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: chrislovero@gmail.com 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/
Pg.1
Task
Addition of HX (Mark)
Reaction
H H H CH3 H H H H X CH3
Notes
*Adds a halide
HX
Addition of HX (Anti-Mark)
H H
H CH3
HX ROOR
H
H CH3
H H
Halide Addition
CH3 D
CH3 X D
CH3
X2
CH3
H2O
D
Forming alkene from vicinal dihalide
X
H H3C
OH D
H H3C Br
Br H CH3
NaI or KI acetone
H CH3
Dehydration to alkene
H2SO4
OH
heat
*Dehydrates to form
OH
POCl3 heat
terminal alkene.
CH3 CH3
OH
Pg.2
CH3 D CH3
CH3 OH D H
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
H 3C
CH3
H3 C D H3 C H H
CH3
H2 Pt, Pd, or Ni
CH3
OsO4 H2O2
*SYN formation *Expensive, toxic *Great Yield *SYN formation *Cheaper, safer *Poorer yield *ANTI Formation
CH3CO3H H2O
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.
1) O3 / CH2Cl2 2) (CH3)2S
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
KMnO4 warm
KMnO4 warm
+ CO2 +
H2O
CH3 D
H H3C CH3 D
CH3
CH2N2 heat
CH2
D
CH2I2 Zn(Cu)
reagent
H H3C
CH2
CH3 D
*mCPBA with nonpolar
CH3 D
CH3
mCPBA CH2Cl2
O D
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+
*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
H3C C
H3C C
C CH3
with 2o or 3o halides
Br
-
H3C C
H3C CH CH3
H3C CH
CH2
test!!!
O
1) H3C
HO C C
-
H3C
C CH3 C C
H3C C CH3
2) then H3O+
H3C
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
vicinal dihalides
HC C CH2 CH3
H3C C
C CH3
Halogenation of alkynes
H3C
Br2 (1 eq)
H Br
Br
H3C C
C H
+
Br H3C H Br H H Br
*Mark *syn addition
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
H3C C
C CH3
H2 Pt, Pd, or Ni
H H
H H
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
H3C C
C CH3
Na / NH3
H H3C
CH3 H O C
an ANTI addition of H
Mercuric Ion
HgSO4 / H2O
H3C CH2 C
C H
H2SO4
H3C CH2 O
CH3
H3C CH2 C
HgSO4 / H2O
C CH3
H2SO4
+
O C H3C CH2 CH2 CH3
Hydroboration
O
1) Sia2BH
H3C CH2 C
C H
2) H2O2 / -OH
H3C C
C CH3
H3C C
C H
O OH O
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
H3C C
C H
1) O3 2) H2O
O H3C
+
OH
H2O
+
H
CO2
H H3C CH C Br
Mg ether
H3C CH
C MgBr
Li
H3C CH2
Br
pentane or hexane
H3C CH2
Li
MgBr
1)
OH
2) H+
2o alcohols. (Grignard and aldehyde)
O
MgBr
1)
2) H+
3o alcohols. (Grignard and ketone)
O
OH
*Know this mechanism! *Carbon attachment
1)
MgBr
2) H+
OH
Pg.8
Task
Grignard and esters or acid halides
Reaction
O OCH3 1)
2) H
+
MgBr
Notes
*Reaction goes until
OH
OH
H3C
MgBr
D2O
H3C D
know.
Corey-House Reaction
Li
CH3Br CH3
CuI
CH3Li
(CH3)2CuLi
Br
*reduces only
NaBH4 EtOH
OH H
O OH
NaBH4 EtOH
*reduces aldehydes,
O OH
H2O
OH H H
O O
+
OH
OH
*KNOW MECHANISM
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
OH O
OH
H
PCC CH2Cl2
*RETENTION from
OH
TSCl
OTos
*X = Br or Cl
OH
0oC
Pg.10
Task
Formation of 1o/2o alkyl halides from 1o/2o alcohols
Reaction
PBr3 CH2Cl2 PCl3
Notes
*Basically an SN2
Br CH3
H3C OH
CH2Cl2 P / I2 CH2Cl2
Cl CH3
CH3
OH CH3 OH H
HIO4
O CH3 H O
1o or 2 o alcohols
Nao OH O Ko OH O
O
-
2o or 3o alcohols
R Br
*Must be identical
2x CH3CH2-OH
H2SO4 140oC
CH3CH2-O-CH2CH3
OH OH
H2SO4
Fischer Estherification
H3C CH2 OH
+
HO C O CH3
H3C CH2 O
C O
CH3