Advanced Organic Chemistry (CHEM 531/731)

Assignment 1 (Oct. 18, 2020)

Q1: i) Identify the neutral element that corresponds with each of the following electron configurations:

(a) 1s22s22p4 (b) 1s22s22p5 (c) 1s22s22p2 (d) 1s22s22p3 (e) 1s22s22p63s23p5

ii) By using the configuration of (c) and (d) as central atom, in its neutral or charged form, complete the
following table with appropriate building blocks.

(NOTE: While completing the table please keep in mind the octet rule and formal charge. Mark cross in
the box if it is not possible). (2 + 8)

(c) 1s22s22p2
Connectivity 4 3 2 1

EPD
4

(d) 1s22s22p3
Connectivity 4 3 2 1

EPD
4

Q2: Propose the structure(s) for a compound with six carbon atoms that exhibits the following features:
(a) All six carbon atoms are sp2 hybridized. (2)

(b) Only one carbon atom is sp hybridized, and the remaining five carbon atoms are all sp3 hybridized
(remember that your compound can have elements other than carbon and hydrogen). (2)

(c) There is a ring, and all the carbon atoms are sp3 hybridized. (2)

(d) All six carbon atoms are sp hybridized, and the compound contains no hydrogen atoms (remember
that a triple bond is linear and therefore cannot be incorporated into a ring of six carbon atoms). (2)

Q3: Disregarding stereoisomers, draw the structures of all compounds with molecular formula C 5H10.
Which ones can exist as stereoisomers? (5)

Q4: In what orbitals are the lone pairs in each of the following molecules? (3)
O
H3C OH H3C C N
H3C CH3

(a) (b) (c)

Q5: In each compound below, two protons are encircled. Determine which of the two protons is more
acidic with logical explanation. (5)
O O O H O
H N H S
O H O H
H H N S
a b c

N H
N O
H O S O
H O H

d e

Q6: i) By keeping in view the charge stability, rationalize the following resonance structures from the
most significant to the lowest significant contributor to the resonance hybrid? Also draw the structure of
resonance hybrid. (4)

O O O O

N N N
N
(a) (b) (c) (d)

ii) Draw resonance contributors and hybrid structure for the following ions without creating additional
charges, and also locate the cross conjugation if present in any of these ions. (6)
Q7: Locate localized and delocalized electrons in lidocaine, one of the most widely used injectable
anesthetics, and histamine (responsible for many physiological responses and is known to mediate the
onset of allergic reactions). Draw all the structure of resonance contributors (max. charge ±1) and
resonance hybrid. (6)
H HN
N
N
N NH2
O

Lidocaine Histamine

Q8: Assign R/S configurations to all the chiral carbons of the first and last molecules drawn below. (2)

b). Draw the enantiomer of each of the molecule. (4)

c). Draw the correct Fischer Projection of the acyclic molecules shown below. (3)
O
OH OH
HO HO

OH O
Cl

Q9: How many stereogenic and chiral centers exist in the molecule drown below? (2)

• Determine the absolute configuration of all chiral center(s) (1)

• Stereochemistry around double bonded carbon atoms (E/Z) (1)

• Draw all the possible stereoisomes of the molecule drawn below and figure out how they are
related to each other (enantiomers or diastereomers) (4)
CH3
H
C2H5
Q10. Case problem: Haider Iqbal is student of CHEM-231 at SSE, LUMS. He is interested in knowing
the effect of resonance on the stability of conjugate base of an acid. He reads some books and articles to
understand the concept and concludes with writing following two points in his notes:

I. Resonance increases the delocalization of negative charge, and hence increases the stability of
conjugate base. Thus, when any acid deprotonates to form a conjugate base, and resonance is
possible in that conjugate base (making it stable)- it implies that the acid forming this conjugate
base was strong.

II. The greater the resonance, the higher would be the stability of conjugate base. Acetic acid
deprotonates to form acetate ion as a conjugate base which has two resonance structures; On the
other hand, phenol deprotonates to form phenoxide ion as a conjugate base and it has 5
resonance structures- making it very stable. Since conjugate base of phenol has higher number of
resonance structures (5) while the conjugate base of acetic acid has only 2 resonance structures,
it indicates that conjugate base of phenol is more stable (owing to higher number of resonance
structures). Thus Phenol is a stronger acid as compared to carboxylic acid.

Keeping in mind the above mentioned scenario, please answer the following questions:

A. Write down reaction equation to show deprotonation (loss of H +) and formation of

conjugate base in case of: i) Phenol and, ii) Acetic acid. (2)

B. Draw possible resonance structures of phenoxide and acetate ions. (2)

Do you agree with Haider Iqbal’s point of view mentioned in point II? Please give justification to support
or negate his understanding that phenol is a stronger acid than acetic acid. (4)

Q11: Draw the MO Diagram of the following compound. (5)

H3C F

• Locate the most important frontier orbitals (HOMO & LUMO). (2)

• Identify the nucleophilic and electrophilic center in the molecule. (2)

Q12: The development of chemical sensors that can detect harmful contaminants, like the toxic cyanide
anion, is an interesting research field. Compound 1 was explored as a chemical sensor for cyanide in
water. When it comes in contact with the cyanide ion, it reversibly forms a fluorescent anion 3, via anion
2. Since 1 is not fluorescent and 3 is, this could afford a powerful way to detect cyanide in drinking water.
 C N N N
O H O C HO C

HO O O HO O O O O O

1 2 3

 Draw curved arrows showing the intramolecular proton transfer that converts 2 into 3. (2)
 Determine the frontier orbitals and type of interaction that are involved in all three
transformations. (4)
 Reaction from 2 to 3 is reversible which is favored in the forward direction as shown by the
position of arrows. Explain why equilibrium is favorable in the forward direction. (2)

Q13: By considering bond order and the given molecular orbital configuration of a homo diatomic
molecule, in its neutral form X2, determine which of its molecular form is more stable. (2)

σ(1s)2 < σ* (1s)2 < σ(2s)2 < σ* (2s)2 σ(2px)2 < σ*(2px)2 < π (2py)2 = π (2pz)2 < π* (2py)2 = π* (pz)2 < σ*
(2px)0

a) X2 b) X2+ c) X2-