Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes
| ISSN: |
0040-4020
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|---|---|
| Source: |
Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
|
| Topics: |
Chemistry and Pharmacology
|
| Type of Medium: |
Electronic Resource
|
| URL: |
| _version_ | 1798291329026883584 |
|---|---|
| autor | Goldsmith, D. Becher, D. Sample, S. Djerassi, C. |
| autorsonst | Goldsmith, D. Becher, D. Sample, S. Djerassi, C. |
| book_url | http://linkinghub.elsevier.com/retrieve/pii/S0040-4020(01)99103-3 |
| datenlieferant | nat_lic_papers |
| fussnote | Aliphatic aldoxime and ketoxime spectra are characterized by substantial McLafferty rearrangement peaks, the site specificity of the accompanying hydrogen rearrangements having been demonstrated by deuterium labeling. In contrast to dipropyl ketone, the McLafferty rearangement of its oxime is accompanied to a small extent by methyl migration. Another diagnostic, though less prevalent process of such oximes is fission of the γ-bond.Alicyclic ketoximes, such as cyclopentanone and cyclohexanone axime, yield more complex spectra with many hydrocarbon ions. A characteristic heteroatom fission is the loss of an oxygen atom from the molecular ion-a reaction which is not observed in aliphatic oximes but does occur in aromatic ones such as benzophenone oxime. The previously claimed occurrence of an electron impact-induced Beckmann rearrangement in benzophenone oxime could not be substantiated.In terms of fragmentation-directing ability, the oxime function does not surpass the carbonyl group as shown by the mass spectra of the oximes of 2-, 3- and 11-keto steroids. Through the aid of several deuterated analogs plausible structures and reaction paths could be presented for several characteristic ions. |
| hauptsatz | hsatz_simple |
| identnr | NLZ175815003 |
| issn | 0040-4020 |
| journal_name | Tetrahedron |
| materialart | 1 |
| package_name | Elsevier |
| publikationsort | Amsterdam |
| publisher | Elsevier |
| reference | 22 (1966), S. 145-173 |
| search_space | articles |
| shingle_author_1 | Goldsmith, D. Becher, D. Sample, S. Djerassi, C. |
| shingle_author_2 | Goldsmith, D. Becher, D. Sample, S. Djerassi, C. |
| shingle_author_3 | Goldsmith, D. Becher, D. Sample, S. Djerassi, C. |
| shingle_author_4 | Goldsmith, D. Becher, D. Sample, S. Djerassi, C. |
| shingle_catch_all_1 | Goldsmith, D. Becher, D. Sample, S. Djerassi, C. Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes 0040-4020 00404020 Elsevier |
| shingle_catch_all_2 | Goldsmith, D. Becher, D. Sample, S. Djerassi, C. Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes 0040-4020 00404020 Elsevier |
| shingle_catch_all_3 | Goldsmith, D. Becher, D. Sample, S. Djerassi, C. Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes 0040-4020 00404020 Elsevier |
| shingle_catch_all_4 | Goldsmith, D. Becher, D. Sample, S. Djerassi, C. Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes 0040-4020 00404020 Elsevier |
| shingle_title_1 | Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes |
| shingle_title_2 | Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes |
| shingle_title_3 | Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes |
| shingle_title_4 | Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes |
| sigel_instance_filter | dkfz geomar wilbert ipn albert fhp |
| source_archive | Elsevier Journal Backfiles on ScienceDirect 1907 - 2002 |
| timestamp | 2024-05-06T08:30:53.611Z |
| titel | Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes |
| titel_suche | Mass spectrometry in structural and stereochemical problems-XCVII - A study of the fragmentation processes of oximes Aliphatic aldoxime and ketoxime spectra are characterized by substantial McLafferty rearrangement peaks, the site specificity of the accompanying hydrogen rearrangements having been demonstrated by deuterium labeling. In contrast to dipropyl ketone, the McLafferty rearangement of its oxime is accompanied to a small extent by methyl migration. Another diagnostic, though less prevalent process of such oximes is fission of the γ-bond.Alicyclic ketoximes, such as cyclopentanone and cyclohexanone axime, yield more complex spectra with many hydrocarbon ions. A characteristic heteroatom fission is the loss of an oxygen atom from the molecular ion-a reaction which is not observed in aliphatic oximes but does occur in aromatic ones such as benzophenone oxime. The previously claimed occurrence of an electron impact-induced Beckmann rearrangement in benzophenone oxime could not be substantiated.In terms of fragmentation-directing ability, the oxime function does not surpass the carbonyl group as shown by the mass spectra of the oximes of 2-, 3- and 11-keto steroids. Through the aid of several deuterated analogs plausible structures and reaction paths could be presented for several characteristic ions. |
| topic | V |
| uid | nat_lic_papers_NLZ175815003 |