Intramolecular Electrophilic Aromatic Substitution in Gas-phase Fragmentation of Protonated N-Benzylbenzaldimines
In this study, the gas-phase fragmentations of protonated N -benzylbenzaldimines were investigated by electrospray ionization tandem mass spectrometry (ESI-MS n ). Upon collisional activation, several characteristic fragment ions are produced and their fragmentation mechanisms are rationalized by el...
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| Veröffentlicht in: | Journal of the American Society for Mass Spectrometry 2014-09, Vol.25 (9), p.1662-1669 |
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| creator | Shen, Shanshan Chai, Yunfeng Weng, Guofeng Pan, Yuanjiang |
| description | In this study, the gas-phase fragmentations of protonated
N
-benzylbenzaldimines were investigated by electrospray ionization tandem mass spectrometry (ESI-MS
n
). Upon collisional activation, several characteristic fragment ions are produced and their fragmentation mechanisms are rationalized by electrophilic aromatic substitution accompanied by benzyl cation transfer. (1) For
N
-(
p
-methoxybenzylidene)-1-phenylmethanimine, concomitant with a loss of HCN, a product ion at
m
/
z
121 was observed. It is proposed to be generated from electrophilic substitution at the
ipso
-position by transferring benzyl cation rather than cleavage of the C-N double bond. (2) For
N
-(
m
-methoxybenzylidene)-1-phenylmethanimine, a product ion at
m
/
z
209 was obtained, corresponding to the elimination of NH
3
carrying two hydrogens from the two aromatic rings respectively. This process can be rationalized by two sequential electrophilic substitutions and cyclodeamination reaction based on the benzyl cation transfer. Deuterium-labeled experiments, density functional theory (DFT) calculation and substituent effect results also corroborate the proposed mechanism.
Figure a
ᅟ |
| doi_str_mv | 10.1007/s13361-014-0935-7 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1552368186</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1950881393</sourcerecordid><originalsourceid>FETCH-LOGICAL-c372t-551f89ebe18c97c00b77265d86a3196727683d72010ceccb07476655c065310d3</originalsourceid><addsrcrecordid>eNp1kU9LHTEUxUOxVGv9AN3IgBs3ae-dvPxbqqgVpC20XYdMJk8jM8kzySz00xv7tJRCN_ceOL97EjiEfET4hADyc0HGBFLAFQXNOJVvyB4qqSliz3aahlVzGPBd8r6UOwCUoOU7stuvNJcMYI_cX8Wa7Zwm75bJ5u68iZrT5jZMwXUnOc22NvFjGUoNdakhxS7E7tIWurm1xXcX2d7MPlb720rr7ntONUVb_dh9pac-Pj5MQ5t2GsMcoi8fyNu1nYo_eNn75NfF-c-zL_T62-XV2ck1dUz2lXKOa6X94FE5LR3AIGUv-KiEZaiF7KVQbJQ9IDjv3AByJYXg3IHgDGFk--R4m7vJ6X7xpZo5FOenyUaflmKQ854JhUo09Ogf9C4tObbfGdQclEKmWaNwS7mcSsl-bTY5zDY_GATz3IfZ9mFaH-a5DyPbzeFL8jLMfvxz8VpAA_otUJoVb3z-6-n_pj4B5fSVpA</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1950881393</pqid></control><display><type>article</type><title>Intramolecular Electrophilic Aromatic Substitution in Gas-phase Fragmentation of Protonated N-Benzylbenzaldimines</title><source>SpringerLink Journals - AutoHoldings</source><creator>Shen, Shanshan ; Chai, Yunfeng ; Weng, Guofeng ; Pan, Yuanjiang</creator><creatorcontrib>Shen, Shanshan ; Chai, Yunfeng ; Weng, Guofeng ; Pan, Yuanjiang</creatorcontrib><description>In this study, the gas-phase fragmentations of protonated
N
-benzylbenzaldimines were investigated by electrospray ionization tandem mass spectrometry (ESI-MS
n
). Upon collisional activation, several characteristic fragment ions are produced and their fragmentation mechanisms are rationalized by electrophilic aromatic substitution accompanied by benzyl cation transfer. (1) For
N
-(
p
-methoxybenzylidene)-1-phenylmethanimine, concomitant with a loss of HCN, a product ion at
m
/
z
121 was observed. It is proposed to be generated from electrophilic substitution at the
ipso
-position by transferring benzyl cation rather than cleavage of the C-N double bond. (2) For
N
-(
m
-methoxybenzylidene)-1-phenylmethanimine, a product ion at
m
/
z
209 was obtained, corresponding to the elimination of NH
3
carrying two hydrogens from the two aromatic rings respectively. This process can be rationalized by two sequential electrophilic substitutions and cyclodeamination reaction based on the benzyl cation transfer. Deuterium-labeled experiments, density functional theory (DFT) calculation and substituent effect results also corroborate the proposed mechanism.
Figure a
ᅟ</description><identifier>ISSN: 1044-0305</identifier><identifier>EISSN: 1879-1123</identifier><identifier>DOI: 10.1007/s13361-014-0935-7</identifier><identifier>PMID: 24957300</identifier><language>eng</language><publisher>Boston: Springer US</publisher><subject>Analytical Chemistry ; Aromatic compounds ; Bioinformatics ; Biotechnology ; Cations ; Chemistry ; Chemistry and Materials Science ; Density functional theory ; Deuterium ; Fragmentation ; Ionization ; Ions ; Mass spectrometry ; Organic Chemistry ; Proteomics ; Research Article</subject><ispartof>Journal of the American Society for Mass Spectrometry, 2014-09, Vol.25 (9), p.1662-1669</ispartof><rights>American Society for Mass Spectrometry 2014</rights><rights>Journal of The American Society for Mass Spectrometry is a copyright of Springer, 2014.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c372t-551f89ebe18c97c00b77265d86a3196727683d72010ceccb07476655c065310d3</citedby><cites>FETCH-LOGICAL-c372t-551f89ebe18c97c00b77265d86a3196727683d72010ceccb07476655c065310d3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1007/s13361-014-0935-7$$EPDF$$P50$$Gspringer$$H</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1007/s13361-014-0935-7$$EHTML$$P50$$Gspringer$$H</linktohtml><link.rule.ids>314,776,780,27903,27904,41467,42536,51297</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/24957300$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Shen, Shanshan</creatorcontrib><creatorcontrib>Chai, Yunfeng</creatorcontrib><creatorcontrib>Weng, Guofeng</creatorcontrib><creatorcontrib>Pan, Yuanjiang</creatorcontrib><title>Intramolecular Electrophilic Aromatic Substitution in Gas-phase Fragmentation of Protonated N-Benzylbenzaldimines</title><title>Journal of the American Society for Mass Spectrometry</title><addtitle>J. Am. Soc. Mass Spectrom</addtitle><addtitle>J Am Soc Mass Spectrom</addtitle><description>In this study, the gas-phase fragmentations of protonated
N
-benzylbenzaldimines were investigated by electrospray ionization tandem mass spectrometry (ESI-MS
n
). Upon collisional activation, several characteristic fragment ions are produced and their fragmentation mechanisms are rationalized by electrophilic aromatic substitution accompanied by benzyl cation transfer. (1) For
N
-(
p
-methoxybenzylidene)-1-phenylmethanimine, concomitant with a loss of HCN, a product ion at
m
/
z
121 was observed. It is proposed to be generated from electrophilic substitution at the
ipso
-position by transferring benzyl cation rather than cleavage of the C-N double bond. (2) For
N
-(
m
-methoxybenzylidene)-1-phenylmethanimine, a product ion at
m
/
z
209 was obtained, corresponding to the elimination of NH
3
carrying two hydrogens from the two aromatic rings respectively. This process can be rationalized by two sequential electrophilic substitutions and cyclodeamination reaction based on the benzyl cation transfer. Deuterium-labeled experiments, density functional theory (DFT) calculation and substituent effect results also corroborate the proposed mechanism.
Figure a
ᅟ</description><subject>Analytical Chemistry</subject><subject>Aromatic compounds</subject><subject>Bioinformatics</subject><subject>Biotechnology</subject><subject>Cations</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Density functional theory</subject><subject>Deuterium</subject><subject>Fragmentation</subject><subject>Ionization</subject><subject>Ions</subject><subject>Mass spectrometry</subject><subject>Organic Chemistry</subject><subject>Proteomics</subject><subject>Research Article</subject><issn>1044-0305</issn><issn>1879-1123</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><sourceid>8G5</sourceid><sourceid>BENPR</sourceid><sourceid>GUQSH</sourceid><sourceid>M2O</sourceid><recordid>eNp1kU9LHTEUxUOxVGv9AN3IgBs3ae-dvPxbqqgVpC20XYdMJk8jM8kzySz00xv7tJRCN_ceOL97EjiEfET4hADyc0HGBFLAFQXNOJVvyB4qqSliz3aahlVzGPBd8r6UOwCUoOU7stuvNJcMYI_cX8Wa7Zwm75bJ5u68iZrT5jZMwXUnOc22NvFjGUoNdakhxS7E7tIWurm1xXcX2d7MPlb720rr7ntONUVb_dh9pac-Pj5MQ5t2GsMcoi8fyNu1nYo_eNn75NfF-c-zL_T62-XV2ck1dUz2lXKOa6X94FE5LR3AIGUv-KiEZaiF7KVQbJQ9IDjv3AByJYXg3IHgDGFk--R4m7vJ6X7xpZo5FOenyUaflmKQ854JhUo09Ogf9C4tObbfGdQclEKmWaNwS7mcSsl-bTY5zDY_GATz3IfZ9mFaH-a5DyPbzeFL8jLMfvxz8VpAA_otUJoVb3z-6-n_pj4B5fSVpA</recordid><startdate>20140901</startdate><enddate>20140901</enddate><creator>Shen, Shanshan</creator><creator>Chai, Yunfeng</creator><creator>Weng, Guofeng</creator><creator>Pan, Yuanjiang</creator><general>Springer US</general><general>Springer Nature B.V</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>3V.</scope><scope>7X7</scope><scope>7XB</scope><scope>88E</scope><scope>8FE</scope><scope>8FG</scope><scope>8FI</scope><scope>8FJ</scope><scope>8FK</scope><scope>8G5</scope><scope>ABUWG</scope><scope>AFKRA</scope><scope>ARAPS</scope><scope>AZQEC</scope><scope>BENPR</scope><scope>BGLVJ</scope><scope>CCPQU</scope><scope>DWQXO</scope><scope>FYUFA</scope><scope>GHDGH</scope><scope>GNUQQ</scope><scope>GUQSH</scope><scope>HCIFZ</scope><scope>K9.</scope><scope>M0S</scope><scope>M1P</scope><scope>M2O</scope><scope>MBDVC</scope><scope>P5Z</scope><scope>P62</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope><scope>PRINS</scope><scope>Q9U</scope><scope>7X8</scope></search><sort><creationdate>20140901</creationdate><title>Intramolecular Electrophilic Aromatic Substitution in Gas-phase Fragmentation of Protonated N-Benzylbenzaldimines</title><author>Shen, Shanshan ; Chai, Yunfeng ; Weng, Guofeng ; Pan, Yuanjiang</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c372t-551f89ebe18c97c00b77265d86a3196727683d72010ceccb07476655c065310d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>Analytical Chemistry</topic><topic>Aromatic compounds</topic><topic>Bioinformatics</topic><topic>Biotechnology</topic><topic>Cations</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Density functional theory</topic><topic>Deuterium</topic><topic>Fragmentation</topic><topic>Ionization</topic><topic>Ions</topic><topic>Mass spectrometry</topic><topic>Organic Chemistry</topic><topic>Proteomics</topic><topic>Research Article</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Shen, Shanshan</creatorcontrib><creatorcontrib>Chai, Yunfeng</creatorcontrib><creatorcontrib>Weng, Guofeng</creatorcontrib><creatorcontrib>Pan, Yuanjiang</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>ProQuest Central (Corporate)</collection><collection>Health & Medical Collection</collection><collection>ProQuest Central (purchase pre-March 2016)</collection><collection>Medical Database (Alumni Edition)</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>Hospital Premium Collection</collection><collection>Hospital Premium Collection (Alumni Edition)</collection><collection>ProQuest Central (Alumni) (purchase pre-March 2016)</collection><collection>Research Library (Alumni Edition)</collection><collection>ProQuest Central (Alumni Edition)</collection><collection>ProQuest Central UK/Ireland</collection><collection>Advanced Technologies & Aerospace Collection</collection><collection>ProQuest Central Essentials</collection><collection>ProQuest Central</collection><collection>Technology Collection</collection><collection>ProQuest One Community College</collection><collection>ProQuest Central Korea</collection><collection>Health Research Premium Collection</collection><collection>Health Research Premium Collection (Alumni)</collection><collection>ProQuest Central Student</collection><collection>Research Library Prep</collection><collection>SciTech Premium Collection</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>Health & Medical Collection (Alumni Edition)</collection><collection>Medical Database</collection><collection>Research Library</collection><collection>Research Library (Corporate)</collection><collection>Advanced Technologies & Aerospace Database</collection><collection>ProQuest Advanced Technologies & Aerospace Collection</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>ProQuest Central China</collection><collection>ProQuest Central Basic</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Society for Mass Spectrometry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Shen, Shanshan</au><au>Chai, Yunfeng</au><au>Weng, Guofeng</au><au>Pan, Yuanjiang</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Intramolecular Electrophilic Aromatic Substitution in Gas-phase Fragmentation of Protonated N-Benzylbenzaldimines</atitle><jtitle>Journal of the American Society for Mass Spectrometry</jtitle><stitle>J. Am. Soc. Mass Spectrom</stitle><addtitle>J Am Soc Mass Spectrom</addtitle><date>2014-09-01</date><risdate>2014</risdate><volume>25</volume><issue>9</issue><spage>1662</spage><epage>1669</epage><pages>1662-1669</pages><issn>1044-0305</issn><eissn>1879-1123</eissn><abstract>In this study, the gas-phase fragmentations of protonated
N
-benzylbenzaldimines were investigated by electrospray ionization tandem mass spectrometry (ESI-MS
n
). Upon collisional activation, several characteristic fragment ions are produced and their fragmentation mechanisms are rationalized by electrophilic aromatic substitution accompanied by benzyl cation transfer. (1) For
N
-(
p
-methoxybenzylidene)-1-phenylmethanimine, concomitant with a loss of HCN, a product ion at
m
/
z
121 was observed. It is proposed to be generated from electrophilic substitution at the
ipso
-position by transferring benzyl cation rather than cleavage of the C-N double bond. (2) For
N
-(
m
-methoxybenzylidene)-1-phenylmethanimine, a product ion at
m
/
z
209 was obtained, corresponding to the elimination of NH
3
carrying two hydrogens from the two aromatic rings respectively. This process can be rationalized by two sequential electrophilic substitutions and cyclodeamination reaction based on the benzyl cation transfer. Deuterium-labeled experiments, density functional theory (DFT) calculation and substituent effect results also corroborate the proposed mechanism.
Figure a
ᅟ</abstract><cop>Boston</cop><pub>Springer US</pub><pmid>24957300</pmid><doi>10.1007/s13361-014-0935-7</doi><tpages>8</tpages></addata></record> |
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| subjects | Analytical Chemistry Aromatic compounds Bioinformatics Biotechnology Cations Chemistry Chemistry and Materials Science Density functional theory Deuterium Fragmentation Ionization Ions Mass spectrometry Organic Chemistry Proteomics Research Article |
| title | Intramolecular Electrophilic Aromatic Substitution in Gas-phase Fragmentation of Protonated N-Benzylbenzaldimines |
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