Carbocyclic Rings
Paper 4201 B
Organic Chemistry
(Special-II)
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CHEMISTRY OF SMALL, MEDIUM AND LARGE RING COMPOUNDS
Classification of monocyclic compounds (on the basis of number of carbon atoms in the ring):
3-4 C-atoms: Small rings
5-7 C-atoms: Normal rings
8-11 C-atoms: Medium rings
>12 C-atoms: Large rings
Baeyer Theory on the Strain in Cycloalkane Rings
Baeyer, suggested that cyclopropane and cyclobutane are less stable than cyclohexane, because the
smaller rings are more "strained". sp3 hybridized carbons in cycloalkanes do not have the expected
ideal bond angle of 109.5o this causes strain in the molecule (Angle Strain).
Figure: Deviation from ideal bond angle of 109.5o
• The deviation is higher for cyclopropane than cyclobutane therefore cyclopropane is more
prone to undergo ring opening reactions.
• Baeyer’s theory is based upon some assumptions that all ring systems are planar. Deviation
from normal tetrahedral angles results in unstable cycloalkanes.
• However, contrary to the Bayer’s theory, the bond angles in cyclohexane and higher
cycloalkanes are not larger than 109.5° because the carbon rings of those compounds are not
planar but they are puckered.
• Strain in small-ring cycloalkanes affect their physical and chemical properties. Cyclopropane
and cyclobutane undergo C−C bond cleavage reactions, like alkenes, that are not observed for
cyclopentane and cyclohexane, or for saturated, open-chain hydrocarbons.
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Paper 4201-B: Supramolecular chemistry and carbocyclic rings Small Rings
Cyclopropanes
• Stable but highly strained compounds (ring strain ~29 kcal/mol).
• C–C bond angles = 60º
• Substituents on cyclopropanes are eclipsed. H–C–H angle is ~120º. As a result, the C–H
bonds have higher s character compared to normal sp3 bonds.
• Highly strained cyclopropane ring shows reactivity analogous to that of alkenes than that of
alkanes.
Some General Strategies for Cyclopropanation
1. BY REACTION OF AN ALKENES WITH A CARBENE
2. VIA CARBENES GENERATED BY DECOMPOSITION OF DIAZO COMPOUNDS
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Paper 4201-B: Supramolecular chemistry and carbocyclic rings Small Rings
3. SIMMONS-SMITH REACTION –– ZINC REAGENTS IN CYCLOPROPANATION
Reaction between diidomethane and a zinc-copper couple gives reactive carbenoid intermediate
Iodomethylzinc iodide (ICH2ZnI)
MECHANISM: Concerted reaction- Simultaneous formation of both C-C bonds .
• Reaction is stereospecific with respect to the alkene
• Diastereoselective cyclopropanation is possible in the presence of directing groups:
•FROM 1,3-DIBROMOPROPANE BY WRUTZ REACTION
1,3-Dibromopropane cyclizes in the presence of sodium metal under anhydrous conditions to
give cyclopropane. The yield of this reaction can be improved by using zinc metal.
+ 2 Na + 2 NaBr
Br Br
+ Zn + ZnBr2
Br Br 4
Paper 4201-B: Supramolecular chemistry and carbocyclic rings Small Rings
Synthetic methods for the Construction of Cyclobutanes: You have studied conventional methods
like 1,3-dibromopropane with malonic acid diethyl ester in the presence of a base etc. at UG level so
we will not discuss those methods.
BY [2+2] CYCLOADDITIONS: Suprafacial [2+2] cycloadditions are photochemically allowed but
thermally forbidden.
•Intramolecular [2+2] Cycloadditions
Intramolecular [2+2] cycloadducts are readily formed. Tethers are generally 2 to 4 atoms long:
Inokuma, S.; Yatsuzuka, T.; Ohtsuki, S.; Hino, S.; Nishimura, J. Synthesis of Crownophanes Possessing Three Pyridine Rings Tetrahedron 2007, 63, 5088– 5094
• Intermolecular [2+2] Cycloadditions
Regioselectivity: In general, H-T isomer is favored when R is electron donating and H-H isomer
is favored when R is electron withdrawing
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Reactions of cyclopropane and Cyclobutanes
The cyclopropane ring undergoes ring substitution reactions such as Halogenation, and ring opening
reactions such as Addition reactions (Hydrohalogenation, bromination, hydrogenation, hydration
etc.).
h Cl2 HBr Br
free radical Markovniknov’a rule is followed in
substitution -HCl Substituted cyclopropanes
reaction
Cl
Br2,
FeBr3
H2, Ni
120oC
Br Br
The cyclobutane ring undergoes ring substitution reactions such as Halogenation, ring opening
reactions such as Addition reactions (Hydrohalogenation, bromination, hydrogenation,
hydration etc.) and ring expansion reactions.
h, Cl2 HBr
Br
Cl
-HCl
free radical Markovniknov’a rule is followed in
substitution Substituted cyclobutanes
reaction H2, Ni
200oC
• Strain in a small rings also induces rearrangements in cyclobutanes. Although a 3ºcarbocation is
initially formed, the angle and torsional strain of the four-membered ring is reduced by a methylene
group shift resulting in ring expansion to a 2ºcarbocation.
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Paper 4201-B: Supramolecular chemistry and carbocyclic rings Small Rings