30469-50-2

Upstream product

• 22553-34-0 (+)-2α-hydroxy-3α-tosyloxypinane 
• 303801-38-9 (1S,5S)-2,6,6-trimethylbicyclo[3.1.1]heptane 
• 80-56-8 Pinene 

Downstream Products

• 57422-89-6 4-isopropyl-6-methylcyclohex-2-en-1-one 

Relevant academic research and scientific papers

Infrared Matrix Isolation and Theoretical Studies of Reactions of Ozone with Bicyclic Alkenes: α-Pinene, Norbornene, and Norbornadiene

The reactions of ozone with three bicyclic alkenes, α-pinene, norbornene, and norbornadiene, were studied by low-temperature (14 K), argon matrix isolation infrared spectroscopy including 18O isotope-labeling studies. Theoretical calculations of some of the proposed reaction intermediates and products were carried out using the Gaussian 09 suite of programs, applying density functional theory (DFT), the B3LYP functional, and the 6-311G++(d,2p) basis set. In the α-pinene/ozone system, the thermal reaction between α-pinene and ozone was too slow to observe under the twin-jet or merged-jet deposition conditions of these experiments. However, red light (λ ≥ 600 nm) irradiation of the argon matrixes containing α-pinene and ozone caused new infrared peaks to appear that could be readily assigned to reaction products of α-pinene with O(3P) resulting from ozone photolysis: α-pinene oxide (with an epoxide ring) and two isomeric ketones. Norbornene and norbornadiene were both found to react with ozone in the gas phase during twin-jet or merged-jet deposition of these mixtures with argon. New peaks observed in the infrared spectra were assigned to the primary ozonides, Criegee intermediates, and secondary ozonides of norbornene and norbornadiene, indicating that the bulk of these reactions proceeded via the "classic" Criegee mechanism for ozonolysis of alkenes. Calculated infrared frequencies and molecular energies support these conclusions. Ultraviolet irradiation of these mixtures resulted in complete decomposition of the early intermediates and the formation of acids, aldehydes, alcohols, carbon dioxide, and carbon monoxide. In any case, no evidence for "unusual" chemistry, prompted by the bicyclic nature of the reactants, was observed. (Figure Presented).

Transition-Metal Catalyzed Autoxidation of cis- and trans-Pinane to a Mixture of Diastereoisomeric Pinanols

Autoxidations of the pinanes, obtained after hydrogenation of naturally occurring Pinus elliottii oil, were performed with or without solvent, using the catalytic system Co(OAc)2/Mn(OAc)2/NH4Br in a 9:1:5 molar ratio, and dioxygen as the oxidant. The best selectivity for the pinanols was 71% (cis:trans ratio, 3:1) with 17% conversion. Autoxidations were also carried out in the absence of catalyst. The hydroperoxides formed with 17% conversion were decomposed with Na2SO3 and PPh3, resulting in 62% pinanols (cis:trans ratio, 5:1). The pyrolysis of the pinanols at 600°C and a contact time of 1.15 × 10-2 s/mol yielded 54% of linalool. The side products were mainly due to an "ene" reaction, giving diastereoisomeric 1,2-dimethyl-3-isopropenylcyclopentanols.

REACTIONS OF p-TOLUENESULFONIC ACID TERPENE DERIVATIVES WITH LITHIUM IN ETHYLAMINE

Reactions of terpene p-toluenesulfonamides and p-toluenesulfonates with lithium in ethylamine were stated to afford, exclusively or mainly, respective amines and alcohols as the result of N-S or O-S bond cleavage.Presence of hydroxyl groups is not a hindrance. 2α-Hydroxy-3α-tosyloxypinane undergoes, partially, a rearrangement.The mechanism of that reaction is discussed.