Vaporization Enthalpies and Vapor Pressures of Some Insect

The appropriate use of insect pheromones is probably among the most sound ecological ways ... methyl decanoate, 110-42-9, Sigma-Aldrich, 0.99 ..... ru...
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Vaporization Enthalpies and Vapor Pressures of Some Insect Pheromones by Correlation Gas Chromatography Sarah Goodrich, Jasmina Hasanovic, Chase Gobble, and James S. Chickos* Department of Chemistry and Biochemistry, University of MissouriSt. Louis, St. Louis, Missouri, 63121, United States S Supporting Information *

ABSTRACT: The vaporization enthalpies and vapor pressures of the following insect pheromones at T/K = 298.15 have been evaluated by correlation gas chromatography: Z-8-dodecenyl acetate, Z-4-tridecenyl acetate, E-11-tetradecenyl acetate, E,E-9,11-tetradecadienyl acetate, Sethyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate, R,S-2-propynyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate, and Z-13-octadecenyl acetate. Also evaluated are vapor pressures as a function of temperature from T/K = 298.15 to 500 which have been fit to a third-order polynomial. Normal boiling temperatures are predicted by extrapolation. The results are compared to available literature values.

1. INTRODUCTION The appropriate use of insect pheromones is probably among the most sound ecological ways of controlling pests in the environment. The pheromones frequently target a specific insect or insects, and while they themselves may not be lethal, combined with appropriate strategies, their use can provide an effective means of controlling their populations. This article reports the vapor pressures and vaporization enthalpies of several pheromones as evaluated by correlation gas chromatography. The compounds studied include: Z-8-dodecenyl acetate, Z-4-tridecenyl acetate, E-11-tetradecenyl acetate, E,E-9,11tetradecadienyl acetate, ethyl-S-(2E,4E)-3,7,11-trimethyl-2,4dodecadienoate (S-hydroprene), R,S-2-propynyl (2E,4E)3,7,11-trimethyl-2,4-dodecadienoate (R,S-kinoprene), and Z13-octadecenyl acetate. The structures of all the target molecules are given in Figure 1. Z-8-Dodecenyl acetate is a component of the sex pheromone of several insects that include the macadamia nut borer (Cryptophlebia ombrodelta), the plum fruit moth (Cydia f unebrana), the oriental fruit moth (Grapholita molesta), and the koa seedworm (Cryptophlebia illepida).1 Z-4-Tridecenyl acetate is used to disrupt the sex pheromone of the Tomato Pin Worm (Keiferia lycopersicella).2 A mixture of E-11-tetradecenyl acetate and E,E-9,11tetradecadienyl acetate (LBAM), found combined in the pheromone and in the commercial material, has been used to control the light brown apple moth (Epiphyas postvittana). LBAM is used to disrupt the mating behavior of the moth.3 SEthyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate (hydroprene) is classified as an insect growth regulator and is considered by the US Environmental Protection Agency as a biopesticide. It is used against cockroaches, beetles, and moths by disrupting normal development and growth.4 Structurally © 2016 American Chemical Society

related S-2-propynyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate (S-kinoprene) is also an insect growth regulator used on other insect species.5

2. EXPERIMENTAL SECTION 2.1. Materials. The supplier and purity of the materials used in this study are provided in Table 1. The purities of the standards are values provided by the supplier. Analyses for some of the target substances were not provided by the suppliers. These were analyzed by gas chromatography. Chemical purity is not a concern with correlation gas chromatography since the chromatography generally separates the impurities. Even in cases where two substances have exhibited identical retention times over the entire temperature range studied, the results suggest that any interference caused by the overlap on the thermochemical properties evaluated were minor and less than the normal experimental uncertainty.6 LBAM pheromone was available commercially as a mixture of E-11-tetradecenyl acetate (79.2%) and E,E-9,11-tetradecadienyl acetate (3.9−5.0%). A total of three peaks at 8.87, 8.97, and 10.46 min were observed in the GCMS chromatogram. In addition to the major peak at 8.87 min, the other two peaks were of comparable intensity. The major peak was identified by the NIST database as E-11-tetradecenyl acetate. The peak at 8.97 was also identified as E-11-tetradecenyl acetate by the software and is most likely either a positional or stereoisomer of 11-tetradecenyl acetate. The peak at 10.46 min was identified by the software as an isomer of E,E-9,11-tetradecadienyl acetate, namely, Z,E-9,12-tetradecadienyl acetate. Given that Received: October 21, 2015 Accepted: March 7, 2016 Published: March 16, 2016 1524

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Figure 1. Structures of the insect pheromones. From left to right, top to bottom: Z-8-dodecenyl acetate, Z-4-tridecenyl acetate, E-11-tetradecenyl acetate, E,E09,11-tetradecadienyl acetate, (S)-ethyl-(2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate, 2-propynyl0(2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate, and Z 13-octadecenyl acetate.

specifically specified by the supplier, we have interpreted this to mean that the sample was racemic. 2.2. Methods. 2.2.1. GCMS Experiments. GC-MS analyses were carried out using a Hewlett-Packard GC/MS System model 5698A system operating in the EI mode at 70 eV, equipped with a Supelco SLB-5 MS capillary column (30 m × 0.25 mm; 0.5 μm film thickness) using He as the carrier at an oven temperature, T/K = 483. The mass spectra were compared with those available in the NIST/EPA/NIH MS library. Comparison spectra are provided in the Supporting Information. 2.2.2. Vaporization Enthalpies and Vapor Pressures by Correlation Gas Chromatography. Experiments were conducted on an HP 5890 gas chromatograph running HP Chemstation on a 15 m Supelco SPBE capillary column, (0.32 mm I. D., 1 μm film thickness) at a split ratio of approximately 100/1. The carrier gas used was helium, and the temperature, controlled by the instrument to T/K = ± 0.1 K, was independently monitored by a Fluke digital thermometer. All analyses were performed over a T/K = 30 temperature range at T/K = 5 intervals in a sequential manner. The standards and targets were injected simultaneously. Retention times are provided in the Supporting Information (Tables S1A−S4A). The residence time on the column, ta, was calculated from the retention time of each analyte and the retention time of a nonretained reference by difference. At the temperatures of these experiments, the solvent was not retained and was used as the nonretained reference. Plots of ln(t0/ta) versus 1/T, where t0 is the reference time 60 s, resulted in a straight line (r2 > 0.99) with a slope numerically equal to the molar enthalpy of transfer of the analyte from the stationary phase of the column to the gas phase divided by the gas constant, −ΔtrnHm(Tm)/R, at the mean temperature of the experiments, Tm. The vaporization enthalpy of the analyte is related to ΔtrnHm(Tm) by eq 1.7

Table 1. Origin and Analysis of the Standards and Targets CAS Registry No.

supplier

Z-8-dodecenyl acetate Z-4-tridecenyl acetate E-11-tetradecenyl acetate

28079-04-1 65954-19-0 33189-72-9

Bedoukian Bedoukian Bedoukian

E,E-9,11-tetradecadienyl acetate S-(+)-ethyl-(2E,4E)-3,7,11trimethyl-2,4dodecadienoate R,S-2-propynyl (2E,4E)3,7,11-trimethyl-2,4dodecadienoate Z-13-octadecenyl acetate standards methyl decanoate

54664-98-1

Bedoukian

65733-18-8

Fluka

42588-37-4

Chem Service

0.987b

60037-58-3

Bedoukian

0.946b

110-42-9

SigmaAldrich SigmaAldrich SigmaAldrich SigmaAldrich SigmaAldrich SigmaAldrich SigmaAldrich

0.99

target

methyl dodecanoate

111-82-0

methyl tetradecanoate

124-10-7

methyl pentadecanoate

7132-64-1

methyl octadecanoate

112-61-8

methyl eicosanoate

1120-28-1

methyl heneicosanoate

6064-90-0

a

mass fraction analysis >0.96 0.96 E11: 0.79; 2E,4E: 0.04a 2E,4E: 0.04; E11: 0.79a 0.95b

>0.97 0.99 0.99 0.97 0.99 0.99

See Section 2.1 for more details. bAnalysis by GC.

the mass spectrum of E,E-9,11-tetradecadienyl acetate is not in the database, this peak was assigned as E,E-9,11-tetradecadienyl acetate. Kinoprene is reported by the supplier as a mixture of isomers. A single sharp peak observed in our gas chromatographic analysis with a mass fraction better than 0.98 was consistent with the purity stated by the supplier. Although not

Δtrn Hm(Tm) = Δl g Hm(Tm) + Δintr Hm(Tm) 1525

(1)

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Table 2. Vaporization Enthalpies and Vapor Pressure Constants for eqs 2 and 3 (po = 101 325) ΔlgHm(298 K) (kJ·mol−1)

standards eq 2: θ/K = 298.15a

66.10 ± 0.17 76.59 ± 0.41 85.94 ± 0.76 89.29 ± 0.79 105.7 ± 3.8 116.43 ± 1.5 ΔlgHm(298 K) (kJ·mol−1)

methyl decanoate methyl dodecanoate methyl tetradecanoate methyl pentadecanoate methyl octadecanoate methyl eicosanoate eq 3b

−4.26 ± 0.05 1.33 ± 0.10 6.73 ± 0.15 9.07 ± 0.4 17.68 ± 0.23 22.74 ± 0.27 B (K)

A

120.90 ± 1.8

methyl heneicosanoate a

ΔlgGm(298 K) (kJ·mol−1)

1.2615

ΔlgCp(298 K) (J·mol−1·K−1)

10−4 C (K2)

−83 −101 −119 −128 −155 −172 10−6 D (K3)

−523.876

5943.62

420.126

From ref 8. bFrom ref 9.

Table 3. Correlation of Vaporization Enthalpies (po/Pa = 101 325) with Enthalpies of Transfera Run 1 methyl decanoate methyl dodecanoate Z-8-dodecenyl acetate Z-4-tridecen-1-yl acetate methyl tetradecanoate methyl pentadecanoate

−slope T/K 5606.9 6450.7 6756.1 7058.6 7303.9 7727.7

± ± ± ± ± ±

20 30 30 30 40 40

intercept 12.544 13.544 13.885 14.210 14.584 15.104

± ± ± ± ± ±

0.06 0.06 0.07 0.07 0.08 0.08

ΔHtrn(450 K) (kJ·mol−1)

ΔlgHm(298 K) (kJ·mol−1) (lit)

± ± ± ± ± ±

66.10 ± 0.17 76.59 ± 0.41

46.61 53.63 56.17 58.68 60.72 64.24

Δl g Hm(298.15 K)/kJ·mol−1 = (1.328 ± 0.065)ΔHtrn(450 K) + (4.72 ± 3.7) r2 = 0.9551 Run 3

−slope T/K

intercept

0.22 0.23 0.26 0.27 0.29 0.31

Uncertainties represent one standard deviation. trimethyl-2,4-dodecadienoate.

b

66.6 75.9 79.3 82.6 85.3 90.0

± ± ± ± ± ±

4.8 5.1 5.3 5.4 5.5 5.6

(5)

ΔHtrn(449 K) (kJ·mol−1)

methyl tetradecanoate 6929.4 ± 40 13.906 ± 0.08 57.61 E-11-tetradecenyl acetate 7265.2 ± 40 14.327 ± 0.09 60.40 methyl pentadecanoate 7321.9 ± 40 14.363 ± 0.09 60.87 E,E-9,11-retradecadienyl acetate 7480.7 ± 40 14.506 ± 0.09 62.19 S-hydropreneb 7487.1 ± 40 15.783 ± 0.09 70.80 R,S-kinoprenec 7927.4 ± 50 15.049 ± 0.1 65.90 methyl octadecanoate 8516.0 ± 50 15.783 ± 0.1 62.24 Z-13-octadecen-1-yl acetate 8757.9 ± 50 16.029 ± 0.1 72.81 methyl eicosanoate 9317.2 ± 50 16.754 ± 0.11 77.46 methyl henicosanoate −9717.2 ± 60 17.241 ± 0.12 80.78 ΔlgHm(298.15 K)/(kJ·mol−1) = (1.552 ± 0.038)ΔHtrn(449 K) + (4.21 ± 2.67) (6) r2 = 0.9982 a

85.94 ± 0.76 89.29 ± 0.79

ΔlgHm(298 K) (kJ·mol−1) (calc)

± ± ± ± ± ± ± ± ± ±

0.34 0.35 0.36 0.36 0.36 0.39 0.41 0.41 0.45 0.47

ΔlgHm(298 K) (kJ·mol−1) (lit)

ΔlgHm(298 K) (kJ·mol−1) (calc)

85.94 ± 0.76

85.2 ± 3.5 89.6 ± 3.5 90.3 ± 3.5 92.3 ± 3.6 92.4 ± 3.6 98.1 ± 3.7 105.7 ± 3.8 108.8 ± 3.9 116.0 ± 4.0 121.2 ± 4.1

89.29 ± 0.79

105.87 ± 1.37 116.43 ± 1.5 120.90 ± 1.8

S-(+)-Ethyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate. cR,S-2-Propynyl (2E,4E)-3,7,11-

Provided appropriate compounds with reliable vaporization enthalpies are chosen preferably that bracket the targets, a second plot of ΔlgHm(298.15 K) versus ΔtrnHm(Tm) of the standards is also linear. The equation of the line combined with ΔtrnHm(Tm) values of the targets affords the vaporization enthalpy of the latter at the reference temperature, T/K = 298.15. If the vapor pressures of the standards are also known, plots of ln(p/po) versus ln(t0/ta) are also found to be linear, frequently as a function of temperature. The vapor pressure of the targets can then be evaluated using a similar protocol. The term po refers to the reference pressure, frequently po/Pa = 101 325. 2.3. Vaporization Enthalpy and Vapor Pressure Standards. The standards used in these experiments and their vaporization enthalpies and constants for calculation of their vapor pressures, eqs 2 and 3, are provided in Table 2. The constants used for the Clarke and Glew equation, eq 2, are those for θ /K = 298.15.8 The constants for eq 3 for methyl heneicosanoate were derived previously from standards whose vapor pressures were calculated from eq 2 but evaluated by correlation gas chromatography.9

R ln(p /po ) = Δl g H °(θ)(1/θ − 1/T ) − Δl g G°(θ )/θ + Δl g Cp(θ ){θ /T − 1 + ln(T /θ }

(2)

ln(p /po ) = A + B(K) × T −1 + C(K2) × T −2 + D(K3) × T −3

(3)

2.4. Uncertainties. All uncertainties refer to one standard deviation unless noted otherwise. Uncertainties in ΔlgHm(298.15 K) were derived from the uncertainty in both the slope and intercept as (σ12 + σ22...)0.5. Vapor pressures evaluated as a function of temperature were fit by nonlinear least-squares. Uncertainties associated with logarithm terms are reported as an average of the two values evaluated. Uncertainties in boiling temperatures were evaluated by setting ln(p/po) = 0 and solved by standard methods. Details are provided in the Supporting Information in the section dealing with estimation of errors. The standard deviations reported are equivalent to the standards uncertainties as defined by the Guide to the Expression of Uncertainty in Measurement.10 2.5. Estimation of Vaporization Enthalpies. Since the vaporization enthalpies of most of the esters studied are not 1526

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Table 4. A Summary of the Vaporization Enthalpies in kJ·mol−1 (po/Pa = 101325) of Runs 1−4 run targets

1

2

Z-8-dodecenyl acetate Z-4-tridecen-1-yl acetate E-11-tetradecenyl acetate E, E-9,11-tetradecadienyl acetate S-hydroprenec R,S-kinoprened Z-13-octadecen-1-yl acetate standards

79.3 ± 5.3 82.6 ± 5.4

79.3 ± 5.5 82.7 ± 5.6

methyl methyl methyl methyl methyl methyl methyl

decanoate dodecanoate tetradecanoate pentadecanoate octadecanoate eicosanoate henicosanoate

1 66.6 75.9 85.3 90.0

± ± ± ±

3

89.6 ± 3.5 92.3 ± 3.6 92.4 ± 3.6 98.1 ± 3.7 108.8 ± 3.9 3

2 4.8 5.1 5.5 5.6

66.6 75.9 85.3 90.0

± ± ± ±

5.0 5.4 5.7 5.9

85.2 ± 3.5 90.3 ± 3.5 105.7 ± 3.8 116.0 ± 4.0 121.2 ± 4.1

4

89.6 ± 3.5 92.3 ± 3.5 92.5 ± 3.6 98.1 ± 3.6 109.0 ± 3.8 4

85.2 ± 3.4 90.3 ± 3.5 105.8 ± 3.8 116.1 ± 4.0 121.1 ± 4.1

averagea 79.3 ± 5.4 82.7 ± 5.5 89.6 ± 3.5 92.3 ± 3.6 92.4 ± 3.6 98.1 ± 3.7 108.8 ± 3.9 averagea 66.6 ± 4.9 75.9 ± 5.3 85.3 ± 4.5 90.2 ± 4.6 105.8 ± 3.8 116.0 ± 4.0 121.2 ± 4.1

estb 79.2 ± 83.9 ± 88.5 ± 88.5 ± 89.2 ± 93.9 ± 108.7e lit.f

4.0 4.2 4.4 4.4 4.5 4.7

66.10 ± 0.17 76.59 ± 0.41 85.94 ± 0.76 89.29 ± 0.79 89.29 ± 0.79 116.43 ± 1.54 120.9 ± 1.8g

a

The uncertainty reported is an average of the standard deviation of runs 1−4; all uncertainties are one standard deviation. bEstimated value, ref 11, unless noted otherwise. cS-Ethyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate. dR,S-2-Propynyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate. eRef 12. fRef 8 unless noted otherwise. gRef 9.

agreement between the two results using two different sets of standards confirms this result. 3.2. Vapor Pressures. As mentioned above, correlations of ln(t0/ta) with ln(p/po) are also linear. Table 5 illustrates the effect of correlating ln(p/po) with ln(t0/ta) at T/K = 298.15. Since duplicate runs of both sets of correlations were run under similar conditions, calculated values of t0/ta from runs 1 and 2 were averaged and correlated as ln(t0/ta)avg; runs 3 and 4 were treated similarly. Equations 7 and 8 below each respective set of runs characterizes the quality of the fit. In addition to T/K = 298.15, this correlation was repeated at T/K = 10 intervals over the temperature range T/K = (310−500). The correlation coefficient, r2, exceeded 0.99 for both sets of runs over the entire temperature range correlated. The resulting data were fit to a third-order polynomial, eq 3, by nonlinear least-squares. The constants for eq 3 are provided in Table 6 for the targets. Values for both standards and targets and the vapor pressures and their uncertainties evaluated at each temperature are available in the Supporting Information (Tables S5, S6, and S7). Boiling temperatures at p/Pa = 101 325 were estimated by solving for T when ln(p/po) = 0. The resulting vapor pressures at T/K = 298.15 and normal boiling temperatures at p/Pa = 101 325 obtained by extrapolation are reported in Table 7. Some comparisons are also presented at reduced pressures. Comparisons with experimental values or with estimated values are included whenever available. Estimated values are reported in italics. Vapor pressure comparisons in Table 7 for Z-8-dodecenyl acetate and Z-4-tridecenyl acetate are estimated values, similarly for E-11-tetradecenyl acetate. Comparisons with estimated values are not terribly good. Comparisons with literature values for the remaining targets become progressively better. The vapor pressures of the standards in runs 1/2 and 3/4 were reproduced within 1.0−5.5% and 5.0−7.0%, of their literature value, respectively, over the temperature range, T/K = 298.15− 500. Also noteworthy is that the literature vapor pressure of Z13-octadecenyl acetate also evaluated by gas chromatography using alkanes as standards12 agrees quite well with the results from this work. Boiling point comparisons for four out of five experimental values reported for the targets are at reduced pressures. No

available, a simple four-parameter equation, eq 4, was used to provide an approximate value.11 The term nC identifies the total number of carbon atoms, nQ refers to the number of quaternary sp3 hybridized carbon atoms, b provides the contribution the heteroatoms of the functional group (bester = 10.5 kJ·mol−1), and C is a branching correction for each carbon branch on an sp3 hybridized carbon (−2.0 kJ·mol−1/branch). Δl g Hm(298.15K)/kJ ·mol−1 = 4.69(nC − nQ ) + 1.3nQ + 3.0 + b + C

(4)

3. RESULTS AND DISCUSSION 3.1. Vaporization Enthalpies. Two sets of correlations were performed, each in duplicate runs. Vaporization enthalpy results for runs 1 and 3 are shown in Table 3. Equations 5 and 6 provided below each respective table for runs 1 and 3 describe the relationship between ΔtrnHm(Tm) and ΔlgHm(298.15 K) and the correlation coefficient provides a measure of the scatter of the data. The remaining runs are provided in the Supporting Information. Table 4 summarizes results from all four runs. Comparisons of the experimental results with estimated values also included in Table 4 are generally within experimental error. The only literature value that that we could locate was for Z-13octadecen-1-yl acetate, 108.7 kJ·mol−1.12 This value for Z-13octadecen-1-yl acetate was also obtained by a similar gas chromatographic technique using a series of alkanes for reference according to Hamilton’s method13 and compares to a value of (108.8 ± 3.9) evaluated in this work. In this case agreement between the two methods is very good. It is often difficult to find sufficient amounts of quality enthalpy data that can be used as standards for substances containing certain functional groups and particularly for more complex substances containing multiple functionality. The demonstration that other functional groups can function as surrogates, offers a potential solution to this problem. Z-13Octadecen-1-yl acetate was chosen for evaluation by correlation gas chromatography also using esters as standards as a test. It has been shown recently that ΔtrnHm(Tm) of alkanes correlate quite well with ΔlgHm (298.15 K) of monoesters.6 The 1527

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Table 5. Correlations between ln(to/ta)avg and Liquid ln(p/po)exp Values at T/K = 298.15 for All Runs, po = 101325; Uncertainties are One Standard Deviation run 1 (top)/run 2 (bottom) methyl decanoate methyl dodecanoate Z-8-dodecenyl acetate Z-4-tridecen-1-yl acetate methyl tetradecanoate methyl pentadecanoate

−slope/K

intercept

ln(t0/ta)avg

ln(p/po)exp

ln(p/p0)calc

5606.9 5665.7 6450.7 6512.1 6756.1 6825.2 7058.6 7134.4 7303.9 7379.0 7727.7 7810.7

12.544 12.695 13.544 13.705 13.885 14.064 14.210 14.406 14.584 14.779 15.104 15.320

−6.285

−9.807

−9.85 ± 0.24

−8.114

−12.063

−12.02 ± 0.27

ln(p /po ) = (1.185 ± 0.022) ln(to/ta) − (2.40 ± 0.197) r = 0.9993 run 3 (top)/run 4 (bottom) −slope/K

−8.801

−12.83 ± 0.28

−9.493

−13.65 ± 0.29

−9.942

−14.241

−14.18 ± 0.29

−10.845

−15.185

−15.25 ± 0.31

intercept

ln(t0/ta)avg

ln(p/po)exp

ln(p/po)calc

13.906 13.834 14.327 14.258 14.363 14.292 14.559 14.481 14.506 14.443 15.049 14.971 15.783 15.711 16.029 15.977 16.754 16.665 17.241 17.137

−9.293

−14.241

−14.18 ± 0.27

(7)

2

methyl tetradecanoate E-11-tetradecenyl acetate methyl pentadecanoate E,E-9,11-tetradecadienyl acetate S-hydroprenea R,S-kinopreneb methyl octadecanoate Z-13-octadecen-1-yl acetate methyl eicosanoate methyl henicosanoate

6929.4 6883.3 7265.2 7220.3 7321.9 7275.7 7480.7 7431.2 7487.1 7445.0 7927.4 7877.6 8516.0 8468.9 8757.9 8721.4 9317.2 9262.2 9717.2 −9655.0

ln(p /po ) = (1.278 ± 0.017) ln(to/ta) − (2.305 ± 0.215) r2 = 0.9994 a

−9.999 −10.152

−15.08 ± 0.27 −15.185

−15.28 ± 0.28

−10.486

−15.71 ± 0.28

−10.566

−15.81 ± 0.28

−11.494

−16.99 ± 0.29

−12.736

−18.659

−18.58 ± 0.31

−13.31

−19.32 ± 0.31

−14.447

−20.7

−20.77 ± 0.33

−15.297

−21.885

−21.86 ± 34

(8)

S-Ethyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate. bR,S-2-Propynyl-(2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate.

Table 6. Constants for the Third-Order Polynomial eq 3 for Evaluated from Runs 1/2 and Runs 3/4a targets: runs 1/2

A

B (K)

10−6 C (K2)

10−6 D (K3)

Z-8-dodecenyl acetate Z-4-tridecenyl acetate targets: runs 3/4

4.8377 ± 0.1147 4.3471 ± 0.1292 A

1722.17 ± 132.54 2162.00 ± 149.37 B (K)

−2.906 ± 0.050 −3.137 ± 0.057 10−6 C (K2)

245.180 ± 6.315 266.067 ± 7.116 10−6 D (K3)

E-11-tetradecenyl acetate E,E-9,11-tetradecadienyl acetate S-hydropreneb R,S-kinoprenec Z-13-octadecen-1-yl acetate

4.5304 4.2442 4.0327 3.6966 2.9275

± ± ± ± ±

0.1307 0.1298 0.1359 0.1261 0.1111

2111.77 2434.36 2602.90 3069.85 4061.90

± ± ± ± ±

151.09 149.96 157.10 145.71 128.36

−3.301 −3.476 −3.540 −3.828 −4.415

± ± ± ± ±

0.057 0.057 0.06 0.055 0.049

276.766 291.272 298.134 320.001 365.763

± ± ± ± ±

7.198 7.145 7.485 6.942 6.116

a

Uncertainties are one standard deviation, p0/Pa = 101 325. bS-Ethyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate. cR,S-2-Propynyl-(2E,4E)-3,7,11trimethyl-2,4-dodecadienoate.

4. SUMMARY

values could be found for 2-propynyl (2E,4E)-3,7,11-trimethyl-

The vaporization enthalpies and vapor pressures of the insect pheromones evaluated in this work are summarized in Table 8. Also included are boiling temperatures predicted at p/Pa = 101 325. The results for LBAM are a demonstration of this

2,4-dodecadienoate, while the value for Z-13-octadecenyl acetate is an estimate. 1528

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Table 7. A Summary of Liquid/Subcooled Liquid Vapor Pressures and Normal Boiling Temperatures (p = 101 325 Pa) and Comparison with Experimental or Estimated Values (in Italics); Uncertainties Are One Standard Deviation run 1/2 targets

(102)p(l)/Pa, 298.15 K, this work

(102)p(l)/Pa, 298.15 K, lit

Tb/K calc

Tb/K lit

Z-8-dodecenyl acetate Z-4-tridecenyl acetate standards

27 ± 7.6 12 ± 3.5 (102)p(l)/Pa, 298.15 K, this work

55a 21a (102)p(l)/Pa, 298.15 K, lit

557.8 ± 1.2, 386b 573.9 ± 1.5 Tb/K calc

376b,c 574.2a Tb/K lit

methyl methyl methyl methyl

540 ± 130 61 ± 17 7.0 ± 0.21 2.4 ± 0.76

decanoate dodecanoate tetradecanoate pentadecanoate run 3/4 targets

560 59 6.6 2.6 (104)p(l)/Pa, 298.15 K, calc (104)p(l)/Pa, 298.15 K,

E-11-tetradecenyl acetate E,E-9,11-tetradecadienyl acetate S-ethyl-(2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate R,S-2-propynyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate Z-13-octadecenyl acetate standards methyl methyl methyl methyl methyl

tetradecanoate pentadecanoate octadecanoate eicosanoate heneicosanoate

4

(10 )p(l)/Pa, 298.15 K, calc

280 ± 80 150 ± 43 140 ± 39 42 ± 12 21 ± 6.9m 4.1 ± 1.3 (104)p(l)/Pa, 298.15 K,

700 ± 190 230 ± 66 8.6 ± 2.7 0.97 ± 0.32 0.33 ± 0.11

1200a 920a 250d 9.6m,n 4.6p lit

660 260 8.0 1.0 0.32

505.2 542.9 578.7 596.1 lit

± ± ± ±

1.0 1.0 1.3 1.6, 419.7e Tb/K calc

591.3 600.3 604.3 618.1

± ± ± ±

1.5, 335g 1.6, 353i 1.8, 398.8k 1.9

646.4 ± 2.3 Tb/K calc 581.1 ± 0.1 595 ± 1.6, 420e 457 ± 2.0 494.6 ± 2.2r 673 ± 2.4

497.2d 540.2d 568.2d 418.2e,f Tb/K lit 353g,h 373i,j 412k,l NAo 652.7 ± 11q Tb/K lit 568.2d 418.2e,f 455.2m 488.2r,s 656a

a

Estimated, ref 14. bAt p/Pa = 267. cRef 15. dRef 16. eAt p/Pa = 400. fExperimental, ref 14. gAt p/Pa = 1.33 Pa. hRef 17. iAt p/Pa = 4. jRef 18. kAt p/Pa = 93.3. lRef 19. mVapor pressure at T/K = 293.2. nRef 20. oNot available. pRef 12. qPredicted value; SciFinder Scholar. rAt p/Pa = 1333. sRef 21.

Table 8. A Summary of Vaporization Enthalpies and Vapor Pressures at T/K = 298.15 and Estimated Boiling Temperatures at po/Pa = 101 325; Uncertainties Are One Standard Deviation ΔlgHm(298 K) (kJ·mol−1)

(104)p(l)/Pa, 298.15 K

79.3 ± 5.4 82.7 ± 5.5 89.6 ± 3.5 92.3 ± 3.6 92.4 ± 3.6 98.1 ± 3.7 108.8 ± 3.9

2700 ± 760 1200 ± 80 280 ± 300 150 ± 40 140 ± 40 40 ± 12 4.1 ± 1.3

Z-8-dodecenyl acetate Z-4-tridecenyl acetate E-11-tetradecenyl acetate E,E-9,11-Tetradecadienyl acetate S-ethyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate R,S-2-propynyl-(2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate Z-13-octadecen-1-yl acetate

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technique on a commercial product that is available as a mixture. While this is not the only example of using this technique in this fashion,22 we are not aware of any other technique currently in use capable of obtaining pure component properties directly from the same components in a mixture.”

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± 1.5 ± 1.5 ± 1.6 ± 1.9 ± 2.3

REFERENCES

(1) The Manual of Biocontrol Agents, 2014. http://www.bcpc.org/ shop/files/library/dodecenyl.pdf; accessed: 8/21/15. (2) http://www.epa.gov/pesticides/chem_search/reg_actions/ reregistration/red_PC-121902_1-Sep-96.pdf; accessed: 8/21/15. (3) Bellas, T. E.; Bartell, R. J.; Hill, A. Identification of two components of the sex pheromone of the moth, Epiphyas postvittana (Lepidoptera, Tortricidae). J. Chem. Ecol. 1983, 9, 503−511. (4) National Pesticide Information Center; http://npic.orst.edu/ npicfact.htm; accessed: 10/13/15. (5) http://www3.epa.gov/pesticides/chem_search/reg_actions/ registration/fs_G-107_06-Dec-01.pdf; accessed: 10/14/15. (6) Gobble, C.; Chickos, J. A Comparison of Results by Correlation Gas Chromatography With Another Gas Chromatographic Retention Time Technique. The Effects of Retention Time Coincidence On Vaporization Enthalpy and Vapor Pressure. J. Chem. Eng. Data 2015, 60, 2739−2748. (7) Peacock, L. A.; Fuchs, R. Enthalpy of Vaporization Measurements by Gas Chromatography. J. Am. Chem. Soc. 1977, 99, 5524−5525. (8) van Genderen, A. C. G.; van Miltenburg, J. C.; Blok, J. G.; van Bommel, M. J.; van Ekeren, P. J.; van den Berg, G. J. K.; Oonk, H. A. J. Liquid-vapour equilibria of the methyl esters of alkanoic acids: vapour pressure as a function of temperature and standard thermodynamic function changes. Fluid Phase Equilib. 2002, 202, 109−120.

ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.5b00892.

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Tb/K calc 557.8 573.9 591.3 600.3 604.3 618.1 646.4

Tables of the experimental retention times and other tables described in the text (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest. 1529

DOI: 10.1021/acs.jced.5b00892 J. Chem. Eng. Data 2016, 61, 1524−1530

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(9) Chickos, J. S.; Zhao, H.; Nichols, G. The vaporization enthalpies and vapor pressures of a series of fatty acid methyl esters from C21 to C23, C25 to C29 by correlation - gas chromatography. Thermochim. Acta 2004, 424, 111−121. (10) http://www.bipm.org/en/publications/guides/gum.html; accessed 12/29/15. (11) Chickos, J. S. In Computational Thermochemistry Prediction and Estimation of Molecular Thermodynamics; Irikura, K. K., Frurip, D. J., Eds.; ACS Symposium Series 677; American Chemical Society: Washington, DC, 1996; Chapter 4. (12) Koutek, B.; Hoskovec, M.; Vrkocova, P.; Feltl, L. Gas chromatographic determination of vapour pressures of pheromone acetates, a reinvestigation. J. Chromatogr. A 1997, 759, 93−109. (13) Hamilton, D. J. Gas chromatographic measurement of volatility of herbicide esters. J. Chromatogr. A 1980, 195, 75−83. (14) Evaluated using the EPI Suite version 4.11 (Estimation Programs Interface). The EPI Suite can be downloaded at http:// www.epa.gov/oppt/exposure/pubs/episuitedl.htm; accessed: 9/10/15. (15) Zakharkin, L. I.; Zhigareva, G. G.; Petrushkina, E. Synthesis of (8Z)-dodecenyl-1-acetate and (9Z)-tetradecen-1-al from 1,1,9-trichloro-1-nonene. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya 1981, 2131−2; from SciFinder Scholar; https://scifinder.cas.org/ scifinder/; accessed: 12/23/15. (16) Hazardous Substances Data Bank, Chemical and Physical Properties. http://toxnet.nlm.nih.gov/cgi-bin/sis/htmlgen?HSDB; accessed: 9/10/15. (17) Popovici, N. A facile and convenient method for insect sex pheromone synthesis. Acta Universitatis Cibiniensis, Seria F: Chemia 2007, 10, 67−75; from SciFinder Scholar; https://scifinder.cas.org/ scifinder/; accessed: 12/23/15. (18) Ceskis, B.; Ivanova, N. M.; Moiseenkov, A. M.; Nefedov, O. M. Simple synthesis of acetogenin transoid insect pheromones based on acetylcyclopropane. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya 1991, 7, 1555−62; from SciFinder Scholar. (19) http://www.sigmaaldrich.com/MSDS/: S-hydroprene; accessed: 12/23/15. (20) http://chem.sis.nlm.nih.gov/chemidplus/rn/42588-37-4; accessed: 9/10/15. (21) Eckel, W. P.; Kind, T. Use of boiling point-Lee retention index correlation for rapid review of gas chromatography-mass spectrometry data. Eckel, W. P.; Kind, T. Anal. Chim. Acta 2003, 494, 235−243. (22) Simmons, D.; Gobble, C.; Chickos, J. Vapor pressure and enthalpy of vaporization of oil of catnip by correlation gas chromatography. J. Chem. Thermodyn. 2016, 92, 126−131.

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DOI: 10.1021/acs.jced.5b00892 J. Chem. Eng. Data 2016, 61, 1524−1530