Salts oxonium

However, when ethers of alcohols are to be prepared the trialkyloxonium salt method will be used only when other, more usual, methods fail. 

As an example, alkylation of a-chlorohydrin to / -halo ethers cannot be carried out by the usual methods. It is effected, however, in excellent yield by means of trialkyloxonium salts 212 

R—CHC1—CH2OH + [R730]BF4------- R—CHC1—CH2OR + HBF4 + R 20 

The action of trialkyloxonium salts on aliphatic ethers leads to exchange of alkyl groups. Sulfoxides,212 nitriles,213 and disulfides214 can be alkylated smoothly by oxonium salts. Saturated aldehydes and ketones can be alkylated only if, like pinacolin and camphor, they contain a tertiary alkyl group neighboring the carbonyl group. Then for instance, the carboxonium salts obtained can be readily converted by alkali alkoxides into acetals and orthoesters which are difficult to obtain in other ways. 

Camphor diethyl acetal, obtained in only 25-30% yield from camphor and orthoformic ester,215 is obtained in 87% yield from O-ethylcamphor oxonium fluoroborate and sodium ethoxide.18 

Reagents i, SbFj-Et20, - 50 C ii. EtjO iii, R2O, several cycles 

Reactions.—Gc/icrn/. Allyl methyl ethers have been reductively transformed into predominantly (Z)-alkenes with carbon-carbon double bond rearrangement (81 82) using TiCU-LiAlH.  

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Oxonium salt formation. Shake up 0 5 ml. of ether with 1 ml. of cone. HCl and note that a clear solution is obtained owing to the formation of a water-soluble oxonium salt. Note that aromatic and aliphatic hydrocarbons do not behave in this way. In general diaryl ethers and alkyl aryl ethers are also insoluble in cone. HCl. 

Many oxygen-containing compounds dissolve because of the formation of oxonium salts the latter are readily decomposed (hydrolysed) by pouring the acid into ice water. 

That some modification to the position so far described might be necessary was indicated by some experiments of Nesmeyanov and his co-workers. Amongst other compounds they nitrated phenyl trimethyl ammonium and triphenyloxonium tetrafluoroborates with mixed acid the former gave 96 % of m- and 4 % of -nitro compound (88 % total yield), whilst the latter gave 80% of the tri-(p-nitrophenyl)oxonium salt. Ridd and his co-workers have made a quantitative study of the phenyl trimethyl ammonium ion. Their results, and those of other recent workers on the nitration of several cations, are collected in table 9.3. 

Direct alkylation or acylation of the oxygen of THF by exchange or addition occurs with the use of trialkyl oxonium salts, carboxonium salts, super-acid esters or anhydrides, acyhum salts, and sometimes carbenium salts. 

Often the requisite THF oxonium ion is generated m situ by using a combination of reagents based on the Meerwein syntheses of trialkyl oxonium salts (150). These combinations include epichlorohydrin or a reactive haUde with a Lewis acid, a reactive hahde with a metal salt, or sometimes just a Lewis acid alone. The epoxide portion is often referred to as a promoter. 

With concentrated sulfuric acid, anthraquinone forms oxonium salts, thus falling into a class of compounds known as " oxygen bases" (15). In an aqueous solution, anthraquinone has an ionisation constant equal to 7 x 10 and a of 7.4 (16). 

Cationic azo dyes carry a positive charge ia the chromophore portion of the molecule. The salt-forming counterion is usually a chloride or acetate. Cl basic dyes are ammonium, sulfonium, or oxonium salts. Commercial basic azo dyes for which chemical stmctures are revealed by U.S. producers are listed ia Table 15. 

Nitrating cellulose with pure HNO is the simplest method of obtaining CN. In practice, nitration does not occur with acid concentrations below 75%. At acid concentrations <75%, an unstable compound (so called Knecht compound) is formed which has been described as a molecular complex or an oxonium salt of the nitric acid (72). HNO concentrations of 75—85% yield CN with 5—8% N, which dissolve in excess acid. CN with % N of 8—10% are formed at acid concentrations of 85—89%. Above 89%, a heterogeneous nitration occurs without apparent swelling of the cellulose fibers. CN with 13.3% N can be obtained with 100% HNO. Addition of inorganic salts to 100% HNO can raise the % N to 13.9. 

Ethers are weakly basic and are converted to unstable oxonium salts by strong acids such as sulfudc acid, perchlodc acid, and hydrobromic acid relatively stable complexes ate formed between ethers and Lewis acids such as boron trifluodde, aluminum chlodde, and Gtignatd reagents (qv) (9) ... 

The classical structures of pyrrole, furan and thiophene (31) suggest that these compounds might show chemical reactions similar to those of amines, ethers and thioethers (32) respectively. On this basis, the initial attack of the electrophile would be expected to take place at the heteroatom and lead to products such as quaternary ammonium and oxonium salts, sulfoxides and sulfones. Products of this type from the heteroaromatic compounds under consideration are relatively rare. 

S.06.3.3.4 Alkyl halides, oxonium salts and related compounds... 

HF is miscible with water in all proportions and the phase diagram (Fig. 17.4a) shows the presence of three compounds H2O.HF (mp — 35.5°), H2O.2HF (mp-75.5°) and H2O.4HF (mp — 100.4°, i.e. 17° below the mp of pure HF). Recent X-ray studies have confirmed earlier conjectures that these compounds are best formulated as H-bonded oxonium salts [HsOJF, [H30][HF2], and [H30][H3F4] with three very strong H bonds per oxonium ion and average O - - F distances of 246.7, 250.2... 

A 10% molar excess of the oxonium salt with regard to the carboxylic acid gives slightly higher yields than does an equimolar quantity. 

Examples of polyfunctional carboxylic acids esterified by this method are shown in Table I. Yields are uniformly high, with the exception of those cases (maleic and fumaric acids) where some of the product appears to be lost during work-up as a result of water solubility. Even with carboxylic acids containing a second functional group (e.g., amide, nitrile) which can readily react with the oxonium salt, the more nucleophilic carboxylate anion is preferentially alkylated. The examples described in detail above illustrate the esterification of an acid containing a labile acetoxy group, which would not survive other procedures such as the traditional Fischer esterification. 

Hall and Steuck polymerized 2 with a variety of Lewis and Bronsted acids or oxonium salts. The best conditions for the polymerization proved to be the use of phosphorus pentafluoride in methylene chloride solution at -78 °C. Yields of methanol-insoluble polymers ranging from 68 to 84% were obtained with inherent viscosities of 0.26—0.33 dl/g. Lower or higher temperatures gave lower yields. Tetra-hydrofuran as solvent at —78 °C gave 68-92% yields of materials having inherent viscosities of 0.12-0.14 dl/g. No incorporation of tetrahydrofuran into the polymer occurred. 

G. Other Oxygen Nucleophiles 10-31 Formation of Oxonium Salts... 

Alkyl halides can be alkylated by ethers or ketones to give oxonium salts, if a very weak, negatively charged nucleophile is present to serve as a counterion and a Lewis... 

A closely related reaction is cleavage of oxonium salts. 

In contrast, the acid-catalyzed hydration of arylbenzoylacetylenes differs markedly from the hydration of a-unsaturated ketones. Hydration of unsaturated ketones has been shown to proceed via a 1,4-addition mechanism where protonation occurs on oxygen to give an oxonium salt, followed by attack of water at the 0-carbon to give a hydroxy enol. The rate-limiting step has been shown to be the protonation of the hydroxy enol (27) ... 

Au-B bonds are also present in metal clusters with intersticial or peripheral boron atoms. An example is the cluster [Fe4(CO)12BH(AuPPh3)2], which was prepared by reaction of [AuCl(PPh3)] with the carbonyl iron dihydride. With the oxonium salt the reaction proceeds to the trinuclear gold derivative [Fe4(CO)12B(AuPPh3)3] (357).2063-2070 The ruthenium analogues and complexes with other ligands have been also synthesized as, for example, (358).2071-2079... 

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