Final EXAM Review - Lecture notes ALL PDF

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FINAL EXAM REVIEW 1 Ranking

FINAL EXAM REVIEW 2

FINAL EXAM REVIEW 3

Tautomers

“tautomerize” (Retro)synthesis

FINAL EXAM REVIEW 4

“Circle”

Predict the Product

FINAL EXAM REVIEW 5

-

PhCO3H (two organic products)

-

(1) 2 Br2 (2) HNO3 H2SO4

-

(1) Cl2

-

(1) SOCl2 pyr (2) CH3S-

-

(1) SOCl2 pyr (2) Mg Et2O

FINAL EXAM REVIEW 6

-

(1) pyr (2) CN-

-

(1) PPh3 DEAD

-

(1) Cl2 H2O (2) NaH (3) LiAlH4 (4) H3O+

-

(1) LiALH4 (2) H3O+

FINAL EXAM REVIEW 7 -

(1) Cl2 H2O (2) NaOH H2O

-

(1) SOCl2 pyr (2) excess NH3 (3) LiAlH4 (4) H3O+

-

NAD+ (two products: show both)

-

NAD+ (two products: show both)

-

(1) Cl2 AlCl3 (2) Mg (3) CH3CHO (4) H3O+

-

(1) Mg (2) CH3CHO (3) H3O+

FINAL EXAM REVIEW 8

-

(1) Mg (2) CO2 (3) H3O+

-

(1) Mg (2) CO2 (3) H3O+

-

(1) Mg (2) CO2 (3) H3O+

-

(1) Mg (2) CO2 (3) H3O+

FINAL EXAM REVIEW 9

-

(1) Mg (2) epoxide (3) H3O+

-

(1) Br2 FeBr3 (2) NaBH4

-

(1) Br2 FeBr3 (2) NaBH4

-

(1) Br2 FeBr3 (2) HNO3 H2SO4

FINAL EXAM REVIEW 10

-

(1) PhCOCl AlCl3

-

(1) PhCOCl AlCl3 (2) OH- H2O heat

-

(1) PhCO3H (2) CH3OH H+

-

(1) excess CrO3 H2SO4 H2O acetone

FINAL EXAM REVIEW 11

-

(1) OH- H2O heat (2) H2 Pd

-

(1) CH3COCl NaOH (2) LiAlH4 (3) H3O+

-

(1) CN- (2) LiAlH4 (3) H3O+

-

(1) NaOEt EtOH (2) excess H2O H+ heat

FINAL EXAM REVIEW 12

-

(1) Ag2O OH- (2) H3O+

-

(1) Ag+ OH- (2) H3O+

-

(1) Ag+ OH- (2) H3O+

-

(1) mCPBA

FINAL EXAM REVIEW 13

-

(1) CH3OH H+

-

(1) CF3CO3H (2) NH3

-

(1) CF3CO3H

-

(1) H C C- Na+ (2) H3O+

FINAL EXAM REVIEW 14

-

(1) CF3CO3H (2) excess H2O NaOH heat

-

(1) NH4CN (2) H3O+ heat

-

(1) NH4CN (2) H3O+ heat

-

(1) LiAlH4 (2) H2O

FINAL EXAM REVIEW 15

-

(1) LiAlH4 (2) H2O

-

(1) LiAlH4 (2) H2O

-

(1) LiAlH4 (2) H3O+

-

(1) LiAlH4 (2) H3O+

-

(1) KCN HCN

FINAL EXAM REVIEW 16

-

(1) KCN HCN (pH 9)

-

(1) H+

-

(1) H+

-

(1) H+

FINAL EXAM REVIEW 17

-

(1) H+

-

(1) H+

-

(1) H+

-

(1) excess NH2CH3 (2) LiAlH4 (3) H3O+

FINAL EXAM REVIEW 18

-

(1) KCN HCN (2) OH- H2O heat (3) H3O+

-

(1) KCN HCN (2) excess H2 Ni heat

-

(1) excess H2 Ni

-

(1) excess H2 Pd

FINAL EXAM REVIEW 19

-

(1) excess H2 Pd

-

(1) morpholine (ring with O and N in it) H+ (2) CH3CH2Br (3) H3O+

-

(1) excess H2O H+ heat

-

(1) excess H2O H+ heat

FINAL EXAM REVIEW 20

-

(1) excess H2O H+ heat

-

(1) excess H2O H+ heat

-

(1) NH3 NaBH4 (pH 6)

-

(1) NaBH4 CH3OH

FINAL EXAM REVIEW 21

-

(1) NaBH4 CH3OH solvent

-

(1) NaBH4 (pH 6)

-

(1) ketone H+

-

(1) piperidine (ring with N) H+

FINAL EXAM REVIEW 22

-

(1) piperidine (ring with N) H+

-

(1) piperidine (ring with N) H+ (2) PhCH2CH2Br (3) H3O+

-

(1) CH3CH2Br (2) H2O

-

(1) excess CH3CH2MgI (2) H3O+

FINAL EXAM REVIEW 23

-

(1) H3O+ (two organic products)

-

(1) H3O+ (two organic products)

-

(1) NaH (2) ketone (3) H3O+

-

(1) NaH (2) H3O+

-

(1) NaH (2) 2-bromobutane (two organic products)

FINAL EXAM REVIEW 24

-

(1) EtO- EtOH (2) ketone molecule

-

(1) H2O Hg2+ H2SO4

-

(1) CH3O- CH3OH (2) CH3I

FINAL EXAM REVIEW 25

-

(1) CH3O- (2) CH3I (3) OH- (4) H3O+ heat

-

(1) CH3O- CH3OH

-

(1) heat (2) NaOH (3) CH3I

-

(1) CH2I2 Zn

FINAL EXAM REVIEW 26

-

(1) heat

-

(1) OH- heat (2) (CH3)2CuLi (3) H3O+

-

(1) OH- (2) H3O+ heat

-

(1) (CH3)3CO- (CH3)3COH heat

FINAL EXAM REVIEW 27

-

(1) OH- heat

-

(1) H+

-

(1) H+

-

(1) H+

-

(1) AlCl3

FINAL EXAM REVIEW 28

-

(1) CH3COCl AlCl3

-

(1) Br2 FeBr3

-

(1) NH2NH2 OH- H2O heat

-

(1) NH2NH2 KOH H2O heat

FINAL EXAM REVIEW 29

-

(1) NH2NH2 KOH H2O heat

-

(1) CH3O- (2) H+

-

(1) LiAlH4 (2) H3O+

-

(1) OH- H2O heat

FINAL EXAM REVIEW 30

-

(1) HNO3 H2SO4 (2) Cl2 FeCl3 (3) H2 Pd (4) NaNO2 HCl (5) CuCl

-

(1) NaNO2 HCl (2) CuNO2

-

(1) HNO3 H2SO4 (2) Ketone AlCl3

-

(1) H2SO4 heat

FINAL EXAM REVIEW 31

-

(1) H2SO4 heat

-

(1) NaOH (2) CH3(CH2)6CH2Br

-

(1) excess CrO3 H2SO4 H2O Acetone

-

(1) excess PCC

FINAL EXAM REVIEW 32

-

(1) H2SO4 heat

-

(1) H3O+ heat

-

(1) H3O+ heat

-

(1) OH- H2O heat

FINAL EXAM REVIEW 33 -

(1) H2 Pd (2) NH2NH2 KOH heat

-

(1) KOH H2O heat

-

(1) KOH H2O heat

-

(1) H2NCH3 NaBH4 (pH 6)

-

(1) NaBH4 (pH 6)

FINAL EXAM REVIEW 34

-

(1) H2NCH3 H+ (2) LiAlH4 (3) H2O

-

(1) OH- H2O heat (2) H2 Pd

-

(1) LDA -78ºC (2) PhCH2Br

-

(1) LDA -78ºC (2) PhCH2Br

-

(1) PhCH2Br (2) H3O+

FINAL EXAM REVIEW 35

-

(1) LDA -78ºC

-

(1) OH- H2O heat

-

(1) LDA -78ºC (2) CH3CHO (3) H3O+ 25ºC

-

(1) CF3CO3H (2) CH3OH H+ (3) PCC

FINAL EXAM REVIEW 36

-

(1) PPh3 DEAD

-

(1) PPh3 DEAD

-

(1) PPh3 (2) NaH (3) PhCHO

-

(1) PPh3 (2) NaH (3) ketone

FINAL EXAM REVIEW 37

-

(1) PPh3 (2) BuLi (3) ketone

-

(1) NaH (2) ketone (3) H3O+

-

(1) H+

-

(1) H+

FINAL EXAM REVIEW 38

-

(1) ketone H+

-

(1) PhCH2CH2MgBr (2) H3O+

-

(1) PhCH2MgBr (2) H3O+

-

(1) H3O+

FINAL EXAM REVIEW 39

-

(1) CN- HCN

-

(1) CN- HCN (2) H2 Rosenmund Pd (3) H3O+

-

(1) NaCN (2) excess H2 Ni heat

-

(1) NaCN HCN (two stereoisomeric products)

FINAL EXAM REVIEW 40

-

(1) NaCN (2) LiAlH4 (3) H2O

-

(1) H3O+ heat

-

(1) H3O+ heat (2) PCC (3) H2 Pd

-

(1) H3O+ heat (more than one organic product)

FINAL EXAM REVIEW 41 -

(1) H3O+ heat (two organic products)

-

(1) CH3O- CH3OH heat

-

(1) CF3CO3H (2) LiAlH4 (3) H2O

-

(1) NaH (2) PhCH2Cl (3) H2 Lindlar

-

(1) CH3O- (2) PhCH2Br (3) H3O+ heat

FINAL EXAM REVIEW 42

-

(1) CH3CH2O- (2) H+

-

(1) CH3CH2O- CH3CH2OH (2) OH- (3) H3O+ heat

-

(1) CH3CH2O-

-

(1) heat

-

(1) heat

FINAL EXAM REVIEW 43

-

(1) heat

-

(1) heat

-

(1) heat

-

(1) H3O+

-

(1) H+

FINAL EXAM REVIEW 44

-

(1) H+

-

(1) H+

-

(1) OH- H2O heat

-

(1) H+

FINAL EXAM REVIEW 45

-

(1) H+

-

(1) H+

-

(1) excess CH3MgI (2) excess H+

-

(1) excess CH3MgI (2) H3O+

FINAL EXAM REVIEW 46 -

(1) CH3MgI (2) H3O+

-

(1) MgCl (2) H3O+

-

(1) excess H3O+

-

(1) excess H3O+ heat

-

(1) H+

FINAL EXAM REVIEW 47

-

(1) CH3MgI (2) H3O+

-

(1) PhMgBr (2) H3O+

-

(1) excess PhMgBr (2) H3O+

FINAL EXAM REVIEW 48

Ring with Amino (NH2) + Ring with Aldehydes/Ketones (C=O)

Ring double bonded to Oxygen, Ring with Oxygen and Nitrogen embedded (synthesis)

Reactant

Solvent/What Is Added

Products

Amino (NH2) Aldehyde/Ketone (C=O)

H+

Conjoined molecule

Rings with Nitrogen embedded (N)

Excess H2O H+

Broken up molecule that still retains some structure

Ring with =O Ring with O and NH

H+

Conjoined molecule

FINAL EXAM REVIEW 49

Ring double bonded to Oxygen (C=O)

Insertion of an oxygen (C-O) inside of an aromatic ring

CHO becomes CO2H

Benzene ring attached to alcohol group

H+

CF3CO3H

CHO

1) Ag+ + OH-

CO2H (from initial

FINAL EXAM REVIEW 50 2) H3O+

(gains oxygen)

Aldehyde/Ketone

Another species (ex. Pentane with Nitrogen embedded) + H+

PhCH2Br H3O+

NaBH4

CHO)

Conjoined molecule

FINAL EXAM REVIEW 51

CH3OH (solvent)

H2 Pd

NH2NH2 KOH H2O heat

FINAL EXAM REVIEW 52

LiAlH4 (LAH) H3 O+

HNR2 H+

FINAL EXAM REVIEW 53

+H2O (when there is a positively charged group present)

NaBH4 or H2 + catalyst OR

FINAL EXAM REVIEW 54

1) LiAlH4 2) H2O

Ag+, OH- H3O+

mCPBA

NaBH4 pH 6

FINAL EXAM REVIEW 55

H+ CH3CH2Br H3 O+

tautomerize

Imine Formation

FINAL EXAM REVIEW 56

-

Imine formation occurs under both acidic and is most rapid under mildly acidic conditions Imine formation is reversible: addition or base (hydrolysis) causes reversion an aldehyde or ketone and a

Reductive Amination

Wolff-Kishner Reaction

Tautomerization

basic conditions, but (pH 6). of water and acid of the imine to 1° amine

NaBH4 or NaB(CN)H3 EtOH (ph 6)

Aldehyde/ketone + hydrazine

OH- + heat

FINAL EXAM REVIEW 57

Enamine Formation

Aldehyde or ketone + 2° amine (HNR2); best under acidic conditions

FINAL EXAM REVIEW 58

-

-

Pay

attention when there carbon–carbon preferentially. Be able to enamines are chain extension formation; (2) hydrolysis.

Reduction of aldehydes and ketones

to the is a double

regiochemistryof enamine formation: choice, the less substituted in the enamine forms

employenamines in nucleophiles and are by the three-step enamine + alkyl

synthesis. used to process halide or

Recall that accomplish (1) enamine epoxide; (3)

FINAL EXAM REVIEW 59

H2 adds to group, delivering • All

the less hydrogens

hindered in a

face of cis fashion.

a

carbonyl

Reaction with LiAlH4 or NaBH4 or NaB(CN)H3 three reagents reduce aldehydes to 1º alcohols and ketones to 2º alcohols. All three reagents deliver hydride to the less hindered face of a carbonyl carbon along the Bürgi–Dunitz trajectory.

LiAlH4 / H3O+

FINAL EXAM REVIEW 60

NaBH4 / H2O (solvent)

NaBH4 / CH3OH (solvent)

NADH

FINAL EXAM REVIEW 61

Reactant

Solvent/What Is Added

Products

OXIDATION of ALDEHYDES and KETONES Tollens’ Oxidation of Aldehydes

-

Reactants/Solvents: Ag2O + OH-, H3O+ Aldehydes are oxidized to carboxylic acids by Tollens’ reagent (Ag+/OH– followed by H+ or H3O+). This reaction accomplishes the same result as the Jones oxidation of an aldehyde, but takes place under basic conditions.

Baeyer-Villager Oxidation

-

Reactants/Solvents: PhCO3H

FINAL EXAM REVIEW 62

-

-

A peroxy acid (RCO3H) inserts oxygen between the carbonyl carbon and the more substituted a carbon of a ketone: Baeyer–Villiger oxidation is a way of making an ester from a ketone. Recall that RCO3H also reacts with alkenes to form epoxides, so Baeyer–Villiger oxidation should not be used to create an ester from a ketone that also has a carbon–carbon double bond.

Random Mechanisms

FINAL EXAM REVIEW 63

FINAL EXAM REVIEW 64

Tautomers - Tautomers are two molecules with the same molecular formula but different connectivity - constitutional isomers, in other words - which can interconvert in a rapid equilibrium. The most common tautomeric relationship in organic chemistry is the keto-enol pair.

FINAL EXAM REVIEW 65

FINAL EXAM REVIEW 66

-

-

Given a table of bond energies, be able to calculate which of two tautomers is more stable. • Be able to recognize keto and enol tautomers. Be aware that the keto tautomer is usually more stable than its enol tautomer, but recognize where this general rule is violated (e.g., phenol (PhOH) is more stable than its keto tautomer and enols whose carbon–carbon double bond is conjugated (participates in resonance) tend to be more stable than their keto tautomer).

Reaction Type

Solvents/ Reagents Needed

Reactants

Pinacol Rearrangement (only for symmetrical)

Products

 +H2SO4 (+H+)  Diol (two alcohols)

 Ketone and water

FINAL EXAM REVIEW 67

 Darzens’ Halogenation

Mitsunobu Reaction

 

+Base

Aldehyde ketone and haloester

 Epoxy ester

 Alcohol (1º or 2º) and acidic NUC with a pKa < 12

 +DEAD and Ph3P  1. 1.

Williamson Ether Synthesis ( check to see if it works in both directions, only one, or not at all!)

 Alcohol (1º or 2º)

 2.



  2.

  STEP 1: STEP 1 AND 2:

Jones Oxidation (Primary Alcohol) Primary alcohol

  Cr6+ (in the form of CrO3 or K2Cr2O7)



 Aldehyde  STEP 2:

FINAL EXAM REVIEW 68

 Carboxylic acid

Jones Oxidation (Secondary Alcohol)

 6+ 

Secondary alcohol

Grignard Reagent/Reaction

 Cr (in the form of CrO3 or K2Cr2O7)

 Aldehyde ketone and Grignard reagent

 Ketone

+H3O+ / +H+ acidic workup  Alcohol

Alcohols as Leaving Groups

+H+ (from acid)



 Sp3 C attached to alcohol group   Dehydration of Alcohol

+H+ (from acid)

 +

→ Loses H →

 Ethane with H+ and OH- on opposing



FINAL EXAM REVIEW 69

carbons

+H2O  

Alcohols (acting as aa  cid)

+OH-





+H





+HCl  

Alcohols (acting as ab  ase)

+H2SO4





+H2O 



FINAL EXAM REVIEW 70



Sulfonation

1º, 2º, or 3º  and 





+pyr (pyridine)

  1.        2. 

1. + pyr (pyridine) +SOCl2

Sulfonation (trans → trans; retention)

  -

2. +NUC (ex. CN)  

 1. + pyr (pyridine) +SOCl2

1.

Sulfonation (trans → cis; i nversion) 





2. +NUC- (ex. CN)

  2.

FINAL EXAM REVIEW 71

 1.

 1.

+PCC  PCC (Pyridinium Chlorochromate)



2.

 2.  +solvent (ex. CHCl2) 

 1. 1.

IBX (“green” method of  oxidation — no 2. heavy toxic metals!)





 2.  IBX  

  Biological oxidation of alcohols (1º)

H2O  

FINAL EXAM REVIEW 72

  

 Biological oxidation of alcohols (2º)



H2O





Prilezhaev Reaction (usually with mCPBA)

N/A 

 

FINAL EXAM REVIEW 73

Halohydrins to Epoxides

+H2O (step 2), NaH ( step 3)

1.



2.



3.



4. 





5.



FINAL EXAM REVIEW 74...