Sodium naphthalenide treatment

Research has shown that defluorination depth of the polymer surface extends about 300 nm (Fig. 14.3) as a result of sodium naphthalenide treatment. They reported that exposure to x-ray decreased the defluorination depth to 30-150 A. The structure of the defluorinated layer is highly porous. The suggested adhesion mechanism is mechanical interlocking of adhesive with this porous structure. Bond failure nearly always occurs by stripping the etched layer as opposed to cohesive failure of the adhesive. 

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

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... 

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]. 

Sodium naphthalenide in THF has also been shown to reduce Na-[M(CO)5] (M = Mn, Re). Initially it was believed that solutions of Na3-[M(CO)4] were obtained, but a more careful examination established that only very fine suspensions of insoluble and impure brown trisodium salts had formed. For example, treatment of Re2(CO)10 with 10 equivalents of NaC10H8 in THF provided a complete conversion to finely divided brown insoluble Na3[Re(CO)4] within an hour at room temperature (19). Although Na3[Re(CO)4] prepared with excess Na[C10H8] was impure, we discovered that these HMPA-free suspensions were useful in reactions in which removal of HMPA was very difficult. Attempts to find practical routes to relatively pure salts of [M(CO)4]3 , which do not involve the use of the toxic and high-boiling HMPA, have not been entirely successful to date. A summary of routes to insoluble (and impure) forms of A3[M(CO)4], where A = Na and K and M = Mn and Re, is shown in Eqs. (2) and (3). 

The insertion of a tin atom into a nonicosahedral carborane framework was first reported by Grimes and co-workers (233), following approaches similar to those which had previously been successful with transition metal reagents. Reduction of c/oso-2,4-C2B5H7 with sodium naphthalenide generates the C2B5H7 dianion, which on treatment with tin dichloride yields... 

Treatment of [(Me2PCH2)3Si-t-Bu]TiCl3(THF) with sodium naphthalenide in THF gives ( -CioH8)Ti[(Me2P CH2)3Si-t-Bn] in 40% yield. ... 

Treatment of J with sodium hydride in THF closed the azetidine ring smoothly to give K in 81% yield. Then, K was reduced with sodium naphthalenide to remove the tosyl group. Penaresidin A [(25,37 ,45,11 5,12 5)-156] was obtained after further deprotection of the TBS group. Peracetylation of 156 afforded the tetraacetyl derivative, whose specuoscopic and chiroptical properties were in accord with those of the tetraacetyl derivative of the natural product. Isomers of penaresidin A with (25,37 ,45,11 7 ,12 5)- and (25,35,45,11 5,12 7 )-configurations were also synthesized, but their physical properties were different from those of the natural penaresidin A. 

Exposure of PPSe to a CH2CI2 solution of N0+PF g, a reagent which renders PPS conductive, leads to dissolution of the polymer to give a red solution. Treatment of this solution with NH3 precipitates a yellow powder which has undergone considerable chain scission. Analogous to PPS (10), PPSe is decomposed by exposure to sodium naphthalenide in THF. 

Electron Spectroscopy for Chemical Analysis. Lap shear test (see Fig. 7.2). Supplied by WL Gore Corporation. Treatment with a 1 mole soulution of sodium naphthalenide in tetrahydrofuran at room temperature. 

Marches , J. A., Ha, K., Garton, A., Swei, G. S., and Kristal, K. W., Adhesion to Sodium Naphthalenide Treated Fluoropolymers. Part II. Effects of Treatment Conditions and Fluoropolymer Structure, J. Adhesion, 36 55-69(1991)... 

Treatment with a 1 mole solution of sodium naphthalenide in tetrahydrofuran at room temperature. 

Reduction of TiCl4(THF)2 with sodium naphthalenide in the presence of 2.1-2.3 equivalent of dmpe in THF at —70 to —80°C followed by treatment with CO at 1 atm gives Ti(CO)3(dmpe)2 as shown in (equation 1). Treatment of Ti(CO)3(dmpe)2 with CO at room temperature gives Ti(CO)5(dmpe). Ti(CO)3(dmpe)2 is monomeric in the solid state, possessing a monocapped octahedral structure. One of the carbonyls in Ti(CO)3(dmpe)2 can be replaced by treatment with PF3 to give Ti(CO)2(PF3)(dmpe)2. ... 

Trichloroethylene is mixed with an excess of combustible solvent and burned in a chemical incinerator equipped with an afterburner and scrubber. It may be destroyed in aqueous waste streams or groundwater by UV peroxidation, involving treatment with hydrogen peroxide in the presence of UV light (Yost 1989 Sundstrom et al. 1990). Oku and Kimura (1990) have reported reductive dechlorination using sodium naphthalenide in tetrahydrofuran at 0°C for 10 minutes. Chlorine is removed as sodium chloride to the extent of 97-100%. 

Acyloin condensation. The usual preparation of acyloins from aliphatic esters is not applicable to aromatic esters. In this case the reaction with sodium results in formation of the sodium carboxylate and a radical from the R group which undergoes further reactions. However, benzoin can be prepared in moderate yield by treatment of the trimethylsilyl ester of benzoic acid with sodium or by treatment of ethyl benzoate with sodium naphthalenide in THF at room temperature (397 yield). ... 

Surface modification and metallization of poly(tetrafluoroethylene) (PTFE) has attracted a considerable attention from viewpoints of fundamental science and applied technology. PTFE has a low surface free energy while it shows excellent thermal and chemical stability. Therefore, the chemical and physical inertness of PTFE makes metallization an extremely difficult process. At present a chemical treatment using a sodium naphthalenide solution (1-4), a radio frequency plasma process (5-8), and electron/ion beam irradiation (9-//) have been employed for the modification of PTFE surface. 

Pre-treatments (1) and (2) are by far the most widely used commercially and a number of proprietary solutions are available for treatment (2). Immersion in a 1 M solution of sodium naphthalenide in tetrahydrofuran for 60 s resulted in a 15 x increase in the... 

Chromium carbenes can also be prepared by the so-called Semmelhack-Hegedus route. Chromium hexacarbonyl is first reduced to a nucleophilic pentacarbonyl dichromate dianion 23 with sodium naphthalenide or potassium carbide. Reaction of this dianion species with an acid chloride gives a metal alkoxide that can be quenched with an electrophile to provide the desired chromate ester 24. Alternatively, the dianion can be added to an amide carbonyl to give a tetrahedral intermediated which collapses to the chromate amide 25 on treatment with trimethylsilyl chloride. 

These non-stick materials can be bonded after surface treatment, which have the effect of introducing polar chemical groups to the surfaces. Methods for polyolefins include flame, corona discharge and chemical etching. Solutions of sodium naphthalenide in THF and sodium in liquid anunonia are used for FITE. 

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. 

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