Dimedon

In the following examples, pinacol is oxidised to acetone, which is identified as its semicarba2one and its 2,4 dinitrophenylhydra2one, and glycerol is oxidised to formaldehyde and formic acid. The formaldehy de is readily detected by the condensation product which it gives with dimedone, 5,5-dimethylcyclohexan-i,3-dione (p, 277). 

B) A solution of 1 g. of dimedone (preparation, p. 277) in 10 ml, of ethanol. This solution will be required only for the glycerol oxidation experiment. 

Dissolve 0 5 ml. of glycerol in 20 ml. of w ater, and add 20 ml. of the above 5% aqueous sodium periodate solution. After 15-20 minutes add 12 ml. of the above 10% ethanolic dimedone solution, and stir well at intervals for another 15 minutes. The addition of the dimedone solution may cause a rapid precipitation of some of the dimedone itself, which is only slightly soluble in water, whereas the formaldehyde-dimedone compound separates more slowly from the solution. 

Filter the mixed product at the pump, and wash it well with ethanol to remove excess of dimedone, and then with water and again with ethanol. The dried white residual methylene-dimedone , m.p. 186-188°, weighs o 55-o-65 g. It may be recrystallised from ethanol containing about 10% of water, and then has m.p. 189°. 

The compound (III) can however lose ethanol by an internal Claisen ester condensation (p. 264) to give the cyclohexane derivative (IV), which, being the ester of a (3-keto acid, in turn readily undergoes hydrolysis and decarboxylation to give 5,5Hiimethyl cyclohexan-i,3Hiione (V) or Dimedone, a valuable reagent for the detection and estimation of formaldehyde. 

The Dimedone (V) in ethanolic solution reacts rapidly with formaldehyde to give methylene-dimedone (VI) which. 

Dimedone derivatives. Dimedone or 6 6-dimethylci/cZohexane-1 3 dioiie j- in saturated aqueous solution J or in 10 per cent. alcohoUc solution gives crystalline derivatives (I) with aldehydes, but not with ketones. The reaction is ... 

The condensation products are almost insoluble in water, but can be crystallised from dilute alcohol. Dimedone is therefore a good reagent for the detection and characterisation of aldehydes. 

The alkylidene dimethone (dimedone) (I) upon boiling with glacial acetic acid, acetic anhydride, hydrochloric acid and other reagents frequently loses water and passes into a substituted octahydroxanthene or the anhydride (II), which often serves as another derivative. The derivatives (I) are soluble in dilute alkali and the resulting solutions give colourations with ferric chloride solution on the other hand, the anhydrides (II) are insoluble in dilute alkali and hence can easily be distinguished from the alkylidene dimedones (I). 

Add 0 1 g. of the aldehyde in 5 ml. of 50 per cent, ethanol to 2 ml. of a 10 per cent, or saturated alcoholic solution of dimedone. If a precipitate does not form immediately, warm for 5 mintues if the solution is still clear at the end of this period, add hot water until the mixture is just cloudy and cool to about 6°. Collect the crystalline derivative and recrystallise it from methanol - water or ethanol - water. 

To prepare the anhydride , boil a solution of 01 g. of the dimedone derivative (I) in 5 ml. of 80 per cent, ethanol to which 1 drop of concentrated hydrochloric. acid has been added for 5 minutes, than add hot water until the mixture is just turbid, cool and collect the anhydride by filtration. Recrystallise it from dilute methanol. 

B.P. Alkylldene Dlmedone (I) Dimedone "Anhydride" (M) 2 4-Dinltn>-phenyl-hydnzone Seml- earbazone />-NItro- phenyl- hydrazone Other Derivatives Cd ss... 

Aromatic aldehydes react with the dimedone reagent (Section 111,70,2). All aromatic aldehydes (i) reduce ammoniacal silver nitrate solution and (ii) restore the colour of SchifiF s reagent many react with sodium bisulphite solution. They do not, in general, reduce Fehling s solution or Benedict s solution. Unlike aliphatic aldehydes, they usually undergo the Cannizzaro reaction (see Section IV,123) under the influence of sodium hydroxide solution. For full experimental details of the above tests, see under Ali-phalic Aldehydes, Section 111,70. They are easily oxidised by dilute alkaline permanganate solution at the ordinary temperature after removal of the manganese dioxide by sulphur dioxide or by sodium bisulphite, the acid can be obtained by acidification of the solution. 

Dimedone derivatives. For experimental details, see under Aliphatic Aldehydes, Section 111,70,2. 

Dimedone " Anhydride of Dimedone 2 4-Dlnltro-phenyl-hydrazone Semi- carbazone Ozime Phenyl- hydrazone />-Nltro. phenyl- hydrazone... 

Section IV, 135,5), but are unaflFected by the dimedone reagent (Section 111,70, 2). The general reactions are similar to those already given under Aliphatic Ketones (Section 111,74). Owing to their higher molecular weight, such derivatives as oximes and phenylhydrazones are frequently quite satisfactory. 

If an unknown compound gives a positive test with the 2 4-dinitrophenylhydrazine reagent, it then becomes necessary to decide whether it is an aldehyde or a ketone. Although the dimedone reagent (Section 111,70,2) reacts only with aldehydes, it is hardly satisfactory for routine use in class reactions. It is much simpler to make use of three other reagents given below, the preparation and properties of which have already been described (Section 111,70). 

The dimedone reagent may, however, be used if it is desired to detect an aldehyde in the presence of a ketone. 

Acetaldehyde can be isolated and identified by the characteristic melting points of the crystalline compounds formed with hydrazines, semicarbazides, etc these derivatives of aldehydes can be separated by paper and column chromatography (104,113). Acetaldehyde has been separated quantitatively from other carbonyl compounds on an ion-exchange resin in the bisulfite form the aldehyde is then eluted from the column with a solution of sodium chloride (114). In larger quantities, acetaldehyde may be isolated by passing the vapor into ether, then saturating with dry ammonia acetaldehyde—ammonia crystallizes from the solution. Reactions with bisulfite, hydrazines, oximes, semicarb azides, and 5,5-dimethyl-1,3-cyclohexanedione [126-81 -8] (dimedone) have also been used to isolate acetaldehyde from various solutions. 

Stmcture (1) is an unstable blue soHd which caimot be obtained in a pure state (167) stmcture (2) [105071-90-7] however, is stable (168). Stmcture (2) was obtained from triphenylbismuth carbonate and dimedone. More recendy a number of bismuthonium yUdes, eg, (3) [119016-81 -8] (169), have been prepared and their reactions studied. 

The butanals form the conventional aldehyde hydra2one, semicarba2one, and dimedone-type derivatives. In the absence of other aldehydes and ketones, -butyraldehyde can be deterrnined by addition of sodium bisulfite and the excess bisulfite deterrnined with iodine or thiosulfate (34). 

Reactions of 6-aminouracils with various 2-substituted cyclohexanones such as the aldehyde (264) give reduced pyrimido[4,5-f ]quinolines (265) (57BRP774095, 58JA3449), and other cyclohexanone derivatives used include the 2-dimethylaminomethyl (Mannich) bases (78AP542) and the 5-benzylidenedimedones (266) formed in situ from dimedone and aldehydes (67KGS395, cf. 67KGS406). 

PdCl2(Ph3P)2, dimedone, THF, 95% yield. This method is also effective for removing the allyloxycarbonyl group from alcohols and amines. 

Pd(Ph3P)4, dimedone, THF, 88-95% yield. The catalyst is not poisoned by the presence of thioethers such as methionine. Diethyl malonate has also been used as a nucleophile to trap the 7r-allylpaladium intermediate and regenerate Pd(0). ... 

ALKYLATION OF DIMEDONE WITH A TRICARBONYL(DIENE)IRON COMPLEX TRlCARBONYL[2-[(2,3,4,5-t))-4-METHOXY 2,4 CYCLOHEXADUEN-l-YLJ-5,5-DIMETHYL-l,3-CYCLOHEXANEDIONE]IRON... 

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