A comparative ion chemistry study of acetone, diacetone alcohol, and mesityl oxide

AFAFKAMAR,'ALEXANDER
BALDWIN
YOUNG,A N D RAYMOND
EVANSMARCH^

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 88.85.252.178 on 07/22/15

For personal use only.

Department of Chemistry, Trent University, Peterborough, Ont., Canada K9J 7B8

Received June 17. 1 9 8 5 ~
AFAFKAMAR,ALEXANDER
BALDWIN
YOUNG,and RAYMOND
EVANS
MARCH.Can. J. Chem. 64, 1979 (1986).
The evolution of ion species by unimolecular and bimolecular reactions, both concurrent and sequential, haa been
investigated for each of 2-propanone, d6-2-propanone, 4-hydroxy-4-methyl-2-pentanone, and 4-methyl-3-penten-2-one.
Infrared multiphoton dissociation (IRMPD) has been used in order to differentiate between gaseous ionic isomers. It is concluded
that the isomeric species, protonated 2-propanone dimer and protonated 4-hydroxy-4-methyl-2-pentanone, both of m / z 117, are
of different structures. The ion species C6Hl10+of m / z 99, and its perdeuterated analogue, which is observed in all three
systems, may exist in two forms, one of which is unique to 2-propanone while an alternative form appears to be common to
4-hydroxy-4-methyl-2-pentanone and 4-methyl-3-penten-2-one. The ion species of m / z 83 (C5H70+)which is observed only in
the latter two systems only could not be differentiated and may have a common structure. In the protonated dimers of 2-propanone
and 4-hydroxy-4-methyl-2-pentanone, evidence obtained by IRMPD indicates that the activation energy for dedimerization
(134 kJ molpl) is less than that for the dehydration process.
BALDWIN
YOUNGet RAYMOND
EVANS
MARCH.Can. J. Chem. 64, 1979 (1986)
AFAFKAMAR,ALEXANDER
On a CtudiC 1'Cvolution des especes ioniques provenant de reactions unimolCculaires ainsi que bimolCculaires, tant des
rCactions qui se produisent d'une faqon concurente que ~Cquentielle,de la propanone-2, de la propanone-2-d6, de I'hydroxy-4
mCthyl-4 pentanone et de la mCthyl-4 pentene-3 one-2. Dans le but de distinguer les divers isomeres ioniques gazeux, on a fait
appel la dissociation multiphotonique infrarouge (DMPIR). On en conclut que les especes isomeres dimeres protonCs de la
propanone-2 et de l'hydroxy-4 mbthyl-4 pentanone-2 protonCe, de m / z = 117, possbdent deux structures diffkrentes. L'espece
ionique C6H1,0+,de m / z = 99, et celle de son analogue perdeutCrC qui est observee dans les trois systemes peut exister sous
deux formes; l'une est unique a la propanone-2 alors qu'une autre forme semble &tre commune a I'hydroxy-4 mCthyl-4
pentanone-2 et 2 la mCthyl-4 penthe-3 one-2. Les especes ioniques de m / s = 83 (C5H70+),qui ne sont observCes que dans
les deux derniers systemes, ne presentent pas de diffkrences et possedent peut Ctre la m&mestructure. Dans le cas des dimeres
protonCs de la propanone-2 et de l'hydroxy-4 methyl-4 pentanone-2, on a obtenu des donnCes a l'aide de la DMPIR a l'effet que
1'Cnergied'activation pour la dCdimCrisation (134 kJ mol-' ) est plus faible que celle requise pour le processus de deshydratation.
[Traduit par la revue]

Introduction
Previous studies employing slow Infrared Multiphoton Dissociation (IRMPD), as a probe of activation energy hierarchies
in the gas phase photolysis of proton-bound dimers, have
been carried out with each of 2-propanol (1-4), ethanol (3,
1-butanol(6), and deuterated propanols (7). With proton-bound
alcohol dimers it is possible to determine in some degree the
hierarchy of activation energies among the reaction channels
leading to loss of alkene, water, and monomer or parent
molecule. With the proton-bound dimers of 2-propanone and
4-hydroxy-4-methyl-2-pentanone studied here, it is possible to
assess the activation energy hierarchy for loss of water and
monomer. IRMPD may be used also to differentiate between
isomeric ion species in the gas phase. The distinguishing criteria
for photochemical differentiation are relative absorptivity at
the wavelength available for laser irradiation and, of greater
importance, the photoproduct distribution, i.e. the ionic species
produced and their relative intensities. In some cases it is
informative to photolyze the species of interest in both the
ground state and in its nascent state; nascent ion internal
excitation is enhanced by multiple photon absorption to access
reaction channels of higher activation energy, limited in
practice, by competition between laser fluence and collision
frequency.
The ion-chemistry for each of 2-propanone, 4-hydroxy-4methyl-2-pentanone, and 4-methyl-3-penten-2-one is presented
'Registered in the Ph.D. programme in Chemistry Department,
Queen's University.
2 ~ d j u n cProfessor,
t
Department of Chemistry. Queen's University,
Kingston.
'~evisionreceived February 21, 1986.

here. These three compounds are related in the following

ways: the proton-bound dimer of 2-propanone is isomeric with
protonated 4-hydroxy-4-methyl-2-pentanone and the ion structures could be identical if aldol condensation occurs in the gas
phase; an ion species of m / z 99 ( C 6 H l 1 0 f )is produced in both
of the above systems and is isomeric with protonated 4-methyl3-penten-2-one; and lastly an ion species of m l z 83 (C5H70+)is
observed only with 4-hydroxy-4-methyl-2-pentanone and 4methyl-3-penten-2-one and is conspicuously absent in 2-propanone. Thus these three compounds present an opportunity for
isomer differentiation using the techniques of ion storage and
IRMPD.

Experimental
Although the basic apparatus has been described previously (1-3), a
brief description of the technique used in this work is presented here. A
three-dimensional quadrupole ion store (QUISTOR) mounted in place
of the ion source of a conventional quadrupole mass filter (Vacuum
Generators QXK 400), serves as the reactor in which ion/molecule
reactions take place over the period 0-200 ms. The ring electrode of the
QUISTOR has two central perforations diametrically opposed. A low
power CW C 0 2 laser beam is directed through a sodium chloride
window and through the first ring perforation, of diameter 3 mm. The
beam passes radially through the centre of the QUISTOR and totally
illuminates the ion cloud which rapidly becomes tightly focused at
the centre of the device. A portion of the beam passes through the
perforation at the opposite side of the ring electrode and is monitored
externally through a second sodium chloride window. The remainder
of the beam is thought to undergo multiple reflections within the
QUISTOR. The laser beam is chopped mechanically and phase-locked
with the pulsing sequence as shown in Fig. 1.
The repetition rate of the pulse sequence is controlled by a squarewave generator (Heathkit SG 18.4). The iaser beam is interrupted by a
PAR 222 chopper phase-locked to the square-wave generator. A range

1980

CAN. J. CHEM. VOL. 64, 1986

Heathkit
SG18A

The proton-bound dimer m/z 117 is produced continuously with

either increasing pressure or increasing storage time by reaction with
parent neutrals

L
JJ

1pZS-b7

I+-

Laser On

[3]

-L

(CH3)2COH+ + (CH3)2C0 S [(CH3)2C0]2Ht*

m/z 59
m/z 117

where * denotes a degree of internal excitation. The nascent protonbound dimer may then be either collisionally deactivated

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 88.85.252.178 on 07/22/15

For personal use only.

Axial Ejection

&--Reaction-+I
Time
. .. . .-

fl
I-

or may dissociate
[5I

Irradiarion+I
Time

[(CH3)zC012Ht*
mlz 117

CH3CO(CH3COCH3)+
rnlz 101

L---,

caI10+
+ H?O
mlz

'dz,"rI

n-e-----

+ CH4

99

An alternative and preferred mechanism for the formation of m/z 101,

is the clustering reaction

Storage Time

------+I

FIG. 1. Pulse sequence used in IRMPD with axial ejection employed

to isolate an ionic species of interest by removal of all lower m/z ions
prior to laser irradiation.
of total storage times was effected using chopper wheels with a variety
of wheel apertures, while variation of the laser irradiation period within
a fixed total storage time was achieved with chopper wheels of different
light-to-dark ratio. The mechanical chopper triggers the creation pulse
(Hewlett Packard pulse generator 214B, PGA) which triggers in turn
the extraction pulse (PGB) and a Brookdeal scan delay generator
(9425) which provides a detection pulse to drive a linear gate
(Brookdeal 9415). The square-wave generator also drives a delay pulse
generator which triggers in turn a Sweep Ciznerator (Wavetek 134)
which is then used to remove, by axial ejection (8), ions of mass-tochxge ratio less than that of protonated dimer prior to laser irradiation.
The ion abundances are obtained by recording mass spectra at zero
storage (electron impact) and at a variety of storage times; the relative
ion intensities are calculated for each species at each storage time to
yield the data points shown in the figures. The temporal variation of the
intensity of each ion species was checked by single ion monitoring over
the storage period employed.
2-Propanone (acetone)
lon/irolecule chemistry
The ion chemistry of 2-propanone has been srudied previously by
Munson (9) and by Blair and Harrison (lo), and is re-examined here
both to resolve the minor differences between the findings of these two
groups and to provide a basis for explanation of our photodissociation
results obtained with proton-bound dimers of 2-propanone and 4hydroxy-4-methyl-2-pentanone.
Munson employea a variable pressure
source and reported on secondary ion intensities as a function of
pressure only. Blair and Harrison, in an electron beam trapping study
with a trapping period of 3 ms, used an ionizing electron energy
sufficient to produce only (CH3)2CO+' and cH3COt as primary ions,
with the former con~prising70% of the primary ion abundance.
Protonated parent molecules, m/z 59, are produced by reactions of
the primary ions

[7]

CH3CO+ + (CH3)2C0-+ (cH~)~co---6---OCCH~*

m/z 43
m/z 101

which is then collisionally stabilized. This species may be regarded

as the product of a mixed associative ion (or a heterogeneous protonbound dimer) of ketene uroton-bridged to 2-urouanone.
Mixed associa.
tive ions of ketene with methanol, ethanol, and 2-propanol have been
reported previously ( I I). The stabilization of this mixed associative
ion, m/z 101, may require a reactant CM3COf of modest internal
excitation only, which would account for the fact that it was observed
by Blair and Harrison under their conditions of low ionizing electron
energy, but not by Munson who employed ionizing electrons of 70 eV
and a high pressure source. The C H 3 C ~ ( C ~ 3 C O ~product
~ 3 ) +reacts
slowly at longer reaction times to produce the proton-bound dimer ion
in a ligand replacement reaction

The species of m/z 99 formed by loss of water in the dissociation

of the protonated dimer, reaction [6], was tentatively identified by
Munson as protonated 4-methyl-3-penten-2-one. Since the protonbound dimer of 2-propanon: is isomeric with protonated 4-hydroxy-4methyl-2-pentanone, it was plausible to propose that gaseous ion
reactions may be observed which correspond with solution ionic
reactions in which the acid-catalyzed formation of 4-hydroxy-4methyl-2-pentanone and 4-methyl-3-penten-2-one is observed from
2-propanone. The requirement of reactant excitation in order for
reaction [6] to proceed in a manner which is endothermic for ground
state reactants would explain the observation of m/z 99 by Munson but
not by Blair and Harrison.
In the work reported here and shown in Fig. 2, both species of
m/z 99 and m/z 101 were observed as the ions were created xith
ionizing electrons of 70 eV and the reactions of both excited and ground
state (collisionally cooled) CH3CO+ ions were monitored.
Perdeuterated 2-propanone was investigated also as there was some
interest in the infrared relative absorptivity of deuteron-bound deuterated dimer ions [(CD3)2C0]2Df,m/z 130.
The ion profiles obtained with 2-propanone and d6-2-propanone are
similar in general form as shown in Figs. 2 and 3.
In 2-propanone, the ions of m/z 99 may be formed by the loss of
water, reaction [6], while ions of m/z 101 may be formed by reaction
[ 5 ] and/or reaction [7] to yield C&II1O+and CsHsOzf, respectively.
The corresponding product ions in d6-2-propanone will be C6D110'
and C5D9O2+,respectively, formed in reactions [9], and I101 and/or
[I I] to produce isobaric species of m/z 110.

KAMAR ET AL.

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 88.85.252.178 on 07/22/15

For personal use only.

100

05

FIG. 2. Variation in the logarithm of normalized ion abundances in

Ton.
2-propanone with storage time 0-200 ms, 0.8 x

Thus the ion profile for m / z 110 in Fig. 3 is a composite of the two
isobaric ions.
While the ions of m / z 80 and m / z 82 observed in d6-2-propanone
were of low relative intensity, they can be reconciled with the
observation of ions of m / z 72,73, and 74 in 2-propanone as shown in
Fig. 2.
(i) Let us examine the possible origin for m / z 82 in d6-2-propanone.
The CSD902+species may lose CO or C2D2 to produce C4D90+and
C3D7O2+,respectively. The corresponding ions in 2-propanone would
be C4H90+,m / z 73 and C3H7O2+,m / z 75. The latter species was not
observed therefore ~ ~ ~ 9 0does
2 ' not lose C2D2.
The isobaric C 6 ~ 1 1 0ion
+ may lose C O to produce CsDll+ or lose
C2D2 to produce C4D90+. The corresponding ions in 2-propanone
would be C S H I + ,m / z 71, which was not observed, and C4H90+,m / z
73, which was observed. Thus we conclude that either reaction [12]
[I21 CsD902+* + C4D90+
or reaction [13]

+ CO

AH1*

/ / '
0

Storage Time lms)

1981

103
Storage T~me (ms)

FIG. 3. Variation in the logarithm of normalized ion abundances in

perdeutero-2-propanone with st~ragetime 0-200 ms, 1.l X l o p 4Torr.
occurs or both occur, where A H l 2 and A H l 3 are the enthalpy changes
for reaction [I21 and [13], respectively. As either reaction [12] or
reaction [13] may account for the observations, it is appropriate to
consider the energetics of the processes bearing in mind that a small
fraction of stored ions may acquire translational energy from the
three-dimensional quadrupole field and produce minor amounts of
fragment ions in super-thermal collisions. As reactions 1121 and [13]
produce a common daughter ion with an assumed common structure,
and the heats of formation of C O and C2H2are - 110 and 227 kJ mol-',
respectively, then for reaction [13] to occur the heat of formation of
C6D110+plus internal excitation must exceed the heat of formation of
C5D9O2+plus iniernal excitation of 337 kJ mol-', provided that AH12
= A H l 3 . Thus the occurrence of reaction [13] is less probable than
reaction [12].
(ii) In a similar examination of the origin of m / z 80 in d6-2propanone, the CsD9o2+ may lose C2D3' or CDO' to produce
C3D602+'or C4D80+',respectively. The corresponding product ions
in 2-propanone are C3H6O2+',m / z 74, and c 4 H 8 0 " , m / z 72. both of
which were observed.
Thus as m / z 74 was observed in 2-propanone, we conclude that
reaction [14] occurs
The observation of m / z 72 in 2-propanone may be explained by the
analogous reactions to either
[I51

CsD902+*J C4D80+' + CDO'

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 88.85.252.178 on 07/22/15

For personal use only.

1982

CAN. J. CHEM. 1JOL. 64, 1986

or both.
The heats of formation of HCO' and C2H3' are reported as 33.9 and
332 kJ m o l l , respectively (12). The observation of m/z 74 infers that
the heat of formation of C3D6O2+is some 332 kJ molp' less than the
heat of formation of C5D902+plus internal excitation when reaction
[I41 is thermoneutral. By an argument similar to that presented above
for reactions [I21 and (131, it can be shown that for reaction [16]
to occur the heat of formation of C6D110+*must exceed that of
C5D901;* by some 298 kJ mol-' again provided that the enthalpy
changes for reactions [15] and [16] are similar. Thus the occurrence of
reaction [16] is less probable than reaction [IS].
The observation of C3H3+as a persistent ion species in each of the
systems studied here is in keeping with previous observations of this
species wherever the parent molecule has a 2-propyl grouping. The
reactivity of C3H3+ is discussed elsewhere (13).
Photochemical studies
The IRMPD of the collisionally relaxed proton-bound dimer of
2-propanone yielded but a single photodissociative channel, as is
[I71

[(CH3)2COlzH+
m/z 117

nhv

(cH~)~~+
o H(CH3)2C0
m/z 59

shown in Fig. 4, that of protonated 2-propanone.

In this figure, two sets of experiments a& shown; the first experiment
employing an initial ionization period followed by 45 ms of ionmolecule reaction time, wherein the proton-bound dimer ion is
produced. Axial ejection removes all ionic species of m/z < 117,
isolating the dimer in the trap. These isolated dimers possess a range of
internal energies and some undergo thermal unimolecular dissociation
to produce the protonated parent m/z 59 during the 80 ms following
isolation and prior to ejection and mass analysis. In the second
experiment shown as solid lines in Fig. 4, the dimer is irradiated at
944 cmpl for the 80 ms period following its isolation in the QUISTOR,
then the trap population is ejected and mass analyzed.
The period of laser irradiation was varied from 50 to 100 ms, that is
one half the total storage time, and in each case greater than 90% of
the proton-bound dimers were dissociated. As proton-bound dimers are
being produced continually, the ions irradiated will have a range of
ages and internal energies. As but a single photoproduct was obtained
we conclude that the energies of activation for reactions [5] and [6]
exceed that of reaction [17] which is reported to be 134 kJ mol-I ( 1 4).
While precise measurements of the cross-section for photodissociation
(ao)were not made. the high absorptivity at 944 cmp' of protonbound dimers of 2-propanone is comparable to that of 2-dl-2-propanol
(7). This high absorptivity is remarkable as neutral 2-propanone has
negligible absorption in the vicinity of 944 c m ' .
In contrast the deuteron-bound dimer of d6-2-propanone exhibited
somewhat lower absorptivity in that approximately 40% only of
this species was photodissociated under similar conditions; reduced
absorptivity in perdeutero-2-propanol has been observed (7) also.
As expected, a single photoproduct, deuteron-bound d6-2-propanone,
was observed upon IRMPD.
4-Hydroxy-4-methyl-2-pentanone (diacetone alcohol)
Ion/molecule chemistry
The ion chemistry of 4-hydroxy-4-methyl-2-pentanone obtained at a
pressure of 6 X lop5Torr is depicted in Fig. 5 where it is seen that the
predominant second order product ion at long skorage times is the
protonated parent molecule, (CH3)2C(OH)CH2COHCH3,m/z 1 17.
Of the two possible structures for the m/z 117 ion structure 11 is

P=lxlO-"orr
Laser 1-1
Nn l a w r (---I

FIG. 4. Experimental sequence and results from IRMPD of 2-propanone protonated dimers at 1.O x l o p 4Torr. Dashed lines correspond
to the ion intensities in an experiment wherein the laser was blocked,
solid lines correspond to ion intensities obtained with laser irradiation
at 944 cmpl for the latter 80 ms of the experimental period.
impact mass spectrum, i.e. 38% relative ion intensity at zero storage
time, is due to CH3CO+, m/z 43; this primary ion reacts rapidly along
with other minor primary ions during the first 20 ms principally by
proton transfer reactions such as
[18]

CH3CO+*
m/z 43

+ (CH3)2C(OH)CH2COCH3
+

+(CH~)~C(OH)CH~COHCH
CH2C0
~

m/z 117
where * denotes a degree of internal excitation.
At this juncture, it is appropriate to consider the nature of the
C2H30+species which is observed in the electron impact fragmentations of simple oxygen-containing molecules. In the 2-propanone
system discussed above, it was suggested that the stabilization and
subsequent observation of the ion of m/z 101 may require a reactant
CH3COt of but modest internal excitation, while in the 4-hydroxy-4methyl-2-pentanone system it is evident from Fig. 5 that two forms of
CzH30+ exist which differ in reactivity. The temporal variation of the
ion abundance of m/z 43 in Fig. 5 clearly shows two linear components
in the decay curve; the bimolecular rate constant derived from the steep
component is almost an order of magnitude greater than that derived
from the shallow component. While one form of C2H30+may derive
its greater reactivity by virtue of internal energy, it is improbable that
the internal energy of some 90% of the initial C2H30+abundance
would survive the many collisions by which deactivation could occur.
The co-existence of C2H30+in three structures from a single precursor
has been reported (16). While as many as eleven possible isomeric
structures for C2H30+ have been examined recently, only five
structures will be considered here.

VI

recommended by Parker et al. (15) on the basis of collisionally

activated dissociation (CAD) studies. The base peak in the electron

VII

Of the potential C2H30- above. the acetyl cation (111). l-hydroxyvinyl cation (IV) and oxiranyl cation (VI) have been well characterized
as being stable, observable species (16-18): the acetyl cation is the
lowest energy isomer. The 1-hydroxyvinyl cation (IV) was found to
lie 181 kJ mol-I above 111, with a barrier to rearrangement by

KAMAR

100

[19]
CH~C~HCH~C(@H~(C~!&

(CH3j2C(0H)CH2COHCH3+*
mlz 117

(CH3j2C(OH)CH2COHCH2+ M
rnlz 117

I1
where M represents a collision partner, or may dissociate
I

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 88.85.252.178 on 07/22/15

For personal use only.

P=6 x

Torr

mlz 99
VIII

rnlz 117

to give m / z 99 of structure VIII which is that of protonated mesityl

oxide (4-methyl-3-penten-2-one). The excited VIII may then either be
collisionally deactivated or eject CH4 to produce an ion of m / z 83

miz 99

60

Storage Time (rnsl

successive 1,2-hydrogen shifts of 287 kJ mol-' (19). CH30C' (V)

was found to be the third lowest isomer in energy of the C2H30+ions
examined, lying 214 kJ mol-' above CH3CO+ (111) (19). There
appears to be no experimental study of CH30C+.The results of a recent
study (16) of metastable peak intensities and shapes and collision
induced processes over a range of pressures provide unequivocal
evidence for identification of the acetyl (111), I-hydroxyvinyl (IV) and
oxiranyl (VI) cations. The oxiranyl cation was predicted (19) to be
244 kJ mol-' above 111with a barrier to rearrangement of 85 kJ m o l ' ,
while VII was ~redictedto collapse without activation energy to either
VI or 111.
The acetyl cation 111 is known to react rapidly with oxygencontaining molecules such as 2-propanone (20). In previous studies we
have noted the rapid reaction of primary C2H30+cations in 1- and
2-propanol and in tetrahydrofuran (unpublished work by the authors)
and conclude that this ion must be of structure 111. However, the ion
chemistry of the 1- and 2-propanol and tetrahydrofuran systems.
following the initial decay of the acetyl cation, is characterized by a
steady accumulation of a C2H30+cation which is presumed to be of a
different but unspecified structure.
While it is proposed that ( C H ~ ) ~ C ( O H ) C H ~ C O H C H
m ~/ z+117,
,
is
formed with excess internal excitation in reaction [18] from an excited
acetyl ion in order to explain the subsequent unimolecular dissociation
of m / z 117, some discussion of the proton affinities of 4-hydroxy-4methyl-2-pentanone and ketene would be useful here. The proton
affinity of the former does not appear in the literature (22) but has
been determined in this laboratory (23) to be 831 2 0.8 kJ mol-'
(198.7 + 0.2 kcal mol-I), while the proton affinity for ketene is
828 kJ mol-' (22). Thus for ground state acetyl ions from which a
proton is transferred and ketene remains, the reaction is virtually
thermoneutral.
The excited protonated parent molecules formed may then be
collisionally deactivated.

miz 99

6=c-"1,

+ CH',

rnlz 83

120

FIG. 5. Variation in the logarithm of normalized ion abundances

in 4-hydroxy-4-methyl-2-pentanone with storage time 0-120 ms,
6 x 10-~Torr.

IX
The possibility of CH4 loss occurring initially from m / z 117
followed by loss of H 2 0 to produce m / z 83 is rejected as no species of
m / z 101 was detected. Although the species of m / z 99 and m / z 83
have been observed previously (15), neither the structures of these
ions nor the identities of the neutral fragments ejected have been
investigated further except for an attempt to photodissociate m / z 99 by
multiphoton absorption as discussed below.
The principal minor primary ions, m / z 57, 59, 98, and 101 reacted
rapidly during the first 10 ms and linear plots of the logarithm of ion
intensities with time have been omitted from Fig. 5 so that the ion
profiles of the more stable ions may be portrayed clearly. After the first
20 ms of reaction time, the remaining unreacted m / z 43 ions isomeric
with CH3CO+ reacted slowly along with ions of m / z 83 and 99 in
proton transfer reactions to produce the protonated parent molecule,
m / z 117. At pressures higher than 6 X lo-' Torr, proton-bound dimers
of 4-hydroxy-4-methyl-2-pentanone of m / z 233 were observed.
Photochemical studies
+
IRMPD of (CH3)2C(OH)CH2COHCH3,m / z 117, was carried out
as described earlier. Two photoproducts as depicted in Fig. 6 were
observed.
nhv 10%
7
H~
CzH30'
'
+ C4H100
[23] ( C H ~ ) ~ C ( O H ) C H ~ C O H C
mlz 43
rnlz 117
I241

C6H1)0++ H 2 0
mlz 99

where n and n' are the minimum number of photons (hv) necessary to
overcome the activation energy barriers for reactions [23] and [24],
respectively. IRMPD has been shown to be a useful probe of activation
energy hierarchies when ground state reactants are irradiated. It is
concluded from the observed ratio of photoproducts obtained with
33 ms of laser irradiation that the activation energy for reaction [24] is
less than that for reaction [23]; this conclusion is supported by the
observation that with prolonged laser irradiation, the fractional yield of
reaction [23] can be increased.

CAN. J . CHEM. VOL. 64, 1986

1984

P ; S X ~ O -Tori
~

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 88.85.252.178 on 07/22/15

For personal use only.

Laser 1-(
No Laser C--1

FIG. 6. Experimental sequences and results from IRMPD of protonated 4-hydroxy-4-methyl-2-pentanone at 6 X lop5 Torr. Dashed
lines correspond to the ion intensities obtained in an experiment
wherein the laser was blocked, solid lines correspond to ion intensities
obtained with laser irradiation at 944 cm-' for the latter 50 ms of the
experimental period.
In the discussion above of the ion chemistry of 4-hydroxy-4-methyl2-pentanone, it was assumed that the unreactive form of C2H30+had
been produced as a fragment ion upon electron impact. However,
during experiments using axial ejection in which all ion species of
mlz < 117 are ejected from the QUISTOR, it was observed that a
relatively unreactive form of C2H30+was generated by dissociation of
protonated parent molecules, as shown in reaction [25] which is the
thermal analogue of the photochemical process, reaction [23].
It is of interest to speculate on the possibility that the products of
reactions [23] and [25] are derived from the protonated keto form via a
4-centred elimination

whereas the products of reaction [24] are derived from the protonated
en01 form via a 6-centred elimination as depicted in reaction [20]. As
activation energies for 6-centred rearrangements are generally lower
than those for 4-centred, then the above speculative mechanistic
argument is consistent with the IRMPD results.
Let us consider now the structures of protonated 4-hydroxy-4methyl-2-pentanone and the isomeric cation formed by the addition of
2-propanone to protonated 2-propanone which has been identified in
reaction [3] as a proton-bound dimer. Parker et al. (15) found a
qualitative similarity between the relative ion abundances in the selfchemical ionization mass spectrometry (self-CIMS) of 2-propanone
and that of 4-hydroxy-4-methyl-2-pentanone; the relative ion abundances are tabulated in ref. 15 and reproduced here as stick form mass
spectra in Fig. 7. Furthermore, the same workers found that the CAD
spectrum of the m / z 117 ion, obtained with the magnetic ( B ) and
electric ( E ) sectors linked so as to maintain a constant B / E value, gave
the same daughter ions for both 2-propanone and 4-hydroxy-4-methyl2-pentanone although no spectra were given. On the basis of the
self-CIMS spectra and the CAD B / E linked-scan spectra, Parker et al.
concluded that the two species of m / z 117 had a common structure and
that protonated 2-propane must undergo an aldol condensation with
2-propanone in the gas phase identical wlth that of the acid-catalyzed
condensation of 2-propanone in the solution phase.
Relative ion intensities obtained by self-CIMS should be comparable
with those of a particular storage time as obtained in this work.

miz
FIG. 7. Relative abundances for self-CIMS of (a) 2-propanone and
( b )4-hydroxy-4-methyl-2-pentanone.

Although the pressures and residence times in various sources may

differ, the dependence of ion intensities on the product of pressure
(raised to the power of the reaction order) and time permit a ready
comparison. Thus the relative ion intensities shown in Fig. 7 a and b
correspond to a storage time of -5 ms in each of Figs. 2 and 5,
respectively. There is, however, a disparity in the ion abundances of
m l z 58 and m l z 59 in Fig. 7 b; only negligible abundances of these ions
were observed in our QUISTOR studies.
We are not convinced that an aldol condensation occurs in the
gas phase with 2-propanone on the basis of the evidence shown in
Fig. 7. On the contrary it has been shown that IRMPD of protonated
4-hydroxy-4-methyl-2-pentanone, m / z 117, isolated in the QUISTOR
yielded two photoproducts m l z 43 and m l z 99 (reactions [23]
and [24]), whereas IRMPD of proton-bound 2-propanone dimers,
m l z 117, carried out under identical conditions, yielded but the single
photoproduct, m l z 59 (reaction [17]).
Thus we conclude that the structures of the ion species of m l z 117
obtained in these two systems are different, and that an aldol
condensation does not occur with 2-propanone in the gas phase.
The species of m / z 99 was irradiated by the laser for periods of
33 ms, 50 ms, and 100 ms which is the entire period of its genesis yet no
photodissociation products were observed. Thus it is concluded that
the m l z 99 species is virtually transparent to the laser irradiation at the
wavelength employed. It had been anticipated that photodissociation of
the m l z 99 species would lead to the formation of the m l z 83 species
by the photo>hemical reaction similar to reaction 1221. As no such
species as m / z 83 was observed even from nascent m / z 99 ions it
was concluded that the m / z 99 species is transparent at the laser
wavelength.
At higher pressure, protonated 4-hydroxy-4-methyl-2-pentanone
reacts with parent neutrals to form the proton-bound dimer, m / z 233.

KAMAR ET AL.

1985

The molecular ion reacted rapidly and completely within 10 ms

presumably by proton transfer to form protonated 4-methyl-3-penten2-one

P=6x

Within 40 ms of storage all primary ions save m l z 83 reacted

completely also presumably to form m / z 99. Only the reactive form
of C2H30+, CH3CO+, was observed in this system. The species of
m / z 53, C4H5+,rose slightly in intensity during the rapid decay of the
molecular ion then reacted slowly and completely.
The intensity due to the protonated 4-methyl-3-penten-2-one rose
rapidly during the first 20 ms of storage (or reaction) time to become the
dominant ion in the system. It reached a maximum intensity after 40 ms
and proved unreactive for the duration of the storage time. The intensity
of another ion, m / z 83, increased initially, then after 40 ms of storage,
remained constant. The behaviour of m / z 99 and m / z 83 suggests that
the proton affinity of the neutral species C5H60(82 mu) must be greater
than that of 4-methyl-3-penten-2-one. The proton affinity of the latter
compound also is not in the literature, but has been determined in
this laboratory (23). Proton-bound dimer ions of m / z 197 were not
observed.
Photochemical studies
The protonated molecule, m l z 99, was isolated and subjected to
laser irradiation but no photoproducts were observed; this species is
thought also to be transparent at the laser wavelength.

Torr

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 88.85.252.178 on 07/22/15

For personal use only.

m/z

50

100

Storage Time (ms)

FIG. 8. Variation in the logarithm of normalized ion abundances in

Torr.
4-methyl-3-penten-2-one with storage time 0- 100 ms, 6 x

1 - H20]+,
In addition, ions were observed at m / z 215 [2M
m / z 175 [2M
1 - 58]+, and m / z 157 [2M
1 - H 2 0 - 58]+.
Isolation of the proton-bound dimer was beyond the limit of the
ramped rf sweep for axial ejection, thus it was not possible to isolate
m / z 233 for irradiation. The intensities of all of the above species
were diminished by IRMPD. As the fractional dissociation of the
[2M + 1 - H20]+ species exceeded that of the [2M 11' species, we
conclude that the former is a mixed associative dimer and the activation
energy for dehydration of [2M 1]+ exceeds that for the dedimerization process.

I261

Discussion
The structure of m l z 99 in 2-propanone constitutes a
problem. The loss of H 2 0 from a proton-bridged 2-propanone
dimer of mlz 117 must be explained. It has been demonstrated
earlier by IRMPD that the structure of the proton-bound dimer
of %-propanonemust differ from that of protonated 4-hydroxy4-methyl-2-pentanone, mlz 117. It is significant here that the
dehydration channel for the proton-bound 2-propanone dimer
is not accessed by laser irradiation. In an attempt to explain
the dehydration channel in the 2-propanone dimer which is
observed thermally only, we have considered the keto and en01
forms of protonated 2-propanone. MIND013 calculations show
the latter to be less stable by 110 W mol-' (15), hence relaxed
protonated 2-propanone is expected to exist as the keto form,
structure X , as opposed to the isomeric enol, structure XI.

nhv
[(CH3)2C(OH)CH2COCH3]x
(CH~)~C(OH)CH~COHCH~
+ (CH3)2C(OH)CH2COCH3

The thermal and photochemical reactions of [2M + 11' will be

compared with those in the a,w-hydroxy thiols in a forthcoming
publication in this journal.
4-Methyl-3-penten-2-one(rnesityl oxide)
Ion/molecule reactions
It was decided to investigate the ion chemistry of 4-methyl-3penten-2-one (mesityl oxide) as the structure of protonated 4-methyl3-penten-2-one was proposed for the major unimolecular product of
protonated 4-hydroxy-4-methyl-2-pentanone and for the ion formed
by loss of water from the proton-bound dimer of 2-propanone [9].
Furthermore the ion chemistry of this compound is not evident in the
literature. The temporal variation of ion intensities of 4-methyl-3penten-2-one at a pressure of 6 x
Torr is shown in Fig. 8.
The base peak in the electron impact mass spectrum is due to m / z 83
while the other major ions were observed at m l z 39, 43, and 55 in
order of decreasing relative intensity. Minor ions (<10%) which were
observed were the molecular ion of m / z 98, and m / z 53.

It is important to recognize that nascent proton-bound 2propanone dimers contain a minimum of 134 W mol-' (14)
excess internal energy if formed from fully relaxed neutrals and
protonated monomers.
As the protonated monomers, m l z 59, are formed via
exothermic proton transfer reactions, the nascent dimers may
contain more than 134 W mol-' and may isomerize to form a
mixed keto-en01 species of structure XI1 as opposed to the
anticipated fully relaxed structure XIII.

While either isomer may dedimerize to produce m/z 59, the

elimination of water is more easily rationalized from the high
energy structure, XIH, as shown in reaction 1281.

CAN. J. CHEM. VOL. 64, 1986

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 88.85.252.178 on 07/22/15

For personal use only.

XIV
XV
preferred form as it is presumably the more stable of the two and
it lacks a 6-hydrogen. The presumption of greater stability of
XIV relative to XV is based on a comparison of the energies of
protonated acetaldehyde, XVI and protonated vinyl alcohol,
XVII

XVI
XVII
The heat of formation of protonated acetaldehyde is given by

[29] AHf (XVI) = AHf(CH3CHO)

+ AHf (H+) - PA(CH3CHO)
where PA is the proton affinity. Similarly
[30] AHf (XVII) = AHf (CH2=CHOH)
AHf(H+) - PA(CH2=CHOH)

I
FIG. 9. Schematic energy profile for rearrangements involving the
proton-bound dimer of 2-propanone.

Thus for XVI to be thermodynamically more stable than XVII

and, by analogy, XIV to be more stable than XV, AHf(XVII) AHf(XVI) should be greater than zero, that is

4Hf(CH2=CHOH) lies in the range

- (1 11- 125) kJ mol-' (24)

In Fig. 9 , the relative enthalpies (AH) of the major ionic

species derived from 2-propanone are shown. The height of the
barrier leading to the formation of the dehydration product,
mlz 99, is unknown, as is the activational energy requirement
to form the enol.
The apparent difference between the observed products of
thermal and photolysis reactions, as shown in Figs. 2 and 4,
respectively, may be explained by noting that in the photolysis
experiment, all ions of m l z < 117 were removed, leaving
''agedWor partially relaxed dimer ions at 80 ms of storage time
which were subsequently photolyzed. In Fig. 2 it is apparent
that thermal genesis of m/z 99 reaches a maximum at -70 ms
storage time, hence the " a g e d dimers photolyzed at the onset
of laser irradiation in the lRMPD study contain insufficient
internal energy for the dehydration process. It has been
demonstrated that in slow IRMPD, laser pumping of vibrational
states is slower than the rate of unimolecular dissociation (7),
hence solely the reaction channel of lowest activation energy
will be accessed if relaxed species are irradiated and the
activation energy requirements for competing channels differ by
at least the energy of the photon employed. The IRMPD results
demonstrate that the dedimerization reaction is of lower E, than
dehydration in proton-bound 2-propanone dimers.
The structure of m l z 99 in 4-methyl-3-penten-2-one may be
either that of the keto. XIV or the en01 XV. Structure XIV is the

The PA(CH2=CHOH) is reported (26) as 47-54 W mol-' less

than PA(C2H50H) which is given (22) as 788 kJ mol-'; hence
PA(CH2=CHOH) lies in the range 734-741 kJ mol-'. As the
sum of the thermodynamic quantities in eq. [31] lies in the
range 81-102 kJ mol-', structure XIV is probably more stable
than XV. The presence of a 6-hydrogen is required for the
elimination of water from protonated ketones (27) and, since
neither structure XIV nor XV has a @-hydrogen, dehydration
is not expected and no dehydration product (m/z 81) was
observed. Apart from the energy consideration discussed
above, no distinction may be made at this time between the keto
and en01 tautomers for the identity of m/z 99.
The identity of m/z 99 derived via dehydration of protonated
4-hydroxy-4-methyl-2-pentanone, m/z 117, was proposed earlier as XIV above, and as such further dehydration was neither
expected, nor observed.
The structure of m l z 83 produced from protonated 4-methyl3-penten-2-one is proposed as IX as shown in the alkane
elimination reaction [22].

XIV

IX

KAMAR ET AL

TABLE1. Activation energies for a-cleavage reactions of ionized methyl ketones estimated
from the appearance energy of the a-cleavage product and the ionization energy of the
methyl ketone

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 88.85.252.178 on 07/22/15

For personal use only.

a-Cleavage reaction

AE (eV)

1E" (eV)

AE

1E- E,

"Reference 28.
'Reference 21.

The protonated ketone, XIV, may also eliminate isobutene, as

shown in reaction [32];
+/H

~321

O'.

-A

+ CH3CO+

AH

136 LJ mol-l

mlz 43

XIV

however, no trace of m / z 43 was observed, thus reaction [32]

is of higher E, than reaction [22]. The enthalpy change for
reaction [22] is not known as the heat of formation of m / z 83
of structure IX is not available. However, an estimate of
the activation energy may be obtained by examination of
the ionization energy (IE) of a number of ketones and the
appearance energy (AE) for the a-cleavage reaction

As the energy of activation may be approximated by the

expression
it is apparent from Table 1 that as the alkyl (or alkenyl) group,
R, is extended the activation energy of the reaction is diminished. Thus it seems probable that the heat of formation of
m / z 83 is less than that for CH3CO+ in reaction [32]; however,
it has been brought to our attention that such may not be
the case as AH?(CH~CO+) in some 240 kJ molpl less than
AN?(CH~=CHCO+) although the AE - IE values in Table 1
suggest otherwise. Therefore, despite a lower AH': for methane
than for isobutene in reaction [32], the enthalpy hierarchy
between reactions [22] and [32] may not be satisfactorily
established.
The structure of m / z 83 formed from protonated 4-hydroxy-

4-methyl-2-pentanone is also proposed as IX above. Although

m / z 43 was observed both thermally and photolytically from the
protonated hydroxy ketone, m / z 117, IRMPD of the isolated
m / z 117 demonstrated that m / z 43 was derived directly from
the protonated parent, rather than from its dehydration product,

m / z 99.

Acknowledgements
The authors acknowledge with thanks the financial support
of the Natural Sciences and Engineering Research Council
of Canada, Trent University, and Queen's University for a
Graduate Student Assistantship to A. Kamar. We acknowledge
also the technical assistance of W. King and J. A. Tomlinson.
We are greatly appreciative of the co-operation of Drs. C . W.
Willis and D. Rayner of the National Research Council of
Canada for the loan of the C 0 2 laser. The constructive
comments of the referees are much appreciated.
1. R. J. HUGHES,
R. E. MARCH,and A. B. YOUNG.Int. J. Mass
Spectrom. Ion Phys. 42, 255 (1982).
R . E. MARCH,and A. B. YOUNG.Int. J. Mass
2. R. J. HUGHES,
Spectrom. Ion Phys. 47, 85 (1983).
R. E. MARCH,
and A. B. YOUNG.
Can. J. Chem.
3. R. J. HUGHES,
61, 834 (1983).
4. R. E. MARCH.
Ionic processes in the gas phase. Edlted b))M. A.
Almoster-Ferreira. D. Reidel Publishing. 1984. p. 359.
5. R. E. MARCH,
R. J. HUGHES,
and A. B. YOUNG.
Proc. 13th Conf.
British Mass Spec. Soc., Wanvick Univ. U.K. Sept. 19-22,
1983.
6. R. J. HUGHES,
R. E. MARCH,
and A. B . YOUNG.
Proc. 31st Ann.
Conf. Am. Soc. Mass Spec. Boston. 1983. p. 747.
7. A. B. YOUNG,
R. E. MARCH,
and R. J. HUGHES.
Can. J. Chem.
63, 2324 (1985).
A. KAMAR,
and
8. R. E. MARCH,A. B. YOUNG,R. J. HUGHES,
M. BARIL.Spectrosc. Int. J. 3, 17 (1984).
9. M. S. B. MUNSON.
J. Am. Chem. Soc. 87, 5313 (1965).
10. A. S. B L A I R ~ G.
~ ~HARRISON.
A.
Can. J. Chem. 51.703 (1973).

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 88.85.252.178 on 07/22/15

For personal use only.

1988

CAN J CHEM VOL 64, 1986

11. G. B. DEBROU,
J. E. FULFORD,
E. G. LEWARS,
and R. E . MARCH.
Int. J. Mass Spectrom. Ion Phys. 26, 345 (1978).
12. J. L. HOLMESand F. P. LOSSING.Int. J. Mass Spectrorn. Ion
Processes, 58, 113 (1984).
and F. P. LOSSING.Can. J. Chem. 57, 249 (1979).
13. J. L. HOLMES
14. J. W. LARSON
and T. B. MCMAHON.J. Am. Chem. Soc. 104,
5255 (1982).
J. E. PARKER,
and G. P. SMITH.
15. J. A. HUNTER,C. A. JOHNSON,
14th Meeting of the British Mass Soc., Heriot-Watt Univ.,
Edinburgh, U.K. Sept. 18-21, 1984. Abstr. p. 24.
J. L. HOLMES,
J. E. SZULEJKO,
A. A. MOMMERS,
16. P. C. BURGERS,
Org. Mass Spectrom. 18, 254 (1983).
and J. K. TERLOUW.
17. J. VOGT,A. D. WILLIAMSON,
and J. L. BEAUCHAMP.
J. Am.
Chem. Soc. 100, 3478 (1978).
18. J. K. TERLOUW,
W. HEERMA,and G. DIJKSTRA.Org. Mass
Spectrom. 15, 660 (1980).
and L. RADOM.
J. Am. Chem. Soc.
19. R. H. NOBES,W. J. BOUMA,
105,309 (1953).
20. K. A. MCNEILand J. H. FUTRELL.J. Phys Chem. 76, 409
(1972).

K. DRAXL,B . W. STEINER,and J. T.
21. H. M. ROSENSTOCK,
HERRON.J. Phys Chem. Ref. Data, 6, Suppl. 1 (1977).
andR. D. LEVIN.J. Phys. Chem. Ref.
22. S. G. LIAS,J. F. LIEBMAN,
Data, 13(3), 695 (1984).
23. A. KAMAR,
R. E. MARCH,and A. 5 . YOUNG.Can. J. Chem.
To be published.
and L. RADOM.J. Am. Chem.
24. W. J. BOUMA,J. K. MACLEOD,
Soc. 101,5540 (1979); J. L. HOLMES,
J. K. TERLOUW,
and F. P.
and
LOSSING.
J. Phys. Chem. 80, 2860 (1976); J. L. HOLMES
F. P. LOSSING.
J. Am. Chem. Soc. 104, 2648 (1982).
25. J. F. Cox and D. PILCHER.Thennochemistry of organic and
organometallic compounds. Academic Press, New York. 1970.
26. W. J. BOUMA,R. N. NOBES,S. SAEBO,and L. RADOM.Chem.
Phys. Lett. 99(2), 112 (1983).
Org. Mass Spectrom.
27. M. L. SIGSBY,
R J. DAY,and R . G. COOKS.
14, 273 (1979).
28. R. D. LEVINand S. G. LIAS. Natl. Stand. Ref. Data Ser. 71
(1982).