Keto acetone

The most commonly used protected derivatives of aldehydes and ketones are 1,3-dioxolanes and 1,3-oxathiolanes. They are obtained from the carbonyl compounds and 1,2-ethanediol or 2-mercaptoethanol, respectively, in aprotic solvents and in the presence of catalysts, e.g. BF, (L.F. Fieser, 1954 G.E. Wilson, Jr., 1968), and water scavengers, e.g. orthoesters (P. Doyle. 1965). Acid-catalyzed exchange dioxolanation with dioxolanes of low boiling ketones, e.g. acetone, which are distilled during the reaction, can also be applied (H. J. Dauben, Jr., 1954). Selective monoketalization of diketones is often used with good success (C. Mercier, 1973). Even from diketones with two keto groups of very similar reactivity monoketals may be obtained by repeated acid-catalyzed equilibration (W.S. Johnson, 1962 A.G. Hortmann, 1969). Most aldehydes are easily converted into acetals. The ketalization of ketones is more difficult for sterical reasons and often requires long reaction times at elevated temperatures. a, -Unsaturated ketones react more slowly than saturated ketones. 2-Mercaptoethanol is more reactive than 1,2-ethanediol (J. Romo, 1951 C. Djerassi, 1952 G.E. Wilson, Jr., 1968). 

Polar solvents shift the keto enol equilibrium toward the enol form (174b). Thus the NMR spectrum in DMSO of 2-phenyl-A-2-thiazoline-4-one is composed of three main signals +10.7 ppm (enolic proton). 7.7 ppm (aromatic protons), and 6.2 ppm (olefinic proton) associated with the enol form and a small signal associated with less than 10% of the keto form. In acetone, equal amounts of keto and enol forms were found (104). In general, a-methylene protons of keto forms appear at approximately 3.5 to 4.3 ppm as an AB spectra or a singlet (386, 419). A coupling constant, Jab - 15.5 Hz, has been reported for 2-[(S-carboxymethyl)thioimidyl]-A-2-thiazoline-4-one 175 (Scheme 92) (419). This high J b value could be of some help in the discussion on the structure of 178 (p. 423). 

AHylestrenol (37) is prepared from (32), an intermediate in the synthesis of norethindrone. Treatment of (32) with ethanedithiol and catalytic boron trifluoride provides a thioketal. Reduction with sodium in Hquid ammonia results in the desired reductive elimination of the thioketal along with reduction of the 17-keto group. Oxidation of this alcohol with chromic acid in acetone followed by addition of aHyl magnesium bromide, completes the synthesis... 

Diacetone Alcohol. Diacetone alcohol (DAA) (4-hydroxy-4-methyl-2-pentanone) is a colorless, mild smelling Hquid which is completely miscible with water and most organic solvents. It is the simplest aldol condensation product of acetone, and because of its keto-alcohol functionahes it has special utility in the coatings industry where it is used to dissolve cellulose acetate to give solutions with high tolerance for water (115). 

Methyl Isoamyl Ketone. Methyl isoamyl ketone [110-12-3] (5-methyl-2-hexanone) is a colorless Hquid with a mild odor. It is produced by the condensation of acetone and isobutyraldehyde (164) in three steps which proceed via the keto-alcohol dehydration to 5-methyl-3-hexen-2-one, and hydrogenation to 5-methyl-2-hexanone. 

Hydroxy-1,2,3,4-tetrahydrocrysene (2) A mixture of 4-keto-1,2 3 4-tetrahydrocrysene 1 (2 75 g, 11 mmol) and aluminium isopropoxide (8 2 g, 40 mmol) in PhMe (25 mL) was refluxed for 1 h After cooling, iPrOH (25 mL) was added and the formed acetone was distilled slowly maintaining the volume constant by addition of iPrOH After all acelone was distilled, the solution was acidified with 0% H2SO4 The separated toluene solution was evaporated to gwe 2 1 g of 2 (76%), mp 156-158 C... 

Keto-L-gulonic acid [526-98-7] M 194.1, m 171 . Crystd from water and washed with acetone. 

This with potassium hydroxide in methanol forms de-OiV-dimethylarmepavine, m.p. 86-7°, (B. HCl, m.p. 229-30°) of which the methiodide, m.p. 233-4°, on treatment with alkali decomposes into trimetHylamine and a -p-anisyl-/3-(3 4-dimethoxy- 6 - vinylphenyl) -ethylene, m.p. 79°. The latter is oxidised by permanganate in acetone to anisic and m-hemipinic acids. With ethyl sulphate and alkali, armepavine gives 0-ethylarmepavine, an oil, which permanganate oxidises to p-ethoxybenzoic acid. Armepavine is similarly oxidised to p-hydroxybenzoic acid and l-keto-6 7-dimethoxy-2-methyl-1 2 3 4-tetiahydrowoquinoline and is therefore 6 7-dimethoxy-l-p-hydroxybenzyI-2-methyI-l 2 3 4-tetrahydrowoquinoline, i.e., it is laudanosine (p. 187) with MeO. at C replaced by H and MeO at C changed to HO. ... 

This is the most efficient way of introducing a A -double bond into a 5a-3-keto corticoid. Alternatively the 2,4-dibromo compound can be treated with sodium iodide in acetone (preferably in the presence of iodoacetone) followed by reduction of the resulting 2-iodo-A -3-ketone to the A -3-ket-... 

The reaction of 17-keto steroids with hydrogen cyanide (or acetone cyanohydrin) to form a mixture of the 17-cyano-17-hydroxy compounds, followed by dehydration and reaction with methyl Grignard reagent, is one of the earliest methods for the conversion of androstanes to pregnanes. 

A-Homo-estra-l 0),2,4c[-triene-4,ll-dione (45) by solvolysis of the l-keto dibromocarbene adduct (43a).A mixture of monoadduct (43a 0.25 g) and silver perchlorate (0.3 g) in aqueous acetone (1 4, 30 ml) is heated under reflux for 30 min. The reaction mixture is filtered to remove the precipi-... 

Anions of (3-keto esters are said to be synthetically equivalent to the enolates of ketones. The anion of ethyl acetoacetate is synthetically equivalent to the enolate of acetone, for example. The use of synthetically equivalent groups is a common tactic in synthetic organic chemistry. One of the skills that characterize the most creative practitioners of organic synthesis is an ability to recognize situations in which otherwise difficult transfonnations can be achieved through the use of synthetically equivalent reagents. 

Which tautomer is lower in energy, acetone or propen-2-oll Use equation (1) to calculate the equilibrium distribution of the two at room temperature. If an experiment is capable of detecting concentrations as low as 1 % of the total, would you expect to observe both keto and enol forms of acetone at room temperature ... 

Which tautomer is more stable Would you expect to be able to observe both tautomers at room temperature Rationalize any differences between this keto-enol equihbrium and that above involving acetone and propen-2-ol. 

Reaction of tryptamine with simple ketones has not been widely explored. Acetone in the presence of benzoyl chloride has been reported to yield 2-benzoyl-1,1 -dimethyl-1,2,3,4-tetrahydro-j8-carbo-line. That the keto group is much less reactive than the aldehyde group is indicated by the fact that j8-keto aldehydes, in the form of their acetals or sodium salts, react with tryptamine at the aldehyde function to yield the conjugated enamine 24, which undergoes ring closure via an intramolecular Michael addition. The potentialities of this interesting modification of the Pictet-Spengler reaction have not yet been fuUy explored. 

In a modified approach, the carbolinyl acetate 393 underwent a Mannich reaction with formaldehyde and acetone to give the keto ester 396 which, with base, cyclized to the diketone 397. This diketone (397) has recently been used to prepare a number of interesting pentacyclic compounds. 

This sequence is equally applicable to keto esters. Thus, condensation of guanidine with ethyl acetoacetate gives the pyrimidone, 134. Elaboration as above gives the pyrimidine, IJ5 acylation with the sulfonyl chloride (88) followed by hydrolysis yields sulfamerazine (107). Reaction of guanidine with beta dicarbonyl compounds gives the pyrimidine directly. Condensation of the base with acetonyl acetone affords the starting amine for sulfadimidine (108). ... 

Most carbonyl compounds exist almost exclusively in the keto form at equilibrium, and it s usually difficult to isolate the pure enol. For example, cyclohexanone contains only about 0.0001% of its enol tautomer at room temperature, and acetone contains only about 0.000 000 1% enol. The percentage of enol tautomer is even less for carboxylic acids, esters, and amides. Even though enols are difficult to isolate and are present only to a small extent at equilibrium., they are nevertheless responsible for much of the chemistry of carbonyl compounds because they are so reactive. 

Side reaction. The luminescence reaction of Cypridina luciferin catalyzed by luciferase involves a side reaction (Fig. 3.1.8). In the luminescence reaction, 85-90% of luciferin is converted into oxyluciferin and CO2 accompanied by light emission, whereas 10-15% of luciferin is converted directly into etioluciferin plus a keto-acid without light emission (Shimomura and Johnson, 1971). In the chemiluminescence reactions of Cypridina luciferin in organic solvents (such as diglyme, acetone, pyridine and DMSO), the proportion of the dark side reaction... 

A. fi(-)-a-(l-Naphthyl)ethylamine. A mixture of 58.44 g. (0.20 mole) of (-)-2,3 4,6-di-0-isopropylidene-2-keto-L-gulonic acid hydrate [(-)-DAG] (Note 1) and 1.7 1. of acetone (Note 2) is placed in a 3-1. Erlenmeyer flask. A boiling chip is added, and the mixture is heated to a gentle boil. To the resulting hot solution is added cautiously but rapidly, over a 1 minute period, 34.24 g. (0.20 mole) of racemic y.- 1 -naphthyl)et hylamine (Note 3) in 100 ml. of acetone. The mixture is allowed to stand at room temperature for approximately 4 hours. The (-)-amine (-)-DAG salt is filtered with suction, washed with 100 ml. of acetone, and dried in a vacuum oven at 60° to constant weight. The yield of the crude (-)-amine (-)DAG salt is 73-76 g., m.p. 205-207° (decomp.) (Note 4), [a]p —14.2° (c 1.01%, methanol). For crystallization, the crude salt and 4.2 1. of ethanol (Note 5) are placed in a 5-1. round-bottomed flask fitted with a reflux condenser and a mechanical stirrer. The mixture is stirred and heated at reflux... 

Colorimetric procedures used In steroid assays are often subject to drug Interference. In the determination of 17-Ketosterolds by the Zimmerman reaction, drugs with the 17-Keto basic structure such as ascorbic acid, morphine and reserplne will cause Increased values. In the determination of 17,21 -dlhydroxysterolds by the Porter-Sllber reaction the dlhydroxy-acetone chain Is the reactive unit. Drugs like meprobamate, chloral hydrate, chloropromazlne and potassium Iodide will Interfere with this reaction and cause elevated values. In the colorimetric determination of vanlllylmandellc acid (VMA) by a dlazo reaction, drugs like methocarbamol and methyl dopa cause... 

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