Etheral solvents

Other Borohydrides. Potassium borohydride was formerly used in color reversal development of photographic film and was preferred over sodium borohydride because of its much lower hygroscopicity. Because other borohydrides are made from sodium borohydride, they are correspondingly more expensive. Generally their reducing properties are not sufficiently different to warrant the added cost. Zinc borohydride [17611-70-0] Zn(BH 2> however, has found many appHcations in stereoselective reductions. It is less basic than NaBH, but is not commercially available owing to poor thermal stabihty. It is usually prepared on site in an ether solvent. Zinc borohydride was initially appHed to stereoselective ketone reductions, especially in prostaglandin syntheses (36), and later to aldehydes, acid haHdes, and esters (37). 

Aluminum hydride, formed from AlCl (44), is a polymeric soHd that is difficult to obtain completely free of the ether solvent used. 

The most hindered of all presently known hydroborating agents is possibly dimesitylborane, an air-stable white soHd, slightly soluble in tetrahydrofuran, the best etheral solvent. It is commercially available or can be prepared according to the following reaction (117) ... 

Quantitative Analysis of All llithium Initiator Solutions. Solutions of alkyUithium compounds frequentiy show turbidity associated with the formation of lithium alkoxides by oxidation reactions or lithium hydroxide by reaction with moisture. Although these species contribute to the total basicity of the solution as determined by simple acid titration, they do not react with allyhc and henzylic chlorides or ethylene dibromide rapidly in ether solvents. This difference is the basis for the double titration method of determining the amount of active carbon-bound lithium reagent in a given sample (55,56). Thus the amount of carbon-bound lithium is calculated from the difference between the total amount of base determined by acid titration and the amount of base remaining after the solution reacts with either benzyl chloride, allyl chloride, or ethylene dibromide. 

Although / -butyUithium is quite soluble in ether solvents, its solutions in these solvents are not stable and thus caimot be stored or shipped. A solution of / -butyUithium in diethylether decomposes to give... 

Ethylene also is a by-product of the cleavage reaction with tetrahydrofuran (99). The rate of loss for / -butyUithium in a variety of ether solvents is given in Table 6. 

Metalation. Benzene reacts with alkaH metal derivatives such as methyl or ethyUithium ia hydrocarbon solvents to produce phenyUithium [591 -51 -5], CgH Li, and methane or ethane. Chloro-, bromo-, or iodobenzene will react with magnesium metal ia ethereal solvents to produce phenyHnagnesium chloride [100-59-4], C H MgCl, bromide, oriodide (Grignard reagents) (32). 

Reagents, such as tri alkyl aluminums (90) and sodium benzophenone (109), are quite useful as reducing agents. Alkyl aluminums have been used to synthesize Cr(CO), Mo(CO), and W(CO) in high yields (90). In one case, hydrogen was used effectively as a reducing agent in petroleum ether solvent (110,111). 

Epichlorohydrin Elastomers without AGE. Polymerization on a commercial scale is done as either a solution or slurry process at 40—130°C in an aromatic, ahphatic, or ether solvent. Typical solvents are toluene, benzene, heptane, and diethyl ether. Trialkylaluniinum-water and triaLkylaluminum—water—acetylacetone catalysts are employed. A cationic, coordination mechanism is proposed for chain propagation. The product is isolated by steam coagulation. Polymerization is done as a continuous process in which the solvent, catalyst, and monomer are fed to a back-mixed reactor. Pinal product composition of ECH—EO is determined by careful control of the unreacted, or background, monomer in the reactor. In the manufacture of copolymers, the relative reactivity ratios must be considered. The reactivity ratio of EO to ECH has been estimated to be approximately 7 (35—37). 

The yield can probably be increased by carrying out the reaction in an ether solvent with an alkyllithium as base, but the simplicity and relative ease of the conditions described appear to make the possible yield advantage secondary. 

For synthetic purposes, carbanions are usually generated in ether solvents, often THF or DME. There are relatively few quantitative data available on hydrocarbon acidity in such solvents. Table 7.2 contains a few entries for Cs salts. The numerical values are scaled with reference to the pAT of 9-phenylfluorene. ... 

The preparation of perfluoroalkylzinc compounds has been achieved earlier 111 ethereal solvents [26] However, solvent effects play a significant role in the course of this reaction When a mixture of acetic anhydride and methylene chloride is used, coupled and cross-coupled products can be formed [27, 28] (equations 19 and 20) However, the cross-coupling reaction often gives mixtures, a fact that seriously restricts the synthetic applicability of this reaction [27, 28, 29]... 

The remarkably facile addition of B2H6 to alkenes and alkynes in ether solvents at room temperatures was discovered by H. C. Brown and B. C. Subba Rao in 1956 ... 

Free borane (2) exists as gaseous dimer—the diborane BaHg. In addition Lewis acid/Lewis base-complexes, as for example formed in an ethereal solvent, e.g. 4, are commercially available ... 

The a -halosulfone, required for the Ramberg-Backlund reaction, can for example be prepared from a sulfide by reaction with thionyl chloride (or with N-chlorosuccinimide) to give an a-chlorosulfide, followed by oxidation to the sulfone—e.g. using m-chloroperbenzoic acid. As base for the Ramberg-Backlund reaction have been used alkoxides—e.g. potassium t-butoxide in an etheral solvent, as well as aqueous alkali hydroxide. In the latter case the use of a phase-transfer catalyst may be of advantage. ... 

Using sulphonic acid ion-exchange resins in ether solvent, selective removal of the trimethylsilyl group from oxygen in bistrimethylsilylated terminal alkynols can be achieved. This method is particularly suitable for low-molecular-weight compounds, where water solubility would make efficient extraction from an aqueous layer difficult. 

Phenol formation is favoured in less coordinating and/or less polar solvents however, for clean reactions affording the Cr(CO)3-coordinated benzannulation products, ethereal solvents are the solvents of choice. 

The electrophilic carbene carbon atom of Fischer carbene complexes is usually stabilised through 7i-donation of an alkoxy or amino substituent. This type of electronic stabilisation renders carbene complexes thermostable nevertheless, they have to be stored and handled under inert gas in order to avoid oxidative decomposition. In a typical benzannulation protocol, the carbene complex is reacted with a 10% excess of the alkyne at a temperature between 45 and 60 °C in an ethereal solvent. On the other hand, the non-stabilised and highly electrophilic diphenylcarbene pentacarbonylchromium complex needs to be stored and handled at temperatures below -20 °C, which allows one to carry out benzannulation reactions at room temperature [34]. Recently, the first syntheses of tricyclic carbene complexes derived from diazo precursors have been performed and applied to benzannulation [35a,b]. The reaction of the non-planar dibenzocycloheptenylidene complex 28 with 1-hexyne afforded the Cr(CO)3-coordinated tetracyclic benzannulation product 29 in a completely regio- and diastereoselective way [35c] (Scheme 18). 

Caution Use of diisopropyl ether from a freshly opened bottle is advised, due to possible formation ofperoxides in aged ethereal solvents. Other solvents were less effective for this recrystallization. 

Polymerization of t-butyl methacrylate initiated by lithium compounds in toluene yields 100% isotactic polymers 64,65), and significantly, of a nearly uniform molecular-weight, while the isotactic polymethyl methacrylate formed under these conditions has a bimodal distribution. Significantly, the propagation of the lithium pairs of the t-Bu ester carbanion, is faster in toluene than in THF. In hydrocarbon solvents the monomers seem to interact strongly with the Li+ cations in the transition state of the addition, while the conventional direct monomer interaction with carbanions, that requires partial dissociation of ion-pair in the transition state of propagation, governs the addition in ethereal solvents. 

The degree of aggregation of polystyryl alkali salts in hydrocarbons, as well as the reactivity of their respective unassociated pairs, decrease along the series Li +, Na+, K +, Cs+ (Ref.Il, pp. 20 21). For example, the propagation constant of the lithium pair in benzene at 25 °C is estimated to be greater than 100 M "1 sec- while those of K +, Rb+, and Cs+ were determined as 47, 24, and 18 M-1 sec-1, respectively. Such a gradation contrasts with that of the reactivities of tight pairs in ethereal solvents,... 

Fig. 12. Temperature dependence of Kd of polystyryl lithium in different ethereal solvents (S. Peeters, M. Van Beylen, Ref. 76 )...

The somewhat exceptional behavior of the lithium salt is manifested in hydrocarbons as well as in ethereal solvents. Thus in THF there is a striking difference in conductance and reactivity of lithium polystyryl as compared with its sodium salt76). This may be appreciated by inspecting Figs. 12 and 13. 

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