Grignard reagents with ethers

The last consideration is the reactivity of the Grignard reagent with the solvent itself. Deleterious reactions of the Grignard reagent with ethereal solvents occurs only under extreme conditions and has been observed, to some extent, in diethyl ether, di-n-butyl ether, THF, r-butylmethyl ether, anisole (155°C), DME, and allylphenyl ether [Eq. (7) 19-24], Since these reactions occur only under extreme conditions, the ethereal solvents are preferred because of the high Grignard reagent solubility (up to 4 M). 

Beryllium dialkyls (BeR2, R = Me, Et, Pr", Pr, Bu etc.) can be made by reacting lithium alkyls or Grignard reagents with BeCl2 in ethereal solution, but the products are difficult to free from ether and, when pure compounds rather than solutions are required, a better route is by heating Be metal with the appropriate mercury dialkyl ... 

Majima et al. prepared ethyl y-(3-indolyl)-y-oxobut3rrate (250) in a similar manner by the condensation of the indole Grignard reagent with -ethoxycarboiiylpropionyl chloride.Methyl y-(3-indolyl)-y-oxobutyrate (251) has been obtained by the action of mcthoxycarbonylpropionyl chloride on indole magnesium iodide in ether. Ballantine et al. prepared methyl y-(5-methoxy-3-... 

Strecker153 was also the First to show that diethyl sulphite reacts with two equivalents of Grignard reagent in ether solution to yield symmetrical sulphoxides (equation 50). Bert156... 

The oxidative dimerization of the anion of methyl phenyl sulfone (from a Grignard reagent) in ethereal solution in the presence of cupric chloride in 5% yield has been reported47. Despite the reported48 poor stability of the a-sulfonyl C-centered radicals, Julia and coworkers49 provoked the dimerization (in 13 to 56% yields) of the lithiated carbanion of alkyl phenyl sulfones using cupric salts as oxidants. The best results are obtained with cupric triflates in THF-isobutyronitrile medium (56% yield for R = H). For allyl phenyl sulfones the coupling in the 3-3 mode is predominant. 

After treatment of the Grignard reagent with chlorine, the solid which separated exploded when shaken [1], This solid was not seen later, using either diethyl ether or THF as solvent [2], (The explosive solid could have been magnesium hypochlorite if moisture were present in the chlorine.)... 

Reaction of 103 with MgBr2 in ether produces a germanium-containing Grignard reagent with a Ge—Mg bond ... 

The CuBr-catalyzed reaction of a Grignard reagent with 1,2-allenyl ether in Et20 at 20 °C afforded terminal alkynes [53]. 

Tetraallyluranium [143, 144) and tetra(2-methylallyl)-uranium(IV) [145) are prepared by the reaction of the Grignard reagents with uranium tetrachloride in diethyl ether. The PMR spectra of these temperature-sensitive compounds are listed in Table 7. The AMgXa [146) pattern exhibited by tetraallyluranium is typical of the symmetrical jr-allyl structure in Fig. 14. The spectrum of tetra-... 

Reactions of Grignard Reagents with Allylic Esters and Ethers... 

Conjugated allenyl ketones 193 react smoothly with Grignard reagents in ether at ... 

Imines, derived from O-benzyllactaldehyde and benzylamine, react with non-stabilized Grignard reagents in ether yielding products with excellent diastereoselectivities (equation... 

Fluorine can be introduced into alkanes indirectly by treating either lithium or Grignard reagents with fluorine (Fig. 70) [165] at -60°C in hydrocarbon ether solvents. The lithium reagents reacted more rapidly than the corresponding Grignard reagents, and primary or secondary alkyl compounds were more reactive than tertiary. 

The synthesis of ieri-butyl ethers by the reaction of Grignard reagents with feri-butyl perbenzoate appears to have considerable... 

Reaction with formic acid. The.reaction of Grignard reagents with formic acid was originally (1905) reported to give aldehydes in low yield and has seen little use. Actually, the reaction proceeds in fair yields even in ether and in higher yields in THE. Aldehydes can also be prepared by the method outlined in equation (I).3... 

---