Cyclooctanols

Suberic Acid. This acid is not produced commercially at this time. However, small quantities of high purity (98%) can be obtained from chemical supply houses. If a demand developed for suberic acid, the most economical method for its preparation would probably be based on one analogous to that developed for adipic and dodecanedioic acids air oxidation of cyclooctane to a mixture of cyclooctanone and cyclooctanol. This mixture is then further oxidized with nitric acid to give suberic acid (37). 

Some alcohols that have been converted into the corresponding fluorides by reactions with diethyldminosulfur trifluoride include 1-octanol, 2-methyl-2-butanol, isobutyl alcohol, cyclooctanol, ethylene glycol, crotyl alcohol, 2-phenylethanol, 2-bromoethanol, ethyl lactate, and ethyl a-hydrox3maphthaleneacetate. ... 

Cyclooctanol, oxidation by chromium trioxide to cyclooctanone, 48, 29 Cyclooctanone, 46, 28... 

Sml2 has also been used to form cyclooctanols by cyclization of 7,8-enones.262 These alkene addition reactions presumably proceed by addition of the ketyl radical to the double bond, followed by a second electron transfer. 

Cycloheptyl and cyclooctyl nitrites on irradiation undergo the Barton reaction yielding 4-nitroso-l-cyclo-heptanol and 4-nitroso-l-cyclooctanol dimers, respectively.28 The products originate from attack of an alkoxy... 

Heptanol, 2-methyl-3-hexanol, 2,4-dimethyl-3-pentanol, cyclo-pentanol, cyclohexanol, cyclo-heptanol, cyclooctanol, cis-and trans-2-methylcyclohexanol, cis- and trans-4-tert-butyl-cyclohexanol ai2o3 180-210 94... 

Under similar conditions, cyclooctanone gave cyclooctanol and a bicyclo-octanol of unknown structure. 

Intermolecular coupling of ketones and alkenes, promoted by SmH, occurs with excellent stereochemical control. In one such reaction, samarium(II) iodide has been used to prepare cyclobutanones and cyclobutanols from chiral, 6-oxohex-2-enoates (equation 137)520. The reaction is performed in THF in the presence of HMPT and occurs in good yield with excellent stereocontrol. If appropriately located carbonyl and alkene moieties are present in a molecule, then Sml2-HMPT can be used to form cyclooctanols by a radical cyclization process in some cases there is a reasonable degree of diastereoselectivity (equation 138)521,522. 

Suzuki et al. reported that the CD derivative with a pyrene moiety attached to C3 (76) is an extremely better host than the one with the moiety attached to C6 (77), as shown by the binding constants 1.9 X 105 M 1 of 76 in contrast to 2.9 X 102 M 1 of 77 for cyclooctanol as a guest [73], The fact that the capping at the secondary hydroxyl side by a hydrophobic moiety has such a large enhancing effect... 

The rearrangement of methyl vinylketoside 45 can be accelerated by using TRIBAL. In this case the reaction affords at room temperature the corresponding cyclooctanol derivative 46 with a high preference for a syn-hydrogen delivery compared to the adjacent benzyloxy function (Scheme 14) [57]. 

Moreover, it is possible to selectively oxidize secondary alcohols in the presence of primary alcohols without using any protecting group, as shown in the case of competitive oxidation of cyclooctanol and 1-octanol (Figure 13.3). 

Figure 13.3 Competitive dehydrogenation of cyclooctanol and 1-octanol. Reaction conditions 1-octanol (0.5 mmol), cyclooctanol (0.5 mmol), styrene (1 mmol), 8% Cu/Al203 (100mg), toluene (8 ml), 363 K, N2 atmosphere.

Sml2 can be also used for the same ring-expansion reaction. Thus, radical ring-expansion reaction of bicyclo[4.2.0]octanone (274) promoted by Sml2 provides a mixture of cyclooctanol (275a) and lactone (275b) (eq. 3.111). In this case, C02Me, CN, and Ph... 

With 9-octyl-9-borabicyclo[3.3.1]nonane the initially formed amide was further oxidized to provide 5-tosylamino-cyclooctanol. 

A solution of the borane (1 mmol) in THF (3 ml) was treated with the ylide (374 mg, 1 mmol) under argon, at room temperature. After stirring for 3 h, 3n aqueous sodium hydroxide (2 ml) and 30% hydrogen peroxide (1 ml) were added to the reaction mixture, which was allowed to stand overnight it was then neutralized with 1 N HC1 (7 ml), extracted with dichloromethane (3x15 ml) and dried. Concentration and purification by preparative TLC (petroleum ether-ether) yielded 5-tosylamino-cyclooctanol (266 mg, 91%) m.p. 88-89°C. 

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