On the fragmentation of stereoisomeric substituted cyclohexylamines under electron impact. Comparison with corresponding alcohols and ethers

Weissdorf, Miriam; Sharvit, Joseph; Mandelbaum, A.

doi:10.1002/oms.1210130307

Org. Mass Spectrom.

1978

DOI: 10.1002/oms.1210130307

|View full text |Cite

On the fragmentation of stereoisomeric substituted cyclohexylamines under electron impact. Comparison with corresponding alcohols and ethers

Miriam Weissdorf

Joseph Sharvit

A. Mandelbaum

Abstract: The stereospecific elimination of H,O and CH,OH from substituted cyclohexanols and their methyl ethers upon electron impact is not reproduced in the corresponding amines. Ring cleavage (Y to the amino group is responsible for the non-stereospecific formation of the most abundant fragments in the amines.

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

1978

1986

Publication Types

Select...

Article5

Relationship

Self Cite1

Independent4

Authors

Journals

Cited by 8 publications

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Der massenspektrometrische Zerfall isomerer Diacetamido‐cyclo‐hexane, ihrer N‐Phenäthyl‐Derivate und Bis (acetamidomethyl)cyclohexane. 32. Mitteilung über massenspektrometrische Untersuchungen,,

Suess¹,

Hesse²

1979

Helvetica Chimica Acta

View full text Add to dashboard Cite

SummaryIn the mass spectra of the six isomeric diacetamidocyclohexanes 2-4 (cis and trans each, Scheme 2) as well as of the six isomeric bis (acetamidomethy1)cyclohexanes 6-8 (cis and trans each, Scheme 5 ) are clear differences between the constitutional isomers, whereas cis/truns isomers show very similar spectra. The lack of stereospecific fragmentations is explained by loss of configurational integrity of the molecular ion before fragmentation.However, the mass spectral fragmentation of epimeric diamidocyclohexanes becomes very stereospecific by the introduction of a phenethyl group on one of the nitrogen atoms: this group avoids epimerization of the molecular ion prior to fragmentation. In the N-phenethyl derivatives 10, 11, 13 and 14 (Scheme 8) the typical fragmentations of the cis-isomer after loss of C7H, from the molecular ion are the elimination of CH,CO by formation of cyclic ions, and the loss ofp-toluenesulfonic acid or benzoic acid, respectively, with subsequent elimination of CH,CN (Scheme 9). In the trans-isomer the typical fragmentations are the loss of the side chain bearing a tertiary nitrogen atom, and the elimination of the tosyl or benzoyl radical, respectively, with subsequent loss of CH,CONH2 (Scheme 10).Bisherige Untersuchungen iiber den massenspektrometrischen Zerfall von substituierten Cycloalkanen betrafen hauptstichlich Alkohole, f t h e r sowie Carbonsauren und deren Ester [2]. Aus diesen Arbeiten geht hervor, dass Fragmentierungen, die durch Umlagerung uber einen cyclischen Ubergangszustand entstehen, I)2, 3 I . Mitt. s. [ 11.

show abstract

Der massenspektrometrische Zerfall isomerer Diacetamido‐cyclo‐hexane, ihrer N‐Phenäthyl‐Derivate und Bis (acetamidomethyl)cyclohexane. 32. Mitteilung über massenspektrometrische Untersuchungen,,

Suess¹,

Hesse²

1979

Helvetica Chimica Acta

View full text Add to dashboard Cite

show abstract

Stereochemical effects in mass spectrometry

Mandelbaum

1983

Mass Spectrometry Reviews

Self Cite

View full text Add to dashboard Cite

Competing ring cleavages in substituted 4‐arylcyclohexanols and their methyl ethers under electron impact

Sharvit

Mandelbaum

1978

Org. Mass Spectrom.

View full text Add to dashboard Cite

In previous publications we discussed the stereospecificity of elimination of H20, CH30H, CH,COOH and RNH, from 4-and 3-arylcyclohexyl alcohols,' methyl ethers,, acetates3 and amines4 respectively, under electron impact. A high degree of stereospecificity was observed in the case of the alcohols, ethers and acetates, but the elimination of RNH, from the corresponding amines is a non-stereospecific process leading to low abundance ions. The different behaviour of the arylcyclohexyl amines was ascribed to the facile ring cleavage a to the amino group which apparently precedes the major fragmentation processes in this group of compound^.^ Ring cleavage a to the oxygen function also precedes the elimination of CH30H from the molecular ions of cis-arylcyclohexyl methyl ethers: but not the dehydration of the cis-and trans -alcohols.Further inspection of the mass spectra of 4-arylcyclohexanols (1) and their methyl ethers (2) revealed interesting fragmentation processes which are governed by the cleavage of the cyclohexane ring at the two positions, a to the oxygen function and a to the aryl group (benzylic position). and e is presented in Scheme 1 ('benzyl' branch). It is suggested that this process is initiated by the cleavage of the cyclohexane ring at the benzylic position, in

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

On the fragmentation of stereoisomeric substituted cyclohexylamines under electron impact. Comparison with corresponding alcohols and ethers

Cited by 8 publications

References 10 publications

Der massenspektrometrische Zerfall isomerer Diacetamido‐cyclo‐hexane, ihrer N‐Phenäthyl‐Derivate und Bis (acetamidomethyl)cyclohexane. 32. Mitteilung über massenspektrometrische Untersuchungen,,

Der massenspektrometrische Zerfall isomerer Diacetamido‐cyclo‐hexane, ihrer N‐Phenäthyl‐Derivate und Bis (acetamidomethyl)cyclohexane. 32. Mitteilung über massenspektrometrische Untersuchungen,,

Stereochemical effects in mass spectrometry

Competing ring cleavages in substituted 4‐arylcyclohexanols and their methyl ethers under electron impact

Contact Info

Product

Resources

About