Organofluorine chemistry: Difluoromethylene motifs spaced 1,3 to each other imparts facial polarity to a cyclohexane ring

2,2-Dimethyl-5-phenyl-1,1,3,3-tetrafluororocyclohexane has been prepared and characterised as an example of a facially polarised cyclohexane containing 1,3 related CF2 groups. The dipolar nature of the ring arises from the axial orientation of two of the C–F bonds pointing in the same direction, and set by the chair conformation of the cyclohexane. This electrostatic profile is revealed experimentally both in the solid-state (X-ray) packing of the rings and by solution (NMR) in different solvents. A computationally derived electrostatic profile of this compound is consistent with a more electronegative and a more electropositive face of the cyclohexane ring. This placing of CF2 groups 1,3 to each other in a cyclohexane ring is introduced as a new design strategy which could be applicable to the preparation of polar hydrophobic cyclohexane motifs.

Download Full-text

The structure of 1-formyl-3-phenyl-Δ2-pyrazoline in the gas phase (DFT calculations), in solution (NMR) and in the solid state (X-ray crystallography)

Journal of Molecular Structure ◽

10.1016/j.molstruc.2003.10.041 ◽

2004 ◽

Vol 689 (3) ◽

pp. 251-254 ◽

Cited By ~ 14

Author(s):

I. Alkorta ◽

J. Elguero ◽

A. Fruchier ◽

N. Jagerovic ◽

G.P.A. Yap

Keyword(s):

Solid State ◽

Dft Calculations ◽

Gas Phase ◽

Solution Nmr ◽

X Ray ◽

X Ray Crystallography

Download Full-text

Synthesis and conformational studies of 9-benzyloxy-18-substituted [3.3]metacyclophanes

Canadian Journal of Chemistry ◽

10.1139/cjc-2015-0174 ◽

2015 ◽

Vol 93 (11) ◽

pp. 1161-1168 ◽

Cited By ~ 9

Author(s):

M. Monarul Islam ◽

Tomiyasu Hirotsugu ◽

Taisuke Matsumoto ◽

Junji Tanaka ◽

Takehiko Yamato

Keyword(s):

Solid State ◽

Intramolecular Cyclization ◽

Acid Treatment ◽

Room Temperature ◽

Coupling Reaction ◽

Chair Conformation ◽

Cyclization Reaction ◽

Conformational Studies ◽

X Ray ◽

H Nmr

A series of syn-[3.3]metacyclophanes (MCPs) containing internal substituted benzyloxy group have been synthesized by the modified TosMIC coupling reaction followed by acid treatment and Wolff–Kishner reduction. anti-Mono- and di-benzyloxy[3.3]MCPs are synthesized by O-benzylation of the corresponding hydroxy[3.3]MCPs, which are obtained by demethylation of methoxy[3.3]MCPs with BBr3 at room temperature. An interesting and intriguing result was obtained when syn-6,15-di-tert-butyl-9-methoxy-18-methyl[3.3]MCP-2,11-dione was treated with TMSI to afford the formation of a dihydrobenzofuran ring by a nucleophilic intramolecular cyclization reaction. The 1H NMR and X-ray analysis of 6a confirms that it adopts a syn (chair–chair) conformation in both solution and solid state.

Download Full-text

Solid state and solution NMR, X-ray and antimicrobial studies of 1:1 and 2:1 complexes of silver(I) cyanide with alkanediamine ligands

Inorganica Chimica Acta ◽

10.1016/j.ica.2007.04.036 ◽

2007 ◽

Vol 360 (12) ◽

pp. 3719-3726 ◽

Cited By ~ 8

Author(s):

Anvarhusein A. Isab ◽

Mohamed I.M. Wazeer ◽

Mohammed Fettouhi ◽

Bassem A. Al-Maythalony ◽

Abdul Rahman Al-Arfaj ◽

...

Keyword(s):

Solid State ◽

Solution Nmr ◽

X Ray ◽

Antimicrobial Studies

Download Full-text

Zinc halide complexes of imidazolidine-2-thione and its derivatives: X-ray structures, solid state, solution NMR and antimicrobial activity studies

Journal of Coordination Chemistry ◽

10.1080/00958970600780965 ◽

2007 ◽

Vol 60 (4) ◽

pp. 369-377 ◽

Cited By ~ 16

Author(s):

Mohammed Fettouhi ◽

Mohamed I. M. Wazeer ◽

Anvarhusein A. Isab

Keyword(s):

Antimicrobial Activity ◽

Solid State ◽

State Solution ◽

Solution Nmr ◽

X Ray ◽

Halide Complexes

Download Full-text

A new modification of [Ag4Br4(PPh3)4]: synthesis, structure and properties

Zeitschrift für Naturforschung B ◽

10.1515/znb-2018-0113 ◽

2018 ◽

Vol 73 (10) ◽

pp. 733-738 ◽

Cited By ~ 1

Author(s):

Xintong Han ◽

Shanshan Mao ◽

Chuang Li ◽

Kesheng Shen ◽

Xinkui Shi ◽

...

Keyword(s):

Solid State ◽

Ir Spectroscopy ◽

Hydrogen Bonds ◽

Elemental Analysis ◽

Supramolecular Structure ◽

Chair Conformation ◽

Cyclic Voltammograms ◽

Structure And Properties ◽

X Ray ◽

X Ray Crystallography

AbstractA new modification of the homometallic silver(I) cluster [Ag4Br4(PPh3)4] has been prepared and characterized by elemental analysis, UV/Vis and IR spectroscopy, and X-ray crystallography. The tetramer shows a polycyclic structure with a chair conformation. The bromine atoms adopt μ2- and μ3-bridging modes. The shortest Ag–Ag distance in the cluster is 3.159(2) Å, which indicates significant Ag–Ag interactions. A supramolecular structure is arranged by hydrogen bonds (C–H···Br). Cyclic voltammograms of the cluster indicate a quasi-reversible Ag+/Ag couple. The fluorescence properties of the ligand and the Ag(I) cluster were studied in the solid state. The emission peaks of the Ag(I) cluster are attributed to ligand-centered luminescence.

Download Full-text

ChemInform Abstract: Synthesis, Solid-State (X-Ray) and Solution (NMR) Studies of the Hydridocarbido Carbonyl Cluster Anion (Re7H2C(CO)21)-.

ChemInform ◽

10.1002/chin.199037264 ◽

1990 ◽

Vol 21 (37) ◽

Author(s):

T. BERINGHELLI ◽

G. D'ALFONSO ◽

G. CIANI ◽

A. SIRONI ◽

H. MOLINARI

Keyword(s):

Solid State ◽

Cluster Anion ◽

Solution Nmr ◽

Carbonyl Cluster ◽

Nmr Studies ◽

X Ray

Download Full-text

Self-association and stereochemistry study of 2-methylthio-, 2-dimethylaminocyclohexanone oximes and the parent cyclohexanone oxime

Acta Crystallographica Section B Structural Science ◽

10.1107/s0108768101009624 ◽

2001 ◽

Vol 57 (5) ◽

pp. 705-713 ◽

Cited By ~ 7

Author(s):

Paulo R. Olivato ◽

Douglas S. Ribeiro ◽

J. Zukerman-Schpector ◽

Gabriella Bombieri

Keyword(s):

Hydrogen Bond ◽

Solid State ◽

Parent Compound ◽

Chair Conformation ◽

Orbital Interaction ◽

Cyclohexanone Oxime ◽

X Ray Diffraction ◽

X Ray ◽

Shift Analysis ◽

Self Association

X-ray diffraction analyses of 2-substituted cyclohexanone oximes C5H9(X)C=NOH [X = SMe (1), NMe2 (2)] and of the parent compound [X = H (3)] showed that their cyclohexyl rings are in a slightly distorted chair conformation. These compounds assume in the solid state the (E) configuration bearing the 2-substituents in the axial conformation. Compounds (1) and (2) exist as dimeric and polymeric hydrogen-bond associates, respectively. Low-temperature X-ray analysis of the cyclohexanone oxime (3) showed that the molecules are associated forming two independent trimers. The dimer in (1) and the trimer in (3) are built up via [O—H...N=C] hydrogen bonds, while the polymer of (2) is via the [OH...NMe2] hydrogen bond. The comparative IR νOH and νC=N analysis of the title compounds, in the solid state and in CCl4 solution, fully supports the nature of the associates for (1)–(3) obtained by X-ray diffraction. The IR azomethyne frequency shift analysis (ΔνC=N) also suggests the occurrence of the πC=N/σ*C—X orbital interaction which stabilizes the axial conformations of (1) and (2).

Download Full-text

3-Benzoyl-4-hydroxy-2,4,6-triphenylcyclohexane-1,1-dicarbonitrile

Acta Crystallographica Section E Structure Reports Online ◽

10.1107/s1600536806012086 ◽

2006 ◽

Vol 62 (5) ◽

pp. o1766-o1767

Author(s):

Liang-Ce Rong ◽

Xiao-Yue Li ◽

Fang Yang ◽

Hai-Ying Wang ◽

Da-Qing Shi

Keyword(s):

Title Compound ◽

Chair Conformation ◽

Solvent Free ◽

Cyclohexane Ring ◽

X Ray ◽

Compound C ◽

Solvent Free Conditions

The title compound, C33H26N2O2, was synthesized by the reaction of chalcone with malononitrile under solvent-free conditions at 353 K. X-ray analysis reveals that the cyclohexane ring adopts a chair conformation.

Download Full-text