Sodium sand

The formation of an organosodium compound (p-tolyl-sodium) is well illustrated by the interaction of sodium sand or wire with p-chlorotoluene in light petroleum (b.p. 40-60°) at about 25°, for when the reaction mixture is added to excess of solid carbon dioxide pure/ -toluic acid is obtained directly in a yield exceeding 70 per cent. ... 

Method B. Place 125 g. (106 -5 ml.) of diethyl phthalate and 25 g. of molecular sodium (sodium sand see Section 11,50,6) in a 500 ml. round-bottomed flask fitted with a reflux condenser and dropping funnel. Heat the flask on a steam bath and add a mixture of 122 5 g. (136 ml.) of dry ethyl acetate and 2 5 ml. of absolute ethanol over a period of 90 minutes. Continue the heating for 6 hours, cool and add 50 ml. of ether. Filter the sodium salt (VI) on a sintered glass funnel and wash it with the minimum volume of ether. Dissolve the sodium salt (96 g.) in 1400 ml. of hot water in a 3-htre beaker, cool the solution to 70°, stir vigorously and add 100 ml. of sulphuric acid (3 parts of concentrated acid to 1 part of... 

In a sophisticated variation of the Knoevenagel condensation ("Panizzi ) methyl 3,3-dimethoxypropanoate (from ketene and dimethoxymethenium tetrafluoroborate D.J. Crosby, 1962) is used as a d -reagent. Because only one carbonyl group activates the methylene group, a strong base with no nucleophilic properties (p. 10) has to be used. A sodium-sand mixture, which presumably reacts to form silicate anions in the heat, was chosen... 

Dlcarboxyfuran-2-acetlc acid (3). To a cooled suspension ol sodium sand (17,2 g,... 

Sodium nitromalonaldehyde momo-iiydrate Warning), 46,104 Sodium sand, 46, 8 reaction with 2 carbomethoxy cyclo-pentanone, 45, 8... 

Catalytic hydrogenation with platinum liberates the hydrocarbon from methylcobalamin (57) and from alkyl-Co-DMG complexes (161), but not from pentacyanides with primary alkyl, vinyl, or benzyl ligands, though the cr-allyl complex yields propylene (109). Sodium sand gives mixtures of hydrocarbons with the alkyl-Co-salen complexes (64). Dithioerythritol will liberate methane from a variety of methyl complexes [cobalamin, DMG, DMG-BF2, G, DPG, CHD, salen, and (DO)(DOH)pn] (156), as will 1,4-butanedithiol from the DMG complex (157), and certain unspecified thiols will reduce DMG complexes with substituted alkyl ligands (e.g., C0-CH2COOH ->CH3C00H) (163, 164). Reaction with thiols can also lead to the formation of thioethers (see Section C,3). 

A 50% dispersion of sodium in paraffin, which was obtained from Alfa Inorganics, Inc., can be used successfully instead of the freshly prepared sodium sand, t Faster addition of dimethylarsine causes aggregation of sodium. 

Hydroxypyrrole-2,4-dicarboxylate (1309, R = H, R1 = Et) could be prepared in 30% yield in the reaction of ethyl JV-ethoxycarbonylglycinate and EMME in the presence of sodium sand in a mixture of benzene and xylene at reflux temperature for 3 hr (62JA635). 

Comparable three-membered metallacycles were also obtained by oxidative addition of C—H bonds. Reduction of TaCls by sodium sand in PMe3 as a solvent afforded [Ta(PMe3)3(r/2-CH2PMe2)(tj2-CHPMe2)] (39 7% yield), whose structure (Figure 31) shows that C(l) is bonded... 

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(PCy2)(PCy2Ph)l2 which was obtained by reducing the nickel(II) complex [NiCl2(PCy2Ph)2] with sodium sand. 27... 

Pivalonitrile (33.2 g) and t-butyl chloride (44.4 g) were added under nitrogen over 1 h to a well-stirred suspension of sodium sand (18.4 g) in a mixture of light petroleum (80 ml), THF (20 ml) and methanol (1ml), keeping the reaction temperature between 15 and 20°C during addition. The mixture was stirred for 3h. Chlorobenzene (2 g) in THF (5 ml) was added dropwise over 10 min, and stirring continued (1 h). Methanol (20 ml) was cautiously added over 0.5 h, followed by water, until clear phases separated. The aqueous phase was extracted with ether (3 X 50 ml). The combined organic phases were dried and concentrated under reduced pressure. Distillation afforded the pure imine (63%), b.p. 62-63°C/19 torr. 

In a typical preparation, Na[Ir(CO)4] was stirred with 3.2 equivalents of sodium sand in HMPA for 12 hr at room temperature under a dynamic... 

Attempts to repeat these experiments did not immediately clarify the situation, since products were often incompletely characterized. The use of Na/Hg amalgam (4, 5), Na/naphthalene (6, 7), and sodium sand (8) in reactions (1), (2), and (3) also led to volatile green solids, again formulated as dimeric species... 

In a 500-mL, three-necked Morton flask fitted with a condenser, mechanical stirrer, and gas inlet tube is placed 8.6 g (0.375 g atom) of sodium and 75 mL of dry xylene (Note 6) the unstirred mixture is heated at reflux under a nitrogen atmosphere. After the xylene has reached its boiling point and the sodium has melted, the solution is rapidly stirred to produce a very fine-grained sodium sand. Quickly the heating mantle is removed and stirring stopped (Note 7), After cooling, the xylene is pipetted or siphoned away from the sodium sand and stored for future use. 

The solution of ca. 0.30 mol of cyclopentadienylsodium is decanted from residual sodium sand with a U-tube into the dropping funnel (Note 12) and is added dropwlse over a 2-hr period (Note 13), A white precipitate of sodium bromide forms during the addition. The heterogeneous solution is stirred overnight at -78 C to insure complete formation of methyl 2,4-cyclopentadiene-1-acetate. 

The efficient formation of cyclopentadienylsodium is of paramount importance for the entire reaction sequence. Variations in the yield of methyl 2,4-cyclopentadiene-l-acetate have been traced to the degree of efficiency in producing a fine sodium sand which is used to produce cyclo-pentadienylsodium. In the alkylation reaction of cyclopentadienylsodium with methyl bromoacetate, the entire process nust be carried out in an Inert dry atmosphere at -78°C. At higher temperatures, the desired product can undergo undesired dimerization and double bond migration side reactions. Methyl 2,4-cyclopentadiene-l-acetate, once formed, is used Immediately. 

Xylene was obtained from Fisher Scientific Company. The xylene is initially dried over sodium and is saved and reused in making additional batches of sodium sand. 

If stirring continues while the xylene cools, the sodium sand... 

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