CHEM 341: Organic Chemistry I

at North Dakota State University Reactions to know Final Exam - Study Guide

Substitution of Alcohols R OH + HX R X + HOH

SN1 Substitution H OH HCl OH - HOH Cl Cl

SN2 Substitution H OH HCl OH Cl

3 carbocation best 2 carbocation ok

- HOH

Cl

1 will not form carbocation R OH + SOCl2

O Cl S Cl

R
Cl

Cl

SO2

HCl

O S O H Cl Cl

OH

SN2 Substitution - will work with 1 and 2 alcohols, not 3 alcohols R OH + PBr3
Br Br P Br

R
Br

Br

H3PO3

Br P

OH

O H

Br

Br

Chem 341 Final Exam Study Guide!

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spring 2012

Free Radical Halogenation

CH4

Cl2

light
or heat

CH3Cl

Initiation Cl Cl Propogation Cl
+

Cl H C H H

Cl H Cl H + H C H H

H H C
+

Cl

Cl

C H

Cl

Cl

H Termination H H C H Elimination of Alcohols H R2C OH CR2

+

H Cl H C H Cl

H+ R2HC CHR2 + HOH

E1 Elimination - proceeds through carbocation, 2 and 3!alcohols H OH H3PO4 O H -H2O H

H H

H2PO4

E2 Elimination - 1 alcohols, requires anti-periplanar arrangement OH H H3PO4 H O

H2PO4

Chem 341 Final Exam Study Guide!

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spring 2012

Elimination of Halides H R2C X CR2

RO R2C CR2 + HOR

E2 Elimination - 1, 2 or 3 halides with strong base requires anti-periplanar arrangement Cl K+ -OCH3

KCl

HOCH3

H E1 elimination can occur under neutral conditions only with 3 halides

Electrophilic Addition to Alkenes

A A+ B-

B A

or
A

overall equivalent reagents

H2O (H+ cat) BH3 then H2O2/OHHX H+ X2

X2/H2O

A+ H+ OH+

BHOHXXHO-

notes Markovnikov syn addn, anti-Markovnikov Markovnikov bridged, anti addn bridged, anti addn, Markovnikov

X+ X+

H3PO4

OH H2O H Markovnikov Addition

H H2O 250C Most stable intermediate Lower energy pathway

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Chem 341 Final Exam Study Guide!

spring 2012

H3C C H3C C

H + H HBr

H3C H3C

H C C H H

Br

H3C H3C

Br H C C H H

Most stable intermediate Lower energy pathway

Markovnikov Addition

Br Br-Br A bromonium Br

Br

Br Bromide can only come from the bottom and kick off the bromine on the top. This reaction forms the trans product selectively.

Br Br-Br CH3 H2O CH3 H2O

Br

CH3

OH Markovnikov Addition even if there is no full carbocation

Hydroboration and Hydrogenation 1) BH3 H BH2 2) H2O2 / NaOH H OH

anti-Markovnikov hydration syn addition H2 Pd/C

H H syn addition of H2

Chem 341 Final Exam Study Guide!

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spring 2012

Reduction (Hydrogenation) Reactions

H2 Pd/C H H2 Pd/C H H2 Lindlar's Catalyst stops at alkene H H Lindlar's Catalyst Pd(OAc)2 quinoline on CaCO3 H H H

Li NH3

H trans alkene H

Electrophilic Addition Reactions

cat. HgSO4 H2SO4 H 2O O

Ketone

HCl 1 equiv
Br2 1 equiv Br

Cl

HCl 1 equiv
Br2 1 equiv

Cl

Cl

Br Br

Br

Br

Br

Oxidation Reactions
O3 then Zn/HOAc O + O

O O3 then
O Cl O O H

OH O

Zn/H+

HO

mCPBA

epoxidation

Chem 341 Final Exam Study Guide!

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spring 2012

Substitution Reactions
!+ H 3C Na !Br CH3

NaNH2

O Cl S Cl

Cl

O O H S Cl Cl

OH

Br Br P Br

Br Br P

OH

O H
Tos-Cl pyridine

Br

Br

O S
O Tos

Cl

OH

O Tos-Cl

Elimination Reactions
Br or Br can be prepared by Br2 addition to an alkene a vinyl bromide KOH or NaNH2 Br KOH or NaNH2

Br

Br

You should know the mechanistic details of SN1, SN2, E1 and E2 mechanisms and what factors influence substitution vs elimination pathways. There are a number of different nucleophiles and electrophiles that participate. You should be familiar with those and be able to recognize what various reactants do.

Chem 341 Final Exam Study Guide!

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SN1 SUBSTRATE NUCLEOPHILE LEAVING GROUP STEREOCHEM SOLVENT 3 >> 2 > 1 Weak OK Stable Anions Racemic Polar Protic

SN2 1 > 2 >> 3 Strong Stable Anions 100% inversion Polar Aprotic

R-X

SN1

E1

SN2

E2

favored

favored with strong base favored with strong base

ok

ok

favored with strong nucleophile X

favored in protic solvents no base

can compete witn SN1

favored with strong or weak base

Good Nucleophiles

Strong Bases

I N3

Br

Cl

CN

SH

SR

OH

OR

NH2

C CR

bulkier is less nucleophilic

Chem 341 Final Exam Study Guide!

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spring 2012

Preparation of Conjugated Dienes

NBS peroxides
Br

KOt-Bu t-BuOH

Note that the allylic position is especially easy to form free radicals. Halides can be eliminated under base conditions to form conjugated dienes. Alcohols can be eliminated under acidic conditions. Reactions of Conjugated Dienes
HBr H H H

not formed
H Br Br H

1,2-addition 71% 15% 29% 85%

1,4-addition

Kinetic Control Thermodynamic Control

0 C 40 C

Diels-Alder Reactions
+
CO2CH3 CO2CH3 CO2CH3

diene

dieneophile
CH3

cyclic transition state

CH3 CH3 H CH3 O opposite sides

+
H CH3 O

+
CH3

H O same side

dieneophile

exo product minor exo transition state

CH3 H3C H O H H3C H opposite sides O H H CH3 H

endo product major

endo transition state

H H CH3

secondary orbital interaction with the carbonyl pi-bond lowers the energy for this transition state

H3C H O H H same side O

Chem 341 Final Exam Study Guide!

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spring 2012

Electrophilic Aromatic Substitution

Br2 FeBr3 H

Br

Br NOT formed Br

H
NEED TO KNOW MECHANISM

Br H Br Br H Br H Br -HBr Br

Br2 FeBr3

Br Br2 + FeBr3 Br electrophile Cl Cl2 + FeCl3 Cl electrophile + FeCl4 + FeBr4

Cl2 FeCl3

I2 CuI2

I2

CuI2

I electrophile

+ CuI3

HNO3 H2SO4

NO2

O HO N O

H2SO4

O N O electrophile

Fuming SO3 H2SO4

SO3H

O O S O

H2SO4

O O S OH electrophile
O

R-Cl AlCl3

+ O

Cl

AlCl3

88%

Chem 341 Final Exam Study Guide!

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spring 2012

Activating Electron Donating Groups ortho, para directors

OR NR2 SR
strongest (resonance)

Deactivating Electron Withdrawing Groups meta directors

NO2 strongest (resonance) SO3H

O
weakest (inductive)

X weak

alkyl

R CN

ortho, para directors but deactivating

Other Reactions of Benzene and Substituents

O C O OH KMnO4 O C OH

CH3

KMnO4

O KMnO4 C OH KMnO4

No Reaction

O N Br NBS O O Ph O O O Ph

Br

O H2

Zn(Hg)

Pd/C R

H3O+ R

H2

Na / NH3

Pt 2000 psi

Chem 341 Final Exam Study Guide!

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spring 2012