N-Pinene

Figure 2 Product range of isomerization of n-pinene oxide...

The oil has been exhanstivcly examined by E. R. Miller, who finds the following substances present thorein i -n-pinene, i-a-pinene, p-eymene, one or two unidentified terpenes, butyric aldehydo, iso-valeric aldehyde, a third aldehyde, possibly piperonal, carvaoroL, thymoquinone, hvdro-thyrnoquinonfi, dihydroxy-thymoqui none, dihydrocuminic alcohol, an iinidtjutified alcohol, aoetio acid, butyric acid, valeric acid, caproic acid, basic substances, and in the aqueous distillate) acetone, formaldehyde, methyl alcohol, for nic acid, and acetic acid. 

That the oil contains the following constituents, 1-a-pinene, d-n pinene, f-limoncne, i-bomcol, bornyl acetate and other esters of borneo), -camphor, cineol, salicylic acid, 3Jd.ehj des formic acetic, butyric ( ) and isovaleric acids, a non-volatile acid or lactone, and a blue congtilucrit of high boiling-point. 

Among chiral dialkylboranes, diisopinocampheylborane (8) is the most important and best-studied asymmetric hydroborating agent. It is obtained in both enantiomeric forms from naturally occurring a-pinene. Several procedures for its synthesis have been developed (151—153). The most convenient one, providing product of essentially 100% ee, involves the hydroboration of a-pinene with borane—dimethyl sulfide in tetrahydrofuran (154). Other chiral dialkylboranes derived from terpenes, eg, 2- and 3-carene (155), limonene (156), and longifolene (157,158), can also be prepared by controlled hydroboration. A more tedious approach to chiral dialkylboranes is based on the resolution of racemates. /n j -2,5-Dimethylborolane, which shows excellent enantioselectivity in the hydroboration of all principal classes of prochiral alkenes except 1,1-disubstituted terminal double bonds, has been... 

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%. 

Phthalimide, potassium [ 1H Isomdole-l,3(2//)-dione, potassium salt], 96 Phth-Gly.Gly-OEt [Glycine, N [(1,3-dihydro-1,3-dioxo-2//-isoindol-2-yl)acelyl], ethyl ester], 93 a-Pinene [Bicyclo 3.1.1]hept 2-ene,... 

Figure 5. Recycling of NH2-MCF-supported TBA4HPW1 lCo039 in a-pinene autoxidation. Reaction conditions a-pinene, 0.1 mmol 02, 1 atm catalyst, 6x10-4 mmol Co-POM MeCN, 1 mL 50 °C, 1 h. Reprinted from J. Catal. 246, Maksimchuk, N. V., et al, 241-248, Copyright (2007), with permission...

German for turpentine) and there are approximately 15000 terpenes. Terpenes are lipophilic, and the building blocks are five-carbon units with the branched carbon skeleton of isopentane. The basic units are sometimes called isoprene (F ig. 11.5fl), because heat decomposes terpenoids to isoprene. Depending on the number of C5 units fused, we distinguish mono- (Cio), sesqui- (C15), di- (C20), tri-(C30), tetra- (C40) and polyterpenoids [(Cs) , with n > 8]. Alpha-Pinene and bor-neol (Fig. 11.56) are examples of monoterpenes. 

Picolinate-N-oxido anion (PICO), transition metal peroxides, 1058, 1095 Picolinic acid (pic), transition metal peroxides, 1054, 1058, 1067, 1076 (—)-/3-Pinene, artemisinin synthesis, 288, 289 Plakorin, 191, 247, 1333 Plakortic add, 190, 191 Plakortin, 190, 191... 

Bicyclo[3,l,l]heptanes.—Spin-lattice relaxation time measurements have facilitated the n.m.r. spectral assignments of paeoniflorin and albiflorin (Vol. 3, p. 71). trans-Pinocarveol (223) has been synthesized from /3-pinene in t-butyl alcohol with hydrogen peroxide in the presence of a catalytic amount of selenium... 

Further details of the photoaddition of N-nitrosopiperidine to a-pinene have been published.The claim of a-fenchen-6-one oxime formation (Vol. 7, p. 43) has been retracted the product is optically active carvone oxime. The stereochemistry and conformations of amino-oximes derived from a-pinene nitroso-chloride have been examined. ... 

Hatakeyama, S., K. Izumi, T. Fukuyama, H. Akimoto, and N. Washida, Reactions of OH with a-Pinene and /3-Pinene in Air Estimate of Global CO Production from the Atmospheric Oxidation of Terpenes, J. Geophys. Res., 96, 947-958 (1991). 

Pandis, S. N., S. E. Paulson, J. H. Seinfeld, and R. C. Flagan, Aerosol Formation in the Photooxidation of Isoprene and a-Pinene, Atmos. Environ., 25A, 997-f008 (f99f). 

Cinnamomum zeglanicum Blume Ceylon Rou Gui (Ceylon cinnamon) (bark) Cinnamic aldehyde, p-cymene, hydrocinnamic aldehyde, pinene, benzaldehyde, cuminic aldehyde, nonylic aldehyde, eugenol, caryophyllene, 1-phellandrine, methyl-n-amyl ketone, 1-linalool.60 Stimulant to digestion, respiration, circulation. 

Oenothera javanica (BI) DC Shui Jin (seed, leaf) Bis (2-ethyl butyl) phthalate, n-butyl-2-ethyl butyl phthalate, diethyl phthalate, myrcene, alpha-pinene, terpinolene, limonene, beta-pinene, alpha-terpinene, persicarin, petroscelinic aicd.48-50 For plethora, cholera, dysuria, fever, hematuria, influenza, jaundice, metrorrhagia, antivinous, hemostat. Externally for abscesses, cancerous swelling, snakebite. 

N.A. Pinenes, delta-linalool, borneol, terpineol, arislolochic acid.107 Treat asthma, sore throats, stomach cramps, recurrence of herpes lesions. 

N.A. Camphor, camphene, dipentene, limonene, phyllandrene, pinene, cinnamaldehyde.99-100 119 Carminative, antispasmodic, antiseptic, and antiviral. 

N.A. Pinene, camphene, bomyl isovalerate, isoborneol." Antifungal, treat vaginitis and vaginal discharge. 

N.A. Linalool, proteins, vitamin C, alpha-pinene, terpinene.99 107 A digestive tonic, carminative, and sedative. 

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