Mass spectral determination of aldehydes, ketones, and carboxylic acids using 1,1-dimethylhydrazine

McDaniel, C. A.; Howard, Ralph W.

doi:10.1007/bf01411416

Cited by 25 publications

(6 citation statements)

References 6 publications

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“…3): a molecular ion at m/z 267, an ion at m/z 252 due to a methyl group loss from the molecular ion, and a base peak at m/z 224 (resulting from loss of C3H7 or CH3CO from the parent ion). The molecular formula of epilachnene was That this compound is not an aldehyde or a ketone is confirmed chemically by the absence of any reaction with N,N-dimethylhydrazine (9,10). Finally, the IR spectrum of epilachnene shows a weak but significant olefinic C-H absorption at 3011 cm-'.…”

Section: Methodsmentioning

confidence: 91%

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Azamacrolides: a family of alkaloids from the pupal defensive secretion of a ladybird beetle (Epilachna varivestis).

Attygalle

McCormick

Blankespoor

et al. 1993

Proc. Natl. Acad. Sci. U.S.A.

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Defensive droplets from glandular hairs of the pupa of the Mexican bean beetle, Epilachna varivestis, contain a group of structurally novel alkaloids, the azamacrolides. The major constituent of this secretion, epilachnene, is shown to be (5Z)-11-propyl-12-azacyclotetradec-5-en-14-olide. The secretion also contains an epilachnadiene and trace amounts of three closely related components. (Fig. 1). Suspecting this fluid to be defensive, we exposed pupae to ant attacks in a series of laboratory presentations. The pupae were individually placed on the bottom of small Petri dishes that served as the foraging arenas for laboratory colonies of the ants (Leptothorax longispinosus). The results, which were videotaped, were consistent and dramatic. The moment an individual ant, in an exploratory approach to the pupa, contacted some of the glandular hairs, it backed away and cleansed itself. While retreating, it repeatedly dragged its mouthparts and/or antennae against the substrate. None of the pupae (n = 10; each in a different arena) were injured during the 10-min presentations, although each was contacted by dozens of ants during this period (all pupae eventually gave rise to adults). We proceeded to collect the secretory droplets for analysis and here report on the chemicals isolated from the fluid (5). MATERIALS AND METHODSSample Collection. Secretion from the glandular hairs, collected with microcapillaries, was sealed directly in glass tubes (1.8 x 20 mm) or extracted with ether or dichloromethane (100 ul). For NMR spectroscopy, a sample (500 pupae) was taken up in 400 ul of C2HC13 (2H, 99.96%).Analytical Procedures. Samples were analyzed by gas chromatography (GC) on a Hewlett-Packard (HP) 5890 instruThe publication costs of this article were defrayed in part by page charge payment. This article must therefore be hereby marked "advertisement" in accordance with 18 U.S.C. §1734 solely to indicate this fact. ment equipped with a split/splitless injector, a flame ionization detector, and an HP 3396A integrator. Undiluted samples in glass capillaries were injected by a solid sampling technique (6, 7); solutions were introduced by splitless injection. Low-resolution mass spectrometry (MS) was carried out with an HP 5890 gas chromatograph linked to a Finnigan ion-trap detector (ITD 800) or an HP mass selective detector. Chemical ionization mass spectra were obtained on the ITD with methane as the reagent gas. High-resolution mass spectra were obtained on a Kratos 890 instrument. Gas-phase IR spectra were obtained with an HP 5890 gas chromatograph linked to an HP 5965A IR detector. Unless otherwise noted, 1H and 13C NMR spectra were obtained in C2HC13 on a Varian XL-400 instrument.Derivatization Techniques. (i) Microhydrogenation. A small sample of secretion in ether (50 ,ul) was placed in a glass vial and =0.5 mg of 10%o Pd on activated charcoal was added. A balloon filled with hydrogen was attached to the vial. After 10 hr, 25 ul of ether was added and the supernatant was withdrawn and examined by GC/MS.(ii) A...

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Section: Methodsmentioning

confidence: 91%

“…To an aliquot ofthe defensive secretion in ether (10 p1I), an ethereal solution of N,N-dimethylhydrazine (50%; 10 ,ul) was added (9,10). After 3 hr, the reaction mixture was examined by GC/MS.…”

Section: Methodsmentioning

confidence: 99%

Azamacrolides: a family of alkaloids from the pupal defensive secretion of a ladybird beetle (Epilachna varivestis).

Attygalle

McCormick

Blankespoor

et al. 1993

Proc. Natl. Acad. Sci. U.S.A.

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“…In addition to hydrazine itself, unsymmetrical dimethylhydrazine (UDMH) is also frequently used [10][11][12]. In modern analytical chemistry hydrazine and its derivatives are important reducers and reagents [13,14] for the deter mination of carbonyl compounds and carbonic acids.…”

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confidence: 99%

Spectrophotometric and fluorometric methods for the determination of hydrazine and its methylated analogues

2012

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“…The m/z 291 ion results from loss of N(CH 3 ) 2 from the molecular ion. 22,23 High-resolution mass spectral data of 1 established the molecular composition of the m/z 156 ion as C 9 H 20 N 2 (calcd for C 9 H 20 N 2 156.1626; found 156.1629).…”

Section: Resultsmentioning

confidence: 99%

Cycloalkene budding: mass spectrometric studies of competitive and dual cycloalkene extrusion reactions from doubly unsaturated aldehydeN,N-dimethylhydrazones

Weibel

Attygalle

Shevy

et al. 2000

Rapid Commun. Mass Spectrom.

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Mass spectral determination of aldehydes, ketones, and carboxylic acids using 1,1-dimethylhydrazine

Cited by 25 publications

References 6 publications

Azamacrolides: a family of alkaloids from the pupal defensive secretion of a ladybird beetle (Epilachna varivestis).

Azamacrolides: a family of alkaloids from the pupal defensive secretion of a ladybird beetle (Epilachna varivestis).

Spectrophotometric and fluorometric methods for the determination of hydrazine and its methylated analogues

Cycloalkene budding: mass spectrometric studies of competitive and dual cycloalkene extrusion reactions from doubly unsaturated aldehydeN,N-dimethylhydrazones

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