Organic Chemistry I Reactions PDF

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Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Notes *Adds a halide

Addition of HX

H

(Mark)

H

H

HBr

Br CH3

H

Addition of HX

H

CH3

H

H

H

CH3

Add two Br's anti

CH3

to alkene

H

D

ROOR

CH3

CH 2Cl2

Br D

Br

CH3

CH3

OH (Mark w/ Br as H

Br2

and anti-planar)

H 2O

D Forming alkene from vicinal dihalide

H3C

Br

*Anti and co planar

*Anti and co planar

OH D *Wedges with wedges

Br

H

Br

to least substituted carbon.

H

Br2

(or CCl 4)

Adding a Br and

*Adds a halide

CH3

H H

carbon.

H

Br H

HBr

(Anti-Mark)

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

H2SO 4

alkene

OH

give terminal alkene

heat *SPECIAL REACTION:

OH

Addition of OH (direct and mark)

POCl3

dehydrates to form

heat

terminal alkene. *CANNOT CONTROL

CH 3

CH3 CH 3

H3O+

CH 3

STEREOCHEM! *Low yield!

OH

*C+ formation!

1

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Oxymercuration/

CH3

demercuration

Notes

CH3 OH

1) Hg(OAc)2 / H2 O

(Add OH from alkene

2) NaBH4

mark and antiplanar)

1) Hg(OAc ) 2/ CH3 OH

CH3 O CH3

2) NaBH4

H

CH3

SPECIAL: Adds alcohol instead to form ethers!

D

D

*Mark and antiplanar

H

D

D

*Complex mechanism

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

Hydroboration

D

D

(Add Oh anti-mark and

CH3 1) BH / THF 3

syn planar)

CH3 H

2) H2O2 / -OH

Catalytic Hydrogenation

H3 C

CH 3

H3 C

(Alkenes -> Alkane, Syn D

Pt, Pd, or Ni CH 3

CH3

*Steric factors must be payed attention to

D

H2

Addition of H)

*Notice Peroxide

OH

*Can use D 2 instead

H 3C H H

*expensive Formation of

CH3

Vicinal Diols

OsO 4

(Syn) H 2O2

D CH3

KMnO 4

D

cold, basic

OH CH3

*toxic *great yield

D OH

OH CH3 D OH

*cheaper *safer *poor yield

2

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task Ozonolysis

Reaction R

Notes *Can use Zn/acetic acid

R

O

1) O 3 / CH2 Cl2

(double bond cleavage)

+

R R

R

R

R H

R

H

R

H

R

R

1) O3 / CH 2Cl 2

O

O

R

R

+

R

H

1) O 3 / CH2 Cl2

O

O

2) (CH3) 2S

+

*Can isolate the formaldehyde.

R

2) (CH3)2S

R

Warm KMnO 4

instead of (CH3) 2S

R

2) (CH3) 2S

R R

O

H

R

H

O

O

*further oxidizes to form KMnO 4

cleavage

+

R R

R

R

R

warm

R

R

R

carboxylic acids *cannot isolate the formaldehyde

R

H

R

H

R

KMnO 4

O R

warm

KMnO 4 warm

H

+

addition (formation of cyclopropane)

OH

O

+ CO2 +

R

H3 C

H2 O

R

CH3

*syn

CH 2N2

*stereochem is preserved

heat

*Second reaction uses the Simmons-Smith

D H

R

R

Carbene / Carbenoid

CH3

O

D

CH3

CH 2I2 Zn(Cu)

D

reagent

H

CH 3

H3C

D *useful for synthesis

Formation of epoxides from alkenes

CH3

CH3 MCPBA

ORGO II)

O D

(ESPECIALLY IN

D

3

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Notes

H3 O

O

NOTE: Can use ROto form ethers. You

+

H2 O

OH

*Basic are like SN2 (least substituted side)

OH -

O

2)H 3O

+

Formation of

Cl CH 3

H3C

CHCl3

*please look up the

Cl

mechanism so you can

H

CH3

KOH

D

D

H3 C

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

CH 3

1) OH

Dichlorocarbenes

side.

D CH 3

Dibromocarbenes and

from more substituted

OH

D

will see this in Orgo II.

*acidic conditions opens

CH3

CH 3

Opening of Epoxides

H3C

C

C H

NaNH2

H 3C C

C

-

that is handy when connecting carbons!

Uses of the acetylide

with methyl or 1o halides

anion

H3C

C

C

-

*SN2 because of the CH3 Br

H3C C

C CH 3

exception we learned from before!!!!

with 2o or 3 o halides

H3 C C

Br -

C

*E2 remember from last

H3C CH CH 3

H3 C CH

CH 2

with carbonyl groups (ketones, aldehydes, and formaldehydes)

*acetylide anion attacks

HO O H3C C CH 3

1) H3C C 2) then H3 O+

-

C

H3C

test!!!

partially positive carbon

C CH 3

*DO NOT FORGET

C

then H3 O+

C H3C

4

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Notes *Need either geminal or

Synthesis of Alkynes

Br Br

o

1) NaNH2 / 100 C

H3 C CH CH CH 3

2) H3 O +

vicinal dihalides

HC C CH2 CH 3

*Look up mechanism *NaNH 2 gives terminal

Br Br

*KOH gives internal

CH 2 CH CH2 CH 3 Br H3C C CH2 CH 3 Br Br HC CH 2 CH2CH 3

o

200 C

Br Halogenation of alkynes

KOH

Br2 and alkyne

H 3C

C

C CH3

H

H3C

*Stereochem cannot be controlled

H3C

C

C H

Br

Br2 (1 eq)

Br

+ Br

H

H3 C HBr and alkyne

Br

Br

HBr

H

*syn addition

(1 eq)

H3 C C

H3C

C H

*Mark

H Br

HBr (2 eq)

Br *Anti mark

HBr and alkyne

HBr

H3C

C

C H

ROOR

H

Br

H 3C

H

*syn addition

*Takes it all the way back

Catalytic reduction with reactive catalyst

H3 C

C

C CH 3

H2

to alkane *generally bad yield

Pt, Pd, or Ni

5

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task Alkyne to Alkene: TRIPLE to DOUBLE

Reaction

Notes *isolates an alkene with

Lindlar's catalyst

H3 C

C

C CH3

H 2 / Pd(BaSO4) quinoline

H

H

a SYN addition of H

H 3C

CH 3

H

CH 3

*isolates an alkene with

Dissolving metal

H3C

C

C CH 3

NaNH3

H3C Addition of H-OH to alkynes

H

Mercuric Ion

C H

*Mark addition

O

HgSO 4 / H2 O

H3C CH2 C

an ANTI addition of H

*If not terminal, you will

C H 2SO 4

CH 3

H3C CH2

get a mixture.

*Formation of ketone

H3C CH 2 C

C CH 3

HgSO 4 / H2 O

O

H 2 SO4

C CH 2 CH 3

H3 C CH 2

+ O C CH 3

H3 C CH 2 CH 2 Hydroboration

*Antimark addition

O 1) Sia 2 BH

H 3C CH 2 C

C H

2) H 2O 2 / -OH

*will get a mixture if not

C H3C CH 2 CH 2

H

terminal

*Formation of aldehyde

Oxidation of alkynes (mild conditions)

H3C

C

C CH 3

*Forms vicinal

O

KMnO4 / H2 O

carbonyls

neutral / cold

*further oxidizes terminal

O

alkynes to form carboxylic acid.

H3C

C

C H

O

KMnO 4 / H2 O neutral / cold

OH O

6

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task Cleavage of Alkynes:

Reaction

Notes

Oxidation of alkyne (strong)

H 3C

C

*Forms H2 O and CO2

O

C CDH 2

1) KMnO4 / H2 O

if terminal.

H 3C

2) - OH / heat

OH

+ O CDH 2

HO H 3C

C

C H

1) KMnO 4 / H2 O

O

+

-

2) OH / heat

H3C

C CDH 2

C

C

C H

H H3C CH

O

H2O

+

CO 2

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

H H3 C CH

C

allyl, vinyl, and aryl

MgBr

The Organolithium

from Grignard

previous

OH

ether

Br

Formation of alcohols

+

*Same products as

CDH2

Mg

C

CO 2

O

+ OH HO

2) H2 O H3 C

2) H2 O

The Grignard Reagent

Reagent

O

1) O 3

1) O3

+

OH

Ozonolysis

H3C

H 2O

*This reagent acts like

Li

H3 C CH 2

Br

pentane or hexane

H3C CH2

Li

1 o alcohols. (Grignard and formaldehyde)

1)

H

*Carbon attachment H

2) H 3O +

OH

2 o alcohols. (Grignard and aldehyde)

*Know this mechanism! O

MgBr

1)

*Carbon attachment

H

2) H 3O +

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

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Notes *Reaction goes until

Grignard and esters

O

OH

MgBr

or acid halides

completion

OCH 3 1)

*Know this mechanism!

2) H 3O

+

Grignard and Epoxides (opening of epoxides)

*SN2 like (attacks least

O

1) 2) H3O

+

substituted side) *Know this mechanism! *This is just good to

Attaching Deuterium to carbons

OH

MgBr

H3C

D2O

MgBr

Corey-House Reaction

Li

CH 3Br

CH3Li

H 3C

CuI

D

know.

*not well understood

(CH 3 )2 CuLi

(do not need to know mechanism)

+

Br

*another way to attach carbons.

Hydride reduction of

*reduces only

mild conditions (NaBH 4 as reagent)

carbonyls

O

aldehydes and

OH

NaBH 4

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) H3 O+

OH

OH

*Two step process

8

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task Raney Nickel

Reaction

Notes *Reduces both carbonyl

O

H2

OH

and alkene.

Ra-Ni

Oxidation of alcohols

*any [ox] can be used

2 o alcohols

Na2 CrO7

*KMnO4 and NO 3 can

H2SO4 / H 2O

OH

be used but they are harsh.

CrO3 / H2SO 4 / H2O

O

acetone / 0oC (Jones reagent)

PCC CH2 Cl2 1 o alcohols

*PCC is the only one

Na2CrO7 H 2SO4 / H 2O

that can isolate

OH

the formaldehyde.

O CrO3 / H 2SO 4 / H2 O

OH

acetone / 0o C (Jones reagent)

H PCC

O

CH 2Cl 2

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

Facilitator: Chris Lovero

Organic Chemistry Reactions 10

Task

Reaction

Notes *Basically an SN2

Formation of 1o /2o

PBr3 o

alkyl halides from 1 /2

o

Br CH3

reaction. (Inversion

CH2 Cl 2

from original alcohol)

alcohols PCl 3

H 3C

OH CH 2 Cl2 P / I2

Cl CH 3

I

CH3

CH 2Cl 2 Formation of acid

*

O

halides from carboxyllic

O

SOCl 2

H

acids

NOT STABLE

Cl O

OH CH3

HIO4

Cl

so don't form that.

OH

Unique cleavage with

O

HIO4

OH

*Vicinal diols must

be syn

CH 3 H

H O Williamson ether synthesis

O

*Basically that SN2

-

exception we learned

H3 C Br

O

Pinacol - Pinacolone

OH OH

Rearrangement

in test 2

*Need vicinal diols

O

*Know mechanism

H2 SO4

(methyl shift!)

*another one of the

Fischer Estherification

H 3C

orgo II reactions

CH 2 OH H

H3 C CH 2 O

+ HO C O

+

CH3

C O

CH3...