bonds: metals bond to nonmetals and a transfer of electrons occurs
3. Metallic bonds: metal atoms bond together and electrons flow freely around their nuclei
Intermolecular forces (forces BETWEEN molecules)

1. Ion-dipole: ionic compounds interacting with polar compounds
2. Hydrogen bonding: H-O, H-N, or H-F
3. Dipole-dipole: Examples: H-Cl, C-O, S-H
4. Dispersion Forces: hydrocarbons, single elements, nonpolar molecules
You also need to know commonly used OC Lab Tests for the DAT. Memorize the summary chart below.
Summary of OC Lab Tests
Test Reagent Functional Group Tested Positive Result
Ag2O / NH3 Sides of flask are coated

Tollens’ Test Aldehydes
or Ag(NH3)2+ with a silver mirror
Yellow precipitate forms
Iodoform Test I2 / OH- Methyl ketones
(CHI3)
Silver Nitrate in AgNO3 in Precipitate of Ag
Alkyl halides
Alcohol alcohol compound formed
Brown color of Bromine
Bromine Test Br2/CCl4 Alkenes and alkynes
disappears
Purple solution turns to
Baeyer Test Dilute KMnO4 Alkenes and alkynes
brown precipitate
Orange reagent turns
Jones Test CrO3 / H2SO4 1° and 2° alcohols
blue-green
2°, 3°, and benzylic Cloudy solution initially,
Lucas Test ZnCl2 / HCl
alcohols then separate layer forms
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Lesson 2 – Effect of IM Forces on Physical Properties
The stronger a molecule’s intermolecular forces:

• The higher its boiling point ↑
• The higher its melting point ↑
• The lower its vapor pressure ↓
Lesson 3 – Melting Points and Extractions
Melting point helps determine a compound’s purity

Extraction techniques rely on using polar and nonpolar solvents
Lesson 4 – Acid-Base Extractions
● For carboxylic acids, extract with aqueous NaOH or NaHCO3

● For phenols, extract with aqueous NaOH
● For amines, extract with aqueous HCl
Lesson 5 – Distillation and Recrystallization
● Distillation separates mixtures of two or more volatile liquids

● Fractional distillation is used when the two volatile liquids have boiling points that are close together
● Recrystallization dissolves an impure compound in hot solvent and gradually precipitates the pure
compound as the solution cools down.
o Note: If you’re cooling down your product in recrystallization and no crystals form, you can scratch
the side of the glass to provide a nucleation site to induce recrystallization. You can also use a seed
crystal.
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Lesson 6 – Chromatography
● Gas-liquid chromatography (or gas chromatography) is used to determine the relative abundance of each
compound in a liquid mixture.
o Separates components in liquid mixture by boiling point.
o Lowest boiling point comes off the fastest.
● Thin Layer Chromatography (TLC) separates compounds by their solubility in the solvent (polarity). Most
soluble compound travels the fastest and furthest up the plate.
o Usually uses a polar plate and nonpolar solvent.
o Compound that travels the furthest with nonpolar solvent is the most nonpolar compound.
o Retention Factor (Rf) is a number we use to tell how far up the TLC plate a compound travels.
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Chapter 7: Reactions of Alkenes and Alkynes

Lesson 1 – Alkene Additions and Hydrohalogenations
Hydrohalogenation (adding HX)
● The H goes on the carbon with more H’s on it. The X goes on the carbon with fewer H’s on it. This is called
the Markovnikov product.
What’s added: H+ and Br–

Regioselectivity: Markovnikov
Intermediate: carbocation
Rearrangements: possible
Carbocation stability
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Lesson 2 – Carbocation Rearrangements
1,2-Hydride Shifts
1,2-Methyl Shifts
Lesson 3 – How to add –OH and –OR to Alkenes
Acid-Catalyzed Hydration
What’s added: H+ and OH–

Rearrangement: possible
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Lesson 3 – How to add –OH and –OR to Alkenes (Continued)
Oxymercuration-Demercuration

Stereoselectivity: Anti addition
Intermediate: mercurinium ion
Rearrangement: **Not possible**
Acid-Catalyzed Alcohol Addition
What’s added: H+ and OR–

Rearrangement: possible
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Lesson 4 – Adding Halogens to Alkenes
Adding Halogens
What’s added: Br+ and Br– (or Cl+ and Cl–)

Stereoselectivity: anti
Intermediate: bromonium ion
Rearrangement: Not possible
Adding Halogens and H2O (or ROH)
What’s added: Br+ and OH– (or Br+ and OR–)

Stereoselectivity: Anti
Intermediate: bromonium ion
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Lesson 5 – Anti-Markovnikov Alkene Additions
Hydroboration-Oxidation

Regioselectivity: Anti-Markovnikov
Stereoselectivity: Syn
Intermediate: hydroxy-boranes
Hydrobromination with Peroxide
What’s added: H• and Br•

Regioselectivity: Anti-Markovnikov
Intermediate: radical
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Lesson 6 – Epoxides and Dihydroxylations
Epoxide Reactions with Alkenes
What’s added: Oxygen

Stereoselectivity: syn
Anti-dihydroxylation
What’s added: OH and OH

Stereoselectivity: anti
Rearrangement: not possible
Syn-dihydroxylation
What’s added: 2 OH’s

Regioselectivity: 1,2
Intermediate: osmate ester
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Lesson 7 – Ozonolysis
Ozonolysis
What happens: The C=C bond gets cut in half. An O gets placed on each half.
● If the workup (step 2) is Zn/H2O or (CH3)2S, then that’s it.
● If the workup (step 2) is H2O2, then one of the H atoms stuck to each alkene carbon gets replaced with an
OH.
● Also, KMnO4 (hot, conc.)/H3O+ does the same thing as O3 and H2O2.
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Lesson 8 – Catalytic Hydrogenation
Catalytic Hydrogenation of Alkenes
Catalytic Hydrogenation of Alkynes
What’s added: two H’s

Alkene + H2/Pd, C → Alkane

Alkyne + H2/Pd, C → Alkane
To stop at the cis/trans isomer of the alkene:

Alkyne + H2/Lindlar’s Catalyst → cis or Z-alkene
Alkyne + Na/NH3 (l) → trans or E-alkene
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Lesson 9 – Alkyne Addition Reactions
Hydrohalogenation of Alkynes
● Terminal alkynes
● Internal alkynes (mixture of products)
Di-Halogenation of Alkynes
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Lesson 9 – Alkyne Addition Reactions (Continued)
Hydrobromination with peroxide
Acid-Catalyzed Hydration of Alkynes
● Reagent: HgSO4/H2SO4/H2O
● You need a Hg catalyst for terminal alkyne hydration.
● This reaction adds an OH with Markovnikov regioselectivity to form an enol.
● The enol product then tautomerizes to form a ketone.
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Lesson 10 – Alkyne Hydration and Alkylation
Anti-Markovnikov Hydration of Alkynes
● Reagents: 1. (Sia)2BH•THF 2. H2O2, OH–, H2O

o (Note: you may also see BH3•THF, B2H6, or even (Sia)2BH drawn out. These all mean the same thing.)
● Regioselectivity: Adds OH Anti-Markovnikov to form an enol. This then tautomerizes to form an aldehyde.
Alkyne Hydration Summary
● Markovnikov conditions:
o Reagent: HgSO4/H2SO4/H2O
o You need a Hg catalyst for terminal alkyne hydration.
o This reaction adds an OH with Markovnikov regioselectivity to form an enol.
o The enol product then tautomerizes to form a ketone.
● Anti-Markovnikov conditions:
o Reagents: 1. (Sia)2BH•THF 2. H2O2, OH–, H2O
o (Note: you may also see BH3•THF, B2H6, or even (Sia)2BH drawn out. These all mean the same thing.)
o Regioselectivity: Adds OH Anti-Markovnikov to form an enol. This then tautomerizes to form an
aldehyde.
Alkylation of Alkynes
Lesson 11 – Forming Alkynes from Alkenes
NaNH2 can remove H from a halogen substituted alkene, creating an alkyne.
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Lesson 12 – Thermodynamic vs. Kinetic Products
Kinetic product:
● Forms fastest
● Comes from the most stable carbocation intermediate
● Favored at low temperature (called kinetic control): –40 ºC or lower
In a conjugated diene addition reaction, the kinetic product is the product that comes from the most stable
carbocation intermediate.
Thermodynamic (“thermo”) product:

● Forms more slowly
● Favored at higher temperature (called thermodynamic control): ~0 ºC or higher
● Is the most substituted (most internalized) alkene product, which is the most stable final product, due to
Zaitsev’s rule.
In a conjugated diene addition reaction, the thermo product is the product that has the most substituted double
bond at the end.
Bootcamp.com 38
Chapter 8: Substitution and Elimination Reactions

Lesson 1 and 2 – Substitution Reactions
SN1 Reaction – Substitution Nucleophilic Unimolecular

Rate = k[electrophile]
SN2 Reaction – Substitution Nucleophilic Bimolecular

Rate = k[electrophile][nucleophile]
Bootcamp.com 39
Lesson 1 and 2 – Substitution Reactions Basics (Continued)
Choosing between SN1 and SN2 reactions
1. Is the carbon bonded to the leaving group 1º, 2º, or 3º?
2. Is my nucleophile strong or weak?

a. Strong nucleophiles have negative charges.
i. Exceptions: negative charges on halogens (Cl–, Br–, l–) or negative charges that are
resonance-stabilized are weak.
b. Some strong nucleophiles (SN2 reactions): CN-, OR-, OH-, RS-, NR2-, R-
c. Some weak nucleophiles (SN1 reactions): RCO2–, HOR, H2O, HSR, HNR2, I–, Br–, or Cl–
SN2 vs. SN1 reactions summary
SN2 SN1
Nucleophile strong weak
Electrophile Methyl > 1° > 2° (no 3°) 3° > 2° (no 1° or methyl)
Solvent aprotic preferred protic
Leaving Group I > Br > Cl > F I > Br > Cl > F
Rearrangement Not possible Possible (hydride/methyl shifts)
Inversion Yes No (racemization)
Bootcamp.com 40
Lesson 3 and 4 – Elimination Reactions
E1 Reactions – Elimination Unimolecular

Rate = k[substrate]
● Forms most substituted double bond (Zaitsev’s Rule)
Zaitsev’s Rule
● E1 and E2 reactions give the more substituted C=C bond and favor the E-alkene.
E2 Reactions – Elimination Bimolecular

Rate = k[substrate][base]
● H and Leaving Group must be antiperiplanar (anti-coplanar)

● Forms most substituted double bond (Zaitsev’s Rule)
● Forms least substituted double bond if bulky base is used like t-butoxide (CH3)3CO-
Bootcamp.com 41
Lesson 3 and 4 – Elimination Reactions (Continued)
Choosing between E1 and E2 reactions
1. Is the carbon bonded to the leaving group 1º, 2º, or 3º, or stabilized?
2. Is my base strong or weak?

a. Strong bases have negative charges.
i. Exceptions: negative charges on halogens (Cl–, Br–, l–) or negative charges that are
resonance-stabilized are weak.
b. Some strong bases (E2 reactions): OR-, OH-, RS-, NR2-, R-
c. Some weak bases (E1 reactions): RCO2–, HOR, H2O, HSR, HNR2, I–, Br–, or Cl–
E2 vs. E1 reactions summary
E2 E1
Base strong weak
Electrophile 3° > 2° > 1° 3° > 2° (no 1° or methyl)
Solvent aprotic preferred protic
Leaving Group I > Br > Cl > F I > Br > Cl > F
Rearrangement Not possible Possible (hydride/methyl shifts)
Stereochemistry Antiperiplanar None
Bootcamp.com 42
Lesson 5 – Choosing Between SN1, SN2, E1, E2
Protic solvents = SN1, E1, and E2 reactions

Aprotic solvents = SN2 and E2 reactions
Protic solvent examples: Anything that hydrogen bonds. Alcohols (methanol, ethanol), water, acetic acid
Aprotic solvent examples: DMSO (dimethylsulfoxide), DMF (dimethylformamide), THF (tetrahydrofuran), ether,
acetone
SN2 E2 SN1 E1
Electrophile CH3 > 1° > 2° 3° > 2° > 1° 3° > 2° 3° > 2°
Nucleophile/ Strong nuc Strong base weak nuc weak base

Base
Solvent aprotic preferred aprotic preferred protic protic
Substitution vs. Elimination Flowchart
Bootcamp.com 43
Lesson 6 – Exception to Substitution and Elimination
One Solvent Exception
One exception to the protic ≠ SN2 rule is alkoxide bases being paired with their conjugate acids:
As it turns out, when using alkoxide nucleophiles, we often choose their protonated counterparts as our solvents.
When a strong SN2 nucleophile like CH3O_ is paired with its conjugate acid (CH3OH) as solvent, the reaction will still
go SN2 even though the solvent is protic.
Exception to Zaitsev’s Rule
When sterically-bulky tert-butoxy bases are used, the less-substituted C=C bond (Anti-Zaitsev) product is
favored.
Sometimes the Z-product is formed because the H and LG have to be antiperiplanar to each other.
In E2 reactions, the eliminated H must be in the same three-dimensional plane, but pointing 180º in the opposite
direction, as the leaving group.
Bootcamp.com 44
Chapter 9: Free Radical Halogenation and Diels Alder

Lesson 1 – Free Radical Halogenation
Radical Reaction
● Bromine is very selective, it likes the most stable radical.

● Chlorine isn’t selective, that’s why we usually use bromine in radical halogenation.
Radical Stability
Mechanism
● Initiation has no radicals on the left side, and radicals on the right side of the equation.
● Propagation has radicals on both sides of the equation.
● Termination has radicals on the left side, and no radicals on the right side of the equation.
Bootcamp.com 45
Lesson 2 – NBS in Radical Halogenation
● NBS (N-BromoSuccinimide) adds Br to the carbon that is one position away from the double bond (the allylic
carbon).
Lesson 3 – Diels-Alder Reaction
● Concerted mechanism
● Pericyclic reaction
Bootcamp.com 46
Chapter 10: Aromatic Compounds

Lesson 1 – How to Determine Aromaticity
1. It must be cyclic or polycyclic
2. No sp3-hybridized atoms in the ring. The ring must be planar.
3. The number of π electrons in the ring must equal 4n + 2 (n = 0, 1, 2, etc.). This is called Hückel’s rule. Usually
2, 6, 10, 14 π electrons in the system.
● Non-aromatic compounds don’t satisfy rules 1 or 2

● Anti-aromatic compounds satisfy rules 1 and 2, but not rule 3
Lesson 2 – Effects of Aromaticity

● Effects on SN1 – If a molecule forms an aromatic carbocation intermediate during SN1, then it will react
through SN1 faster since the intermediate step is more stable.
● Effects on Acidity – If the conjugate base is more stable due to aromaticity, then the acid will be more acidic.
Lesson 3 – Side Reactions of Benzenes

Side Chain Oxidation
● You can only do this if your benzylic carbon is bonded to at least one H.
Side Chain Reduction
Bootcamp.com 47
Lesson 4 – Electrophilic Aromatic Substitution (EAS)
EAS Reactions
Ortho/Para and Meta Directors
Note: Halogens are a bit of an exception. Halogens are ortho/para directing, however because of their strong
electronegativity, they are electron withdrawers.
Bootcamp.com 48
Lesson 5 – Diazonium Salts
Bootcamp.com 49
Chapter 11: Alcohols, Ethers, Epoxides

Lesson 1 – Substitution and Elimination of Alcohols
Substitution Reaction with H-X

● Proceeds via SN2 for 1° alcohols and methanol
● Proceeds via SN1 for 3° and 2° alcohols
Reaction with PBr3 (1° and 2° alcohols)
Reaction with SOCl2 (1° and 2° alcohols)
Conversion to Sulfonate Esters (tosylates and mesylates)
Dehydration with H2SO4 or H3PO4
● E2 for 1° alcohols
● E1 for 3° and 2° alcohols
Bootcamp.com 50
Lesson 2 – Oxidizing Alcohols
● Chromium reagents oxidize 1° alcohols and aldehydes to carboxylic acids

● 2° alcohols are oxidized into ketones
● PCC oxidizes 1° alcohols to aldehydes and 2° alcohols to ketones
● Swern oxidation does the same thing as PCC, it oxidizes 1° alcohols to aldehydes and 2° alcohols to
ketones
Bootcamp.com 51
Lesson 3 – Reactions of Ethers
William Ether Synthesis (SN2)
Adding H-X to Ethers
● The reaction will proceed through an SN1 mechanism if you have a secondary or tertiary carbon group.
● If not, it’ll go SN2 and attack the least sterically hindered side.
Lesson 4 – Reactions of Epoxides
Epoxide Synthesis
Ring Opening of Epoxides

Base-Catalyzed (Nucleophile attacks less substituted side)
Acid-Catalyzed (Nucleophile attacks the more substituted side
Bootcamp.com 52
Chapter 12: Aldehydes and Ketones

Lesson 1 – Alcohol Reactions with Carbonyls
Addition of Alcohols
Base-catalyzed (forms hemi-acetal/hemi-ketals)
Acid-catalyzed (forms acetal/ketal)
● Ketals can be used to protect aldehydes and ketones during synthesis
Bootcamp.com 53
Lesson 2 – Amine Reactions with Carbonyls
Addition of 1° Amines (forms Imines, aka Schiff bases)
Addition of 2° Amines (forms enamines)
Lesson 3 – Hydride Reductions
LiAlH4 is a powerful source of hydride, can also reduce esters
Lesson 4 – Grignards and Organolithium Reactions with Carbonyls
Grignard Reagents
Organolithium Reagents
Bootcamp.com 54
Lesson 5 – Wittig Reaction
Mechanism of Wittig Reaction
Lesson 6 – Michael Additions (1,4-Addition)
● Add a nucleophile to the β carbon instead of the carbonyl carbon

● Need a weaker nucleophile to prefer the 1,4-addition
o Michael donors:
o R2CuLi, CN-, HNR2, HSR
Mechanism of Michael Addition
Bootcamp.com 55
Chapter 13: Carboxylic Acids and Acid Derivatives

Lesson 1 – Interconversion of Acid Derivatives
Nucleophilic Acyl Substitution
Reactivity = acid chloride > anhydrides > esters/carboxylic acids > amides > carboxylates
Lesson 2 – Physical Properties of Carboxylic Acids

● Carboxylic acids have a higher boiling point due to dimerization and H-bonding
Bootcamp.com 56
Lesson 3 – Fischer Esterification and Saponification
Fischer Esterification
Saponification
Bootcamp.com 57
Lesson 4 – Hydride Reductions of Acid Derivatives

NaBH4 reduces ketones, aldehydes, and acid chlorides, and acid anhydrides
LiAlH4 reduces ketones, aldehydes, acid chlorides, esters, carboxylic acids, amides, etc.
(*amides are reduced to an amine)
Hoffman Rearrangement
● Turns amides into amines and also removes 1 carbon
Bootcamp.com 58
Lesson 5 – Mild Hydride Reductions

DIBAL-H reduces esters to aldehydes
LTBA (Lithium tri-t-butoxy aluminum hydride) reduces acid chlorides to aldehydes
Structure of LTBA
Lesson 6 – LAH and Grignards with Nitriles and Carboxylic Acid Derivatives
Adding LAH to Nitriles

Reduce nitrile to 1° amine
Bootcamp.com 59
Lesson 6 – LAH and Grignards with Nitriles and Carboxylic Acid Derivatives (Continued)
Reacting Esters and Acid Chlorides with Grignards

Add the R” group twice to form 3° alcohol
Reacting Carboxylic Acids with Grignards

Grignard reacts with acidic hydrogen, forms a carboxylate. *Does not add R” group
Reacting Amides with Grignards

Grignard reacts with hydrogen on amide, forming deprotonated amide. *Does not add R” group
Reacting Nitriles with Grignards

Grignard reacts with nitrile to form ketone. Does not go all the way to a 3° alcohol.
Bootcamp.com 60
Chapter 14: Alpha Substitution Reactions of Carbonyls

Lesson 1 – Alpha Substitution Reactions
Enolates and Enols
● Enolates are better nucleophiles because they have a negative charge
Keto-enol tautomerization
How to deprotonate α-hydrogen

More substituted α-hydrogen gets deprotonated with typical base (-OH)
Less substituted α-hydrogen gets deprotonated with LDA
Bootcamp.com 61
Lesson 2 – Alpha Halogenation and Haloform Reaction
Base-promoted Alpha Halogenation (all alpha hydrogens replaced with halogen)
Acid-catalyzed Alpha Halogenation (only one alpha hydrogen replaced with halogen)
Alpha-Deuteration (all alpha hydrogens replaced with D atom regardless of acidic or basic)
Haloform Reaction (need a CH3)
● Produces a yellow precipitate if methyl ketone is present – useful lab test
Bootcamp.com 62
Lesson 3 – Aldol Condensation
Aldol Shortcut
Lesson 4 – Claisen Condensation

● Just like Aldol Condensation, except with esters. Enolate adds to an ester.
Claisen Shortcut
Beta-Decarboxylation
Bootcamp.com 63
Lesson 5 – Acetoacetic Ester Synthesis
Lesson 6 – Malonic Ester Synthesis
Bootcamp.com 64

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Dr.

Mike’s O-Chem Outline

Chapter 1: Bonding, Resonance, and Molecular

Lesson 2 – Molecular Bonding Geometry and Hybridization

3 Trigonal planar 120 sp2

4 Tetrahedral 109.5 sp3

Lesson 3 – Condensed Formulas and Line-Bond Formulas

Lesson 4 – Sigma and Pi Bonds

Type of covalent bond Number of bonds

Single bond one sigma (σ)

Double bond one sigma (σ) + one pi (π)

Triple bond one sigma (σ) and two pi (π)

Lesson 5 – Orbital Hybridization

Lesson 6 – Resonance Structures

Determining Greatest Resonance Contributor

Lesson 7 – Newman Projections

Lesson 8 – Cycloalkanes and Ring Strain

How to draw chair conformations of cyclohexane (follow along!):

Axial vs. Equatorial

Trans vs. Cis cyclohexanes

Cis – two substituents going in same direction

Chapter 2: Acids and Bases

● A Lewis acid is a substance that accepts electrons.

Lesson 2 – Conjugate Base-Acid Relationship and pH Scale

↑ KA = ↓ pKA = ↑ acid strength

pKas for Organic Compounds

Lesson 3 – Ranking Acids and Bases with CARDIO (Charge)

● The more positively-charged the compound = the more acidic

Lesson 4 – Ranking Acids and Bases with CARDIO (Atom)

● goes left-to-right across a row on the periodic table (increasing electronegativity)

Lesson 5 – Ranking Acids and Bases with CARDIO (Resonance)

Lesson 6 – Ranking Acids and Bases with CARDIO (Dipole Induction)

● Electron Withdrawing groups increase acidity

Lesson 7 – Ranking Acids and Bases with CARDIO (Orbitals)

Lesson 8 – Acid and Base Review

How to Sort Acids and Bases by Strength

First, convert the acid to its conjugate base.

Lesson 9 – pH and Amino Acids

To determine the structure or charge of any amino acid:

Lesson 2 – Naming Cycloalkanes and Alkyl Halides

Naming Alkyl Halides

Lesson 3 – Naming Alkenes and Alkynes

Lesson 4 – Naming Alcohols, Ethers, and Amines

When naming ethers:

Lesson 5 – Naming Aldehydes and Ketones

Lesson 6 – Naming Carboxylic Acids and Derivatives

When naming acid halides:

When naming esters:

Lesson 6 – Naming Carboxylic Acids and Derivatives (Continued)

When naming acid anhydrides:

Lesson 7 – Naming Aromatics

When naming substituted benzenes:

Lesson 8 – Naming Polyfunctional Compounds

When naming poly-functional compounds:

Priority of Functional Groups

Lesson 9 – Naming Spiro and Bicyclic Alkanes

Constitutional Isomers vs. Diastereomers vs. Enantiomers

Lesson 2 – Chiral Centers

A chirality center is a carbon center that contains four unique substituents.

When using the R,S naming system: