Ketones analysis

Analysis Start with the a,p-unsaturated relationship as the alternative (the 1,2-di O) is no good at the start. After the first disconnection we have a methyl ketone which can come from an acetylene ... 

Analysis This is a t-alk ketone so a pinacol rearrangement route will be possible ... 

Analysis Either way round will do, so let s arbitrarily chose ketone and a-halo ester ... 

Analysis Start with the only recognisably helpful relationship, the a,p-imsaturated ketone ... 

Both A and B are 1,5-dicarbonyl compounds, but only B can be discormected in the usual way. The result is two molecules of an a,p-unsaturated ketone and we can continue the analysis ... 

Analysis The most suitable discoimection follows the strategy we originally used (b, in frames 335, and 171-175). But can we make the right enamine fi om the unsaturated ketone, and does it alkylate in the right place It turns out that it can and does. 

Analysis continued I suggest to give 383A since one can then disconnect the a,p-unsaturated ketone and get a starting material with only one ring ... 

Analysis Another lactone FGl reveals the true TM (A). Our normal discormection a of an a,p-unsaturated carbonyl compound gives us the 1,5-dicarbonyl compound (B) and the ketone (C) clearly derived from phenol. Alternatively we could disconnect bond b to the keto-ester (D) with the further discormection shown ... 

The reaction product is cooled to room temperature, is washed with 10 ml of H2O to the purpose of removing lithium iodide and is then dehydrated over NaiS04. 3.57 g is obtained of dimethoxy-phenylacetone (III), as determined by gas-chromatographic analysis with an inner standard of 4,4 -dimethoxybeniophenone. The yield of ketone (III) relative to the olefin ( ) used as the starting material is of 87.1%. 

Alkenes are cleaved to carbonyl compounds by ozonolysis This reaction IS useful both for synthesis (preparation of aldehydes ketones or car boxyhc acids) and analysis When applied to analysis the carbonyl com pounds are isolated and identified allowing the substituents attached to the double bond to be deduced... 

FIGURE 14 2 Aretrosyn thetic analysis of alcohol preparation by way of the addition of a Grignard reagent to an aldehyde or ketone... 

This chapter is divided into two parts The first and major portion is devoted to carbohydrate structure You will see how the principles of stereochemistry and confer matronal analysis combine to aid our understanding of this complex subject The remain der of the chapter describes chemical reactions of carbohydrates Most of these reactions are simply extensions of what you have already learned concerning alcohols aldehydes ketones and acetals... 

Liquid-liquid extractions using ammonium pyrrolidine dithiocarbamate (APDC) as a metal chelating agent are commonly encountered in the analysis of metal ions in aqueous samples. The sample and APDC are mixed together, and the resulting metal-ligand complexes are extracted into methyl isobutyl ketone before analysis. 

The purity of a synthetic preparation of methylethyl ketone (C4H8O) can be determined by reacting the ketone with hydroxylamine hydrochloride, liberating HCl (see Table 9.10). In a typical analysis, a 3.00-mL sample was diluted to 50.00 ml and treated with an excess of hydroxylamine hydrochloride. The liberated HCl was titrated with 0.9989 M NaOH, requiring 32.68 ml to reach the end point. Report the percent purity of the sample, given that the density of methylethyl ketone is 0.805 g/mL. 

A sensitive method for the flow injection analysis of Cu + is based on its ability to catalyze the oxidation of di-2-pyridyl ketone hydrazone (DPKH) by atmospheric oxygen. The product of the reaction is fluorescent and can be used to generate a signal when using a fluorometer as a detector. The yield of the reaction is at a maximum when the solution is made basic with NaOH. The fluorescence, however, is greatest in the presence of HCl. Sketch an FIA manifold that will be appropriate for this analysis. 

Aldehydes, enals, dienals, ketones, and hydrocarbons, which are responsible for disagreeable odors, generally bok at lower temperatures than fatty acids. Analysis showkig a free fatty acid concentration of less than 0.05% is an kidication that deodorization is sufficientiy complete. Some of the dienals have very low odor thresholds and sensory evaluation of the finished ok is a judicious quaHty assurance step. 

Solvent extraction techniques are useful in the quantitative analysis of niobium. The fluoro complexes are amenable to extraction by a wide variety of ketones. Some of the water-insoluble complexes with organic precipitants are extractable by organic solvents and colorimetry is performed on the extract. An example is the extraction of the niobium—oxine complex with chloroform (41). The extraction of the niobium—pyrocatechol violet complex with tridodecylethylammonium bromide and the extraction of niobium—pyrocatechol—sparteine complex with chloroform are examples of extractions of water-soluble complexes. Colorimetry is performed on the extract (42,43). Colorimetry may also be performed directly on the water-soluble complex, eg, using ascorbic acid and 5-nitrosahcyhc acid (44,45). 

Since muscone (101), by itself, does not reproduce the total odor impression of this musk, IFF chemists (56) as early as 1971 in an analysis of tincture of Tonquin musk, reported a series of macrocycHc ketones (Table 16) which play a key role in creating the characteristic odor of this musk (11). The introduction of a double bond into a macrocycHc ketone (eg, 102) changes the odor from flowery musk to animal musk. 

Schmidt reaction of ketones, 7, 530 from thienylnitrenes, 4, 820 tautomers, 7, 492 thermal reactions, 7, 503 transition metal complexes reactivity, 7, 28 tungsten complexes, 7, 523 UV spectra, 7, 501 X-ray analysis, 7, 494 1 H-Azepines conformation, 7, 492 cycloaddition reactions, 7, 520, 522 dimerization, 7, 508 H NMR, 7, 495 isomerization, 7, 519 metal complexes, 7, 512 photoaddition reactions with oxygen, 7, 523 protonation, 7, 509 ring contractions, 7, 506 sigmatropic rearrangements, 7, 506 stability, 7, 492 N-substituted mass spectra, 7, 501 rearrangements, 7, 504 synthesis, 7, 536-537... 

Corrective Action Application Case 1 - Groundwater at the MEMOREX Computer Tape Plant (Santa Clara, California) was contaminated by a leaking underground solvent storage tank (Skladany et al., 1987). Chemical analysis of the groundwater identified the presence of methyl ethyl ketone (MEK) up to 500 ppm xylenes together with ethyl benzene up to 40 ppm cyclohexanone up to 30 ppm cyclohexanol up to 10 ppm acetone up to 10 ppm and toluene, tetrahydrofuran, 2-butanol, and methyl propyl ketone each less than 1 ppm. A biological... 

Residual aromatic ether concentrations are determined from the absorbance at 278 mfi of the crude reduction products in methanol solution. Steroidal ether concentrations of 1 mg/ml are employed. The content of 1,4-dihydro compound is determined, when possible, by hydrolysis to the a, -unsaturated ketone followed by ultraviolet analysis. A solution of the crude reaction product (usually 0.01 mg/ml cone) in methanol containing about 1/15 its volume of water and concentrated hydrochloric acid respectively is kept at room temperature for 2 to 4 hr. The absorbance at ca. 240 mfi is measured and, from this, the content of 1,4-dihydro compound can be calculated. Longer hydrolysis times do not increase the absorbance at 240 mp.. 

Reductive opening of the cyclopropyl ring in 9j5,19-cycloandrostan-ll-one (234) has been achieved by treatment with a large excess of sodium in iso-propanol-OD. Analysis of the product for isotopic purity after oxidation to the corresponding ketone and base-catalyzed back exchange of the 9a-deuterium [(235) (236)] shows 19% do and 10% 62 isotopic impurities. The 10% 62 product is probably due to incomplete back exchange. 

The optical rotatory dispersion curves of steroidal ketones permit a distinction to be made between the conformations, and assignment of configuration is possible without resorting to chemical methods (see, e.g. ref. 36) which are often tedious. The axial halo ketone rule and, in the more general form, the octant rule summarize this principle and have revealed examples inconsistent with the theory of invariable axial attack in ketone bromination. 2-Methyl-3-ketones have been subjected to a particularly detailed analysis. There are a considerable number of examples where the products isolated from kinetically controlled brominations have the equatorial orientation. These results have been interpreted in terms of direct equatorial attack rather than initial formation of the axial boat form. 

The NMR study of steroidal epoxides (discussed in section II-F) parallels that of the analogous thiiranes. It is possible to relate the location and configuration of the thiirane group with the angular methyl and thiirane proton resonances. The proton NMR relationships for the intermediate thiocyanatohydrins have been included inageneral NMR study of steroids. Electronic spectra may be used in the analysis of steroidal thiiranes. Spectroscopic measurements have shown the existence of a low intensity absorption in the 240-260 m region. The regular patterns of rotatory contributions of thiiranes which are comparable with those of ketones prompted an accumulation of ORD and CD data for steroidal thiiranes. 

Note 2. Under conditions described in Note 1 VPC analysis of the crude material indicated 90.2% of 6j6, 19-ether and only 6.5% of ketone. In this case direct crystallization from ether-hexane affords pure 6j6, 19-ether. 

TLC analysis of the crude reaction product reveals no additional products. Similarly quantitative results are obtained using benzene, /-butanol and ether as the solvents in the irradiation of (39). The reaction is less sensitive to oxygen than most ketone photolyses resulting in products from a-cleavage processes. 

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