N-(6-Chloro-3-nitropyridin-2-yl)-5-(1-methyl-1H-pyrazol-4-yl)isoquinolin-3-amine

Here we describe the synthesis of N-(6-chloro-3-nitropyridin-2-yl)5-(1-methyl-1H-pyrazol-4-yl)isoquinolin-3-amine via a three-step procedure including a Buchwald–Hartwig arylamination with benzophenone imine and a highly regioselective nucleophilic aromatic substitution. The title compound was analyzed by nuclear magnetic resonance spectroscopy (1H, 13C, HSQC, HMBC, COSY, DEPT90 and NOESY), high resolution mass spectrometry (ESI-TOF-HRMS) and infrared spectroscopy (ATR-IR) and its structure was confirmed by single crystal X-ray diffraction. The inhibitory potency of the title compound was evaluated for selected kinases harboring a rare cysteine in the hinge region (MPS1, MAPKAPK2 and p70S6Kβ/S6K2).

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N1-{4-[2-(Methylthio)-1H-imidazol-5-yl]pyridin-2-yl}benzene-1,4-diamine

Molbank ◽

10.3390/m1048 ◽

2019 ◽

Vol 2019 (1) ◽

pp. M1048

Author(s):

Ahmed El-Gokha ◽

Francesco Ansideri ◽

Stanislav Andreev ◽

Dieter Schollmeyer ◽

Stefan Laufer ◽

...

Keyword(s):

Protein Kinase ◽

13C Nmr ◽

Title Compound ◽

Mitogen Activated Protein Kinase ◽

Nucleophilic Aromatic Substitution ◽

Aromatic Substitution ◽

X Ray Diffraction ◽

X Ray ◽

Mitogen Activated Protein ◽

Acidic Conditions

The title compound N1-{4-[2-(methylthio)-1H-imidazol-5-yl]pyridin-2-yl}benzene-1,4-diamine (2) was synthesized via nucleophilic aromatic substitution of 2-chloro-4-[2-(methylthio)-1H-imidazol-5-yl]pyridine (3) and p-phenylenediamine under acidic conditions. The synthesized compound 2 was characterized by 1H-NMR, 13C-NMR, MS HPLC, IR and UV-VIS. Additionally, the structure of 2 was confirmed by single crystal X-ray diffraction. Pyridinylimidazole 2 displays moderate affinity towards the c-Jun N-terminal kinase 3 and shows selectivity versus the closely related p38α mitogen-activated protein kinase.

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Nitroxide radicals appended to phthalonitriles: synthesis, structural characterization and photophysical properties

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229621001832 ◽

2021 ◽

Vol 77 (3) ◽

pp. 137-143

Author(s):

Ismail Fidan ◽

Emel Onal ◽

Catherine Hirel

Keyword(s):

Magnetic Measurements ◽

Photophysical Properties ◽

Nucleophilic Aromatic Substitution ◽

Structural Studies ◽

Aromatic Substitution ◽

Nitronyl Nitroxide ◽

X Ray Diffraction ◽

X Ray ◽

Microwave Assisted ◽

Ft Ir

The syntheses of 4-[4-(4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl-2-yl)phenoxy]phthalonitrile (3, C21H19N4O3) and 4-[4-(4,4,5,5-tetramethyl-2-imidazoline-1-oxyl-2-yl)phenoxy]phthalonitrile (4) were carried out by microwave-assisted nucleophilic aromatic substitution of 4-nitrophthalonitrile (2) by the pre-formed 2-(4-hydroxyphenyl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (1). Compounds 3 and 4 were characterized unambiguously by a rich array of analyses, such as melting point, FT–IR, MALDI–TOF MS, elemental analysis, UV–Vis, CV, EPR, magnetic measurements and single-crystal X-ray diffraction. Structural studies demonstrate that the C—H...X and C—X...π (X = O and N) interactions in the radical nitronyl nitroxide groups play an important role in the assembly of the crystal structures. Moreover, cyclic voltammetry analyses show that the phthalonitrile substituent retains the redox properties of the Ullman radicals.

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Improved Access to 1,8-Dichloro-10-(ethynyl)anthracene: A Useful Building Block for (Semi-)rigid Organic Frameworks

Synthesis ◽

10.1055/s-0036-1591925 ◽

2018 ◽

Vol 50 (10) ◽

pp. 2009-2018

Author(s):

Jan-Hendrik Lamm ◽

Philipp Niermeier ◽

Leif Körte ◽

Beate Neumann ◽

Hans-Georg Stammler ◽

...

Keyword(s):

Mass Spectrometry ◽

Building Block ◽

High Resolution Mass Spectrometry ◽

Cross Coupling ◽

Easy Access ◽

Coupling Reactions ◽

X Ray Diffraction ◽

X Ray ◽

Cross Coupling Reactions ◽

Resolution Mass

An easy access to 1,8-dichloro-10-(ethynyl)anthracene is reported, which is widely applicable for building up rigid linkers between two 1,8-dichloroanthracene units. For this, 1,8-dichloroanthren-10(9H)-one was reacted with ethynylmagnesium bromide in the presence of CeCl3; the yield was 65%. This building block was used as a substrate in (cross-)coupling reactions and some examples of linked 1,8-dichloroanthracen-10-yls (e.g., 1,8-bis[(1,8-dichloroanthracen-10-yl)-ethynyl]naphthalene or 1,2-bis[(1,8-dichloroanthracen-10-yl)ethynyl]-benzene) were synthesized in good to moderate yields. Linked 1,8-dichloroanthracen-10-yl derivatives were also synthesized by cross-coupling reactions using 10-bromo-1,8-dichloroanthracene and doubly ethynyl-substituted substrates. Linkers between the 1,8-dichloroanthracene units were: butadiynediyl, dimethylsilyldiethynyl, octa-1,7-diyne-1,8-diyl, propane-1,3-diylbis(dimethylsilyl)diethynyl, benzene-1,2-diethynyl, naphthalene-1,8-diyldiethynyl, and anthracene-1,8-diyldiethynyl. The new anthracene compounds were characterized by NMR spectroscopy, high-resolution mass spectrometry, and, in part, by X-ray diffraction experiments.

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Structural Identification of Products from the Chloromethylation of Salicylaldehyde

Synlett ◽

10.1055/s-0037-1610334 ◽

2018 ◽

Vol 30 (01) ◽

pp. 44-48 ◽

Cited By ~ 2

Author(s):

Muhammad Bala ◽

Ebrahim Kadwa ◽

Holger Friedrich

Keyword(s):

Mass Spectrometry ◽

Nmr Spectroscopy ◽

High Resolution Mass Spectrometry ◽

Structural Identification ◽

Spectroscopic Techniques ◽

X Ray Diffraction ◽

X Ray ◽

Multinuclear Nmr Spectroscopy ◽

Ir Spectroscopic ◽

Resolution Mass

In the functionalization of salicylaldehyde to give 5-(chloromethyl)salicylaldehyde, two byproducts [5-(hydroxymethyl)salicylaldehyde and 5,5′-methylenebis(salicylaldehyde)] were also isolated. Detailed characterizations and structural analyses of all three products by single-crystal X-ray diffraction, multinuclear NMR spectroscopy, high-resolution mass spectrometry, and IR spectroscopic techniques are presented and discussed. A strategy is presented for the preferential isolation of the two byproducts through column chromatography.

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3-[N-(4-Methoxybenzyl)amino]benzo[de]anthracen-7-one

Molbank ◽

10.3390/m1287 ◽

2021 ◽

Vol 2021 (4) ◽

pp. M1287

Author(s):

Alise Kirilova ◽

Aleksandrs Pučkins ◽

Sergey Belyakov ◽

Elena Kirilova

Keyword(s):

Mass Spectrometry ◽

Nuclear Magnetic Resonance ◽

Infrared Spectroscopy ◽

Resonance Spectroscopy ◽

Gravimetric Analysis ◽

Thermal Gravimetric ◽

X Ray Diffraction ◽

X Ray ◽

Step Procedure ◽

Ft Ir

Herein, we describe the synthesis of 3-[N-(4-methoxybenzyl)amino]benzo[de]anthracen-7-one via a two-step procedure including 3-aminobenzanthrone condensation with anisaldehyde and following reduction of obtained imine to appropriate amine by sodium borohydride. The structure of the synthesized compounds was established by elemental analysis, nuclear magnetic resonance spectroscopy, mass spectrometry (EI-MS), and infrared spectroscopy (FT-IR) and confirmed by single-crystal X-ray diffraction. The title compound was analyzed by thermal gravimetric analysis, UV/vis, and fluorescence spectroscopy.

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Two Propanediurea-based Cucurbituril Analogues: Bis-ns-TD[8] and NH-ns-TD[4]

Synlett ◽

10.1055/s-0037-1610632 ◽

2018 ◽

Vol 29 (18) ◽

pp. 2381-2384

Author(s):

Qiaochun Wang ◽

Chunhua Dai ◽

Yenan Shen

Keyword(s):

Mass Spectrometry ◽

1H Nmr Spectroscopy ◽

High Resolution Mass Spectrometry ◽

The Other ◽

Amine Group ◽

X Ray Diffraction ◽

Excellent Thermal Stability ◽

X Ray ◽

Secondary Amine Group ◽

Resolution Mass

Two new cucurbituril members, one containing two equivalent cavities and the other having an active secondary amine group, were synthesized by condensation of propanediurea (2,4,6,8-tetraazabicyclo[3.3.1]nonane-3,7-dione) with formaldehyde. These two macrocycles exhibit excellent thermal stability, and their structures were confirmed by single-crystal X-ray diffraction, 1H NMR spectroscopy, and high-resolution mass spectrometry.

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KI-catalyzed synthesis of S-Thiocarbamates by cross-coupling of cyclohexyl isocyanide with sulfonyl chlorides

Journal of Chemical Research ◽

10.1177/1747519819866401 ◽

2019 ◽

Vol 43 (9-10) ◽

pp. 347-351

Author(s):

Liangwei Lin ◽

Zhengjun Fang ◽

Yajun Li ◽

Feng Wu ◽

Chaktong Au ◽

...

Keyword(s):

Functional Group ◽

High Resolution Mass Spectrometry ◽

Cross Coupling ◽

Crystallographic Analysis ◽

Resonance Spectroscopy ◽

Reaction Conditions ◽

Sulfonyl Chlorides ◽

X Ray ◽

Direct Generation ◽

Resolution Mass

A simple and efficient process for direct generation of various S-thiocarbamates is developed by cross-coupling of readily available sulfonyl chlorides with cyclohexyl isocyanide. The yields are excellent and the structures of the generated S-thiocarbamates are characterized by nuclear magnetic resonance spectroscopy, infrared spectroscopy, and high-resolution mass spectrometry together with X-ray crystallographic analysis. The protocol has the advantages of using easily available reagents, employs inexpensive KI as the reagent, demonstrates good functional group tolerance, and utilizes mild reaction conditions.

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Synthesis, C-13 NMR, and X-ray crystal structure of N6,N9-octamethylenepurinecyclophane

Canadian Journal of Chemistry ◽

10.1139/v92-030 ◽

1992 ◽

Vol 70 (1) ◽

pp. 186-196 ◽

Cited By ~ 2

Author(s):

R. A. Bell ◽

R. Faggiani ◽

H. N. Hunter ◽

C. J. L. Lock

Keyword(s):

Crystal Structure ◽

Direct Methods ◽

Chloride Ion ◽

Nucleophilic Aromatic Substitution ◽

Nucleophilic Attack ◽

Aliphatic Chain ◽

Aromatic Substitution ◽

X Ray Diffraction ◽

X Ray ◽

Small Distortion

The synthesis and structure determination of N6,N9-octamethylenepurine cyclophane by single crystal X-ray diffraction is reported. The cyclophane was prepared from 6-chloropurine and 8-aminooctanoic acid as starting materials. The aminooctyl fragment was first attached to N9 of 6-chloropurine by means of the Mitsunobu reaction and cyclization to the cyclophane effected by nucleophilic attack of the amino group at the C6 position and displacement of chloride ion. Reversing the reaction strategy did not result in formation of the cyclophane. Crystals of the cyclophane were monoclinic, P2/n, a = 9.620(3), b = 12.266(3), c = 11.994(2), Å, β = 111.25(2)°, Z = 4. Intensities were measured with a Nicolet P3 diffractometer and MoKα radiation at room temperature. The structure was solved by direct methods and refined to R = 0.0683, Rw = 0.0493 based on 1730 reflections. The molecule shows some strain, but bond lengths and angles are normal. Attempts to relieve the strain are made by a small distortion of the purine rings and bending of the N6 and C8′ atoms out of the planes to which they are attached (0.314(4), 0.459(5) Å). Further, the N6,H6,Cl′ group is twisted by 30° from the pyrimidine plane and the torsion angles in the aliphatic chain are distorted from the idealized 60, 120, 180° (average, 13.6°; range 5.1–24.9°). These distortions result in some weakening of the π-bonding in the adenine moiety. Keywords: purinophane synthesis, nucleophilic aromatic substitution, conformational analysis, crystal structure.

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Synthesis and Molecular Structure of tert-Butyl 3-oxo-2-oxa-5-azabicyclo[2.2.2]octane-5-carboxylate

Journal of Crystallography ◽

10.1155/2014/645079 ◽

2014 ◽

Vol 2014 ◽

pp. 1-6 ◽

Cited By ~ 1

Author(s):

Tetsuji Moriguchi ◽

Suvratha Krishnamurthy ◽

Toru Arai ◽

Taisuke Matsumoto ◽

Koji Araki ◽

...

Keyword(s):

Molecular Structure ◽

Mass Spectrometry ◽

High Resolution Mass Spectrometry ◽

Amino Acid Ester ◽

Piperidine Ring ◽

Monoclinic Space Group ◽

X Ray Diffraction ◽

X Ray ◽

H Nmr ◽

Resolution Mass

The compound tert-butyl 3-oxo-2-oxa-5-azabicyclo[2.2.2]octane-5-carboxylate was synthesized as a cyclic amino acid ester from the corresponding ethyl 2-amino-4-(2-oxiranyl)butanoate HCl salt via an intramolecular lactonization reaction and was characterized by using 1H NMR spectroscopy and high-resolution mass spectrometry. The product was then recrystallized from dichloromethane/diethyl ether and its structure was determined via single crystal X-ray diffraction analysis. The crystal was found to be of the monoclinic space group P21/c (no. 14) with a = 10.217(2) Å, b = 11.676(3) Å, c = 10.273(3) Å, β = 114.186(13)°, and Dcalc = 1.350 g/cm3 at 123 K. The compound has bicyclo[2.2.2]octane structure including a lactone moiety and a piperidine ring, and the two diastereomers of the molecules are present in a 1 : 1 ratio in the crystal.

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(S)-1-(Ethoxycarbonyl)ethyl(2R,5S)-2,5-dimethyl-1,3-dioxolan-4-one-2-carboxylate

Molbank ◽

10.3390/m1178 ◽

2021 ◽

Vol 2021 (1) ◽

pp. M1178

Author(s):

R. Aitken ◽

Oliver Haslett ◽

Alexandra Slawin

Keyword(s):

Lactic Acid ◽

Title Compound ◽

Ethyl Pyruvate ◽

X Ray Diffraction ◽

X Ray ◽

Nmr Methods

The title compound was obtained in low yield in the condensation of ethyl pyruvate and lactic acid. Its structure is determined by NMR methods and x-ray diffraction and the mechanism for formation of this 1:2 adduct from the initial 1:1 adduct is considered.

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