Adamantane, ketonization

Mathias et al. synthesized poly(ether sulfone)s and poly(ether ether ketone)s with pendent adamantane groups.192 Incorporating adamantane into a polymer as a pendent group has been demonstrated to significantly increase the glass transition temperature. 

This dry ozonation procedure is a general method for hydrox-ylation of tertiary carbon atoms in saturated compounds (Table 1). The substitution reaction occurs with predominant retention of configuration. Thus cis-decalin gives the cis-l-decalol, whereas cis- and frans-l,4-dimethylcyclohexane afford cis- and trans-1,4-dimethylcyclohexanol, respectively. The amount of epimeric alcohol formed in these ozonation reactions is usually less than 1%. The tertiary alcohols may be further oxidized to diols by repeating the ozonation however, the yields in these reactions are poorer. For instance, 1-adamantanol is oxidized to 1,3-adamantane-diol in 43% yield. Secondary alcohols are converted to the corresponding ketone. This method has been employed for the hydroxylation of tertiary positions in saturated acetates and bromides. 

Pioneering work on the desulphonylation of jS-ketosulphones was carried out by Corey and Chaykovsky - . This reaction was part of a sequence which could be used in the synthesis of ketones, as shown in equation (53). The main thrust of this work was in the use of sulphoxides, but Corey did stress the merits of both sulphones and sulphonamides for different applications of this type of reaction. The method soon found application by Stetter and Hesse for the synthesis of 3-methyl-2,4-dioxa-adamantane , and by House and Larson in an ingenious synthesis of intermediates directed towards the gibberellin skeleton, and also for more standard applications . Other applications of the method have also been madealthough it does suffer from certain limitations in that further alkylation of an a-alkyl- -ketosulphone is a very sluggish, inefficient process. Kurth and O Brien have proposed an alternative, one-pot sequence of reactions (equation 54), carried out at — 78 to — 50°, with yields better than 50%. The major difference between the two routes is that the one-pot process uses the desulphonylation step to generate the enolate anion, whereas in the Corey-House procedure, the desulphonylation with aluminium amalgam is a separate, non-productive step. 

The reagents RuCl3/Na(Br03) /aq. M Naj(C03) and RuCl3/K3(S30j)/aq. M KOH oxidised activated primary alkyl halides RX to carboxylic acids and secondary alkyl halides to ketones, e.g. 1-bromophenylethane to acetophenone [213]. Stoicheiometrically fran -Ba[Ru(OH)2(0)3]/CF3COOH/(bpy)/CH3Cl3 oxidised alkanes (e.g. cyclohexane, adamantane, n-hexane, ethane) to ketones or acids, perhaps via Ru (0) (bpy)(CF C(O)O) [550]. 

As stoich. [Ru(0)((N 0)p7CH3CN it oxidised primary alcohols to aldehydes, secondary alcohols to ketones, alkenes to aldehydes, tetrahydrofuran to y-butyrolactone. Styrene, cis- and tran -stilbenes gave benzaldehyde and adamantane gave 1-adamantol exclusively, while cyclohexanol gave cyclohexanone, suggesting that the complex is an effective oxidant for unactivated C-H bonds [636]. Immobilisation of the catalyst within Nation films on a basal plane pyrohtic graphite electrode was achieved, but the... 

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],... 

A mixture of 0.27 mtnol of tricyclo[3.3.1.1 3,7]decane (adamantane), 0.054 mmol of (Bu4N)4Wl()032, and 3 mg of platinum in 10 mL of acetonitrile under argon in a Pyrex Schlenk flask is irradiated with a 550 W mercury arc lamp. The reaction turns deep blue on photolysis. Every 16 h, photolysis is Stopped, the catalyst is reoxidized under air, the sample is degassed and again placed under an argon atmosphere, and irradiation is resumed. After a total of 64 h there is 58% conversion of adamantane and a 40% yield of the methyl ketone (by VPC). 

POLYHYDROGEN FLUORIDE REAGENT 1-FLUORO-ADAMANTANE. Dichloroalkane synthesis is shown in cis-DI-CHLOROALKANES FROM EPOXIDES cis-1,2-DICHLORO-CYCLOHEXANE. Nitrile functionality can be introduced from a ketone, as in NITRILES FROM KETONES CYCLOHEXANENITRILE, or from a reactive diene, as shown in 2,3-DICYANOBUTADIENE AS A REACTIVE INTERMEDIATE BY in situ GENERATION FROM 1,2-DICYANO CYCLOBUTENE 2,3-DICYANO-1,4,4a,9a -TETRAHYDRO-FLUORENE. 

It is interesting to note that in a somewhat similar catalytic system consisting of iron powder, acetic acid, and heptanal, aerobic oxidation of adamantane gave 1-adaman-tanol with high selectivity, while cycloalkanes were transformed to ketones as the main products.163... 

In 1983, Barton et al. described a new procedure for the oxidation of saturated hydrocarbons [1] by the use of metallic iron, adamantane, hydrogen sulfide or sodium sulfide, pyridine, acetic acid and a small amount of water. The reactions were run under air and afforded adamant-l-ol together with a mixture of adamant-2-ol and adamantanone. The substrate scope could be extended to other hydrocarbons. However, all of them led to product mixtures of the corresponding alcohol(s) and ketone (Scheme 3.1). 

Treatment of 1-bromoadamantane with AlBr3 in the presence of ethylene at -75 °C to give l-(j3-bromoethyl)-adamantane 202) followed by reduction 20°) results in good yields of 1-ethyladamantane (Eq. (63)). Wolf-Kishner 164) or Clemensen 203) reduction of commercially available methyl adamantyl ketone provides an alternative route for the preparation of this compound. 

Reaction with ketone and imine functionalities was studied in detail for silylene 85. Reaction of this silylene with ketones such as benzophenone, 3,3-dimethylbutan-2-one, and 2-adamantan-2-one afforded the disilaoxetane compounds 139 in high yields (Scheme 15). The formation of these products most likely occurs via a [2+1] cycloaddition to form a short-lived oxasilacyclopropane intermediate 140, which further reacts with a second silylene to form the final product C19970M4861, 1997PS537>. 

Sanin etal. described the reaction of a,/3-unsaturated fluorinated ketones 88 with ammonium sulfide in ethanol, which led to the formation of thiopyran- Wdioxide derivatives 89 (Equation 28) <1996JOC1986>. However, one of the studied ketones (3-adamantan-2-ylidene-l,l,l-trifluoro-propan-2-one 90) demonstrated an unusual behavior in the course of this reaction, which led to the formation of the fused-ring thietane 31 in 86% yield (Equation 29) <1996JOC1986>. 

In the past decade, there has appeared only one report, which can be classified under this heading, on the monodeoxygenation of spiro-adamantane-l,2-dioxetanes induced by catalytic amounts of tris-(2,4-dibromophenyl)-aminium hexachloroantimonate <1998T6939>. An electron-transfer mechanism from the aminium salt has been proposed for the observed formation of various ketones. Reports citing the electrophilic ring opening of dioxetanes by boron trifluoride, trifluoroacetic acid, and various other Lewis acids have been summarized in CHEC-II(1996) <1996CHEC-II(1B)1041>. 

Bott (1969 a, b), by allowing adamantan-l-ol and acetylene to react in 95% Hj5S04 at 4-7°, observed the formation of aldehyde 26 as the main product, together with ketones 25 and 27. The yields of ketone 25... 

From adamantan-l-ol and acetylene in 90% H2S04 Kell and McQuillin (1969) obtained exclusively the aldehyde 26 and ketone 27. Addition to substituted adamantyl acetylenes, AdC=CR (R==Ph, n-Pr, n-Hexyl) resulted in the formation of ketones AdCH2COR. 

The authors proposed that the peroxide is decomposed by the metal catalysts to the ketone and alcohol in a manner similar to that previously reported (30-34). This later system was also reactive toward adamantane (giving a high 3°/2° carbon activation ratio of 3.5) and other saturated alkanes. These catalysts also oxidize toluene at both the aliphatic and aromatic carbons (ratio benzylic/aromatic = 3.4 0.9) (Table IV). Activation of the aromatic ring was attributed to the formation of hydroxyl radicals. 

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