Halides silver® oxide

If the thallium dipiieiiyl cliloride be replaced by thallium diethyl bromide, only thallous iodide is isolated from the reaction. It has been pointed out that thallium dialkyJ halides when treated with moist silver oxide yield the corresponding hydroxides, and that the latter with acids give salts. In the aromatic series, it is found that the best method of preparing the salts is to boil together a mixture of the halide, silver oxide, and the organic acid in toluene. Alcoholic potassium hydroxide transforms the halides to oxides, and these are also available for production of salts. 

Alkyl halide, silver oxide (no solvent) 2.1 C(l)-protected esterified uronic acids substances which tend to undergo base-promoted degradation Free sugars and other easily oxidizable substances 0-Acyl groups may migrate... 

From the work of Takegami et aL, and Heck, it must foUow that cobalt hydrocarbonyl reacts with epoxides in the acid form. The reaction of epoxide compounds should be accelerated by addition of small amounts of alcohols, ketones, ethers and esters [303], as well as copper oxide or halide, silver oxide and aluminium chloride [304]. 

The halide anion of quaternary ammonium iodides may be replaced by hydroxide by treatment with an aqueous slurry of silver oxide Silver iodide precipitates and a solu tion of the quaternary ammonium hydroxide is formed... 

A useful variation of the Williamson synthesis involves silver oxide, Ag20, as a mild base rather than NaH. Under these conditions, the free alcohol reacts directly with alkyl halide, so there is no need to preform the metal alkoxide intermediate. Sugars react particularly well glucose, for example, reacts with excess iodomethane in the presence of Ag20 to generate a pentaether in 85% yield. 

Many of the reactions of amines are familiar from past chapters. Thus, amines react with alkyl halides in S 2 reactions and with acid chlorides in nucleophilic acyl substitution reactions. Amines also undergo E2 elimination to yield alkenes if they are first qualernized by treatment with iodomethane and then heated with silver oxide, a process called the Hofmann elimination. 

In the Koenigs-Knorr method and in the Helferich or Zemplen modifications thereof, a glycosyl halide (bromide or chloride iodides can be produced in situ by the addition of tetraalkylammonium iodide) is allowed to react with a hydrox-ylic compound in the presence of a heavy-metal promoter such as silver oxide, carbonate, perchlorate, or mercuric bromide and/or oxide,19-21 or by silver triflu-oromethanesulfonate22 (AgOTf). Related to this is the use of glycosyl fluoride donors,23 which normally are prepared from thioglycosides.24... 

Alkyl halides can be hydrolyzed to alcohols. Hydroxide ion is usually required, except that especially active substrates such as allylic or benzylic types can be hydrolyzed by water. Ordinary halides can also be hydrolyzed by water, if the solvent is HMPA or A-methyl-2-pyrrolidinone." In contrast to most nucleophilic substitutions at saturated carbons, this reaction can be performed on tertiary substrates without significant interference from elimination side reactions. Tertiary alkyl a-halocarbonyl compounds can be converted to the corresponding alcohol with silver oxide in aqueous acetonitrile." The reaction is not frequently used for synthetic purposes, because alkyl halides are usually obtained from alcohols. 

Alkyl halides in the presence of silver oxide will convert any non-hindered carboxylic acid (or its salt) to the corresponding alkyl ester in minutes, and phenolic or thiol groups will also be alkylated rapidly [436]. Hydroxyl groups are alkylated slowly an ot always to completion. The alkyl halides most frequently uJQp are the lower molecular weight aliphatic... 

Divalent metals, ferrites of, 24 543 Divalent samarium halides, 24 649 Divalent zinc-silver oxide batteries, 3 454-455 Divergence, 24 656... 

Acetimidate formation with A-methylacetamide and acylated glycosyl halides according to Sinay et al (212,213), using three equivalents of silver oxide as an activator, leads neither to particularly stable nor to reactive donors. Any other developments along these lines have already been summarized in previous reviews (1,3). The same is mainly true for anomeric... 

Because of their high lipophobic character, compared with other ammonium salts, quaternary ammonium hydroxides are not readily prepared by liquidrliquid anion exchange. Only with quaternary ammonium hydrogen sulphates is it possible to transfer the ammonium hydroxide into the organic phase in any viable degree of concentration [30] and this procedure remains the cheapest and simplest procedure. Other methods include treatment of quaternary ammonium halides with silver oxide [31] and by anion exchange using polymer bound hydroxide [e.g. 32]. 

The reactions which will be discussed here are basic in the application of dyes as sensitizer for photographic materials like silver halides, zinc oxide and others. Model experiments can be performed at electrodes of such materials which help to understand the mechanism of spectral sensitization in photography. 

Other Alkyl Ethers. Sucrose has been selectively etherified by electrochemical means to generate a sucrose anion followed by reaction with an alkyl halide (21,22). The benzylation of sucrose using this technique gives 2-O-benzyl- (49%), T-O-benzyl- (41%), and 3 -O-benzyl- (10%) sucrose (22). The benzylation of sucrose with benzyl bromide and silver oxide in DMF also produces the 2-O-benzyl ether as the principal product, but smaller proportions of T- and 3 -ethers (23). Octadienyl ether derivatives of sucrose, intermediates for polymers, have been prepared by a palladium-catalyzed telomerization reaction with butadiene in 2-propanol—water (24). 

Triphenylbismuth oxide [7173-99-1], C18H15BiO, has been prepared from triphenylbismuth dicyanide [41083-16-3], C20H15BiN2, and mercuric oxide (151), and from triphenylbismuth dichloride and moist silver oxide (152). The ir and Raman spectra of this compound suggest that it is polymeric and has Bi—O—Bi bonds (153). Triphenylbismuth dihydroxide, C18H17Bi02, and triarylbismuth hydroxide halides, eg, triphenylbismuth hydroxide chloride [66214-57-1], C18H16BiC10, have been reported in the earlier chemical literature. There is, however, no modem research on these types of compounds, and... 

Silver(I) carboxylates have been obtained by the addition of equivalent amounts of freshly prepared silver oxide to aqueous solutions of the appropriate acid.247 Their degradation by halogens provides a convenient method for the preparation of alkyl halides (Hunsdiecker reaction) or esters (Simonini reaction).248 Equations (14)-(18) have been proposed to account for the products obtained and were the result of extensive studies. 

In relation to carbohydrate chemistry, the Koenigs-Knorr synthesis of glycosides involves the treatment of glycosyl halides with an alcohol or phenol in the presence of a heavy metal salt.267 Karrer268 discovered that reaction of silver salts of hydros acids could also be used and use of these reagents has been extended more recently. Numerous variations and improvements on the original method have now been reported, and silver oxide, silver carbonate or silver trifluoromethanesulfonate have since become the accepted standard reagents.267... 

The majority of inorganic systems reported to exhibit photochromism are solids, examples being alkali and alkaline earth halides and oxides, titanates, mercuric chloride and silver halides.184 185 The coloration is generally believed to result from the trapping of electrons or holes by crystal lattice defects. Alternatively, if the sample crystal is doped with an impurity capable of existing in variable oxidation states (i.e. iron or molybdenum), an electron transfer mechanism is possible. 

This compound is prepared in the same way as in (I) for the nitrate except that 7ml of concentrated hydrochloric acid is used to catch the filtrate from the silver oxide. Any silver halide or unchanged starting materials are filtered off. The product Is precipitated as an orange-red solid by cooling tiie filtrate in ice while 100ml of an ice-cold 1 mixture of concentrated hydrochloric add and alcohol is added. After filtering, the material is washed with 95% alcohol and with ether. 

The tetraalkylammonium halides formed by complete alkylation of amines are ionic compounds that resemble alkali-metal salts. When silver oxide is used to precipitate the halide ion, tetraalkylammonium halides are converted to tetraalkylammonium hydroxides, which are strongly basic substances similar to sodium or potassium hydroxide ... 

The interaction of diaryl tellurides and the esters of halogenated fatty acids, e.g. methyl bromacetate, gives diarvl-telluretin halide alkyl esters, e.g. (C6H5)2Te(Br).CH2.COOCH3. The halogen present may be chlorine, bromine or iodine, moist silver oxide replacing the bromine by the hydroxyl group. 

The elimination of a quarternsry ammonium salt usually follows an E2 mechanism requiring a strong base. The quaternary alkyl halide, typically an ammonium iodide, is converted to a quaternary ammonium hydroxide using silver oxide. 

Other active methylene compounds also react with both palladium(ll) <2002POL2653> and gold(m) <1997JOM243> to produce metallacyclobutane complexes (Scheme 34). The gold complex is not sufficiently stable for isolation. In these reactions, the silver oxide functions both as a base and a reagent for halide abstraction. In the gold series, 1,1,3,3-tetracyanopropane is also a competent pro-nucleophile <1999JOM219>. 

The reaction can be performed at room temperature with various heteroaryl halides (Equation 73) <20050L697>. It was found that (2-pyridyl)allyldimethylsilanes are pyridyl-transfer reagents in palladium-catalyzed coupling reactions of aryl iodides in the presence of silver oxide as an activator <20060L729>. 

Silver salts are also common activators in numerous Suzuki coupling reactions. The earliest example could probably be found in the Kishi s palytoxin synthesis. Silver oxide as well as thallium hydroxide provided dramatic rate enhancements in the couplings of vinylboronic acids (Scheme 10.41).69 Both thallium and silver ions are most probably abstracting halide in palladium intermediates, but silver is clearly the most efficient. Moreover, with the right counterion, the silver salt also acts as a mild base and activator. 

Ethers For the synthesis of ether, the Williamson ether synthesis is considered as the best method. It involves the SN2 reaction between a metal alkoxide and a primary alkyl halide or tosylate. The alkoxide needed for the reaction is obtained by treating an alcohol with a strong base like sodium hydride. An alternative procedure is to treat the alcohol directly with the alkyl halide in the presence of silver oxide, thus avoiding the need to prepare the alkoxide beforehand. 

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