their ring struc-

~ p o u n d s are called alicyclic (ali from aliphatic acid cyclic from

they resembl e aliphati c compou nds in most of
tures) compounds. These compounds are f.O named because
nature, they differ from aliphati c
their properties but possess cyclic structures. However, due to their cyclic
nds since their rings
compounds in some respects. Alicyclic compounds are also called carbocyclic compou
are made up of only carbon atoms.
Saturat ed
Like open chain hydrocarbons, alicyclic compounds can also be saturate d or unsaturated.
ra:frm~ those
alicyclic compounds corresponding to alkanes or paraffins are called cycloal kanes or cyclopa
cycloalkynes.
corresponding to alkenes are called cycloalkenes while those corresponding to alkynes are called
tion, chemic al propert ies and the
In this unit, we shall discuss the nomenclature, general methods of prepara
effect of ring size on the relative stabilities of cycloalkanes.
~NO M'ENtttAlURi.t
alkenes are
The general formula of cycloalkanes is CnH2n or (CH2)n where n = 3, 4, 5, 6 ... etc. Since
. Further , since in these
represented by the same formula , therefore, cycloalkanes are isomeric with alkenes
are also called
compounds, a number of methyle ne (CH2) units are joined togethe r to form a ring, they
obtaine d by attachi ng the prefix
polymethylelies. The name of any saturate d alicyclic hydroca rbon is then
tri-, tetra-, penta-, hexa-, etc. to the word methylene accordi ng as the number
of carbon atoms in the ring
are three, four, five, six, etc. respectively.
indi-
In the IUPAC system, the saturated alicylic hydrocarbons are called cycloalkanes. The name of an
ding alkane having the
vidual cycloalkane is obtained by prefixing the word cyclo to the name of the co~n
represented by
same number of carbon atoms as the ring. For convenience, alicyclic compounds are usually
for cyclobutane,
simple geometric figures also called the polygon formula : a triangle for cyclopropane, a square
a pentagon for cyclopentane, a hexagon for cyclohexane and so on. In such
representations, it is understood that
e,
each corner represents a CI-Ii group unless some other substituent is indicated. For exampl

Cyclopropane □
Cyclobutane
0
Cyclopentnno
0
Cyclohexano
.~....
~1,j=;1. IUPAC NAMES OF SUBSTITUTED CYCLOALKANES
The following rules are generall~ followed :
in such_ a way
1. In case of substitu ted cycloal kanes, the numbering of the ring carbon atoms is done
that the substituents get the lowest possible numberls. The name of the substituted cycloalk
kane. In
an~ :{. th
case, ere 5
•r
obtained by prefixin g the name of the substitu ent to the name of the parent cycloal

•
 more than one substitucnt. each substituent prefixed by its locant is arranged In alphabetical Orr/ff'

6'
the name ofthe parent alkane.

&CH, &CH CH3 2

H~,
3
CH2CH3
Ethylcyclopentane l. 2-Dimethylcyclopentane 1-Ethyl-2-mcthylcyclohexano 3-Ethyl-1, J -dimethylcyclo~
2. (a) Ifthe ~ing contains more or equal number ofcarbon atoms than the alkyl group attached to It,
is named as a d_erivati1 1e ofcycloalkane and the alkyl group is treated as a ~ubslituent group, otherw;• 11 :
named as a denvotive ofalkone and the cycloalli.)'I group is considered as a substituent group. For exatnnt..
◄

CH36-0l2-CH3
I 2 3
OCH2CH2CH,CH3
1 2
CH3-CH26-CH,-CH,
3 4 5-~

(2-Butyl)cyclohexane Pcn~·lcyclopcntn110 3-Cyclobutylpentane

Note that parentheses are used "hercver necessary to avoid confusion. Here, in the first example, 2-
butyl group bas been enclosed in parentheses to emphasize that tbe locant 2 refers to the substituent on the
alkane and :not on the ring (i.e. cycloalkane).

L
(b) lf, howe1.1e,; the side tlza11 contains a multiple bond or a functional group, the alicyc/ic ring 18
treated as the szibstituent irrespective ofthe size of the ring. For example,
3 2
CH= CH,
I
c5 4 3
= CH-COCH3
21

3-Cyclopropylprop--l-ene 4-Cyclohexylbut-3-en-2-one
(c) ff, hawever, more than one alicyclic ring is attached to a single chain, the compound is named as a
derrvarive ofalkane irrespective of the number of carbon atoms in the ring or the chain. For example,
I 3

Dicyclopropylmethane 1, 3-Dicyclohexylpropane
3. Jfa multiple {double or triple) bond and some other substituents are present in the ring, the number-
mg 1s done in such a way that the carbon atoms of the multiple bond get lowest locants 1 and 2 and the
subsfltuent groups get the lower locants at the first point of difference. For example,
CH3 N02

6LCH 3

J, 5-Dimeth,Y,lcyclopent I enc
6:
3-Nitrocyclohex-1-ene
4. Jfthe ring contains a multiple bond and the side chain contains a functional group, then the ring is
treated as the suhs1lluent and the compound ts named as a derivative of the side chain. For example,
3 2 I
CHo-CHzOH
3 2 l
CH3 H2 CH2 COOH
2
3
2-(Cyclopent-3-en-l-yl)propan-1-ol

-:,J·
3-(4-Methylcyclohcx-2-en- l-yl)propanoic acid
224 !EFliif iHYP0.!?1'-~~~~J~~~):iy1tif1-~
 08
5. If th~ ring~ well as th~ side chain contain functional groups, the compound II ntllMd a ~a;
mre of the side chain or the al,cyclic ring according as the side chain or the ring contains the pr,nciptl
Juncnonal group. For example,
~
~l~
O 2 N ~ H = CH-CO
2 1
OH HON V
1 2
_H2CH2
I
CHO

3-(4-Ilydroxyiminocyclohex-l-yl)propmal .
3-(4-Nitrocyclohex-l-en-l-yl)prop-2-cn-l-oic ncid
th
If, howeve~ th ~ alicyclic :ing an~ the side chain contain the same functional grouf, e co"!pou~d;;
named as a derivative of th e side cham of the ring according as the side chain or the rmg contams high
number of carbon atoms. For example,
OH OH
one 2
~ CH,1 H-CH2CH3
1 2-6 1
' ( Y H2-[CH2 ],CHO
U"" 1 2 3 4
7-(3-Formylcyclopent-1-yl)heptanal
2-(2-Hydroxylbut-1-yl)cyclohexan-1-ol
6. If a compound contains an alicyclic ring directly Jinked to the benzene ring, it is named as
a
derivative of benzene, i.e., the compound having lowest state of hydrogenation. For example,

o- -@ 4

Cyclohexylbenzene
1-(2-Methylcyclohexyl)-4-nitrobenzene

1. If some functional group along with other substituent groups are present in the ring, it is indicated
by some appropriate prefix or suffix and its position is indicated by numbering the carbon atoms of
the ring
in such a way that the functional group gets the lowest number. For example,
OH 0

aCH 3
3-Methylcyclohexan-1-ol
:ct::
4
3

3
5, 6-Dimethylcyclohex-2-en-l-one 3-Hydroxycyclohexan-1-one
the
8. If an a/icyclic compound contains carbon containing functional groups, the carbon atoms of
functional groups are not included in the parent name of the alicyclic system. Therefore. for such systems.
the following prefixes and suffixes for the functional groups are commonly used.

Functional group Prefix Suffix

-CHO Formyl Carbaldehyde

-COOR Carboxy Carboxylic acid
-cox Halocarbonyl Carbonyl halide
(X = F, Cl, Br, I)
-COOR Alkoxycarbonyl or CarbalkO:\')' Alkyl carbox')'late
-CONH2 Carbamoyl Carboxamide •
-CN Cyano Carbonitrile
-
 For example.
CN CHO

6
Cyclohcxanecarbonitri\e
6
Cyclohcxnnccnrbaldchydc 2-0xocyclohexanecarba
ldchydc
CONH2 0

6-CH3 (j-cooH 0

l)1coo~H 5
2 M th l l tan l
- e ) cboyc o~dn c- 2-0xocyclohexane-1-
car x.anu e - carboxylic acid Ethyl (2-oxocyclobexan
e )-1-
i~it-1. IUPAC NAMES carboxylate
OF BICYCLIC CYCL
Many hydrocarbons and their de OALKANES*
rivatives contain two or m
the rings are called bridge ore rings . The carbon at
head atoms and each bo o~s common to ~
head atoms called a br nd or chain of carbon ato
18 idge . The bridge may contain m s co nnecting both the bridge
0, 1, 2...... etc . carbon ato
Bndgehead m s. For example,
Zero carbon
carbcn at001 ~ atom bridge Bridge head
One carooo
CH Moo•t~

rn/ C ~ bridge

/
One carbon
bndge
~

/
CH
/
CH 2. ..- On ec M ~
bridge ,::;-;oJ c\H2
bridge l
CH 2
L
I 2
c\
CH 2
H2} ~:n
bridge
I\I
~c/
Bridge head
carbon atom

(J
Bridge h e a d / 111
CM ~a ro m

The bicyclic compou

having the same total nu nds are named by attaching the prefix 'bicyclo
these three bridges conn mber of carbon atoms as in the two rings. The ' to the name of the hydrocarboD
ec nu
2......etc. These arabic nu ting the two bridge head carbon atoms is indica mber of carbon atoms in each of
and then enclosed in sq erals are arranged in descending order : sepa ted by arabic numerals, i.e., 0, l,
m
ua rated from one another by
placing these brackets co re brackets. The complete IUPAC name of the full stoPS
(containing the same tot ntaining the arabic numerals between the prefix hydrocarbon is then obtained by
al number of carbon atoms bi clo and the name of
as in the two rings). Focy the alkaDC

&
Bicyclo[l.1.0]butane
(J C)
r example,

(X)
Bicyclo[2 .2. l]heptane
If a substituent is present, Dicycl
bridge head atoms, procee atoms of the bicyclic ring o[3. l.l ]heptane Bicyclo[4.4.0]decane (De
cal1n)
ds first along the longest are numbered. Th e num bering begins with one of
next longest bridge to the bridg tbD
• first bridge head and is fin e to the second bridge head atom, continues along
ally completed along the
shortest ~t h. For example
tbD
,
•Included only in the sylla
bus of Kashmir University.

ti-Hill AHii ~1.'!!~!f~<:Jc[iq:r

:;if k 1
1:5 II
 r{"(Cl
2 3

3~5 4
J
4 s
g..Qilorobic) clo[3 .2.1 ]octane Bicyclol 2.2.1 ]hcpt-2-cno 2, 6, 6--Trimethylbicyclo[3. l.l Jhept-2-ene

· ·-<~ PROBLEMS FOR PRACTICE

(i)o-o
1. Gh·e the IUPAC names of the following compounds :

(iii) \)-=cH = CH4H--CH2CH3

CH 3

(vi)
Q
HOCH2-C-CH = CHCH2COOH
I
CH3

n
C2H5 [CH2]9CH3 OH

(vii)
0 (viii)
CH3[CH2]9 [CHi)9CH3
(ix)
6
(x)
CH3

Qc=o (xi)
DCOOH0

(xii) 0- CONHC 6H 5
OHC
ANSWERS
(,) Cyclohex:ylcyclohexane (iz) 2-(2-Methylcyclobut-l-en-l-yl)ethanal
(iiz) l-Cyclopropyl-3-methylpent-l-ene (iv) 2-(3-0xobutyl)cyclohexan-l-one
(v) Methyl (2-oxocyclopentane)-1-carbox:ylate (vz) 5-Cyclohexyl-6 hydroxy-5-methylhex-3-en-l-oic acid
(viz) l-Ethyl-4-methylcyclohexane (viii) 1, 3, 5-Tris(decyl)cyclohexane
(ix) Cyclohex-2--en-1-ol (x) Cyclohex:ylidenemethanone
(xi) 4-Forrn 1-2-oxocyclohexane-l-carboxylic acid (xii) Cyclohexanecarboxanillide

. ..SYNTH~sfsf"il(~t¢t♦.4tKAN'.Ml)\NDJTil!'l)l:/ijjltt,VAlN:l$ ~:1
' Some important general methods of~thesis of cycloalkanes and their derivatives are discussed below:
1-. Cycloaddition reactions. An addition reaction between two unsaturated components (molecules,
ions or neutral species) leading to the formation of a cyclic product are called cycloaddition reactions. In
these reactions, the 1t-electrons of the two components form two new a-bonds. These reactions are usually
designated by writing the n-electrons of the two components usually in the descending order separated by a
plus sign in a square bracket. For example, (2 + 2), l4 + 2), (6 + 4) cycloaddition reactions. For example, a
[2 + 2] cycloaddition reaction involves addition of two alkene molecules to fonn a cyclobutane derivative.
These reactions do not involve ionic or free radical intermediates and occur in a single step (concerted
reactions) via cyclic transition state in which bond-making and bond breaking occur simultaneously. Such
 h tc transition states are called
concerted reactions which occur througd cy~~itiated either by heat or light. pericy clic reactio;?
reactions do not require any cata/ySI an are 1 '
Th fl 11 . g cycloaddition reactions can be used to prepare cycloalkancs.
'-':t'."--J. [ ; :2i°.::1oaddition reac~ions. These cyc~oaddition reactions can be used
to prepare both Cl$:10blltal
and •clo ropane derivatives as discussed below .
C} p
- -{a) Synth~•s
cyclobutane denv~u
.
_of d rivativcs One of the most important methods for the synthesis c,
c~~-~t,~:~~~ a~dition of.two molecules of the same (dimerization) or ~eren t alk-
enes. These reacuonvcs II occur under photochemical conditions by a concerted mechanism via I
s genera y

r- r
cyclic tranSition state. For example.

CH2: CH2 1,v [:1I ~II 2

-.. -..
2
] -
CH2= CH2 (Dimeri:atioll) cr.r;~ CII2 CH2 -- Cfli
Ethylene (two molecllles) Transitio n state Cyclobutane
fu case of substituted alkenes, although the addition takes place. on the ~e f~ (sup,:a[aciaf) ~f the
alkene. yet the two molecules of the alkene may approach each other m two different ways
gtvmg a nnxtnre
ofrno products. For example, CH CH CH CH
3 -~ - -· 3 3 :'Ir--- ~ 3
hv ··· H
(Suprafacia/
addition)
cis-2-Butene
All cis-tetramethyl-
cis-anli-cis-
cyclobutane
Tetramethylcyclobutme
Similarly, trans-2-butene on photochemical dirnerization gives a mixture of two
products, viz.. cis-
anti-cis and all trans-tetramethylcyclobutane.
It may be noted here that substituted alkenes containing electron-withdrawing substituents
such as (-F,
-COR , -CN, -COO R, etc.) form cyclobutane derivatives under thermal conditi
ons. These reacrwns
proceed via a free radical mechanism involving di radical intermediates.
F2C C F2 F2C-CF2
ll + II /). I I
R2C CR2 ~ R2C · · CR2
Diradical
F2C-CH2 F2C-CH2
I I ~ I I
R2C· ·CH-C6H5 R2C-CH -C6H5
Diradical
(b) Synthesis of cyclopropane derivative~ Another example off2 + 2] cycload
dition reaction involves the
• 'dition of free carbenes or carbenoid~· (carbene bke species) to alkenes to give cyclo}fropane derivatives.
(i) Addition of free carbenes. Photolysis of diazornethanc in prescJ}ce of
(a free carbene) which then adds to propcnc to give methycyclopropane. Thus, propcn e first gives methylene
- + hv
:CH2- N= N : CII 2 + Na N
►
Diazomethane Methylene
CH3- CH = CH2 + : CH hv
2 CHr-,/CH 2
Propene
CH2
Methylcyclopropane

J
 Methylen~__itself is ve1:Y reactive and hence gives many side reactions, especially insertion reactions
which greatly reduce th e yields of cycloaddition reactions. Hnloeaffllltcs, on the other hand, bemg less
reactiVe than melhylene do not undergo insertion reactions and hence give good yields of cycloaddition
proaucts. For example,

(CH,),a rK" + CHCI, ' (CH,),COH I ~: cA:

L'
] Cl
K+ Slow ~ :CCl2
D1chlorocarbene
+ K+cr

I
JJI

0 Cl
:CCl2

or CHCl3 '(CII3)JCOK Cl
6,
Cyclohex.ene H
7, 7-Dichlorob1cyclo [4 .1.0) heptane (590/4)
Mechanism. The reaction is believed to occur by the following steps :
Step 1. Photolysis of diazomethanegives methylene (a carbene) which is a highly reactive chemical
species.
hv

Methylen'C

The methylene thus produced may be either singlet or triplet depending upon the reaction conditions
employed such as the wavelength of light used, reaction phase (liquid or gaseous). presence of inert gases
such as argon, nitrogen, etc. and presence of photosensitizers. Singlet methylene is usually formed in the
liquid phase photolysis while triplet methylene is produced either by gas phase photolysis especially in the
presence of an inert gas like N2 or AI, or by photosensitization.
Step 2. The methylene produced above adds across the double bond. According to Skell theory, the
mode of addition, however, depends upon the type of methylene produced in step 1. Singlet methylene
reacts by a one-step (concerted) mechanism and gives stereospecific cis-addition products, i.e., the stere-
ochemistry of the original alkene is retained in the product. In other words, if in the original alkene. the
substituents are trans, they will be trans in the product and if they are cis they will be cis in the product. For
example,

C/S•2•J:3utcne

trans-2-Butene

Triplet methylene, on the other hand, reacts by a two-step free radical mechanism and gives non-
stereo~pecific addition products. For example, the reaction of either cis or trans-2-butene with triplet meth-
ylene gives the same mixture of cis- and tran\·• 1, 2-dimethylcyclopropanes.
• l'NN.•-,;,,• :,.:,,;.~'♦-:' I' :H,,:❖''6❖',::•:-,:«0:~·• !-'·!•'•'l,:,•,:•:'°❖':N.•:•:-X'❖'~{❖-.:❖••:, .,..,: '❖'H,!,',««,, .

A reaction is said to be stereospecific if a particular stereo isomer of the reactant produces a specific stereoi-
111

somer of the product.

 cis-2-Butcnc lnp let methylene

! Rotabon around C- C bond

Spin inveraion l
H, t /C H3 CH3, .J,
CH :;/
' C -C "- c- -e / CH3
/ "-,.H
iO H. H/
iCH2
I ""
I1 , / CH 3 CH 3 ,
l Ring clOllte

' c- -- e ......,c--c , ~CH3

CH 3 / \/
H/ \ / "H
CH 2
CH2
cyc lopropane trans-1, 2-Dimethyl
Similarly, we can show that trans- cis-1, 2-Dimethylcycl~
2-bute ne also gives the same
dimeth)-Icyclopropane. mixture of cis- and trans-I, 2-
(i1) Addition of a carbenoid
-Simmons-Smith reaction. Ad
.3ields of g •clopropane derivatives dition of methylene to alkenes gh·
since it being extremely reactive es low
insertion reactions. Therefore, wh und ergoes many side reactions especia
en it is desired to add CH for pre lly
used. Instead a carbene like specie 2 parative purposes, free carbene
s called the carbenoid is use d which greatly improves the yie
is n«
cycloaddition product by reducing lds of the
the insertion reactions. One such
tion ~·hich uses diiodomethane reaction is called Simmons-Smith
in presence of Zn -C u couple* reac-
addition is stereospecifically syn as a source of carbene like specie
and occurs by a concerted mecha s. The
nism as shown below :
Diethyl ether

lodomethylenezinc iodide

C H ~ /H
C.
I ······· cH ········ ... Zn\ l
.... 2 ..... :
C .... ········I
CIl3 / "'-. II
cis-2-Butene
Transition state
cis-1, 2-Dimethylcyclopropanc
On the other hand, the reaction
of trans-2-butene with Cll 1 in
trans-I, 2-dimethylcyclopropane. 22 presence of Zn -C u couple give
s
II. (4 + 2] Cycloaddition rcactio
ns- DiclN Alder reaction
This reaction involves the additio
n of an alkcne or an alkyne molec
to a conjugated diene (41t-electro ule {21t-electrons) called the dienop
ns) resulting iu the founation hile
cyclohexene is obtained by heating of a six-membered ring. For examp
#7/61"✓.::~;,-,: :o-o:::;,.::,:,;:-,r. •,• u.· oX❖,❖:Ol'f❖,. ❖X❖!❖:OX❖:--.-:,;,:,:.:,~,:.•,:
a mixture ofbutadiene and ethyle le,
,;,*.-X: 1❖: :•h W • •:"v--:•:•:•:❖~-·~ ~,;'•d• ···;·:,:,
ne at 475 K.
*A convenient method of preparing ,,,', , , · ,;,:,,O:-:•:•:•:•,•:•:•:•;,;,;,;,;,:u .;";,:,:,:•:
•:❖: 0:,:,:❖;•:❖'>!•'\❖,,;·•-.,-..;,-:;.:~-.:~,,~ ~'«❖•°'-.'"''
,
Zn Cu couple is .. 'i:
atmosphere. by heating zinc dus t with CuCl
in ether under N2

f Eiih tRPIU OR GANIC c ~ ,, ;,•tliPMI

 2
/C H2 415 K H C /C H '--CH
H C ir
I
H C 'C H2
+
• H~'-CH ,,,.&:
c yc,...~ ~
Eth)-lene (Dienophile) ...wn•
her healed
e two components are eit
1, 3-Butadiene. (Diene) .
d qm rc any ca talys t. Th D jl 6w
A l der reactio n oc s not rc ch loro bc nz cn e, etc .
'fhe Diels as benzene. toluene, C
ted in some sol\'ent such as >C = o, -cHO, -C ~
an clcctron-wi~1drawi ca med out at a muc~ lower tcmpe.abue ~
ng gro _up such
~e noph ile cont ain s
o r~ the -N 02• etc., the reactio
n c:111 be

~:--:-:l :0·
anm-dride, qwnone. --CN.
J7J K •
~2C H O
CHO
cin
Acrol Jdehydo
I, 3-Butadiene Cyclohc.ir-3-cno- l •ca rba
iU tdra~ving grou ps more rcactrve thee~ the most
is
-w
ber o( such el~cu·?n a useful d1enophile while tetracyanoethyJen 15
furth er. gr eater the .num 1s
dnde
r ~c tl on s. male1c anhy
nius, in Diels-i\!dedi ered so far.
~crn·e dienophile scov

' + & 298K

:<£> HO
O arboxylic acid anhydride
I, 3-Butadtene
Cyclohex-4-ene-1,2-dic
Maleic anhydride pentadiene.
isoprene (2-methyl-l, 3-butadiene) and cyclo
Other useful dienes are 3
3
~ C 02CH
+ 5
· ~ C 02CH3
6
Dimethyl acetylene -4-methylphthalate
Isoprene Dimethyl 3, 6-dihydro stereoc.bemistry
dicarboxylate action, i.e., the
lder reaction is stereospecific cis addition re
A
Stereochemistry. Diels-e) is retained in the product. For example,
(or the dien /C 02 H
of the dienophile H '\ 5 4
H 02C '\ /C 02H C =C
C =C ►
'\H ~ H 02c / '\H
6~3
H/
Maleic acid
(cis)
~
I, 3-Butadicne
Fumaric acid
(trans)
H H C02H
1,uns-C) clooex-4-411•
I, 2-dicatbQxylic aad
cis-Cyclohex-4-ene- e e:~
I, 2-dicarboxylic acid cts ar.e p~ssible. These are ca!led endopoannedntthbut
od_u
c, two cis-additionthpre d1enopl11Je JJes underneath the d1ene
com
If the diene is cyclict, the m olecule of ample,
ducts. In the endo addu nents project away from each other. For ex 7
com po
exo-adduct, the two 7
5

0 l
1• 3-Cyclopentadiene
+
CHO_.
Acrolein
/!.
~H
CHO
a a··
.•

uo-BicyoJo (2.2. IJ
CHO

do (""1t0r)
endo-Bicyclo [2.2. I] hept-S.eno-2-carbaJdohy
hyde (major)
he t-5 e-2-carbaldc
-en
{ ... ...
 It may be noted here that in Diels-Alder reactions, it is the thermodynamically less stable enc1o
uct which always predominates over the more stable exo-adduct. P.,.._
--1: Dehalogenation of a, ro-dihaloalkanes--Freund 's method. J1tis I]I~thod involves the action of
metals such as zinc or sodiwn on a suitable ex., ro-dihafoalkane (alkane having the halogen atoms on t h e ~
carbon atoms). This reaction may be regarded as an mtramolecular Wurtz reaction. For example, ~-..._...
_....-----CH 2 -Br /CH2
C.H2 +Zn CH2 ......_ I + ZnBr2
"-CH 2 -Br "'-CH2
1, 3-Dibromopropane Cyclopropane

/ CH 2 -CH 2 -Br t1
CH.2 '-._ + Zn ~
CH 2 --CH 2 -CH 2 -Br
1, 6-Dibromohexano Cyclobexane
This reaction gh-es good yields for only cyclopropane. a., ro-Dihalides in which the tw~ halogen atoms cl?t
funher apart than the 1, 6-positions, do not fonn ring compounds but undergo Wurtz reaction. For example,
Br-{CH2)n-Br Zn Br(CH2)2nBr + Br(CHz)3n8r, etc.
Wurtz reaction
(n>6)
3. Dieckmann cyclization or condensation. Esters of ex., co-dicarboxylic acids undergo intramolecu-
lar Gaisen condensation called Dieckmann cyclization or condensation in presence of molecular sodium
(sodium dust) or sodium methoxide (or ethox:ide) to form cyclic f3-ketoesters. These cyclic f3-ketoesters on
subsequent hydrolysis and decarboxylation yield cycloalkanones which can be converted to the correspond-
ing cycloalkanes by Clemmensen reduction. For example, cyclopentane can be synthesized from diethyl
adipate by the following sequence of reactions :
(i) Dieckmann condensation
CTI2 ---CH2 ---COOCiH5 (i)NaOCiHs CTI2--CH2"-.
I (ii) H+ I H20
I C=O
GI 2 ---CH2 ---COOCiH5 GI-CH/
Diethyl adipate
2 I
COOCiH 5
2-Carbethoxycyclopentanone
Mechanism:
0
II
CH2-CH2-C--OC2Hs
I ~~H5 4
CH2-C~H --C2H50H
I
COOC2H 5
Dietli/1 adipate

CH2-CH2
/
CH2-CH
)c-o
I
COOC2H 5
 (ii) _Hydrolysis of 2-carbethoxycyclopentanone to 2-carboxycyclopenta
none. This is the ~ . acidic
the ester will dil. HCl
bydrOHSlysiso of an ester to the corresponding carboxylic acid and is achieved by heating
or 2 4•
CHI2-CH 2' OI2-C H2 '-
"c= o IP m20 I 'c=o
CH2-CH,,.,,,.. -C:2115011 CH -CH /
I z I
COOCzH 5 COOH
2-Carbcthox-ycyclopentanone 2-Carboxycyctopentanone

. (iii) De~ar~oxyla~ion of2-carboxycyc/ope11ta11011e to cyclopentanone.

Since 2-carboxycyclopentanone
lS a P-ketoacid, it readily undergoes dccarbo~')'latio
n on heating to give cyclopentanone :
CHI2-CH 2 " t:, CH2-CH2 '-
C =O -- I '-C=O
CH2-CH / -CO2 CH -CH 2 /
2
I Cyclopentanone
COOH
2-Carboi.-ycyclopenlanone
(iv) Reduction of cyclopentanone to cyc/opentane. The conversion of cyclop
entanone to cyclopentane
is conveniently achieved by Clemmensen reduction.
CH2-CH2'-...,
Zn-Hg/HCI
I CH2
Clemmensen reduction OI2- CH2 /
Cyclopenlanone Cyclopenlane
pimelate,
Similarly, Dieckmann cyclization can be used to prepare cyclohexane from diethyl
/ CH2CH2COOCzHs
CH2 "-.
CH2CH 2COOCzH5
method.
~ - Pyrolysis of Oalcium or Barium salts of dicarboxylic acid~ islice nus
on heating, which can be
Calcium, barium or thorium salts of dicarbo>-.-ylic acids yiel~cloalkanones
(Zn-Hg/HCl). For example,
readily reduced to the corresponding cycloalkanes by Clemmensen reduction
C1½CH2COO- CH 2CH2 , CH2CH2 "-.
565-57 5K I 'C=O--w_-_11g_t_H_c1_ _
I Ba2..
/ Clemmensen reduction I CH2
-BaC°-3 CH
CH 2 2 ' CH CH /
CH2CH2COO- 2 2
Cyclopentanone Cyclopentanl!
Barium adipate
565-57SK
-CaC03

Cydohl!Xat1onl!
/CH 2CH 2 '-...,
Zn-llg/ HCI
CH2 '-.. CH2
Cll!nun.:n~en 1edm;tion /
CH2CH2
Cycloh-,xane
In accordance with Blanc :S- rule, this method gives good yields for 5- and
6-membered rings .

•
 Bl ,
states anc ~ rule. Tl~e eff~t of heat
on dicarboxylic acids can be sum man. • fl rm of Blanc srule which
1 3-d
that dicarboxy/1c acids in which the two zed mth~ same carbon atom (I.e.,
· b · . carboxyl groups are attached 10
' . ica r oxyhc Ii
acids) upon heating undergo decarb
oxylat,.on toform mono car boxy c ac ids '• J' 4 and J•
S-dicarboxylic acids 011 heating
alone or upon distillation with ace 'd fi m cyclic anhydrides;
1' 6 d I 7 . tic anh~dr, e .0 1". nhvdride give cyc
an , -d,carboxy/ic acids on hea lic
k t
e ones wit. h the loss ofone carbon ting alone or upon d'1s I'll
1 at'10n with ace_,tic a ..,,
. . I
atom as carbon dwx1de w ii 1,e 1, 8 and higher uecar ~.r boY V/ic aci ds remain
unaffected. Thus,
/C OO H
CH2 CH3 COOH + CO2
"C OO H Acetic acid

Malonic acid
(A 1, 3-dicarboxylic acuf)

CH2-C OO H 11 CH 2-- C O '

I or Dis til with
I O +H 20
aI2-C OO H (CH3C0)20
CH2-- C O /
Succinic acid Succinic anhydricl e
(A 1, 4-dicarborybc acid)

CH2--COOH /C H2-- C O "

11
CH 2/ CH2 O +H 20
or Distil with
"-- cH2--COOH (CH3CO)i0 '-._ CH --CO /
2
Glutaric acid Glutaric anhydride
(A J 5-dicarboxybc acid)

CH 2--C H2--COOH CH2--CH2'-.._

11
I or Distil with
I C = 0 + CO2 + H2 0
CH 2--C H2-C OO H CH 2-C H 2/
(CH3C0)20
Adipicacid Cyclopentanone
(A 1, 6-d1carboxylic acul)

/ CH2--CH2--COOH
11 /C H 2-C H 2 '-.
CH2
CH 2 C= O+ C02 +H 2 0
' CH2--C H2--COOH
Pimelic acid
or Distil with
(CH3CO)iO '-c H, -C H
Cyclohexanone
2
/

(A 1, 7-dicarboxy/ic acid)
This rule is quite useful in detenninin
g the ring size of a cyclic compound.
bond is introduced into the ring by som For this purpose, a double
e known method. The ring is then oxi
to give a dicarboxylic acid, the pyroly dised with the help ofK Mn 0
sis of which helps us to determine the 4
5. Thorpe-Ziegler reaction. This is size of the ring.
the best method for preparing large
yields . It consists of treating an ex., ro- macrocyclic rings in good
dinitrile (in which the nitrite groups
are at the terminal carbon atoms)
with a base such as lithium diethy +-
lamide, LiN (~H sh commonly abb
+- reviated as LOA or lithium
ethylphenylamide, LiN(½Hs)~Hs
in benzene or toluene. The dinitrile
densation called Thorpe reaction to undergoes an intramolecular con-
form a cyclic P-iminonitrile which
sponding cyclic ketone in good yield. upon hydrolysis gives the corre-
The cyclic ketone can then be reduce
the corresponding cycloalkane. For exa d by Clemmensen method to give
mple,

OR GA NI C CH EM IS TR
Y, ~-
 CH2C=N ff+/Hp
(CH2) ,,/
'-cH2C= N
a, co-Dinitrile

(CH 2 )n
/
CH2
'-c =O _c1emmen
_ Zn_-_H=-g/_HC-:---1~➔➔
sen reduction
-CO2
(Decarboxylation) '-cH2 /
Cycloalkanone

P-Ketoacid CH2
(CH2),,/ "-rn2
'-cH2 /
Cycloalkane
red rings.
Like Dieckmann cyclization, this reaction also gives good yields only for five and six membe
prepare d in good yields. In
However, by using Ziegler high dilution technique, macrocyclic rings have been
the basic catalyst
this technique, a very dilute solution of the dinitrile in benzene is added to the solution of
reducin g the intemwlecular
in large excess of ether. This ensures intramolecular reaction by considerably
60-80% (rings
reaction. In this way, yields of 95% (seven membered ring), 86% (eight membered ring), and
r, less than 15%.
with 14 or more carbons) have been obtained; yields of 9-13 membered rings are, howeve
evident from
Mechanism. The mechanism of this reaction is similar to Dieckmann condensation as is
the formation of iminonitrile sketched below :

_,.,,.,,-CH 2 '\.
CH 2 '\
I C=NH
CH2"'-._CH /
I
CN
P-Iminonitrile
I, 6-Hexanedinitrile
of alicyclic
6. Demjanov rearrangement. This is a very useful method for expansion or contraction
are obtained by
ring systems through carbocation intermediates. The carbocations, needed for the purpose
either react with a
deamination of alicyclic amines with nitrous acid. The initially formed carbocation may
(elimination
nucleophile to form the substitution product or may eliminate a proton to fonn an alkene
reaction). Alternatively, the initially formed carbocation may undergo rearrangement
to the more stable
the elimination
carbocation either by ring expansion or contraction before undergoing the substitution or
reaction mentioned above.
intennediate
Ring expansion. Demjanov rearrangement involves ring e:\-pansion when the carbocation
For example,
has the positive charge on the carbon atom which is directly attached to the alicyclic ring.
l as nonnal prod-
deamination of cyclobutylmethylarnine gives methylenecyclobutane and cyclobutyl carbino
:
ucts while cyclopentene and cyclopentanol are formed by ring expansion as shown below

•
 (1) Normal products :

Jl2C CII c11 ,il e N

I I
TI2C-C TT2
C) clobut) lmctb) famine

-t / H
1-H'
-H+
Cll CH 0, H2C-C H = CH2
I VII I I
CH2 H2C -CH2
C) clobut) car:binol Mcthylenecyclobutane
(11) Rmg expans,on products :

(i)+H 20:

(ii) -H+

Cyclopentanol

Cyclopentene
Ring contraction. Demjanov rearrangement involves ring contraction
dia1e has the positive charge on the alicyclic carbon atom. For exam wh~n ~e carbocation inte~e-
gives a mixture of cyclobutanol (normal product) and cyclopropy
ple, deammat1on of cyclobutylamme
l carbinol.

H,G-----CH..a~N H,C--jiH
I I
l--!iC-CH2 ~
-N2 HzC
l1JCH2 (li) - H+
Cyclobutylamine
Cyclobutyl Cyclobutanol
carbocation (II) (normal product)

(1) i II 20
l D~mjanov
rearrangement

t
<--.- I J2C - Cl l-Cl12
(11) - II-!
\I
CI12
Cyclopropylcarbinol Ill
It may be noted here that the carbocations (JI and IU) do not elimi
ing alkcnes because cyclobutene and methylenecyclopropane are quitenate a proton lo fonn the correspond-
unstable due to angle strain.
7. From active methylene compounds. A large number of alicyclic
by the action of active methylene compounds such as malonic compounds have been synthesized
ester or acetoacctic ester on suitable
dihaloalkanes. Alicyclic carboxylic esters thus formed are hydrolysed
are produced. For example, and decarboxylatcd when cycloalkanes

• IFE·h-lP♦Af ~RG ANI C CHEMl8TRY, B l

 (i) fl,rough malonic ester

c2H50 ~ - a H (C02C2H5)i
sod. ethoxide Malonic c~ter
Monosodium malomo ester

/cu,~~
4Na OC2Hs
--+ CH
Nlll3r 2 ~HsOH
"-.
CH2 -Br

tt+/H20
Hydrolysis

CH 2-CH CON H2 ffi2- CH -NH 2

Cll2-CH COO H (i)PCl5 Br2/KOH
I I
A
I l (ii)NH3
I I Hofmann bromamide ffi2 -0I2
(-CO i) Cll2 -CH 2 CH2-CH2 reaction
Cyclobutane- Cyclobutyl.amine
Cyclobutane-
c:uboxylic acid carboxamide
+
CH 2-CH -N( CH3) 30H- CH 2-CH H2/Ni
i I -(CH3)JN ,
I II 373K
(ii )AgOH CH2-CH2 CH2-CH
(Hofmarm exhaustive -H20
methylation ) Cyclobutane
obtained cannot be decarbo:\,lated directl)
It may be noted here that cyclobutanecarboxylic acid thus
erted to cyclobutane indirectly as discussed above.
since it undergoes ring cleavage. However, it can be conv
ration of cycloalkanes. If instead of 1, 3-
This is commonly known as Perkin's method of prepa
e, etc. are used in the above synthesis, cyclopro~
dibromopropane, 1, 2-dibromoethane, 1, 4-dibromobutan
pane, cyclopentane, etc. can be synthesized.
(ii) Through acetoacetic ester
CH3-CO "-. ~
[?" + Na+ OC2H5
HsC iOO C/ "'-._H Sod. ethoxide

Acetoacetic ester Monosodium

acetoacetic es1cr

CH3-CO"'-. /? 1 1 ,~ r
CH Na+ + I
H5C20 2C/ CH2-CH2-Br
Monosodium 1,4-Dibrooiobutane
acetoacetic ester
 CH2-CH2"-. /COCH3
bH2-CH2/~COOCiHs
Acidic hydro!)a·
(i) Cone. I<oa II, l.t
{ii) H 'fH20

Kctonic hydrolysi~ i.e.

(i)D1l KOH
(it) lt+H;O

CHrCH:"-.c(COCH3
bHrCH{/ "--cooH
al ...CO2

CHz-(H1"-.
I /CHCOCH3
CHrCH2
Acetykyclopentane

CHi--CH2"-.
I
i Zn-Hg/HCl
(Clemmensen reduction)

/CHCH2CH3
Cyclopentanecarboxylic acid

CHr-CH2
Ethylcyclopentane

By using other dihaloalkanes, a variety of alicyclic compounds can be synthesized by the above reac-
tion.

Cycloalkanes closely resemble their open-chain analogues, i.e., alkanes in their physical properties,
although their melting points, boiling points and densities are somewhat higher. This is probably due to the
reason that zig-zag alkane molecules are constantly oscillating and hence cannot be closely packed in the
crystal lattice. On the other hand, cycloalkanes, because of tl1eir rigid ring structures, overcome this oscilla-
tion to a great extent and hence are comparatively more closely packed. This closer packing results in
stronger intermolecular forces (van der Waals) of attraction and hence cyc/oa/kanes have higher melting
points than the corresponding alkanes. In the liquid state also, the cycloalkane molecules are a little more
strongly held and hence have higher boiling points than corresponding alkanes. Further because of close
packing, cycloalkanes have higher densities than corresponding alkanes.
The melting points, boiling points and densities of some cycloalkanes are given in table 4.2 .

• CFifiiilPW ~
,.
JSTR
 TABLE 4.2. .,
=~--~~77
.

Cyclobutane 286 0·746

Cyclopentane 179 322 0·746
Cyclohexane 279·5 354 0·778
Cycloheptane 261 391 0·810
Cyclooctane 287 422 i ~,. 0·830

Like alkanes, cycloalkanes are non polar molecules and hence are soluble in non-polar solvents such as
carbon tetrachloride, petroleum ether etc. but are insoluble in polar solvents such as water, alcohols etc.

4-16· Gl:NERA1.JCHtMttA~-~ fffAl }lf]

The general formula of the cycloalkanes (CnH2n) suggests that they should be unsaturated ~ hen~
therr
should resemble alkenes. However, because of their cyclic nature, they closely resemble alkanes m
chemical properties.
in
Their similarity to alkanes is attributed to the fact that all the carbon atoms in these compounds, like
alkanes, are sp3-hybridized forming only C- C and C-H, a-bonds. But all the cycloalkanes are not equally
are
stable and unreactive. Only cycloalkanes from cyclopentane onwards show a high degree of stability and
quite unreactive. As such, they are not attacked by chemical reagents like strong acids, strong alkalies.
they
common oxidising agents (KMn0 4) and powerful reducing agents (LiAIHJ . However, like alkanes.
undergo free-radical substitution reactions.
On the other hand, cyclopropane and cyclobutane show a high degree of reactivity ; cyclopropane being
tane
partiatlarly more reactive than cyclobutane. This is due to the reason that cyclopropane and cyclobu
. Thus, they
rings are not very stable and have a tendency to undergo ring cleavage forming addition products
Some
resemble alkenes in undergoing addition reactions. However, they are much less reactive than alkenes.
of the important chemical reactions of cycloalkanes are discussed below :
1. Free-radical substitution reactions. Cycloalkanes undergo the typical free-radical substitution re-
actions when treated with halogens at 525-575 Kin the dark or at room temperature in presence oflight.
For example,
CH2, CH2"'-
hv
I / CH2 +Cl2 298K
I / CHCl + HCl
CH 2 Cll2
Cyclopropane Chlorocyolopropnno

C1¾ CI-Ii CH2-CH2

l,v
I I +B'i I I HIBr
C1¾--C8i Clli--C l IBr
Cyclobutane Bromocycloh111ani3
CH 2
/c~ /'\.
Ciii CH2 CH 2 CllBr
I I +B":z S1SK I I +HBr
CH2-CH2 CH2-CH2
Ethylcyclopentane Bromocyclopentane

: ..... . · . · · · · asr··
 Cl-12 CH2
~
CH2 CH1 515K
c(bm ,
I I +Br2 I I +HBr

""/
CH2 CH2 CH2 CH2
CH 2
"'-/
CH 2
C'yclohc,anc Bromocyclohexane

2. Addition reactions. As discussed above, like alkcncs, cyclopropanc undergoes addition reactions.
Some of the important addition reactions are :
/ CIJ2-CI
2
C11 ""
CH2 -Cl
J,3-Dicl1loropropane
/ CH2-Br

CH, CH2 ~
CH2-B r
CH.:!"" I- l ,3-Dibromopropantl
CH2 / CH3
Cyclopropane HBr
CH,
-""CH2Br
n-Propyl bromide
CH 3
H2/Ni /
CH 2"-"-.
353K
CH3
Propantl ,

Ho\'\ e\ er unlike alk:enes, cyclopropane does not add ozone and also does not undergo hydro\.-ylation
3

with ag. KMnO4 solution.

Cyclobutane, on the other hand, is less reactive than cyclopropane and hence does not undergo addition
reactions under ordinary conditions. However, on hydrogenation at higher temperature, it gives n-butane.

Cyclobutane n-Butane

From the abo~e discussion, it is evident that cyclopropane is the most reactive of all the cycloalkanes
·
and undergoes many addition reactions through ring cleavage. Cyclobutane is less reactive than cyc/oprv
pane and undergoes only addition ofhydrogen while rest ofthe cycloa/kanes are unreactive and do not form
addition products. Instead ltke alkanes they yield substitution products.
Now, question arises as how to account for this special behaviour of three and four membered ring
compounds. .

~ SAEYEws·.srfti:IN. 'tHEORV. ANtJ. R~t.wrora.$TAfOtrT·1t·•,$>.•~....OPi..JJ.

j~ . ·. . .. • . . • . .· ..
f '~Y¢•:~~ff
I-~~~-
.
~IN~N
. . . . .. I' ............. ,•, .•~.,~

To explain the relative stabilities of cycloalkancs and the exceptional behaviour of three and four
membered rings(f.ldof von Baeyer in 1885, proposed a theory known after his name as Baeyer's strain
tbeory:\The main postulates of this theoryarc given as under : '

• I iidfihiiAil ORGA NIC CHEM ISTR~ Y.:OC

 ,l'adj
1 A carbon atom bonded tofiour other atoms ls tetrahedral, I.e., tht nngle between any pair 0J a-
\./. .
cent bonds ,s tetrahedral, 1090_28'.
h d ti
✓ 2 All the carbon atoms com' .rt 1 I' mol ecule lie In a plane. As a resu lt, the on ang, -.s
u mg a cycloalkane
• / 109°-]8'.
longer equal to the normal tetrahedral angles 0
between any two adjacent carbon atoms are no
They are either less or more than this angle.
y 10
deviation or di stortion from this normal tetrahedral angle Imparts slam and hence ms/abilit
c). Any
ly referred to as onglc strain.
the resulcant molecule. This strai11 is common
hence
th tetralwdral ~ngle, greater is the angle strain and
4. The grealer e deviation from the normal
e)
greater is the instability ofthe resultant molecul
5. The greater the stability of a rmg system,
more easily it faformed.
relative
upon the size of the ring. In order to explain the
The ex.tent of angle strain introduced depends
rent cycl oalk anes , let us detennin e the magnitude of angle strain in each one of them
stabilities of diffe
following the expression.

Angle strain= 1(109°-28'-bond angle in the planar ring).

The cyclopropane ring can be regarded as an equi
.
lateral triangle with bond angles of 60°. This imp
lies
- .
that the angle strain in cyclopropane = (1091°-28'-00°) = 2~ - 44' as ~hown in Fig. 4.2 (a).
r
0 On the other

hand, cyclobutane ring is a square with bond

angles of 90°.

0
?f 'f'1
tane
w,; Angle strain In cyclopropane and cyclobu

1 4.2 (b).
th 1 t ·n ·n cyclobut ane = 2 (109°-28'- 90) -= 9°-44° as shown in Fig.
There1ore, e ang e s r
r. 31 1

ulate the angle strains in various cycloalkanes

as given in
· h dure , we can calc
Fo11owmg t e same proce
table 4.3.
 various c cloal
TABLE 4.3. An le strain and heat of combusti n r CH grou in

1. Cyclopropane 60° .!. (1090-281-60) =+ 240-441 696·4

2
(Equilateral triangle)
2. Cyclobutane 90° .!. (109°-281 90°) = + 9°-441 685·5
2
(Square planar)
3. C)clopentane 108° .!_ ( I09°-281 l 080) = I- 00 441 663·4
2
(Regular pentagon)
4. Cyclobcxane 120° J.2 (109° 28' 120°) - 5°-161 657·9

(Regular hexagon)
5. Orclohcptane 128°261 .!.2 (109°-28'-128°-261) = - 9°-33 1 661·7

6. Cyclooctane 135° _!_ (109°-28'-135°) = - 12°-44' 662·9

2

The positive , ·alues of angle strain indicate that the bond angles are compressed while negative ~lues
mean e>.J>ansion of the bond angles from the tetrahedral angle. In b~th t~e cas~s, the mo~ecule will be
strained. fn other words, it is the magnitude ofthe angle strain and not its sign which detenmnes the strazn
and hence the instability of the molecule.
From the table 4.3, it follows that angle strain falls rapidly in going from cyclopropane to cyclopentane
and then increases slowly. This means that cyclopropane with ibe greatest magnitude ofangle strain should
rbe least stable and hence most reactive of all the cycloalkanes, while cyclobutane with less angle strmn
should be little more stable and hence less reactive than cyclopropane:further, cyclopentane with the least
amount ofangle strain should be the most stable of all the cyc/oalkanes. All these predictions are in agree-
ment with the experimental facts.
On the basis of his theory, Baeyer predicted, of course wrongly, that cyclohexane with more angle strain
should be less stable than cyclopentane and rings larger than C7 should not exist and if at all they exist, they
shoul? ~ highly strained and hence highly unstable. There was no way to test these predictions since rings
contairung seven or more carbon atoms were not known at that time
points in favour of Baeyer strain theory
given belowin-: sup11ort of Baeyer strain theory. Some important
/_Evidence
are
----1. Reactivity of the doublr bond. A double bond may be regarded as a two membercd ring with a
1

~
carbo~-carbon boud angle of O'. TJ1erefore, 1he angle s1 rain = (I 09"- 28'- 0") = + •-4 ,. Since this angle
54 4
stram is the highest of all the cycJoalkanes h I .
I
ment with the observed facts. 1
cuce te alkencs should be lughly reactive which is in agree-
/ 2. Reactivity of cyclopropane and cyclobutane A .
reveaJs that cyclopropane and cycJobuta • compai Ison of the heats of combustion of cycloalkantll
ha th ne possess more eucrgy (38·5• kl an d 27·6 kJ respectively)
. per C"'-
A"
group t ". e corresponding straight chain alka 0
correspondmg n-alkanes-a fact in agreeme t . esB. Consequently, they should be less stable than thO
believ tha h · n wit11 aeyer's t · h .
e t t eir tendency to undergo addi't• . s rain t eory. ll 1s therefore reasonable to
ton reactions th h · . ' '
roug nng fission is related to this instability.

lilll Iii •
 of Baeyer'i stlain theary ._•Ill-■
_.Atatton• of Baey er'• ltrain .theohry. Some of the limitation
s
Y,-- -~the baSiS of Baeyer ' s ~tram t cory, a carbon-carbon double bond should bf! 4ifficalt
on
to,._.•11._
uc-aa1,oa41 lM
rast, it is a know n fact that a caub
~·_ ,., reactive and henc e lugh ly unst able . In cont
.. etc
;t ;s Jtl~ silv ro-nncd by dehydrohaloge ffiitfon of alkyl halides, dehydration of alcohols' ·
dis ca . . and rings havi ng seve n or more cm1,cm . . _
cycl? hcxa nc
b011 on the basis of Baey er's stram theory, ane, cyclote;e,e
l,be Jess stable than cycl o~n~ c. But heat
of combustion data reveal that cyclopent
s arc equally stabl e.
shoul~ s containing seven or more carb on atom
s11dnn8
1e-l~Ht§£A:ai:fSt!.·~ :cgd.M. M. ]!S!l]OST~.·[MlO~N~
,o~,r~ ·
....·. ·istuU~[!ltl~Jtt'!]iBg.~m1
. ,· A~Nr:!J.D~·:_ga&§:!L~AgJrtlJ!Vl! . I
J 1·gg
ound I•
We that heat of com b~sti~n is the amo unt of heat evolved when one mole of a comp
I-.
e (hea ts of com bust ion) furn ish valuable ildo l._.
knOW
/etely burnt t~ form c~~~on dwx1de ~nd water. Thes s ~ COlllbm
poun ds. Let us now exam ine whe ther the heat
~"'~bout the relaUve stab1hu es of orga mc com aa of a
ry or not. Table 4 .4 lists the heats of COlilbum
~on f the vario us cyclo alka ncs supp ort Ba eyer 's theo
uono
nuniber of cycloalkanes.
anes.
TAB LE 4.4. Hea ts of combustion of cycloaJk

10 662·9
3 696·4
11 662· l
4 685·5
663· 4 12 658· 8
5
657·9 13 659·6
6
661· 7 14 657·9
7
15 658·4
8 662· 9
17 657· 1
9 663· 8
n-Alkanes (Reference)= 657·9
per CH2 group for cyclopropane and cyclOOJ9Jac
Fro}ll the table 4.4, it is clear that heats of combustion
cyclopentane and cyclohexane are 663·4 811d 657·9
are 696·4 and 685·5 kl/mole respectively and those for
CH2 group of n-alkanes.
kl/mole respectively as compared to 657·9 kl/mole per
to the overall heat of combustion of a compo11NI
A CH2 group may be expected to contribute equally
CO 2 and H 20 (-C H2- + ~ 0 2 ~ CC>i + ~O
+
becaus_e it yield s the sam e prod ucts of com bustion, i.e.,
group is present. But the fact that cyclopropane and
heat), irrespective of the compound in which the CH,
butan e evol ve mor e heat per CH grou p than cycl opcntane or cyclohexane or n-alkanes means tbat
cyclo ,._
CH 2 group than cyclopentane or cyclohexanc or
2
cyclopropane and cyclobutane contain more energy per
should be less stable than cyclopentane or cydobcx-
alkanes. In other words, cyclopropane and cyclobutane
ane or straight chain alkanes and this is in agreeme
nt with Bacycr's strain theory.
cyclopcntanc and cyclohexane should be increas-
. According to Baeyer's strain theory, rings larger than ring si1.e in-
the magnitude of the angle strain as the -"'·
tng Yless stable due to a corresponding increase in
1 ·~..
creas es Th s ·r strai n theo ry were correct, then it wou ld be expe cted that heats of COlllUUDUVK per
CH · u , Baeycr 1 's 81
anes from cyclopcn tane (and cycl ohex anc) onw ards should steadily increase_ the
rin~ ~oup of cycloalk
s1 that this is not true since the heats of combustlOD per
CH ze Increases. But from the table 4.4, it follows e
of cyclo alka nes from cyclobut ane onw ards near ly remains constant (663 ·4-6 57· l) and the vahl15
is cfogroup
tha cycl oalk anes from cyclopentane onwards should be
~se to t of n-al kane s (657 ·9). This sugg ests that

~ : :M a}¢ v . ~ $ .i!!i#.t:1t :il~ ~t< AN ffll t:!l

 n atoms arc aliilost as stable as cycJ
stable as n-alkanes. Actually, rings containing seven to eleven carbo
per CH2 group (663· 4-662 ·1). B u t ~
since they have almos t the same value for heat of combustion
inin~ twelve or more carbo n atoms are hear;
of combustion per CH2 group of cyclohexanc and rings conta
in contr ast to Baey cr's strain theo:ry, cycJ 8boiit
the same (658· 8-6~7 _' I) as that of n-alkancs. In other words,
lcl~ly free of angle strain and hence '
ane and rings conta llnng n,:h· e or more carbo n atoms are comp
large rmg comp ound s such as cycl arc Ill
stable as n-alk ancs. This 1s suppo rted by the fact these
musc one (perfu me isolat ed from m u ~
cyclodecapentanone, civeto ne (perfume isolated from civet cat).
ed from natur al sources. Once these large . )
etc. have been eithe r synth esized in the laboratory or isolat
ncy at all to under go the ring opening ~
comp ounds have been ~nthe sized they show little or no tende
tions chara cteris tic of cyclo propa ne and cyclobutane.

As discussed above. Baey er 's theor y could expla in the

reactivity/stability of rings containing five
conta ining six or mor~ carbon atoms. ;
less carbo n atom s but failed to accou nt for the stability of rings
Sachs'? and M?hr , re-exam.med the models of
accou nt for the stability of six-m embe red and large r rings,
rding to this theory, the carbon atoms ofa
cycloalkanes. and propo sed the theory of strainless ring◊cco
lated by Baeyer, but in six-membered and
jive-m embe red and small er rings can be in a single plane as postu
conta ining five or less carbon atoms are
larger rings ,hey lie in different planes. In other words, the rings·
carbo n atom s are essen tially non-planar or
either plana r or very nearl y planar*, but those ofsix and more
pucke red. } ·
As a result of this puckering, each carbon atom retains, its norm al tetrah edral a11gle (109° -28] and
'six_:m embe red and large r rings are strainless
1here is negli gible or no strain in the molec ule) In. other woras
and M ohr, were able to const ruct the models
and hence the name, theory of strainless rings. 'Further, Sachse
the chair forms (Fig. 4 .3). These forms of
of the mo puckered forms of cyclo hexan e-cal led the boat and
C) clohexane are readily interconvertible by
rotation about single bonas and hence repre sent the oonforma-
flons of cyclohexane) Simil arly, rings larger than
six carbo n -atom s can have negli gible angle strain by
_.-
assuming puckered arran geme nt of atoms in their molecules.

OR

0 G
Chair confor mation Boat confor mation

.,..,_,,_.,.,.,..,. . . ., ., , ..:.kJJ_.f&fffP%tf(ffilffW®!!Ji7'1,, ,-.ftJ4P8ltf4ji/{:brr.,~"'·· .,.,,t1,J:~:;;/,t:,~i,r,,,,~/~Hgt11\t¥@½Wllld1t·

form s of cyclo hexan e
Non-p lanar or Puck ered
they diffic ult to synth esize ? Bae)er's
Now the quest ion arises if the large rings are stable why are
sarily unsta ble is not corre ct. Actually, for ring
assumption that a comp ound difficult to synth esize is neces
n chain posse ssing the funct ional groups must
closure to occur, it is essen tial that the two ends of a carbo
ntly, large r the ring to be synthesized, Jarg~r
come sufficiently close toget her to react with each other. Evide
likeli hood of the two ends of tl1e same cbaJll
must be the chain from which it is made and hence less is the
d be great er proba bility for the two di1ferent
appro achin g each other. Unde r these condi tions, there woul :•.-:*-:,:-:,..,;;~:,:,:❖:•:~•:❖:-}:::-:❖:•»~::~~:-:•.~"-"<:-"; ~ •
:»:•,•,-!•X❖$:-:,:,~•X-:-'C❖,• «-X❖• • ..-.·!!❖,•: :»:•o❖' ~❖}.- :-:,:,,.::,:~❖;;:.: •' ••. .•~:
. ?.-, ;.•.,.7.,::_.,.~.;.-:,;,,:;;.;:: :~••❖..-,•,❖.-;•~•!❖.-.•:•,•!{:;;;;:.;,:,;;:,»,❖:,;c;;.:
• • •

r but puckering here would ~

,. • •' ❖ ,,., :-": ;;;
plana
*A three -mem ~e~ ~g is plana r. A four-membered ring need not be
r but a plana r arrangement here woulio
be plana
crea~ the angle stram. Sumlarly, a five-membered ring need not
four and five-m embered rings are know n to be puckered
~ t ~e bond angles to be nearly tetrahedral. In fact,
1p1te of increased angle strain.

ORG ANI C CHE MIS TR~

•
 . oouplin8 together (intermolecular condensation) rather than the two ends of the IIDle chain
~
0
closure (intrarnolecular conden~atlon) as shown in Fla. 4.4. ~
jpg JIPO
Intramolccular
condcnaation

~CH2XXCH2~ rS'CIJ2X

c;l CH2X XCII2

\ _lnltnnolctular
condcnntlon ►

, . ·• ~-~-~,~~~~iEJQYRJillJhJ;/'.;.,,»,. ... ;,,,,;;,J;N,;filfdk<r;

[ntramolecular (upper) and intermolecular (lower) condematJon.

Thus, the difficulty encountered in the synthesis of large membered rings is the competition between
. ter· and intramolecular condensations with the former predominating. However, reccutly this difficulty
:S
·ons
been overcome by ~ng out ~e reacti~n _in _highly di!ute solutions. Un~er these conditions, the colli-
between the two different chams are m1rumised considerably and the nng closing reaction. although
g .
slo\\\ is the principal reactton.

¢™E CJlSE'. tte11mm1111are11Nm1t1nsn1t::

Cyclopropane offers an interesting case of bent C-C covalent bonds. It is a planar molecule and its
internal bond angle 0 must be of 60°. Therefore, there is a considerable deviation from the tetrahedral angle
of 109°-28'. But carbon cannot have hybridized orbitals oriented at an angle less than 90° to each other.
Since there are four bonds on each carbon, therefore, the angles have to be more than 900. 1n other words, in
cyclopropane, the ring n-bonds cannot be formed by overlap of pure atomic orbitals. To explain this imbiguity.
it has been shown that hybridization of orbitals occurs in such a way that the ring forming orbitals have a
slightly greater p-character than those forming the normal cr-bonds between carbon atoms in saturated
molecules. This explains why the angle ~ between two such orbitals of one carbon atom in cyclopropane is
104°, little less than the tetrahedral angle of 109°- 28'. Thus, the major axes of symmetry of the orbitals
fonning C-C bonds in cyclopropane do not point towards one another but outwards from the molecule with
the result tliat the C-C bonding MO's are not symmetrical about their internuclear axes but are bent giving
the appearance of bananas. It is because of this reason that the carbon-carbon bonds in cyclopropane are
often referred to as 'bent' or banana bonds.

i . Further due to higher p-character of the h)bridized orbitals, there is small but appreciable pi-delocal-
:tion around the ring. However, dclocalization occurs within the plane of the ring and not above and below
.e carbon framework of the aromatic systems . 11m in-11/a11e p1-de/ocalization adds some stability to the
n~

•
-:-:.
...)¢¥ ../. ....... ·.· ....... E.S)::i