Evidence for molecular complexes in the mechanism of additions of iodine mono-

chloride to alkenes
GEORGEH. SCHMID'AND JAMESW. GORDON
Department of Chemistry, Universig of Toronto, Toronto, Ont., Canada M5S I A l
Received February 8, 1984
This paper is dedicated to Professor Peter Yates on the occasion of his 60th birthday

GEORGE H. SCHMID and JAMESW. GORDON. Can. J. Chem. 62, 2526 (1984).
Immediately upon mixing ICI and 2,3-dimethyl-2-butene in CC1, at 25'C a new absorption band due to an alkene-IC1
molecular complex appears at 295 ? 5 nm and decreases rapidly with time. The rate law under conditions of (alkene),, >> (ICl),,
for the electrophilic addition of IC1 to 2,3-dimethyl-2-butene, E- and Z-2-butene, and E- and Z- I-phenylpropene is -d(ICl)/dt
= k,,p,(alkene)(~C1)3/{l + ~ ~ , ( a l k e n e ) }where
j KAD is the equilibrium constant for the formation of a I : 1 alkene-IC1
molecular complex. The addition of IC1 to the Z and E isomers of 2-butene and 1-phenylpropene occurs by anti-stereospecific
addition. The negative enthalpy of activation for the addition of ICI to 2,3-dimethyl-2-butene is evidence that one or more
complexes are involved on the reaction coordinate prior to the rate-determining step. On the basis of analysis of the enthalpy
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changes during the reaction, it is proposed that both a I : I and a 1 : 2 alkene-IC1 molecular complex is involved in the
mechanism prior to the rate-determining step.

GEORGE
H. SCHMID
et JAMES
W. GORDON.
Can. J. Chem. 62, 2526 (1984).
Des que l'on mtlange du ICl et du dimtthyl-2,3 butene-2 dans du CCL B 25"C, il y a apparition, B 295 ? 5 nm, d'une
nouvelle bande d'absorption qui est due i un complexe molCculaire alcene-1C1; I'intensitC de cette bande diminue rapidement
avec le temps. La loi de vitesse qui s'applique, si (alcene),, >> (ICI),,, pour l'addition Clectrophile de 1C1 sur le dimethyl-2,3
butene-2, sur les butenes-2 (E ou Z) ou sur les phtnyl-l propenes (E ou Z) est -d(ICl)/dt = k,,p,(alc~ne)(~C1)3/{1 +
, K,, est la constante d'tquilibre pour la formation d'un complexe molCculaire 1 : 1 alckne-ICI. La sttrto-
~ ~ , ( a l c k n e ) you
chimie de l'addition du IC1 sur les isomtres E et Z du butene-2 et du phtnyl-1 propene est sttrCosptcifiquement anti. Le fait
que l'enthalpie d'activation de l'addition du IC1 sur le dimtthyl-2,3 butkne-2 soit ntgative est une preuve qu'un ou plusieurs
complexes sont impliquCs dans les coordonnCes de la rCaction avant d'atteindre l'ttape dtterminante. Sur la base d'une analyse
des changements d'enthalpie au cours de la riaction, on propose que des complexes molCculaires alcene-IC1 1 : 1 ainsi que
1 :2 sont impliquCs dans le mCcanisme avant d'atteindre l'ttape diterminante.
[Traduit par le journal]

The stoichiometry of the addition of iodine monochloride
(ICl) to alkenes is 1 : I in a number of solvents (1 -5). Because
of this fact, solutions of IC1 in acetic acid (Wijs' solution) are
used to determine iodine values of fats and oils (6). Despite
such widespread use, little work has been done on the kinetics
and mechanism of this addition of ICl to alkenes and some of
the work is contradictory. White and Robertson (1) reported
that the addition of IC1 to allyl acetate in acetic acid follows an
overall third-order rate law, first order in alkene and second
order in ICl. A similar rate law was reported by Viswanathan
and co-workers (2) for ICl addition to some allyl and vinyl
compounds in acetic acid, and by Sergeev and Smirnov (3) for
the addition of ICl to both cyclohexene and 1-hexene in CCld.
In contrast, Heublein (4) reported a second-order rate law, first
order in both ICl and alkene, for the addition of IC1 to trans-
stilbene in acetic acid, dibutyl ether, and acetonitrile.
The products of addition of 1C1 to alkenes are sometimes
formed by anti-stereospecific addition (4-7), while in other
cases by anti-stereoselective addition (8). Regiospecific addi-
tion to styrene (9) is reported, while nonregiospecific addition
occurs to 1-hexene (10). Furthermore, solvent incorporated
(10) and rearranged products have also been reported (1 1).
The work reported in the literature is fragmented, with each
worker or group of workers employing different compounds
and different solvent systems. Frequently only the rates of
addition with no product study are carried out or vice versa. It
is clear that a systematic study of both the rates and products
of this reaction is long overdue. We have undertaken such a
study. In this first paper we report the rate law, the effect of
'Author to whom correspondence may be addressed.
temperature on the rate, and the stereo- and regiochemistry of
the addition of ICl to 2,3-dimethyl-2-butene, E- and Z-1-
phenylpropene, and E- and Z-2-butene.
Results and discussion
Kinetic and thermochemical stlidy
The rate of addition of ICl to 2,3-dimethyl-2-butene in CCl,
at 25°C was measured by monitoring the disappearance with
time of IC1 at 460 nm by means of a Durmm-Gibson stopped-
flow spectrophotometer. The rate measurements were made
with (alkene)o >> (ICl)o.
Immediately on mixing IC1 and 2,3-dimethyl-2-butene a new
absorption band, absent in either reactant or product, appears
at 295 ? 5 nm and decreases rapidly with time. This new band
is attributed to the presence of an intermediate IC1-alkene
molecular complex. Reversible formation of labile molecular
complexes between alkenes and halogens are well documented
(2). While fewer data are available for alkene-interhalogen
complexes, cyclohexene and 1-hexene are known to form mo-
lecular complexes with ICl in CC14 at room temperature, char-
acterized by absorbances at 267 and 257 nm respectively (3).
The molecular complexes of IC1 and several allyl and vinyl
compounds have characteristic absorbances in dry acetic acid
in the region 290-310 nm (2). The position of the band for the
complex of ICl and 2,3-dimethyl-2-butene at longer wave-
length (295 nm), compared to the complexes of ICl and cy-
clohexene (267 nm) and 1-hexene (257 nm), is expected for the
more highly substituted alkene (12a). Thus we conclude that
the band at 295 nm in CC1, at 25°C is consistent with the
formation of a molecular complex between ICl and
2,3-dimethyl-2-butene.
 SCHMID PiND GORDON 2527
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I I I I I
0 0.02 0.04 0.06 0.08 0.10 0.12
TIME (s)
FIG.2. Third-order kinetic plot for the addition of 1C1 to
2,3-dimethyl-2-butene in CCI, at 25°C.
system
FIG. 1. Ketelaar plot for the 2,3-dimethyl-2-butene-1C1
measured at 300 nm in CCI, at 25°C. TABLEI . Slope and intercept obtained by
fitting eq. [4] to the data from the reactions
The Ketelaar equation (13) was used to obtain the equi- of a series of solutions of constant
(2,3-dimethyl-2-butene),, = 0.1 188 M and
librium constant for the formation of the molecular complex, varying (ICI),, in CCl, at 25°C
KAD.Briefly, the method is to measure the variation of initial
absorbance values with varying initial concentrations of alkene (1Cl)o
under conditions where (alkene)o >> (ICl),. The analysis was (M) x 10' Intercept Slope
carried out in CC14 at 25°C and at 300 nm. The equation is as
follows:

where E,,, is the apparent extinction coefficient and EAD is the

extinction coefficient of the molecular complex. The apparent
extinction coefficient is defined by eq. [2].
The straight line obtained by plotting l/(e,,, - eICI)versus
l/(alkene), is shown in Fig. 1. Values of KAD= 19 + 6 M-I
and = 1.4 --f 0.5 X lo4 M - I cm-' are obtained from the
values of the slope, intercept with the ordinate axis, and their
ratio. The value of KADobtained in this study is larger than the
value of 2 M-' for the equilibrium constant of the formation of
the molecular complex in the reaction of 1-hexene and ICl in
CC14 at 25°C obtained by Sergeev et al. (14a).
If it is assumed that the IC1-alkene molecular complex is
rapidly established relative to the rate of addition of ICl (14b),
then Beer's law (eq. [3]) will be valid for the total or stoichio-
metric ICI concentration at all times t under the conditions
(alkene), > (ICl)o.2
[3] Abs, - Abs, = eappl(IC1),
The pseudo-order rate law, eq. [4], is third order with respect
to IC1.
rearranging gives the pseudo-order experimental rate equation
[51.
+ {2kapp/(e,pp1)2)t
[5] (Abs, - Abs,)-' = {~~,,1(ICl)o}-~
The plot of a typical run is given in Fig. 2. The apparent
pseudo-order rate constant is readily calculated from the inter-
cept, slope, and (ICl),. As shown by the data in Table 1, there
is no apparent trend in the values of the slope as required by eq.
[4] for a series of solutions of constant (alkene), and varying
(ICl),. Furthermore, the values of K,,, are not dependent on the
wavelength
" used to follow the kinetics.
The initial concentration of alkene was varied over the range
from 3.33 X M to 4.25 X 10-I M to determine the
dependence of alkene in the rate law. Equation [6] describes the
experimentally observed variation of the pseudo-third-order
rate constant k,,, with initial alkene concentration where C I and
C2 are constants.

The linear plot of {(alkene)o/k,pp}"3versus (alkene), is shown

Substituting eq. [3] into the integrated form of eq. [4] and
'The symbol (X) represents the total, stoichiometric, or analytical
concentration of X in solution in mol/L; [XI represents the free,
uncomplexed concentration of X in solution in mol/L.
in Fig. 3. From the intercept and the ratio of slope to intercept,
valuesofCl = 9 2 1 X 108M-3s-l andC2 = 17.8 + 0.8M-'
are obtained.
The complete rate law describing the rate of addition of IC1
to 2,3-dimethyl-2-butene in CCIJ at 25°C in terms of their total
 2528 CAN. 1. CHEM.
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FIG.3. Experimental test of eq. [6] for the addition of ICI to
2,3-dimethyl-2-butene in CC14 at 25°C.
or stoichiometric concentrations is given in eq. [7] for (alkene),
>> (ICl),. The constants C I and C, can be identified as a rate
constants k and K A Drespectively in the following way. Equa-
tions [8] and [9] relate the stoichiometric and free concen-
trations of both 2,3-dimethyl-2-butene and IC1 at time t under
the condition (alkene), >> (ICl)o. Comparison of eqs. [7] and
191
[8] [alkene] = (alkene),
strongly suggests that the experimental parameter Cz be identi-
fied as the equilibrium constant K A D .This assignment is further
substantiated by the fact that the value of Cz is identical
within experimental error with the value of K A D obtained
independently from analysis of the initial absorbance data.
The experimental rate law can now be written in terms of the
actual, free or uncomplexed, concentrations of ICl and
2,3-dimethyl-2-butene as given in eq. [ 101.
[lo] - d(ICl)/dt = k [alkene][IC1I3
In eq. [lo], the experimental parameter C I has been redefined
as rate constant k. Since C I and Cz are identified, the complete
rate law when (alkene), >> (ICl), can be written as given in eq.
[I 1.1.
The rate law given in eq. [ l l ] is not unique to
2,3-dimethyl-2-butene since the additions of ICl to E- and
Z-2-butene and E- and Z-1-phenylpropene in CC14 at 25°C
follow exactly the same rate law. Treating the rate data in the
same way as described for 2,3-dimethyl-2-butene allows us to
determine the values of k and KADfor both pairs of Z and E
isomers. The data are summarized in Table 2.
The structure-reactivity pattern of these five compounds
'OL. 62. 1984
TABLE2. Values of k and K A Dfor the addition of ICI to
selected alkenes in CC14 at 25°C
Alkene k (M-3 S - I ) KAD (M-')
given in Table 2 is consistent with a reaction that occurs by an
electrophilic addition mechanism (15). Further evidence for an
ionic mechanism is the fact that the rate of addition is un-
affected by the presence of small amounts of I,. Furthermore,
chlorocyclohexane is not formed when the addition of IC1 to
2,3-dimethyl-2-butene is carried out in cyclohexane.
The product of the addition of ICl to alkenes reacts further
with ICl to form a vicinal dichloro compound. This subsequent
reaction has been shown to be much slower and does not
compete with the fast addition of ICl to any of the alkenes
reported here under conditions where (alkene), >> (ICl)o(16).
The observation of a molecular complex in the reaction of
IC1 and alkenes does not necessarily mean that it is on the
reaction coordinate. In order to establish that the molecular
complex is involved in the reaction, variation in k and K A Dwith
temperature was determined for the addition of ICl to
2,3-dimethyl-2-butene. The data are given in Table 3. The rate
of the addition actually decreases with increasing temperature.
Furthermore, the value of the enthalpy of activation is an ex-
tremely large negative value. Such temperature dependence of
the rate of reaction is good evidence for a complex reaction
mechanism (17). Thus the negative enthalpy of activation ob-
served for this reaction may be taken as kinetic proof that a
complex or several complexes are involved on the reaction
coordinate prior to the rate determining transition site.
Product stereo- and regiochemistry
The products of the addition of IC1 to E- and Z-2-butene and
E- and Z-1-phenylpropene were examined to establish the
stereo- and regiochemistry of this reaction in CC14at 25OC. The
addition to Z-2-butene forms a single adduct while addition to
the E isomer also forms only one product whose 'H nmr, given
in Table 4, is different from that of the product of addition to
the Z isomer. Such a result is consistent with a stereospecific
addition of ICl. The vicinal methine H-H coupling constants
(Jab)of the products can be used to determine the stereo-
chemistry of the adducts. Usually the vicinal methine H-H
coupling constant in 1,2-disubstituted-l,2-dihaloethanes is
larger for the erythro (or meso) than the corresponding threo
(or dl) isomer (18). On this basis we can assign the threo
configuration to the product of addition of ICl to Z-2-butene
and the erythro configuration to the product formed by addition
of ICl to E-2-butene.
To verify this stereochemical assignment the two adducts
were independently synthesized by the series of reactions
shown in Fig. 4. The addition of iodine to a mixture of Z-2-
butene and yellow mercuric oxide in 80% aqueous acetonitrile
forms threo-3-iodo-2-butanol. The threo configuration of the
product was established by means of a base-induced ring clo-
sure reaction to form the epoxide. This reaction is known to
occur with a single inversion of configuration at the carbon
atom bearing the halogen atom (19). Thus treatment of threo-
3-iodo-2-butanol with moist sodium aluminate in methylene
 SCHMID AND GORDON

TABLE3. Thermodynamic parameters obtained from the temperature dependence of k and KAD for the addition
of iodine monochloride to 2,3-dimethyl-2-butene in CCI,

10-8.k A~+(ex~t) ~~+(;xpt) AHAD AS,XD

T("C) (M-3 S-I) (kcal mol-l) (cal deg- mol-I) KAD(M-') (kcal mol-') (cal deg-' mol-I)

TABLE4. 'H nuclear magnetic resonance spectra of adducts of addition of IC1 to E and
Z isomers of 2-butene and 1-phenylpropene

Chemical shift (6)"

Adduct Configuration Ha HP HY H6 JP.~
-
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Cl
alP r 6
CH,CHCHCH, erythro 1.67d 3.96dq 4.23dq 2.00d 7.6
I
I

CH~CHCHCH, threo 1.62d 4.1 1dq 4.48dq 1.96d 3.0

CI
IP r 6
C6H5CHCHCH3 erythro - 4.99d 4.50dq 2.12d 9.0
I

I
C6H5CHCHCH, threo - 4.96d 4.56dq 1.87d 6.0
I

I
IP r 6
C6H5CHCHCH3 eryrhro

I
C6H5CHCHCH, rhreo - 5.10d 4.47dq 1.48d 6.5
I

"In ppm downfield from (CH,),Si. Abbreviations are d = doublet, q = quartet, dq = double
quartet.

chloride forms the known cis-2,3-dimethyloxirane (19c).
Reaction of threo-3-iodo-2-butanol with neat thionyl chlo-
ride forms 2-chloro-3-iodobutane whose 'H nmr spectrum is
identical to the product formed by addition of IC1 to Z-2-
butene. The configuration of the product of the thionyl cliloride
reaction is assigned on the basis of the mechanism of this
reaction (20). In neat thionyl chloride, replacement of the hy-
droxy group by chloride occurs with retention of configuration.
Retention of configuration is also expected because of the in-
volvement of the iodine atom as a neighboring group (21).
Consequently the product of the reaction of threo-3-iodo-2-
butanol with neat thionyl chloride has the threo configuration.
The erythro-3-iodo-2-butanol was synthesized by an identi-
cal series of reactions starting with E-2-butene as shown in Fig.
4. The 'H nmr spectrum of 2-chloro-3-iodobutane prepared in
this way is identical to the product formed by the addition of ICl
to E-1-butene. Thus these results are conclusive evidence that
the addition of ICl to Z- and E-2-butene occurs in an anti
stereospecific manner.
To determine the regiochemistry as well as the stereo-
chemistry, the addition of IC1 to E- and Z-1-phenylpropene was
carried out. As in the case of the 2-butenes, the 'H nmr spec-
trum of the product of addition to Z-1-phenylpropene is differ-
ent than that of the product obtained by addition of E-l-
phenylpropene as shown in Table 4. To unambigously deter-
mine the stereo- and regiochemistry of addition in this system,
 2530 CAN. J. CHEM. VOL. 62, 1984
80% aq.
ru. H CH-CN
Can. J. Chem. Downloaded from cdnsciencepub.com by 49.36.43.151 on 03/15/24
80%aq.
CH3, ,CH3 CH3CN
,C=C
H \H I2/HgO +
F n . 4. Synthetic scheme for preparation of erythro- and threo-2- chloro-3-iodobutane.
it is necessary to prepare authentic samples of the four possible
adducts: erythro- and threo- 1-chloro-2-iodo-1-phenylpropane
and erythro- and threo-2-chloro-1-iodo- 1-phenylpropane. The
synthesis of the two stereoisomers of 1-chloro-2-iodo-1-
phenylpropane has been reported (16). The threo and erythro
isomers of 2-chloro- 1-iodo- l -phenylpropane were synthesized
as shown in Fig. 5.
erythro- 1-Chloro-1-phenyl-2-propanol was prepared from
E- 1-phenylpropene by using the oxymercuration reaction (22)
followed by a chlorodemercuration reaction (23). Reaction of
the chlorohydrin product with base forms trans-2-methyl-3-
phenyloxirane. This reaction again establishes the config-
uration of the chlorohydrin as being erythro. The position of
the chlorine atom in the chlorohydrin was established by means
of the ring opening of trans-2-methyl-3-phenyloxirane by HCI.
Such acid-catalyzed ring opening reactions of oxiranes are
known to form the product resulting from the more stable
carbonium ion (24). Thus the reaction of trans-2-methyl-3-
phenyloxirane with aqueous concentration HCl forms a mixture
of 45% erythro- and 55% threo- 1-chloro- 1-phenyl-2-propanol.
The treatment of erythro- 1-chloro-1-phenyl-2-propanol with
o-phenylene phosphorochloridite in pyridine followed by io-
dine in CCl, forms a mixture of 41% threo- and 59% erythro-
2-chloro- 1-iodo-1-phenylpropane (25). The same mixture of
products could be prepared by the same series of reactions
starting with Z-1-phenylpropene as shown in Fig. 5. The 'H
nrnr spectra of these two compounds are different than those of
erythro
!
H, 1/CH? base
U
/ \
erythro
? n
/"\
CH3 base
d
H H
OH
threo
erythro- and threo- 1-chloro-2-iodo- 1-phenylpropane. The data
are summarized in Table 4.
The value of preparing all four stereo- and regioisomers is
that we can now use well-established 'H nmr relationships to
verify their structure and stereochemistry. For a pair of
threo-erythro stereoisomers, it is known that the methyl pro-
tons of the threo isomer of 1,2-disubstituted-2-arylpropanes are
found at higher field than those of the erythro isomer (26).
Thus the methyl protons of threo- 1-chloro-2-iodo-1-phenyl-
propane are found at 6 1.87 while those of its erythro isomer
are found further downfield at 6 2.12 ppm. A similar rela-
tionship exists between the threo (6 1.48 ppm) and the erythro
(6 1.85 ppm) isomers of 2-chloro- 1-iodo- 1-phenylpropane.
As well, the JH,Hcoupling constant of the erythro isomer is
larger than that of the threo isomer. Thus the proton magnetic
resonance spectra are in accord with our assignment of
stereochemistry.
The chemical shift of a proton next to iodine is further
downfield than the same proton next to chlorine (27). We can
make use of this relationship to verify the regiochemistry of the
four compounds. Compare the methyl protons first. In erythro-
1-chloro-2-iodo-1-phenylpropane,the methyl protons are
found at 6 2.12 ppm downfield from the methyl protons of the
isomeric erythro-2-chloro- 1-iodo- 1-phenylpropane at 6 1 .85
ppm. The same relationship exists for the threo isomers
(ICHCH, 6 1.87 ppm; CICHCH, 6 1.48 ppm). A similar re-
lationship exists for protons at benzylic carbons bonded to
 SCHMID AND GORDON
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C6H5\ ,H (1) Hg(02cCH3)~ Qf)-cl

/c=c +
H \CH~ (2) Clz C6Hs H

FIG.5. Synthetic scheme for the preparation of erythro- and tkreo- 2-chloro-1-iodo-1-phenylpropane.

chlorine and iodine. Thus the proton magnetic resonance Mechanism A.

A = I C t D = Alkene
spectra of these four isomers are in accord with our assignment A D = i : l Alkene-ICI molecular complex
of both the stereochemistry and regiochemistry of the A+D %AD
A2D=1:2 Alkene-ICI molecular complex
compounds. A + A %A2
In summary, addition to all four alkenes is anti-stereo- A 2 = I C t dimer
specific. Furthermore, addition to the I-phenylpropenes is AD+A~L
product
regiospecific: only the product of Markownikoff orientation is
formed. No Markownikoff to anti-Markownikoff isomer-
ization of the products of addition to Z- or E--1phenylpropene Mechanism B.
has been observed (28).
Proposed mechanism
Two possible mechanisms for this reaction are shown in
Fig. 6. Both mechanisms involve only bimolecular processes,
a rate-determining step that contains 3 molecules of ICl and one
A+A~D &-Product
of alkene, and two equilibria prior to the rate-determining step. FIG.6. Two proposed mechanisms for the addition of IC1 to
The first equilibrium in both mechanisms is the formation of a alkenes in CC14 at 25OC.
1 : 1 alkene-ICl molecular complex. Formation of an IC1 dimer
is the second equilibrium in mechanism A while formation of mental error by eq. [9]. 'The predicted rate law for both mech-
a 1 :2 alkene-ICl molecular complex is the second equilibrium anisms is then given by eq. [lo] where k = k3KADKA2 (for
in mechanism B. Both mechanisms are consistent with our mechanism A) or k = k3KADK2(for mechanism B). Again
data. Johnson and Bowen (29) have shown that linear substituting for [ICl], in eq. [lo], we obtain the rate law given
Benesi-Hildebrand (B-H) or Ketelaar plots can be obtained in eq. [I I]. Thus both mechanisms are in accord with the
for reactions that involve both 1 : 1 and 1 :2 molecular com- experimentally determined rate law.
plexes. Thus both mechanisms are in accord with our linear The assumption of two equilibria can be substantiated by
Ketelaar plot. quantitative consideration of the enthalpy changes in the reac-
When (alkene)o >> (ICl)o,the concentration of the product of tion as shown in Fig. 7. It is clear that the enthalpy change,
the second equilibrium in either mechanism (ICl dimer in AHAD,for the formation of a 1: 1 alkene-IC1 complex (-9
mechanism A or 1 :2 alkene-IC1 molecular complex in mech- kcal/mol) cannot account for the large negative enthalpy of
anism B) will always be small compared to the concentration activation (- 17 kcal/mol). Another intermediate is needed
of the 1 : 1 alkene-IC1 ~ o m p l e x As
. ~ a result, the stoichiomet- whose value of AH, 5 -8 kcal/m01.~
ric concentration of ICl can be approximated within experi- Dimers of halogens are known and the equilibrium constants

'For example, when the ratio KA2D/K,,Dis 100, the ratio 41f the enthalpy of activation for step 3 is taken into account, AH,
[A2D]/(AD)will be less than 0.01. becomes even more negative than -8 kcal/mol.
 2532 CAN. J.
FIG.7. Enthalpy change in the addition of IC1 to 2,3-dimethyl-
2-butene in CCIAat 25OC.
TABLE
5. Values of K,,?E;? at selected
wavelengths in CC14 at 25OC
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and enthalpies of formation for the dimers of several halogens
in solution and in the gas phase have been determined (30). The
most common method for determining these quantities is to
examine deviations from the Beer-Lambert Law (31). If ICl
and its dimer both contribute to the uv absorbance, eq. [12] can
be written.
where e i 2is the extinction coefficient of the dimer. If the extent
of dimer formation is very small than eq. [12] becomes
[I31 eapp-
-
Abs" = +KA~~~~(IC~)
A
From linear plots of e:,, versus (ICl), values of KA2eA2were
obtained and are given in Table 5.
From our data, it is impossible to determine KA2from the
product KA2eA2. It is possible, however, to obtain an upper limit
to KA2in the following way. If KA2were appreciable, the exact
A
equation for E,,, is as follows:
Synthetic data were generated from eq. [14] using values of e:,,
= 10 and eA2KA2= 100, which correspond closely to the
experimental values obtained in CCl, at 290 to 3 10 nm. Sets of
values of E:,, were calculated for various values of KA2(0.1 to
5.0 M-I). The values of e:,, obtained for a particular value of
KA2were then plotted according to eq. [13]. Any value of KA2
greater than 0.5 M-' causes a definitive curvature of plots of
CHEM. \IOL. 62, 1984
eq. [13]. Thus the value of KA25 0.5 M-' in order to account
for the experimentally observed linear plots of eq. [13].
The enthalpy of formation of the ICl dimer was estimated by
the method of Keefer and Allen (32). Literature values of AHAD
and AGADfor a wide range of donor-IC1 complexes in CCI, at
25°C are given in Table 6. When AGADis plotted against AHAD
the following linear relationship is obtained:
Equation [15] should be valid for the ICl dimer. A KADvalue
of 0.5 M-' predicts a value of AHA, of -3 kcal/mol, very
similar to the literature values of A H , for the iodine dimer in
C C 4 at 25°C (- 1.0 + 0.2 kcal/mol (41); -1.96 kcal/mol
(42); - 1.52 + 0.29 (43). We may state with some confidence
that AHA2for the ICl dimer is more positive than -4 kcal/mol.
Returning to Fig. 7, it is clear that AHA, is not sufficient to
account for the value of AH,. On this basis, it is concluded
that the IC1 dimer, while present in CCl,, is not involved
on the reaction coordinate of the addition of ICl to
2,3-dimeth~l-2-butene.~
Mechanism B, Fig. 6, involves successive equilibria for the
formation of 1 : 1 and 1 :2 alkene-IC1 molecular complexes.
There is no experimental evidence for such 1 :2 alkene-IC1
molecular complexes. However, experimental data are avail-
able for 1 : 2 alkene-Br2 complexes. Kimer'fel'd et al. (44)
have observed both 1: 1 and 1 :2 cyclohexene-Br2 complexes in
solid solutions at - 185OC in ir and Raman spectroscopy.
Sergeev et al. and Lishnevskii et al, have demonstrated the
existence of a 1 : 1 and 1 :2 propene- Br2 complexes at low
temperatures by thermographic ( 4 3 , uv (46), and ir (46)
studies. Sergeev et al. (47) have also postulated a 1:2
cyclohexene-Br2 complex in Freon 113 at ambient tem-
perature on the basis of a uv study in the range 250-270 nm.
A structure of these 1 :2 alkene- Br, complexes has been pro-
posed in which the two bromine molecules are on opposite
sides and perpendicular to the plane of the double bond (44).
A similar structure would be expected for a 1 : 2 alkene-IC1
complex. While it seems reasonable to propose the existence of
a 1 : 2 alkene-IC1 complex on the reaction coordinate of IC1
additions to alkenes, its verification awaits further data.
Summary
Observation of a negative activation enthalpy for the reaction
of ICl and 2,3-dimethyl-2-butene in C C 4 at 25OC provides
strong evidence for the existence of one or more molecular
complexes on the reaction coordinate. The rate law requires a
rate-determining step that contains one molecule of alkene and
three of ICl. Quantitative analysis of the enthalpy change in the
reaction rules out the involvement of the IC1 dimer on the
reaction coordinate. The involvement of a 1 : 2 alkene-IC1
complex in the mechanism is proposed.
Experimental
All boiling and melting points are uncorrected. The glc analysis was
carried out using a Varian Aerograph Series 2740 analytical instru-
ment equipped with a FID. Proton magnetic resonance spectra were
recorded on a Varian T-60 or HA-100 spectrometer in CDCI, contain-
ing (CH3)4Si as internal standard. ACS grade CC14, CH2CI2, and
CH,CN were used without further purification. E- and Z-1-
phenylpropene, E- and Z-Zbutene, and 2,3-dimethyl-2-butene were
'We estimate the errors in ~ ~ * ( e xand
~ tAHAD
) to be k 10% using
the method of Benson (17a).
 SCHMID AND CORDON
TABLE6. Literature thermodynamic parameters for selected donor
CCI, at 25°C
Donor K,\D ( M - ' ) , 25°C AH,\D (kcal mol-I)
1,2-Epoxycyclohexane
4-Chlorotoluene
Benzene
p-Xylene
1,2,4-Triethylbenzene
Mesitylene
Pentamethylbenzene
Hexamethy lbenzene
Can. J. Chem. Downloaded from cdnsciencepub.com by 49.36.43.151 on 03/15/24
Hexaethylbenzene
Dichloroacetonitrile
Monochloroacetonitrile
Acetonitrile
Propionitrile
Dimethylcyanamide
N,N-dimethylacetamide
"AS,, (average) was calculated to be -(14.3 k 2.5) eu.
obtained commercially and used without further purification. Iodine
monochloride was purified by fractional crystallization from the melt,
discarding the remaining liquid portion (48).
threo-3-Iodo-2-butanol was prepared by adding 8.0 g (0.035 mol)
of finely ground iodine in several portions over 5- 10 min to a vigo-
rously stirred solution of 40 g (0.0185 mol) of yellow mercuric oxide
and excess Z-2-butene in 15 mL of 80% aqueous acetonitrile at room
temperature. After an additional 10- 15 min, the reaction mixture was
filtered by suction to remove the red mercuric iodide using a small
amount of acetonitrile as a rinse solution. The filtrate was poured into
a separatory funnel containing a two-fold excess of ether. The re-
sulting solution was washed successively with a 5% aqueous KI solu-
tion, a 5% aqueous NaHS03 solution, and a saturated NaCl solution.
The organic layer was separated, dried over anhydrous MgSO,, fil-
tered, and solvent removed at reduced pressure to yield 3.28 g (0.0164
mol, 52%), bp 45-47"C/5 Torr (I Torr = 133.3 Pa) (lit. (49) bp
43 .0°C/2.5 Torr); 'H nmr 6: 1.23 (d, J = 6.0 Hz, 3H), 1.92 (d, J =
7.0 Hz, 3H), 3.20 (dq, J = 4.5, 6.0 Hz, IH), 4.15 (dq, J = 3.5, 7.0
Hz, 1H).
erythro-3-Iodo-2-butanol was prepared in 80% yield by the same
method as the threo isomer but using E-2-butene as the starting alkene,
bp 50-52"C/5 Torr (lit. (49) bp 34.3-34.9OC10.9 Torr); 'H nmr 6:
1.21 ( d , J = 6.0Hz,3H), 1 . 8 2 ( d , J = 7 . 0 H z , 3 H ) , 4 . 3 1 ( d q , J =
3.5, 7.0 Hz, IH), 3.32 (dq, J = 3.5, 6.0 Hz, IH).
cis-2,3-Dirnethyloxiranewas prepared by adding excess moist sodi-
um aluminate to 2.00 g (0.010 mol) of threo-3-iodo-2-butanol in 10
mL CS2. The sodium aluminate was prepared by adding with stirring
1 mL of 10 N NaOH solution per 5 g of chromatographic grade
alumina. A t'hree-fold excess of base was used. The reaction mixture
was allowed to stand for 10 h with occasional stirring. The mixture
was filtered and the solid was thoroughly washed with CH2CI2. The
solvent was removed at reduced pressure to yield 0.56 g (80% yield)
of product, bp 55-57°C (lit. (53) bp 53.5-53.7"C); 'H nmr 6: 1.22
(d, J = 6 Hz, 3H), 2.91 (m, 1H). '
trans-2,3-Dirnethyloxirane was prepared in 67% yield by the same
method as the cis isomer except that erythro-3-iodo-2-butanol was
used as the starting iodohydrin, bp 55-56°C (lit. (49) bp
53.5-54.0°C); 'H nmr 6 1.27 (d, J = 5Hz, 3H), 2.62 (m, 1H).
threo-2-Chloro-3-iodobutane was prepared by adding 16.6 g (0.014
mol) SOClz to 20 g (0.010 mol) threo-3-iodo-3-butanol. After copious
evolution of HCI, the solution was stirred for 30 min at room tem-
perature. The reaction mixture was transferred to a separatory funnel
containing a 10-fold excess of CHzC12.The organic layer was washed
- iodine monochloride complexes in
AS,\D (cal deg-' mol-I)" References
with a 5% aqueous NaHC03 solution, a 5% aqueous NaHSO,
solution, and a saturated NaCl solution. The organic layer was dried
over KzS03, filtered, and the solvent removed at reduced pressure to
give 1.5 g (68%) of product, bp 35-37"C/5 Torr (lit. (49) bp
32.2-33.514 Torr).
erythro-2-Chloro-3-iodobutanewas prepared in 88% yield by the
same method as the threo isomer except that erythro-3-iodo-2-butanol
was used as the starting iodohydrin; bp 35-37°C 5 Torr (lit. (49) bp
34.8-35.3OC1.5 Torr).
threo-l-Chloro-l-phenyl-2-propanol was prepared by adding 4.72
g (0.040 mol) of Z-I-phenylpropene to a stirred ice-cold solution of
15.9 g (0.050 mol) of mercuric acetate in 200 mL of 50% aqueous
acetonitrile. Stirring was continued for 4 days at room temperature. To
the reaction mixture was added 50 mL of a saturated NaCl solution.
Stirring was continued for an additional 15 min. The resulting mixture
was poured into 200 mL of water and extracted with 3 X 125 mL
portions of ether. The combined ether extracts were washed with 2 X
100 mL portions of water and 100 mL of saturated NaCl solution. The
ether layer was dried over MgS04, filtered, and the ether removed to
give 9.6 g of threo-2-hydroxy-l-methyl-2-phenylethyl mercuric chlo-
ride. A solution of 1.60 g (4.31 mmol) of the organomercurial in 25
mL of dry pyridine in a 50-mL flask fitted with a magnetic stirrer,
CaC12 drying tube, and a gas bubbler was cooled to between -50 and
-60°C and Cl? was bubbled through for 5 min. The reaction mixture
was poured into 150 mL of ether. The ether solution was washed with
2 X 50 mL 5% aqueous HCI solution, 2 X 50 mL 5% aqueous
NaHC03 solution, 25 mL of a 1% aqueous NaHS03 solution, and 50
mL saturated NaCl solution. The ether layer was dried over anhydrous
MgS04, filtered, and the solvent removed at reduced pressure to give
0.60 g (81%) of product; 'H nmr 6: 1.05 (d, J = 6.0 Hz, 3H), 4.00
( d q , J = 6.0,7.0Hz, l H ) , 4 . 6 8 ( d , J = 7.0Hz, l H ) , 7 . 2 7 ( ~ , 5 H ) .
erythro-l-Chloro-l-phenyl-2-propanol was prepared in 75% yield
by the same method as the threo isomer except that E-l-phenylpropene
was used as the starting alkene; 'H nmr 6: 1.22 (d, J = 6.0 Hz, 3H),
4.04 (dq, J = 6.0 Hz, IH), 4.74 (d, J = 6.0 Hz, IH), 7.27 (s, 5H).
Reaction of the 2-rnethyl-3-phenyloxiraneand HCl
A solution of epoxide in CHzClzcooled in an ice bath was treated
with enough concentrated HCI solution so that a 1.5 to 2.0-fold excess
of HCI was present. After stirring for 1 h, the reaction mixture was
diluted with an equal volume of CH,CI,. The CHzC12layer was sepa-
rated and washed with 3 portions of H,O and one portion of saturated
NaCl solution. The organic layer was dried over anhydrous MgSO,,
 2534 CAN. J. CHEM. \

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