1.2- di methoxyethane

Under the best conditions, sodium cyclopentadienide gives pale yellow or orange solutions. Traces of air lead to red or purple solutions, as does insufficiently purified solvent, without, however, lowering the reaction yield appreciably. If 1,2-di-methoxyethane is used, in which sodium cyclopentadienide is less soluble than in tetrahydrofuran, white crystals may be obtained at this point. 

The extent to which 151 phosphorylates the aromatic amine in the phenyl ring is highly dependent upon the solvent. For instance, aromatic substitution of N-methylaniline is largely suppressed in the presence of dioxane or acetonitrile while pho.sphoramidate formation shows a pronounced concomitant increase. The presence of a fourfold excess (v/v) or pyridine, acetonitrile, dioxane, or 1,2-di-methoxyethane likewise suppresses aromatic substitution of N,N-diethylaniline below the detection limit. It appears reasonable to assume that 151 forms complexes of type 173 and 174 with these solvents — resembling the stable dioxane-S03 adduct 175 — which in turn represent phosphorylating reagents. They are, however, weaker than monomeric metaphosphate 151 and can only react with strong nucleophiles. 

Lyle and LaMattina selectively hydrogenated 4-substituted 2,6-dinitroanilines to the corresponding nitrophenylenediamines over 10% Pd-C in 1,2-dimethoxyethane-chloroform as solvent (eq. 9.56).135 With use of ethanol instead of 1,2-di-methoxyethane, 4-trifluoromethyl-2,6-dinitroaniline was completely hydrogenated to give the corresponding triaminobenzene. 

Rg. 4104. Mdar conductivity of UBF4 solutions in 1,2-di-methoxyethane at -45 and 25 °C, showing negative temperature co-effidents at moderate concentrations (J. Barthel and H.nJ. Gores,... 

A soln. of phthalic anhydride and Na-trichloroacetate in anhydrous 1,2-di-methoxyethane refluxed 20 min. with stirring, more solvent added after thick paste has formed, heating continued 45 min., the resulting salt treated with water, filtered, and acidified with HGl 3-hydroxy-3-trichloromethylphthalide. Y 80%. F. e. and ring-chain tautomerism between a)-hydroxylactones and ketocarboxylic acids s. A. Winston et al., J. Org. Ghem. 30, 2784 (1965). 

Dibenzenevanadium( — 1) and dibenzenechromium( 1 —) may be obtained by reduction of V(PhH)2 by metallic potassium in aprotic chelating solvents such as 1,2-di-methoxyethane or hexamethylphosphoramide. The compound Ru2Cl4(PhH)2 reacts with sodium hydroxide to give [Ru2(ju-OH)3 (PhH)2]Cl, while with sodium carbonate it furnishes the tetranuclear complex [Ru4(OH)4 (PhH)4](S04)2 I2H2O (Figure 10.4c). Many similar reactions in which the arene ligands are not involved may also be carried out. 

Diethyl N-cyclohexylphosphoramidate allowed to react with NaH in 1,2-di-methoxyethane, and phenyl isocyanate added to the resulting phosphoramidate anion N-phenyl-N -cyclohexylcarbodiimide. Y 60%.— Phosphoramidates, which are readily available, provide convenient laboratory procedures for the prepn. of unsatd. nitrogen compounds such as imines, ketenimines, isocyanates, or isothiocyanates. F. reactions s. W. S. Wadsworth, Jr., and W. D. Emmons, Am. Soc. 64, 1316 (1962). 

Bromopropyltriphenylphosphonium bromide added at room temp, under Ng to a suspension of 2 equivalents of a 53%-NaH-mineral oil dispersion in 1,2-di-methoxyethane, a little ethanol added, stirred 6 hrs. at 60-70°, benzophenone... 

A high molecular weight product was obtained by the anionic polymerization of 2,6-diphenyl-1,6-heptadiene (55). The use of phenyllithium in 1,2-di-methoxyethane at -40° to -50°C yielded a polymer of lower molecular weight (92). 

Methyllithium and titanium trichloride mixed at -78 under Ng in 1,2-di-methoxyethane, after a few min. benzyl alcohol added, warmed to room temp, during 10 min., finally refluxed 15 min. at 80-82° bibenzyl. Y 68% 78% based on startg. m. consumed. Also sym. and unsym. coupling of allyl alcohols to form 1,5-dienes s. K. B. Sharpless, R. P. Hanzlik, and E. E. van Tamelen, Am. Soc. 90, 209 (1968). 

Hydroxymethyl-5,6-methylenedioxybenzo[b] thiophene refluxed 4 hrs. in di-methoxyethane containing some polyphosphoric acid 6,12-dihydrobenzo-[1,2-b 4,5-b ]bis-5,6-methylenedioxybenzo[b] thiophene. Y 75%. E. Campaigne and E. S. Neiss, J. Heterocyclic Ghem. 2, 100 (1965). 

Di(methylol)>methoxyethane [Bis(hy-droxymethyl)-2-methoxy]-ethane or 2-Methyl-... 

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