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Microwave-Assisted Preparation of 1-Aryl-1H-pyrazole-5-amines
Published on: June 23, 2019
4-[2-(4-Fluoro-phen-yl)furan-3-yl]pyridine
Summary
The crystal structure of C(15)H(10)FNO reveals specific dihedral angles between its furan, pyridine, and 4-fluorophenyl rings. These molecular interactions are stabilized by non-conventional hydrogen bonds, influencing crystal packing.
Area of Science:
- Crystallography
- Organic Chemistry
- Materials Science
Background:
- Understanding the three-dimensional arrangement of atoms in organic molecules is crucial for predicting their properties.
- The specific compound C(15)H(10)FNO, containing furan, pyridine, and fluorophenyl moieties, presents an interesting case for structural analysis.
- Investigating intermolecular forces, such as hydrogen bonding, provides insights into crystal lattice stability.
Purpose of the Study:
- To determine and analyze the crystal structure of the title compound, C(15)H(10)FNO.
- To quantify the dihedral angles between the aromatic rings within the crystal structure.
- To identify and characterize the types of hydrogen bonding contributing to crystal stabilization.
Main Methods:
- Single-crystal X-ray diffraction was employed to obtain the precise atomic coordinates.
- Crystallographic software was used to analyze bond lengths, bond angles, and dihedral angles.
- Analysis of intermolecular interactions, including hydrogen bonds, was performed using crystallographic data.
Main Results:
- The crystal structure of C(15)H(10)FNO was successfully elucidated.
- Dihedral angles were measured: furan-pyridine (40.04(11)°), furan-4-fluorophenyl (25.71(11)°), and pyridine-4-fluorophenyl (49.51(10)°).
- Non-conventional C-H⋯F and C-H⋯N hydrogen bonds were identified as key stabilizing forces in the crystal.
Conclusions:
- The determined dihedral angles provide a precise geometric description of the molecule in the solid state.
- The presence of C-H⋯F and C-H⋯N hydrogen bonds plays a significant role in the overall stability of the crystal structure.
- This structural information can be valuable for understanding structure-property relationships in related fluorinated organic compounds.
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Five-Membered Heterocyclic Aromatic Compounds: Overview
Heterocyclic aromatic compounds are cyclic compounds that are aromatic and have one or more heteroatoms—atoms other than carbon, in the ring. Depending upon the number of atoms present in the ring, they can be either five or six-membered. Examples of five-membered heterocyclic aromatic compounds include pyrrole, furan, thiophene, and imidazole. Pyrrole consists of one nitrogen atom having one lone pair of electrons. Furan and thiophene have one oxygen and one sulfur heteroatom, respectively.
Basicity of Heterocyclic Aromatic Amines
Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine having a nitrogen atom as part of an aromatic ring has much less basicity than its corresponding alicyclic counterpart. For this reason, as presented in Figure 1, piperidine (pKb = 2.8) is significantly more basic than pyridine (pKb = 8.8).
Nomenclature of Aryl and Heterocyclic Amines
The simplest aromatic amine is phenylamine, which contains an –NH2 functionality directly attached to an aromatic ring. The name aniline is designated for this skeleton. As shown in Figure 1, the common names of the functionalized anilines involve prefixes ortho-, meta-, and para- to indicate the substitution position. Different functionalized aniline derivatives also have notable trivial names.
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
Aromatic Hydrocarbon Cations: Structural Overview
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Removing one hydrogen from the intervening CH2 group with both...

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