6
Tetrahedron
A quantitative agreement between theory and experiment was
compute due to incomplete electron correlation energy account
ACCEPTED MANUSCRIPT
achieved for the gas-phase cyclohexene oxidation with N2O.
The observed difference in the contribution of the cleavage
route for cis- and trans- isomers of olefins is responsible for
different behavior of the polydienes containing cis- or trans- 1,4-
butadiene units with respect to the cleavage during their
ketonization with nitrous oxide.
and finite size of the basis set.
All calculations were performed with the Gaussian 09
software.15 Visualization of the results was performed using the
MOLDEN program.16
Acknowledgements
4. Experimental Section
This work was supported by the Russian Foundation for Basic
Research (Grant No. 14-03-31052 mol_а) and by Russian
Academy of Sciences and Federal Agency of Scientific
Organizations (project V.44.2.3).
4.1. Chemicals
Cis-3-heptene (96%), trans-3-heptene (99%), and cyclohexane
(99.9%) were purchased from Sigma-Aldrich. Medical grade
nitrous oxide (99.8%) was purchased from Cherepovets Azot
Plant.
References and notes
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Today., 2005, 100, 115-131; (b) J.L. Motz, H. Heinichen, W.F.
Holderich, J. Molec. Catal. A, 1998, 136, 175-184; (c) D.P.
Ivanov, L.V. Pirutko, G.I. Panov, J. Catal., 2014, 311, 424–432;
(d) G. Kiefer, L. Jeanbourquin, K. Severin, Angew. Chem. Int. Ed.,
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Hashimoto, Y. Kitaichi, K. Suzuki, T. Ikeno, Chem. Lett., 2001,
4.2. Typical procedure for oxidation reaction
The liquid phase oxidation of cis-3-heptene or trans-3-heptene
with nitrous oxide was carried out using a 25 ml Parr reactor
equipped with a stirrer. In a typical experiment, a solution
containing 0.005 mol of 3-heptene and 0.067 mol of cyclohexane
(a solvent) was loaded to the reactor. To remove air, the reactor
was purged with helium and then filled with 0.08 mol N2O by the
method described elsewhere.7 The reactor was heated at a 6
K/min ramp to the required reaction temperature and kept for 6-
24 h. After termination of the reaction, the reactor was cooled to
room temperature and the pressure was slowly released. The
reaction products were analyzed by the 13C NMR method. The
spectra were recorded at 100.61 MHz with a Bruker Avance
spectrometer. 13C NMR spectral data for сis-3-heptene, trans-3-
heptene and the reaction products were as follows:
30,
268-269; (g) T.L. Stuchinskaya, M. Musawir, E.F.
Kozhevnikova, I.V. Kozhevnikov, J. Catal., 2005, 231, 41–47;
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F.S. Bridson-Jones; G.D. Buckley; L.H. Cross, A.P. Driver,
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React. Kinet. Catal. Lett., 2002, 76, 401-406; (b) K.A. Dubkov,
G.I. Panov, E.V. Starokon, V.N. Parmon, React. Kinet. Catal.
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Babushkin, V. N. Parmon, G. I. Panov, Adv. Synth. Catal., 2004,
346, 268-274; (d) I. Hermans, B. Moens, J. Peeters, P. Jacobs, B.
Sels, Phys. Chem. Chem. Phys., 2007, 9, 4269-4274; (e) I.
Hermans, K. Janssen, B. Moens, A. Philippaerts, B. Van Berlo, J.
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Heterogeneous Oxidation Catalysis: Design, Reactions and
Characterization (Ed. Noritaka Mizuno), 2009, WILEY-VCH,
Weinheim, pp 217-252; (g) D.P. Ivanov, K.A. Dubkov, S.V.
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4166-4173.
cis-3-Heptene (1): 131.43, 128.72, 29.27, 23.04, 20.58, 14.04,
13.40
trans-3-Heptene (2): 132.00, 128.96, 34.90, 25.79, 22.90, 13.75,
13.28
3-Heptanone (3): 206.14 (C=O, C3), 41.64 (CH2, C4), 35.38
(CH2, C2), 26.01 (CH2, C5), 22.55 (CH2, C6), 13.56 (CH3, C7),
7.34 (CH3, C1).
4-Heptanone (4): 205.70 (1C, C=O, C4), 44.34 (2C, CH2, C3 and
C5), 17.15 (2C, CH2, C2 and C6), 13.44 (2C, CH3, C1 and C7).
2-Ethylpentanal (5): 200.70 (CHO, C1), 53.22 (CH, C2), 30.90
(CH2, C3), 22.00 (CH2, Et), 20.41 (CH2, C4), 11.07 (CH3, Et).
Propanal (6): 197.55 (CHO, C1), 37.14 (CH2, C2), 5.58 (CH3,
C3).
4. BASF News Release. BASF starts up a new production facility for
intermediates. November 30, 2009.
New-Production-Facility-For-0001
5. (a) K.A. Dubkov, S.V. Semikolenov, D.E. Babushkin, L.G.
Echevskaya, M.A. Matsko, D.P. Ivanov, V.A. Zakharov, V.N.
Parmon, G.I. Panov, J. Polym. Science, Part A, 2006, 44, 2510-
2520; (b) S.V. Semikolenov, K.A. Dubkov, D.P. Ivanov, D.E.
Babushkin, M.A. Matsko, G.I. Panov, Eur. Polym. J., 2009, 45,
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D.E. Babushkin, M.A. Matsko, G.I. Panov, J. Appl. Polym. Sci.,
2009, 114, 1241-1249.
Butanal (7): 197.43 (CHO, C1), 45.80 (CH2, C2), 15.65 (CH2,
C3).
1-Butene (8): 139.81 (=CH-, C2), 112.85 (=CH2, C1).
Propene (9): 132.81 (=CH-, C2), 115.28 (=CH2, C1).
4.3. Quantum-chemical methods
6. (a) V.I. Avdeev, S.Ph. Ruzankin, G.M. Zhidomirov, Chem.
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3050; (c) A. Padwa, 1, 3-Dipolar Cycloaddition Chemistry, Wiley
and Sons Inc, New York, 1984.
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2057.
10. M.W. Chase, Jr., NIST-JANAF Themochemical Tables, Fourth
Edition, J. Phys. Chem. Ref. Data, Monograph 9, 1998, 1-1951.
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88, 3684-3688.
In order to rationalize 1,2-alkyl shift and the C-C cleavage
dependence on the cis/trans-substrate isomer observed
experimentally in this study, Density Functional Theory (DFT)
calculations were carried out. Potential Energy Surfaces (PESs)
of relevant reaction steps were constructed at the DFT level using
the B3LYP functional.13 Optimal geometry search and
subsequent vibrational and intrinsic reaction coordinate (IRC)
analysis were performed using B3LYP/6-311G(2d,d,p).
Geometry optimization and vibrational analysis at the selected
B3LYP/6-311G(2d,d,p) level are actually the first steps of
composite method applied here: CBS-QB3.14 This is a Complete
Basis Set (CBS) method developed by George Peterson and
coworkers. It extrapolates several single-point energies in order
to get the best estimate of the total energy, which is hard to