Acetone, condensation with

Furfural condenses with acetone in the presence of sodium hydroxide solution to yield 2-furfuralacetone (compare Bemalacelone, Section IV,128) ... 

MIBK is a flammable, water-white Hquid that boils at 116°C. It is sparingly soluble in water, but is miscible with common organic solvents. It forms an a2eotrope with water as shown in Table 2. Condensation of MIBK with another methyl ketone can produce ketones containing 9—15 carbons. For example, condensation with acetone produces diisobutyl ketone, and self-condensation of two MIBK molecules produces 2,6,8-trimethyl-4-nonanone [123-17-1]. Condensation with 2-ethylhexanal gives 1-tetradecanol (7-ethyl-2-methyl-4-undecanol), avaluable surfactant intermediate (58). 

In the presence of an alkali metal hydroxide at about 50°C, chloroform condenses with acetone to give l,l,l-trichloro-2-methyl-2-propanol, [57-15-8] ie, chlorobutanol, chloretone, or acetone—chloroform (9,10). Chlorobutanol is a white crystalline substance with a campborlike odor its sedative, anesthetic, and antiseptic properties have given the compound some importance in the pharmaceutical industry. 

Mehrling and Welde first determined if hydro-aromatic ring aldehydes in general gave violet like odours when condensed with acetone, and it was found that in the case of the four following aldehydes only the first yields a body having a violet odour —... 

The complex [Co(NH3)5(OS02CF3)]2+ undergoes triflate substitution by cyanate and condensation with acetone to form the unusual bis-bidentate imine complex (213)917 in a reaction reminiscent of the classic Curtis condensation of acetone with ethylenediamine. Apart from the novelty of the synthesis, the reported crystal structure was only the second of a CoN6 complex bearing a cyanate ligand. 

Acetals and Ketals.—When D-glucosone condenses with acetone in the presence of sulfuric acid, crystalline 1,2 2,3 5,6-tri-0-isopropylidene(2-hydroxy-D-orobmo-hexose) (XLI) may be isolated.7 On graded hydrolysis... 

These reactions are catalyzed by ammonium acetate, the function of which is to generate protonated imines (322). Under mild reaction conditions, condensation of a- hydroxyamino-oximes with acetone dialkylketals takes place. The procedure can be successfully applied in cases where direct condensation with acetone... 

A consideration of the individual carbon atoms of the sugar chain thus leads to the conclusion that this trimethylglucose is the 2,3,6-isomer and ample confirmation of this conclusion has been forthcoming. To mention only two cases (a) oxidative degradation yields L-threo-di-methoxysuccinic acid,143 and (b) the sugar does not condense with acetone.130... 

The conversion of D-mannose (20) into L-gulose (9) was reported by Evans and Parrish,15 and is shown in Scheme 4. D-Mannose (20) was converted into 21 by condensation with acetone, methanol, and 2,2-di-methoxypropane in the presence of an acid, and mild hydrolysis of 21 afforded 22. Methanesulfonylation of 22 provided 23, which was transformed into 24 with sodium acetate in refluxing N,N-dimethyl-formamide. The overall yield of 24 from D-mannose was >50%. Base hydrolysis, followed by acid hydrolysis, afforded L-gulose (9). 

Diethyl malonate, condensation with acetone, 50, 39 Diethyl 5-methylcoprost-3-en-yl phosphate, 52, 109 Diethyl phosphorochloridate,... 

D-Ribono-1,4-lactone (1) readily condenses with acetone, under acidic catalysis with mineral acids or anhydrous copper sulfate, to give 2,3-0-isopropylidene-D-ribono-1,4-lactone (16a), which was employed for the synthesis of 5-deoxy and 5-0-substituted derivatives of D-ribono- 1,4-lactone and D-ribitol (24). Acid removal of the 1,3-dioxolane protecting group gave products having probable inhibitory activity of arabinose 5-phosphate isomerase (25). Other applications of 16a for the synthesis of natural products will be discussed later. 

The synthesis of the 13-methylene isomer was performed from P-ionylideneacetaldehyde (EIZ 80/20). Condensation with acetone provided the conjugated ketone which, after formylation... 

Stabilizing rings may also be created by forming O-isopropylidene acetals. Condensation of methyl D-ribopyranoside with acetone was shown by Levene and Stiller166 to give equal amounts of the 2,3-O-isopropylidene furanoside and the 3,4-O-isopropylidene pyranoside Barker and Spoors,157 investigating this reaction further, concluded that the isomerization occurs after the condensation with acetone. 

The methylene bi -telluritrichloride condenses with acetone as shown to form methylene fo s-telluriacetone dichloride. The formation of the trichloride may take place in one of the three following ways ... 

A common side reaction during Oppenauer oxidations consists of the base-catalyzed condensation of the carbonyl compound, resulting from the oxidation, with the carbonyl compound used as oxidant. Sometimes, advantage is taken from this side reaction for synthetic purposes. For example, oxidation of primary alcohols with an aluminium alkoxide and acetone results in the formation of an intermediate aldehyde that condenses with acetone, resulting in a synthetically useful formation of an enone.59... 

Charge the inner vessel of the condenser with acetone-Cardice, surround the flask with a cooling bath of acetone-Cardice, and allow the gaseous reagent to flow slowly through the condenser inlet from a preparative assembly or from a compressed gas cylinder. 

Asymmetric alkylation andaldol condensations.2 The enolate (2) of 1 reacts with primary iodides to give essentially a single product (3), in which the alkyl group is syn to the cyclopentadieny ring. Aldol condensation with acetone leads to only one observable product (4). Only two isomeric products are obtained on aldol condensation with prochiral aldehydes and ketones as expected for a rranx-enolate, the i/ww-aldol predominates or is the exclusive product (5) as in the case of pivaldehyde. 

The amino moiety of the 3-carbohydrazide group of unsaturated and 6,7,8,9-tetrahydro-4-oxo-47/-pyrido[l,2-n]pyrimidine-3-carbohydrazides was condensed with acetone and 5-nitro-2-furoaldehyde (830MR687 88EUP252809). The reaction of 6-methyl-6,7,8,9-tetrahydro-4-oxo-4//-pyrido[l,2-a]pyrimidine-3-carbohydrazide with diethyl 2-[2-dimethyl-amino)vinyl]-6-methylpyridine-3,5-dicarboxylate in boiling ethanol for 4 hours afforded N-( 1,6-naphthyridin-6-yl)-4-oxo-4//-pyrido[ 1,2-a]pyrimi-dine-3-carboxamide 426 (85MIP1). 

Fe(en)3]Cl2 (en = ethylenediamine) The complex forms when, under anhydrous and anaerobic conditions, an excess of ethylenediamine is added to a solution of iron(II) chloride in ethanol. The product may be condensed with acetone, producing a tetraazacyclotetradecadiene macrocycle by way of a metal template reaction (88). [Fe(en)3]Cl3 is produced in a similar manner by reacting anhydrous iron(III) chloride with ethylenediamine (89). 

When acetone, sodium cyanide and ammonium chloride are reacted with each other for a longer time, but reversibly, an alternative reaction occurs between the continuously reformed reactants (Figure 9.9, bottom) ammonia undergoes condensation with acetone to give an iminium ion (mechanism Figure 9.23) that irreversibly reacts with cyanide to furnish the a-aminonitrile as shown. 

Methyl-5-tosyl-L-arabofuranosides (a/3 mixture) (XXXI) on condensation with acetone containing hydrogen chloride gave the 1,2-iso-propylidene derivative (XXXII). Methylation gave 1,2-isopropylidene-3-methyl-5-tosyl-L-arabofuranose (XXXIII) from which the tosyl... 

Methyl-D-fucose has been prepared by two methods.68 In the first, methyl a-D-galactopyranoside was converted into the 6-tosyl derivative, from which by condensation with acetone methyl 3,4-isopropylidene-6-tosyl-a-D-galactopyranoside (LXIV) was obtained. Methylation gave the corresponding 2-methyl ether which was converted into the 6-deoxy iodide (LXV) by heating with sodium iodide in acetone solution at 140°. Reduction with Raney nickel gave sirupy methyl 2-methyl-3,4-isopro-pylidene-a-D-fucopyranoside (LXVI) from which 2-methyl-D-fucose was obtained on hydrolysis. 

Schmidt and Wernicke74 have described a synthesis of digitalose starting with D-fucose dibenzyl mercaptal, which on condensation with acetone yielded the 4,5-isopropylidene derivative (LXXIV). Elimination of the dibenzyl mercaptal residues with mercuric chloride and cadmium carbonate in methanol gave 4,5-isopropylidene-D-fucose dimethylacetal (LXXV), from which the 2-benzyl ether was obtained on treatment with sodium and benzyl chloride. Methylation produced 2-benzyl-3-methyl-4,5-iso-propylidene-D-fucose dimethyl acetal (LXXVI), from which the iso-propylidene group was eliminated on treatment with methanolic hydrogen chloride, which also effected glycopyranoside formation (LXXVII). The... 

---