Carbonyl compounds derivatization

In connection with the problem of carbonyl compounds derivatization, it is expedient to touch upon a question of the application of new proposed reagents which are not yet widely used in GC analytical practice, but seem like promising ones in accordance with different criteria. One of them is low-boiling trimethyl-trifluoromethyl silane (CH3)3SiCF3 which converts the carbonyl groups into a-trifluoromethyl O-TMS carbinol fragments ... 

The identification and quantification of potentially cytotoxic carbonyl compounds (e.g. aldehydes such as pentanal, hexanal, traw-2-octenal and 4-hydroxy-/mAW-2-nonenal, and ketones such as propan- and hexan-2-ones) also serves as a useful marker of the oxidative deterioration of PUFAs in isolated biological samples and chemical model systems. One method developed utilizes HPLC coupled with spectrophotometric detection and involves precolumn derivatization of peroxidized PUFA-derived aldehydes and alternative carbonyl compounds with 2,4-DNPH followed by separation of the resulting chromophoric 2,4-dinitrophenylhydrazones on a reversed-phase column and spectrophotometric detection at a wavelength of378 nm. This method has a relatively high level of sensitivity, and has been successfully applied to the analysis of such products in rat hepatocytes and rat liver microsomal suspensions stimulated with carbon tetrachloride or ADP-iron complexes (Poli etui., 1985). 

A one pot formation and purification of a 5-arylidine 4-thiazolidinone library has also been reported using polymer scavenging as the principle method of purification. An automated synthesizer was employed to make a parallel array of 4080 4-thiazolidinones, prepared simultaneously from a 3-component condensation of mercaptoacetic acid with an amine and a carbonyl compound. Further structural decoration was then introduced using the libraries from libraries principle where the core template was derivatized via an aldol reaction with a second carbonyl unit at the 5-methylene position (Scheme 2.57) [84]. After both synthetic steps. 

Determination of Carbonyl Compounds in Drinking Water by DNPH Derivatization and HPLC... 

Chemicals. The carbonyl compound standards 2-methylpropanal, 2-methylbutanal, 3-methylbutanal, pentanal, hexanal, furfural, methional, phenylacetaldehyde, and (E)-2-nonenal were purchased from Sigma-Aldrich (Milwaukee, Wl). A stock solution containing a mixture of the standard compounds in ethanol was prepared daily in a concentration of 100 ppb each. An aqueous solution of the derivatization agent 0-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBOA) (Sigma-Aldrich, Milwaukee, WI) was prepared at a concentration of 6 g/L. PFBOA solution was prepared every 3 months and kept refrigerated. 

A simple way to increase the selectivity of extraction techniques is to derivatize the carbonyl compounds. 

HPLC methods with fluorescence detection have also been developed for the determination of nitro-policyclic aromatic hydrocarbons (PAHs) (among which 9-nitroanthracene and 1-nitronaph-thalene) [238] in atmosphere. Samples have been collected in a standard high-volume sampler with a Teflon-coated glass fiber filter, and the Soxhlet extraction was performed with dichloromethane as the solvent. RP HPLC/UV techniques are used for the determination of aldehydes, ketones, and carbonylic compounds after derivatization with DNPH [239],... 

The final synthetic analogues we consider are the trioxolanes prepared by Vennerstrom and coworkers. These are prepared by a very efficient co-ozonolysis procedure from oxime 90 and a carbonyl compound 91 (Scheme 37A). This provides the 1,2,4-trioxolane in yields of greater than 50%. Further studies on 4-substituted cyclohexanones (e.g. 92) revealed that this reaction proceeds with very good cisitrans selectivity to produce the ester 93, which was derivatized to produce a clinical candidate OZ 277 (6) as shown. The chemistry for the synthesis of this compound has been scaled up beyond 30 kg (Scheme 37B). 

In addition to the spectroscopic methods, there are a number of derivatization methods, in which a derivative of the carbonyl compound that can be easily separated and measured is formed. The most common of these is the use of 2,4-dinitrophenylhydrazine (DNPH), which reacts to form the hydrazone ... 

Table 1. Chiral Imines by Derivatization of Carbonyl Compounds with Chiral Amines...

Ethanol and a long list of carbonyl compounds and aliphatic acids occur in fresh milk (Table 1.5). Some of them have been detected in only a few of the samples in which they were sought. Techniques for detecting such compounds include derivatization with 2,4-dinitrophe-nylhydrazine and various methods of volatilization, extraction, and chromatography (Harper and Huber 1956 Morr et al. 1957 Harper et al. 1961 Wong and Patton 1962 Scanlan et al. 1968 Marsili et al. 1981). The sum of the concentrations of acids listed in Table 1.5 is only 1-3 mmol/liter, compared to the citrate concentration of 10 mmol/liter. Oxalate has been reported to occur in milk (Zarembski and Hodgkin-son 1962) on the basis of a certain colorimetric reaction, but positive identification has not been made. 

Metallated polystyrenes are versatile intermediates for the preparation of a number of polystyrene derivatives. Metallated polystyrene has been prepared from haloge-nated polystyrenes by halogen-metal exchange [41,42,65,66] and by direct metallation of polystyrene [67-69] (see Chapter 4). Electrophiles suitable for the derivatization of metallated polystyrene include carbon dioxide, carbonyl compounds, sulfur, trimethyl borate, isocyanates, chlorosilanes, alkyl bromides, chlorodiphenylphosphine, DMF, oxirane, selenium [70], dimethyldiselenide [71], organotin halides [69], oxygen [72], etc. [41,42,65-67],... 

If the compounds are derivatized with DNPH and the derivatives are determined by GC or HPLC, the equivalent concentrations of the parent carbonyl compounds in the sample may be stoichiometrically determined as shown below in the following example. 

Useful in derivatizing carbonyl compounds and also provides a spot test for these compounds... 

Zwiener, C., T. Glauner, and F.H. Frimmel. 2002. Method optimization for the determination of carbonyl compounds in disinfected water by DNPH derivatization and LC-ESI-MS-MS. Anal. Bioanal. Chem. 372 615-621. 

Copper(II) polyamine complexes are substitutionally labile, in a manner similar to the corresponding nickel(II) complexes. This means that individual donor atoms may at times decoordinate and thus be available for derivatization reactions, e.g., with suitable carbonyl compounds. More complex ligands may thus be constructed, including macrocycles (35), polymacrocycles (36 38), and concave chelators (35). The copper(II) complex of 1 was synthesized as a starting material for reactions aiming at the derivatization of the pentaamine ligand (24-28). 

The term carbonyl derivatives covers here several types of organic compounds which, first, can be obtained by simple derivatization of carbonyl compounds 208 under conditions of isohypsic reactions126 and, second, possess an oxidation level of 2, equal to that for carbonyl compounds17. The sense of this generalization is the intention to... 

Many other electrophiles are able to react with metalated ferrocenylalkyl amines, e.g., trimethyl borate (Fig. 4-27 a), which gives, after hydrolytic workup, compounds like (S,S)-l-(iV,iV-dimethyl-l-aminoethyl)ferrocene-2-boronic acid [106]. Important intermediates for further derivatization are the halogens. For the lithiation technique, I2 (Fig. 4-27b) [151] and BrCN [106] lead to the desired compounds, but when BrCN is used, partial substitution of the dimethylamino group by cyanide occurs (see Sect. 4.3.3.2 and Fig. 4-17). For palladated amines, Brj is applicable [152]. (i ,S)-l-Iodo-2-(iV,iV-dimethyl-l-aminoethyl)ferrocene is the starting material for catalytically active zinc compounds for the enantioselective addition of zinc alkyls to carbonyl compounds [151] (see Chapter 3 for this topic). 

Spectra of LPO products with aldehydic or carbonylic groups are often not very characteristic. They sometimes become more typical after derivatization. Especially useful is derivatization with pentafluorobenzylhydroxylamine [274,275] the derivatives, pentafluorobenzyloximes, are easily recognized by intense peaks corresponding to the pentafluorobenzyl ion of mass 181. If the GC is registered instead by a flame ionization detector by measuring only the ion current of the peak of mass 181 all carbonyl containing compounds are detectable with high sensitivity even if the carbonyl compounds are present in trace amounts only [276]. 

The special type of carbonyl-group derivatization is aimed for gas chromatography-mass spectrometry (GC-MS) determination of double-bond C = C positions in the unsaturated long-chain acids. The analytical derivatives for the solution of this problem are nitrogen-containing heterocycles. These compounds can be synthesized by condensation of carboxylic acids with 2-amino-2-methyl-l-propanol (2-substituted 4,4-dimethyloxazolines), 2-aminophenol (2-substituted benzoxazoles), and so forth. 

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