ALKENES
Preparation:
1. Dehydrohalogenation
of 2º or 3º alkyl halides:
H
X
C
C
KOH
R
C
C
C
C
H 2O
+
R
KX
+
- HX
2. Dehydration of alcohols:
H
OH
C
C
H2SO4, D
or
H3PO4, D
Reactions:
H2 / Pt, Pd, Ni, etc.
C
1. Catalytic Hydrogenation:
(Reduction)
C
H 2O
+
H
H
C
C
1 atm., 25 ºC
alkane
X
X2 (Br 2 or Cl 2) in CCl 4
2. Halogenation:
(qualitative test)
C
C
C
C
X
trans, vic (1.2) alkyl dihalide
3. Halohydrin formation:
OH
X2 (Br 2 or Cl 2) in H2O
C
C
C
or HOX
C
X
trans halohydrin
4. Hydration (possible C+ rearrangement)
or Hydration by
Oxymercuration/Demercuration:
(without C+ rearrangement)
C
dilute aq. H2SO4
or
C
1. Hg(OAc)2 in aq. THF
2. NaBH4
(anti addition)
5. Hydration by
Hydroboration/Oxidation:
(AntiMarkovnikov product):
C
OH
C
C
Markovnikov alcohol
1. BH3 in THF
2. H2O2, OH , pH 8
C
H
OH
H
C
C
syn, antiMarkovnikov alcohol
6. Addition of H2SO4
(qualitative test):
H
C
C
conc. H2SO4
O
C
C
O
S
H
OH
alkyl bisulfate
C
8. Addition of HBr:
(anitMarkovnikov product)
C
ORGANIC REACTIONS
C
C
C
C
OH
D
O
7. Addition of Alkyl Halides:
(Markovnikov product)
H 2O
Markovnikov alcohol
H
X
C
C
Br
H
C
C
HX
HBr, H2O2
Markovnikov alkyl halide
antiMarkovnikov alkyl bromide
1
-
+
O K
O
9. Oxidation without Cleavage
(Hydroxylation)
(Baeyer’s Test):
C
C
Mn
cold, dil. KMnO4
neutral or basic
O
O
C
C
OH
OH
C
C
MnO2
+
brown
precipitate
syn, vic diol
10. Oxidation with Cleavage
R
hot, dil. KMnO4
acidic or basic
C
C
C
C
R
H
H
H
R
C
H
R
HO
+
O
ketone
C
R
O
+
O
C
C
+
OH
CO2
carboxylic acid
carbon
dioxide
O
O
O
C
C
1. O3 in CH2Cl2 at -78ºC
2. Zn in aq. CH3COOH R
Ozonylsis yields only aldehydes and ketones
O
H
H
aldehyde
ketone
C
H
+
H
formaldehyde
ALKYNES
Preparation:
1. Alkene halogenation/dehydrohalogenation:
X2 (Br 2 or Cl 2) in CCl 4
C
H
C
H
H
X
C
C
X
KOH
NaNH2
C
-HX
H
C
C
C
-HX
X
H
trans, vic (1.2) alkyl dihalide
2. Alkylation of alkynides:
NaNH2
C
C
H
C
-NH3
terminal alkyne
methyl or 1º
R X
-
C : Na+
alkynide
C
C
R
+
Na+X-
H
H
C
C
larger alkyne
Reactions:
1. Catalytic
Hydrogenation:
C
C
or
C
C
1 atm., 25 ºC
C
(complete reduction)
X
X2 in CCl 4
C
H2 / Pt, Pd, Ni, etc.
trans-alkene
Li in liq. NH3
2. Halogenation:
(qualitative test)
cis-alkene
H2 / Lindlar cat.
deactivated Pd
1 atm., 25 ºC
C
X2 in CCl 4
C
X
antiaddition product
3. Hydrohalogenation:
C
C
C
C
X
C
C
X
X
X
H
C
C
X
H
HX
X
antiaddition product
4. Hydration:
HgSO4, dil., aq. H2SO4
C
HO
H
C
C
enol
ORGANIC REACTIONS
X
H
HX
C
alkane
gem dihalide
tautomerization
O
H
C
C
H
ketone
2
AROMATIC REACTIONS
H
H
H
Electrophilic Aromatic Substitution (EAS):
An electrophile (E+) substitutes for (replaces)
hydrogen on an aromatic ring:
H
+
+ E
H
H
E
H
H
+
H
H
H
H
- H+
H
E
H
H
H
H
H
1.
Bromination:
H
H
H
+
Br 2
Br
H
H
+
FeBr 3
H
H
H
HBr
H
H
H
H
2.
Chlorination:
H
H
+
Cl
H
H
Cl2
H
H
3.
Iodination:
H
H
H
HNO3
or
H
I
CuCl2
H
H
H2SO4
H
NO2
H
H
H
I2
+
H
H
Nitration:
H
H
H
H
H
H
Sulfonation:
H
H
SO3H
H
H
SO3
+
H
Friedel-Crafts Alkylation:
an arom atic
sulfonic acid
H
H
6.
H2O
H
H2SO4
H
H
+
H
H
5.
HI
H
HNO3
+
+
H
H
4.
AlCl3
H
H
H
+
H
H
CH3
H
H
+
CH3Cl
H
H



HCl
H
H

HCl
+
FeCl3
H
H
H
The aromatic ring must be as reactive as a halobenzene. Less reactive rings do not react. Even
amino-substituted aromatics don't react because the amino groups are converted to electron
withdrawing groups (cationic quaternary amines) by reaction with the catalyst.
Vinyl and aryl halides do not react.
The alkyl halide can be methyl, ethyl, 2, or 3. Other primary alkyl halide C+'s rearrange.
Polysubstitution produces mixed products. (The product is more reactive than the reagent.)
O
7.
Friedel-Crafts Acylation:
H
H
O
AlCl3
H
+
R
C
H
H
Cl
H
H
H
C
H
H
R
+
HCl
H
 As with F.C. Alkylation, the aromatic ring must be as reactive as a halobenzene (amino groups also fail)
 Aryl halides will react. (Vinyl acyl compounds do not exist).
 Rearrangements do not occur.
 Polysubstitution will not occur. (The reagent is more reactive than the product.)
ORGANIC REACTIONS
3
8.
Reduction of Nitro Groups
forming Aromatic Amines:
1. SnCl2, H3O+
2. OH-
H
H
NO2
or
H2/Pt 1 atm ., 25ºC
H
H
H
9.
:O :
Alkali Fusion of Aromatic Sulfonates
forming Phenols:
..
O
..
H
H
NH2
H
H
H
H
1. NaOH, 300ºC
2. H3O+
..
OH
..
S
OH
H
:O :
H
H
H
H
H
H
H
H
Nucleophilic Aromatic Substitution (NAS):
Aromatic compounds with a halogen ortho- or para- to one or more nitro-groups are weak
electrophiles. Nucleophiles such as OH-, OR- and NH3 will substitute for (replace) the halogen.
H
H
H
NO2
H
..
Cl
.. :
H
H
:
-
Nu:
H
-
.. : Cl :
H
H
H
H
H
..
Cl
.. :
H
OH
H
NO2
.. :
Na+ : Cl
..
+
H
H
11. Nitroamines by NAS:
NO2
H
..
Cl
.. :
H
Nu
H
1. NaOH, 100ºC
2. H3O+
NO2
H
NO2
H
..
Cl
.. :
Nu
H
H
10. Nitrophenols by NAS:
-
H
NO2
H
1. NH 3, 100ºC
2. NaOH
NO2
H
.. :
Na+ : Cl
..
+
H
NH2
H
O
H
12. Oxidation of Alkylbenzene
Side Chains:
CH2CH2CH3
H
H
KMnO4
H2O, D
O
OH
+
H
H
H
H
C
H
HO
C CH3
H
H
Benzylic C's with one or more H's are oxidized to carboxylic acids
Br
13. Bromination of Alkylbenzene
Side Chains:
H
H
O
C
C
H2C
CH2
CH2CH2CH3
H
H
N
O
R
..
O
..
..
O
..
R
CCl4
H
CHBrCH2CH3
H
H
H
H
H
NBS (N-bromosuccinimide), in the presence of a peroxide, releases bromine free radicals
(Br) which brominate the benzylic carbon rather than the ring.
14. Catalytic Reduction of Aromatics and Aryl Alkyl Ketones (from F.C. Acylations):
H2 on Pt, Pd, Ni, etc.
1 atm ., 25ºC
or
O
H
H
H
H
H
H2 on Rh
1 atm ., 25ºC
H
ORGANIC REACTIONS
H
H
H
H
H
H
H
H
H
C
H
H
R
Clem m ensen: [Zn(Hg)], HCl
or
Wolf Kishner: NH2NH2 , KOH
H
CH2
H
H
H
H
4
R
ALCOHOLS
Preparation:
X
OH
KOH
C
1. Hydrolysis of Methyl or
of 1º alkyl halides:
H
C
C
H
C
SN2
H
+
KX
H
(2 or 3  alkenes by E2)
2. Hydration (possible C+ rearrangement)
or Hydration by
Oxymercuration/Demercuration:
C
dilute aq. H2SO4
or
C
1. Hg(OAc)2 in aq. THF
2. NaBH4
(anti addition)
(without C+ rearrangement)
Hydration by
Hydroboration/Oxidation:
C
(AntiMarkovnikov product):
3. Hydride Reduction of
Aldehydes,
Ketones,
Esters &
Carboxylic Acids:
OH
C
C
Markovnikov alcohol
1. BH3 in THF
2. H2O2, OH , pH 8
C
H
OH
H
C
C
syn, antiMarkovnikov alcohol
aldehyde
R
C
H
O
ketone
R
C
H
NaBH 4 in EtOH
or
LiAlH4 in ether
1.
O
2.
H3O+
1.
NaBH 4 in EtOH
or
LiAlH4 in ether
R
O
R
C
1º alcohol
H
O
R
2º alcohol
R
C
H3O+
2.
H
H
H
H
O
ester
R
C
1.
2 LiAlH 4
2.
H3O+
R'
O
O
R
C
H
H
+
HO
R'
1º alcohol
H
O
carboxylic
acid
4. Grignard Reduction of
Aldehydes,
Ketones &
Esters:
R
C
O
1.
3 LiAlH 4
2.
H3O+
H
O
R
C
H
1º alcohol
H
H
O
aldehyde
R
C
1.
R'MgX in ether
2.
H3O+
O
H
R
C
R
Br
H
O
ketone
R
C
ORGANIC REACTIONS
1.
R'MgX in ether
2.
H3O+
R
O
R
Mg in ether
(Grignard may be alkyl,
aryl or vinylic but cannot
be prepared when acidic
groups are present
with the halide)
2º alcohol
R'
Grignard Preparation
- +
R: MgBr
H
R
C
3º alcohol
R'
H
O
ester
R
C
O
1.
2 R'MgX in ether
2.
H3O+
R
O
R
C
R'
+
R'
3º alcohol
HO
R
5
ALCOHOL REACTIONS
1. Dehydration to Alkenes:
H
OH
C
C
H2SO4, D
for 3º or 2º
E1
C
N:
POCl 3 in
for 1º or 2º
2. Conversion to Alkyl Halide:
C
H 2O
+
E2
3º or 2º
HCl, ZnCl 2
SN1
1º or 2º
SOCl 2
SN2
HBr
SN1
1º or 2º PBr 3
SN2
Cl
C
OH
C
C
C
3º or 2º
Br
C
3. Neutralizing a Strong Base:
C
-
(Alcohols have pKb ca. 16 like H2O)
R
O
+
H
R
Na
strong base
weak acid
O
Na+
+
1
/ 2 H2
alkoxide
mild oxidation
(oxidants in non aq. solvents)
4. Oxidation of Alcohols:
OH
R
O
PCC (in CH2Cl2)
R
Collins reagent (CrO3 in pyridine)
aldehyde
C
CH2
1º alcohol
O
moderate oxidation
(oxidants in aq. solvents)
R
C
OH
carboxylic
acid
Jones reagent (CrO3 in aq. H 2SO4 & acetone)
KMnO4, HNO3, etc.
O
mild or moderate oxidation
(in non aq. solvents or any cold aq. solvent)
R
R
PCC (in CH2Cl2)
Collins reagent (CrO3 in pyridine)
OH
CH
C
R
enol
ketone
hot conc. KMnO4
HNO3 or H2CrO4
Jones reagent (CrO 3 in aq. H2SO4 & acetone)
cold acidic or basic KMnO4, HNO3, etc.
R
2º alcohol
O
severe oxidation
(hot aq. KMnO 4 or HNO 3)
C
R
CH
2 R
R
alkene
dehydration
C
OH
carboxylic acid
mild or moderate oxidation
(any anhydrous or cold aq. oxidant)
OH
R
H
no rxn.
O
R
severe oxidation
R
(hot aq. KMnO 4 or HNO 3)
3º alcohol
R
CH
2 R
R
alkene
dehydration
C
OH
carboxylic acid
5. Reduction to Alkanes:
a) Dehydrate to alkenes (1. above), then hydrogenate (H2 / Ni) to alkane
or
b) Prepare alkyl tosyate (good leaving group), then replace with H: - (following)
O
R
OH
+
Cl
S
O
tosyl chloride, TsCl
ORGANIC REACTIONS
O
-HCl
CH 3
R
O
S
O
1. LiAlH4
CH3
R
H
2. H3O+
alkane
alkyl tosylate
6
THIOLS
pKa = 7.0
Preparation:
H 2S
pKb = -1.74
pKb = 7.0
NaOH
Na+ HS+
sodium
hydrosulfide
+
(from hydrogen sulfide, H2S
and then hydrosulfide, HS- )
Na+ HSweak base
+
R
X
Me, 1º, 2º
alkyl halide
v. good Nu:-
R
SN2
SH
pKeq = -8.7 (100%)
H 2O
Na+ X-
+
thiol
Reactions:
1. Reaction as acid
with a base:
pKa ca. 8.0
R
Williamson Ether Synthesis:
[alkoxide substitution (SN2)
with Me or 1 alkyl halide]
pKb ca. 6.0
NaOH
R
S- Na+
sodium
alkyl sulfide
+
SH
2. Sulfide formation by
substitution (SN2) with
Me, 1, or 2 alkyl halides:
ETHERS s
pKb = -1.74
S- Na+
R
+
R'
weak base
+
R'
R
alkoxide
strong base
good Nu:-
S
Na+ X-
+
R'
sulfide
R
X
SN2
Me or 1º
alkyl halide
pKeq = -7.7 (100%)
H2O
SN2
Me, 1º, 2º
alkyl halide
v. good Nu:-
pKb ca. -2
.. _
R
O : Na+
..
X
+
O
R'
Na+ X-
+
ether
HO
Epoxide Ring Opening:
(Most ethers are unreactive but
epoxides are reactive because
of their high ring strain.)
+
O
H3O
-
or
H2O, OH
trans, vic diol
OH
ALDEHYDES & KETONES
1. Mild Oxidation of 1 Alcohols:
2. Reduction of Carboxylic Acid
Derivatives:
R
CH2
acid chloride
R
C
O
ORGANIC REACTIONS
2.
H3O+
R'
O
C
R
H3O+
1.
1 equivalent
DIBAH @ -78ºC
2.
H3O+
N:
C
H
O
1 equivalent
DIBAH @ -78ºC
2.
H
O
R
1.
C
R
1 equivalent
DIBAH @ -78ºC
Cl
(use 1 equivalent of a mild hydride, i.e.,
DIBAH in cold inert solvent @ -78C)
R
1.
C
aldehyde
Collins reagent (CrO3 in pyridine)
O
nitrile
R
PCC (in CH2Cl2)
1º alcohol
ester
O
mild oxidation
(oxidants in non aq. solvents)
OH
Preparation of Aldehydes:
C
H
+
HO
R'
O
R
C
H
7
Preparation of Ketones:
mild or moderate oxidation
(in non aq. solvents or any cold aq. solvent)
OH
1. Oxidation of 2 Alcohols:
(mild or moderate oxidants)
R
CH
R
R
2º alcohol
2. Oxidative Cleavage of
substituted alkenes:
R
C
C
C
R
H
H
H
3. Friedel Crafts Acylation
of Aromatics:
C
Jones reagent (CrO 3 in aq. H 2SO4 & acetone)
cold acidic or basic KMnO4, HNO3, etc.
hot, dil. KMnO4
acidic or basic
C
O
PCC (in CH2Cl2)
Collins reagent (CrO3 in pyridine)
R
C
H
R
HO
+
O
O
O
C
C
+
OH
CO2
carbon
dioxide
carboxylic acid
ketone
R
ketone
O
H
H
O
H
+
R
C
C
H
Cl
H
H
H
AlCl3
HCl
+
H
H
R
H
H
 As with F.C. Alkylation, the aromatic ring must be as reactive as a halobenzene (and fails with animo groups)
 Aryl halides will react. (Vinyl acyl compounds do not exist).
 Rearrangements do not occur.
 Polysubstitution will not occur. (The reagent is more reactive than the product.)
4.
Hydration of Alkynes:
(non symmetrical internal
alkynes give mixed products)
C
C
dil., aq. H2SO4
O
(a mild Grignard-like reagent, R’2CuLi
in cold inert solvent @ -78C)
R
C
(ketones are not easily oxidized
except under severe conditions.
The enol isomer is cleaved.)
1.
R'2CuLi, ether @ -78ºC
2.
H3O+
C
C
H
ketone
O
R
R'
C
ketone
C
O
H
PCC (in CH2Cl2)
Collins reagent (CrO3 in pyridine)
R
Jones reagent (CrO 3 in aq. H 2SO4 & acetone)
cold acidic or basic KMnO4, HNO3, etc.
O
H
C
R
OH
C
enol
R
C
OH
carboxylic
acid
ketone
no reaction except for
severe oxidation
R'
ORGANIC REACTIONS
enol
H
mild or moderate oxidation
aldehyde
R'
C
O
(in non aq. solvents or any cold aq. solvent)
O
R
tautomerization
Cl
acid
chloride
Reactions of Aldehydes and Ketones:
(aldehydes are easily oxidized)
H
C
5. Acid chloride + Gilman Reagent:
1. Oxidation of
Aldehydes
& Ketones:
HO
HgSO4,
(hot aq. KMnO 4 or HNO 3)
O
R'
C
OH
carboxylic acid
8
2. Hydration of
Aldehydes
& Ketones:
O
OH
H3O+ or H2O, OH2
[acid(H3O+) or base (OH-) catalysis
is required as H2O is a weak Nu:-]
(equilibrium favors the carbonyl)
3
C
sp C
sp C, a gem diol
C
aldehyde
or ketone
OH
OH
C
H3O+, D or OH-, H2O, D
3. Addition of HCN
forming a cyanohydrin:
(the cyanohydrin can be
reduced to an amine or
hydrolyzed to an acid)
+
OH
O
1.
N:
C
aldehyde
or ketone
2.
a cyanohydrin
LiAlH4
OH
H3O+
C
amine
CH2
4. Addition of Alcohols
forming Acetals (diethers):
: O:
(useful as protecting groups
which are inert to strong bases)
[Reaction is reversible. Use
anhydrous acid to form acetal
and aqueous acid back to the
original aldehyde or ketone]
H+
+
C
NH3
C
HCN & NaCN
C
COOH
R
..
O
..
..
O
..
2 ROH
NH2
R
+
C
H 2O
H3O+, D
aldehyde
or ketone
acetal
H
O
5. Grignard Reduction of
Aldehydes to 2 Alcohols
&
Ketones to 3 Alcohols:
aldehyde
R
C
1.
R'MgX in ether
2.
H3O+
O
H
R
C
H
2º alcohol
R'
H
O
ketone
R
C
1.
R'MgX in ether
2.
H3O+
O
R
R
R
C
3º alcohol
R'
6. Hydride Reduction of
Aldehydes to 1 Alcohols
&
Ketones to 2 Alcohols:
1.
O
aldehyde
R
C
H
O
ketone
R
C
2.
H3O+
1.
NaBH4 in EtOH
or
LiAlH4 in ether
R
2.
7. Reduction of Carbonyl (C=O)
group to Methylene (CH2) group
by Wolf Kishner (N2H4 + KOH)
or Clemmensen (Zn[Hg] + H3O+)
ORGANIC REACTIONS
O
NaBH4 in EtOH
or
LiAlH4 in ether
H3O+
Wolf Kishner
N2H4 , KOH
C
aldehyde
or ketone
or
Clemmensen
Zn[Hg], H3O+
H
O
R
C
H
1º alcohol
H
H
O
R
R
C
2º alcohol
H
H
H
C
9
8. Addition of 1 Amines
forming Imines
or
2 Amines
forming Enamines:
H
R
N
1º amine
H
R
..
N
..
+
H
C
: O:
H 2O
C
NH2R
H
C
imine
C
R
H
aldehyde or ketone
NHR 2
:
N
R
..
N
2º
R
+
enamine
C
amine
H 2O
C
R
Examples of Imines:
(Derivatives)
NO2
O
NO2
H
N
N
H
C
NO2
C
H
NO2
H 2O
+
a 2,4-dinitrophenylhydrazone
O
O
H
N
H
aldehyde
or ketone
2,4-dinitrophenylhydrazine
N
O
N
N
H
C
C
NH 2
N
C
N
C
NH2
H 2O
+
H
aldehyde
or ketone
semicarbazide
H
a semicarbazone
O
H
C
N
H
C
hydroxylamine
9. Conjugate 1,4-Addition
of 1 equiv. of Amine
or
1 equiv. of Gilman Reagent:
(In , -unsaturated carbonyls,
addition occurs at the -carbon
and the -carbon is saturated
while the carbonyl is unreacted)
[It only works with these 2 reagents.
Other nucleophiles add directly to
the carbonyl C]
(Excess amine or Gilman reagent
will add to the carbonyl carbon
after the  and -carbons are
saturated)
ORGANIC REACTIONS
aldoxime
or
ketoxime
OH
aldehyde
or ketone
: O:
N
OH
an oxime
4
: O:
H
C
2
3
C
:N
C
1
R
R
H
C
C
C
R
..
N
R
 , -unsaturated
aldehyde or ketone
1,4-conjugate addtion
product
: O:
: O:
C
C
C
1. R 2CuLi, ether
2. H 3O+
C
H
C
C
R
10
CARBOXYLIC ACIDS
O
H
Preparation:
1.
CH2CH2CH3
H
Oxidation of Alkylbenzene
Side Chains:
(Benzylic C's with one or more H's
H
KMnO4
H2O, D
+
H
H
H
H
O
OH
C
H
C CH3
HO
H
H
are oxidized to carboxylic acids)
2. Oxidation with Cleavage:
hot, dil. KMnO4
acidic or basic
C
C
C
C
R
H
H
H
R
C
H
R
R
+
O
HO
O
O
C
C
CH2
CO2
carbon
dioxide
carboxylic acid
ketone
O
R
C
OH
carboxylic
acid
Jones reagent (CrO3 in aq. H2SO4 & acetone)
KMnO4, HNO3, etc.
1º alcohol
+
OH
moderate oxidation
(oxidants in aq. solvents)
OH
3. Oxidation of 1 Alcohols:
(with moderate oxidants)
R
mild or moderate oxidation
4. Oxidation of Aldehydes:
(mild or moderate oxidants)
R
O
(in non aq. solvents or any cold aq. solvent)
C
PCC (in CH2Cl2)
Collins reagent (CrO3 in pyridine)
H
aldehyde
O
R
Jones reagent (CrO 3 in aq. H 2SO4 & acetone)
cold acidic or basic KMnO4, HNO3, etc.
C
OH
carboxylic
acid
O
5. Hydrolysis of Nitriles:
R
(acidic or basic hydrolysis)
6. Grignards are
Carboxylated:
C
H3O+, D
N:
R
C
OH
carboxylic
acid
or OH-, H2O, D
..
1. O
..
_
:R +MgBr
..
O
..
C
: O:
R
C
_
..
:
O
..
2.
:O:
H3O+
R
+
MgBr
C
..
OH
carboxylate
Reactions:
1. Reduction with
LiAlH4 or BH3
in THF solvent:
1.
O
R
C
2.
O
2.
O
ORGANIC REACTIONS
R
C
..
O
..
carboxylic
acid
H
O
R
or
1.
H
H3O+
H
carboxylic
acid
2. Neutralization with
a base:
3 LiAlH4 in THF, D
BH3 in THF
C
H
H
1º alcohol
+
H 3O
O
Na+OHR
C
.. -
:
O
..
Na+
+
H2O
carboxylate salt
11
3. Conversion to
Acid Chloride:
O
O
R
C
+
OH
O
S
R
Cl
Cl
C
Cl
+
+
SO2
HCl
acid chloride
thionyl chloride
4. Dehydration to
Acid Anhydride:
(Reaction is reversible.
Anhydride can be
hydrated back to
2 carboxylic acids)
R
D
O
O
C
O
+
H
H
O
C
_ H O
2
R
R
D
carboxylic acids
O
O
C
O
C
R
acid anhydride
+ H 2O
ORANOMETALLICS
Preparation:
1. Organosodium or
Organolithium:
pentane
R
X
+
R
X
+
2 Na
R
R
+
+
Na
-
Na X
(Finely dispersed metal is
added to dilute RX in HC solvent)
2.
pentane
Wurtz Coupling:
(When Na is not dispersed, Me
or 1 RX react with R-Na via SN2)
3.
Grignard Reagents:
+
-
Na X
- +
Br
R MgBr
Gilman Reagent:
(Any alkyllithium complexes
with CuI in ether)
+
R
R
Mg in ether
R
(Finely divided Mg in ether
is inserted between any R-X bond)
4.
Na
ether
2 R
Li
+
R
Cu
R
+
Li
CuI
or
simply
(R) 2CuLi
a Gilm an reagent
Reactions:
1.
Organosodium/lithium
converted to alkanes:
H2O
R
Na
(And other reactions
where R is nucleophilic)
2.
Grignards converted
to alkanes:
(And other reactions
where R is nucleophilic)
3.
Substitution with any
RX forming larger alkanes:
H2O
- +
R MgBr
R
H
alkane
+
R
H
NaOH
+
MgBrOH
alkane
R'
X
+
(R) 2CuLi
R'
R
+
RCu
+
LiX
(And other reactions
where R is nucleophilic)
ORGANIC REACTIONS
12