Mass spectroscopy Esters

Using on-line mass spectroscopy [65] carbon dioxide and formic acid were demonstrated as soluble products of methanol oxidation. The former gives the most intense MS signal according to the fact that it is the main product. There are two main problems to detect formic acid as such. In the presence of carbon dioxide most of the m/e signals of HCOOH overlap with signals of the major product. Besides this, in the presence of methanol, formic acid reacts to form the methyl ester ... 

Results and data gathered on mass spectroscopy of various indole alkaloids have been summarized by Hesse (320). The derivation of the characteristic fragments of indolo[2,3-a]quinolizidines has been interpreted by Gribble and Nelson (321), who investigated C-3, C-5, C-6, C-20, and C-21 deuterated derivatives of octahydroindolo[2,3-a]quinolizine (1). Kametani et al. have observed and proved, with labeled compounds, a methyl transfer from the ester function of reserpine derivatives to the basic nitrogen atom during mass-spectroscopic measurement (322). 

Although the metabolism of several phthalate esters has been studied in vitro, essentially all of the in vivo studies have involved DEHP. A summary of these experiments which involved exposure offish to aqueous - C-DEHP is presented in Table IV (11,12). Tissue C was isolated and separated into parent and the various metabolites by preparative thin layer chromatography on silica gel. Metabolites were hydrolyzed where appropriate and identified by gas chromatography-mass spectroscopy. In whole catfish, whole fathead minnow and trout muscle, the major metabolite was the monoester while in trout bile the major metabolite was the monoester glucuronide. The fact that in all cases the major metabolite was monoester or monoester glucuronide despite the differences in species, exposure level and duration, etc. represented by these data, suggests that hydrolysis of DEHP to monoester is important in the biotransformation of DEHP by fish. 

This method suffered from sensitivity problems initially as the bile-acid molecules lack a chromophore, but did offer the distinct advantage that conjugated bile acids could be determined without hydrolysis. The sensitivity issue was addressed by use of fluorescent derivatives such as dimethoxycoumarin esters with a C18 reverse phase column and were able to resolve endogenous mixtures of bile acids. The combination of hplc and mass-spectroscopy detection has further improved the sensitivity along with providing specific identification, important as the resolution of bile acids by hplc is not as good as capillary column glc. ... 

As already mentioned, it is the volatile constituents that serve to identify fruit type and variety. Broadly speaking, qualitative analysis will identify the principal substances present in the volatiles fraction as representative of a particular fruit type, but it is the relative proportions of these substances that will reflect the variety. Alcohols, volatile acids, esters, carbonyl compounds, and low-boiling hydrocarbons are the principal groups represented. Analysis by GC-MS (gas chromatography coupled with mass spectroscopy) can be used to provide quantification and identification of the various constituents. 

To a suspension of the ester (1) (0.120 g, 0.329 mmol) in 75% aqueous methanol (2 mL) was added potassium hydroxide (0.055 g). The reaction mixture was stirred at 60°C for 1 h during which time the material dissolved. The solution was cooled to room temperature, acidified with 1 N aqueous hydrochloric acid, and then extracted with 80% ethyl acetate/hexane. The combined organic layers were dried over anhydrous MgS04, filtered and concentrated to afford a white solid (0.109 g). Recrystallization from benzene/hexane afforded (2) as a white, crystalline solid (0.102 g, 89%) m.p. 209°-212°C. The structure of the product was also confirmed using IR, iH NMR and mass spectroscopy. 

To a suspension of methyltriphenylphosphonium bromide (0.196 g, 0.55 mmol) in 1 mL of benzene under argon at room temperature was added a 0.5 M solution of potassium hexamethyldisilazide in toluene (1.2 mL, 0.6 mmol), and the yellow solution was stirred for 5 min. A solution of keto-ester (1) (0.1 g, 0.274 mmol) in 1.5 mL of benzene was added and the orange solution was stirred for 3 h at room temperature. The reaction mixture was filtered through a plug of silica gel with 40% ethyl acetate/hexane. The filtrate was concentrated to afford a solid. Flash chromatography (30% 40% dichloromethane/hexane) yielded the desired product (3) as a white solid (0.077 g, 78%) m.p. 167°-168°C Rf 0.4 (50% dichloromethane/hexane). The structure of the product was also confirmed using IR, iH NMR and mass spectroscopy. 

Non-hemiterpenoid Quinolines.—New sources of the simple quinolines 4-methoxy-l-methyl-2-quinolone and its 8-methoxy-derivative (folimine) have been reported the former was isolated from Myrtopsis sellingii9 and from Zanthoxylum cuspidatum,16 and folimine was shown to be a constituent of Haplophyllum perforatum.5 The latter species also contains foliosidine (9), previously isolated from H. foliosum. The micro-organism Pseudomonas aertiginosa has been shown to contain 2-(hept-l-enyl)-4-quinolone (12).10 The structure of the alkaloid was established by n.m.r. and mass spectroscopy and by its synthesis from aniline and the j3-keto-ester Me(CH2)4CH=CHC0CH2C02Me. 

Highly purified esters were obtained by preparahve HPLC [5, 17]. The chemical structure of the purified monoesters was determined by and H nuclear magnetic resonance (NMR) and their molecular masses were determined by a mass spectroscopy (MS) technique as reported elsewhere [5, 17]. 

The mass spectroscopy signal of ethyl acetate ester mainly appears during the negative going scan and is delayed compared to the ethanol oxidation Faradic current (Fig. 37a). This delay was explained as an experimental artefact, namely slow ester permeation through the Teflon membrane which establishes the interface between the electrochemical setup and the mass spectrometer due to the large size of ester molecule. 

Maleic acid, 338 Maionic ester, 380 Markovnikoff s rule, 96 Mass spectroscopy, 247/T Mechanism, alcohol dehydration, 92 alkane halogenation, 56 benzyne, 217 El and E2, UOff SnI and Sn2, 122 ... 

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