Organic Chemistry Exam 2

Front 1

Williamson Ether synthesis

Back 1

1. NaH

2. X-R'

Deprotonate an alcohol and introduce an alkyl halide for SN2 substitution.

requires primary alkyl halide

Front 2

Ether synthesis with dehydration of an alcohol

Back 2

1. H2SO4

The alcohol will protonate and leave as an H2O molecule. The same molecule will perform an SN2 reaction forming an either.

Front 3

Dehydration of a Tertiary alcohol

Back 3

The alcohol will favor elimination over ether synthesis

Front 4

Williamson Danger

Back 4

If a primary alykyl halide is not use, E2 reaction occurs on the alkyl halide

Front 5

Formation of most stable alcohol on alkene

Back 5

1. Hg(OAc)2, H2O

2. NaBH4, NaOH

Front 6

Alkoxymercuration/ demercuration

Back 6

1. Hg(OAc)2 R-OH

2. NaBH4, NaOH

Front 7

Hydroxyl vs O-R leaving group ability

Back 7

The alcohol or O-R bond is a strong base and thus a harder bond to break than a hydroxyl

Front 8

Halogenation of a hydroxyl group

Back 8

R-C-OH

1. HI(heat) reacts to replace hydroxyl forming R-C-I. Can be used for ether synthesis attacks the less substituted side.

Front 9

Excess Halogenation with ether

Back 9

1. HI excess

This will place an Iodine on both carbons instead of just the less substituted one.

Will not work with phenols because of stability of the cation.

Front 10

Epoxide synthesis

Back 10

1. NaOH or NaH

With adjacent anti periplanar hydroxyl and halogen, to form epoxide

Front 11

Hydration Bromination of Alkene

Back 11

Br2 in H2O

Br to less stable and OH to more stable carbon

Front 12

Epoxide synthesis with alkene

Back 12

MCPBA

1.Br2 in H2O

2. NaOH or NaH

Front 13

Acid-catalyzed epoxide opening

Back 13

R-OH in H2SO4, will protonate the epoxide and the alcohol will attack the partial positive.

Front 14

Nucleophilic epoxide opening

Back 14

OH in H2O or grignards, or NaOCH3 in CH3OH

will attack less substituted carbon

Front 15

Organometalic with ethylene oxide

Back 15

1. R-MgBr react to Ethylene oxide

2. H3O+

Adds two carbons and forms a hydroxyl group

Front 16

Claisen-Williamson reaction of phenol

Back 16

1. Naoh primary alkylene halide

2. Heat

Allows the formation of alkylene to othro or para positions to the hydroxyl only.

The carbonyl forms and then tautomerizes

Front 17

Alkylating agent

Back 17

1. S(CH3)3

will add methyl to lon pair on carbon or nitrogen

Front 18

Oxidation of sulfide

Back 18

1. NaIO4

Forms 1 carbonyl

Front 19

Double carbonyl formation on sulfide

Back 19

H2O2

peroxides or ROOR

Front 20

Oxidation of alcohol to form carbonyl

Back 20

PCC in CH2Cl2

Primary alcohol = aldehyde

Secondary Alcohol = Ketone

Front 21

reduction of Carboxylic acid to alcohol

Back 21

1. LiAlH4

2. H2O

Turns carboxylic acid into a primary alcohol

Front 22

Friedel-Crafts Acylation

Back 22

Cl-CO-R in AlCl3 to do aromatic substitution

Front 23

Gatterman-Koch Formylation

Back 23

CO, HCl, AlCl3, CuCl

To form aldehyde

Front 24

Oxidation of phenol

Back 24

NaCr2O7 H2SO4, H2O will form carboxylic acid

PCC in dry CH2Cl2 will form the aldehyde or ketone with the phenol

Front 25

Alkyne Carbonyl Most stable

Back 25

HgSO4, H2SO4, H2O

will for alcohol in most stable carbon and will tautomerize to a carbonyl

Front 26

To form an aldehyde from an alkyne

Back 26

1. SiaBH

2. H2O2, NaOH

Front 27

Form an aldehyde from an ester

Back 27

1. Dibal-H in hexane -78C

2. H2O

Front 28

Form aldehyde from acyl Chloride

Back 28

1. LiAlH(OtBu)3 -78C

2. H2O

Turns acyl chloride into an aldehyde

Front 29

Formation of Ketone from Acyl Chloride

Back 29

R-CuLi -78C Et2O

To form.a ketone from an aldehyde

Front 30

Ozonolysis

Back 30

1. O3

2. S(Ch3)2

Front 31

Formation of ketone from nitrile

Back 31

1. R-MgBr

2. H3O+

Grignards reaction with nitrile will create a ketone

Front 32

Acyl Chloride to aldehyde

Back 32

1. LiAlH(OtBu)3

2. H3O+

Reduction of acyl chloride to aldehyde

LiAlH4 will create a primary alcohol

Front 33

Dithiane protection of carbonyl

Back 33

HS-C-C-C-SH in acid

Front 34

Deprotonation and alkylation of protected carbonyl

Back 34

1.Li-butyl for deprotonation

2. Primary alkyl halide

Can synthesize any aldehyde or ketone from this reaction

Front 35

Removal of Dithiane protection

Back 35

HgCl2 in H2O

Front 36

How to improve reactivity of ketone?

Back 36

Add acid

Front 37

Will ketone react with H2O

Back 37

No, the product would be too crowded.

Formaldehyde is better.

If acid catalyst is present, ketone will react.

Front 38

What do acid catalysts do?

Back 38

Create a better electrophile

Front 39

What do base catalsyst do?

Back 39

Create a better nucleophile

Front 40

What do electron withdrawing groups do to ketones and aldehydes?

Back 40

Make it more electrophilic

Front 41

How do hemiacetals react in acidic environment

Back 41

They form an acetal with the alcohol, which is a more stable product.

Front 42

Dithiol carbonyl protection

Back 42

HO-C-C-OH in acid, will protect the carbonyl.

Front 43

Removal of acetal protection grouo

Back 43

Acid, H3O+

Front 44

What is BuLi?

Back 44

Lithium butyl, a strong base to remove hydrogens from protected carbonyl groups.

Front 45

Carbo anion with a carbonyl

Back 45

Carboanion can act as a nucleophile and attack a carbonyl group.

Front 46

What happens when a carbonyl is attacked by a nuclephile?

Back 46

Formation of a negative charged oxygen which can be protonated with alcohol

Front 47

Amine nuclophile with carbonyl

Back 47

Forms the hydroxyl group without acid, as the oxygen deprotonates the amino group.

Front 48

How to form imine

Back 48

1. NH3 react with carbonyl

2. Acid to remove hydroxyl as H2O

3. H2O to deprotonate iminium ion.

Ammonia simple acts as a nucleophile for the carbonyl

Front 49

Decorated amino reaction with carbonyl

Back 49

The nitrogen will replace the oxygen and form an imine with the terminal group being the substituent.

Front 50

Wolff Kishner reduction of carbonyl

Back 50

1. H2N-NH2

2. H3O+

3. KOH Heat

Will turn carbonyl into an alkyl.

Front 51

Phosphorus Ylide reaction with carbonyl

Back 51

1. Ph3-P=R

Will Replace oxygen with alkyl chain.

Double bond remains.

Front 52

Sulfur Ylide with carbonyl

Back 52

1. Ph2-S=R

Forms epoxide

Front 53

Odixative cleavage of alkenes

Back 53

1. Hot Conc KMnO4 NaOH, H2O

2. H3O+

Will form hydroxyls from hydrogens.

Front 54

Benzyllic oxidation

Back 54

1. Hot KMnO4, NaOH, H2O

2. H3O+

With presence of benzyllic hydrogen, Carboxylic acid will form.

Front 55

Oxidation of Aldehyde and primary alcohols

Back 55

1. Hot KMnO4, NaOH, H2O

2. H3O+

or chromate.

These will oxidize to caeboxylic acids

Front 56

Oxidation if methyl ketones

Back 56

1. X2, NaOH

2. H3O+

X = Halogen

Will turn the methyl of a ketone into a hydroxyl, forming a carboxylic acid

Front 57

Hydrolysis of Nitrile

Back 57

Introduction of H3O+ to a nitrile will form a carboxylic acid.

Front 58

Carbonation of grignard reaction

Back 58

1. Mg/Ether

2. CO2

3. H3O+

Form a grignard and then introduce CO2, which is a good electrophile, and acid will protonate the Oxygen.

Front 59

Turning a halogen into a nitrile

Back 59

1. NaCN in DMF

Front 60

Carbonyl's reaction with nitrile

Back 60

1. KCN in H2SO4

Forms an acetal and nitrile adds as a nucleophile and forms a hydroxyl from the carbonyl

Front 61

Dehydration of an amide

Back 61

1. POCl3 in pyridine

or

P2O5 in pyridine

SOCl2 Pyridine

Turns an amide into a nitrile

Front 62

Reudction of Nitriles to amine

Back 62

1. LiAlH4

2. H2O

Reducted to an amine

Front 63

Reduction of nitrile to Aldehyde

Back 63

1. Dibal-H

2. H2O

reduced to a nitrile

Front 64

Hydrolysis of Imine

Back 64

1. H3O+

To form a ketone from the Imine

Front 65

Reduction of Amide to Imine

Back 65

1. P4O10 in heat reduced to nitrile

2. Grignards R-MgBr

3. H3O+

4. H3O+

The last hydrolysia forms a carbonyl from imine

Front 66

Formation of epoxide from alkene, no peracid

Back 66

1. Br2 in H2O

2. NaOH

Will form epoxide

Front 67

Li in liquid NH3

Back 67

Forms trans product in alkyne

Front 68

Elimination of Hydroxyls

Back 68

POCl3 in pyridine

Will form an alkene

Front 69

Ketone into a carboxylic acid

Back 69

H2Cr2O7 in H2O

Front 70

Carboxylic acid into a ketone

Back 70

1. H2Cr2O7 in H2O

2. R-CuLi @ -78C in Et2O

Front 71

Chance alkene between cis and trans

Back 71

1. MCPBA

2. Ph3P