Oxidation pinenes

As the anhydride of nitrous and perchloric acids, it is a very powerful oxidant. Pinene explodes sharply acetone and ethanol ignite, then explode ether evolves gas, then explodes after a few s delay. Small amounts of primary aromatic amines-aniline, toluidines, xylidines, mesidine-ignite on contact, while larger amounts exploded dangerously, probably owing to rapid formation of diazonium perchlorates. Urea ignites on stirring with the perchlorate, (probably for a similar reason). 

Cineole Ascaridole Limonene Oxide Pinene Oxide Figure 12.6 Structural formulas of some terpenes used as penetration enhancers. 

Borneol and isoboineol are respectively the endo and exo forms of the alcohol. Borneol can be prepared by reduction of camphor inactive borneol is also obtained by the acid hydration of pinene or camphene. Borneol has a smell like camphor. The m.p. of the optically active forms is 208-5 C but the racemic form has m.p. 210-5 C. Oxidized to camphor, dehydrated to camphene. 

Ordinary commercial camphor is (-i-)-cam phor, from the wood of the camphor tree. Cinnamonum camphora. Camphor is of great technical importance, being used in the manufacture of celluloid and explosives, and for medical purposes, /t is manufactured from pinene through bornyl chloride to camphene, which is either directly oxidized to camphor or is hydrated to isoborneol, which is then oxidized to camphor. A large number of camphor derivatives have been prepared, including halogen, nitro and hydroxy derivatives and sulphonic acids. 

Hydroboration-oxidation of a pinene (page 235) like catalytic IS stereoselective Addition takes place at the less hindered face and a single alcohol is produced in high yield (89%) Sug... 

In several important cases, new synthetic strategies have been developed into new production schemes. An outstanding example of this is the production of an entire family of terpene derivatives from a-pinene (29), the major component of most turpentines, via linalool (3) (12). Many of these materials had been produced from P-pinene, a lesser component of turpentine, via pyrolysis to myrcene and further chemical processing. The newer method offers greater manufacturing dexibiUty and better economics, and is environmentally friendly in that catalytic air oxidation is used to introduce functionality. 

Another important use of a-pinene is the hydrogenation to i j -pinane (21). One use of the i j -pinane is based on oxidation to cis- and /n j -pinane hydroperoxide and their subsequent catalytic reduction to cis- and /n j -pinanol (22 and 23) in about an 80 20 ratio (53,54). Pyrolysis of the i j -pinanol is an important route to linalool overall the yield of linalool (3) from a-pinene is about 30%. Linalool can be readily isomerized to nerol and geraniol using an ortho vanadate catalyst (55). Because the isomerization is an equiUbrium process, use of borate esters in the process improves the yield of nerol and geraniol to as high as 90% (56). 

Another important process for linalool manufacture is the pyrolysis of i j -pinanol, which is produced from a-pinene. The a-pinene is hydrogenated to (73 -pinane, which is then oxidized to cis- and /n j -pinane hydroperoxide. Catalytic reduction of the hydroperoxides gives cis- and /n j -pinanol, which are then fractionally distilled subsequendy the i j -pinanol is thermally isomerized to linalool. Overall, the yield of linalool from a-pinene is estimated to be about 30%. 

One method of synthesis of taxol analogues starts with a-pinene (8), the readily available and inexpensive monoterpene derived from the processing of turpentine from the pine tree (200). The a-pinene is oxidized to verbenone, which is then alkylated and converted to taxol analogues in a multistep process. 

Camphor was originally obtained from the camphor tree Lauras eamphora in which it appeared in the optically active dextro-rotary form. Since about 1920 the racemic ( ) mixture derived from oil of turpentine has been more generally used. By fractional distillation of oil of turpentine the product pinene is obtained. By treating this with hydrochloric acid, pinene hydrochloride (also known as bomyl chloride) may be produced. This is then boiled with acetic acid to hydrolyse the material to the racemic bomeol, which on oxidation yields camphor. Camphor is a white crystalline solid (m.p. 175°C) with the structure shown in Figure 22.3. 

Hydroboration-oxidation of a-pinene (page 235), like catalytic... 

Sometimes, on account of the difiiculty in preparing the nitroso-chloride from a highly active o-pinene, it is necessary to examine the oxidation products before it is possible to come definitely to a conclusion as to the presence or absence of the hydrocarbon. Pinene yields numerous acids as the result of oxidising processes, so that the method of preparing the product to be examined must be rigidly adhei ed to if useful results are to be obtained. The terpene is transformed into pinonic acid, CjoHj Og, in the following manner A solution of 233... 

CIS of potassium permanganate in 2000 c.c. of water is placed in a, and an emulsion of 100 grams of the hydrocarbon in 600 c.c. of water is gradually added in small portions. The mixture is kept cool by means of a current of cold water, and shaken continuously. The oxidation products are then treated as follows The liquid is filtered from manganese oxide, and evaporated to about 1000 c.c., saturated with carbon dioxide, and the neutral and unaltered compounds removed ly extract jn with ether in the usual manner. The crude pinonic acid is separated from its potassium salt by sulphuric acid and is then extracted with ether. If /S-pinene be present, nopinic acid will be present... 

By oxidation of d- and Z-pinene of high rotatory power, Barbier and Grignard obtained the optically active forms of pinonic acid. Z-pinene from French turpentine oil (boiling-point 155 to 157 , od - 37 2 157 to 160 , tto - 32 3°) was oxidised with permanganate. From the product of oxidation, which (after elimination of the volatile acids and of nopinic acid) boiled at 189 to 195 under 18 mm. pressure, Z-pinonic acid separated out in long crystalline needles, which, after recrystallisation from a mixture of ether and petroleum ether, melted at 67° to 69 . The acid was easily soluble in water and ether, fairly soluble in chloroform, and almost insoluble in petroleum ether. Its specific rotation is [a]o - 90-5 in chloroform solution. Oximation produced two oximes one, laevo-rotatory, melting-point 128 and the other, dextro-rotatory, melting-point 189° to 191°. 

To 19 8 of well-agitated distilled water plus 18 g of ditertiary-butyl-ppinene oxide that was about half racemic, half d-form. The temperature was maintained at 30°C to 50°C, first with ice bath cooling and then with tap water cooling. The addition of the pinene oxide required 1 h hours. After the addition was complete and the exothermic reaction was about over, the mixture was stirred for 1 h hours at about 30°C, and then centrifuged to separate the crude sobrerol from the liquid phase consisting of oil and water. 

The epoxidation method developed by Noyori was subsequently applied to the direct formation of dicarboxylic acids from olefins [55], Cyclohexene was oxidized to adipic acid in 93% yield with the tungstate/ammonium bisulfate system and 4 equivalents of hydrogen peroxide. The selectivity problem associated with the Noyori method was circumvented to a certain degree by the improvements introduced by Jacobs and coworkers [56]. Additional amounts of (aminomethyl)phos-phonic acid and Na2W04 were introduced into the standard catalytic mixture, and the pH of the reaction media was adjusted to 4.2-5 with aqueous NaOH. These changes allowed for the formation of epoxides from ot-pinene, 1 -phenyl- 1-cyclohex-ene, and indene, with high levels of conversion and good selectivity (Scheme 6.3). 

Use of the reagent diisopinocampheylborane SO (prepared by treating optically active a-pinene with BH3) results in enantioselective hydroboration-oxidation. ° Since both (-I-) and (-) a-pinene are readily available, both enantiomers can be prepared. Alcohols with optical purities as high as 98% have been obtained in this... 

CioHi S0-56-S) see Sobrerol ( )-a-pinene oxide (Ci( H,jO 95044-43-2) see Sobrerol L-pipecolic acid... 

The turpentine fraction is gasified during the process, and valuable chemicals, such as a-pinene and carene can be separated by distillation. They can be further processed by catalytic treatment, such as isomerization and oxidation [6-8]. 

Corma, G.A., Eduardo Domine, M., Susarte, R.M., and Rey, G.F. (2002) MCM-41 type microporous materials containing titanium and their utilization as catalysts in a- pinene oxidation, Patent W00054880. 

Gas-phase products from the reactions of ozone with the monoterpenes (-)-p-pinene and (+)-sabinene included the ketones formed by oxidative fission of the exocyclic C=C bonds as well as ozonides from the addition of ozone to this bond (Griesbaum et al. 1998). 

Grosjean D, EL Williams, E Grosjean, JM Andino, JH Seinfeld (1993c) Atmospheric oxidation of biogenic hydrocarbons reaction of ozone with 3-pinene, D-limonene, and rra -caryophyllene. Environ Sci Technol 27 2754-2758. 

Griffiths ET, SM Bociek, PC Harries, R Jeffcoat, DJ Sissons, PW Trudgill (1987) Bacterial metabolism of a-pinene pathway from a-pinene oxide to acyclic metabolites in Nocardia sp strain P183. J Bacteriol 169 4972-4979. 

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