III.

Classification of organic compounds

1. Hydrocarbons CH3-CH3; CH2=CH2; CHCH;
conjugated double bonds

CH2=CH-CH=CH2 CH2=CH-CH2-CH=CH2

isolated double bonds

2.

Compounds with single-bonded functional groups R-OH alcohols; R-O-R ethers; R-NH2 amines; R-CH2-X alkyl halides
(X= -F; -Cl; -Br; -I)

3.

Carbonyl compounds
R C O R'

R' = -H aldehydes; -R (alkyl, aryl) ketones; -OH carboxylic acids

N
N

4.

Heterocycles

III. Classification of organic compounds 1. Hydrocarbons 1

Hydrocarbons

Hydrocarbons aliphatic hydrocarbons

aromatic hydrocarbons
e.g. benzene
HC HC H C C H CH CH

alkanes CnH2n+2
e.g. ethane

alkenes CnH2n
ethene
H2C CH2

alkines CnH2n-2
ethine
HC CH
H2C H2C

cycloalkanes CnH2n
cyclohexane
H2 C C H2 CH2 CH2

H3C CH3

III. Classification of organic compounds 1. Hydrocarbons 2

Aliphatic hydrocarbons
Alkanes CnH2n+2 Number of Summation Name C-atoms formula
1 2 3 4 5 6 7 8 9 10

Alkenes CnH2n Summation Name formula C 2H 4 C 3H 6 C 4H 8 C5H10 C6H12 C7H14 C8H16 C9H18 C10H20 Ethene Propene Butene Pentene Hexene Heptene Octene Nonene Dekene

Alkines CnH2n-2 Summation Name formula C 2H 2 C 3H 4 C 4H 6 C 5H 8 C6H10 C7H12 C8H14 C9H16 C10H18 Ethine Propine Butine Pentine Hexine Heptine Octine Nonine Dekine

CH4 C 2H 6 C 3H 8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22

Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Dekane

III. Classification of organic compounds 1. Hydrocarbons 3

Alkanes

CnH2n+2
Properties poor reactivity formation of structural isomers C1 - C4 gases; C5 - C16 liquids; from C17 solids non-polar compounds, hydrophobic Natural sources methane: ethane, propane, butane: higher alkanes, cycloalkanes: natural gas, biogas, in rumen (from cellulose) natural gas petroleum, plants (terpenes)

III. Classification of organic compounds 1. Hydrocarbons 4

Isomerism of alkanes Isomers are compounds with equal summation formula, but different molecular structure. Structural isomers are compounds with a different constitution (constitutional isomers) They differ in the order in which their atoms are connected to each other. They have different chemical and physical properties. Chain isomers are compounds with different chain structure (chain branching). Summation Name formula CH4 C 2H 6 C 3H 8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 C20H42 Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Dekane Eicosane Number of isomers 1 1 1 2 3 5 9 18 35 75 366319

III. Classification of organic compounds 1. Hydrocarbons 5

Structural isomerism
greek: isos meros equal part

n- compound C4H10
C C C C

i -compound
C C C C C C C C C
1 2 3 1 2 3 1 2 3

2-methylpropane isobutane
C
4

n-butane C5H12
C C C C C

2-methylbutane isopentane

n-pentane

C C C C

2,2-dimethylpropane
5

C6H14 C C C C C C n-hexane

C C C C
C C C C
1 2 3

C C

2-methylpentane isohexane

C C

3-methylpentane

C C C C C
1 2

2,3-dimethylbutane

C C

C C C

2,2-dimethylbutane

III. Classification of organic compounds 1. Hydrocarbons 6

Names of different carbon atoms

6 5 4 3

C
1

C C C C C
8

C
1, 5, 6, 7, 8 3 4 2

primary C-atoms: secondary C-atom: tertiary C-atom: quaternary C-atom:

III. Classification of organic compounds 1. Hydrocarbons 7

Application of alkanes

for heating purpose (ox. with O2) fuels (ox. with O2) solvents, extracting agents (e.g. for vegetable oils) surfactants preparation of ethylene, propylene

methane, ethane, propane, butane, fuel oil, petroleum hydrocarbons gasoline (octan number), diesel fuel, kerosene pentane, hexane, heptane, cyclohexane C12-C18 n-alkanes dehydrogenation of ethane, propane

III. Classification of organic compounds 1. Hydrocarbons 8

Reactions of alkanes

Halogenation of alkanes:
C 6H 14 + Br2

C6H13Br

HBr

Oxidation of paraffines:
H H H H H3C C C C C CH3 H H H H

O2 / cat.

H H H H H3C C C C C COOH H H H H

Sulfochlorination:
H H H H H3C C C C C CH3 H H H H

SO2Cl2 - HCl

H H H H H3C C C C C SO2Cl H H H H

III. Classification of organic compounds 1. Hydrocarbons 9

Cycloalkanes

cyclopropane (bp. -34,5C) bond angle: 60 strong ring strain

cyclobutane (bp. 11C)

cyclopentane (bp. 49,5C)

cyclohexane (bp. 80,8C)

bond angle: 109 free of tension

Stress theory by BAYER

chair-form (more stable)

boat-form

III. Classification of organic compounds 1. Hydrocarbons 10

Alkenes - olefins

CnH2n
Natural sources like alkanes: petroleum, natural gas, plants (terpenes)

Application products synthetics (polymers) (PE, PP, PVC) synthetic rubber isooctane (OZ=100) alcohols (2-Propanol) starting materials H2C=CH2; H2C=CH-CH3; H2C=CHCl H2C=CH-CH=CH2 isobutene propene

III. Classification of organic compounds 1. Hydrocarbons 11

Typical reactions of olefines addition:

+ Br Br Br Br

polymerisation:
n H2C CH2 H2C CH2 n

cycloaddition:

ethene

1,3-butadiene

cyclohexene

III. Classification of organic compounds 1. Hydrocarbons 12

Unsaturated cyclic compounds

4 5 6 1
cyclohexene 1,3-cyclohexadiene

3 2

III. Classification of organic compounds 1. Hydrocarbons 13

Aromatic hydrocarbons

benzene

aromaticity
cyclic conjugation is a necessary but non sufficient requirement Hckels rule: number of -electrons must be equal to 4n + 2, where n is an integer benzene: 6 -electrons (n = 1)

mesomerism of benzene

H H H H H H

III. Classification of organic compounds 1. Hydrocarbons 14

Positional isomers of dichloro benzene

Cl

Cl Cl
Cl
1,2-dichloro benzene o- dichloro benzene o = ortho position

Cl

Cl
1,4- dichloro benzene p- dichloro benzene p = para position
III. Classification of organic compounds 1. Hydrocarbons 15

1,3- dichloro benzene m- dichloro benzene m = meta position

Technical important aromatic compounds

CH3

NO2

O2N CH3
BENZENE in the past: solvent TOLUENE solvent, production of insecticides and TNT, additive for fuels

NO2

TNT (explosive)

BIPHENYL preserving agent (E 230), production of PCB (polychlorinated biphenyl)

NAPHTHALIN production of insecticides, pharmaceutical products and dyes

III. Classification of organic compounds 1. Hydrocarbons 16

Toxicity of aromatic compounds (cause long-term demage) CH3

NH2

Cln
BENZENE TOLUENE CHLOROBENZEN
E

R
DERIVATIVES OF ANILIN

blood, nervous blood, system nervous system carcinogenic

liver, kidney

blood, nervous system

NHNH2 R
DERIVATIVES OF PHENYLHYDRAZIN

OH

NO2 R
DERIVATIVES OF NITROBENZENE

R
DERIVATIVES OF PHENOLE

liver, kidney, blood

carcinogenic

blood carcinogenic?

Cl
BIPHENYL, PCB

Cl
BENZ[a]-PYRENE
strong carcinogenic

liver, kidney, blood, nervous system carcinogenic

III. Classification of organic compounds 1. Hydrocarbons 17

Alkines

CnH2n-2
most important: acetylene (ethine) HCCH

Preparation pyrolysis of hydrocarbons Properties of acetylene colourless gas mixtures with air are explosive (content of acetylene 3 -70 %) Application of acetylene: preparation of 1,4-butanediol, trichloroethylene, acrylic acid vinylation of higher acids and alcohols welding of steel

III. Classification of organic compounds 1. Hydrocarbons 18

Addition to the triple bond

2 H 2,N i

N a,f . H 3 lN

H C C H

trans

H 2,Pd H C C

C H

cis

Cl Cl Cl 2 C Cl C Cl Cl 2 C C

Cl Cl H Cl C

HCl

HCl C H C Cl C Cl H H

H 2O H gSO 4,H 2SO 4

C H

C OH

C H

C O

III. Classification of organic compounds 1. Hydrocarbons 19