Electron ionization-induced loss of SO2 from 2-nitrodiaryl sulfides

Lambert, P.; Bertin, Sophie; Lacoste, Jean‐Eric; Volland, Jean‐Paul; Krick, A.; Furet, Éric; Botrel, Alain; Guénot, Pierre

doi:10.1002/(sici)1096-9888(199803)33:3<242::aid-jms627>3.0.co;2-g

Cited by 6 publications

(6 citation statements)

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“…gas phase rearrangement is probably an ipso process, 19 and gas-phase Smiles processes have been proposed for 2-hydroxybenzyl-N-pyrimidinylamine, 20 phenoxy-N-phenyl acetamide anions, 21 deprotonated 2-(4,6-dimethoxypyrimidine-2ylsulfanyl)-N-phenylbenzamide 22 and other systems. [23][24][25][26] (3) When we first reported the gas phase Smiles rearrangement, as in eqn (1), the conclusions of the experimental study were based primarily on heavy atom labelling data. We did not then have access to supercomputers capable of handling high-level calculations of molecules containing phenyl rings.…”

Section: Introductionmentioning

confidence: 99%

The gas phase Smiles rearrangement of anions PhO(CH2)nO− (n = 2–4). A joint theoretical and experimental approach

2010

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A combination of experimental data [using (18)O labelling fragmentation data together with metastable ion studies in a reverse sector mass spectrometer (from a previous study)] and ab initio reaction coordinate studies at the CCSD(T)/6-31++G(d,p)//B3LYP/6-31++G(d,p) level of theory, have provided the following data concerning the formation of PhO(-) in the gas-phase from energized systems PhO(CH(2))(n)O(-) (n = 2-4). All DeltaG values were calculated at 298 K. (1) PhO(CH(2))(2)O(-) effects an ipso Smiles rearrangement (DeltaG(r) = +35 kJ mol(-1); barrier to transition state DeltaG(#) = +40 kJ mol(-1)) equilibrating the two oxygen atoms. The Smiles intermediate reverts to PhO(CH(2))(2)O(-) which then undergoes an S(N)i reaction to form PhO(-) and ethylene oxide (DeltaG(r) = -24 kJ mol(-1); DeltaG(#) = +54 kJ mol(-1)). (2) The formation of PhO(-) from energized PhO(CH(2))(3)O(-) is more complex. Some 85% of the PhO(-) formed originates via a Smiles intermediate (DeltaG(r) = +52 kJ mol(-1); DeltaG(#) = +61 kJ mol(-1)). This species reconverts to PhO(CH(2))(3)O(-) which then fragments to PhO(-) by two competing processes, namely, (a) an S(N)i process yielding PhO(-) and trimethylene oxide (DeltaG(r) = -27 kJ mol(-1); DeltaG(#) = +69 kJ mol(-1)), and (b) a dissociation process giving PhO(-), ethylene and formaldehyde (DeltaG(r) = -65 kJ mol(-1); DeltaG(#) = +69 kJ mol(-1)). The other fifteen percent of PhO(-) is formed prior to formation of the Smiles intermediate, occurring directly by the S(N)i and dissociation processes outlined above. The operation of two fragmentation pathways is supported by the presence of a composite metastable ion peak. (3) Energized PhO(CH(2))(4)O(-) fragments exclusively by an S(N)i process to form PhO(-) and tetrahydrofuran (DeltaG(r) = -101 kJ mol(-1); DeltaG(#) = +53 kJ mol(-1)). The Smiles ipso cyclization (DeltaG(r) = +64 kJ mol(-1); DeltaG(#) = +74 kJ mol(-1)) is not detected in this system.

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Section: Introductionmentioning

confidence: 99%

The gas phase Smiles rearrangement of anions PhO(CH2)nO− (n = 2–4). A joint theoretical and experimental approach

2010

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“…13 C NMR (62 MHz, CDCl 3 ): δ ) 15.5 (d, 3 J CF ) 29 Hz, CH 3 ), 35.5 (CH 2 ), 50.5 (NCH 2 ), 55.7 (OCH 3 ), 55.9 (OCH 3 ), 94.8 (d, 2 J CF ) 32 Hz, 7-C), 111.7 (C-Ar′), 112.0 (C-Ar′), 120.2 (4-C), 120.9 (C-Ar′), 125.5 (d, 2 J CF ) 24 Hz, 5-C q ), 129.4 (1′-C q ), 133.5 (d, 3 J CF ) 8 Hz, 7a-NC q ), 148.2 (C q -Ar′), 149.1 (C q -Ar′), 161.6 (d, 1 J CF ) 254 Hz, 6-C q ) ppm. 19 1-(4′-Trifluormethylbenzene)-1H-benzotriazole (18x). Cleavage from 13a as described in the General Procedures 6a section.…”

Section: -(2′4′-dimethyl-phenethyl)-1h-benzotriazole (18k)mentioning

confidence: 99%

Hartwig–Buchwald Amination on Solid Supports: a Novel Access to a Diverse Set of 1H-Benzotriazoles

Zimmermann

Bräse

2007

J. Comb. Chem.

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Hartwig-Buchwald amination reactions of bromo- and chloroarenes were performed on solid supports with triazene-linked arenes. Immobilized 2-haloarenes were treated with diverse primary amines and anilines at 100 degrees C under palladium catalysis to yield N-substituted 2-aminoarenes. The latter were alternatively formed through reaction of bromo- and chloroarenes with immobilized primary 2-aminobenzenes. Subsequent acidic cleavage furnished 1H-benzotriazoles in high purities. The two described routes allow a broad range of the substitution pattern of N-substituted 1H-benzotriazoles.

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“…Turecek and coworkers used tandem mass spectrometry in combination with density functional theory to study an oxygen-transfer, gas-phase reaction giving the elimination of H 2 CO 3 from an ionized copper complex of nitro tyrosine [3]. The electron-ionization (EI) induced oxygen transfer from a nitro group leading to intramolecular oxidation of sulfur, alkyl or alkenyl groups in aromatic nitro compounds is well established [6,7]. The intramolecular oxidation involves either the transfer of oxygen atoms from the nitro group to the heteroatom or side chain [6] within the radical cation or the abstraction of hydrogen atoms from the side chain to the nitro group.…”

Section: Introductionmentioning

confidence: 99%

“…The intramolecular oxidation involves either the transfer of oxygen atoms from the nitro group to the heteroatom or side chain [6] within the radical cation or the abstraction of hydrogen atoms from the side chain to the nitro group. The process leads to the elimination of small molecules via a process termed an ortho effect [7]. Such rearrangements are not common for protonated molecules (closed-shell ions) generated by electrospray ionization (ESI) and activated in low-energy collisions, probably owing to the absence of a radical site.…”

Section: Introductionmentioning

confidence: 99%

Protonated N -alkyl-2-nitroanilines undergo intramolecular oxidation of the alkyl chain upon collisional activation

Paulose

Cyriac

George

et al. 2017

International Journal of Mass Spectrometry

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The collisional activation of protonated N-propyl-2-nitroaniline obtained by electrospray ionization shows two major competitive dissociation pathways: the elimination of the elements of propionic acid, [M + H – C3H6O2]+ to give an m/z 107 ion, and of the elements of ethanol, [M + H – C2H6O]+ to give an m/z 135 ion. The mechanistic study reported here addresses these unusual fragmentations to reveal that both occur via a common intermediate formed by the transfer of an oxygen atom from the nitro group to the first carbon atom of the propyl group, allowing elimination of propionic acid and (H2O + ethene), respectively. The corresponding loss of CH4O does not occur when the propyl group is replaced by an ethyl group, but elimination of the elements of propanol does occur when propyl is replaced by a butyl group. Further, the product ions of m/z 107 and 135 are also formed when the propyl chain is replaced with a hexyl group.

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Electron ionization-induced loss of SO2 from 2-nitrodiaryl sulfides

Cited by 6 publications

References 4 publications

The gas phase Smiles rearrangement of anions PhO(CH2)nO− (n = 2–4). A joint theoretical and experimental approach

The gas phase Smiles rearrangement of anions PhO(CH2)nO− (n = 2–4). A joint theoretical and experimental approach

Hartwig–Buchwald Amination on Solid Supports: a Novel Access to a Diverse Set of 1H-Benzotriazoles

Protonated N -alkyl-2-nitroanilines undergo intramolecular oxidation of the alkyl chain upon collisional activation

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