IONIZATION AND DISSOCIATION OF FORMATE ESTERS

BY ELECTRON IMPACT

D. VAN RAALTEAND A. G. HARRIS ON^

Department of Chemistry, University of Toronto, Toronto, Ontario
Received March 19, 1963
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ABSTRACT
The mass spectra of methyl formate-d, ethyl formate-d, and isopropyl formate-d are com-
pared with the mass spectra of the undeuterated compounds. By use of the deuterium labelling
and appearance potential studies the dissociation reactions leading t o a number of the oxygen-
containing ions have been elucidated. The proton affinity of formic acid is estimated to be
157 kcal/mole from the appearance potential of the HC(OH)2+ion in the mass spectra of
ethyl formate and isopropyl formate.

INTRODUCTION
A survey of the mass spectra of aliphatic esters by Sharkey and co-workers (I) has
established the main dissociation reactions on electron impact and has pointed out a
number of important rearrangement processes. Beynon et al. (2) have extended this work
by using high-resolution mass spectrometry to determine the empirical formulae of the
Can. J. Chem. 1963.41:2054-2059.

ions formed. Some information on the energetics and mechanism of ion formation has
been obtained by King and Long (3) in a detailed study of C13-labelled methyl formate
and methyl acetate, while more recently Godbole and Kebarle (4) have studied some of
the rearrangement processes in various deuterated ethyl and isopropyl acetates and ethyl
formate. The present paper reports the mass spectra of methyl formate-d, ethyl formate-d,
and isopropyl formate-d. The use of deuterium labelling combined with appearance
potential studies has permitted the elucidation of the mechanism of a number of the
important rearrangement processes.
EXPERIMENTAL
T h e mass spectra were obtained with a n Associated Electrical Industries MS-2 mass spectrometer. T h e
operating conditions were 50 v electron energy, 20 ba ionizing current, and 3 v repeller (-7 v/cm field
strength). T h e appearance potentials were determined as previously described (5) using xenon as the
calibrating gas.
The deuterated compounds were obtained from Merck, Sharp and Dohme of Canada. The.isotopic
purity was checked by low-energy analysis as will be discussed below. The mass spectra showed no other
detectable impurities. The unlabelled methyl and ethyl formates were commercial samples which were
distilled before use. The isopropyl formate was prepared by standard methods and purified by distillation.

RESULTS A X D DISCUSSION
The major peaks in the mass spectra of the deuterated and undetuerated esters are
presented in Table I. The intensities are expressed as percentage of the total ion yield
and ion currents less than 0.5% have not been listed unless they are of special interest.
The spectra have all been corrected for C13isotope contribution and in the case of methyl
formate-d for 0.5y0 undeuterated methyl for~nateas determined by low-energy analysis.
Low-energy analysis of ethyl formate-d and isopropyl formate-d showed less than 1%
isotopic impurity in each case; no correction for this has been made. The isotopic analysis
of the isopropyl formate was carried out in the mass 45-46 region due to the low intensity
of the parent ion.
'Alfred P. Sloan Research Fellow 1969-1964.
Canadian Journal of Chemistry. Volume 41 (1963)

2054
 VAN RAALTE A N D HARRISON: FORMATE ESTERS 2055

TABLE I
Mass spectra o f formate esters*
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Can. J. Chem. 1963.41:2054-2059.

*Intensities expressed as percentage of total ion yield. .~.

Table I1 lists the appearance potentials of some of the more important ions for the
three esters. In general, the agreement with previously published results is within experi-
mental error.
Of particular interest in the mass spectra are the oxygen-containing ions a t masses*
7 3 , 59, 47, 4 5 , 31, and 19, and their counterparts in the deuterated isomers. These ions
can be divided into two classes, those which are formed by direct dissociation and those
which are formed by a rearrangement reaction.
Ions Formed by Direct Dissociation
( a ) Loss of H
T h e small ion current a t mass 7 3 (loss of deuterium) in ethyl formate-d indicates that
loss of the formyl hydrogen occurs to a significant extent in ethyl formate. The mass
spectrum of HC02CD2CH3showed (4) a much larger loss of H than can be accounted
for by loss of the formyl hydrogen. Since Godbole and Kebarle (4) also observed loss of
deuterium, it is apparent that all hydrogens are lost to some extent from ethyl formate.
*Since doubly charged ions are not discussed, the mass-to-charge ratio will he referred to as the mass throughout.
 CAXADIAN JOURNAL O F CHEMISTRY. VOL. 41, 1963

TABLE I1
Appearance potentials in formate esters

Appearance potential ( v i O . 1 v)
Compound nz/e This work Literature
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The mass 59 ion of methyl forinate corresponds to loss of hydrogen. The observation
Can. J. Chem. 1963.41:2054-2059.

of both mass 59 (loss of D) and mass 60 (loss of H ) in the mass spectrum of methyl
formate-d indicates that both the formyl and the methyl hydrogens are lost, with loss of
the methyl hydrogen accounting for approximatel~r20y0 of the ion current. The observa-
tion of loss of the methyl hydrogen is in contrast to the results of Renaud and Leitch (B),
-who concluded, from the mass spectrum of HCOOCDd, that only the formyl hydrogen
was lost. I t should be noted, however, that their reported spectra gave mass 63/mass
62 = 0.0456 for HCOOCDBcompared to mass 60/mass 59 = 0.0186 for HCOOCH3. This
suggests an appreciable impurity of HCOOCDZH in the HCOOCD, and makes interpre-
tation of the results difficult.
( b ) Loss of CHB
The mass 73 ion in isopropyl formate corresponds to loss of CHX. The observation of
this ion a t mass 74 in the deuterated compound indicates t h a t the form>-1hydrogen is
retained. I t is probable that the methyl is lost without isotopic mixing.
T h e mass 59 ion of ethyl formate has been shown (2) t o have the empirical formula
C2H302+,formed by loss of CH3. In DCOOCaH5 this ion is observed a t mass 60, while in
HCOOCD2CH3 the ion is observed (4) a t mass 61. These results indicate the structure
HCOOCH2+, the methyl group being lost without isotopic mixing.
(c) Formation of CzH60+ from Ethyl Formate
High-resolution work by Beynon et al. (2) has shown that the mass 45 ion in ethyl
formate has the empirical formula CzH50+ with negligible contribution from HC02+.
Both masses 45 and 46 are found in the mass spectrum of ethyl formate-d. The former
must be C2H50f, consisting of the original ethoxy group of the ester, while the latter ion,
incorporating the formyl hydrogen, is presumably the DOCHCH3+ ion. The relative
intensities indicate that in ethyl formate approximately 65% of the mass 45 ion is a re-
arrangement ion incorporating the formyl hydrogen. Godbole and Kebarle (4) observed
both CH,CD20+ and CH,CDOH+ in the mass spectrum of HCOOCDzCH3. From the
relative intensities they assigned, one calculates 43% retention of the two deuteriums.
This is significantly higher than the 35% retention of the total ethoxy group calculated
in the present work and suggests that some of the mass 45 ion may be formed by loss of
one of the methyl hydrogens with transfer of the formyl hydrogen.
 V 4 N RAALTE A S D HARRISON: FORMATE ESTERS 2057

The appearance potential of mass 45 (CsHjOf) in the ethyl formate-d is in agreement

with A(mass 45) = 11.55 ev. in the undeuterated compound. Using AH,(ethyl formate) =
-88 kcal/mole (7) this appearance potential leads t o AHf(C2HjO+)= 152 kcal/mole
assuming H + CO as the neutral fragments and 178 kcal/mole assuming HCO as the
neutral fragment. The lower value is only slightly higher than AHf(CH3CHOH+)= 145
kcal/mole, obtained from appearance potential studies of the simple alcohols (8, 9).
Although no reliable value for AH,(C2H6Of) has been established, both the values 152
and 178 kcaljmole are too low by comparison with AHf(CH30+) = 212 kcal/mole (7).
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I t appears likely that the ion has rearranged t o the more stable carbinyl structure and is
formed with H + CO as the neutral fragments.
Ions Formed by Rearrangement
A number of the major rearrangement reactions which occur can be represented by
the follo~vinggeneral reaction first suggested by King and Long (3):

The main driving force for this rearrangement is undoubtedly the stability of the CO
Can. J. Chem. 1963.41:2054-2059.

produced and the stability of the hydroxycarbinyl ion.

(a) Loss of H + CO (Rz = H)
The loss of H + CO from isopropyl forrnate leads to the formation of mass 59, which
has been shown (2) to have the empirical formula C3H@+. In isopropyl formate-d this
ion has moved to mass 60, indicating retention of the formyl hydrogen. The ion is thus
not the original isopropoxy group of the ester but is a rearrangement ion formed by reaction
[I], the h j drogen lost probably being the tertiary hydrogen of the isopropyl group.
As discussed above the large intensity a t mass 46 in ethyl formate-d indicates approxi-
mately f 1 3 7 ~retention of the formyl hydrogen in formation of the C2Hj0+ion. The ion
probably has the structure HOCHCH3+ formed rearrangement reaction [I].
A(CH3CHOD+) from ethyl formate-d is in agreement with A(mass 46) reported by
Bernecker and Long (7). The appearance potential leads to AHf(CH3CHOD+) = 162
kcaljmole assuming the neutral fragments H + CO. This is considerably higher than the
best value for this ion and implies the presence of excess energy in the rearrangement
process.
The mass 31 ion in methyl formate has been postulated (3) to be the original methoxy
group formed with HCO as the neutral fragment. The large intensity a t mass 32 in methyl
formate-d indicates that the major fraction of this ion incorporates the formyl hydrogen
and is thus the CH20Hf ion formed by reaction [I] with H + CO as neutral fragments.
Comparison of the mass 32 intensity in DCOOCH3 with the mass 31 intensity in
HCOOCH3 indicates formyl hydrogen retention neglecting any isotope effects.
T h e appearance potential of mass 31 from methyl formate leads t o AHf(CH20H+)
= 176%3 kcal/rnole, using AHf(HCOOCH3) = -83.7 kcal/mole (7) and assuming
H + CO as the neutral fragments. This is in reasonable agreement with AHf(CH20H+) =
1 8 0 ~ kcaljmole
3 obtained from simple alcohols (8, 9).
(b) Loss of CH3 + CO (Rs = CH3)
+
l\lass 45 in isopropyl formate corresponds to loss of CH3 CO. In isopropyl formate-d
this ion has moved quantitatively to mass 46, indicating retention of the formyl hydrogen.
The ion is thus formed by rearrangement reaction [I] with R z = CH3.
 2058 CANADIAN JOURNAL O F CHEMISTRY. VOL. 41, 1963

The appearance potential of CH3CHOH+ from isopropyl formate leads to

AH,(CH3CHOH+) = 163 kcal/mole using AH,(isopropyl formate) = -97 kcal/mole as
estimated from the heats of formation of other formate esters. Again this is considerably
higher than the best estimates for this ion and implies the involvement of excess energy
in the rearrangement process.
The mass 31 in ethyl formate has moved to mass 32 in DCOOCZHS. This result, in
conjunction with the observation of the ion a t mass 33 in HCOOCD2CH3 (4), clearly
shows retention of the formyl hydrogen and loss of the terminal methyl group without
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isotopic mixing in the rearrangement reaction. The appearance potential of mass 31 from
ethyl formate obtained in the present work is slightly lower than that obtained previously
and leads to AHf(CHpOHf) = 1 8 3 f 3 kcal/mole, in reasonable agreement with the best
value of 180 kcal/mole (8, 9).
(c) Formation of ~ W a s 31
s from Isopropyl Formate
In contrast t o the above results, the rearrangement t o form mass 31 in isopropyl
formate follows a somewhat different mechanism. As shown in Table I the ion has moved
to mass 32 in isopropyl formate-d, indicating retention of the formyl hydrogen. The most
reasonable mechanism for formation of this ion is through the mass 59 ((CH3)2COH+)as
follows :
HCOOCH(CH,)z+ -+ H + CO + HOC(CHs)zC CzH, + HOCHzA. [21
Can. J. Chem. 1963.41:2054-2059.

--t

Deuterium labelling (11) has shown that formation of mass 31 from isopropyl alcohol
occurs with retention of the hydroxyl hydrogen and complete loss of the tertiary hydrogen,
while recent work in this laboratory (9) indicates that the reaction proceeds through the
mass 59 intermediate as indicated by the above mechanism and in agreement with the
labelling evidence.
The appearance potential of CH20H+ from isopropyl formate was found to be 13.45 ev
compared t o 13.53 ev for A(CH20D+) from isopropyl formate-d. The average value,
13.49f 0.1 ev, leads to AHf(CHzOH+) = 1 7 7 f 3 kcal/mole assuming the above mech-
anism. Considering the possible errors in the estimation of the heat of formation of the
ester this is in satisfactory agreement with the best value of 180 kcal/mole. This result
affords further support for the mechanism of formation proposed.
I t is apparent from the above results that mass 31 in methyl formate and in ethyl
formate, mass 46 in ethyl formate-d, and masses 45 and 59 in isopropyl formate arise by
similar rearrangement reactions represented by the general reaction [I]. Three possibilities
must be considered when discussing the time sequence by which the reaction occurs.
These are :
(a) CO leaves first;
(b) Rz leaves first;
(c) concerted rearrangement in which Rz and CO leave simultaneously.
Sequence (a) should lead to significant ion currents for the corresponding alcohol ions
in the case of methyl and ethyl formates. For methyl formate a significant ion current for
CH30H+ is observed. Subsequent loss of R Z = H would be consistent with the labelling
results, since the mass spectra of deuterated methanols show predominantly methyl
hydrogen loss (9, 10). The mass 31 intensity in methyl formate is greater than might be
expected from decomposition of the methanol ion and it is probable that one or both of
sequences (b) and (c) contribute.
The absence of the CH3CHZ0H+ ion in the spectrum ethyl formate would argue
against the occurrence of reaction [l] by sequence ( a ) in this case. For the formation of
 VAN RAALTE AND HARRISON: FORMATE ESTERS 2059

CH20H+ from ethyl formate the observation (4) of a metastable form a t mass 16.3
corresponding to the transition

indicates for this ion a significant occurrence of the rearrangement [I] by a time sequence
in which R 2 is lost first. For the other cases the present results do not permit decisions as
t o the time sequence of the rearrangement.
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,Wass 19
The mass spectra of ethyl formate and isopropyl formate both show significant ion
currents a t mass 19 corresponding to the hydroniuin ion. For both esters the spectra of
the deuterated isomers show that the major part of this ion incorporates the formyl
hydrogen. The energetics and mechanism of hydronium ion formation in esters and
alcohols will be discussed in a further communication.
Proton Afinity of Formic Acid
The mass sepctra of ethyl and isopropyl formates show significant ion currents a t mass
47 which must correspond to a protonated formic acid molecule. The spectra of the
deuterated molecules show that this ion incorporates the formyl hydrogen. The three
Can. J. Chem. 1963.41:2054-2059.

reported appearance potentials for HC(OH)2+ from ethyl formate (Table 11) agree within
experimental error. The average value, 11.66f 0.1 ev, leads to AHf(HC(OH)2+) = l l 5 f 3
kcal/mole assuming CzH3 (AH, = 65 kcal/mole (7)) as the neutral fragment.
A(HC(OH)2+) = 10.87f 0.1 ev from isopropyl formate leads to AH,(HC(OH)z+) =
122&3 kcal/mole assuming C3H5 (AH, = 30 kcal/mole (7)) as the neutral fragment.
This mechanism is similar to that proposed by McLafferty and Hamming (12) for the
similar rearrangement in isobutyl esters. Although the agreement of the two estimates
is barely within experimental error the results suggest that AHf(HC(OH)2+) = 118
kcal/mole is not in serious error. Combination of this value with AH,(HCOOH) = -90
kcal/mole and AHI(H+) = 365 kcal/mole (7) leads to 157 kcal/mole for the proton
affinity of formic acid in the gas phase. This is substantially less than the estimate of
177 kcal/mole by Godbole and Kebarle (4) for the proton affinity of acetic acid, but is
not unexpected in view of the stabilizing effect of the methyl group compared to hydrogen.

ACKNOWLEDGMEKTS
The authors are indebted to the Advisory Committee on Scientific Research, University
of Toronto, and the National Research Council of Canada for financial support.

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