A/ define the degree of unsaturation?

Degree of unsaturation
Degree of Unsaturation (DOU) is also known as (Double Bond Equivalent). In
the analysis of the molecular formula of organic molecules, the degree of
unsaturation (also known as the index of hydrogen deficiency (IHD), double bond
equivalents, or unsaturation index) is a calculation that determines the total number
of rings and π bonds.

A formula is used in organic chemistry to help draw chemical structures. For

hydrocarbons, the DBE (or IHD) tells us the number of rings and/or extra bonds in
a non-saturated structure, which equals to the number of hydrogen pairs that are
required to make the structure saturated, simply because joining two elements to
form a ring or adding one extra bond in a structure reduces the need for two H's.
(For non-hydrocarbons, the elements in a pair can include any elements in the
lithium family and the fluorine family in the periodic table.)

 One degree of unsaturation is equivalent to 1 ring or 1 double bond

(1 π bond) but not both.
 Two degrees of unsaturation is equivalent to 2 double bonds, 1 ring and
1 double bond, 2 rings, or 1 triple bond (2 π bonds).
 Three degrees of unsaturation is equivalent to 3 rings, 2 rings+1 double
bond, 1 ring+2 double bonds, 1 ring+1 triple bond, 1 double bond+1 triple
bond, or 3 double bonds.
 Four degrees of unsaturation is equivalent to one ring and three double
bonds.
 Five degrees of unsaturation is equivalent to 4 benzene ring and 1 like
number one.

Any substance with an index of four or more may contain a benzenoid ring, a
substance with an index less than four cannot contain such a ring.

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General formula:

The formula for degree of unsaturation is:

Where ni is the number of atoms with valence vi.

That is, an atom that has a valence of (x) contributes a total of (x – 2) to the degree
of unsaturation. The result is then halved and increased by 1.

Simplified formula:

For certain classes of molecules, the general formula can be simplified or rewritten
more clearly. For example:

Where:

a = number of carbon atoms in the compound

b = number of hydrogen atoms in the compound

c = number of nitrogen atoms in the compound

f = number of halogen atoms in the compound

Or,

Where:

C = number of Carbons, H = number of Hydrogens, X = number of Halogens and

N = number of Nitrogens, gives an equivalent result.

In either case, oxygen and other divalent atoms do not contribute to the degree of
unsaturation, as 2 − 2 = 0.

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A popular form of the formula is as follows:

IHD = C + 1 + N/2 – H/2 – X/2

Where:

C, N, H and X represent the number of Carbon, Nitrogen, Hydrogen and Halogen

atoms, respectively. Each of the terms on the RHS can be explained, respectively,
as follows:

1. Except the terminal carbons, each of the carbon chained to the structure with
a single bond requires a pair of hydrogen atoms attached to it -- that is why
the number C is in the formula, which actually represents the number of
hydrogen pairs requires for that number of carbons in a saturated structure.
(This is also true if a carbon is added into the structure, whether it is inserted
to a backbone chain, attached to a terminal to replace an H, or branched out
from a carbon to replace an H.)
2. Each of the two terminal carbons needs one extra hydrogen – that is why 1 is
added to the formula. (A branch’s terminal doesn’t need an extra hydrogen
added in the calculation because an hydrogen at where the branch attached
to must have been replaced, which is true for a branch terminated with any
element.)
3. Except the terminal nitrogens, each nitrogen in the chain only requires one H
attached to it, which is half a pair of hydrogens– that is why +N/2 is in the
formula, which gives a value of 1 for every two nitrogens. (This is also true
if an nitrogen is added into the structure, whether it is inserted to a backbone
chain, attached to a terminal to replace an hydrogen, or branched out from a
carbon to replace an hydrogen.)
4. The H/2 represents the number of hydrogen pairs because it gives a value of
1 for every two hydrogen atoms. It is subtracted in the formula to count how
many pairs of hydrogen atoms are missing in the unsaturated structure,
which tells us the degree of hydrogen deficiency. (No hydrogen pair is
missing if IHD = 0, which corresponds to no H-deficiency.)
5. The presence of X/2 is for a reason similar to H/2.

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Adding an oxygen atom in the structure requires no hydrogen added, which is why
the number of oxygen atoms does not appears in the formula, also (S) sulfur or any
other bivalent atom. Furthermore, the formula can be generalized to include all
elements of Group I (the hydrogen and lithium family or halide) i.e., any
monovalent atom, Group IV (the carbon family and Si) i.e., any tetravalent atom,
Group V (the nitrogen family and P) i.e., any trivalent atom and Group VII (the
fluorine family) of CAS A group in the periodic table as follows:

IHD = G4 + 1 + G5 /2 – G1 /2 – G7 /2

Or simply,

IHD = G4 + 1 – (G1 + G7 – G5)/2

Or,

IHD = IV - ½ I + ½ III + I

The numerals I- IV designate the numbers of the mono-, di-, tri-, and tetravalent
atoms respectively.

A saturated molecule contains only single bonds and no rings while unsaturated
molecules contain double bond(s), triple bond(s) and/or ring(s).Another way of
interpreting this is that a saturated molecule has the maximum number of hydrogen
atoms possible to be an acyclic alkane. Thus, the number of hydrogens can be
represented by 2C+2, which is the general molecular representation of an alkane.

CnH(2n+2)

(Number of hydrogen molecules in saturated molecule – number of hydrogens in

giving molecular formula)/2

For example:

Determine the number of degrees of unsaturation for the chemical formula C6H10?

 Take the original number of hydrogens found C6H10

 Use the calculation of saturated alkanes

CnH(2n+2) = C6H2(6)+2=14

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  Subtract the original hydrogens from saturated alkenes

14-10=4 hydrogens

 For every two hydrogens (divide by two) that are missing 1 degree of
unsaturated is found.

4 hydrogens / 2 = 2 degree of unsaturation (answer)

But what about molecules that contain atoms other than hydrogen and carbon? In
such cases, you need to convert these multi-atom molecular formulas into
equivalent formulas that contain just carbon and hydrogen so they can be plugged
into the preceding equation. To do so, you use the following conversion factors:

 Halogens (F, Cl, Br, I): Add one hydrogen to the molecular formula for
each halogen present.

 Nitrogen: Subtract one hydrogen for each nitrogen present.

 Oxygen or sulfur: Ignore.

For example:

Determine the number of degrees of unsaturation for the chemical formula

C8H6F3NO2?

First, make the proper substitutions for all atoms that are not hydrogen and carbon.
Fluorine is a halogen, so you add three hydrogen atoms to the molecular formula
(one for each F). The molecule contains one nitrogen, so you subtract one
hydrogen from the molecular formula. The two oxygens in the molecule you
ignore.

This gives a reduced equation of C8H6+3–1 = C8H8, CnH(2n+2) = C8H2(8)+2= C8H18

18 - 8 = 10/2 = 5 (answer)

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In other words, both the formula C8H6F3NO2 and the formula C8H8 have identical
numbers of degrees of unsaturation. Plugging this reduced formula into the
preceding equation gives five degrees of unsaturation for the molecular formula
C8H6F3NO2
If the molecular formula is given, plug in the numbers into this formula:

DOU= [2C+2+N-X-H]/2

Where:

C is the number of Carbons

N is the number of Nitrogens
X is the number of Halogens (F, Cl, Br, I)
H is the number of Hydrogens

EXAMPLE: BENZENE

What is the Degree of Unsaturation for Benzene?

SOLUTION:

The molecular formula for benzene is C6H6. Thus,

DOU= 4 (answer), where:

C=6, N=0, X=0, and H=6. 1 DOU can equal 1 ring and three double bonds. This
corresponds to benzene containing 1 ring and 3 double bonds.

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B/ Calculate the degree of unsaturation for the following chemical formulas:

1- C4H8
IHD = IV - ½ I + ½ III + 1

= 4 – 8/2 + 0/2 + 1

=4–4+0+1

= 1 (answer)

Also can be calculated by:

CnH(2n+2)

= C4H10

(Hydrogen in saturated molecule – Hydrogen in given formula)/2

10 – 8 = 2 / 2 = 1 (answer)

2- C8H11CL
IHD = IV - ½ I + ½ III + 1

= 8 – (11+1)/2 + 0/2 + 1

=8–6+0+1

= 3 (answer)

Also can be calculated by:

CnH(2n+2)

Add one hydrogen to the molecular formula for each halogen present since we
have one chloride atom so:

C8H11+1 = C8H12

CnH(2n+2)

= C8H18

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(Hydrogen in saturated molecule – Hydrogen in given formula)/2

= 18 – 12 = 6 / 2 = 3 (answer)

C/ Suggest two chemical structures for the following chemical formula

(C3H6O) ?

IHD = IV - ½ I + ½ III + 1

= 3 – 6/2 + 0/2 + 1

=3–3+0+1

=1

Also can be calculated by:

CnH(2n+2)

= C3H8

(Hydrogen in saturated molecule – Hydrogen in given formula)/2

8–6=2/2=1

IHD = 1 means must have one double bond or one ring, but not both. If no double
bond is present, the compound is cyclic and saturated.

The molecular formula C3H6O may refer to:

1-Alcohols

 Allyl alcohol or 2-propen-1-ol, CH2=CH-CH2OH

 cyclopropanol or cyclopropyl alcohol, cyclo (-CH2-CH2-HOHC-)

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2-Aldehydes

Propanal or propionaldehyde, CH3CH2-CHO

3-Ketones

Propanone or acetone, CH3-CO-CH3

4-Enols (tautomers of aldehydes and ketones)

 (E)-1-propen-1-ol, CH3-CH=CH-OH
 (Z)-1-propen-1-ol, CH3-CH=CH-OH
 propen-2-ol, CH2=C(OH)-CH3

5-Ethers

 Methyl vinyl ether or methoxyethene, H3C-O-CH=CH2

 Oxetane or trimethylene oxide, cyclo(-CH2-CH2-O-CH2-)

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 1,2-epoxy-propane or Propylene oxide or methyl oxirane, cyclo(-C*H(CH3)-
CH2-O-), C* chiral

 (R)-(+)-methyl oxirane
 (S)-(–)-methyl oxirane

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