Barium allylic

Thermal stabilisers for PVC are often heavy metal stearates (lead, barium), tin thiolates (R2Sn(SR2) = MZ2), and work by reacting the allylic... 

The alcohol may be made practically anhydrous by refluxing with successive portions of fused potassium carbonate until no further action is observed. The carbonate will remain finely divided and will not become sticky when water is absent. A considerable amount of allyl alcohol is lost mechanically during the drying in this way, so that the potassium carbonate which is used here should be employed for the salting out of fresh portions of allyl alcohol in the first part of subsequent preparations. The allyl alcohol thus produced is dry enough for all practical purposes (98-99 per cent) and it is unnecessary to dry with lime or barium oxide as advised in the literature in order to remove all of the water. The allyl alcohol obtained by this process boils at 94-97°-... 

CH OH - CHOH CH Cl. which is made by reaction of hypochlorous acid and allyl alcohol with barium hydroxide. With hydrogen chloride, glycide alcohol yields epichlorohydrin... 

Keywords allylic alcohol, manganese dioxide, barium manganate, aldehyde, ketone... 

Silver oxide in DMF was successfully applied for the regioselective reaction of (26) with allyl bromide to give compound (27) in 74% yield [231]. Hydroxyl groups in. positions 2 and 6 in cycloheptaamylose were selectively protected by reaction with allyl bromide, barium oxide, and barium hydroxide octahydrate in a DMF-DMSO mixture [232]. 

REGIO- AND STEREOSELECTIVE CARBOXYLATION OF ALLYLIC BARIUM REAGENTS (E)-4,8-DIMETHYL-3,7-NONADIENOIC ACID... 

REGIO- AND STEREOSELECTIVE CARBOXYLATION OF ALLYLIC BARIUM REAGENTS... 

The next four procedures all involve the preparation of useful olefin derivatives. p.y-Unsaturated carboxylic acids such as (E)-4,8-DIMETHYL-3,7-NONADIENOIC ACID are important intermediates for many natural products syntheses. Allylic barium... 

Regio- and Stereoselective Carboxylation of Allylic Barium Reagents (E)-4,8-Dimethyl-3,7-nonadienoic Acid. 

Except for MMA, these are rather uncommon monomers, such as allyl-, cinnamyl-, 2-hyd-roxyethyl-, and methyl methacrylate barium-, 2-ethylhexyl-, and 2-hydroxypropylacrylate diallyl phthalate diallyl isophalate diallyl terephthalatg N, A -methylenebisacrylamide pentaerythritoltetramethyl acrylate tetraethyleneglycol dimethacrylate N-vinylcarbazole vinyl-2-furyl acrylate,... 

The selective oxidation of diols in which one or both hydroxy groups are allylic has been reported on a number of occasions. Reagents which have proved use for this include silver carbonate on Celite, barium manganate/ and manganese dioxide, as illustrated in equations (29)-(31). 

Oxidation of allylic aicohols. Barium manganate is also effective for this oxidation. Thus 1 is oxidized to the ketone 2 in 80-85% yield. The yield with MnOj as oxidant is 38%. Two-phase Jones oxidation gives a complex mixture. 

Strontium enolate chemistry is almost nonexistent barium enolate chemistry is rare radium enolate chemistry is unknown. Allyl chlorides react with barium to form the corresponding organometallics, which in turn react with o ,/ -unsaturated ketones to form the metal enolate . These enolates may also be formed in situ by the reaction of a-chloroketones with barium metal in the presence of an aldehyde, resulting in addition products. These reactions and the enthalpies of formation of the precursor a-haloketones and enones are seemingly ideal candidates for calorimetric investigation. 

The oxidation of diols having alcoholic groups of the same nature, for example, both alcoholic groups are primary, secondary, allylic, or benzylic, is usually carried out at both groups to yield dialdehydes [832] or diketones [552], Such reactions are achieved by chromium trioxide [582], barium manganate [832], dimethyl sulfoxide activated with acetic anhydride [1013], and others (equations 284 and 285). 

The most general method of preparing allyl ethers is to react the alcohol with allyl bromide or iodide in the presence of sodium hydride. The reaction is best carried out in a polar solvent, usually DMF [72]. Alcohols may also be alkylated after conversion to their barium salts. This technique is employed in the case of A-acyl derivatives of aminosugars to avoid any risk of alkylation at nitrogen which would accompany the use of sodium hydride as the base [73,74]. Conversion of alcohols to allyl carbonates, followed by palladium-catalyzed extrusion of CO2, constitutes a milder alternative to the classical Williamson-type pro-... 

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