SN2

SN2
Primary substrate (steric hindrance), no rearrangement,
polar aprotic solvent ( no H bonding), complete stereo
inversion, reaction rate = k [Nuc][Elect]

Primary substrate (steric hindrance), no rearrangement,

polar aprotic solvent ( no H bonding), complete stereo
inversion, reaction rate = k [Nuc][Elect]
SN1 substrate

SN1 substrate
tertiary

tertiary
SN1 rearrangementss

SN1 rearrangementss
possible, from less stable to more stable

possible, from less stable to more stable

SN1 solvent

SN1 solvent
polar protic (H bonding) to stabilize carbocation

polar protic (H bonding) to stabilize carbocation

Stereochemistry SN1

Stereochemistry SN1
racemic mixture

racemic mixture
SN1 rate law

SN1 rate law

rate = k [electrophile]

rate = k [electrophile]
Dehydration of alcohols

Dehydration of alcohols
alcohol -> alkene, favored by strong H+ and high T,
possible rearrangements

alcohol -> alkene, favored by strong H+ and high T,

possible rearrangements
Formation of haloalkanes

Formation of haloalkanes
 alcohol + PBr3
alcohol + SOCl2

alcohol + PBr3
alcohol + SOCl2
E1 substrate

E1 substrate
tertiary

tertiary
E1 solvent

E1 solvent
protic, H bonding to stabilize carbocation

protic, H bonding to stabilize carbocation

E1 product

E1 product
major - more substituted alkene

major - more substituted alkene

E1 rate law

E1 rate law
rate = k[haloalkane]

rate = k[haloalkane]
E1 conditions

E1 conditions
high T, strong base

high T, strong base

E2 substrate

E2 substrate
tertiary

tertiary
E2 solvent

E2 solvent
polar aprotic, no H bonding

polar aprotic, no H bonding

E2 stereochemistry

E2 stereochemistry
anti of proton and leaving group

anti of proton and leaving group

E2 rate law

E2 rate law
rate = k [base][haloalkane]

rate = k [base][haloalkane]
HX additon to alkenes

HX additon to alkenes
Markovnikov addition, racemic mixture, possible
rearrangements

Markovnikov addition, racemic mixture, possible

rearrangements
HBr + peroxides addition

HBr + peroxides addition

no rearrangements , anti markovnikov, only for HBr

no rearrangements , anti markovnikov, only for HBr

Oxymercuration-Demercuration

Oxymercuration-Demercuration
alkene - alcohol, Markovnikov addition, no
rearrangement

alkene - alcohol, Markovnikov addition, no

rearrangement
Hydroboration oxidation

Hydroboration oxidation
anti Markovnikov alcohol, BH3/H2O2, OH on less
substituted carbon

anti Markovnikov alcohol, BH3/H2O2, OH on less

substituted carbon
Hydrogenation of alkenes

Hydrogenation of alkenes
syn addition, only in the presence of catalyst

syn addition, only in the presence of catalyst

Hydrogenation of alkynes with Lindlar catatlyst

Hydrogenation of alkynes with Lindlar catatlyst

stops at alkene , syn addition

stops at alkene , syn addition

Hydrogenation of alkynes with Na/NH3

Hydrogenation of alkynes with Na/NH3

stops at alkene, trans addition

stops at alkene, trans addition

Addition of X2 to alkenes

Addition of X2 to alkenes
intermediate halonium ion, positive charge on bridged
halogen, anti addition, no rearrangements

intermediate halonium ion, positive charge on bridged

halogen, anti addition, no rearrangements
Epoxide formation

Epoxide formation
alkene + peroxy acid = epoxide + carboxylic acid

alkene + peroxy acid = epoxide + carboxylic acid

Epoxide hydrolysis results in

Epoxide hydrolysis results in

trans diol

trans diol
In order to form cis diol need to react alkene with

In order to form cis diol need to react alkene with

KMnO4 or OsO4

KMnO4 or OsO4
Ozonolysis results in cleavage of double bond and
formation of

Ozonolysis results in cleavage of double bond and

formation of
aldehydes and ketones

aldehydes and ketones

Criteria for aromaticity

Criteria for aromaticity

1.cyclic system with unhybridized p orbitals
2.flat and planar
3.4n+2 e's

1.cyclic system with unhybridized p orbitals

2.flat and planar
3.4n+2 e's
Ortho para directors

Ortho para directors

activating groups - NR2, OH, OR, amides, esters, R
groups

Cl, Br, I deactivators but ortho para

activating groups - NR2, OH, OR, amides, esters, R

groups

Cl, Br, I deactivators but ortho para

Meta directing

Meta directing
 e-n withdraawing groups
NR3, NO2, cyanide, ketones, carbox acids etc

e-n withdraawing groups

NR3, NO2, cyanide, ketones, carbox acids etc
Acetal formation

Acetal formation
 ketone + HCl/ROH - hemiacetal
hemiacetal + ROH (-H2O) - Acetal

ketone + HCl/ROH - hemiacetal

hemiacetal + ROH (-H2O) - Acetal
Extraction

Extraction
technique that allows separation of a substance from a
mixture of substancesby adding a solvent that the
compound of interest s highly soluble in

technique that allows separation of a substance from a

mixture of substancesby adding a solvent that the
compound of interest s highly soluble in
Crystallization

Crystallization
method of separation that relies on differential
solubilities of two compounds in given solvent

method of separation that relies on differential

solubilities of two compounds in given solvent
Thin layer chromatography

Thin layer chromatography

compounds separated based on polarity

compounds separated based on polarity

Polar components move slower or faster?

Polar components move slower or faster?

move slower since interact with polar stationary phase

move slower since interact with polar stationary phase

calculating R for TLC

calculating R for TLC

R = distance traveled/distance to solvent front

R = distance traveled/distance to solvent front

Gas chromatography

Gas chromatography
separation technique based on ifferent volatility

separation technique based on ifferent volatility

Rates of movement in GC

Rates of movement in GC
more volatile faster, less volatile slower

more volatile faster, less volatile slower

Simple distillation

Simple distillation
when trace impurities need to be removed from
relatively pure compound or in a mixture with
significantly different boiling points

when trace impurities need to be removed from

relatively pure compound or in a mixture with
significantly different boiling points
Fractional distillation

Fractional distillation
small difference in boiling points

small difference in boiling points

IR of alkenes

IR of alkenes
double bond stretch at 1650 cm

double bond stretch at 1650 cm

IR carbonyl

IR carbonyl
1700

1700
IR alkynes

IR alkynes
2600

2600
IR nitriles

IR nitriles
2100

2100
IR OH

IR OH
36000

36000
CH stretch

CH stretch
3000-3300

3000-3300
What can be seen from NMR

What can be seen from NMR

 1.# of sets of peaks = # different H's
2. chemical shift - chemical environment
3.integration # - # of Hs in the set
4.splitting pattern - neighbours

1.# of sets of peaks = # different H's

2. chemical shift - chemical environment
3.integration # - # of Hs in the set
4.splitting pattern - neighbours
If protons near electronegative group - downfield or
upfield?

If protons near electronegative group - downfield or

upfield?
downfield and deshielded

downfield and deshielded

WHich amino acid is not chiral?

WHich amino acid is not chiral?

glycine

glycine
All animal amino acids have... configuration

All animal amino acids have... configuration

L, amino group on the left

L, amino group on the left

All carbohydrates have ... configuration

All carbohydrates have ... configuration

D

D
Amino acid is
a. basic
b. acidic
c. both

Amino acid is
a. basic
b. acidic
c. both
c, amphoteric

c, amphoteric
Hydrophobic amino acids

Hydrophobic amino acids

either aliphatic or aromatic side chains

either aliphatic or aromatic side chains

Amino acid with aliphatic side chains

Amino acid with aliphatic side chains

glycine, alanine, valine, leucine, isoleucine

glycine, alanine, valine, leucine, isoleucine

Amino acids with aromatic side chains

Amino acids with aromatic side chains

phenylalanine, tyrosine, tryptophan

phenylalanine, tyrosine, tryptophan

Hydrophilic amino acids

Hydrophilic amino acids

acidic, basic and uncharged

acidic, basic and uncharged

Acidic hydrophilic amino acids

Acidic hydrophilic amino acids

glutamic and aspartic amino acids

glutamic and aspartic amino acids

Basic hydrophlic amino acids

Basic hydrophlic amino acids

lysine, arginine and histidine

lysine, arginine and histidine

Histidine - proton acceptor or donor?

Histidine - proton acceptor or donor?

both, His goes both ways

both, His goes both ways

uncharged polar amino acids

uncharged polar amino acids

serie, threonine, asparagine, glutamine

serie, threonine, asparagine, glutamine

Sulfur containing amino acids

Sulfur containing amino acids

methionine, cysteine

methionine, cysteine
Denaturation

Denaturation
disruption of proteins shape w/out breaking peptide
bonds

disruption of proteins shape w/out breaking peptide

bonds
Proteins can be denatured by

Proteins can be denatured by

urea, extremes of pH, extremes of temp, changes in
salt concentration

urea, extremes of pH, extremes of temp, changes in

salt concentration
Primary structure

Primary structure
amino acid sequence, determined by peptide bond

amino acid sequence, determined by peptide bond

Secondary structure

Secondary structure
hydrogen bonds between backbone groups

hydrogen bonds between backbone groups

Tertiary structure

Tertiary structure
Hydrophobic/hydrophilic interactions

Hydrophobic/hydrophilic interactions
Quaternary structure

Quaternary structure
Various bonds between separate chains

Various bonds between separate chains

Formula of carbohydrate

Formula of carbohydrate
CnH2nOn

CnH2nOn
What gives positive Benedicts test?

What gives positive Benedicts test?

aldehydes, ketones, hemiacetals

aldehydes, ketones, hemiacetals

What gives negative Benedicts test?

What gives negative Benedicts test?

acetals

acetals
Soaps

Soaps
 sodium salts of fatty acids
amphipathic, both hydrophilic and hydrophobic

sodium salts of fatty acids

amphipathic, both hydrophilic and hydrophobic
Fatty acids

Fatty acids
stored as fat, fat- triacylglycerol

stored as fat, fat- triacylglycerol

Triglyceride

Triglyceride
three fatty acids esterified to a glycerol

three fatty acids esterified to a glycerol

Glycerol

Glycerol
three hydroxyl groups can be esterified to fatty acids

three hydroxyl groups can be esterified to fatty acids

Saponification

Saponification
Triacylglycerol + NaOH ->>glycerol + 3 fatty acids

Triacylglycerol + NaOH ->>glycerol + 3 fatty acids