EXPERIMENT 7:

CLASSIFICATION TESTS FOR

HYDROXYL AND CARBONYL
CONTAINING COMPOUNDS
(POST-LAB DISCUSSION)
 Alifa Camille N. Santos, M.Sc.

ALCOHOL
• An organic compound in which the hydroxyl functional group (–
OH) is bound to a carbon.

• may be considered as a derivative of water in which one of the

hydrogen atom of water molecule (H-O-H) has been substituted
by an alkyl (-R) group.

• The alkyl group could be primary, secondary, or tertiary, and may

be an open chain or cyclic.
ALCOHOL
• Physical properties are mainly influenced by hydrogen bonding.

- hydrophobic and hydrophilic

- high water miscibility

ALDEHYDES & KETONES
• organic compounds which incorporate a carbonyl functional
group (C=O).

• The carbon atom of this group has two remaining bonds that may
be occupied by hydrogen, alkyl, or aryl substituents.

- If at least one of these substituents is hydrogen, the

compound is an aldehyde.

- If neither is hydrogen, the compound is a ketone.

ALDEHYDES & KETONES
• Reactivity is influenced by conjugation
- 3 or more atoms with the ability to resonate are adjacent or
overlapping each other (π delocalization).
- α,β unsaturated carbonyls

-can undergo:

1,2 addition

1,4 addition
(more favorable)
EXPERIMENT 7A
I. Solubility of Alcohol in Water

• Solubility decreases with increasing number of carbons

EXPERIMENT 7A

Tert -butanol

> > >

> benzyl alcohol
sec - butanol n - butanol
ethanol

decreasing solubility

Solubility increases with branching ethanol > tert-butanol > sec-butanol > n-butanol > benzyl alcohol
EXPERIMENT 7A
II. Ester Formation

• carboxylic acid and alcohol are heated in the presence of a

catalyst (conc. H2SO4).

• condensation reaction (two molecules join together to form one

larger molecule)

pineapple-like odor
EXPERIMENT 7A
II. Ester Formation
• This mechanism of esterification generally involves protonation
as a method of enhancing the electrophilicity of the acid
substrate toward nucleophilic attack by ethanol
EXPERIMENT 7A
EXPERIMENT 7A
II. Ester Formation

Plastic balloon-like odor

II. Ester Formation
EXPERIMENT 7A
III. Lucas Test

• also called Hydrochloric acid/Zinc chloride test

• used to differentiate primary, secondary, and tertiary alcohols
based on the reaction times
• Positive result: cloudy suspension
• Involves SN1 type of reaction
EXPERIMENT 7A
III. Lucas Test

• the more stable the resulting carbocation, the more favorable the
reaction

• at room temperature:
EXPERIMENT 7A
EXPERIMENT 7A
III. Lucas Test

of cloudy suspension

tert-butanol

tert-butanol > sec-butanol > n-butanol

decreasing rate of reaction
EXPERIMENT 7A
IV. Jones Oxidation

• also called chromic acid test

• Positive result: immediate formation of

green solution

• Positive for 1o alcohols, 2oalcohols, and

aldehydes

Color change:
EXPERIMENT 7A
Orange sol’n Green sol’n
EXPERIMENT 7A
IV. Jones Oxidation

Cr6+ Cr3+
EXPERIMENT 7B
V. 2,4-Dinitrophenylhydrazone Test

• also called Brady’s Test • A test for

aldehydes and ketones

• Positive result:

- yellow precipitate = unconjugated

hydrazone
EXPERIMENT 7B
- orange-red precipitate = conjugated hydrazone

** Allyl alcohols (the –OH bearing carbon is bonded to an alkyl

that has a double bond) are also oxidized to aldehydes or
ketones which yields a positive result.
EXPERIMENT 7B
V. 2,4-Dinitrophenylhydrazone Test

Aldehyde or Ketone 2,4-Dinitrophenylhydrazine

2,4-Dinitrophenylhydrazone

• Over-all, a condensation reaction

• Specifically, an addition-elimination reaction

EXPERIMENT 7B
(nucleophilic addition of the -NH2 group to the C=O carbonyl group,
followed by the elimination of a H2O molecule)

VI. Fehling’s Test

• A test for aldehydes except for aromatic aldehydes

• Positive Result:
EXPERIMENT 7B
-brick-red ppt.

-muddy green suspension

with brick-red ppt.

**α-hydroxyketones and other

carbohydrates also give a
positive result
EXPERIMENT 7B
VI. Fehling’s Test

Cu2+ Cu1+

• Aldehyde is oxidized to carboxylic acid by Cu2+ complex which is

then reduced to Cu1+ (Redox reaction).

• Aromatic aldehydes (i.e. benzaldehydes) do not

react with Fehling’s reagent due to the lack of α
hydrogen (an enolate cannot be formed in the
rate determining step).
EXPERIMENT 7B
VII. Tollens Test

• also called silver-mirror test

• a test for aldehydes including aromatic

aldehydes

• Positive Result:

silver (metallic) mirror ppt.

 EXPERIMENT 7B
**α-alkoxy, α-dialkylamino ketones, diphenylamine,
aromatic amines, sugars, and 1-napthols also yield a
positive result.
EXPERIMENT 7B
VII. Tollens Test

• The aldehyde is oxidized to its corresponding carboxylic acid salt

and the Ag+1 is reduced to Ag0 (Redox reaction).

• Alcohols do not produce a positive result do to its lack of

C=O functional group.
EXPERIMENT 7B
VIII. Iodoform Test

• A test for secondary alcohol and methyl

ketone

• Positive Result:

formation of yellow ppt.

EXPERIMENT 7B
EXPERIMENT 7B
VIII. Iodoform Test

• 2o alcohol is oxidized to a methyl ketone which under basic

conditions forms a triiodointermediate.
EXPERIMENT 7B
VIII. Iodoform Test

• The triiodo intermediate is then oxidized to the sodium salt of the

acid and iodoform (foul-smelling/antiseptic-like odor yellow
precipitate)
EXPERIMENT 7
SUMMARY
Test Positive Result
According to decreasing solubility:
Solubility in water
Ethanol >tert-BuOH > sec-BuOH > n-BuOH
>benzyl alcohol
+ ethanol = plastic-balloon odor
Ester formation (reaction with acetic acid)
+ isopropanol = banana-like odor
According to decreasing turbidity:
Lucas Test
tert-BuOH > sec-BuOH ≠ n-BuOH
Immediate formation of green sol’n for
Jones Oxidation
n-BuOH, sec-BuOH, acetaldehyde,
benzaldehyde
EXPERIMENT 7
SUMMARY
Test Positive Result
yellow ppt.= acetaldehyde, benzaldehyde,
acetone
2,4-DNP Test
orange-red ppt. = acetophenone

muddy green sol’n with brick-red ppt. =

Fehling’s Test
acetaldehyde

silver-mirror ppt. = acetaldehyde,

Tollen’s Test
benzaldehyde

Iodoform test light yellow ppt. = isopropanol, acetone

 BASIC NAMING OF
ALCOHOLS,
ALDEHYDES,
AND KETONES
(IUPAC NOMENCLATURE)
NAMING ALCOHOLS
1. Name the parent compound

- Find the longest chain that has the hydroxyl substituent attached
(replace the -e ending with –ol).
NAMING ALCOHOLS
2. Number the carbon atoms in the main chain

- Begin at the end nearer the hydroxyl group, ignoring the location
of other substituents.

- In a cyclic alcohol, the carbon that bears the –OH group is #1.
NAMING ALCOHOLS
3. Write the name

- Place the number that locates the hydroxyl group immediately

before the parent compound name.
- In a cyclic alcohol the number “1” for the location of the –OH
group is not needed.
NAMING ALCOHOLS
• When the molecule has more than one alcohol group, the
complete alkane name is used.

• A suffix “diol” is added to the parent name

NAMING ALCOHOLS

• For unsaturated alcohols, the hydroxyl group takes the highest

priority (assign the α carbon the lowest possible number).

pent-3-en-2-ol
NAMING ALCOHOLS
Practice: Give the IUPAC name of these compounds.
NAMING ALCOHOLS
Practice: Give the IUPAC name of this compound.
NAMING ALDEHYDES
1. Select the longest carbon chain containing the carbonyl carbon
(C=O).
 -The carbonyl carbon is always numbered “1” therefore, it is not
necessary to include the number in the name.
Parent chain: 7 carbons = “hept”

NAMING ALDEHYDES
2. The “-e” ending of the parent alkane is replaced by the suffix
“-al”.
3. Name the substituents attached to the chain in the usual way

5,5-dimethylheptanal
NAMING ALDEHYDES
4. When the -CHO functional group is attached to a ring the suffix
-carbaldehyde is added, and the carbon attached to that group
is C#1.
NAMING ALDEHYDES
5. For dialdehydes the location numbers for both carbonyls are
omitted because the aldehyde functional groups are expected
to occupy the ends of the parent chain. The ending –dial is
added to the end of the parent chain name.
NAMING
ALDEHYDES
Practice: Give the IUPAC name of
these compounds.
NAMING KETONES
1. Select the longest carbon chain containing the C=O group.

2. The ending -e of the parent chain is removed and replaced with

-one.
3. Substituents are named as usual wherein, the carbon in C=O
gets the lowest locator number.

NAMING KETONES
4. For diketones both carbonyls require a location number. The
suffix -dione is added to the end of the parent chain
NAMING KETONES
5. In cyclic ketones the carbonyl group is assigned location position
#1, and this number is not included in the name, unless more
than one carbonyl group is present.
6. The rest of the ring is numbered to give substituents the lowest
possible location numbers. The prefix cyclo is included before
the parent chain name to indicate that it is in a ring.
NAMING KETONES 1-

Practice: Give the IUPAC name of these compounds.

 phenylethanone

2-methylpenta-3-one
NAMING COMPOUNDS CONTAINING DIFFERENT
FUNCTIONAL GROUPS

- In naming molecules containing one or more of the functional groups in Group A, the
group of highest priority is indicated by suffix; the others are indicated by prefix, with
priority equivalent to any other substituents.
NAMING COMPOUNDS CONTAINING DIFFERENT
FUNCTIONAL GROUPS
1. Find the highest priority functional group. Determine and name
the longest continuous carbon chain that includes this group.

2. Number the chain so that the highest priority functional group

is assigned the lower number.

3. If the carbon chain includes multiple bonds (Group B), replace

“ane” with “ene” for an alkene or “yne” for an alkyne.
NAMING COMPOUNDS CONTAINING DIFFERENT
4. If the molecule includes Group A functional groups, replace the
last “e” with the suffix of the highest priority functional group,
and include its position number.
NAMING COMPOUNDS CONTAINING DIFFERENT
FUNCTIONAL GROUPS
5. Indicate all alkyl, halogen, and Group A functional groups of
lower priority, with a prefix. Place the prefixes, with
appropriate position numbers, in alphabetical order before the
root name
NAMING COMPOUNDS CONTAINING
DIFFERENT
FUNCTIONAL GROUPS
Practice: Give the IUPAC name of these compounds.
NAMING COMPOUNDS CONTAINING
DIFFERENT

END