7
16
ANIKEEV et al.
Table 2. Products of sulfate terpentine decomposition in su-
percritical ethanol
2. S. A. Osadchii and G. A. Tolstikov, Khim. Interesah
Ustoich. Razvit., No. 5, 79 (1997).
3
. R. E. Fuguitt and J. E. Hawkins, Chem. Soc. 67, 242
1945).
Composition
α-Pyronene
Content
330°C
380°C
(
–
0.3
79.4
0.3
1.2
4.1
–
2.2
0.3
8.2
0.3
–
4. J. J. Gajewski, I. Kuchuk, C. Hawkins, and R. Stine, Tet-
rahedron 58 (34), 6943 (2002).
Tricyclene
α-Pinene
5
6
. K. J. Crowley and S. G. Traynor, Tetrahedron 34 (18),
783 (1978).
2.6
2
α-Fenchene
Camphene
β-Pinene
0.3
0.4
1.4
–
. J. J. Gajewski and C. M. Hawkins, J. Am. Chem. Soc.
108 (4), 838 (1986).
1.4
2.5
7. D. Chouchi, D. Gougouillon, M. Courel, et al., Ind. Eng.
Chem. Res. 40, 2551 (2001).
β-Myrcene
β-Pyronene
0.9
0.7
14.7
11.1
1.0
44.7
4.3
4.2
9.0
8
9
. Y. Ikushima, Adv. Colloid Interface Sci. 71–72, 259
1997).
–
2.4
(
3
-Carene
10.8
0.2
2.9
–
11.0
0.8
. V. I. Anikeev, A. Yermakova, and M. Goto, Ind. Eng.
Chem. Res. 43, 8141 (2004).
p-Cymene
Limonene
44.0
21.3
7.2
10. V. I. Anikeev and A. Ermakova, Zh. Fiz. Khim. 77 (2),
65 (2003) [Russ. J. Phys. Chem. 77 (2), 211 (2003)].
1. B. T. Baliga and E. Whalley, Can. J. Chem. 9, 2453
1965).
2. R. Narayan and M. J. Antal, J. Am. Chem. Soc. 112,
927 (1990).
2
Alloocimene
Neoalloocimene
Other products
1
1
1
1
1
1
1
1
1
2
2
–
(
0.8
5.5
1
3. N. Akiya and P. E. Savage, J. Phys. Chem. A 104, 4441
The qualitative and quantitative composition of the
products of turpentine conversion in supercritical etha-
nol is listed in Table 2 for two temperatures. First, we
see that virtually complete transformation of α-pinene
occurs above 330°C. Secondly, an increase in the tem-
perature of the reaction substantially increases the yield
of α- and β-pyronenes and decreases the yield of alloo-
cimene.
(2000).
4. C. B. Roberts, J. Zhang, J. E. Chateauneuf, and J. F. Bren-
necke, J. Am. Chem. Soc. 117, 6553 (1995).
5. M. Klein,Y. G. Mentha, and L.A. Torry, Ind. Eng. Chem.
Res. 31, 182 (1992).
6. L. Zhou, C. Erkey, and A. Akgerman, AIChE J. 41, 2122
(1995).
7. J. C. Meyer, P.A. Marrone, and J. W. Tester,AIChE J. 41,
108 (1995).
8. Y. Guo andA. Akgerman, Ind. Eng. Chem. Res. 36, 4581
To summarize, our experimental study and mathe-
2
matical data processing showed that supercritical C1–
C alcohols are an effective reaction medium for the
3
(1997).
thermal isomerization of terpene compounds. For
instance, the rate of α-pinene isomerization in super-
critical ethanol is higher than the rate of isomerization
in the gas or liquid phase by several orders of magni-
tude, the selectivity with respect to the desired reaction
products remaining unchanged.
9. K. Tomita, S. Koda, and Y. Oshima, Ind. Eng. Chem.
Res. 41, 3341 (2002).
0. J. B. Ellington, K. M. Park, and J. F. Brennecke, Ind.
Eng. Chem. Res. 33, 956 (1994).
1. D. P. Roek, J. E. Chateauneuf, and J. F. Brennecke, Ind.
Eng. Chem. Res. 39, 3090 (2000).
2
2
2. J. Eser and S. Yu, Ind. Eng. Chem. Res. 36, 585 (1997).
ACKNOWLEDGMENTS
3. N. A. Collins, P. G. Debenedetti, and S. Sundaresan,
AIChE J. 34, 1211 (1988).
This work was financially supported by the Russian
Foundation for Basic Research, project nos. 05-08- 24. O. Kajimoto, Chem. Rev. 99, 355 (1999).
6
5437a and 06-08-00024a.
25. F. A. Carey and R. J. Sundberg, Advanced Organic
Chemistry, Part A: Structure and Mechanisms (Plenum,
New York, 1977).
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RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 81 No. 5 2007