Organic Chemistry I

The Unofficial Reaction Sheet

Notice to User
Find the latest reaction sheet at the following website: http://kmr86.com/index.html This reaction sheet was made to supplement the students in my workshop for UHs Fundamentals of Organic Chemistry I. Usage of this reaction sheet will not guarantee you a passing grade on your exam. It is highly recommended to thoroughly review important mechanisms as indicated by your instructor. Flash cards or generating your own sheet similar to this one is also helpful. But remember, just memorizing this reaction sheet will only hurt you in the future when you have to take your ACS test. You must memorize AND understand. Also understand that this reaction sheet was student made and may contain mistakes. If you find any errors, please email me at the address below with a detailed description so I may fix it. Email errors to: [email protected] Good luck! And I hope you find this useful! For additional practice outside of school assigned material, I found the following websites very useful: http://zadefaraj.com/ http://www.ochemweb.com/

Facilitator: Chris Lovero

Organic Chemistry Reactions v2.1

Pg.1

Task
Addition of HX (Mark)

Reaction
H H H CH3 H H H H X CH3

Notes
*Adds a halide

HX

to more substituted carbon. *X = F, Br, Cl, etc *Adds a halide

Addition of HX (Anti-Mark)

H H

H CH3

HX ROOR
H

H CH3

to least substituted carbon. *X = F, Br, Cl, etc

H H

Halide Addition

CH3 D

X2 CH2Cl2 (or CCl4)

CH3 X D

*Anti and co planar *X = F, Br, Cl, etc

Halohydrin Reaction (Mark w/ X as H and anti-planar)

CH3
X2

CH3
H2O

*Anti and co planar *X = F, Br, Cl, etc

D
Forming alkene from vicinal dihalide

X
H H3C

OH D

H H3C Br

Br H CH3

*Wedges with wedges

NaI or KI acetone

H CH3

and dashes with dashes *E2 Like!

Dehydration to alkene

*E1 like and it cannot

H2SO4
OH

give terminal alkene

heat
*Dehydrates to form

OH

POCl3 heat

terminal alkene.

Addition of OH (direct and mark)

CH3 CH3 H3O+

CH3 CH3
OH

*RACEMIC MIXTURE *Low yield! *C+ formation!

Facilitator: Chris Lovero Task

Organic Chemistry Reactions v2.1 Reaction Notes

Pg.2

CH3 D CH3

1) Hg(OAc)2/ H2O 2) NaBH4

CH3 OH D H

*Complex mechanism *Mark and antiplanar

SPECIAL: Adds alcohol instead to form ethers!

1) Hg(OAc)2/ CH3OH

CH3 O CH3 D
D

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

D
Hydroboration (Add Oh anti-mark and syn planar)

2) NaBH4

CH3 1) BH / THF 3
2) H2O2 / -OH

OH CH3 H

*Notice Peroxide

Catalytic Hydrogenation (Alkenes -> Alkane, Syn Addition of H)

H 3C

CH3

H3 C D H3 C H H

CH3

*Steric factors must be payed attention to *Can use D2 instead

H2 Pt, Pd, or Ni
CH3

Glycol Synthesis from Alkene Oxidation

CH3 D CH3 D CH3 D

OsO4 H2O2

OH CH3 D OH OH CH3 D OH CH3 OH D OH

*SYN formation *Expensive, toxic *Great Yield *SYN formation *Cheaper, safer *Poorer yield *ANTI Formation

KMnO4 cold, basic

CH3CO3H H2O

*oxirane intermediate *See opening of epoxide in acidic conditions

Facilitator: Chris Lovero Task

Organic Chemistry Reactions v2.1 Reaction

Pg.3

Notes
*Can use Zn/acetic acid

O R R O R R O R R

+ +

O R R O R H O H H
*further oxidizes to form instead of (CH3)2S *Can isolate the formaldehyde.

2) (CH3)2S 1) O3 / CH2Cl2 2) (CH3)2S

1) O3 / CH2Cl2 2) (CH3)2S

Warm KMnO4 cleavage

R R R R R R

R R R H H H

KMnO4 warm

O R R O R R O R R

+ +

O R R O R OH

carboxylic acids *cannot isolate the formaldehyde

KMnO4 warm

KMnO4 warm

+ CO2 +

H2O

Carbene / Carbenoid addition (formation of cyclopropane)

CH3 D
H H3C CH3 D

CH3
CH2N2 heat

*syn *stereochem is preserved *Second reaction uses the Simmons-Smith

CH2

D
CH2I2 Zn(Cu)

reagent

H H3C

CH2

CH3 D
*mCPBA with nonpolar

Oxidation of Alkenes: oxirane synthesis

CH3 D

CH3
mCPBA CH2Cl2

solvent can isolate oxirane

O D

Facilitator: Chris Lovero

Organic Chemistry Reactions v2.1

Pg.4

Task
Opening of Epoxides

Reaction

Notes

CH3
H+

CH3 OH OH D OH
1) OH
-

*acidic conditions opens from more substituted side. *Basic are like SN2 (least substituted side) *Please look up mechanism.

NOTE: Can use ROto form ethers. You will see this in Orgo II.

O D CH3 O D

H2O

CH3 D OH
Cl Cl C
CH3 D

2) H+

Formation of Dibromocarbenes and Dichlorocarbenes

*please look up the mechanism so you can see how the carbene is formed

H H3C

CH3 D

CHCl3 KOH

H H3C

CH3 D
Formation of the acetylide anion

CH3
C Br Br

CHBr3 KOH

D
*forms the nucleophile NaNH2
-

H3C C

C H

H3C C

that is handy when connecting carbons!

Uses of the acetylide anion

with methyl or 1o halides

*SN2 because of the CH3Br

H3C C

H3C C

C CH3

exception we learned from before!!!!

with 2o or 3o halides

Br
-

*E2 remember from last

H3C C

H3C CH CH3

H3C CH

CH2

test!!!

with carbonyl groups (ketones, aldehydes, and formaldehydes)

*acetylide anion attacks

O
1) H3C

HO C C
-

partially positive carbon *DO NOT FORGET then H3O+

H3C

C CH3 C C

H3C C CH3

2) then H3O+

H3C

Facilitator: Chris Lovero

Organic Chemistry Reactions v2.1

Pg.5

Task
Synthesis of Alkynes

Reaction
Br Br H3C CHCH CH3 Br Br CH2CHCH2CH3 Br H3C C CH2 CH3 Br Br HC CH2 CH2CH3 Br
KOH 200oC

Notes
*Need either geminal or

1) NaNH2 / 100oC 2) H3O+

vicinal dihalides

HC C CH2 CH3

*Look up mechanism *NaNH2 FAVORS terminal *KOH FAVORS internal

H3C C

C CH3

Halogenation of alkynes

Br2 and alkyne

H3C
Br2 (1 eq)

H Br

*Stereochem cannot be controlled

Br

H3C C

C H

+
Br H3C H Br H H Br
*Mark *syn addition

HBr and alkyne

HBr (1 eq)

Br H3C

H3C C

C H
HBr (2 eq)

H H
*Anti mark

Br
HBr and alkyne

HBr

H H3C

Br H

*syn addition

H3C C

C H

ROOR

Catalytic reduction with reactive catalyst

*Takes it all the way back

H3C C

C CH3

H2 Pt, Pd, or Ni

H H

H H

to alkane *generally bad yield

Facilitator: Chris Lovero

Organic Chemistry Reactions v2.1

Pg.6

Task
Alkyne to Alkene: TRIPLE to DOUBLE
Lindlar's catalyst

Reaction
H H3C H CH3

Notes
*isolates an alkene with

H3C C

C CH3

H2 / Pd(BaSO4) quinoline

a SYN addition of H

Dissolving metal

*isolates an alkene with

H3C C

C CH3

Na / NH3

H H3C

CH3 H O C

an ANTI addition of H

Addition of H-OH to alkynes

Mercuric Ion

*Mark addition *If not terminal, you will

HgSO4 / H2O

H3C CH2 C

C H

H2SO4

H3C CH2 O

CH3

get a mixture. *Formation of ketone

H3C CH2 C

HgSO4 / H2O

C CH3

H2SO4

C H3C CH2 CH2 CH3

+
O C H3C CH2 CH2 CH3
Hydroboration

O
1) Sia2BH

*Antimark addition *will get a mixture if not

H3C CH2 C

C H

C H3C CH2 CH2 H

2) H2O2 / -OH

terminal *Formation of aldehyde

Oxidation of alkynes (mild conditions)

H3C C

C CH3

KMnO4 / H2O neutral / cold

*Forms vicinal carbonyls *further oxidizes terminal

alkynes to form carboxylic acid.

H3C C

C H

KMnO4 / H2O neutral / cold

O OH O

Facilitator: Chris Lovero

Organic Chemistry Reactions v2.1

Pg.7

Task
Cleavage of Alkynes:
Oxidation of alkyne (strong)

Reaction
O
1) KMnO4 / H2O 2) -OH / heat

Notes
*Forms H2O and CO2 if terminal.

H3C C

C CDH2

H3C

OH

+
O CDH2 H2O

HO H3C C C H
1) KMnO4 / H2O 2) OH / heat
Ozonolysis
-

O H3C O

+
OH

CO2

H3C C

C CDH2

1) O3 2) H2O H3C

+
OH HO

O CDH2

*Same products as previous

H3C C

C H

1) O3 2) H2O

O H3C

+
OH

H2O

+
H

CO2

The Grignard Reagent

H H3C CH C Br

Mg ether

*Forms from 1o, 2o, 3o, allyl, vinyl, and aryl

H3C CH

C MgBr

carbons. *This reagent acts like

The Organolithium Reagent

Li

H3C CH2

Br

pentane or hexane

H3C CH2

Li

grignard but is stronger.

Formation of alcohols from Grignard

1o alcohols. (Grignard and formaldehyde)

*Know this mechanism! *Carbon attachment

MgBr

1)

OH

2) H+
2o alcohols. (Grignard and aldehyde)
O

*Know this mechanism! *Carbon attachment

MgBr

1)

2) H+
3o alcohols. (Grignard and ketone)
O

OH
*Know this mechanism! *Carbon attachment

1)

MgBr

2) H+

OH

Facilitator: Chris Lovero

Organic Chemistry Reactions v2.1

Pg.8

Task
Grignard and esters or acid halides

Reaction
O OCH3 1)
2) H
+
MgBr

Notes
*Reaction goes until

OH

completion *Know this mechanism!

Grignard and Epoxides (opening of epoxides)

*SN2 like (attacks least 1)

OH

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

2) H+ Attaching Deuterium to carbons

H3C

MgBr

D2O

H3C D

know.

Corey-House Reaction

Li

CH3Br CH3

CuI

*not well understood

CH3Li

(CH3)2CuLi

(do not need to know mechanism)

Br

*another way to attach carbons.

Hydride reduction of carbonyls

mild conditions (NaBH4 as reagent)

*reduces only

NaBH4 EtOH

OH H

aldehydes and ketones *use alcohols as a solvent. *KNOW MECHANISM

O OH

NaBH4 EtOH

not desired product

strong conditions (LiAlH4 as reagent)

*reduces aldehydes,

O OH

1) LiAlH4 / ether 2) H3O+

ketones, esters, acid

H2O

halides, carboxyllic acids (ALL Carbonyls) *Use ethers solvents

OH H H

O O

1) LiAlH4 / ether 2) H3O+

+
OH

OH

*KNOW MECHANISM

Facilitator: Chris Lovero

Organic Chemistry Reactions v2.1

Pg.9

Task
Raney Nickel

Reaction
O
H2 Ra-Ni

Notes
*Reduces both carbonyl

OH

and alkene.

Oxidation of alcohols

2o alcohols

*any [ox] can be used Na2CrO7 H2SO4 / H2O *KMnO4 and NO3 can be used but they are harsh.
CrO3 / H2SO4 / H2O acetone / 0oC (Jones reagent)

OH

PCC CH2Cl2
1o alcohols

Na2CrO7 H2SO4 / H2O

*PCC is the only one

OH O

that can isolate the formaldehyde.

CrO3 / H2SO4 / H2O

OH

acetone / 0oC (Jones reagent)

H
PCC CH2Cl2

Formation of the Tosylate Ester

*RETENTION from

OH

TSCl

OTos

where alcohol was originally (SN2 purposes)

Formation of alkyl halide from 3o alcohols HX / ether

*X = Br or Cl

OH

0oC

Facilitator: Chris Lovero

Organic Chemistry Reactions v2.1

Pg.10

Task
Formation of 1o/2o alkyl halides from 1o/2o alcohols

Reaction
PBr3 CH2Cl2 PCl3

Notes
*Basically an SN2

Br CH3

reaction. (Inversion from original alcohol) *Can also use SOCl2

H3C OH

CH2Cl2 P / I2 CH2Cl2

Cl CH3

for Cl, but it undergoes a special mechanism!

CH3

Unique cleavage with HIO4

OH CH3 OH H
HIO4

O CH3 H O

*Vicinal diols must be syn

Formation of Alkoxide Anion

1o or 2 o alcohols

Nao OH O Ko OH O
O
-

2o or 3o alcohols

Williamson ether synthesis

*Basically that SN2

R Br

exception we learned in test 2

Ethers from intermolecular dehydration

*Must be identical

2x CH3CH2-OH

H2SO4 140oC

CH3CH2-O-CH2CH3

alcohols or else you will get a mixture!!!

Pinacol - Pinacolone Rearrangement

OH OH
H2SO4

*Need vicinal diols *Know mechanism (methyl shift!)

Fischer Estherification

H3C CH2 OH

*CAN USE ACID

+
HO C O CH3

H3C CH2 O

C O

CH3

HALIDE instead of carboxyllic acid!!!