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Solution of Tutorial 3-Part 1-1

The document is a tutorial on inductive effects in organic chemistry. It contains multiple choice questions and open questions about how inductive effects impact properties like acidity, basicity, and stability of carbocations, carbanions, and carboradicals in different organic molecules.

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Mamita Ka
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10 views

Solution of Tutorial 3-Part 1-1

The document is a tutorial on inductive effects in organic chemistry. It contains multiple choice questions and open questions about how inductive effects impact properties like acidity, basicity, and stability of carbocations, carbanions, and carboradicals in different organic molecules.

Uploaded by

Mamita Ka
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 4

ENSTI-Annaba-CPST-2nd year Organic chemistry (2023/2024)

Solution of tutorial 3. Reactivity in organic chemistry


Part 1. Inductive effect

Answer the following Multiple Choice Questions (MCQs) or Questions (Qs), and justify on
the basis of inductive effect, indicating if necessary its direction in the molecules.

MCQ1. An inductive effect refers to the movement of electrons through:


o 𝜋 bonds
o Non-polar bonds
o Polar sigma bonds
o 𝑝 orbitals

MCQ2. Why inductive effect is called transmission effect?


o Because it is an electron delocalization along a carbon chain.
o Because the polarization is transmitted through sigma bonds.
o Because it spreads and it is negligible often after the 3rd carbon atom.

MCQ3. In which molecule the dipole moment is the highest?


o propane
o chloropropane
o fluoropropane
o tetrafluoromethane

In the propane molecule, the carbon and hydrogen atoms have a closed electronegativity;
𝐶 − 𝐻 bonds are very weakly polar and the molecule does not contain a center of symmetry.
Propane has a small dipole moment of 0.08𝐷 and it considers as non-polar molecule.

In chloropropane and fluoropropane, the polarity of these molecules is due to the polarity of
𝐶 − 𝐶𝑙 and 𝐶 − 𝐹 bonds respectively.
The dipole moments of these compounds do not depend only on the electronegativity of
halogens X, the charge (𝛿𝑒) or the bond length (d) of 𝐶 − 𝑋, but they depend also on their
conformations.

𝐶𝐹4 is a symmetrical molecule. Therefore, the dipole moments of all


𝐶 − 𝐹 bonds cancel each other. The resultant dipole moment of the
molecule is zero.

So these compounds can be arranged in the increasing order of their dipole moments as:

𝐶𝐹4 < 𝑝𝑟𝑜𝑝𝑎𝑛𝑒 < 𝑓𝑙𝑢𝑜𝑟𝑜𝑝𝑟𝑜𝑝𝑎𝑛𝑒 (𝑔𝑎𝑢𝑐ℎ𝑒) < 𝑐ℎ𝑙𝑜𝑟𝑜𝑝𝑟𝑜𝑝𝑎𝑛𝑒 (𝑔𝑎𝑢𝑐ℎ𝑒)


Or;
𝐶𝐹4 < 𝑝𝑟𝑜𝑝𝑎𝑛𝑒 < 𝑐ℎ𝑙𝑜𝑟𝑜𝑝𝑟𝑜𝑝𝑎𝑛𝑒 (𝑎𝑛𝑡𝑖) < 𝑓𝑙𝑢𝑜𝑟𝑜𝑝𝑟𝑜𝑝𝑎𝑛𝑒 (𝑎𝑛𝑡𝑖)

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ENSTI-Annaba-CPST-2nd year Organic chemistry (2023/2024)
MCQ4. Which of the following orders is correct regarding the (+𝐼) effect of the substituents?
o 𝑡 − 𝐵𝑢 < 𝑖 − 𝑃𝑟 < 𝐸𝑡
o 𝐸𝑡 > 𝑖 − 𝑃𝑟 > 𝑡 − 𝐵𝑢
o 𝑖 − 𝑃𝑟 > 𝐸𝑡 > 𝑡 − 𝐵𝑢
o 𝑡 − 𝐵𝑢 > 𝑖 − 𝑃𝑟 > 𝐸𝑡
The response is based on the cumulative inductive effect of alkyl groups.

MCQ5. Which of the following orders are correct regarding the (– 𝐼) effect of the substituents?
o 𝐹 < −𝑂𝐻 < −𝑁𝐻2
o 𝐹 > −𝑂𝐻 > −𝑁𝐻2
o – 𝑁𝐻2 < −𝑂𝐻 < 𝐹
o – 𝑁𝐻2 > −𝑂𝐻 > 𝐹
The response is based on the decreasing order 𝑥(𝐹) > 𝑥(𝑂) > 𝑥(𝑁) or the increasing
order 𝑥(𝑁) < 𝑥(𝑂) < 𝑥 (𝐹 ) of the electronegativity of the atoms.

MCQ6. Which of the following acids has the smallest 𝑝𝐾𝑎 value (𝑝𝐾𝑎 = 0,52).

The response is based on the inductive effect of 𝑅 group of the carboxylic acid 𝑅 − 𝐶𝑂𝑂𝐻. The
electron-withdrawing effect (−𝐼) of −𝐶𝐹3 group increases the polarization of the 𝑂𝐻 bond and
facilitates deprotonation. The strongest acid has the smallest 𝑝𝐾𝑎 value.

MCQ7. The correct order of 𝑝𝐾𝑎 values of these alcohols is respectively:

o 15.5, 16, 17.1, 19.2


o 19.2, 17.1, 16, 15.5
o 17.1, 16, 15.5, 19.2
o 17.1, 15.5, 16, 19.2
The response is based on the increasing order of the cumulative effect of alkyl groups, more the
power of electron-donating group (+𝐼) is intensified, more the polarization of OH bond and the
acidity of alcohols decrease, and the order of 𝑝𝐾𝑎 values increases.

Q8. Rank from 1 to 4 in order of decreasing acidity:

The order of decreasing acidity is based on the nature of the substituent and the inductive effect
that it exerts. The electron-donating effect of 𝐶𝐻3 is greater in 2-methylcyclopropanecarboxylic
acid than in 3-methylcyclopropanecarboxylic acid. More 𝐶𝐻3 is closer to COOH group, more the
strength of the acid is less. The electron-withdrawing effect of halogen increases acidity, and
the most electronegative fluorine atom increases acidity more and more due to the greatest
inductive effect.

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ENSTI-Annaba-CPST-2nd year Organic chemistry (2023/2024)
Q9. Rank from 1 to 4 in order of increasing acidity:

-Attribute the corresponding 𝑝𝐾𝑎 values 2.68, 2.97, 3.89, 4.


The order of increasing acidity is based on the position and electronegativity of the halogen
atom having (-I) effect. More the halogen is closer to the COOH, the acidity increases, and when
the halogen atom is more electronegative, the acidity increases more and more.
The corresponding 𝑝𝐾𝑎 values of acids are: 1(4) < 2(3.89) < 3(2.97) < 4(2.68)

Q10. Rank from 1 to 3 in order of increasing basicity:

-Attribute the corresponding 𝑝𝐾𝑎 values 8.25, 10.7, 11.09.


The order of increasing basicity is based on the nature of 𝑅 group(s) attached to the amine. The
diethyl amine has two Et groups (+I), it is more basic than ethylamine which has one Et group
(+I).
The chlorine atom attracts the electron density on the nitrogen atom due to his (-I) effect and
decreases the availability of its electronic pair for protonation, then the basicity and 𝑝𝐾𝑎 value
decrease.
The corresponding 𝑝𝐾𝑎 values of amines are: 1(8.25) < 2(10.7) < 3(11.09)

Q11. Rank from 1 to 3 in order of decreasing basicity:

-Attribute the corresponding 𝑝𝐾𝑎 values 8.33, 10.66, 11.12.

Secondary amines like piperidine are generally more basic than primary amines like
cyclohexylamine. Carbon attached donates electron density to the nitrogen better than
hydrogen. In morpholine, the oxygen atom exerts (– 𝐼) effect, it decreases the availability of
electron pair on nitrogen.
The corresponding 𝑝𝐾𝑎 values of amines are: 1(11.12) > 2(10.66) > 3(8.33)

Q12. Rank from 1 to 3 in order of increasing basicity:

-Attribute the corresponding 𝑝𝐾𝑎 values 11.12, 9.33, 8.48.

The presence of fluorine atom on the piperidine, decreases the availability of electron pair on
nitrogen by its electron-withdrawing effect, more the fluorine atom is closer to NH, more the
amine is less basic.
The corresponding 𝑝𝐾𝑎 values of amines are: 1(8.48) < 2(9.33) < 3(11.12)

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ENSTI-Annaba-CPST-2nd year Organic chemistry (2023/2024)
Q13. Rank from 1 to 3 in order of increasing carbocation stability:

The electron-withdrawing 𝐶𝐹3 group destabilizes the carbocation more by intensifying the
positive charge than hydrogen atoms, which have zero inductive effect.
In +𝐶 𝐹3 , the positive charge is dispersed by delocalization of the lone pair of the fluorine atom
(mesomeric effect).

Q14. Rank from 1 to 4 in order of increasing carbanion stability:

The order of increasing carbanion stability is based on the nature of inductive effect of the
group attached, 𝐸𝑡 (+𝐼) destabilizes the carbonion, then the increasing electron withdrawing
effect is as follow for 𝑎𝑙𝑙𝑦𝑙 < 𝑃ℎ < 𝐶𝑙 which stabilize more and more the carbanion.

Q15. Rank from 1 to 4 in order of decreasing carboradical stability:

The order of decreasing carboradical stability is based on the class of the carboradical and the
number of alkyl groups (+I). The hydrogen atoms have zero inductive effect.

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