Trimethylbicyclo heptane

Principal terpene alcohol components of piae oils are a-terpiueol, y-terpiueol, P-terpiueol, a-fenchol, bomeol, terpiuen-l-ol, and terpiaen-4-ol. The ethers, 1,4- and 1,8-ciaeole, are also formed by cycli2ation of the p-v( enthane-1,4- and 1,8-diols. The bicycHc alcohols, a-fenchol [512-13-0] (61) and bomeol (62), are also formed by the Wagner-Meerweiu rearrangement of the piaanyl carbonium ion and subsequent hydration. Bomeol is i7(9-l,7,7-trimethylbicyclo[2.2.1]heptan-2-ol [507-70-0]. Many other components of piae oils are also found, depending on the source of the turpentine used and the method of production. 

DMBCOl), dimethylbicyclo[3.2.1]octanes (DMBC02), ethylsubstituted bicyclooctanes (EBCO) and trimethylbicycloheptanes (TMBCH). The last group consists of trimethylbicyclo[2.2.1]heptanes, trimethylbicyclo[3.1.1]heptanes and dimethylbicyclo[2.2.2]octanes. Some representative structures of the Iso groups are shown in Figure 2. Major cracking products (CP) were identified as cyclic hydrocarbons C5-C9 and isobutane. The main heavy products (HP) were methyl-and dimethyldecalins, or their isomers. No olefins and only traces of aromatics were found in the products. Detailed information about the product analysis is reported elsewhere (22). 

The vicinal diol of the monoterpene series, (15,2S,3/ ,5S)-(+)-2,6,6-trimethylbicyclo [3.1.1]heptane-2,3-diol (1), was converted upon reaction with methyl dichloro-phosphite into a tricyclic phosphite 2 showing a 95 5 ratio of epimers differing at the phosphorus stereocentre (Scheme 1). Its complexes with Rh(I) and Pd(II) were found to have the structures (u-Cl)2[Rh(CO)L, and ris-CL,PdL2 respectively [16]. 

Acetoxy-4-iodo-3,7,7-trimethylbicyclo[4.1.0]heptane, 3544 Ammonium iodate, 4513... 

Treatment of 3,7,7-trimethylbicyclo[4.1.0]heptane (A3-carene) with iodine and copper acetate in methanol gave 3-iodo-4-methoxy-4,7,7-trimethylbicyclo[4.1.0] heptane. A 50 g sample exploded violently after standing at ambient temperature in a closed container for 10 days. This and the corresponding iodoacetoxy... 

Synonyms AI3-18783 Alphanon 2-Bornanone DL-Bornan-2-one BRN 1907611 BRN 3196099 2-Camphanone DL-Camphor Camphor-natural Camphor-synthetic Caswell No. 155 EINECS 200-945-0 EINECS 207-355-2 EINECS 244-350-4 EPA pesticide chemical code 015602 Formosa camphor Gum camphor Iphanon Japan camphor 2-Keto-l,7,7-trimethyl-norcamphane Laurel camphor Matricaria camphor Norcamphor 2-Oxobornane Root bark oil Sarna Spirit of camphor Synthetic camphor l,7,7-Trimethylbicyclo[2.2.1]heptan-2-one 1,7,7-Trimethylnorcamphor UN 2717. 

Trimethylbicyclo[2.2.1]heptan-2-one, see Camphor Trimethyl carbinol, see ferf-Butyl alcohol... 

A class II aldolase-mimicking synthetic polymer was prepared by the molecular imprinting of a complex of cobalt (II) ion and either (lS,3S,4S)-3-benzoyl-l,7,7-trimethylbicyclo[2.2.1] heptan-2-one (4a) or (lR,3R,4R)-3-benzoyl-l,7,7-trimethylbicyclo[2.2.1]heptan-2-one (4b)... 

Partial catalytic hydrogenation in the pyridazine unit of (l/J,3 >4iJ)-3-(6-substituted[l,2,4]triazolo[4,3-/ ]pyridazin-3-yl)-l,7,7-trimethylbicyclo[2.2.1]heptan-2-ones could be achieved with Pd/C catalyst using 50 bar of H2 <2006TA79>. Good to excellent de s were obtained. 

Figure 20. Simultaneous enantiomer separation of various classes of compounds ( Schurig test mixture 184) on CP-Cyclodextrin-/3-2,3,6-M-19 (permethylatcd /3-cyclodextrin in OV-1701) [25 m x 0.25 mm (i.d.) column, 70°C for 5 min followed by 3cC/miu, 0.65 bar hydrogen]143. 1+2 2,6,6-trimethylbicy-clo[3.1.1]hept-2-ene (x-pinene), 3 ( + )-(lJR)-//ms-2,6,6-trimethylbicyclo[3.1. l]heptane (pinane), 4 (-)-(lS )-fra/M-pinanc. 5 (-)-(lS)-fw-pinane, 6 ( + )-(l/J)-cw-pinane, 7 + 8 2,3-butancdiol. 9 meso-2,3-butanediol, 10 + 11 tetrahydro-5-methyl-2-furanone (y-valerolactone). 12 + 13 1-phenylethanaminc. 14 + 15 1-phenylethanol, 16 + 17 2-ethylhexanoic acid.

The first useful asymmetric synthesis with a-halo boronic esters utilized (S)-pinanediol [1S-(la,2/1.3//,5a)]-2,6,6-trimethylbicyclo[3.1.1]heptane-2,3-diol as the chiral director39,40. This diol is easily prepared from ( + )-a-pinene by a catalytic hydroxylation with osmium tetroxide, and its enantiomer (i )-pinanediol is available from (-)-(a)-pinene41,42. Pinanediol esters remain useful in view of their excellent stability as well as the ease of preparation of the diol. and their stereoselectivity is very high even though it is no longer the state of the art. 

Nearly all examples of epoxidation of alkylidenecyclobutanes involve 3-chloroperoxybenzoic acid.15 58-70 This is because the conditions are mild, the workup is easy and few byproducts are formed. Generally, dichloromethane or chloroform is used as solvent. Solid sodium hydrogen carbonate is occasionally added to avoid acid-catalyzed rearrangement of the spiro compound. For example, 6-isopropylidene-l,4,4-trimethylbicyclo[3.2.0]heptan-3-one reacted with 3-chloroperoxybenzoic acid and sodium hydrogen carbonate to give 2,2,3, 3, 6-pentamethyl-spiro[3-oxabicyclo[4.2.0]octane-8,2 -oxirane]-4-one (4) in quantitative yield. However, without the use of sodium hydrogen carbonate, substantial amounts of 2,2,6,9,9-pentamethyl-3-oxa-bicyclo[4.3.0]nonane-4,8-dione (5) and 2,2,6,8,8-pentamethyl-3-oxabicyclo[4.3.0]nonane-4,9-dione (6) were also formed.15-64... 

Although cycloreversion is the dominant route in 2,7,7-trimethylbicyclo[3.1.1]heptane (pinane) pyrolysis, appropriate substituents on the pinane skeleton can in fact retard cycloreversion, thereby allowing formation of more products through carbon bond rupture and hydrogen transfer.100,102,106 In support of this feature it has been found that the pyrolysis of isoverbanone [(lS,2JR,5 )-2,6,6-trimethylbicyclo[3.1.1]heptan-4-one, 10] at 580°C gives, in addition to unreacted starting material, a mixture of five components, from which the major product m-3-methyl-4-isopropenylcyclohexanone (15) was isolated in 20% yield. The other products are 2,6-dimethylocta-2,7-dien-4-one (12 15%) and 5,7-dimethylocta-l,6-dien-3-one... 

In support of the above mechanism, (lS,2S,57 )-2,6,6-trimethylbicyclo[3.1. l]heptan-3-one [(-)-isopinocamphone, 22] does not yield a hydrogen transfer product because its carbonyl group is unable to provide -stabilization to the corresponding secondary radical.106... 

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