Sodium naphthalenide halides

It is important to note that SNAr displacement reactions of heteroatom functional groups other than halides have been demonstrated on purine substrates, including mesitylenesulfonates <20000L927>, sulfones (see Section 10.11.7.5), nitro substituents <2006S2993>, and T-azoles (see Section 10.11.7.3.2). Halopurines have been reduced using sodium naphthalenide <1997T6295>. 

ALLYL ALCOHOLS Benzeneselenenyl halides. Methylene triphenylphosphorane. Sodium naphthalenide. 

Reactions of metal organic compounds with alkyl halides, such as alkyl-lithium-alkylhalide reactions 2 .c,d,f,h,ii8 -d io) and reactions of Grignard compounds and sodium-naphthalenide D with alkylhalides,... 

In his paper dealing with the separation of radical and anion cyclizations Garst also comments on the apparent halogen effects on product distributions in both sodium naphthalenide and sodium mirror reactions 96 While there are other possible explanations, the possibility that alkyl halide radical anions could be intermediates that undergo reactions other than fragmentation to alkyl radicals and halide ions should be kept in mind. ... 

Review. Bergbreiter and Killough have discussed the various uses of CsK, particularly in comparison with the reactions of the soluble analog sodium naphthalenide. Perhaps the most useful role of CsK is for the rapid formation of alkoxides from alcohols and of stabilized carbanions from carbonyl compounds. In these two reactions, it reacts more readily than potassium itself and can be separated from the products by filtration. The authors conclude that it has only limited value for reduction of alkyl and aryl halides and sulfonates, reactions accomplished more readily by other reagents. They also note that CeK can be regarded as a suitable reagent for reactions in which sodium naphthalenide is useful. 

Radicals can also be generated via the fragmentation of radical anions. Single electron reduction of various alkyl or aryl halides will lead to bond cleavage, as shown in Eqs. 10.44 and 10.45. The reductions commonly occur from dissolving metals such as Na and K, sodium naphthalenide (Na Ar ), sodium benzophenone ketyl, or from pulse radiolysis (e ). 

Alkoxides are readily formed from partially substituted polyols and sugars by treatment with sodium naphthalenide 19) in 1,2-dimethoxy-ethane solution and subsequent reaction with alkyl halides then produces ethers 20). The reaction sequence is simple to apply, and the method deserves further investigation. 

Alternatively, disodium tetracarbonylferrate can be conveniently generated in situ from pentacarbonyliron, sodium and naphthalene instead of benzophenone (Scheme 4-2, eq. 1) or by treatment of iron(III) chloride with sodium naphthalenide in tetrahydrofuran in a carbon monoxide atmosphere (Scheme 4-2, eq. 2). The Collman s reagent thus obtained is directly reacted with electrophiles such as organic halides to give anionic acyliron complexes (Scheme 4—2, eq. 3). The latter can be easily transformed into... 

The smallest and perhaps the most important ones are the cyclotrisilanes,103 -germanes,104 -stannanes,105 and their mixed compounds.106 These are normally prepared by reaction of halides of the type R2EX2 with sodium or lithium naphthalenide, as in... 

The reduction of alkyl halides by solutions of dissolved metals like, e.g. sodium in ammonia or alkali metal naphthalenides in tetrahydrofuran, provides a convenient means of removing halogens to produce hydrocarbons or to prepare alkali metal organic compounds. It is generally accepted that these reductions involve free radical intermediates R pathway A, Scheme 12) . 

Garst and coworkers have used the reactions of l-methyl-5-hexenyl halides 136, (X = Hal) with alkali metals or alkali metal naphthalenides such as sodium naphthal-enide Na+N", as a mechanistic probe over the years95 . A 1984 publication96 discloses the possibility of differentiating between the radical 134 and anion 138 cyclization. 

Sodium telluride and ditelluride are readily generated in situ from Te by reduction with thiourea dioxide, and subsequent treatment with alkyl halide provides the corresponding dialkyl tellurides and ditellurides. E Thiourea dioxide and NaOH in 1 1 water/THF added to Te under N2, the mixture refluxed for 1 h, n-octyl halide and a little cetyltrimethylammonium bromide in THF added, and refluxing continued for 1 h - dioctyl telluride. Y 85%. The method is cheap, simple and does not require very dry conditions. F.e. and sym. ditellurides s. J.T.B. Ferreira et al., Synth. Commun. 19, 239-44 (1989) prepn. of Na2Te from ultra-pure Te-ingots/Na-naphthalenide, or from Te/Na and a little naphthalene, s. K.T. Higa, D.C. Harris, Organometallics 8, 1674-8 (1989). 

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