Limonene, hydrogenation

Preferential hydrogenation. Freshly distilled (+)-limonene hydrogenated with 5%-Pt-on Darco G 60 at an initial pressure of 52 lbs. until 1 mole H2 is consumed after 1 hr. -p-menthene. Y 97.6%. W. F. Newhall, J. Org. Chem. 23, 1274 (1958). 

By oxidation with permanganate it forms pinonic acid, C,oH,<503, a monobasic acid derived from cyclobutane. With strong sulphuric acid it forms a mixture of limonene, dipentene, terpinolene, terpinene, camphene and p-cymene. Hydrogen chloride reacts with turpentine oil to give CioHijCl, bomyl chloride, artificial camphor . 

To 0.165 mole of BMB (prepared as in the preceding experiment) maintained at 0°, is added 20.4 g (0.15 mole) of /-limonene over a period of 5 minutes. The reaction mixture is allowed to stand at room temperature for approximately 3 hours. It is then oxidized by the addition of 50 ml of 3 A sodium hydroxide followed by 50 ml of 30% hydrogen peroxide. The alcohol is worked up in the usual manner. Upon distillation, the primary terpineol is obtained, bp 115-116710 mm. 

Several generalities can be formulated regarding selective reduction of polyolefins. Usually the least hindered double bond is hydrogenated pre ferentially (123), and, with steric hindrance about equal, the most strained bond will be reduced first. Exocyclic olefins are reduced more easily than those in the ring (R)-(+ )-Limonene, 190 g, was shaken with W-4 Raney nickel (12 g) under hydrogen at atmospheric pressure. After 31.9 1 of hydrogen had been absorbed, the solution was filtered. Essentially, pure (R)-( -i- )-carvomenthene was obtained in 96% yield (58). 

Addition of molten sulfur to limonene in a 9 kl reactor led to a violent runaway exothermic reaction. Small scale pilot runs had not shown the possibility of this. Heating terpenes strongly with sulfur usually leads to formation of benzene derivatives with evolution of hydrogen sulfide. 

It is generally observed that the less hindered double bond in a diolefin is preferentially hydrogenated as found in the reaction of limonene (equation 16)56. 

Both uncalcined and calcined LDHs have also been shown to be effective supports for noble metal catalysts [18-25]. For example, palladium supported on Cu/Mg/Al LDHs has been used in the liquid phase oxidation of limonene [24], and on calcined Mg/Al LDHs for the one-pot synthesis of 4-methyl-2-pentanone (methyl isobutyl ketone) from acetone and hydrogen at atmospheric pressure [25]. In the latter case, the performance depends on the interplay between the acid-base and hydrogenation properties. More recently. 

The double-bond isomerization of cyclic materials possessing two double bonds takes place readily. When 1,4-cyclooctadiene is contacted with high-surface sodium on alumina at 0° for a short time, over 95% of the 1,3-cyclooctadiene results (IIS). However an even more interesting reaction takes place when the cyclic diolefin possesses a six-membered ring. An example is the reaction (D) of d-limonene which yields p-cymene and hydrogen (6). 

The monosubstituted double bond in 4-vinylcyclohexene is hydrogenated over P-1 nickel in preference to the disubstituted double bond in the ring, giving 98% of 4-ethylcyclohexane [73]. Similarly in limonene the double bond in the side chain is reduced while the double bond in the ring is left intact if the compound is treated with hydrogen over 5% platinum on carbon at 60° and 3.7 atm (yield 97.6%) [348]. 

R = vinyl or ethynyl) predominates (c/. Vol. 1, p. 36 Vol. 2, p. 35). Base treatment of a 2-alkoxypyridinium tosylate of nerol gives expected e.g. limonene 82%) cyclic hydrocarbons whereas the corresponding geraniol salt yields similar amounts of cyclic and acyclic hydrocarbons. SnCU-catalysed cyclization of the N-benzylimine derived from R-(+)-citronellal yields the expected menthylamines after catalytic hydrogenation. ... 

The preferred industrial method of carvone synthesis utilizes the selective addition of nitrosyl chloride to the endocyclic double bond of limonene. If a lower aliphatic alcohol is used as solvent, limonene nitrosochloride is obtained in high yield. It is converted into carvone oxime by elimination of hydrogen chloride in the presence of a weak base. Acid hydrolysis in the presence of a hydroxylamine acceptor, such as acetone, yields carvone [88]. 

Many EOs also exhibit antioxidant activity and therefore several studies have been carried out in order to elucidate the activity of the components [139,153]. For instance, y-terpinene retarded the peroxidation of linoleic acid [139, 154-156], sabinene showed strong radical-scavenging capacity [139, 157], a-pinene [158] and limonene [146] showed low antioxidant activity in the 2,2-diphenyl-1-picrylhydrazyl (DPPH) test, while terpinene and terpinolene showed high hydrogen-donating capacity against the DPPH radical [146, 150, 155, 158],... 

The main renewable resource for L-carvone is spearmint oil (Mentha spicata), which contains up to 75% of this flavour chemical. There also exists a synthetic process for the manufacturing of L-carvone, which is based on (-t)-limonene, which is available as a by-product of the citrus juice industry as a major component of orange peel oil (Scheme 13.4). The synthesis was developed in the nineteenth century and starts with the reaction of (-t)-limonene and nitrosyl chloride, which ensures the asymmetry of the ring. Treatment with base of the nitrosyl chloride adduct results in elimination of hydrogen chloride and rearrangement of the nitrosyl function to an oxime. Acid treatment of the oxime finally results in l-carvone. 

---