Acetylacetonate

Dechter J J, Henriksson U, Kowalewski J and Nilsson A-C 1982 Metal nucleus quadrupole coupling constants in aluminum, gallium and indium acetylacetonates J. Magn. Reson. 48 503-11... 

Dimethylpyrazole (III) may be prepared from acetylacetone (I) and hydrazine (II) (produced from hydrazine sulphate and aqueous alkali). The reaction may be represented as ... 

The horon difluoride coordination complex is decomposed by heating under reflux with an aqueous solution of 2 mols of sodium acetate per mol of anhydride, whereupon the p diketone (acetylacetone) is liberated. 

The acylation of ketones with esters an example of the Clalsen condensation is generally effected with a basic reagent, such as sodium ethoxide, sodium, sodamide or sodium hy dride. Thus acetone and ethyl acetate condense in the presence of sodium ethoxide to yield acetylacetone ... 

Decant the liquid layer into a 2 5 litre flask, and dissolve the sodium derivative of acetylacetone in 1600 ml. of ice water transfer the solution to the flask. Separate the impiue ethyl acetate layer as rapidly as possible extract the aqueous layer with two 200 ml. portions of ether and discard the ethereal extracts. Treat the aqueous layer with ice-cold dilute sulphimic acid (100 g. of concentrated sulphiu-ic acid and 270 g. of crushed ice) until it is just acid to htmus. Extract the diketone from the solution with four 200 ml. portions of ether. Leave the combined ether extracts standing over 40 g. of anhydrous sodium sulphate (or the equivalent quantity of anhydrous magnesium sulphate) for 24 hours in the ice chest. Decant the ether solution into a 1500 ml. round-bottomed flask, shake the desiccant with 100 ml. of sodium-dried ether and add the extract to the ether solution. Distil off the ether on a water bath. Transfer the residue from a Claisen flask with fractionating side arm (Figs. II, 24, 4r-5) collect the fraction boiling between 130° and 139°. Dry this over 5 g. of anhydrous potassium carbonate, remove the desiccant, and redistil from the same flask. Collect the pure acetji-acetone at 134r-136°. The yield is 85 g. 

Nonanedione, another 1,3-difunctional target molecule, may be obtained from the reaction of hexanoyl chloride with acetonide anion (disconnection 1). The 2,4-dioxo substitution pattern, however, is already present in inexpensive, symmetrical acetylacetone (2,4-pentanedione). Disconnection 2 would therefore offer a tempting alternative. A problem arises because of the acidity of protons at C-3 of acetylacetone. This, however, would probably not be a serious obstacle if one produces the dianion with strong base, since the strongly basic terminal carbanion would be a much more reactive nucleophile than the central one (K.G. Hampton, 1973 see p. 9f.). 

Diethyl 3-oxoheptanedioate, for example, is clearly derived from giutaryl and acetic acid synthons (e.g. acetoacetic ester M. Guha, 1973 disconnection 1). Disconnection 2 leads to acrylic and acetoacetic esters as reagents. The dianion of acetoacetic ester could, in prin-ciple,be used as described for acetylacetone (p. 9f.), but the reaction with acrylic ester would inevitably yield by-products from aldol-type side-reactions. 

Attention should be paid to the fact that the ratio of Pd and phosphine ligand in active catalysts is crucial for determining the reaction paths. It is believed that dba is displaced completely with phosphines when Pd2(dba)3 is mixed with phosphines in solution. However the displacement is not eom-plcte[16]. Also, it should be considered that dba itself is a monodentate alkene ligand, and it may inhibit the coordination of a sterically hindered olefinic bond in substrates. In such a case, no reaction takes place, and it is recommended to prepare Pd(0) catalysts by the reaction of Pd(OAc)2 with a definite amount of phosphinesflO]. In this way a coordinatively unsaturated Pd(0) catalyst can be generated. Preparation of Pd3(tbaa)3 tbaa == tribenzylidene-acetylacetone) was reported[17], but the complex actually obtained was Pd(dba)2[l8],... 

Br , citrate, CE, CN , E, NH3, SCN , S20 , thiourea, thioglycolic acid, diethyldithiocarba-mate, thiosemicarbazide, bis(2-hydroxyethyl)dithiocarbamate Acetate, acetylacetone, BE4, citrate, C20 , EDTA, E , formate, 8-hydroxyquinoline-5-sul-fonic acid, mannitol, 2,3-mercaptopropanol, OH , salicylate, sulfosalicylate, tartrate, triethanolamine, tiron... 

Acetylacetone, ascorbic acid, citrate, C20j, EDTA, F , H2O2, hydrazine, mannitol, NagP30io, NH2OH HCI, oxidation to molybdate, 8CN , tartrate, tiron, triphosphate... 

Th Acetate, acetylacetone, citrate, EDTA, F , SO , 4-sulfobenzenearsonic acid, sulfosalicylic... 

Chemical ingenuity in using the properties of the elements and their compounds has allowed analyses to be carried out by processes analogous to the generation of hydrides. Osmium tetroxide is very volatile and can be formed easily by oxidation of osmium compounds. Some metals form volatile acetylacetonates (acac), such as iron, zinc, cobalt, chromium, and manganese (Figure 15.4). Iodides can be oxidized easily to iodine (another volatile element in itself), and carbonates or bicarbonates can be examined as COj after reaction with acid. 

The chemical structure of a typical divalent metal acetylacetonate, for which the abbreviation would be MCacac). These compounds are internally bonded ionically and complexed to oxygen at the same time. Thus, their intramolecular forces are very strong (they are stable), but their interraolecular forces are weak (they are volatile). 

Other volatile compounds of elements can be used to transport samples into the plasma flame. For example, hydride reduction of mercury compounds gives the element (Hg), which is very volatile. Osmium can be oxidized to its volatile tetroxide (OSO4), and some elements can be measured as their volatile acetylacetonate (acac) derivatives, as with Zn(acac)2. 

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