Octane octanone

Base-induced rearrangement of bicyclo[2.2.2]octane oxide 67 gives predominantly bicyclo[2.2.2]octanone 68 (Scheme 5.15), which once again indicates that close proximity between the carbenoid center and the C-H bond into which it may insert is important if such an insertion is to occur [30]. In comparison, the sense of product distribution is reversed for the related substrate bicyclo[2.2.2]octadiene oxide 70 on treatment with LDA [15, 22], alcohol 72 being the favored product. 

In yet another version of adopting a biphase system, oxidation of alkanes with rert-butyl hydroperoxide has been conducted with an aqueous phase. Launay et al. (1998) have developed an efficient and highly selective conversion of cyclo-octane to cyclo-octanone using Ru colloidial particles formed in situ from RuCli. 5H2O. The aqueous phase can be recycled. 

It was also recently shown that VO(OBu )3 catalyzes the oxidation of n-octane by TBHP to a mixture of isomeric octanones with yields close to 80%, and reactive Vv t-butyl peroxides have been detected as intermediates.233... 

Interestingly, zirconacyclopentane 246 formed by the reaction of 1,6-heptadiene with the Zr complex has the firms ring junction mainly [108]. It should be noted that the preparation of the trans ring junction in the bicyclo[3.3.0]octane system by other means is difficult. Carbonylation of 246 affords trans-fuzed bicyclo[3.3.0]octanone 247 [109,111]. The diacetoxy compound 248 is obtained by oxidative cleavage of 246. Protonation affords the frans-dimethylcyclopentane skeleton. Similar reactions occur with 1,6-enynes, and Pauson Khand-type cyclopentenone synthesis is possible by carbonylation. 

The overall reversibility of the process was shown by the recovery of 2-octanone when 2,2-bis(difluoroamino)octane was shaken with H2S04 at room temperature for 1 hr (17). In the presence of strong acids, aldehydes (RCHO) react to give bis(a-difluoroaminoalkyl)ethers [RCH-(NF2)OCH(NF2)R, 50-60% yield], and gem-bis(difluoroamino)alkanes [RCH(NF2)2, 20-40% yield] (108, 109). The reactions of HNF2 with a-hydroxyketones and a-/ -diketones in fuming sulfuric acid lead to difluoroamino-l,3-dioxa-2-thiolane-2,2-dioxides (215). 

In contrast to the inertness of alkyl-silanes and -stannanes, alkylplumbanes in the presence of TiCU add to aldehydes. The effectiveness of BF3 as the promoter eliminates the possibility of organotitanium species occurring as intermediates. Addition of R4Pb to a mixture of an aldehyde and TiCU is important, as clean reaction does not occur when the order of addition is reversed, i.e. addition of the aldehyde to a mixture of R4Pb and TiQ. As the reagent reacts only with aldehydes and not with ketones, octanal can be butylated selectively in the presence of 2-octanone (equation 15). ... 

Oxidations. Sulfides are convene combination of iron(lll) nitrate and silic effects oxidation of benzylic alcohols to al Bicyclo[3.3.0]octan-3-ones. 1-Tri verted to the bicyclo(3.3.0]octanone by... 

Sesquiterpenes of the patchouli family were made by a synthetic sequence involving construction of tricyclo[3.2.1.0 ]octanone 25 by vinylphosphonium bicycloannulation of substituted cy-clohexenone. Lithium/ammonia reduction, with in situ methylation, gave 1,3,3-trimethyl-6-(1 -methylvinyl)bicyclo[2.2.2]octan-2-one (26) as the cleavage product, which was then converted to patchouli alcohol by further synthetic transformations. ... 

A simple route to a bicyclo[2.2.2]octanone system was achieved by Michael reaction under microwave irradiation of a mixture of cyclohexenones and ethyl acetoacetate adsorbed on the surface of solid lithium (5)-( )-prolinate followed by intramolecular aldolization on a column of basic Al2O3 5 (Scheme 5.31). The bicyclo[2.2.2]octane system is the core unit of several biologically active natural products and a useful intermediate for synthetic manipulation. ... 

Two groups have reported syntheses of the bicyclo[3.2.1]octane ring system found in certain tetracyclic diterpenes in which the key step is an intramolecular carbenoid insertion reaction. Thus decomposition of the diazoketone (4) in the presence of copper(II) sulfate gives the cyclopropyl ketone (5) in 48% yield. Acid hydrolysis of the acetal grouping is accompanied by concomitant fragmentation to the substituted bicyclo[3.2.1]octanone derivative (6).3... 

D.6) (D.6) 2-Octanone, octan-2-one, hexyl methyl ketone [111-13-7] FEMA 2802... 

D.15) (D.15) 3-Octanone, octan-3-one, ethyl pentyl ketone, amyl ethyl ketone [106-68-3] FEMA 2803... 

A13-05612 Butyroin EINECS 207-830-4 FEMA No. 2587 5-Hydroxyoctan-4-one 5-Hydroxy-4-octanone NSC 1479 Octan-4-ol-5-one 5-Octanol-4-one 4-Octanone, 5-bydroxy-. Chemical intermediate. Liquid mp = -10° bp = 185° dj 0.9107. 

The carbonyl profile of freshly ground C. arietinum grain was studied later and 18 different compounds were identified [91] of which ten were new to those identified in the study by Rembold [89]. They confirmed the presence of 98, 99, 100, 105, 107, 108, 109, 110 but also identified formaldehyde (213), acetaldehyde (214), butanal (215), pentanal (216), octanal (217), octanone (218), octenal (219), nonenal (220), decenal (221) and decadienal (222) [91]. They noted that the concentration of total... 

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