Sodium naphthalide

It is a convenient aspect of electrochemical doping of the polymer that the electrolyte can provide the counter ion, although a similar result can be achieved via chemical doping under certain circumstances, e.g., Using a radical ion containing species such as sodium naphthalide, Na+ npthT, i.e.,... 

Hindered di-t-alkylamines RNHBu1 (R = t-Bu, t-octyl or 1-adamantyl) have been synthesized from t-alkylamines as follows. Reaction with peracetic acid gave the nitrosoalkanes RNO, which were treated with t-butyl radicals, generated from t-butylhydrazine and lead(IV) oxide, to yield t-butyloxyhydroxylamines. Reduction with sodium naphthalide in THF gave the products (equation 12). The di-t-alkyl-amines are inert to methyl iodide and dimethyl sulphate but can be alkylated by methyl fluorosulphonate42. 

Unfortunately, efforts were thwarted by the formation of the endocyclic alkene 134. In these cases, use of sodium naphthalide afforded the desired adducts, 135 and 137, though the yields in both of the cases portrayed in Scheme 8, were poor. 

The tosyl protecting group of 4a is removed with sodium naphthalide at -60 °C, and an intramolecular nucleophilic attack of the nitrogen lone pair to the epoxide takes place spontaneously to afford the pyrrolidine hydroxy ester as a labile reaction product, which is immediately protected as the corresponding silyl ether 3a in 68%... 

Other Compounds. Adsorption of MeNC into a cobalt(ii) zeolite at — 196"C was followed by e.s.r. spectroscopy, and the presence of low-spin [Co-(CNMe)j] and [Co(CNMe) ] complex cations demonstrated.This work represents one of the few successful attempts to produce well-characterized transition-metal complexes in a zeolite framework. Addition of NaCp to CoClj and [(BgC2H,Q)CoCp], previously reduced with sodium naphthalide gives a new bimetallic complex, for which structure (94) is proposed. ... 

The chemical removal of water can be done in several ways. For anionic polymerisations it is customary to rinse all the glassware repeatedly with a solution of sodium naphthalide which reacts with water to form naphthalene and NaOH, both of which are adequately soluble in the usual solvent tetrahydrofuran (THF) at the low concentrations used. This method, however, requires that the whole reactor assembly be detachable from the vacuum line so that it can be tilted around for the sodium naphtalide solution to reach all parts of the system. Care If much water is to be removed and the volume of the purging solution is too small, some NaOH may be precipitated ). 

Crystallisable salts and related compounds. Almost all crystallisable catalysts, such as sodium and lithium aromatic compounds (e.g. sodium naphthalide), -oyl salts such as aroyl hexafluorophosphates, alkoxides, and many others can be prepared in a vacuum system and then purified by repeated crystallisations and washings in a closed system (see Chapter 5) thereafter they can be distributed into breakable phials or other devices as described in Chapter 3. 

In the course of an extensive study of the mode of action of anionic catalysts, A. G. Evans used exclusively h.v.t. His investigation of the electron-transfer reactions involving 1,1,3,3-tetraphenylbutene-l, tetraphenylethylene and sodium naphthalide is of particular interest here because all the reaction mixtures were prepared by h.v.t. and both UV and ESR spectra were measured (J. E. Bennett et al, 1963). The paper contains full experimental details. 

Sodium naphthalide doping was performed using a selected polyazomethine with a THF slurry of sodium naphthalide and stirring for 24 hours. Thereafter the mixture was concentrated and the doped polymer stored at ambient temperature until needed. Testing data for -doped experimental agents not supplied by the author of the current invention. 

Some interesting electron-transfer reactions of sodium naphthalide have recently been reported. Reaction with phenylmercuric chloride or benzylmercuric chloride gives better than 70% yields of the symmetric diphenyl- or dibenzylmercury compounds. Solutions of alkali metals in HMPA lead to the same results (88). Evidence for the reaction of sodium naphthalide with methylene halides to give methylene anion radical, CH2T, has recently appeared (22). 

The simplest complex is the binuclear [Au2(PPh3)2], prepared by reaction of [AuI(PPh3)] with sodium naphthalide, NaCi0H8. It is isoelectronic with Hg2Cl2 but, curiously, has the trans bent structure (99) with r(AuAu) = 276 pm and angle AuAuP = 129°, rather than the expected linear structure. 

Even the chemically robust perfluoroalkanes can undergo electron-transfer reactions (equation 4) because of their relatively high electron affinities [89]. Strong reducing agents like alkali metals [90] or sodium naphthalide [91] are normally required for reaction, but perfluoroalkanes with low-energy, tert-C-F 0 anti-... 

Kovacic polyphenylene is brown with about 1 spin/chain detectable by ESR. Yamamoto polymer is yellow with a shorter chain length and fewer spins. In Kovacic polymer the spins and colour may both be due to polynuclear species. Polyphenylene produced from the poly(dihydrocatechol) precursor 249) is also yellow, but has a high molecular weight, of the order of 10s. It contains about 15% o-linkages, and the aromatization procedure may leave a high level of twists in the chain originating from the flexible precursor. This material dopes only to low levels of conductivity with sodium naphthalide (6x 10 3 Scm-1) and iron chloride (1.5 x 10-2 Scm-1) but reaches a level comparable to Kovacic and Yamamoto polyphenylenes with AsFs (102 S cm-1). 

Polymer-attached Cp2TiCl2 has been reduced by sodium naphthalide, and the resultant species, which may contain a mixture of Ti(IV), Ti(III), and Ti(II), are more active hydrogenation catalysts for olefins than is the unsupported Cp2TiCl2 (72). Although distinct Ti-H-containing species were not identified, it has been suggested that the complete reaction occurs at one metal center, in contrast to earlier suggestions that such reductions involve a bimolecular reaction of an intermediate titanocene alkyl and a titanocene hydride (30). 

Reaction of sodium naphthalide with B2C14 at room temperature was reported to give a liquid product with a suggested structure, 17. The compound 17 reacts with four equivalents of (CH3)3N to form an adduct which decomposes above 100 °C to give the bis(trimethylamine) adduct of B2C14 and an unstable product that is thought to be 18 (Scheme 3). It was reported that the trimethylamine complex of tetra(methyl)diborane(4) was obtained from the reduction of bromodimethylborane with sodium or silver in trimethylamine.52... 

The reduction of MoVI nitrides with iodide has also been reported. As shown in Eq. (22), reaction of nitrido MoVI nitrides with MePh3PI afforded the corresponding Mov nitride complex 65 [30]. In a related process, treatment of a nitrido MoVI complex with sodium naphthalide leads not only to the Mov nitride but also to the formation of a Moiv2Mov2 (p-N)4 tetramer [31]. The structure of the latter product has been firmly established via single crystal X-ray crystallography. 

Diallyl Tellurium (Tellurium-Sodium-Naphthalene Method)1 A tellurium ingot is broken into pieces by shaking in a polyethylene container. A 25-ml Schlenk flask is charged with 6.1 g (48 mmol) tellurium pieces, 2.2 g (96 mmol) sodium, 0.1 g (0.8 mmol) naphthalene, and 20 mi tetrahydrofuran. The mixture is stirred under an argon atmosphere at 25° for 4 days and then filtered. The filter cake is washed with 20 ml fresh tetrahydrofuran and dried under vacuum to give 7.6 g (92%) disodium telluride. Alternatively, 60-mesh tellurium powder and 2 molar equivalents of sodium naphthalide are stirred for 4 h in tetrahydrofuran. Disodium telluride was isolated as a beige-colored solid. 

The isomeric 3-iodo-4/3,5/8-epoxides (50) are reduced either by sodium naphthalide or by butyl-lithium to give the allylic alcohol (51), apparently by a non-concerted mechanism involving a rate-determining one-electron transfer.72... 

Typical oxidising dopants used include iodine, arsenic pentachloride, iron(III) chloride and NOPF6. A typical reductive dopant is sodium naphthalide. The main criteria is its ability to oxidise or reduce the polymer without lowering its stability or whether or not they are capable of initiating side reactions that inhibit the polymers ability to conduct electricity. An example of the latter is the doping of a conjugated polymer with bromine. Bromine it too powerful an oxidant and adds across the double bonds to form sp3 carbons. The same reaction may occur with NOPF, but at a lower rate. 

Reduction with sodium naphthalide followed by treatment with Mel gave 127 and 128 in an excellent combined yield. Exposure of 73 to AgBF4-Et3SiH resulted in a novel skeletal rearrangement leading to compound 129... 

This procedure is based on that previously described by Wilke.1 The use of NaBH4 and sodium naphthalide as reducing agents has been more recently reported by Ugo.2... 

The simple dinuclear complex [Au2(PPh3)2] has the trans bent stracture with fi (Au-Au) = 2.76 A and Au-Au-P angle of 129°. It was prepared from the reaction of [AuI(PPh3)] with sodium naphthalide. The trinuclear gold-cluster (17), p = PPh2, is photoluminescent in solution. ... 

A scrupulously clean and dry solution of styrene (5 g) in 50 ml tetrahy-drofuran was held at -IQPC. Sodium (l.Og) and naphthalene (6.0 g) were stirred together in 50 ml dry tetrahydrofuran to form a dark green solution of sodium naphthalide (Eq. 9-10). When 1.0 ml of this green solution was injected into the styrene solution the latter turned reddish orange. After a few minutes the reaction was complete. The color was quenched by adding a few milliliters methanol, the reaction mixture was allowed to warm to warm temperature, and the polymer formed was precipitated and washed with methanol. What is of the polystyrene formed in the absence of side reactions What should of the product be if the polymerization were carried out so that the growth of all macromolecules was started and ended simultaneously ... 

The chemical reduction (Na/Hg, sodium naphthalide) revealed that the primary product disproportionated to give ferrocene and an arene [356). 

Another versatile chemical reductant which has not been widely applied in electron-transfer chemistry is sodium naphthalide. This arene radical anion is easy to generate and capable of reducing carbonyl compounds to the corresponding ketyl... 

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