Silver complexes alcohols

A paper dating from 1976 investigated the reaction of olefins or alcohols with cationic copper and silver complexes of carbon monoxide 49 The remarkable outcome of these kinetic measurements is that there is no difference between the catalytic behavior of Cu(CO) + and Ag(CO)2 +. 

Spot test To 1 drop of the test solution add 1 drop nitric acid (2m), then 1 drop of the reagent. A red-violet precipitate or stain is formed if silver ions are present. Alternatively, the test may be performed on a spot plate, or in a semimicro test tube in the latter case the excess of the reagent is extracted with diethyl ether or amyl alcohol, when violet specks of the silver complex will be visible under the yellow solvent layer. 

D-Glucose orthoesters of complex alcohols can be easily obtained with the help of silver salicylate Alcohols and amines can be conveniently prepared from olefins by ozonization-reduction and ozoni-zation-reductive amination respectively without isolation of intermediates Inverted amines can be obtained from optically-active alcohols through stereospecific formation of N-alkylphthalimides 3-Methoxy-l-phenyl-l-propyne has been used as starting material for the synthesis of a,/ -unsatd. carbonyl compounds through allenic di-carbanions a-Ketocarboxylic acids can be easily prepared from cyanohydrins through a Ritter reaction... 

In coated-wire electrodes (CWE) the membrane is placed directly on the electrode. The electrode can be a wire of noble metal, graphite wire, silver paste or Ag/AgCl electrode, which is the most popular solution. The role of the inner solution of ISE-s can be played in CWE-s by poli(hydroxyethyl methacrylate), polyvinyl alcohol or a hydrogel saturated with NaCl solution, placed between the electrode and the membrane. The membrane stability can be improved through addition of silver complexes to the membrane. The advantage of CWE-s over ISE-s is the possibility of cheap, mass production. The disadvantage of CWE-s is that the membrane can easily unstick from the electrode. Moreover, due to the high contact surface between the membrane and the solution, the membrane contents, i.e., the plasticizer and the ionophore, can be easily washed out into the membrane, which deteriorates the characteristics of the sensor in time. 

It is well known that olefins may form complexes with some metals [80, 81]. Mercuric acetate can form complexes with polyolefins selectively, being removed by acid treatment [82]. Such complexes have been used in the separation of unsaturated fatty acids from mixtures [83]. Subbarao [84] has protected olefins aginst reduction using silver complexes, and Cope used reversible platinum complex formation [85, 86] for the resolution of medium ring trans olefins. Landesburg [87] used the iron tricarbonyl complex of the alcohol (13) to protect it during oxidation to the ketone (14) which was regenerated from the complex by photolysis [88a]. 

X. Tang, C. Qi, H. He, H. Jiang, Y. Ren, G. Yuan, Polystyrene-supported N-heterocyclic carbene-silver complexes as robust and efficient catalysts for the reaction of carbon dioxide and propargylic alcohols, Adv. Synth. Catal. 355 (2013) 2019-2028. 

It would be advantageous to develop a chlorodecarboxylation reaction that only required catalytic amounts of the heavy metal. To address this issue, a method that was catalytic with respect to the silver salt was devised (Scheme 7.28) [49]. The key to the chemistry was the use of tert-butyl hypochlorite as the chlorine source. The redesigned reactions proceeded under very mild conditions using only 5% of a silver complex. Primary, secondary, and tertiary alcohols as well as bulky substrates were all successfully chlorinated using this approach. 

The conversion of primary alcohols and aldehydes into carboxylic acids is generally possible with all strong oxidants. Silver(II) oxide in THF/water is particularly useful as a neutral oxidant (E.J. Corey, 1968 A). The direct conversion of primary alcohols into carboxylic esters is achieved with MnOj in the presence of hydrogen cyanide and alcohols (E.J. Corey, 1968 A,D). The remarkably smooth oxidation of ethers to esters by ruthenium tetroxide has been employed quite often (D.G. Lee, 1973). Dibutyl ether affords butyl butanoate, and tetra-hydrofuran yields butyrolactone almost quantitatively. More complex educts also give acceptable yields (M.E. Wolff, 1963). 

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