Sodium naphthalenide

The first living polymer studied in detail was polystyrene polymerized with sodium naphthalenide in tetrahydrofuran at low temperatures ... 

In practice the various trityl derivatives are cleaved with acid, but the monomethoxy derivative can be cleaved with sodium naphthalenide in HMPA (90% yield).It is not cleaved by sodium anthracenide, used to cleave a-naphthyldi-phenylmethyl ethers. 

Sulfonamides (R2NSO2R ) are prepared from an amine and sulfonyl chloride in the presence of pyridine or aqueous base. The sulfonamide is one of the most stable nitrogen protective groups. Arylsulfonamides are stable to alkaline hydrolysis, and to catalytic reduction they are cleaved by Na/NH3, Na/butanol, sodium naphthalenide, or sodium anthracenide, and by refluxing in acid (48% HBr/cat. phenol). Sulfonamides of less basic amines such as pyrroles and indoles are much easier to cleave than are those of the more basic alkyl amines. In fact, sulfonamides of the less basic amines (pyrroles, indoles, and imidazoles) can be cleaved by basic hydrolysis, which is almost impossible for the alkyl amines. Because of the inherent differences between the aromatic — NH group and simple aliphatic amines, the protection of these compounds (pyrroles, indoles, and imidazoles) will be described in a separate section. One appealing proj>erty of sulfonamides is that the derivatives are more crystalline than amides or carbamates. 

Sodium naphthalenide. This reagent has been used to remove the tosyl group from an amide. ... 

A number of nitrogen-fixing bacteria contain vanadium and it has been shown that in one of these, Azotobacter, there are three distinct nitrogenase systems based in turn on Mo, V and Fe, each of which has an underlying functional and structural similarity.This discovery has prompted a search for models and the brown compound [Na(thf)]+[V(N2)2(dppe)2] (dppe = Pli2PCH2CH2PPh2) has recently been prepared by reduction of VCI3 by sodium naphthalenide... 

Sn2 addition 413 Sn2 displacement 215 Sn2 lactone opening 412 ff. sodium bis(2-methoxyethoxy)-aluminium hydride see Red-Al sodium chlorite 516 - oxidation 772 sodium hypochlorite 550 f. sodium naphthalenide 739 f. sodium trimethoxyborohydride 390 SOMO 409... 

Diols can also be deoxygenated via Mv-sulfonate esters using sodium naphthalenide.294 Cyclic sulfate esters are also cleanly reduced by lithium naphthalenide.295... 

This reaction, using sodium naphthalenide, has been used to prepare unsaturated nucleosides. 

Bridging of macrolides.1 A number of natural products are known to consist of oxapolycyclic systems. A potential route to such systems involves bridging of the more readily available macrolides (or the corresponding dithionolides, available by thionation with Lawesson s reagent) by electron-transfer reactions initiated with sodium naphthalenide (Scheme I). 

Analogous transformations have been initiated using alternative methods. Tributyltin hydride and sodium naphthalenide [101], for example, were examined in an effort to probe the possible intermediacy of a radical or carbanion, respectively. The results were compared with those achieved electrochemically. As illustrated, the results were different for each set of reagents, though the sodium naphthalenide and electrochemical results are most similar. This information has b n used to suggest that a carbanion is formed electrochemically and participates in the cyclization event. 

Disodium pentacarbonylchromate is prepared by adding a solution of sodium naphthalenide (88 mmol) in THF (160 mL) to chromium hexacarbonyl (40 mmol) in THF (240 mL). The resulting solution of disodium pentacarbonylchromate is transferred to a 500-mL graduated cylinder (to estimate the concentration). This solution can be stored at -20 °C under argon for at least two months. 

Alkene formation can also be achieved using potassium/graphite (C8K) or sodium naphthalenide for reduction.172 The reductant prepared in this way is more efficient at... 

THF tetrahydrofuran, NaNap sodium naphthalenide, Na2St disodium stilbene dianion, BP benzoyl peroxide, DME 1,2-dimethoxyethane, TMBD tetramethylbenzidine dication diperchlorate, WBP Wurster s blue perchlorate, LP lauroyl peroxide, FLSPEC fluorescence spectrum obtained, FPSPEC fluorescence and phosphorescence spectrum obtained, FXSPEC fluorescence and eximer spectra obtained, DPAC12 9,10-dichlorO 9,10-dihydro-9,10-diphenylanthracene. 

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>. 

Cyclostannanes (R2Sn) are obtained, primarily as the hexamer (n = 6), by treatment of the diorganotin dichloride R2SnCl2 with sodium naphthalenide [eqn (2.4)]. ... 

Sodium a-(N,N-dunethylammo)naphthalenide (1). The radical anion is prepared and used in the same way as sodium naphthalenide. However the derived a-dimethyl-aminonaphthalene can be separated from products simply by an aqueous wash.1... 

The dropwise addition of sodium naphthalenide to THF containing vanadium trichloride and l,2-bis(dimethylphosphino)ethane (dmpe) causes changes of colours suggesting a stepwise reduction from +2 to 0. Brown [V(dmpe)3] was isolated41 (fieff = 2.10BM) and IR data suggest octahedral coordination. The same complex was synthesized by a metal vapour technique.42 The ESR was that expected and the unit cell is cubic with a = 11.041(3) A. 

The monomeric carbonyl complexes of d M1 isolated so far are mainly the seven-coordinated [MX(CO)2(dmpe)2] compounds (M = Nb, X = Cl, Br, N3 697 M = Ta, X = H, Cl, Br, CN, Me, Et, Pr ) (53) has been obtained by reduction of [TaCl2(dmpe)2] with one equivalent of sodium naphthalenide under CO the other tantalum derivatives were generally prepared by oxidative additions to [Ta(CO)2(dmpe)2] formed in situ by reduction of (53 Scheme 10). The niobium analogs were formed by reductive carbonylation of [NbCU(dmpe)2].698... 

Treatment of [TaCl4(dmpe)2] with sodium naphthalenide afforded [TaCl(dmpe)2( /4-C,0H8)] (64), which was reduced by further addition of sodium naphthalenide to unisolated Na[Ta(dmpe)2(n4-Ci0Hs)]. Protonation or methylation of this anion afforded the Ta1 adduct [TaX(dmpe)2(i74-CioHs)] (X = H, Me). Related procedures gave the analogous 1,3-cyclohexadiene adduct [TaCl(dmpe)2(i74-C6H8)] in poor yields.709... 

Reduction reactions of nickel(If) compounds. The reduction of nickel(II) compounds to yield nickel(0) phosphine complexes has been carried out using a variety of reducing agents such as sodium amalgam, sodium sand, sodium borohydride, sodium naphthalenide and aluminum trialkyls. In some cases the phosphine ligand itself was found to act as the reducing agent. 

Ni C6H4(PEt2)2 2 sodium naphthalenide Ni(L—L)2(N03)2 + NaBH4 Warm acetone or ethanol 66... 

Cyclic sulfates, efficiently prepared from vic-diols in a two-step one-pot procedure [225], were converted into alkenes by treatment with sodium naphthalenide in THF [226]. 

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