Organic+I+Reactions+(COMPLETE).pdf

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Notes *Adds a halide

Addition of HX (Mark)

H

H

H

HBr

Br CH3

H

Addition of HX

H

CH3

H

H

Add two Br's anti

CH3

to alkene

ROOR

H

CH3

CH3

Br2

CH3

CH3

OH (Mark w/ Br as H

Br2

Forming alkene

H2O

from vicinal dihalide

H3C

*Wedges with wedges

Br

H Br

*Anti and co planar

OH D Br

and anti-planar)

D

*Anti and co planar

Br D Br

(or CCl4)

Adding a Br and

to least substituted carbon.

H H

CH2Cl2

D

*Adds a halide

Br H

HBr

CH3

carbon.

H H

(Anti-Mark)

H

to more substituted

H

NaI or KI

CH3

acetone

H

H

H3C

CH3

and dashes with dashes *E2 Like!

*E1 like and it cannot

Dehydration to

H2SO4

alkene

OH

give terminal alkene

heat *SPECIAL REACTION:

OH

Addition of OH (direct and mark)

POCl3

dehydrates to form

heat

terminal alkene. *CANNOT CONTROL

CH3

CH3 CH3

H3O+

CH3

STEREOCHEM! *Low yield!

OH

*C+ formation!

1



Task

Reaction

Oxymercuration/

CH3

demercuration

Notes

CH3 OH

1) Hg(OAc)2/ H2O

(Add OH from alkene

2) NaBH4

mark and antiplanar)

CH3 O CH3

CH3

SPECIAL: Adds alcohol

1) Hg(OAc)2/ CH3OH

instead to form ethers!

2) NaBH4

D

D

*Mark and antiplanar

H

D

D

*Complex mechanism

H

*Complex mechanism *Mark and antiplanar *WILL BE SEEING THIS MORE IN ORGO II *Anti-mark

Hydroboration

D

D

(Add Oh anti-mark and

CH3

syn planar)

CH3

1) BH3 / THF

H

2) H2O2 / -OH

Catalytic Hydrogenation

H 3C

CH3

H3 C

(Alkenes -> Alkane, Syn D

Pt, Pd, or Ni CH3

CH3

*Steric factors must be payed attention to

D

H2

Addition of H)

*Notice Peroxide

OH

*Can use D2 instead

H3 C H H

*expensive Formation of

CH3

Vicinal Diols

OsO4

(Syn)

H2O2

D CH3

KMnO4

D

cold, basic

OH CH3

*toxic *great yield

D OH

OH CH3 D OH

*cheaper *safer *poor yield

2



Task Ozonolysis

Reaction R

R

Notes O

1) O3 / CH2Cl2

(double bond cleavage)

+

R R

R

R

R

R

R

1) O3 / CH2Cl2

O

O

Warm KMnO4

H

R

H

R

H

R

R

2) (CH3)2S

R

1) O3 / CH2Cl2

O

2) (CH3)2S

+

*Can isolate the formaldehyde.

R H

+

R

*Can use Zn/acetic acid instead of (CH3)2S

R

2) (CH3)2S

R R

O

O H

R

H

O

O

*further oxidizes to form KMnO4

cleavage

R

warm

R

+

R

R

R

R

carboxylic acids *cannot isolate the formaldehyde

R

R

R

H

R

H

R

KMnO4

O R

warm

warm

addition (formation of cyclopropane)

R OH

O

+ CO2 +

R

H2O

R

Carbene / Carbenoid

CH3

O

R

KMnO4

H

+

CH3 CH2N2

the Simmons-Smith

D

H3C

*stereochem is preserved *Second reaction uses

heat

H

*syn

D

CH3

CH2I2 Zn(Cu)

D

H

reagent

CH3 D

H3C

*useful for synthesis

Formation of epoxides from alkenes

CH3

CH3 MCPBA

ORGO II)

O D

(ESPECIALLY IN

D

3



Task

Reaction

Notes

O

to form ethers. You

H2O

OH

CH3

OH

O

2)H3O+

Formation of

H3C

CHCl3

*please look up the

Cl

Cl CH3

mechanism so you can

H

CH3

KOH

D

D

H 3C

CH3

see how the carbene is formed

CH3 Br

CHBr3 KOH

D

Br

D

*forms the nucleophile

Formation of the acetylide anion

mechanism.

D OH

D H

*Please look up

CH3

1) OH

Dichlorocarbenes

*Basic are like SN2 (least substituted side)

-

Dibromocarbenes and

side.

D

D

will see this in Orgo II.

from more substituted

OH

H3O+ NOTE: Can use RO-

*acidic conditions opens

CH3

CH3

Opening of Epoxides

H 3C C

NaNH2

C H

H3C C

C

-

that is handy when connecting carbons!

Uses of the acetylide anion

*SN2 because of the

with methyl or 1o halides

H 3C C

C

-

CH3Br

C CH3

exception we learned from before!!!!

with 2o or 3o halides

H 3C C

H3C C

C

Br -

*E2 remember from last

H3C CH CH3

CH2

H3C CH

with carbonyl groups (ketones, aldehydes, and formaldehydes)

*acetylide anion attacks

HO O H3C C CH3

1) H3C

C

2) then H3O+

-

C

test!!!

H3C

partially positive carbon

C CH3

*DO NOT FORGET

C

then H3O+

C H3C

4



Task

Reaction

Notes *Need either geminal or

Synthesis of Alkynes

Br Br

1) NaNH2 / 100oC

H3C CHCH CH3

2) H3O+

vicinal dihalides

C CH2 CH3

HC

*Look up mechanism *NaNH2 gives terminal

Br Br

*KOH gives internal

CH2CHCH2CH3 Br H3C C CH2 CH3 Br Br KOH

HC CH2 CH2CH3

200oC

Br Halogenation of alkynes

Br2 and alkyne

H 3C

C

C

H 3C

CH3

H

*Stereochem cannot be controlled

H 3C

C

C

H

Br

Br2 (1 eq)

Br

+ Br

H

H 3C HBr and alkyne

Br

Br

HBr

H

*syn addition

(1 eq)

H 3C

C

C

H 3C

H

*Mark

H Br

HBr (2 eq)

Br *Anti mark

HBr and alkyne

HBr

H 3C

C

C

H

ROOR

H H 3C

Br

*syn addition

H *Takes it all the way back

Catalytic reduction with reactive catalyst

H 3C

C

C

CH3

H2

to alkane *generally bad yield

Pt, Pd, or Ni

5



Task

Reaction

Alkyne to Alkene:

Lindlar's catalyst

TRIPLE to DOUBLE

H 3C

C

Notes *isolates an alkene with

C

H2 / Pd(BaSO4)

CH3

quinoline

H

H

a SYN addition of H

H 3C

CH3

H

CH3

*isolates an alkene with

Dissolving metal

H 3C

C

C

NaNH3

CH3

H 3C Addition of H-OH to alkynes

H

Mercuric Ion

HgSO4 / H2O

H3C CH2 C

C

H

H2SO4

an ANTI addition of H

O

*Mark addition

C

*If not terminal, you will

CH3

H3C CH2

get a mixture.

*Formation of ketone

H3C CH2 C

C

CH3

HgSO4 / H2O

O

H2SO4

C CH2 CH3

H3C CH2

+ O C CH3

H3C CH2 CH2 Hydroboration

*Antimark addition

O 1) Sia2BH

H3C CH2 C

C

H

2) H2O2 / -OH

*will get a mixture if not

C H3C CH2 CH2

H

terminal

*Formation of aldehyde

Oxidation of alkynes (mild conditions)

H 3C

C

C

CH3

*Forms vicinal

O

KMnO4 / H2O

carbonyls

neutral / cold

*further oxidizes terminal

O

alkynes to form carboxylic acid.

H 3C

C

C

H

O

KMnO4 / H2O neutral / cold

OH O

6



Task Cleavage of Alkynes:

Reaction

Notes

Oxidation of alkyne (strong)

H 3C

C

*Forms H2O and CO2

O

C CDH2

1) KMnO4 / H2O

if terminal.

H 3C

2) -OH / heat

OH

+ O CDH2

HO H 3C

C

C

H

1) KMnO4 / H2O

O

-

2) OH / heat

H 3C

C CDH2

C

C

C

H

1) O3

H H3C CH

from Grignard

*Same products as previous

CDH2

+

H 2O

+

CO2

OH *Forms from 1o, 2o, 3o,

H H3C CH

C

allyl, vinyl, and aryl

MgBr

The Organolithium

Formation of alcohols

+

O

ether

Br

CO2

O

Mg

C

+

OH HO

2) H2O H3C

2) H2O

The Grignard Reagent

Reagent

O

1) O3

H 2O

OH

Ozonolysis

H 3C

+

*This reagent acts like

Li

H3C CH2

Br

pentane or hexane

H3C CH2

Li

1o alcohols. (Grignard and formaldehyde)

1)

H

*Carbon attachment H

2) H3O+

OH

2o alcohols. (Grignard and aldehyde)

*Know this mechanism! O

MgBr

1)

*Carbon attachment

H

2) H3O+

OH

3o alcohols. (Grignard and ketone)

*Know this mechanism! O

MgBr

grignard but is stronger.

*Know this mechanism!

O

MgBr

carbons.

*Carbon attachment

1) 2) H3O+

OH

7



Task

Reaction

Notes *Reaction goes until

Grignard and esters

O

OH

MgBr

completion

or acid halides

OCH3 1)

*Know this mechanism!

2) H3O

+

Grignard and Epoxides (opening of epoxides)

*SN2 like (attacks least

O

MgBr

1)

OH

2) H3O+

*Know this mechanism! *This is just good to

Attaching Deuterium to carbons

substituted side)

D2O

MgBr

H 3C

Corey-House Reaction

Li

CH3Br

H 3C

CuI

CH3Li

D

know.

*not well understood

(CH3)2CuLi

(do not need to know mechanism)

+

Br

*another way to attach carbons.

Hydride reduction of

*reduces only

mild conditions (NaBH4 as reagent)

carbonyls

O

aldehydes and

OH

NaBH4

ketones.

EtOH

*use alcohols as a

O

NaBH4

solvent.

no reaction

EtOH

Cl *reduces aldehydes,

strong conditions (LiAlH4 as reagent)

ketones, esters, acid

O OH

1) LiAlH4 / ether

halides, carboxyllic

2) H3O+

acids.

OH

*Use ethers solvents

O O

+

1) LiAlH4 / ether 2) H3O+

OH

OH

*Two step process

8



Task Raney Nickel

Reaction

Notes *Reduces both carbonyl

O

H2

OH

and alkene.

Ra-Ni

Oxidation of alcohols

*any [ox] can be used

2o alcohols

Na2CrO7

*KMnO4 and NO3 can

H2SO4 / H2O

OH

be used but they are harsh.

CrO3 / H2SO4 / H2O

O

acetone / 0oC (Jones reagent)

PCC CH2Cl2 1o alcohols

*PCC is the only one

Na2CrO7 H2SO4 / H2O

that can isolate

OH

the formaldehyde.

O CrO3 / H2SO4 / H2O

OH

acetone / 0oC (Jones reagent)

H PCC

O

CH2Cl2

Formation of the

*RETENTION from

Tosylate Ester

OH

TSCl

OTos

where alcohol was originally (SN2

purposes) Formation of alkyl halide from 3o alcohols

OH

HCl / ether 0oC

Cl

9


Organic Chemistry Reactions 10

Task

Reaction

Notes *Basically an SN2

Formation of 1o/2o

PBr3

alkyl halides from 1o/2o

Br CH3

reaction. (Inversion

CH2Cl2

from original alcohol)

alcohols

*Can also use SOCl2

PCl3

H3C OH

CH2Cl2

Cl CH3

for Cl, but it undergoes a special mechanism!

P / I2

I

CH3

CH2Cl2 Unique cleavage with

O

OH CH3

HIO4

HIO4

*Vicinal diols must

CH3

be syn

OH

H

H O Formation of Alkoxide

1o or 2 o alcohols

Nao OH

Anion

O Ko

2o or 3o alcohols

O

OH O

Williamson ether synthesis

-

-

*Basically that SN2

Br

H 3C

-

exception we learned

O

in test 2 *Must be identical

Ethers from intermolecular dehydration

2x CH3CH2-OH

H2SO4

CH3CH2-O-CH2CH3

140oC

Pinacol - Pinacolone

O

OH OH

Rearrangement

alcohols or else you will get a mixture!!!

*Need vicinal diols *Know mechanism

H2SO4

(methyl shift!) Fischer Estherification

H 3C

CH2 OH

C O

*CAN USE ACID

+

H3C CH2 O

+ HO

H

CH3

C O

CH3

HALIDE instead of carboxyllic acid!!!

Organic+I+Reactions+(COMPLETE).pdf

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