Diglyme, as solvents

Figure 11. Mooney-Rivlin plot of stress-strain data (32) for three triol-based polyester networks prepared from sebacoyl chloride and LHT240 at various initial dilutions in diglyme as solvent. Conditions P100 is 0% solvent P130 is 30% solvent PI 65 is 65% solvent.

Scheme 6.114, a carbene-carbene rearrangement transforms diphenylcarbene to o-phenylphenylcarbene, which is the progenitor of 565. Two phenylbicydo[4.1.0]-hepta-2,4,6-trienes and l-phenyl-l,2,4,6-cycloheptatetraene (562) have to be assumed as further intermediates. The participation of 562 is supported by the structure of the products 563 and 564, which should result from the addition of 562 to diphenylcarbene and the dimerization of 562, respectively. By thermolysis of the sodium salt of 2-phenyltropone tosylhydrazone, 562 was generated directly. At 100 °C in diglyme as solvent, 564 was identified as the only product and at 340°C/4Torr in the gas... 

Until recently, the synthesis of the yellow [M(CO)6] required the reduction of Nb2Cli0 by Na or Na-K alloy in diglyme as solvent under a high pressure of CO (>360 atm), and only poor and non-reproducible yields (<14%) of the anions were obtained.716 Several mild and efficient carbonylation procedures have now become available. The reductive carbonylation of MCI5 using the Mg/Zn couple as reductant and pyridine as reactive solvent occurs at room temperature under one atmosphere of CO (yields = 48% and 35% for M = Nb and Ta respectively). The reduction is largely due to magnesium.717... 

For the zwitterionic spirocyclic compound 49, the equilibrium is totally shifted toward the colored form at - 30°C in diglyme as solvent,36 allowing the measurement of the molar absorptivity and then the equilibrium constants at higher temperature by UV-visible spectroscopy (AT =300 at 20°C in diglyme). 

Active In, prepared by the codeposition method, with EtI gives a mixture of Etjinl, Etinij and Ini. The best results are obtained with (CH30CH2CH2)20 (diglyme) as solvent. Reduction of InClj with potassium metal in refluxing xylene under Ar delivers highly active In (In ) metal ... 

The formation of the four-membered ring is explained by an anionic rearrangement accompanied by ring contraction . The isomerization of cyclotri- and cyclodisila-zanes depends on the conditions . The substitution of silylgroups is preferred at low T in diglyme as solvent . Isomerization reactions are observed at higher T, e.g., at -i-60°C in diglyme ... 

In this scheme, the unstable intermediate form could derive greater stability through interaction with a solvent molecule acting as a transient donor at the boron atom written on the left. Thus in diethyl ether the energy barrier is reduced to 4.8 kcal mole, whereas with the polyether diglyme as solvent it is reduced still further, since the change in the spectrum is complete at lower temperatures (114). ... 

The solubility of hydrogen in liquid diborane has been measured (153), and that of diborane in a number of solvents has been extensively investigated. Of particular importance because of the practical significance of the system involved are the studies with the polyether diglyme as solvent (127, 332), but solubility measurements have also been conducted in simple hydrocarbons (213, 258), ditertiary-butyl sulfide (332), furfural (66), nitrobenzene (66), and tetraethoxysi-lane (66), among other substances. 

Lithium aluminium hydride in ether selectively reduces tosylates to alkanes in the presence of alkyl iodides and bromides in contrast, with diglyme as solvent only the halides are reduced. 1-5 Mol% of Cul in LiAlH4 facilitates the selective reduction of conjugated enones to saturated ketones. 

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