Mesityl oxide, condensation with

Other examples of template cyclization reactions leading to macrocycles with amine double bonds that can be reduced to the fully saturated systems will be discussed later. Often, without the template ion, small 1 1 cyclizations take place. In the case of the Curtis reaction, a seven-membered ring was formed without the template ion (Montecatini, 1968). Ethylenediamine condensed with mesityl oxide or with other a,/3-unsaturated ketones to give tetrahydro-l,4-diazepines without the template ion (Elguero et al., 1969 Guareshi, 1894 Mushkalo and Shokol, 1960). However, in the case of reactions of rigid arylideneacetone or benzylideneacetophenone with ethyl-... 

This reaction was first reported by Engler and Riehm in 1885. It is a synthesis of 2,4-dimethylquinoline from the thermal condensation of aniline hydrochloride and acetone or mesityl oxide along with the evolution of water and methane, and is known as the Riehm quinoline synthesis. This reaction can occur under the conditions with or without any condensation reagents and may evolve other hydrocarbons as well. ... 

Assemble a 250 ml. three-necked flask, fitted with a stirrer, a reflux condenser and a dropping-funnel, as in Fig. 22(A) and (j), p. 43, or Fig. 23(c), p. 46 (or a two-necked flask, with the funnel fitted by a grooved cork (p. 255) to the top of the condenser). Place 40 ml. of ethanol in the flask, and then add 2-3 g. of sodium cut into small pieces. When all the sodium has dissolved, heat the stirred solution on the water-bath, and run in from the funnel 17 g. (17 ml.) of ethyl malonate and then (more slowly) io-2 g. (12 ml.) of mesityl oxide, the reaction-mixture meanwhile forming a thick slurry. Boil the stirred mixture under reflux for i hour, and then add a solution of 10 g. of sodium hydroxide in 50 ml. of water, and continue boiling the pale honey-coloured solution for ij hours more. 

Fit a 750 ml. round-bottomed flask with a fractionating column attached to a condenser set for downward distillation. Place 500 g. of diacetone alcohol (the crude product is quite satisfactory), 01 g. of iodine and a few fragments of porous porcelain in the flask. Distil slowly. with a small free flame (best in an air bath) and collect the following fractions (a) 56-80° (acetone and a little mesityl oxide) (6) 80-126° (two layers, water and mesityl oxide) and (c) 126-131° (mesityl oxide). Whilst fraction (c) is distilling, separate the water from fraction (6), dry with anhydrous potassium carbonate or anhydrous magnesium sulphate, and fractionate from a small flask collect the mesityl oxide at 126-131°. The yield is about 400 g. 

Fit a 1-litre three-necked flask with two double surface condensers and a glycerine-scaled stirrer (Fig. II, 7, 10). Place 25 g. (29 ml.) of mesityl oxide (Section 111,79), 50 ml. of dioxan and a cold (10°) solution... 

Mesityl oxide (Section 111,79) (I) condenses with ethyl malonate in the presence of sodium ethoxide to give the sodium derivative of (II) this upon hydrolysis with aqueous potassium hydroxide, followed by acidification, gives the cyclic diketone 5 5-dimethyl-l 3-cycfohexanedione (III), of which the enoUc form is 5 5-dimethyldihydroresorcinol (IV) ... 

Various 4-, 5-, or 4,5-disubstituted 2-aryIamino thiazoles (124), R, = QH4R with R = 0-, m-, or p-Me, HO C, Cl, Br, H N, NHAc, NR2, OH, OR, or OjN, were obtained by condensing the corresponding N-arylthiourea with chloroacetone (81, 86, 423), dichloroacetone (510, 618), phenacyichloride or its p-substituted methyl, f-butyl, n-dodecyl or undecyl (653), or 2-chlorocyclohexanone (653) (Method A) or with 2-butanone (423), acetophenone or its p-substituted derivatives (399, 439), ethyl acetate (400), ethyl acetyl propionate (621), a- or 3-unsaturated ketones (691), benzylidene acetone, furfurylidene acetone, and mesityl oxide in the presence of Btj or Ij as condensing agent (Method B) (Table 11-17). 

Furfural reacts with ketones to form strong, crosslinked resins of technical interest in the former Soviet Union the U.S. Air Force has also shown some interest (42,43). The so-called furfurylidene acetone monomer, a mixture of 2-furfurylidene methyl ketone [623-15-4] (1 )> bis-(2-furfurylidene) ketone [886-77-1] (14), mesityl oxide, and other oligomers, is obtained by condensation of furfural and acetone under basic conditions (44,45). Treatment of the "monomer" with an acidic catalyst leads initially to polymer of low molecular weight and ultimately to cross-linked, black, insoluble, heat-resistant resin (46). 

Malonic acid, amino-, diethyl ester, HYDROCHLORIDE, 40, 24 Malonic acid, bts(hydroxymethyl)-, DIETHYL ETHER, 40, 27 Malonitrile, condensation with tetra-cyanoethylene, 41, 99 2-Mercaptopyrimidine, 43, 6S hydrochloride of, 43, 68 Mercuric oxide in preparation of bromo-cyclopropane, 43, 9 Mesityl isocyanide, 41,103 5-Methallyl-l,2,3,4,5-pentachlorocyclo-pentadiene, 43, 92 Methane, dimesityl-, 43, 57 Methanesiileinyl chloride, 40, 62 Methanesulfonic acid, solvent for making peroxybenzoic acid from benzoic acid, 43, 93... 

The reaction mechanism is shown in Figure 4 and is adapted from work by Fiego et al. [9] on the acid catalysed condensation of acetone by basic molecular sieves. The scheme has been modified to include the hydrogenation of mesityl oxide to MIBK. The scheme begins with the self-condensation of acetone to form diacetone alcohol as the primary product. The dehydration of DAA forms mesityl oxide, which undergoes addition of an addition acetone to form phorone that then can cyclise, via a 1,6-Michael addition to produce isophorone. Alternatively, the mesityl oxide can hydrogenate to form MIBK. 

In a 2-1. four-necked flask (or a three-necked flask with a Y-tube connector) equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer extending nearly, to the bottom of the flask is placed 550 ml. (595 g., 5.83 moles) of acetic anhydride which is cooled to 0° with an ice-salt bath. Then 180 ml. (300 g., 2.09 moles) of a 70% solution of perchloric acid is added with stirring at a rate such that the temperature does not rise above 8° (Note 1). This step takes about 3 hours. The mixture is continually cooled and stirred, and 240 ml. (204 g., 2.09 moles) of mesityl oxide is then added slowly. The slow addition of 370 ml. (400 g., 3.92 moles) of acetic anhydride follows. The ice bath is then replaced by a water bath the temperature of the reaction mixture will usually rise to 50-70° because of the heat liberated by the exothermic reaction, and the reaction mixture will turn dark. The reaction mixture is heated on a steam bath for 15 minutes to complete the reaction, and the mixture is then allowed to cool and stand at room temperature for 2 hours. The crystals,... 

One of the most thoroughly investigated aldol condensations is the selfcondensation of acetone. This is an important industrial reaction for the production of diacetone alcohol (DA) (Scheme 11), which is valuable as a chloride-free solvent and an intermediate in the synthesis of industrially important products such as mesityl oxide (MO), isophorone, methyl isobutyl ketone, and 3,5-xylenol. The reaction is exothermic, with the yield of DA decreasing with increasing reaction temperature it is usually performed with NaOH or KOH as a basic catalyst 118). 

LXVIII), a constituent of aviation fuel. The reaction of acetone with acetylene may also lead to developments of importance in finding new uses for acetone. For example, acetone reacts with acetylene in the presence of a metal acetylide catal5rst to form the compound LXIX, which could be converted into isopentane (LXX), another constituent of aviation fuel. There may be possibilities of using the condensation products of acetone such as mesityl oxide (LXXI), which could be converted through the saturated ketone, methyl isobutyl ketone (LXXII), into 4-methylpentane (LXXIII). 

The material is prepared by Diels-Alder reaction of 1,3-pentadiene and mesityl oxide and subsequent aldol condensation of the resulting acetyl trimethyl cyclohexene with acetaldehyde [99]. 5-Damascone is used in perfumes to create masculine notes. 

Munson and Haw (151) reported the first in situ NMR study of acetaldehyde in a zeolite. Figure 27 shows 13C spectra of this species reacting on HZSM-5 in the presence of water to form crotonaldehyde with high selectivity (an example of aldol condensation). We later reported a very detailed study of the aldol reactions of acetone and cyclopentanone on various zeolites (Scheme 4) (147). Dimerization of acetone followed by dehydration gives mesityl oxide (31), and the I3C isotropic shifts of this conjugated ketone are strongly dependent on state of protonation. Farcasiu and Ghen-ciu (152,153) have reported extensive measurements of the 13C shifts of 31... 

Improvements in the double Skraup synthesis of 1,7-phenanthroline from m-phenylenediamine now enable a yield of 70% to be achieved.163 The Skraup reaction continues to be used for the synthesis of 1,7-phen-anthrolines starting from the substituted 5-aminoquinolines. S-Chloro-6-hydroxy-1,7-phenanthroline (18) has been prepared in this way,164 and an improved synthesis of 6-hydroxy-1,7-phenanthroline was reported.165 As expected, the Skraup reaction on 5-aminoquinaldine affords 8-methyl-1,7-phenanthroline,166 not 2-methyl-1,7-phenanthroline as it was previously named.8 The extension of the Skraup reaction using methyl vinyl ketone instead of glycerol has been applied to 5-aminoquinoline to afford 4-methyl-1,7-phenanthroline.166 A related condensation using 2-hydroxymethylenecyclohexanone provides a route to benzo-substituted 1,7-phenanthrolines.167 7-Aminoquinoline with mesityl oxide in the presence of iodine gives 8,8,10-trimethyl-7,8-dihydro-l,7-phenanthroline (19).168... 

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