Preparation of Poly(diazo) Compounds as Precursors of Organo-Magnetic Materials by Utilizing Diazo Compound as Building Blocks

The benzoxanthene ethers Ia–IIb are obtained in good yields by the action of tetrachloro-and tetrabromo-o-benzoquiuone on 1,2- and 3,4-benzoxanthione, respectively. The benzopyran analogues IIIa–IIIb are obtained by the interaction of the corresponding haloquinone and coumarin hydrazone. The latter, which is now readily obtained by the action of hydrazine hydrate on coumarin-2-thione, condenses with thioketones to give coumarin azines. The benzopyran ethers IIIa and IIIb are cleaved by malononitrile, cyanoacetic ester, hydrazine hydrate, phenylhydrazine, and benzoylhydrazine, yielding the unsaturated nitriles (Va–Vb) and the corresponding hydrazones, respectively.1,2-Benzoxanthione reacts with 9-diazoxanthene, diphenyldiazomethane, and diphenylenediazomethane to give the ethylene sulfides VI–VIII, respectively. However, coumarin-2-thione reacts with the diazo compounds in a different manner; it gives the ethylenes X and XI directly, together with the symmetrical thiiranes XII and XIII, in the cases of diphenyldiazomethane and 9-diazoxanthene, respectively, whereas the cyclopropane derivative XIV is produced in the case of diphenylenediazomethane. XIV is also obtained by the photochemical interaction of coumarin itself and the diazo compound.

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INTERACTION OF HYDRIDE Σ-COMPLEX OF 5,7-DINITRO-8-HYDROXYQUINOLINE WITH SALTS OF AROMATIC DIAZO COMPOUNDS

IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENIY KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA ◽

10.6060/ivkkt.20196211.5916 ◽

2019 ◽

Vol 62 (11) ◽

pp. 85-91 ◽

Cited By ~ 1

Author(s):

Il'ya I. Ustinov ◽

Nikolay V. Khlytin ◽

Igor' V. Blokhin ◽

Irina V. Shakhkel'dyan ◽

Yuriy M. Atroshchenko ◽

...

Keyword(s):

Diazo Compound ◽

Coupling Reaction ◽

Diazo Compounds ◽

Azo Compounds ◽

Azo Coupling ◽

Absorption Bands ◽

Stretching Vibrations ◽

Intramolecular Hydrogen ◽

Yield And Purity ◽

Mild Acid

Interaction between 5,7-dinitro-8-hydroxyquinoline hydride anionic σ-adduct and chlorides of substituted aryldiazonium in water yielded 5-arylazo-7-nitro-8-hydroxyquinolines, the substitution products of the nitro group at the C-5 σ-adduct position. The direction of the reaction agrees with the quantum-chemical calculations carried out earlier and the GMLA principle, which assumes that the mild acid, which is a diazocathione, will attack the reaction center to which the softest base corresponds, that is, the least negatively charged C-5 carbon atom, in contrast to the C-7 atom. It is shown that the yield of the product increases with the presence of an electron-withdrawing substituent in the diazocomponent. Also in this study, the synthesis of the hydride σ-adduct of 5,7-dinitro-8-hydroxyquinoline was optimized. It was found that the use of pure dimethylacetamide as a solvent, as well as the addition of sodium carbonate, increases the yield and purity of the synthesized σ-adduct. The structure of the obtained compounds was proved by the methods of NMR and IR spectroscopy. In the IR spectra of all synthesized azo compounds, weak absorption bands corresponding to the stretching vibrations of the azogroup (N = N) are fixed in the range of 1400-1465 cm-1, which also indirectly confirms the expected direction of the reaction. Otherwise, the bands of the azogroup vibrations would be shifted to the 1500-1600 cm-1 region as a result of azo-hydrazoic tautomerism. In 1H NMR spectra of synthesized compounds, there is no proton signal of intramolecular hydrogen bond at δ 14-15 ppm, characteristic of the hydrazine form. The proton signals of the arylazo group also confirm the presence of the latter. The use of anionic hydride σ-complexes of dinitroquinoline derivatives as azo-component in the reaction with aromatic diazo compound expands the synthetic possibilities of the azo coupling reaction and allows to obtaine new nitroazoquinolines.

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Pd-Catalyzed Dearomative Three-Component Reaction of Bromoarenes with Diazo Compounds and Allylborates

10.26434/chemrxiv.8989130.v1 ◽

2019 ◽

Author(s):

Masaaki Komatsuda ◽

Hiroki Kato ◽

Kei Muto ◽

Junichiro Yamaguchi

Keyword(s):

Diazo Compound ◽

Diazo Compounds ◽

Reaction Conditions ◽

Three Component Reaction

Acatalytic dearomative three-component reaction of bromoarenes with TMS-diazomethane and allyl borate was developed. The key of this assembling reaction is the use of a diazo compound to generate a Pd-π-benzyl intermediate through a Pd-carbenoid species. This method allowed for a dearomative functionalization using arenes as limiting reagents. Heteroaryl bromides were also applicable to give dearomatized structures under the reaction conditions.

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Magnetic Materials Based on Nitronyl Nitroxide Radicals Complexes: From Mononuclear Building Blocks to One- and Two-Dimensional Compounds

Molecular Crystals and Liquid Crystals Science and Technology Section A Molecular Crystals and Liquid Crystals ◽

10.1080/10587259908023348 ◽

1999 ◽

Vol 334 (1) ◽

pp. 521-532 ◽

Cited By ~ 6

Author(s):

Karine Fegy ◽

Christophe Lescop ◽

Dominique Luneau ◽

Paul Rey

Keyword(s):

Magnetic Materials ◽

Building Blocks ◽

Two Dimensional ◽

Nitronyl Nitroxide ◽

Nitroxide Radicals

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DFT investigation on mechanism of dirhodium tetracarboxylate-catalyzed O-H insertion of diazo compounds with H2O

Open Chemistry ◽

10.2478/s11532-009-0118-8 ◽

2010 ◽

Vol 8 (1) ◽

pp. 223-228 ◽

Cited By ~ 4

Author(s):

Zhenfeng Liu ◽

Jianyong Liu

Keyword(s):

Dft Calculations ◽

Nucleophilic Addition ◽

Diazo Compound ◽

Experimental Results ◽

Diazo Compounds ◽

Reaction Pathways ◽

Insertion Reaction ◽

Oxonium Ylides ◽

Oxonium Ylide ◽

Very High

AbstractThe mechanism of the dirhodium tetracarboxylate-catalyzed O-H insertion reaction of diazomethane and methyl diazoacetate with H2O has been studied in detail using DFT calculations. The rhodium catalyst and a diazo compound couple to form a rhodiumcarbene complex. Of two reaction pathways of the Rh(II)-carbene complex with H2O, the stepwise pathway is more preferable than the concerted one. Formation of a Rh(II) complex-associated oxonium ylide is an exothermal process, and direct decomposition of the ylide gives a very high barrier. The high barriers for the 1,2-H shift of Rh(II) complex-associated oxonium ylides make the ylides become stable intermediates in both reactions, especially for the reactions in solution. Difficulty in formation of a free oxonium ylide supports experimental results, indicating that the Rh(II) complex-catalyzed nucleophilic addition of a diazo compound proceeds via a Rh(II) complex-associated oxonium ylide rather than via a free oxonium ylide.

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Synthetic Approaches to Contemporary Drugs that Contain the Cyclopropyl Moiety

Synthesis ◽

10.1055/s-0039-1690058 ◽

2020 ◽

Vol 52 (09) ◽

pp. 1315-1345 ◽

Cited By ~ 3

Author(s):

Zdenko Časar

Keyword(s):

Drug Administration ◽

Structural Diversity ◽

Building Blocks ◽

Time Frame ◽

New Drugs ◽

Diazo Compounds ◽

Structural Motif ◽

Ch Acids ◽

Synthetic Approaches ◽

The U.S

The U.S. Food and Drug Administration approved 18 new drugs that incorporate the cyclopropyl structural motif in the time frame from 2012 to 2018. This review provides an overview of synthetic approaches to these drugs with emphasis on the construction of the cyclopropyl moiety or its incorporation into the key building blocks for assembly of the highlighted drugs. Based on the structural diversity of these drugs, synthetic approaches for the construction and introduction of the cyclopropyl moiety into their structure are diverse and include: cycloalkylation (double alkylation) of CH-acids, catalytic cyclopropanation of alkenes with diazo compounds, the Simmons–Smith reaction, the Corey–Chaykovsky reaction, the Kulinkovich reaction, the Horner–Wadsworth–Emmons reaction, and cycloaddition. In addition, the cyclopropyl structure was also introduced into the drug substance intermediates via simple cyclopropyl-moiety-containing building blocks, such as cyclopropylamine, cyclopropanesulfonamide, cyclopropanecarbonyl chloride, and cyclopropylmagnesium bromide.1 Introduction2 Synthesis of Recently Approved Cyclopropyl-Moiety-Containing Drugs2.1 Cabozantinib2.2 Trametinib2.3 Simeprevir2.4 Ledipasvir2.5 Olaparib2.6 Tasimelteon2.7 Finafloxacin2.8 Paritaprevir2.9 Lenvatinib2.10 Lumacaftor2.11 Lesinurad2.12 Grazoprevir2.13 Glecaprevir2.14 Ozenoxacin2.15 Voxilaprevir2.16 Naldemedine2.17 Tezacaftor2.18 Tecovirimat3 Conclusion

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