Pinene a- and

Turpentine is a mixture of CioHie volatile terpenes (hydrocarbons made of isoprene units). There are actually four different types and methods of making turpentine, including steam distillation of wood. The two pinenes, a and P, are major components of turpentine. Other compounds found in abundant amounts are camphene, dipentene, terpinolene, and A -carene. Although it has been replaced by petroleum hydrocarbons as paint thinners (lower price, less odor), turpentine is still a good solvent and thinner in many specialty applications. The use pattern for turpentine is as follows synthetic... 

Figure 5.4 Mass spectra. The monoterpenes -pinene (A) and limonene (B) both have the molecular formula C10H16 and their mass spectra are similar however, the obvious differences at m/z 68 and m/z 93, coupled with accurate and reproducible retention times from GC, enable an identification for each compound. (C) The oxide eucalyptol (1,8-cineole), with molecular formula C H, produces this characteristic pattern when analyzed by mass spectrometry. MS data supplied by Bill Morden of Analytical Intelligence Ltd.

The pinenes (a- and P-) have been built up again from the pinic acid skeleton. Diethyl pinate (232) can be converted to a mixture of acyloins [e.g. (233)] by the... 

Terpenes, specifically monoterpenes, are naturally occurring monomers that are usually obtained as by-products of the paper and citms industries. Monoterpenes that are typically employed in hydrocarbon resins are shown in Figure 2. Optically active tf-limonene is obtained from various natural oils, particularly citms oils (81). a and P-pinenes are obtained from sulfate turpentine produced in the kraft (sulfate) pulping process. Southeastern U.S. sulfate turpentine contains approximately 60—70 wt % a-pinene and 20—25 wt % P-pinene (see Terpenoids). Dipentene, which is a complex mixture of if,/-Hmonene, a- and P-pheUandrene, a- and y-terpinene, and terpinolene, is also obtained from the processing of sulfate Hquor (82). 

Turpentine Oil. The world s largest-volume essential oil, turpentine [8006-64-2] is produced ia many parts of the world. Various species of piaes and balsamiferous woods are used, and several different methods are appHed to obtain the oils. Types of turpentines include dry-distiUed wood turpentine from dry distillation of the chopped woods and roots of pines steam-distilled wood turpentine which is steam-distilled from pine wood or from solvent extracts of the wood and sulfate turpentine, which is a by-product of the production of sulfate ceUulose. From a perfumery standpoint, steam-distilled wood turpentine is the only important turpentine oil. It is rectified to yield pine oil, yellow or white as well as wood spirits of turpentine. Steam-distilled turpentine oil is a water-white mobile Hquid with a refreshing warm-balsamic odor. American turpentine oil contains 25—35% P-pinene (22) and about 50% a-pinene (44). European and East Indian turpentines are rich in a-pinene (44) withHtfle P-pinene (22), and thus are exceUent raw materials... 

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. 

By-Products. There are three stages within the pulping operation at which wood-derived chemicals can be recovered as by-products. Turpentine is obtained from the reHef of gases after an initial steaming of chips in the digester. Better yields of turpentine are obtained from batch digesters than from continuous systems. Pines and firs give the best yields. Turpentine is composed principally of unsaturated bicycHc hydrocarbons, of which ca 90% are a- and P-pinenes and 5—12% other terpenes. 

Turpentine from the western United States is different from that of the southern states in that it contains 3-carene ranging from 12—43%, depending on the species of pine tree. Indian turpentine also contains about 60% 3-carene and about 15% of the sesquiterpene longifolene. Turpentine from Sweden, Finland, CIS, and Austria all contain 3-carene however, a- and P-pinene are commercially the most important components of the turpentines. 

Although the turpentine is largely desulfurized in the stripping stage and again in the fractionation stages, many appHcations for a- and P-pinene requite further desulfurization. Such methods involve adsorption on carbon, hypochlorite treatment, hydrogen peroxide treatment, treatment with metals, or a combination of techniques (6—15). 

Thermal isomerization of a-pinene, usually at about 450°C, gives a mixture of equal amounts of dipentene (15) and aHoocimene (16) (49,50). Ocimene (17) is produced initially but is unstable and rearranges to aHoocimene, which is subject to cyclization at higher temperatures to produce a- and P-pyronenes (18 and 19). The pyrolysis conditions are usually optimized to give the maximum amount of aHoocimene. Ocimenes can be produced by a technique using shorter contact time and rapid quenching or steam dilution (51). 

Fig. 3. Conversion of a-pinene (8) to P-pinene (20) and to i j -pinane (21) and subsequent reactions.

The pulse sequence which is used to record CH COSY Involves the H- C polarisation transfer which is the basis of the DEPT sequence and which Increases the sensitivity by a factor of up to four. Consequently, a CH COSY experiment does not require any more sample than a H broadband decoupled C NMR spectrum. The result is a two-dimensional CH correlation, in which the C shift is mapped on to the abscissa and the H shift is mapped on to the ordinate (or vice versa). The C and //shifts of the //and C nuclei which are bonded to one another are read as coordinates of the cross signal as shown in the CH COSY stacked plot (Fig. 2.14b) and the associated contour plots of the a-plnene (Fig. 2.14a and c). To evaluate them, one need only read off the coordinates of the correlation signals. In Fig. 2.14c, for example, the protons with shifts Sh= 1.16 (proton A) and 2.34 (proton B of an AB system) are bonded to the C atom at c = 31.5. Formula 1 shows all of the C//connectivities (C//bonds) of a-pinene which can be read from Fig. 2.14. 

Alkenes are hydrocarbons that contain a carbon-carbon double bond. A carbon-carbon double bond is both an important structural unit and an important functional group in organic chemistry. The shape of an organic molecule is influenced by the presence of this bond, and the double bond is the site of most of the chemical reactions that alkenes undergo. Some representative alkenes include isobutylene (an industrial chemical), a-pinene (a fragrant liquid obtained from pine trees), and famesene (a naturally occuning alkene with three double bonds). 

Mondello et al. (2, 20-23) have used a multidimensional gas chromatographic system based on the use of mechanical valves which were stable at high temperatures developed in their laboratory for the determination of the enantiomeric distribution of monoterpene hydrocarbons (/3-pinene, sabinene and limonene) and monoterpene alcohols (linalol, terpinen-4-ol and a-terpineol) of citrus oils (lemon, mandarin, lime and bergamot). Linalyl acetate was also studied in bergamot oil. The system consisted of two Shimadzu Model 17 gas chromatographs, a six-port two-position valve and a hot transfer line. The system made it possible to carry out fully... 

The principal constitaenta of liussian turpentine are, according to Sohindeltaeiser, fl-pinene, sylvestrene, and dipentene. A little deifro-ti-... 

It is soinble in about 1 volumes of IQ 24 volumes of "0 per cent, alcohol. I /H-piuene and tracea ot salicylic aud honicol was cousidered probable, but Phellaudrecc was not present, and u aldehydes or ketones, phenols or camphor. The chief conatitnent pinene, a mixture of the dextro-aud laevo-rotatory vatielief... 

F.w.alyplut apicuinia l.s a New- South Wales tree, tbe leaves nf which yield 0 6.fi pec cent, of essential oil containing pinene, pipericoue, and a small amount of encalyptol, and having the following characters —... 

About 2 per cent, of euoalyptol is present, teith 60 to f-K) per cent, of pinene, a small amount of a seaquiU-rpene, and 6 to h per cent, of ter-... 

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... 

An alkene, sometimes caJled an olefin, is a hydrocarbon that contains a carbon-carbon double bond. Alkenes occur abundantly in nature. Ethylene, for instance, is a plant hormone that induces ripening in fruit, and o-pinene is the major component of turpentine. Life itself would be impossible without such alkenes as /3-carotene, a compound that contains 11 double bonds. An orange pigment responsible for the color of carrots, /3-carotene is a valuable dietary source of vitamin A and is thought to offer some protection against certain types of cancer. 

Kennedy, J. P. and Chou,T. Poly (isobutylene-co-fS-Pinene) A New Sulfur Vulcanizable, Ozone Resistant Elastomer by Cationic Isomerization Copolymerization. Vol. 21, pp. 1—39. 

Sf.I.f-Tfst F.1B The compound a-pinene, a natural antiseptic found in the resin of the pinon tree, has been used since ancient times by Zuni healers. A 7.50-g sample of a-pinene contains 6.61 g of carbon and 0.89 g of hydrogen. What are the mass percentages of carbon and hydrogen in a-pinene ... 

Plants produce a vast array of terpenes, alkenes built in multiples of five carbon atoms. Many terpenes have characteristic fragrances. For example, the fresh odor of a pine forest is due to pinene, a ten-carbon molecule with a ring structure and one double bond. The fragrances of terpenes make them important in the flavor and fragrance industry. Limonene, another ten-carbon molecule with a ring and two double bonds, is the principal component of lemon oil. Geraniol, a chainlike molecule with two double bonds, is one of the molecules that is responsible for the fragrance of roses and is used in many perfumes. Many other terpenes have important medicinal properties. 

---