OXYGEN CONTAINING ORGANIC COMPOUNDS

ALCOHOLS

Alcohol contains a hydroxyl group (–OH) that replaces a hydrogen atom in a

hydrocarbon.

CLASSIFICATION

1. According to the structure of the carbon chain:

Saturated Unsaturated Aromatic
derivatives of saturated unsaturated hydrocarbon aromatic hydrocarbon
hydrocarbons derivatives derivatives with the
formula C6H5ROH
Eхаmple: Eхаmple: Eхаmple:
СН3 – СН2 – ОН СН2 = СН − СН2 – ОН
ethanol 2-propen-1-ol
benzyl alcohol

2. According to the number of hydroxyl groups:

monohydroxy alcohols Polyhydroxy alcohols
have one –OH group have more one –OH groups
Eхаmple: Eхаmples:
СН3 − ОН

3. According to the number of carbon atoms bound to the hydroxyl-bearing

carbon:
Primary Secondary Tertiary
has one alkyl group has two alkyl groups has three alkyl groups
attached to the carbon attached to the carbon attached to the carbon
bound to the –OH bound to the –OH bound to the –OH
Eхаmple: Eхаmple: Eхаmple:
 SATURATED MONOHYDROXY ALCOHOLS
Saturated monohydroxy alcohols are derivatives of alkanes with one -ОН
group.

General formula: СnH2n+1OH or СnH2n+2O.

where n is the number of carbon atoms in the molecule.

STRUCTURE
3
Alcohols having an sp hybridized tetrahedraloxygen atom with nonbonding
pairs of electrons occupying two of the four sp3hybrid orbitals. Alkyl groups are
generally bulkier than hydrogen atoms, however, so the R−O−H bond angle in
alcohols is generally larger than the 104.5° H−O−H bond angle in water. For
example, the 108.9° bond angle in methanol shows the effect of the methyl group,
which is larger than the hydrogen atom of water.

NOMENCLATURE
The names of alcohols is dropped from the alkane containing the “-OH” group
and replaced with the suffix “-ol”. The location of the hydroxyl group must be
specified in alcohols containing three or more carbons. The chain is numbered in a
manner which places the lowest number on the carbon containing the –OH group.
The rules for naming alcohols are a slight variation on the rules for naming
alkanes.
General Guideline
• The parent name is the longest chain that contains the –OH group.
• Number the carbon chain from the end nearest to the –OH group (location of
OH group take precedence over alkyl groups).
• Name and number all substituted groups on the parent chain. In cases of
multiple substitutions, list them in alphabetical order.
• Locate the –OH group using the carbon number it’s attached to.
 СН3 – ОН methanol (methyl alcohol)
СН3 – СН2 – ОН ethanol (ethyl alcohol)
СН3 – СН2 – СН2 – ОН propanol -1 (propyl alcohol )
` propanol - 2 (isopropyl alcohol)

5- methyl-4-ethylhexanol -2

PHYSICAL PROPERTIES
Low alcohols (СН3ОН – С11Н23ОН) are colorless liquids of specific odour
(unpleasant from C4), narcotic effect, toxic. Higher alcohols (from C12) are solid
compounds. Alcohols with low molar masses (methanol, ethanol, and propanol)
are very soluble in water because they are capable of forming hydrogen bonds with
water molecules. Alcohols with higher molar masses are less soluble in water
because the increasing size of the nonpolar chain disrupts the hydrogen bonding
network. There is a solubility limit on the carbon chain length for alcohols.
Alcohols have higher boiling points than alkanes.

CHEMICAL PROPERTIES

1. Interaction with metals

2R – OH + 2Na → 2R – ONa + H2↑

2С2Н5ОН + 2Na → 2C2H5ONa + H2↑

2. Interaction with acid

 3. Hydrohalogenation of alcohols

R – ОН + HHal t
R – Hal + H2O
С2Н5 – ОН + НBr t
C2H5 – Br + H2O

4. Interaction with ammonia

t , p , Al2O3
С2Н5ОН + NH3 C2H5NH2 + H2O

5. Dehydration of alcohols
a)

b)

6. Oxidation of alcohols
С2Н5ОН + 3О2 t 2СО2↑ + 3Н2О + Q

PREPARATION
1.

2.

3.
 4.

t, p, H
Н2С = СН2 + Н2О СН3СН2ОН

2Н2 + СО t, p, кат СН3ОН

EXERCISES
Name alcohols on systematic nomenclature:
1.

1) 4)

2) 5)

6)
3)
 7)

8) 9)

2. Write the structural formulas for:

1) 2,3-dimethyl-3-ethylhexanol-1;
2) 4-isopropyl- 2,3,4-trimethylhexanol-2;
3) 3- isopropyl -2-methyl -4- ethylhexanol-3;
4) 4- isopropyl -2,3,3,5-tetramethylhexanol-2;
6) 2,2,3,3-tetramethylheptanol-1.

3. Finish the possible reactions of the equation describing the chemical properties
of alcohols, specifying where applicable, the conditions of their occurrence:
1) СН3ОН + Na →
2) C2H5OH + Al →
3) C3H7OK + H2O →
4) C2H5OH + NaOH →
5) СН3ОН + C2H5COOH →
6) CН3– СН(ОН) – СH3 + CH3COOH →

7) CH3OH + HNO3 0 С 
0 С , ( 2 : 1)
8) CH3CH2OH + H2SO4
0 С , (1 : 1)
9) CH3OH + H2SO4
10) C2H5OH + HCl →
11) CН3СH2CН2OH + HBr →
t , p , Al2O3
12) *
СН3ОН + NH3 
t 140 С , H 2 SO4 ( конц.)
13) C2H5OH
t 140  С , H 2 SO4 ( конц.)
14) CН3 – СН(CН3) – СН(ОН) – СH3
t 140 С , H 2 SO4 ( конц.)
15) C2H5OH
425 С , Al2O3 , ZnO
16) C2H5OH
t , p , Rh / I 2
17) CН3СH2OH + CO
18) CН3СH2CН2OH + CuO t
t
19) CН3– СH2 – СН(ОН) – СH3 + CuO
K 2 Cr2 O7 , H
20) CН3–СН(ОН) – СH3 + [O]
 4. Write the reactions the following transformations:

8) CH4 → C2H2 → C2H4 → C2H5OH →C2H5ONa → C2H5OH → C2H5Cl → C4H10;

9) CH4 → CH3Cl → C2H6→ C2H5Cl → C2H5OH → C2H4 → C2H2 → C2H6;

 PHENOLS

Phenols is an organic compounds in which the hydroxyl group is directly

attached to the benzene ring.
The simplest way to draw the structure of phenol is:

phenol

General formula: СnH2n – 7OH,

where n is the number of carbon atoms in the molecule.

CLASSIFICATION

Mono hydroxyl phenols Poly hydroxyl phenols

Phenols with a single Phenols with more than one hydroxyl groups in the
hydroxyl group molecule
Eхаmple: Eхаmples:

NOMENCLATURE
Number the chain starting at the end closer to the –OH. Give the location and name
of each substituent relative to the –OH group. Methyl derivatives – cresols.

2-methylphenol 3- methylphenol 4- methylphenol

(o-cresol) (m-cresol) (p-cresol)
 2-bromophenol 3-bromo-2-nitrophenol

Dihydroxybenzenes С6Н4(ОН)2

1, 2- dihydroxybenzenes 1, 3- dihydroxybenzenes 1, 4- dihydroxybenzenes

Trihydroxybenzenes С6Н3(ОН)3

1, 2, 3- trihydroxybenzenes 1, 3, 5- trihydroxybenzenes

STRUCTURE
The alcohol functional group consists of an O atom bonded to an sp2-
hybridised aromatic C atom and a H atom via σ bonds. Both the C-O and the O-
H bonds are polar due to the high electronegativity of the O atom. Conjugation
exists between an unshared electron pair on the oxygen and the aromatic ring.
This results in, compared to simple alcohols:
o a shorter carbon-oxygen bond distance
o a more basic hydroxyl oxygen
o a more acidic hydroxyl proton (-OH)
 PHYSICAL PROPERTIES
Low molecular weight phenols are normally liquids or low melting solids. Due
to hydrogen bonding, most low molecular weight phenols are water‐soluble.
Phenols tend to have higher boiling points than alcohols of similar molecular
weight because they have stronger intermolecular hydrogen bonding.

CHEMICAL PROPERTIES
1. Dissociation
Phenol is weak acid.
С6Н5ОН ↔ С6Н5О– + Н+

2. Interaction with metals

3. Interaction with base

4. Reduction of phenol

5. Halogenation
6. Nitration

7. Interaction with aldehydes

PREPARATION
 EXERCISES

1. From these formulas, select the ones that are responsible phenols:

1) С6Н6О; 4) С7Н8О;
2) С6Н6О3; 5) С7Н14О;
3) С6Н12О; 6) С6Н14О.

2. Select the phenols:

3. Finish the possible reactions describing the chemical properties of phenol,

specifying where applicable, the conditions of their occurrence:

1) С6Н5OH (aqueous solution) ↔

2) C6H5OH + K →
3) C6H5OH + KOH →
4) С6Н5OK + СO2 + Н2О →
5) С6Н5ОН +НCl →
t , H 2SO4 (конц.)
6) C6H5OH + CH3COOH
7) C6H5OH + Zn t
8) C6H5OH + Br2 (aqueous solution) →
t , H 2SO4 (конц.)
9) C6H5OH + HNO3(conc.)
10) С6Н5OH + H2 →
11) С6Н5OH + НСНО H

4. Finish the equation obtained by the reaction of phenol, where appropriate,

specify the conditions of their occurrence:

H2SO4 О2 , кат.
1) C6H6 + CH3CH(Cl)CH3 Х …Y
О2 , / кат., H 2SO4
2) C6H6 + CH2 = CH−CH3 Х …
3) С6Н5ОNa + HCl →
4) С6Н5ОNa + H2O + CO2 →
H O, p, t
5) C6H5Cl + NaOH(exess) . . . 2. Х HCl
5. Write the reaction of following transformation: