An unexpected course of the Meisenheimer reaction : aryl phosphates in the reaction of phosphoryl chloride with 2, 3-diphenylquinoxaline-N1-oxide.

Nasielski, Jacques; Heilporn, Sylvie; Nasielski-Hinkens, R.; Geerts-Evrard, F.

doi:10.1016/s0040-4020(01)90308-4

Cited by 13 publications

(11 citation statements)

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“…Even if it is commonly accepted that the hydrolysis of BTI produces PhIO, this hydrolysis is generally carried out under alkaline conditions. 39 Disproportionation or hydrolysis of BTI leading to PhIO 2 was confirmed by high-resolution mass spectrometry, infrared spectroscopy, and 1 H and 13 C NMR data, which are in agreement with the reported chemical shifts. 40 Furthermore, we also verified that this hydrolysis product was not the oxidative species, confirming therefore that BTI is the real oxidative species in the BTI-mediated quinoxaline oxidation.…”

supporting

confidence: 75%

“…General. 1 H NMR and 13 C NMR spectra were recorded on a 300 MHz spectrometer using DMSO-d 6 as the solvent. Chemical shifts are reported in ppm using the relative solvent peak as a reference standard.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…1 H NMR (300.1 MHz, DMSO-d 6 ): δ 4.19 (s, 3H), 7.41 (d, 1H, J = 9.0 Hz), 7.73 (d, 1H, J = 9.0 Hz), 8.53 (s, 1H), 11.96 (bs, 1H), 12.26 (bs, 1H). 13 C spectra for compound 4b could not be obtained because of the extremely low solubility of this compound in conventional organic solvents. EI(+)-MS m/z (%): 216 (100) (M + − CO), 244 (70) (M + ).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…1 H NMR (300.1 MHz, DMSO-d 6 ): δ 7.80 (d, 1H, J = 9.0 Hz), 8.02 (d, 1H, J = 9.0 Hz), 9.29 (s, 1H), 10.17 (s, 1H), 12.26 (bs, 1H), 12.50 (bs, 1H). 13 C NMR (75.5 MHz, DMSO-d 6 ): δ 192.5, 155.8, 154.9, 145.1, 141.5, 137.5, 132.6, 127.0, 124.4, 121.3, 119.9. EI(+)-MS m/z (%): 214 (100) (M + − CO), 242 (52) (M + ), 158 (48) (M + − 3CO), 186 (46) (M + − 2CO).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…1 H NMR (300.1 MHz, DMSO-d 6 ): δ 2.71 (s, 3H), 7.61 (d, 1H, J = 9.0 Hz), 7.73 (d, 1H, J = 9.0 Hz), 8.85 (s, 1H), 12.05 (bs, 1H), 12.24 (bs, 1H). 13 6-Chloroquinoxaline-2,3(1H,4H)-dione (14b). The product was obtained as a white solid with a yield of 82% (80.7 mg) following the general procedure described for the oxidation using bis-(trifluoroacetoxy)iodobenzene.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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A Direct Method for Oxidizing Quinoxaline, Tetraazaphenanthrene, and Hexaazatriphenylene Moieties Using Hypervalent λ³-Iodinane Compounds

et al. 2013

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An efficient oxidation reaction of various electron-poor quinoxaline-core-containing compounds, such as quinoxalines, 1,4,5,8-tetraazaphenanthrenes, and 1,4,5,8,9,12-hexaazatriphenylene, using [bis(trifluoroacetoxy)iodo]benzene is reported. These compounds are converted into the corresponding quinoxalinediones in good to high yields at room temperature using an acetonitrile/water solvent mixture. This unprecedented reaction should enable the synthesis of a wide variety of compounds useful in several fields of chemistry.

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supporting

confidence: 75%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 3 more Smart Citations

A Direct Method for Oxidizing Quinoxaline, Tetraazaphenanthrene, and Hexaazatriphenylene Moieties Using Hypervalent λ³-Iodinane Compounds

et al. 2013

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Nucleophilic substitutions on 2‐Chloro‐3‐Nitroquinoxaline

Nasielski-Hinkens

Kaisin

Grandjean

et al. 1988

Bulletin des Soc Chimique

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SUMMARYPiperidine, cyclohexylamine, methoxide ion and para-thiocresolate ion react with 2-chloro-3-nitroquinoxaline 1 by selectively substituting the nitro group, in contrast to the behavior of most ortho-chloronitroaromatics which loose halide when subjected to nucleophilic substitution reactions. This inversion is interpreted as being due to the lack of activation of the 2-position by the nitro group in the 3-position because of the low value of the ,,-bond index between these two vertices. It is also suggested that the substitution by neutral reagents such as amines is strongly influenced by stabilizing interactions between the negatively charged nitro group and the ammonium moiety in the complex; this built-in solvation may be responsible for inversions in the chemoselectivity between chloro and nitro nucleofugicities. INTRODUCTIONOur current recent interest in the chemistry of quinoxaline derivatives('), with the aim of synthesizing potential ligands for transition metad2), led us to reexamine the chemoselectivity in the nucleophilic displacements undergone by various chloronitroquinoxalines and more specifically by 2-chloro-3-nitroquinoxaline 1. In connection with this question, Hartman and S~hwering(~) had already found that 1 reacts with I-aminopropane-2,3-diol by exclusive aminolysis of the nitro group; this is opposite to the behaviour of 2-chloro-3-nitropyrazine 2 which selectively undergoes substitution of chlorine by the same amine.Such a reversal of nucleofugicities between CI and NO2 for very similar structures was already noticed by the authors(3) who gave a qualitative interpretation based on a less efficient charge dispersal in the bicyclic compound 1 than in the monocyclic analog 2. We felt that this interpretation deserved closer scrutiny but, before any attempt was made in that direction, it was thought that a more systematic study of this chemoselectivity was necessary. We now report on the reactions of 1 with four other nucleophiles : piperidine, cyclohexylamine, methoxide ion and parathiocresolate ion.

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The Reaction of Quinoxaline‐ and Phenazine‐N‐Oxides with Thionyl Chloride and Paratoluenesulfonyl Chloride

Nasielski

Heilporn

Chauveheid

et al. 1990

Bulletin des Soc Chimique

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-.2,3-Diphenylquinoxaline-N-oxide 1 with thionyl chloride gives only 5-chloro-and 6-chloroquinoxaliie and very little deoxygenation. Phenazine-Ng-oxide 2, in the same conditions, gives mainly 2-chlorophenazine and minor amounts of I-chlorophenazine, but here deoxygenation is an important pathway. Freshly recrystallized para-toluenesulfonyl chloride gives a high chlorination-to-tosyloxylation ratio. All these results point to a variable ability of acid chlorides to yield homocycle chlorination or acyloxylation; this is confirmed by the observation that phenazine-Ng-oxide and phosphoryl chloride give fair amounts of aryl phosphate. Intmductioq.Previous work from this laboratory (l) has shown that 2.3-diphenylquinoxaline-N-oxide 1 refluxed in phosphoryl chloride (the Meisenheimer reaction) mainly gives aryl dihydrogen phosphates or their derivatives rather than the expected aryl chlorides. Also of interest was the obsetvation that, contrary to the usual sequence of reactivities of a and p positions in naphtalene-type topologies, the majority of substitution products originate from attack at a p type position of the homocycle. In our search for more efficient chlorination reagents, which would minimize the contribution of these unwanted side-reactions, we tried sulfur-derived acid chlorides and selected to test thionyl chloride and para-toluenesulfonyl chloride on 1 and on its analog, phenazineNg-oxide 2. Contrary to sulfuryl chloride S02C12, which has already been used (2) as a chlorinating reagent of Noxides, its reduced analog thionyl chloride SOCl2 does not seem to have been examined for that purpose.Our results with this reagent are collected in Table I. When 2,3-diphenylquinoxaline-N-oxide 1 is refluxed in SOC12, it gives an overall 83 % yield of 5-chloro-2,3-diphenylquinoxaline 3 and 6-chloro-2,3-diphenylquinoxaline 4 in a n approximate 4:5 ratio with 6 % deoxygenation to 5. Dilution with toluene reverses the 3/4 ratio to 6:4, whereas adding chloride ions leads to predominant deoxygenation and a significant increase of the proportion of the 6-isomer.Two points emerge from these results. First, thionyl chloride is the reagent leading to the least amount of by-products: there is almost no deoxygenation, and no aryl-oxygen bond is formed. Next, the relative amount of 5-chlorination is much higher here than with phosphoryl chloride: the 5-CV6-Cl reaches 6:4. whereas it was 1:4 with POc13 (l).-783 -

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An unexpected course of the Meisenheimer reaction : aryl phosphates in the reaction of phosphoryl chloride with 2, 3-diphenylquinoxaline-N1-oxide.

Cited by 13 publications

References 10 publications

A Direct Method for Oxidizing Quinoxaline, Tetraazaphenanthrene, and Hexaazatriphenylene Moieties Using Hypervalent λ³-Iodinane Compounds

A Direct Method for Oxidizing Quinoxaline, Tetraazaphenanthrene, and Hexaazatriphenylene Moieties Using Hypervalent λ³-Iodinane Compounds

Nucleophilic substitutions on 2‐Chloro‐3‐Nitroquinoxaline

The Reaction of Quinoxaline‐ and Phenazine‐N‐Oxides with Thionyl Chloride and Paratoluenesulfonyl Chloride

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An unexpected course of the Meisenheimer reaction : aryl phosphates in the reaction of phosphoryl chloride with 2, 3-diphenylquinoxaline-N1-oxide.

Cited by 13 publications

References 10 publications

A Direct Method for Oxidizing Quinoxaline, Tetraazaphenanthrene, and Hexaazatriphenylene Moieties Using Hypervalent λ3-Iodinane Compounds

A Direct Method for Oxidizing Quinoxaline, Tetraazaphenanthrene, and Hexaazatriphenylene Moieties Using Hypervalent λ3-Iodinane Compounds

Nucleophilic substitutions on 2‐Chloro‐3‐Nitroquinoxaline

The Reaction of Quinoxaline‐ and Phenazine‐N‐Oxides with Thionyl Chloride and Paratoluenesulfonyl Chloride

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A Direct Method for Oxidizing Quinoxaline, Tetraazaphenanthrene, and Hexaazatriphenylene Moieties Using Hypervalent λ³-Iodinane Compounds

A Direct Method for Oxidizing Quinoxaline, Tetraazaphenanthrene, and Hexaazatriphenylene Moieties Using Hypervalent λ³-Iodinane Compounds