Molecular structure of opiate alkaloids. Part I. Crystal structure of two 16-alkyl analogues of thebaine and oripavine

1988 ◽  
Vol 66 (10) ◽  
pp. 2498-2505 ◽  
Author(s):  
André G. Michel ◽  
M. Proulx ◽  
G. Evrard ◽  
B. Norberg ◽  
E. Milchert
Keyword(s):  
Molecular Structure ◽  
Crystal Structures ◽  
Intramolecular Hydrogen Bonding ◽  
Opiate Receptor ◽  
Ring System ◽  
Agonist Activity ◽  
High Potency ◽  
Alkyl Substitution ◽  
Intramolecular Hydrogen ◽  
Very High

The crystal structures of two 16-alkyl thebaine and oripavine analogues are described, in an attempt to put forward the particular requirements of these compounds to interact with the opiate receptor. Conformational congruencies accounting for the very high potency of these compounds are also emphasized.In light of the crystal structures, the influence of the 16-alkyl substitution is discussed, as well as the differentiation in the agonist activity observed between diastereomers at C(19) characterizing these classes of opioids.Significant distortions in the condensed ring system and the existence of an intramolecular hydrogen bonding are the main geometrical observations. They are invoked to account for particular modulations in the analgesic activity.

Molecular and crystal structure of azadirachtin-H

1996 ◽  
Vol 52 (1) ◽  
pp. 145-150 ◽  
Author(s):  
T. R. Govindachari ◽  
Geetha Gopalakrishnan ◽  
S. S. Rajan ◽  
V. Kabaleeswaran ◽  
L. Lessinger
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Intramolecular Hydrogen Bonding ◽  
Hydroxyl Group ◽  
Inhibiting Activity ◽  
Nmr Studies ◽  
Rotation Axes ◽  
Intramolecular Hydrogen ◽  
Azadirachtin A

Azadirachtin-H, isolated from the seed kernels of Azadirachta indica (neem), crystallizes in space group I4, Z = 8, with disordered ethyl acetate solvent filling channels along the fourfold rotation axes. The crystal structure determination showed that the previously reported molecular structure deduced from NMR studies was correct except for the stereochemistry at C(11). Azadirachtin-H, which belongs to a group of C-seco-tetranortriterpenoids (C-seco-limonoids) of great interest for their insect antifeedant and ecdysis-inhibiting activity, has some unusual features: the absence of a carbomethoxy group at C(11); the presence of a cyclic hemiacetal function at C(11); the α-orientation of the hydroxyl group on C(11), opposite to that in all other known azadirachtins with a hydroxyl group on C(11), except azadirachtin-I. There is no intramolecular hydrogen bonding. In this crystal the rotation of the two major moieties of the azadirachtin-H molecule about the single connecting C(8)—C(14) bond is quite different from that in azadirachtin-A, whose crystal structure has recently been determined.

Molecular Structure and Photoinduced Intramolecular Hydrogen Bonding in 2-Pyrrolylmethylidene Cycloalkanones

2015 ◽  
Vol 80 (21) ◽  
pp. 10521-10535 ◽  
Author(s):  
Mark Sigalov ◽  
Bagrat Shainyan ◽  
Nina Chipanina ◽  
Larisa Oznobikhina ◽  
Natalia Strashnikova ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Hydrogen Bonding ◽  
Intramolecular Hydrogen Bonding ◽  
Intramolecular Hydrogen

Two terphenyl-based diol hosts and corresponding solvent inclusions with dimethylformamide and acetonitrile

2015 ◽  
Vol 71 (9) ◽  
pp. 768-775
Author(s):  
Hendrik Klien ◽  
Wilhelm Seichter ◽  
Konstantinos Skobridis ◽  
Edwin Weber
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Structures ◽  
Solvent Molecule ◽  
Intramolecular Hydrogen Bonding ◽  
Host Lattice ◽  
Solvent Free ◽  
Guest Molecules ◽  
Solvent Molecules ◽  
Intramolecular Hydrogen ◽  
Supramolecular Aggregates

Having reference to an elongated structural modification of 2,2′-bis(hydroxydiphenylmethyl)biphenyl, (I), the two 1,1′:4′,1′′-terphenyl-based diol hosts 2,2′′-bis(hydroxydiphenylmethyl)-1,1′:4′,1′′-terphenyl, C44H34O2, (II), and 2,2′′-bis[hydroxybis(4-methylphenyl)methyl]-1,1′:4′,1′′-terphenyl, C48H42O2, (III), have been synthesized and studied with regard to their crystal structures involving different inclusions,i.e.(II) with dimethylformamide (DMF), C44H34O2·C2H6NO, denoted (IIa), (III) with DMF, C48H42O2·C2H6NO, denoted (IIIa), and (III) with acetonitrile, C48H42O2·CH3CN, denoted (IIIb). In the solvent-free crystals of (II) and (III), the hydroxy H atoms are involved in intramolecular O—H...π hydrogen bonding, with the central arene ring of the terphenyl unit acting as an acceptor. The corresponding crystal structures are stabilized by intermolecular C—H...π contacts. Due to the distinctive acceptor character of the included DMF solvent species in the crystal structures of (IIa) and (IIIa), the guest molecule is coordinated to the hostviaO—H...O=C hydrogen bonding. In both crystal structures, infinite strands composed of alternating host and guest molecules represent the basic supramolecular aggregates. Within a given strand, the O atom of the solvent molecule acts as a bifurcated acceptor. Similar to the solvent-free cases, the hydroxy H atoms in inclusion structure (IIIb) are involved in intramolecular hydrogen bonding, and there is thus a lack of host–guest interaction. As a result, the solvent molecules are accommodated as C—H...N hydrogen-bonded inversion-symmetric dimers in the channel-like voids of the host lattice.

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