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• solubility
–
gives
a
clue
on
the
functional
groups
that
a
§ polar
compounds
with
few
h-‐bonding
compound
contains
groups/sites
• information
§ IMFA:
van
der
waals
w/
diethyl
ether
o presence
of
functional
groups
–
polar
or
§ –OH,
–NH2,
–COOH,
–CONH2,
nonpolar
aldehydes,
ketones,
esters
o specific
information
(ex.
weak
or
strong
acid)
o Class
S2
o estimation
of
molecular
size
and
composition
§ polar
compounds
with
many
h-‐bonding
§ 5-‐carbon
chain
rule
(Kamm’s
rule)
groups/sites
• types
of
solubility
§ salts
of
organic
acids,
RNH3Cl,
amino
o due
to
miscibility
–
dissolution
due
to
the
same
acids,
carbohydrates
IMFA
(part
of
the
chart
that
is
soluble
in
H2O)
• Class
A
o due
to
chemical
reactions
–
dissolution
due
to
∗ acidic
+
reactions
with
solvent
that
produces
a
soluble
∗ H
ready
to
react
with
base
product
(part
of
the
chart
that
is
insoluble
in
o Class
A1
H2O)
§ strong;
insoluble
in
weak
bases
• factors
in
solubility
o Class
A2
o temperature
§ weak
o polarity
• Class
B
o molecular
size
(↑MW:
↑IMF:
less
soluble)
o soluble
in
5%
HCl
by
chemical
reaction
o chain
branching
(↑branching:
↓IMF:
more
o most
contain
nitrogen
soluble)
o with
amines
(up
to
tertiary
amines):
R–NH2,
R2–
NH,
R3–N
Classes
of
Compounds
• Class
M
• Class
S
o miscellaneous:
neither
acidic
nor
basic
∗ water-‐soluble
compounds
with
H-‐bonding
o amides
or
nitro
compounds
functional
groups
(–OH,
–NH2,
–COOH,
–CONH2)
• Class
N
∗ limited
to
5-‐carbons
per
H-‐bonding
group
o react
with
concentration
H2SO4
through
forced
o Class
S1
protonation
o with
oxygen
or
unsaturated
Chem
31.
Midterms
Reviewer
1
/steffigatdula/
o ketones,
aldehydes,
alcohols,
alkenes,
alkynes
o saturated
and
aromatic
hydrocarbons
• Class
I
o alkanes,
aromatics,
alkyl
halides
o no
reaction
with
H2SO4
Alcohols
precipitate
• have
a
hydroxyl
group
bonded
to
a
saturated
C
atom
Oxidation
of
Phenols
Lucas
Test
• oxidized
to
quinones
• modified
SN1
mechanism,
meaning
that
the
reaction
rate
• quinones
are
unsaturated
ketones
which
are
usually
is
determined
by
the
rate
of
formation
of
the
carbocation
colored
• the
reagent
favors
SN1
because
it
is:
• positive
result:
brown
precipitate
o acidic
o it
has
ZnCl2
which
is
a
lewis
acid
Experiment
8:
Aliphatic
and
Aromatic
Hydrocarbons
o as
a
solvent,
highly
polar
ionic
• positive
result:
formation
of
layers
and
cloudiness
Hydrocarbons
o 3°
>
2°
>
1°
>
CH3OH
• aliphatic
–
alkanes,
alkenes,
alkynes
o benzyl
alcohol
gives
a
false
positive
since
there
• aromatic
is
formation
of
layers
but
no
reaction
• alkanes
–
free
radical
substitution
Neutral
KMnO4:
Oxidation
of
Alcohols
• alkenes
and
alkynes
–
electrophilic
substitution
• 1°
and
2°
alcohols
give
the
positive
result,
while
3°
• aromatics
-‐
unsaturated,
delocalized
pi
electrons
which
alcohols
will
not
react
at
all
make
them
stable;
to
preserve
the
resonance
stabilized
• for
a
compounds
to
be
oxidixed,
it
has
to
have
at
least
1
ring,
it
only
reacts
through
substitution
α-‐hydrogen
(hydrogen
directly
bonded
to
the
first
carbon
atom
bonded
to
a
functional
group)
Br2
in
Light
Conditions
• 1°
alcohols
are
converted
to
carboxylic
acids
and
2°
• free
radical
substitution
alcohols
to
ketones
• stability
of
free
radicals:
b
≈
a
3°
>
2°
>
1°
>
CH3OH
• positive
result:
decolorization
and
brown
precipitate
Br2
in
Dark
Conditions
• general
test
for
unsaturation
Chem
31.
Midterms
Reviewer
5
/steffigatdula/
• decolorization
in
dark
conditions
means
unsaturation
is
Electron
Withdrawing
Groups
present
• characterized
by
having
a
positive
or
partial
positive
• mechanisms:
electrophilic
addition
charge
+
• aromatics
do
not
undergo
bromination
addition
reaction
• strong:
–NO2,
–NR3 ,
–CX3
to
preserve
the
aromatic
ring
• moderate:
–CN,
–COOH,
–COOR,
–CHO,
–COR,
–CONH2,
–SO3H
Baeyer’s
Test
• weak
(only
in
the
ortho-‐para
positions):
–F,
–Cl,
–Br,
–I
+
• general
test
for
unsaturation
• ↓
rate
of
E ArS
when
EWG
are
in
the
meta
positions
• positive
result:
precipitate,
MnO2
• inconclusive
since
all
easily
oxidizable
organic
compounds
like
1°
and
2°
alcohols,
aldehydes,
aryl
halides
and
phenols
give
positive
results
Friedel-‐Crafts
Alkylation
Test
• general
test
for
presence
of
aromatic
ring
• change
in
color
of
AlCl3
crystal
indicates
the
presence
of
an
aromatic
ring
• benzene:
yellow
→
orange
Flame
Test
• combustion
of
hydrocarbons
may
also
suggest
the
type
of
hydrocarbon
present
• high
C–to–H
ration
produces
yellow,
smoky,
sooty
flame
o due
to
the
production
of
C
in
the
form
of
soot
as
a
result
of
incomplete
combustion
(alkenes,
alkynes)
Test
for
Alkynes
• presence
of
terminal
alkynes
detected
by
allowing
it
to
react
with
[Ag(NH3)2]NO
• positive
result:
white
to
gray
precipitate
Steam
Distillation
• steam
distillation:
for
heat
sensitive
liquids
• immiscible
mixtures
where
steam
is
used
to
provide
one
of
the
immiscible
phases
• desired
material
distills
at
>100°C
• limonene
distills
instead
of
decomposing
• Patm
=
↑PT
=
PLIM
+
↑PSTEAM
Experiment
9:
Relative
Rates
of
Electrophilic
Aromatic
Substitution
• Br2/CH3COOH
is
the
polarizing
solvent
(distorts
the
electron
cloud)
• AlBr3/FeBr3
is
the
catalyst
(lewis
acid)
Electron
Donating
Groups
• characterized
by
having
lone
pairs
• strong:
–OH,
–NH,
–NHR,
–NR2
• moderate:
–OR,
–NHCOOR
• weak:
–C6H3,
alkyl
(R)
groups
+
• ↑
rate
of
E ArS
when
EDG
are
in
the
ortho-‐para
positions