A Novel [2 + 3] Cycloaddition Reaction:  Singlet Oxygen Mediated Formation of 1,3-Dipole from Iminodiacetic Acid Dimethyl Ester and Its Addition to Maleimides

Cheng, Humin; Gan, Liangbing; Shi, Yaru; Wei, Xianzhe

doi:10.1021/jo015749m

Cited by 25 publications

(11 citation statements)

References 31 publications

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“…Reaction of this active oxygen species with RF ground state can produce RF ·+ and the superoxide radical anion, as does the photoionization process (see above). There are sufficient examples in the literature on the reaction of singlet oxygen with aliphatic amines (as the piperazinyl ring of RF); the reported result is the generation of an amine radical cation and O 2 ·− (25–27). The subsequent step is the formation of an iminium ion, which may be hydrolyzed to dealkylated amines plus carbonyl compounds (28).…”

Section: Discussionmentioning

confidence: 99%

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Photoinduced N-Demethylation of Rufloxacin and its Methyl Ester Under Aerobic Conditions¶

Belvedere

Boscá

Cuquerella

et al. 2007

Photochemistry and Photobiology

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Irradiation of rufloxacin (RF) under aerobic conditions gives rise to N‐demethylation of the piperazinyl ring, which is enhanced in aerated D2O. Two primary processes seem to be involved in RF N‐demethylation: photoionization from 1RF and singlet oxygen generation from 3RF. Both processes may lead to the same key intermediates, namely, RF·+ and superoxide radical anion; coupling of these intermediates explains N‐demethylation of RF via an iminium cation. Formation of the hydrated electron by a monophotonic process (with a quantum yield of 0.09) is detected along with 3RF (with a intersystem‐crossing quantum yield φISC= 0.36) by laser flash photolysis. Studies performed on RF methyl ester give qualitatively similar results.

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Section: Discussionmentioning

confidence: 99%

“…•Ϫ (25)(26)(27). The subsequent step is the formation of an iminium ion, which may be hydrolyzed to dealkylated amines plus carbonyl compounds (28).…”

Section: Discussionmentioning

confidence: 99%

Photoinduced N-Demethylation of Rufloxacin and its Methyl Ester Under Aerobic Conditions¶

Belvedere

Boscá

Cuquerella

et al. 2007

Photochemistry and Photobiology

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“…In medical related sciences, iminodiacetic acid derivatives are used as solid phase supports for peptide synthesis [7] and as base for chemical libraries in combinatory chemistry [8]. Iminodiacetic acid is also of great importance in organic chemistry, namely on the synthesis of maleimides [9] and 3,4 di-substituted pyrroles [10] by Friedman method. Following the preparation of the manganese complex of -octaphenyl-porphyrin for our studies of metalloporphyrin-based oxidation of hydrocarbons [11], we synthesised several iminodiacetic derivatives as pyrrole precursors, amongst them, the title compound.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of iminodiacetic acid monomethyl ester monohydrate, C5H9NO4 · H2O

Silva¹,

Beja²,

Paixão³

et al. 2002

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialA mixture of iminodiacetic acid (16.8 g, 0.13 mol), thionyl chloride (30.9 g, 0.26 mol) and methanol (85 ml) was placed in a 250 ml round bottoned flask fitted with a reflux condenser and a silica guard tube. The mixture was stirred and heated under reflux for 4 hours. The solution was then washed with water/dichloromethane and the organic layer dried with anhydrous Na2SC>4, evaporated under reduced pressure and left to crystallise from dichloromethane/n-hexane. The (methoxycarbonylmethylamino)-acetic acid was obtained with 15% yield. Melting point: 411 Κ -413 Κ. Ft-IR (cm -1 ; group): (1643; C=0 ketone form), (3503; Ν-H). Experimental detailsThe structure was solved by direct methods. The hydrogen atoms of the main residue were placed at calculated positions and refined as riding using the SHELXL-97 defaults [1], The crystal structure contains one water molecule disordered over three positions, sum of the their freely refined occupancies is 1.00(3). The isotropic temperature factors of the three water O atoms were constrained to be equal, the water Η atoms could not be located. DiscussionIminodiacetic acid and its derivatives are important compounds in coordination chemistry. The presence of two close carboxylic groups makes this molecule and its derivatives excellent ion coordination agents. This property has been fully exploited in the preparation of modified polymers and resins for ion capture, both for analytical [2][3][4] or industrial uses [5,6]. In medical related sciences, iminodiacetic acid derivatives are used as solid phase supports for peptide synthesis [7] and as base for chemical libraries in combinatory chemistry [8]. Iminodiacetic acid is also of great importance in organic chemistry, namely on the synthesis of maleimides [9] and 3,4 di-substituted pyrroles [10] by Friedman method. Following the preparation of the manganese complex of -octaphenyl-porphyrin for our studies of metalloporphyrin-based oxidation of hydrocarbons [11], we synthesised several iminodiacetic derivatives as pyrrole precursors, amongst them, the title compound. The conformation of the zwitterion is close to that found in the second polymorph form of iminodiacetic acid, IMDA2 [12]. The C4 atom is gauche to C1 when the ion is viewed along Ν-C3 and with C3 trans to C2 when viewed along Ν-C1. The formal negative charge is spread over the carboxylate group 03-C4-04 (C-O distances are: d(C4-03) = 1.250(2) Â, d(C4-04) = 1.243(3) Â). The bond distances of the carboxylic acid group indicate one double bond (d(C2=02) = 1.196(3) Â) and one single bond (d(C2-Ol) = 1.326(3) Â). The substituted half of the iminodiacetic acid molecule is approximated planar with Cl, C2, 01,02, C5 lying in a plane (rms deviation from L.S. plane 0.02 À), the nitrogen atom is 0.186(3) Â away from that plane. The zwitterions are bonded together by hydrogen bonds forming layers.

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“…However, a photochemical reaction of tertiary amines with C 60 is possible and leads to complex mixtures of addition products [52][53][54][55][56][57][58][59][60][61][62]. Tertiary amines can not form similar addition products, rather an electron transfer under formation of zwitterions is often observed (Section 3.3).…”

Section: Addition Of Tertiary Aminesmentioning

confidence: 99%

“…For the formation of 15 (Figure 6.9) a different mechanism has been proposed [62]. Reaction of singlet oxygen with the corresponding amine (iminodiacetic methylester) leads -after two H-abstractions -to an azomethine ylide as a key intermediate.…”

Section: Scheme 69mentioning

confidence: 99%

Radical Additions

2004

Fullerenes

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A Novel [2 + 3] Cycloaddition Reaction: Singlet Oxygen Mediated Formation of 1,3-Dipole from Iminodiacetic Acid Dimethyl Ester and Its Addition to Maleimides

Cited by 25 publications

References 31 publications

Photoinduced N-Demethylation of Rufloxacin and its Methyl Ester Under Aerobic Conditions¶

Photoinduced N-Demethylation of Rufloxacin and its Methyl Ester Under Aerobic Conditions¶

Crystal structure of iminodiacetic acid monomethyl ester monohydrate, C5H9NO4 · H2O

Radical Additions

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