Acetate mercuric

If one is absolutely serious about ultra pure safrole then it can be separated from the eugenol-free sassafras oil by treatment with mercuric acetate [1,2,3,4] which likes that terminal double bond that only safrole has. The Hg(AcO)2 latches on to safrole at that double bond bringing it into solution as a solid sort of like the way that eugenol was. The safrole can then be separated from its still oily buddies by vacuum filtration. Safrole is then regenerated to its normal oily form by treatment with hydrochloric acid (HCI) which flicks the Hg(AcO)2 off the safrole and the safrole double bond reforms. As it so happens, the mercuric acetate also reforms intact so that it can be reused again such as in one of those... 

Strike got the journal article for this recipe as literature citation used in the original Wacker oxidation Strike used for Method 2. In it both mercuric acetate, and to an extent, lead acetate produced ketones as described. Someone-Who-ls-Not-Strike also got a certain ketone. But maybe they were lucky or just plain wrong. Most people on Strike s site say this mercuric acetate thing... 

For top ten 2 (Mercuric Acetate method) use the following in place of reagent grade materials ... 

Ether - Starting fluid (works great - Quaaaaack ) 2. Home made mercuric acetate (Now this stuff can be special ordered from ones chem supplier but there s a delay, may look funny - Quaaaaack , and is more expensive. So what is the solution to this Make it yourself Its easy, quantitative, and cheaper. Strike mentions this in the book and points ducks to a reference. Follow the EXACT same procedure for Mercuric Propionate except use glacial acetic acid...quack ). You ll need to use 20 to 25% more of the home brew mercuric acetate since it is a little contaminated with acetic (ducks can t get it totally dry without a vacuum oven). 3. NaOH washed Brazillian is fine Quack No need to purify further for starting material ... 

This following article was sent to Strike by Osmium and Feck (are they the same person ). It involves the direct addition of azide to a terminal alkene (you-know-who) by the in situ production of the reactant mercury (II) azide from mercuric acetate and sodium azide (please don t ask) [80]. 

General Procedure - To a solution of 0.3 moles of sodium azide and 0.1 mole of mercuric acetate in 200mL of 50% aqueous tetra-... 

Mercuric acetate heated for 18 hr at 100°C in acetic acid with 2-acetamidothiazole yields 2-acetamido-4,5-diacetoxymercurithiazole (214) (396). This product may then be transformed to the 4.5-diiodo derivative of 2-acetamidothiazole (215) (Scheme 135). 

Acetamido-4-methylselenazole can react with mercuric acetate to yield 5-mercuriacetate derivatives that can be converted to the chloro derivatives by the action of sodium chloride. Treatment with potassium iodide leads to reduction regenerating the initial compound with loss of mercury (Scheme 16) (4). 

Treatment of this same 4, 5 -dibromofluorescein intermediate with mercuric acetate and conversion to the disodium salt yields the hydroxymercuric analogue merbromin or mercurochrome [129-16-8] (41). It was once a widely used antiseptic, especially for skin disinfection, and was even adrninistered internally. However, it has been replaced by more effective antibacterial agents. 

Chemical assay is preferably performed by gas—hquid chromatography (glc) or by the conventional methods for determination of unsaturation such as bromination or addition of mercaptan, sodium bisulfite, or mercuric acetate. 

Mercuric Acetate. Mercuric acetate/7ti(9(9-27-7/, Hg(C2H202)2, is a white, water-soluble, crystalline powder, soluble in water and many organic solvents. It is prepared by dissolving mercuric oxide in warm 20% acetic acid. A slight excess of acetic acid is helpful in reducing hydrolysis. 

Another method of preparing mercuric acetate is the oxidation of mercury metal using peracetic acid dissolved in acetic acid. Careful control of the temperature is extremely important because the reaction is quite exothermic. A preferred procedure is the addition of approximately half to two-thirds of the required total of peracetic acid solution to a dispersion of mercury metal in acetic acid to obtain the mercurous salt, followed by addition of the remainder of the peracetic acid to form the mercuric salt. The exothermic reaction is carried to completion by heating slowly and cautiously to reflux. This also serves to decompose excess peracid. It is possible and perhaps more economical to use 50% hydrogen peroxide instead of peracetic acid, but the reaction does not go quite as smoothly. 

The primary use of mercuric acetate is as a starting material for the manufacture of organic mercury compounds. 

Merbrornin/725 -/ )-< 7, disodium2,7-dibromo-4-hydroxymercuri luoresceiQ, (2), commonly called mercurochrome, is prepared by refluxing dibromofluoresceia with mercuric acetate ia acetic acid. The precipitate is dissolved ia water containing the stoichiometric amount of sodium hydroxide and evaporated. 

Diuretics. Chlomieodrin [62-37-3] (methoxy(urea)propylmercuric chloride) (8), is prepared ia the same sort of reaction used for chloromethoxypropylmercuric acetate. Ahyl urea is used instead of aHyl chloride, together with methanol and mercuric acetate. The product, after dilution with water and neutralization, is precipitated with sodium chloride ... 

With mercuric acetate (Hg(OOCCH2)2), olefins and / fZ-butyl hydroperoxide form organomercury-containing peroxides (66,100). The organomercury compound can be treated with bromine or a mild reducing agent, such as sodium borohydride, to remove the mercury. 

Unsaturation value can be determined by the reaction of the akyl or propenyl end group with mercuric acetate ia a methanolic solution to give acetoxymercuric methoxy compounds and acetic acid (ASTM D4671-87). The amount of acetic acid released ia this equimolar reaction is determined by titration with standard alcohoHc potassium hydroxide. Sodium bromide is normally added to convert the iasoluble mercuric oxide (a titration iaterference) to mercuric bromide. The value is usually expressed as meg KOH/g polyol which can be converted to OH No. units usiag multiplication by 56.1 or to percentage of vinyl usiag multiplication by 2.7. 

Methylation of avermectins B and B2 leads to the corresponding derivatives of the A series (49). A procedure involving the oxidation of the 5-methoxy group with mercuric acetate and NaBH reduction of the 5-keto-intermediate allows the conversion of the A to the B components (50). The 23-hydroxy group of the "2" components, after selective protection of the other secondary hydroxy groups, is converted to a thionocarbonate, which can be elirninated to give the 22,23-double bond of the "1" components alternatively it can be reduced with tributyltin hydride to the 22,23-dihydro derivatives (= ivermectins) (51). 

Mercuration-Thallation. Mercuric acetate and thallium ttifluoroacetate react with benzene to yield phenyHnercuric acetate [62-38-4] or phenylthaHic ttifluoroacetate. The arylthalHum compounds can be converted iato phenols, nitriles, or aryl iodides (31). 

In a similar manner to the formation of pyridazines from AT-aminopyrroles, cinnolines or phthalazines are obtainable from the corresponding 1-aminooxindoles or 2-amino-phthalimides. If the relatively inaccessible 1-aminooxindoles are treated with lead tetraacetate, mercuric acetate, r-butyl hypochlorite (69JCS(C)772) or other agents, cinnolones are formed as shown in Scheme 105. The reaction was postulated to proceed via an intermediate... 

The olefin of the Voc group is very susceptible to electrophilic reagents and thus is readily cleaved by reaction with bromine or mercuric acetate. 

Dextran [9004-54-0] Mf 6,000-220,000. Solutions keeps indefinitely at room temperature if 0.2mL of Roccal (10% alkyldimethylbenzylammonium chloride) or 2mg phenyl mercuric acetate are added per lOOmL solution. [Scott and Melvin Anal Biochem 25 1656 7955.]... 

The reactivity of mercury salts is a fimction of both the solvent and the counterion in the mercury salt. Mercuric chloride, for example, is unreactive, and mercuric acetate is usually used. When higher reactivity is required, salts of electronegatively substituted carboxylic acids such as mercuric trifiuoroacetate can be used. Mercuric nitrate and mercuric perchlorate are also highly reactive. Soft anions reduce the reactivity of the Hg " son by coordination, which reduces the electrophilicity of the cation. The harder oxygen anions leave the mercuric ion in a more reactive state. Organomercury compounds have a number of valuable synthetic applications, and these will be discussed in Chapter 8 of Part B. 

Alkynes react with mercuric acetate in acetic acid to give addition products. In the case of 3-hexyne, the product has -stereochemistry, but the Z-isomer is isolated from diphenylacetylene. The kinetics of the addition reaction are first-order in both alkyne and... 

This reagent can also be formed by reaction of bromine with mercuric acetate ... 

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