Cyclo octanes

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. 

Fujii, T., and Y. Saito, Thermocatalytic formation of molecular hydrogen and cyclo-octene from cyclo-octane by rhodium complexes. /. Chem. Soc., Chem. Commun., 757-758 (1990). 

An interesting additional experiment to follow the iridium nanoparticles formation was demonstrated by Watzky and Finke ]30], who used a direct method of monitoring by gas-hquid chromatography (GLC) the evolution of cyclo-octane... 

Hence, two methods are available that can be applied to follow nanoparticles formation and growth (i) an indirect method that utilizes the consumption of molecular hydrogen pressure versus time and (ii) a direct method that follows the loss of precursor by the 1 1 conversion of its cyclo-octadiene ligand to cyclo-octane by GLC measurements. The mechanism developed by Watzky and Finke suggests that the nanoparticles act as Hving-metal polymers -a concept that could be used to obtain particles with defined sizes simply by adding the appropriate amounts of catalyst precursors [32]. 

RuCl3(dppe](BF ) and [RuCl2(dppp)](BF ) (dppe=l,2-(diphenylphosphino)ethane, dppp=l,2-(diphenylphosphino)propane) are made from RuClj and the ligands in the presence of (NO)BF. The system [RuCl Cdppe] [RuCl3(dppp)] /PhIO or KCHSO )/ (BDTAC)/CH Cl2 oxidised adamantane, cyclo-octane and cyclohexane to alcohols and ketones. The same results were obtained with [RuCKdppp) ] as catalyst [816]. 

CIS-[Ru(H20)2(dinso) ] is made from as-RuClj(dmso) and Ag(BF ) in aq. EtOH. The system c/s-[Ru(H20)j(dmso) ] Vaq. Na(ClO) or TBHP/CH Cl oxidised alkanes such as adamantane, cyclo-octane, -heptane and -hexane to the corresponding alcohols and ketones as did [Ru(Hj0) PWjj(0)3g ] . A free-radical mechanism may be involved for the TBHP oxidations, but those with (C10) probably involve oxoruthenate(VI) or oxoruthenate(IV) intermediates [823], The oxidative destruction of a-chlorinated alkenes by CM-[Ru(HjO)2(dmso) ] Vaq. Oxone /Me(CH3) jN(HSO ) MCj to carboxylic acids and ultimately to CO and HCl was reported [946],... 

Cyclo-octane Cyclo-octyl tiifluoroacetate + cylcohexanone L [65]... 

Cycloalkanes R R R H and chelating arenes ArH were oxidatively cross-conpled to Ar R R R by [RuClj(p-cymene)]2/TBHP/135°C (the reactants were the solvent) thus 2-phenylpyridine and cyclo-octane were cross-coupled cf. mech. Ch. 1. Other complexes (Ru(acac)3, [RuCl CCOD)] and RuHj(CO)(PPh3)3) also catalysed the reaction [78]. 

In this section, we shall examine the results which have been obtained for the exchange of the saturated hydrocarbons methane, ethane, cyclopentane, cyclohexane, cycloheptane, cyclo-octane, and neopentane. The common characteristic of this group is that all the carbon-hydrogen bonds in each individual molecule are similar in nature. An attempt will be made to indicate how the results fit into the classifications outlined in Sec. II. 

Diri itroso-1,3,5,7-tetraozabicyclo[3.3.2]-nonone. CA name for 3,7-Dinitroso-l,5-endom ethylene-1,3,5,7-tetraaza-2,4,6,8-cyclooctane, described under 1,5-Endo-methylene-l,3,5,7-tetraaza-2,4,6,8-cyclo octane and Derivatives... 

Trifluoromethyl-undccafluoro- ElOa. 79 (Application), 659 (Cyclo-octane + CoF3),662(F.n + CoF3 CH3 - CF3) ElObj. 364/366 368/370 (Educt)... 

The hydrogenation of 1,5-cyclo-octadien (COD) to cyclo-octene (COE) is performed in a slurry reactor. The reaction is relevant because the product is an intermediate for the production of special polymers. However, this reaction suffers from the drawback that the hydrogenation does not stop at cyclo-octene, because a full hydrogenation to cyclo-octane (COA) is possible, as shown in Figure 4.1.12. 

Benzothiophen 2-Amino-3-cyan-5,7-dimethyl- E6a, 223 (Cyclohe-xanon + NC—CH2 —CN/S8) Cyclooctalblthiophen 2-Amino-6-tert.-butyl-3-cyan-4,5,6,7,8,9-hexahydro- E6a, 223 (Oxo-cyclo-octan + NC —CH2 —CN/S8) Sulfimid N-(4-Cyan-phenyl)-S-methyl-S-propyl- Ell, 896 (R2S + R-NH2/NCS)... 

Photocycloaddition of ethoxyethene to the enone (81) at 254 nm in methanol affords the adduct (82). Addition of the same alkene to the enone (83) also proceeds via a cyclobutane intermediate but this is unstable and ring opens to afford the cyclo-octane derivative (84). A study of the addition of the optically active alkene (85) to the enone (86) affords four cyclobutane adducts two from head-to-head addition and two from head-to-tail addition. These cycloadditions load to a double induction giving either increased or decreased diastereoselectivity.The intermolecular cycloaddition of ethylene to the enone (87) yields the two adducts (88) and (89). The photoadducts are apparently susceptible to secondary irradiation and the maximum yields of the adducts was obtained at 50% consumption of the starting material (87). Under these conditions (88) and (89) were obtained in 71 and 23% respectively. The isomer (88) was taken on through several steps to afford ultimately racemic starpuric acid a... 

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