Organic Chemistry I Review Page 1/6

Introductory Material 4) Hybridization Effect

Electronegativity and acidity increases with increasing s-character.
Molecular Shape and Hybridization
pKa Values:
Linear Trigonal Planar Tetrahedral sp3 H H H Alkane C-H = 50
HC C sp 2 sp
180° bond angle 120° bond angle 109.5° bond angle Alkene C-H = 45
Increasing s-character Alkyne C-H = 25
Increasing Acidity
sp sp 2 sp3
Some Other Representative pKa Values
Bond Dipoles O O OH
R OH (16) O O (10)
A bond dipole points from a less electronegative atom to a more electronegative atom. (5) (20)
Electronegativity increases diagonally up the periodic table from Fr to F. H
An atom with more s-character is more electronegative. R NH 2 (35) OH H (9)
Bond Length & Bond Strength **Take note of the important unusual exception: Terminal Alkynes (pKa 25) are more
acidic than amines (pKa 35)
For the atoms joined in a bond,
shorter longer increasing s-character corresponds Alkanes and Cycloalkanes
stronger weaker to a stronger & shorter bond.
Alkane Nomenclature
Formal Charge 1. Identify the Parent - the longest continuous carbon chain.
2. Name it based on the number of carbon atoms.
O FC = 6 - 3 - 2 = +1 1C = methane; 2C = ethane; 3C = propane; 4C = butane; 5C = pentane; 6C = hexane; 8C =
FC = Group # - # Bonds - # non-bonding e- octane; 9C = nonane; 10C = decane
3. Number the chain starting at the end that gives the 1st substitutent the lowest number.
Acids and Bases 4. Assemble the name by alphabetizing the substitutent (with numbers) followed by the parent.
More acidic molecules have more stable conjugate bases. Some Substituents
As acidity increases, pKa decreases.
Acid/Base Reactions lie to the side of the more stable conjugate base and weaker acid. CH 3 CH2CH 3 Br
O O Rxn lies to the right. methyl ethyl bromo isopropyl tert-butyl sec-butyl
+ OH + H 2O Water is the weaker
H acid. The conjugate Example
O O base is more stable 8
acid base conj. base conj. acid 9
than the base. 7
Factors that Stabilize the Conjugate Base 5 5-bromo-6-ethyl-4-isopropyl-2-methylnonane
4 6
1 2 3
1) Atom Effect Br
Atoms in the same row: A negative charge Atoms in the same column: A negative
is more stable if it is on a more e-neg atom charge on a larger atom is more stable. Cycloalkane Nomenclature
1. Identify the Cycloalkane Parent
CH 3 NH 2 OH OH SH 2. Number around the ring so as to get the lowest possible substitutent numbering.
3. Assenble the name by alphabetizing the substituents followed by the parent name.
Increasing Electronegativity Increasing Size 2 3
Increasing Acidity Increasing Acidity Substituents at 1,3,4 Substituents at 1,2,4
1 3 Adds up to 8 4 2 Adds up to 7 = Better
2) Resonance Effect 6 4 Incorrect Numbering 5 1 Correct Numbering
5 6
A conjugate base that is stabilized by resonance is more stable than one that is not.
1-ethyl-2,4-dimethylcyclohexane
O O O Intermolecular Forces & Boiling Point
H H H vs H As the strength of the intermolecular forces increases, the boiling point of a molecule increases.
O O O O O O Van der Waals Forces < Dipole-Dipole Interactions < Hydrogen Bonding
Negative on this O is
Most acidic proton in the molecule Increasing IMF Strength
resonance stabilized
3) Inductive Effect All covalent compounds have
Nearby electronegative atoms help to stabilize the conjugate base. Cl OH
VDW Forces.
VDW VDW VDW VDW Butane has a larger surface
H 3C H Cl2HC H Cl 3C H F 3C H The size of the halogen does D-D D-D area & thus stronger VDW
not matter since the acidic H-Bond forces than propane.
Increasing Acidity proton isn't directly attached.
Increasing Boiling Point
 Organic Chemistry I Review Page 2/6

Newman Projections Assignment of R/S Configuration Optical Activity

R and S is used to assign the configuration at a chiral center. A single enantiomer of a
A Newman projection is a way of visualizing the rotational conformations of an acyclic molecule.
A pair of enantiomers have opposite R/S assignments. chiral molecule will be
CH 3 H 3C CH 3 CH 3 optically active - it will
e H H CH 3 1. Look at four atoms directly attached to the chiral center.
sid iew H CH 3 H H
2. Prioritize the atoms based on atomic number (Highest AN = Priority 1). rotate plane polarized
v H 3. If there is a tie, move out to the next atom in the chain and compare. light in the (+) or (-)
H H H H H H direction.
H 3C H front C CH 3 H H
4. Orient the molecule such that the priority 4 group is pointing back.
H 5. Draw a curved arrow from 1 to 2 to 3.
back C Staggered, Anti Eclipsed Staggered, Gauche Achiral molecules are
Most Stable Least Stable R-Configuration S-Configuration optically inactive
Lowest Energy Highest Energy
Chair Conformations Example A racemic (±) mixture (1:1
Br Rotate "4" mixture of enantiomers) is
Every carbon in cyclohexane has two substituents. In chair cyclohexane each carbon has one 3 3 2 3 1 optically inactive.
axial (straight up or straight down) substituent and one equatorial (sideways) substituent. 2 Simplify to back

H OH 4 1 2 4 R-Configuration
4 1 Draw arrow from 1
axials to 2 to 3.
equatorials
Fischer Projections
A Fischer projection is a way to view three dimensional structures.
Cis substituents should both point up or down. With trans substituents, one will point up and one By definition the horizontal bonds in a Fischer projection are pointing "out" and the vertical bonds
will point down. are pointing "back."
(ax) Ring (ax) During a ring flip, F F
CH 3 CH 3 F F
Flip CH2CH 3 axials become
cis = equatorials and = H OH H OH
CH equatorials
H OH H OH =
CH2CH 3 CH2CH 3 3
H OH H OH
(eq) (eq) become axials. CH 3 CH 3
Lower Energy CH 3 CH 3
The lowest energy chair conformation is the one that puts the largest substituent(s) in the Manipulating Fischer Projections
equatorial position.
1. Fischer Projections can be rotated 180° 2. You can rotate the top three groups or
Stereochemistry without changing the molecule the bottom three groups without chaning
the molecule
CH 3 CH2OH
Structural Relationships CH 3 H
Constitutional Isomers - Compounds with the same mol. formula, but different atom connectivity. H OH HO H
Stereoisomers - Compounds with different 3D arrangements of the atoms. is the H OH HO CH 3
same as is the
Enantiomers - Stereoisomers that are non-superimposable mirror images. H OH HO H same as
Diastereomers - Stereoisomers that are non-superimposable and are not mirror images. H OH H OH
Chiral Center - An atom that has four different groups attached to it. CH2OH CH 3
CH2OH CH2OH
Chiral Molecule - A compound that has one or more chiral centers, and no plane of symmetry.

OH OH 3. Rotating a Fischer Projection 90° changes

OH OH Enantiomers can have
the configuration at the chiral center
one or more chiral CH 3 CH 3
centers.
* * * * * * CH 3 H
H OH HO H
mirror Enantiomer Enantiomer drawn by H OH is not the Br CH 3
enantiomers drawn as the
Cl Cl same as
enantiomers inverting all chiral centers. H OH HO H
mirror image Br OH
90°
CH2OH CH2OH
In a pair of diastereomers, at least one, but A meso compound is a molecule R-configuration rotation S-configuration enantiomers
not all of the chiral centers are inverted. that has two or more chiral centers,
but is achiral due to the molecule
OH OH having a plane of symmetry. Assigning R/S Configuration
CH 3 CH 3
Cl symmetry plane F1 H OH HO H
* * * * * * Trick: It looks like R-config, but since
* 4 2 the H is pointing out (by definition)
H OH the configuration is actually S. H OH H OH
Diastereomers must Cl
diastereomers have at least 2 chiral * 3 CH 3 S CH2OH CH2OH
centers. Not including diastereomers
alkene diastereomers. achiral (meso)
 Organic Chemistry I Review Page 3/6

Alkenes
CH2I 2 1. O3 O
Alkene Stability O +
Zn(Cu) 2. DMS
Simmons-Smith Cyclopropanation Ozonolysis - Reductive Workup
H H H CH 3 H 3C CH 3 H CH 3 H 3C CH 3 H 3C CH 3
Alkynes
H H H H H H H 3C H H 3C H H 3C CH 3 Alkyne Alkylation
mono-sub cis di-sub trans di-sub tri-sub tetra-sub Terminal alkynes can be alkylation by reacting the alkyne with a base followed by addition of R-X.
Increasing Substitution
Increasing Alkene Stability The carbon bonded
H NaNH 2 Br
E/Z Assignment to the halogen must
1 Z Config be sp3.
Using the same priority rules as with assigning R/S configurations, the
configuration of an alkene double bond can be assigned as E or Z. Br 1
E-Configuration - Priority 1 Groups on opposite sides of the double bond. 2 Addition Reactions
Z-Configuration - Priority 1 Groups on same side of double bond. H2 X X
X2 X2 X
Reactions of Alkenes R X X = Cl, Br, I
(1 equiv) R (2nd equiv) R
The most common reactions of alkenes are addition reactions where two atoms are added across
the alkene π-bond. X X
Markovnikov Addition - H adds to the side with more H (less substituted side).
Anti-Markovnikov Addition - H adds to the side with less H (more substituted side).
X X X = Cl, Br, I
HX HX X
HX X H OH R H HX adds to the
(1 equiv) R (2nd equiv) R terminal alkyne in
H H 2O H Markovnikov fashion.
H H
HX = HCl, HBr, HI Hydration
Markovnikov Addition Markovnikov Addition Hydrogenation (Also an Addition Reaction)
R' H H
H2 Complete reduction of the
H OR 1. Hg(OAc) 2 R'
OH R alkyne to an alkane
HOR H H 2O R Pd/C
2. NaBH 4 H H H
Markovnikov Addition
Oxymercuration/Demercuration H H
X Markovnikov Addition R' R'
X2 H2 H Na/NH 3(l) R
X H R' R'
BaSO 4
X2 = Cl2, Br 2, I 2 R R
H2 (Lindlar Cat.) R H
Halogenation H Lindlar's Catalyst gives partial Sodium in liquid ammonia gives partial
Pd/C reduction to the cis-alkene reduction to the trans-alkene
X2 OH
Hydrogenation
H 2O X OH
Alkene/Alkyne Nomenclature
Halohydrin Formation 1. Find the parent chain - the longest carbon chain that contains both carbons of the unsaturation.
OsO4
OH 2. Number the parent from the end that gives the unsaturation the lowest numbers.
NMO, H 2O 3. Change parent ending -ane to -ene (alkene) or -ane to -yne (alkyne)
1. BH 3 H 4. Assemble name: Alkene: (E or Z)-substitutents-alkene C #-parent
Syn-Dihydroxylation
Alkyne: substituents-alkyne C #-parent
2. NaOH OH 1
O 6 8
H 2O2 2 5 7 9
RCO 3H
Hydroboration/Oxidation E 3 7 3
1 2
Anti-Markovnikov Addition Epoxidation 4 5 6 4
Br
(E)-7-bromo-3,5-dimethyl-2-heptene 7-ethyl-2-methyl-4-nonyne
 Organic Chemistry I Review Page 4/6

Delocalized Electrons and Resonance Substitution Reactions

Delocalization of electrons through resonance helps to stabilize a structure. SN 2 - Substitution Nucleophilic Bimolecular
Common Resonance Patterns
O O H 3C X + Nu H 3C Nu + X Rate = k H 3C X Nu -
OH OR
allylic anion allylic cation Only a single step in the reaction A Better Leaving Group = Faster Reaction
lone pair lone pair next π-bond between Conjugated π- A Stronger Nu = Faster Reaction
next to cation This single step must then = slow step
to π-bond atoms of different bonds in cycle
e-neg
NaCN In SN 2 the nucleophile adds from
Assessing Relative Importance of Resonance Contributors Br CN + NaBr the backside of the leaving group
1. A resonance structure where charges are minimized is more important. providing the inversion product.
2. A resonance structure where all atoms have an octet is more important.
3. A resonance structure that puts the negative on the more e- neg atom is more important.
SN1 - Substitution Nucleophilic Unimolecular
all atoms have an octet
O O
N N X + Nu Nu + X
H H "slow step"
Major C does not Major
have an The SN1 reaction involves a carbocation intermediate.
Contributor Contributor Formation of this carbocation is the rate determining step.
by rule 1 octet by rule 2 Rate = k X
A Better Leaving Group = Faster Reaction
A More Stable Carbocation Intermediate = Faster Reaction
H H Major SN1 reactions are sometimes referred to as solvolysis reactions.
Contributor A substrate is most likely to ionize in a polar protic solvent if it has a good leaving group and can
O O by rule 3 form a relatively stable carbocation (allylic, benzylic, or tertiary).
Carbocation Stability

Radicals and Radical Reactions

CH 3
CH 3
Increasing Stability
vinyl methyl 1o 2o 3o allylic benzylic
Alkyl Halide Reactivity
Increasing Stability
X X
Radical Halogenation of Alkanes
X X
H 3C X X
Br 2 Br Bromination Selectivity: 3o>2o>1o
methyl primary secondary allylic benzilic tertiary
Δ or hν Radical chlorination is much less selective

SN 2 Only SN1 or SN 2 SN1 Only

Allylic Bromination using NBS
Bromination at the allylic position. Proceeds via an Some Good Leaving Groups
NBS Br allylic radical intermediate. NBS can also be used for O
Δ or hν benzylic bromination.
R I R Br R Cl R OH2 R OTs Ts = S
Radical Addition of HBr to Alkenes O
Reaction Solvent
HBr H Anti-Markovnikov addition - H goes to the SN1 goes best in polar protic solvents: H 2O, ROH Some Polar Aprotic Solvents
more substituted carbon and Br goes to the SN 2 goes best in polar aprotic solvents.
Br O O O
HOOR less substituted carbon.
S

DMSO THF acetone

 Organic Chemistry I Review Page 5/6

Elimination Reactions Inversion vs Retention of Configuration

E2 - Elimination Bimolecular

β PBr 3 H NaCN (R) CN Double

X + Base + H-Base + X D Inversion =
H α (S) SN 2
H D Net Retention
Rate depends on both the ability of the leaving group (R)
Br
Rate = k X OH
and the strength of the base. H Base
E1 - Elimination Unimolecular H D
TsCl (R) OTs NaCN H
β
H H (S) D Inversion
Base + H-Base Pyr H D SN 2
X + X CN
β α β *Conversion of R-OH to R-OTs does not change configuration!
In E1, the base has no effect on the reaction rate. Rate = k X
The reaction involves a carbocation intermediate.
Tertiary, Benzylic, and Allylic Halides can undergo E1 Elimination Dehydration of an Alcohol with Acid
H
Solving an Elimination Problem H 2SO 4
+ H 2O
Identify Identify β-H Eliminate HBr across all Δ
α-C & β-C Small Base Bulky Base
α,β bonds with α-H
HO -
OH
Br Br RO - O
α α H 2N - Alcohol Oxidation
H + Zaitsev
β β H β β Hofmann
OH
H Major Major [O] O [O] O PCC will stop at aldehyde
tri-substituted di-substituted Na 2Cr2O7 /H2SO 4 or CrO 3/H+ will
Zaitsev Prod. Hofmann Prod. H completely oxidize 1 o OH to COOH.
H H OH
For E2 elimination, the H and Leaving Group must be antiperiplanar.
When dealing with a ring, the hydrogen eliminated and LG must be anti. OH [O] O PCC, Na 2Cr2O7 /H2SO 4, and CrO 3/H+
H H will oxidize 2o OH to ketone
Not anti to Br so this CH 3 OCH3 CH 3
β-H can't eliminate + HOCH 3 + Br -
Br Williamson Ether Synthesis
H H H R
OH 1. NaH O
NaH is one of several bases that can be used.
2. R-X
Reactions of Alcohols
Alcohol Substitution
Reactions of Epoxides
OH HX X OH PX 3 X Nucleophilic Opening

1. Nu OH
O Under nucleophilic conditions, the nucleophile
HX = HCl, HBr, HI X = Cl, Br attacks the less substituted epoxide carbon.
2. H + Nu
Tosylate Formation

O Acidic Opening
OH TsCl OTs OTs is an
Ts =
excellent leaving S O HX HO X Under acidic conditions, the acid protonates the
Pyridine group.
O epoxide oxygen. X- then attacks the more
substituted epoxide carbon.
 Organic Chemistry I Review Page 6/6

Infrared Spectroscopy UV-Vis Spectroscopy

-Useful for detecting functional groups in a molecule. Upon irradiation of UV light, conjugated compounds absorb light energy promote a π-electron
-Upon absorption of IR light, functional groups will exhibit characteristic stretching and bending from the HOMO to the LUMO.
vibrations.
Increasing conjugation decreases the energy gap between the HOMO and LUMO levels. A
Key IR Regions (Memorize These!) smaller HOMO-LUMO gap means less energy is required excitation.
Group Region (cm -1)
OH & NH Stretch 3200-3600; fairly broad E = hc As conjugation increases, the energy required for excitation decreases. Since E and λ
λ are inversely proportional, lower E = Higher λmax.
Terminal Alkyne C-H 3300; sharp & narrow
Csp2-H Stretch Just above 3000 COOH derivatives tend to be higher.
Csp 3-H Stretch Just below 3000 Conjugation lowers C=O stretch by
~20 wavenumbers.
C≡C Stretch ~2100
C=O Stretch ~1700; strong Increasing Conjugation — Decreasing E gap — Increasing λmax
Can be useful to distinguish
C=C Stretch ~1650 constitutional isomers where one has
-CH3 bending Just below 1400 a methyl group and the other doesn’t. NMR Spectroscopy
1H NMR - Every distinct type of proton in a molecule gives rise to a signal.
13 C NMR - Every distinct type of carbon in a molecule gives rise to a signal.
Mass Spectrometry
Useful for obtaining the atomic mass and certain structural features for a molecule. O b b Cl
b c H2 H2 a
a H CH 3 a C C a H 3C OH
Typically focus in on the right most grouping of peaks. Often, the tallest peak in this group will H 3C C H 3C C CH 3 C d
correspond to the molecular ion (M +). The m/z of this molecular ion = atomic mass of the molecule. c H2 b H2
CH 3 3-distinct H c 3-distinct H c 4-distinct H
CH 3
100
Molecular Ion [M] + at m/z 16 Chemical Shift Regions (Memorize these Regions!)
Relative Abundance

Atomic Mass of Molecule = 16

Z

Low δ / Upfield / Shielded

High δ / Downfield /
[M+1] + at m/z 17 H H
Peak one mass unit higher than M +, due to small O O Z=

Deshielded
H O,C
% of 13 C in the sample. OH H H
X

id c
0

e
15 16 17 20
aromatic vinyl

ac xyli

yd
m/z
Csp3-H

eh
rb o
Halogens in the Molecule X = O, N,

ald
saturated

ca
halogen
The presence of an [M+2] + peak indicates the presence of a halogen.
100 100
12 10 8 6 4 2 0
PPM
Relative Abundance

Relative Abundance

Integration
The area under each signal is proportional to the number of hydrogen that the signal represents.
Splitting (Coupling)
For simple systems, the signal corresponding to a particular proton is split into (n+1) peaks where
72
0 0
n = the number of hydrogen on the adjacent atom(s).
64 66 72 64 66
m/z m/z
H2 O CH 3 sex
1:1 Ratio of [M] + and [M+2] + 3:1 Ratio of [M] + and [M+2] + C CH 3 H2
m O s
Indicative of Br Indicative of Cl Cl C s C H H 3C
C
C CH 3
H2 H 3C C CH 3 d
Nitrogen Rule t H2
d H2
t
-An odd molecular weight indicates the presence of an odd # of N in the molecule. n=2+3=5
-An even molecular weight indicates the presence of no nitrogen or an even number of N in the n + 1 = 5 + 1 = 6 (sextet)
molecule. multiplicities: s (singlet); d (doublet), t (triplet), q
(quartet), quin (quintet), sex (sextet), sep (septet),
NH 2 H 2N NH 2 m (multiplet)
MW = 72 MW = 73 MW = 74