1-Methyl camphene

Toxaphene, see Chlorinated camphene Tributyl phosphate 1,1,1 -Trichloroethane, see Methyl chloroform 10.7 20.25 0.020 0.3... 

The only difference between the two reactions evidently consists in the shift of the double bond in respect of the methyl group, from a, b, to b, c. For between a and b, through stereochemical reasons, no double bond can exist, since, in accordance with Bredt s rule, none of the C-atoms which are common to both rings of a bicyclic system of the camphene type can take part in an unsaturated linkage. 

The retention of optical activity of camphene rules out methyl migration (Nametkin rearrangement) (71) or a symmetrical intermediate. On the acidic alumina at low contact time the retention of optical activity is high, about 80%. At longer contact time, however, there is essentially complete racemization. Hence, the dehydration mechanism seems to be the same on the acidic and on the base-modified alumina. The acidic alumina, however, causes the readsorption of the dehydration product leading to isomerization and equilibration. 

China Valeriana altemifolia Bunge. V. amurensis R Smira. ex Kom. V. fauriei Briq. V.fauriei Briq. var. dasycarpa V. subbipinnatifolia A. Baranow Bomyl isovalerate, isovaleric acid, bomeol, camphene, pinene, d-terpineol, 1-limonene, pyrryl-a-methyl ketone, alpha-fenchene, myrcene, phellandrene, 1-caryophyllene, erpinene, terpinolene, eremophilene, selinene, cadinene, valerianol, valerenone, myrtenol, bisabolene, chatinine, caffeic acid.48 Antispasmodic, aphrodisiac, emmenagogue, stimulant, sudorific, backache, cramps, influenza, nausea, numbness. 

Solvent Norbor- 3-Bromo- 3-Bromo 3-Methyl- 1-Methyl- Camphor 3-Bromo- 9,3-Di- Fenchone Camphene... 

Isocamphane Dihydro- camphene 2,2,3-TriC methyl 3 norbomane -- -- ... 

These names are confusing and misleading — for example, a fenchane (No. 81) contains a third methyl at position No. 1 which is concealed in the name bomane. The correct formula for camphene (No. 84) can be written more readily from the systematic and simpler name (2,2-dimethyl-3-methylenenorbomane) than from the demethyl name. 

Approximately 45 constituents have been determined from fennel seed oil (Fig. 12.1), the main constituents being transanethole (60-65%, but up to 90%), fen-chone (2-20%), estragol (methyl chavicol), limonene, camphene, a-pinene and other monoterpenes, fenchyl alcohol and anisalde-hyde. The major compounds in supercritical... 

In summary, Foeniculum is stated to have three species, F. vulgare (fennel), F. azoricum Mill. (Florence fennel) and F. dulce (sweet fennel). Fennel is widely cultivated, both in its native habitat and elsewhere, for its edible, strongly flavoured leaves and seeds. The flavour is similar to, but milder than, that of anise and star anise. Anethole and fenchone are the major constituents of the solvent extract of seed phenols, free fatty acids, carbohydrates, proteins, vitamins and minerals have been reported in varying proportions. In the mature fruit, up to 95% of the essential oil is located in the fruit, greater amounts being found in the fully ripe fruit. Approximately 45 constituents have been determined from fennel seed oil, the main constituents being frans-anethole, fenchone, estragol (methyl chavicol), limonene, camphene, a-pinene and other monoterpenes, fenchyl alcohol and... 

The reaction of linalool with boron trifluoride etherate has been re-examined no pinenes or camphene were obtained.146 Dehydrolinalool reacts with methyl iso-propenyl ether under acidic conditions by Claisen rearrangement to give the allene (58).147 Further papers in this section include reaction of monoterpenoid alcohols with paraformaldehyde-acetic anhydride-sodium acetate,148 rearrangement of the alcohol (47 X = OH) to the oxabicycloheptane (59) and the ketone (60),149 and the rearrangement of a typical monoterpenoid vicinal hydroxy-ester to an epoxide.150... 

The addition of methanol to alpha-pinene in the presence of the above mentioned beta zeolite as catalyst in the batch reactor results in the cleavage of the cyclobutane ring and yields l-methyl-4-[alpha-methoxy-isopropyl]-l-cyclohexene (alpha-terpinyl methyl ether) as the main reaction product. The most common by-products to be found are isomerization compounds like camphene, limonene and terpinolene, and several bicyclic and double addition products, e.g. endo- or exo-methylbomylether, endo- or exo-methylfenchylether and cis- or trans-1,8-dimethoxy-p-menthane. 

Two new syntheses of /3-santalene (106) have been reported. In the first one, the starting material (105) was obtained from the Diels-Alder reaction between cyclopentadiene and methyl buta-2,3-dienoate followed by hydrogenation (Scheme 16). The second synthesis (Scheme 17) starts from camphene and... 

The number of metal zeolites and their application to the epoxidation of olefins rose in parallel from the late 1980s. TS-2, Ti,Al-P, Ti-P, Ti-MWW and, rarely, Ti-MOR are catalysts that have been studied in some detail [7-9, 35, 77-84]. TS-2 behaves, according to the few studies published, similarly to TS-1. The greater spaciousness of pores in Ti-Beta zeolites and of external cups in Ti-MWW allows the epoxidation, under mild conditions, of olefins unable to diffuse in TS-1 and TS-2, such as methylcyclohexenes, cyclododecene, norbornene, camphene and methyl oleate [80-83]. Steric constraints still prevail over electronic factors, however, as in medium pore Ti-zeolites, even in the epoxidation of linear olefins (Table 18.9). It is generally believed that active sites and epoxidation mechanisms are not significantly different from those of TS-1. 

Furthermore, Landrum etal. and other scientists [41,44,47,48] did not apply the correct IUPAC numbering of the carbon skeleton [49, 50]. Therefore, the correct name of the component isolated by Landrum et al. has to be 3-exo, 5-exo,6-exo,8,8,9,10- or 3-exo,5-exo,6-exo,8,9,9,10-heptachlorodihydrocam-phene. Until now, the IUPAC rules do not distinguish between carbons C8 and C9 [51] but, due to the alphabetic order of the second letter in endo and exo,the endo-methyl group has been labeled as C8 and the exo-methyl group as C9 in this presentation (see Fig. 2). Presently, IUPAC is working on a definite nomenclature of camphene [52]. 

To test these alternative hypotheses, a tremendous amount of work has been done, by Brown and by others. For example, camphene hydrochloride is known to undergo ethanolysis 6000 times as fast as rer/-butyl chloride, and this had been attributed to anchimeric assistance with formation of a bridged ion. Brown pointed out that the wrong standard for comparison had been chosen. He showed that a number of substituted (3°) cyclopentyl chlorides (examine the structure of camphene hydrochloride closely) also react much faster than rerr-butyl chloride. He attributed these fast reactions—including that of camphene hydrochloride—to relief of steric strain. On ionization, chloride ion is lost and the methyl group on the ap hybridized carbon moves into the plane of the ring four non-bonded interactions thus disappear, two for chlorine and two for methyl. For certain systems at least, it became clear that one need not invoke a nonclassical ion to account for the facts. 

CHj, CO, CO2. propene, isobutene, dimethyl kelene, acroleih. altyl alcohol, glycidol. glycidyl methyl ether, methyl methacrylate, glycidyl methacrylate, chain fragments distribution varies with copolynrer composition methyl methacr ate, isobomyl methacrylate, camphene. camphene isomers... 

This argument cannot be applied to our examples when large amounts of polymers are formed. Besides, Deno and co-workers 41) have detected in concentrated sulfuric acid solutions of camphene and related compounds (borneol, fenchol) high concentrations of a mono-cyclic cyclohexenic carbonium ion, produced also by proton addition to l-methyl-3-isopropylidene-l-cyclohexene, a clear case of ring breaking in acid media. More recently, Olah and co-workers reported that in highly acidic systems such as HF or HSO3F and SbFs, cyclohexane produces, besides the expected cyclohexyl- and methylcyclopentyl carbonium ions, hexyl and isohexyl carbonium ions 42). 

Terpenes are reputed to increase cholesterol solubility in bile, though are less effective than bile acids. There are two such preparations available, Rowatinex and Rowachol , containing some combination of the following anethol, borneol, camphene, cineole, mendone, menthol, pipene and renchone, in olive oil. Direct contact dissolution by direct injection of organic solvents, such as methyl tert-butyl ether (MTBE), is sometimes used. 

Camphene condensed with methyl propiolate under the influence of Lewis acids to give spiro-cyclobutene derivatives525 and with PCl2Me-AlCl3 to form C-3—C-8 bridged phosphorus adducts.526 Isocamphan-10-al condensed with rhodanine to yield a fungicidal product.527 Camphenyl-lithium can readily be converted into the tetra-alkyl-chromium or -uranium derivatives.528... 

The epoxidation of terpenic substrates is of interest in the flavor and fragrance industry [55,56]. Terpenes are derivatives of isoprene, which has formula CsHg (2-methyl-frans-butadiene). There are tens of examples of terpenes, including limonene, a-pinene, geraniol, citronellol, myrcene, ocimene, camphene, a-terpin-eol, menthol, and isopugelol. Limonene is an abundant monoterpene extracted from citrus oil, which can be epoxidized to obtain fragrances, perfumes, and... 

---