1.2- Epoxy octane

Benzene, toluene, and xylene are made mosdy from catalytic reforming of naphthas with units similar to those already discussed. As a gross mixture, these aromatics are the backbone of gasoline blending for high octane numbers. However, there are many chemicals derived from these same aromatics thus many aromatic petrochemicals have their beginning by selective extraction from naphtha or gas—oil reformate. Benzene and cyclohexane are responsible for products such as nylon and polyester fibers, polystyrene, epoxy resins (qv), phenolic resins (qv), and polyurethanes (see Fibers Styrene plastics Urethane POLYiffiRs). 

The rearrangement of isopent-3-enyl epoxy esters with Cp2ZrCl2/AgC104 yields ABO esters (2,7,8-trioxabicyclo[3.2.1]octane Asymmetric Bicyclo-Octane esters), which are base-stable protecting groups for carboxylic acids [57,79,80] (Scheme 8.40). 

Fig. 16. Free energy curves for hexane-, octane-, and decane-modified epoxies at a constant temperature (T=315 K) and conversion (q=0)...

A further increase in the amount of solvent leads to the development of a bi-modal pore size distribution, as observed with SEM on samples prepared with concentrations of 10-15 wt % hexane (Fig. 18c,d). Similar bimodal distributions have also been reported with the octane and decane based systems [88,89] as well as in in rubber-modified epoxies prepared via phase separation [67,95-98]. 

Diepoxy-7,8-dioxabicyclo[2.2.2]octane, 2339 Endrin, 3459 t 1,2-Epoxy butane, 1609 t 3,4-Epoxy butene, 1520... 

The full paper on the synthesis of onikulactone and mitsugashiwalactone (Vol. 7, p. 24) has been published.Whitesell reports two further useful sequences (cf. Vol. 7, p. 26) from accessible bicyclo[3,3,0]octanes which may lead to iridoids (123 X=H2, Y = H) may be converted into (124) via (123 X = H2, Y = C02Me), the product of ester enolate Claisen rearrangement of the derived allylic alcohol and oxidative decarboxylation/ whereas (123 X = 0, Y = H) readily leads to (125), a known derivative of antirride (126) via an alkylation-dehydration-epoxi-dation-rearrangement sequence. Aucubigenin (121 X = OH, R = H), which is stable at —20°C and readily obtained by enzymic hydrolysis of aucubin (121 X = OH, R = j8-Glu), is converted by mild acid into (127) ° with no dialdehyde detected sodium borohydride reduction of aucubigenin yields the non-naturally occurring isoeucommiol (128 X=H,OH) probably via the aldehyde (128 X = O). ... 

In agreement with this mechanism, it was found that the epoxide (4RS)-4,4-(epoxy-methano)tricyclo[5.1.0.02,5]octane-e c/o-8-carbaldehyde 2,2-dimethylpropaneT,3-diyl acetal (1) gave 4-oxotricyclo[6.1.0.02,6]nonane- ,/ttreatment with lithium iodide in tetrahydrofuran.71 Several examples employing this oxaspirohexane to cyclopentanone isomerization method are shown (see Table 7).69-80 Lithium bromide in the presence of hexamethylphosphoric triamide was also effective in these transformations.70,74,76 79,80... 

Octane, 4,5-epoxy-, trans- (8) Oxirane, 2,3-dipropyl-, trans- (9) (1689-70-9)... 

Newman and co-workere 240 published in lt)4D a careful study of tile variation in production composition when 1,2-epoxy octane was reduced over Raney nickel at 150° under neutral, alkaline, and acidic conditions. Their results, Bonmarized in Eq. (3 1), are rather striking. 

Triethylsilyoxy epoxy alcohol was also converted into the corresponding chiral octanal, (II), using a rare earth catalyst as illustrated in Eq. 2 and described by the author. 

Cyclization epoxy -fceto esters. Treatment of I with BF3 etherate effects cyclization to the S,8-dioxabicyclo[3.2.1]octane 2 in higli yield. This basic skeleton had been encountered in several sex pheromones of bawk beetles such as frontalin (3), which can be synthesized readily by the -keto ester cyclization, since the carboxylic acid corresponding to 2 is readily decarboxylated when heated at 220°. ... 

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