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Kin 20149
Kin 20149
Isomerization of 1,1,2,2-
Tetramethylcyclopropane
DAVID K. LEWIS,1 TIMOTHY GRAY,1 VLAD KATSVA,1 KYLE PARCELLA,1 JESSICA SCHLIER,1
BANSI L. KALRA,2 JANET CHO,2 DEBRA MISH2
1
Department of Chemistry, Connecticut College, New London, CT 06320
2
Department of Chemistry, Hollins University, Roanoke, VA 24020
Received 1 July 2003; revised 8 September 2005; accepted 21 September 2005
DOI 10.1002/kin.20149
Published online in Wiley InterScience (www.interscience.wiley.com).
energy barrier for formation of a diradical intermediate. 1077–1151 K. Under the extremely homogeneous con-
An earlier study of 1,1,2-trimethylcyclopropane (tri- ditions in the shock tube, he found evidence of only one
MCP) isomerization gave a value of E a , 61.1 kcal/mol channel for tetra-MCP depletion, the isomerization to
[5]; however, in our systematic re-examination of these 2,4-DMP; at rates given by E a = 62.2 kcal/mol, log
reactions, that isomerization has yielded a somewhat A = 14.82. However, Tsang did note considerable in-
higher E a value, 63.7 kcal/mol [6]. This suggests that stability of the product at these temperatures and had
factors other than just the strength of the C C bond to correct for its loss in calculating rate constants for
being broken become important as more hydrogen the tetra-MCP isomerization [10].
atoms on the cyclopropane ring are replaced by methyl Given the similarity in absolute rates reported in the
groups. The added steric interactions may distort the two experimental static reactor studies [7,8], and the
transition state or block some easy pathways to it. care with which all three previous experimental studies
Continuing this exploration of the effects of suc- appear to have been carried out [7,8,10], it is unlikely
cessive methyl-for-hydrogen substitutions on the ki- that there are large errors in the reported experiment-
netics and energetics of cyclopropane isomerizations, based Arrhenius parameters. Still, in each of those stud-
we have now looked at the next more highly substituted ies, rate constant corrections were necessary for the
member of the series, 1,1,2,2-tetramethylcyclopropane appearance of side products in experiments that con-
(tetra-MCP). This should be an ideal molecule for sumed substantial fractions of the reactant. Considering
kinetic-mechanistic studies, both experimental and the- the importance of cyclopropane isomerizations to the
oretical, because isomerization via the expected dirad- development and verification of computational meth-
ical intermediate should form only a single product, ods, activation parameters of the highest accuracy now
2,4-dimethyl-2-pentene (2,4-DMP). possible should be made available. That is the purpose
There have been three previous reports of experi- of this study.
mental rate studies of tetra-MCP isomerization. Frey In the work described here, the isomerization of
and Marshall [7] performed a static reactor study over tetra-MCP to 2,4-DMP was studied over 672–750 K in
the range 708–757 K and found the reaction to be ho- three glass static reactor cells, and at 1000–1120 K in a
mogeneous and unimolecular, with E a = 64.4 kcal/ glass single pulse shock tube, using two alternate ref-
mol and log (A, s−1 ) = 15.83 (later adjusted slightly to erence reactions for temperature determination. Com-
E a = 64.7 kcal/mol, log A = 15.55) [8]. Believing the bining the two experimental methods, we were able to
work of Frey and Marshall basically sound but possibly cover a wide temperature range, 448◦ in this study. We
affected by a systematic error due to the small temper- were also able to restrict the rate data we used to runs
ature range covered (50◦ C), Benson and O’Neal [9] in which extents of depletion of the reactant tetra-MCP
combined a calculated pre-exponential factor based on were relatively small (generally <25%), eliminating
a diradical transition state with the experimental rate the need to know whether any side products observed
constants in the center of Frey and Marshall’s temper- were produced directly from the reactant or from sub-
ature range and concluded that E a = 59.7 kcal/mol, sequent reactions of the primary isomerization product
log A = 14.4 best described the rate of this isomer- 2,4-DMP.
ization, thus continuing the trend of lower E a with in-
creasing methyl substitution reported for other methyl-
substituted cyclopropanes. At that time, no other alkyl- EXPERIMENTAL SECTION
cyclopropane isomerization showed such a large dis-
crepancy between measured [7] and predicted [9] Ar- Materials
rhenius parameters.
Shortly thereafter, two other experimental studies Tetra-MCP (99.96%)1 was obtained from the API Stan-
were carried out to resolve this discrepancy. Blumstein dard Reference Materials project at Carnegie Mellon
et al. [8] repeated the work in a static reactor at University. Either Matheson CP grade (99%) cyclo-
699–759 K, and reported E a = 63.93 kcal/mol, log propane (CP) or Aldrich reagent grade (99%) cyclo-
A = 15.27, within experimental error of the findings hexene (CH) was added to each reactant mixture
of Frey and Marshall [7]. However, they believed this as an internal thermometer. These reagents, in ap-
to be the result of two parallel channels for loss of propriate ratios, were diluted with Matheson reagent
tetra-MCP, the expected isomerization to 2,4-DMP grade (99.9999%) argon to prepare reaction mixtures.
(with E a = 62.3 kcal/mol) plus a minor but signifi-
cant decomposition pathway via loss of methyl radi- 1
Reagent purities listed here are as specified by the vendors from
cal (with E a = 77 kcal/mol). Tsang [10] studied tetra- whom the samples were obtained. GC analyses confirmed these
MCP isomerization in a single-pulse shock tube at percentages.
KINETICS OF THE THERMAL ISOMERIZATION OF 1,1,2,2-TETRAMETHYLCYCLOPROPANE 485
Table II Reaction Temperatures, Times, and Rate and E a = 66.6 kcal/mol, log (A, s−1 ) = 15.15 for CH
Constants Displayed in Fig. 1 [10]. For ln[(CP)t /(CP)0 ], we used GC peak heights
Temp (K) Time k (s−1 ) of CP and its isomerization product propene in heated
samples, again corrected for differences in GC detec-
685.9 120 min 8.83 × 10−6 tor response: ln[(CP)/(CP + propene)]. Similarly, GC
689.9 90 min 1.21 × 10−5
responses to 1,3-butadiene and CH were used for tem-
697.0 90 min 1.50 × 10−5
perature calculations for the samples to which CH
694.1 120 min 1.28 × 10−5
672.5 90 min 4.67 × 10−6
had been added. This assumes that all losses of CP
674.4 120 min 5.41 × 10−6 or CH were accounted for through product propene
712.0 90 min 3.41 × 10−5 or 1,3-butadiene, respectively. We believe that this is
749.7 45 min 3.65 × 10−4 supported by the absence of other product peaks at-
741.2 60 min 1.64 × 10−4 tributable to CP or CH decomposition, other than the
718.1 90 min 4.01 × 10−5 ethene co-produced from CH.
740.8 60 min 1.23 × 10−4
729.7 60 min 8.25 × 10−5
730.7 60 min 8.27 × 10−5 RESULTS AND DISCUSSION
723.3 60 min 7.90 × 10−5
705.8 60 min 2.11 × 10−5 At temperatures below 1200 K, structural isomeriza-
711.8 60 min 3.32 × 10−5
tion of cyclopropanes is generally believed to occur
1081 8.0 × 10−4 s 2.77 × 102
mainly via cleavage of a C C bond to form a 1,3-
1120 8.0 × 10−4 s 7.55 × 102
diradical, followed by 1,2-hydrogen transfer to form
1105 8.0 × 10−4 s 5.15 × 101
1091 8.0 × 10−4 s 4.03 × 102 a product alkene. As expected from this mechanism,
1090 8.0 × 10−4 s 3.96 × 102 2,4-DMP was the major product, and in most experi-
1006 8.0 × 10−4 s 3.62 × 101 ments the only product, formed from tetra-MCP iso-
1017 8.0 × 10−4 s 3.75 × 101 merization. Conditions that produced other detectable
1087 8.0 × 10−4 s 2.92 × 102 products are described below.
1062 8.0 × 10−4 s 1.53 × 102
1015 8.0 × 10−4 s 3.95 × 101
1098 8.0 × 10−4 s 2.14 × 102
1023 8.0 × 10−4 s 4.79 × 101
1004 8.0 × 10−4 s 2.95 × 102
1000 8.0 × 10−4 s 2.82 × 101
that the sample taken for analysis (compressed more Table II lists the reaction temperatures, times, and
than five-fold during the reaction) resided very close to tetra-MCP isomerization rate constants for the 30 ki-
the end plate where reaction time was measured, while netic runs in the static reactor and the shock tube, and
reacting. the data are displayed in Fig. 1. Linear least squares
regression of the data gives log10 (A, s−1 ) = 15.47
(±0.13), E a = 64.7 (±0.5) kcal/mol. The error lim-
Calculations
its represent one standard deviation; uncertainties at
Rate constants for the thermal isomerization of tetra- the 95% confidence level are twice as large. These re-
MCP were calculated from the extent of its conversion sults lie at the top of the ranges of log A and E a values
to 2,4-DMP, as determined from the GC peak heights, presented in the three earlier published experimental
corrected for measured sensitivity differences, of the studies [7,8,10], but within the probable error ranges
hydrocarbons in the product samples. Rate constants of those three studies. Figure 2 repeats the data presen-
were calculated from the integrated rate expression tation of Fig. 1, with the data from the three previous
for an irreversible first-order reaction. Reaction tem- studies added for comparison.
peratures were determined from the extent of conver- The isomerization of CP was used as the internal
sion of CP to propene or of CH to 1,3-butadiene plus thermometer in our earlier studies of other methylcy-
ethene, using the well-established Arrhenius param- clopropane isomerizations [2,3,6], but we were con-
eters for these irreversible first-order isomerizations: cerned that, in spite of the relatively high total pres-
E a = 65.0 kcal/mol, log (A, s−1 ) = 15.2 for CP [1] sures and reactant loadings in the shock tube, the CP
KINETICS OF THE THERMAL ISOMERIZATION OF 1,1,2,2-TETRAMETHYLCYCLOPROPANE 487
Table III Activation Parameters for Total Structural Isomerization Reactions (to All Product Isomers) for
Cyclopropane and Four Methylcyclopropanes
Reactant log10 (A, s−1 ) E a (kcal/mol) k700 K (s−1 ) k1100 K (s−1 ) E a ** Ref.
CP 15.20 65.0 0.8 × 10−5 1.9 × 102 65.0 [1]
MCP 15.37 64.4 1.8 × 10−5 3.8 × 102 63.8 [2]
di-MCP 15.04 61.8 5.6 × 10−5 5.8 × 102 62.3 [3]
tri-MCP 15.28 63.7 2.5 × 10−5 4.2 × 102 63.4 [6]
tetra-MCP 15.47 64.7 1.9 × 10−5 4.1 × 102 63.8 This work
Rate constants at 700 and 1100 K are taken from the least squares reduction of each data set. For the explanation of E a∗∗ see text.