Methyl ethyl ketone, derivative

The p-substituted amino ketones can be reduced readily to the more stable P-dialkylamino alcohols, many of which are useful local anaesthetics. Thus the local anaesthetic Tutocaine is made from the Mannich base derived from formaldehyde, methyl ethyl ketone and dimethylamine, followed by reduction and conversion into the p-aminobenzoate ... 

Derivative Formation. Hydrogen peroxide is an important reagent in the manufacture of organic peroxides, including tert-huty hydroperoxide, benzoyl peroxide, peroxyacetic acid, esters such as tert-huty peroxyacetate, and ketone derivatives such as methyl ethyl ketone peroxide. These are used as polymerization catalysts, cross-linking agents, and oxidants (see Peroxides and peroxide compounds). 

Aldehydes and ketones such as acetaldehyde, ben2aldehyde, acetone, acetophenone, cyclohexanone, cyclopentanone, and methyl ethyl ketone have been condensed with CPD in the presence of alkaline agents to produce colored hilvene derivatives. A typical condensation with a ketone is depicted as follows ... 

Exposure to other chemicals can influence the metabolism of -hexane. The effect of oral pretreatment with methyl ethyl ketone (MEK) on the metabolism of inhaled -hexane was investigated in male Fischer 344 rats (Robertson et al. 1989). Groups of 2-4 rats were given MEK (1.87 mL/kg, approximately 1,500 mg/kg) by gavage for 4 days prior to a single 6-hour inhalation exposure to w-hexane (1,000 ppm). Animals were sacrificed at 0, 1, 2, 4, 6, 8, and 18 hours after exposure ended, and samples of blood, liver, testis, and sciatic nerve were obtained and analyzed for -hexane, MEK, and their metabolites. Significant increases in the levels of the neurotoxic metabolite 2,5-hexanedione and 2,5-dimethylfuran (derived from 2,5-hexanedione) were found in blood and sciatic nerve of rats pretreated with MEK. Levels of 2,5-hexanedione in blood were approximately 10-fold higher than control immediately after -hexane exposure in rats and fell rapidly to approximately 2-fold after 6 hours. In sciatic nerve, increases in 2,5-hexanedione were approximately 6-fold at 2 hours and 3-fold at 4 hours. Similar patterns were found with 2,5-dimethylfuran. 2,5-Hexanedione was not detected in the testis of non-pretreated rats levels were measurable but very low in pretreated rats (0.3-0.6 g/g compared to... 

Extension of this condensation to mixed ketones (95) provided further confirmation for the above interpretation. Thus, methyl ethyl ketone and p-chlorophenylbiguanide gave successively the triazine derivatives (CXXVIII) and (CXXIX). The latter (CXXIX) was resolvable into its enantiomers by (+)-tartaric acid this observation supports the six-membered ring structure of (CXXIX) and, because of the very gentle conditions of its isomerisation, that of its isomer (CXXVIII). 

In this paper a generalized approach is presented to the derivation of H-H-S equations for multispecies polymers created by addition polymerization across single double bonds in the monomers. The special cases of copolymers and terpolymers are derived. This development is combined with experimental results to evaluate the numerical parameters in the equations for poly(styrene-acrylonitrile ) (SAN) in three separate solvents and for poly(styrene-maleic anhydride-methyl methacrylate) (S/HA/MM) in a single solvent. The three solvents in the case of SAN are dimethyl formamide (DMF), tetrahydrofuran (THF), and methyl ethyl ketone (MEK) and the solvent for S/HA/HH is HER. 

Direct Oxidation. Direct oxidation of petroleum hydrocarbons has been practiced on a small scale since 1926 methanol, formaldehyde, and acetaldehyde are produced. A much larger project (29) began operating in 1945. The main product of the latter operation is acetic acid, used for the manufacture of cellulose acetate rayon. The oxidation process consists of mixing air with a butane-propane mixture and passing the compressed mixture over a catalyst in a tubular reaction furnace. The product mixture includes acetaldehyde, formaldehyde, acetone, propyl and butyl alcohols, methyl ethyl ketone, and propylene oxide and glycols. The acetaldehyde is oxidized to acetic acid in a separate plant. Thus the products of this operation are the same as those (or their derivatives) produced by olefin hydration and other aliphatic syntheses. 

Reactions of 2-chloro- and 2,3-dichloroquinoxalines with carbanions give 2-quinoxalinyl ketones and 3-chloro-2-quinoxalinyl ketones, respectively e.g., 2-quinoxalinylacetophenone (151) from acetophenone anion.161 However, 2,3-dimethoxy- and 2,3-diethoxy-quinoxaline with methyl ethyl ketone and sodamide in anhydrous benzene give 2-amino derivatives rather than ketones.162... 

The slow combustion reactions of acetone, methyl ethyl ketone, and diethyl ketone possess most of the features of hydrocarbon oxidation, but their mechanisms are simpler since the confusing effects of olefin formation are unimportant. Specifically, the low temperature combustion of acetone is simpler than that of propane, and the intermediate responsible for degenerate chain branching is methyl hydroperoxide. The Arrhenius parameters for its unimolecular decomposition can be derived by the theory previously developed by Knox. Analytical studies of the slow combustion of methyl ethyl ketone and diethyl ketone show many similarities to that of acetone. The reactions of methyl radicals with oxygen are considered in relation to their thermochemistry. Competition between them provides a simple explanation of the negative temperature coefficient and of cool flames. 

Starting with ketones and hydrogen peroxide in the presence of a catalytic amount of acid, mixtures of up to eight components have been identified, i.e.. (1, X = OH. R3 = H), (1, X = OOH, R3 = H), (2, X = Y = OH). (2, X = Y = OOH), (2, Y = OH, Y = OOH), (3). (4), and (5). The ketone structure and reaction conditions, i.e., acid strength, reactant molar ratios, temperature, and time, determine which compounds form and predominate. Mixtures of several peroxide structures usually are present. Individual peroxides have been isolated from several ketones under different conditions (Table 5). The pure peroxides should be handled with extreme caution since most, especially those derived from the low moleculai weight ketones, ate shock- and friction-sensitive and can explode violently. Methyl ethyl ketone peroxide (MEKP) mixtures are produced commercially only as solutions containing <40 wt% MEKPs in solvents, commonly dialkyl phthalates. 

Reaction of 9-bromomethyl-4-oxo-4//-pyrido[ 1,2-a]pyrimidine-3-carboxylates 505 and their homologs with 2,4-dihydroxy-3-propyl-and -3-allyl-acetophenone 506 in boiling methyl ethyl ketone in the presence of potassium carbonate afforded 9-(4-acetyl-3-hydroxy-2-substituted phenoxymethyl) derivatives (507) [87EUP242230 88JAP(K)88/246375]. 

A 200-mL aliquot of an aqueous sample was pH buffered and derivatized with DNPH. The DNPH derivatives were extracted with methylene chloride and the extract was solvent exchanged to 50 mL acetonitrile. Analysis by HPLC-UV showed the presence of methyl ethyl ketone (MEK) derivative which was quantitated as 2.7 mg/L in the extract, using the calibration standards prepared from the solid derivative. Determine the concentration of the MEK in the sample. 

Epoxyglycerides react with ketones in the presence of boron trifluoride to give 1,3-dioxolane derivatives. In this form they were analysed by GC on a column packed with 3% of OV-1 with temperature programming at 4°C/min from 260° C [649]. Cyclo-pentanone was recommended as the most suitable reagent, and acetone, methyl ethyl ketone, methyl isobutyl ketone and others can also be used. 

Fig. 8. Dimensionless reciprocal compressibility vs. reduced concentration plotted on a log-log scale, measured through static light-scattering by Wiltzius et al. (1983). Symbols denote data for various molecular weight polystyrenes in toluene and methyl ethyl ketone at 25°C. The solid curve is the prediction derived from Eq. (21) the proportionality of X to c is fixed by an independent measurement so the curve requires no adjustable parameters.

Thin-layer chromatography on alumina,271 silica gel,139,271>272 cellulose,262,272 Avicel,250,262 and polyamide273 thin layers has extended considerably the applications of chromatography to the separation and purification of imidazoles. Polyamide layers are useful especially for the separation of imidazoles and their 1-methyl derivatives and (using methyl ethyl ketone as solvent) allows separation of the more polar co mpounds su ch as 1,3 -dimethylimidazolium iodide.2 7 3 Imidazolines have also been separated by thin-layer chromatography.274... 

The critical temperature for the thermal rearrangement of 3a under various conditions (in the melt,96 in quinoline20 or naphthalene17) appears to be in the vicinity of 180°. The 3-methoxy derivative (70) isomerizes readily with lithium iodide (in methyl ethyl ketone at 64°).17,96 When ethyl iodide is added to this reaction, i r-methylsaccharin (8) and iV-ethylsaccharin (22) are formed together.96 Lithium iodide catalysis is particularly useful in rearranging nucleoside derivatives, e.g., 71.17 The 3-benzyloxy derivative (73) reacts with debenzylation.17 Even more complex systems like derivatives of steroid alcohols17,20 are isomerized on heating in reasonable yields. When the optically active 3-(2-(cZ)octyloxy)benz[d]isothiazole-l, 1-dioxide was thermally re-... 

Recent work on the thermal indolization of arylhydrazones has introduced new synthetic possibilities for azaindoles. Kelly et al. refluxed cyclohexanone and deoxybenzoin 2-pyridylhydrazones in diethylene glycol to give 5,6,7,8-tetrahydro-a-carboline (42, R = H) and 2,3-diphenyl-7-azaindole in 70 and 56% yields, respectively, compared with 53 and 12% reported earlier. Similarly, y-carboline 29 was obtained in 95 % yield from cyclohexanone 4-pyTidylhydrazone (lit. 48% ). Several 7-azaindole derivatives were prepared in the same manner. The yields ranged from 5 % for azaindolenine (31) to 88% for 3-phenyl-7-azaindole. 3,3-Dimethyl-7-azaindolenine was obtained in 47 % yield from the isobutyralaldehyde hydrazone. The novel cyclic compounds 40 and 41 were obtained from the 2-pyridylhydrazones of cyclopentanone, a-indanone, and a-tetralone in 67, 95, and 77% yields, respectively. Unfortunately, all attempts to cyclize the acetone, pyruvic acid, and ethyl pyruvate hydrazones were unsuccessful. Also, cyclohexanone and methyl ethyl ketone 5-nitro-2-... 

Compounds having active methylene groups react with nitrous acid to form oximino derivatives. The attack on the a-methylene group of ketones is illustrated by the action of ethyl nitrite on methyl ethyl ketone, and by the action of methyl nitrite on propiophenone, to form biacetyl monoxime (60%) and isonitrosopropiophenone (68%), respectively. Methyl and ethyl nitrites are passed in gaseous form into the ketones in the presence of hydrochloric acid. In other preparations, n-butyl, amyl, or octyl nitrite in liquid form is employed. ... 

Henbest [68] has demonstrated a useful improvement in the yields of substitution products when the reactions are carried out in dipolar aprotic solvents The most effective solvents for this purpose are A -methylpyrrolidone (NMP) and A, iV-dimethylformamide (DMF) dimethylsulphoxide and methyl ethyl ketone are somewhat less effective. Under these conditions substitution by a variety of nucleophiles converted 3 -tosylates into 3a derivatives in yields generally exceeding 70%. Even the axial 3a-tosylates gave abnormally high conversions into 3 -substituted (equatorial) products, with effective suppression of the more usual elimination. 

On the other hand, methyl ethyl ketone, the primary material in the preparation of this war gas, is easily obtainable even in wartime, for it is a by-product in the manufacture of acetone from pyroligneous acid. The monobromo- derivative of methyl ethyl ketone has similar aggressive properties to bromoacetone and was used by both the French and the Germans in the war of 1914-18,... 

Iso-nitroso and Oxime Compounds.—This iso-nitroso derivative of the mono-ketone (methyl ethyl ketone) is also an oxime of the di-ketone (di-acetyl) as may be shown by the following relationships. 

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