Diether

Many substances have more than one ether linkage Two such compounds often used as solvents are the diethers 1 2 dimethoxyethane and 1 4 dioxane Diglyme also a commonly used solvent is a triether... 

Many of the most interesting and useful reactions of aldehydes and ketones involve trans formation of the initial product of nucleophilic addition to some other substance under the reaction conditions An example is the reaction of aldehydes with alcohols under con ditions of acid catalysis The expected product of nucleophilic addition of the alcohol to the carbonyl group is called a hemiacetal The product actually isolated however cor responds to reaction of one mole of the aldehyde with two moles of alcohol to give gem mal diethers known as acetals... 

Glymes The Grant Family of Glycol Diethers, brochure. Grant Chemical Div., Ferro Corp., La., 1992. 

Magnesium iodide is soluble in alcohols and many other organic solvents, and forms numerous addition compounds with alcohols, ethers, aldehydes, esters, and amines. One example is magnesium iodide dietherate [29964-67-8], Mgl2 prepared by gradual addition of iodine to a... 

LB Films of Polymeric Amphiphile. Since the first successful deposition of a polymeric LB film (61), there have been a large number of studies examining different stmctural parameters on the transferabiHty and stabiHty of the polymeric LB films (4). One interesting idea for polymers for LB films is the use of a spacer group (mosdy hydrophilic) to decouple the motion of the polymer from that of the Hpid membrane (62,63). Monolayers from a poljmier (10) having hydrophilic phosphate groups and a tetraethylene oxide spacer were used to link a glycerol diether to the polymer chain (63). 

These reactions ate carried out in the presence of acidic and basic catalysts. The acid-cataly2ed addition of ethyl alcohol to acetylene or to a vinyl ether produces acetals (diethers of 1,1-dihydroxyethane). The acid-cataly2ed reaction of ethyl alcohol with an aldehyde or ketone also gives acetals. 

Catechols can be protected as diethers or diesters by methods that have been described to protect phenols. However, formation of cyclic acetals and ketals (e.g., methylenedioxy, acetonide, cyclohexylidenedioxy, diphenylmethylenedioxy derivatives) or cyclic esters (e.g., borates or carbonates) selectively protects the two adjacent hydroxyl groups in the presence of isolated phenol groups. 

In this case the Ar and/or Ar group(s) will contain an ether oxygen. As before if Ar = A then basically identical products may be made by the two polysulphonylation routes (see e.g. Figure 21.4). Where a diether and a disulphonyl chloride are co-condensed there may be some reaction at o- and m-positions in addition to the desired reaction at the para-position. It has been found that o- and m-linked polymers are more brittle, at least in the above example. It is of interest to note that self-condensation of the monosulphonyl chloride of diphenyl ether, on the other hand, can proceed so as to give a virtually all-para and hence tough material. Whilst the self-condensation polysulphonylation route has been used commercially it is understood not to be in current commercial use. 

Mention may also be made of fixed diethers, some of which are unsaturated. These materials may be cured by a variety of mechanisms. An example is the allyl glycilyl mixed ether of bis-phenol A (Figure 26.15)... 

When a better leaving group than LiNSC R (e.g., OMe) is present at the a-position, retention of the potentially useful sulfonamide moiety occurs (e. g., in the conversion of aziridine 271 into the highly functionalized amino ether 272 Scheme 5.69) [98]. It should be noted that the analogous chemistry with epoxides of allylic diethers failed this could again (see above) be possibly due to the higher pKa of the epoxide proton relative to the aziridine proton. 

The reaction of butyllithium with 1-naphthaldehyde cyclohexylimine in the presence of (/C )-l,2-diphenylethane-1,2-diol dimethyl ether in toluene at —78 °C, followed by treatment with acetate buffer, gave 2-butyl-1,2-dihydronaphthalene-l-carbaldehyde, which was then reduced with sodium borohydride in methanol to afford (1 R,2.S)-2-butyl-1 -hydroxymcthyl-1,2-dihydronaphthalene in 80% overall yield with 91 % ee83. Similarly, the enantioselective conjugate addition of organolithium reagents to several a,/J-unsaturated aldimines took place in the presence of C2-symmetric chiral diethers, such as (/, / )-1,2-butanediol dimethyl ether and (/, / )- ,2-diphenylethane-1,2-diol dimethyl ether. 

Addition of organolithiutn reagents in toluene to A-cyclohexyl enimines in the presence of chiral nonracemic diethers or diamines (1.2-2,4 equiv) gives, after hydrolysis, //-substituted aldehydes2. It is important to note that these reactions do not occur in the absence of the chiral additive which can be recovered quantitatively for reuse without loss of enantiomeric purity6. 

The mem-dichlorobenzene complex reacts with protected 0-aryltyrosines to give aryl ethers. Both chlorine atoms can be sequentially substituted to give symmetrical or disymmetrical triaryl diethers (Scheme XVI). The building up of such diaryl ethers from phenolic compounds which have amino groups in their side chains... 

Rundle and co-worker performed x-ray diffraction studies on solid phenylmag-nesium bromide dietherate and on ethylmagnesium bromide dietherate, which they obtained by cooling ordinary ethereal Grignard solutions until the solids crystallized. They found that the structures were monomeric ... 

List B contains all compounds that form peroxides which become dangerous when they reach a critical concentration. The danger will often become apparent during distillation operations. For hydrocarbons, this is the case for deca- and tetrahydronaphthalene, cyclohexene, dicyclopentadiene, propyne and butadiene. S ondary alcohols such as 2-butanol also form part of this list. Finally, for ethers there are diethyl ethers, ethyl and vinyl ethers, tetrahydrofuran, 1,4-dioxan, ethylene glycol diethers and monoethers. 

The LiC104-diethyl ether system shows a considerable dependency on concentration, with the maximal effect around 5 M, which may be due to the detailed structure of LiC104 in ether. The optimum reactivity may be associated with a monosolvate. Dilute solutions have more of the dietherate, whereas in more concentrated solution LiC104 may form less reactive aggregates.35 LiN(S02SCF3)2 has been recommended as an alternative to avoid the use of a perchlorate salt.36... 

Based on these reports, we started investigation of the asymmetric addition of acetylide to pMB protected 5, mainly in the presence of chiral P-amino alcohols. Many types of chiral amines were also screened (e.g., diamines, diethers), and it was soon found that addition of P-amino alkoxides effectively induced enantiose-lectivity on the addition. Since the best result was obtained with a stoichiometric amount of chiral amino alcohols, we focused our screen on readily available chiral P-amino alcohols and the results are summarized in Table 1.2. 

Detlef Selent,3 Klaus-Diether Wiese,b and Armin Borneo... 

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