Dat-o-chem Reactions

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