The role of water release from the cyclodextrin cavity in the complexation of benzoyl chlorides by dimethyl-β-cyclodextrin

The influence of temperature on the solvolysis of substituted benzoyl chlorides in the presence of dimethyl-β-cyclodextrin (DM-β-CD) was studied. Based on the influence of the DM-β-CD concentration on chemical reactivity in this process, the cyclodextrin has a catalytic effect on the solvolysis of 4-nitrobenzoyl chloride (4-NO₂) but an inhibitory effect on that of 4-methoxy-(4-MeO), 3-chloro-(3-Cl) and 3-trifluoromethyl-(3-CF₃) benzoyl chlorides. These disparate effects are related to a difference in reaction mechanism; thus, DM-β-CD catalyses associative solvolysis and inhibits dissociative solvolysis. Examining the influence of temperature on the solvolytic process allowed the stoichiometry of the host-guest complexes formed to be established. The formation constants for the complexes of meta-substituted benzoyl chlorides increased with increasing temperature. On the other hand, the equilibrium formation constants for the 1:1 host-guest complexes of para-substituted benzoyl chlorides exhibited the opposite trend. The equilibrium formation constant for 2:1 host-guest complexes for the para-substituted benzoyl chlorides increased with increasing temperature. These differences are ascribed to the release of water from the DM-β-CD cavity during the formation of the host-guest complex.     

Carbon-13 NMR of quinone methides

The ¹³C NMR spectra of four ortho- and seven para-quinone methides were assigned using chemical shift and long-range carbon-proton coupling information. The carbonyl shifts are compared with those in ortho- and para-benzoquinones. The chemical shifts of the carbonyls of the p-quinone methides are observed at δ 186.2–186.4 for the three ortho-di-tert-butyl-substituted compounds and at δ 180.7–181.5 for the four ortho-oxy-substituted compounds. In the three o-quinone methides with meta, para-dioxy substituents, the carbonyl signals are at δ 184.2–185.4. The carbonyl signal of the one o-quinone methide with no oxygen substitution is shifted downfield to δ 200.9, apparently as a result of hydrogen bonding to the nearby hydroxyl.     

Chemical ionization mass spectra of mononitroarenes

The H₂ and CH₄ chemical ionization mass spectra of a selection of substituted nitrobenzenes have been determined. It is shown that reduction of the nitro group to the amine is favoured by high source temperatures and the presence of water in the ion source. The H₂ chemical ionization mass spectra are much more useful for distinguishing between isomeric compounds than the CH₄ CI mass spectra because of the more extensive fragmentation. For ortho substituents bearing a labile hydrogen abundant [MH ? H₂O]⁺ fragments are observed. When the substituent is electron-releasing both ortho and para substituted nitrobenzenes show abundant [MH? OH]⁺ fragment ions while meta substituted compounds show abundant loss of NO and NO₂ from [MH]⁺. The latter fragmentation is interpreted in terms of protonation para to the substituent or ortho to the vitro function, while the first two fragmentation routes arise from protonation at the nitro group. When the substituent is electron-attracting the chemical ionization mass spectra of isomers are very similar except for the H₂O loss reaction for ortho compounds.     

Preparation and characterization of 16-benzoylated tetraaza[14]annulenes

The condensation reaction between tetraaza[14]annulene ( 1 ) and a series of para-substituted benzoyl chlorides led to the 16-benzoylated corresponding products in 13–21% yields, but 1 was unreactive with alkyl acid chlorides and easily cleaved in macrocyclic framework. The mass spectra show the presence of molecular ion peaks which support the 16-benzoylated products. A strong ir band due to the C = N stretching mode of the macrocyclic moiety was observed at 1610 cm^?1 and shifted slightly toward higher energy upon benzoylation. An intense ir band which was associated with a C = 0 stretching mode was newly observed at 1640 cm¹. The very strong absorption band about 29000 cm^?1 was attributed to the π ? π* transition and gave a slight shift to higher frequency on benzoylation. All proton signals except for methyl protons exhibit downfield shifts due to the deshielding effect of the substituted benzene ring, but the methyl proton peaks show upfield shifts due to the shielding effect caused by the magnetic anisotropy of the substituted benzene ring. The ¹³C nmr result is also in accord with that of ¹H nmr.     

17O NMR studies of ortho‐substituent effects in substituted phenyl tosylates

¹⁷O NMR spectra for 35 ortho‐, para‐, and meta‐substituted phenyl tosylates (phenyl 4‐methylbenzenesulfonates), 4‐CH₃‐C₆H₄SO₂OC₆H₄‐X, at natural abundance in acetonitrile at 50 °C were recorded. The ¹⁷O NMR chemical shifts, δ(¹⁷O), of the sulfonyl (SO₂) and the single‐bonded phenoxy (OPh) oxygens for para and meta derivatives correlated well with dual substituent parameter treatment using the Taft inductive, σ_I, and resonance, σº_R, constants. The influence of ortho substituents on the sulfonyl oxygen and the single‐bonded phenoxy oxygen chemical shifts, δ(¹⁷O), was found to be nicely described by the Charton equation: δ(¹⁷O)_ortho = δ(¹⁷O)_H + ρ_Iσ_I + ρ_Rσ°_R + δE_s^B when the data treatment was performed separately for electron‐donating +R substituents and electron‐attracting ?R substituents. Electron‐attracting meta and para substituents in the phenyl moiety caused deshielding while the electron‐donating meta, para and ortho +R substituents produce shielding effects on the sulfonyl (SO₂) and single‐bonded phenoxy (OPh) oxygens. The influence of ortho inductive and resonance effects in the case of +R substituents was found to be approximately twice higher than the corresponding influence from the para position. Due to the steric effect of ortho substituents a decrease in shielding of the oxygens at the sulfonyl group (δE_s^B > 0, E_s^B < 0) was detected. Copyright © 2012 John Wiley & Sons, Ltd.     

Efficient NMR enantiodiscrimination of bridge fluorinated paracyclophanes using lanthanide tris β-diketonate complexes

A selection of amino-substituted 1,1,2,2,9,9,10,10 octafluoro[2.2]paracyclophanes were tested for enantiodiscrimination by ¹H and ¹⁹F NMR spectroscopy via their interaction with different lanthanide tris β-diketonate chiral shift reagents. The amino-, and the pseudo-ortho di-amino substituted octafluoro[2.2]paracyclophanes, both of which exhibit planar chirality, revealed significant shifts and splittings of various ¹H and ¹⁹F NMR signals upon the addition of the chiral shift reagents, which allowed the easy determination of the enantiomeric purity. When the chiral shift reagent was added to an inseparable mixture of the (chiral) pseudo-meta, and (achiral) pseudo-para diamino analogues, both the chiral and achiral molecules revealed NMR doubling. In the case of the achiral molecule, this NMR behavior is due to the meso nature of the pseudo-para species.     

Degradation thermique des trois isomeres Ortho,meta, para du polymethoxymethylstyrene

A kinetic study of the overall thermal decomposition of the three isomers (ortho, meta and para) of polymethoxymethylstyrene has been carried out. The reaction order is one over a wide interval of mass loss, for the meta and para polymers; there is no order for the first one. The corresponding activation energy has been calculated as 32.5 kcal mol⁻¹ for the meta polymer and 31 kcal mol⁻¹ for the para polymer.The volatile compounds, identified by gas chromatography coupled with mass spectrometry, are chiefly monomers. The thermal decomposition reaction is probably a depolymerization reaction coupled with crosslinking for the meta and para isomers.     

(Trifluoromethoxy)Phenylboronic Acids: Structures,Properties, and Antibacterial Activity

Three isomers of (trifluoromethoxy)phenylboronic acids were studied in the context of their physicochemical, structural, antimicrobial and spectroscopic properties. They were characterized by ¹H, ¹³C, ¹¹B and ¹⁹F NMR spectroscopy. The acidity of all the isomers was evaluated by both spectrophotometric and potentiometric titrations. The introduction of the -OCF₃ group influences the acidity, depending, however, on the position of a substituent, with the ortho isomer being the least acidic. Molecular and crystal structures of ortho and para isomers were determined by the single crystal XRD method. Hydrogen bonded dimers are the basic structural motives of the investigated molecules in the solid state. In the case of the ortho isomer, intramolecular hydrogen bond with the -OCF₃ group is additionally formed, weaker, however, than that in the analogous -OCH₃ derivative, which has been determined by both X-Ray measurements as well as theoretical DFT calculations. Docking studies showed possible interactions of the investigated compounds with LeuRS of Escherichia coli. Finally, the antibacterial potency of studied boronic acids in vitro were evaluated against Escherichia coli and Bacillus cereus.     

σ,π-conjugation and 199Hg shielding constants in benzyl derivatives of mercury

The ¹⁹⁹Hg chemical shifts in a number of benzylmercuric chlorides containing methyl substituents in various positions of the benzene nucleus are studied by the heteronuclear ¹H-{¹⁹⁹Hg} double resonance technique. Meta- and para-methyl substituents are shown to have no pronounced action on the shielding whereas ortho-methyl groups each shift the signal by 30 ppm downfield. The observed effect is due to an increase in the population of conformers with the CHg bond lying out of the aromatic cycle plane. The departure from planarity favours conjugation between the electrons of the CHg bond and the π-electronic system of the ring. The J(¹H¹⁹⁹Hg) and J(¹³C¹⁹⁹Hg) coupling constant values obtained in this work confirm the latter conclusion.     

Theoretical and experimental interpretations of phenol oxidation by the hydroxyl radical

Phenol oxidation by OH radicals produced by the Fenton reaction was studied and the oxidation process was monitored by the UV–visible, ¹³C NMR and LC techniques. The results show that benzoquinone is formed. In the NMR and LC experiments, since the peaks corresponding to isomers ortho and para- benzoquinones are unresolved, DFT was used to determine the branching ratios of the isomers formation that coincides with their ΔG values (ortho > para > meta): 72% for ortho, 23% for para and 5.0% for meta. Furthermore, the energy profile of the OH attack at ortho is quite similar to that at the para position while the meta position attack is less favored by 2.0 kcal/mol.     

Regiospecific oxidation of polycyclic aromatic phenols to quinones by hypervalent iodine reagents

The hypervalent iodine reagents o-iodoxybenzoic acid (IBX) and bis(trifluoro-acetoxy)iodobenzene (BTI) are shown to be general reagents for regio-controlled oxidation of polycyclic aromatic phenols (PAPs) to specific isomers (ortho, para, or remote) of polycyclic aromatic quinones (PAQs). The oxidations of a series of PAPs with IBX take place under mild conditions to furnish the corresponding ortho-PAQs. In contrast, oxidations of the same series of PAPs with BTI exhibit variable regiospecificity, affording para-PAQs where structurally feasible and ortho-PAQs or remote PAQ isomers in other cases. The structures of the specific PAQ isomers formed are predictable on the basis of the inherent regioselectivities of the hypervalent iodine reagents in combination with the structural requirements of the phenol precursors. IBX and BTI are recommended as the preferred reagents for regio-controlled oxidation of PAPs to PAQs.     

A comparative study between para‐aminophenyl and ortho‐aminophenyl benzothiazoles using NMR and DFT calculations

Ortho‐substituted and para‐substituted aminophenyl benzothiazoles were synthesised and characterised using NMR spectroscopy. A comparison of the proton chemical shift values reveals significant differences in the observed chemical shift values for the NH protons indicating the presence of a hydrogen bond in all ortho‐substituted compounds as compared to the para compounds. The presence of intramolecular hydrogen bond in the ortho amino substituted aminophenyl benzothiazole forces the molecule to be planar which may be an additional advantage in developing these compounds as Alzheimer's imaging agent because the binding to amyloid fibrils prefers planar compounds. The splitting pattern of the methylene proton next to the amino group also showed significant coupling to the amino proton consistent with the notion of the existence of slow exchange and hydrogen bond in the ortho‐substituted compounds. This is further verified by density functional theory calculations which yielded a near planar low energy conformer for all the o‐aminophenyl benzothiazoles and displayed a hydrogen bond from the amine proton to the nitrogen of the thiazole ring. A detailed analysis of the ¹H, ¹³C and ¹⁵N NMR chemical shifts and density functional theory calculated structures of the compounds are described. Copyright © 2014 John Wiley & Sons, Ltd.     

Solution structure of bis(acetoxy)iodoarenes as observed by O NMR spectroscopy

A group of para-substituted bis(acetoxy)iodoarenes has been studied by ¹⁷O and ¹³C NMR. Only one signal for all the oxygens of the acetoxy groups has been observed. Both ¹⁷O and ¹³C chemical shifts of this group show a strong invariance with para substitution. The absence of covalent I-O bonds and an ion pair structure is proposed for the title compounds.     

Ortho effects in mass spectrometric fragmentation processes

The mass spectra of the phenylhydrazones and 2,4-dinitrophenylhydrazones of ortho substituted benzaldehydes and acetophenones (X = I, Br, Cl, OCH₃, OH) show characteristic [M ? X]⁺ ions which allow the ortho derivatives to be distinguished from their meta and para isomers.     

Electronic effects in the cyclopentadienyl ring. The 13C NMR spectraof monosubstituted ferrocenes

The chemical shifts of C(2,5) and C(3,4) carbons in the ¹³C NMR spectra of monosubstituted ferrocenes have been assigned using deuterium labelling. An analogy is observed between the shielding of C(2,5) and C(3,4) carbons of ferrocene derivatives and ortho- and para-carbons of benzene derivatives withthe same substituents. Electron-density distribution in the cyclopentadienyl ring is discussed on the basis of ¹³C NMR data.     

Metallation reactions. Part 35: A change of the regiochemistry in the metallation of (alkylthio)arenes

The metallation reaction of bromo(alkylthio)benzenes is described. The results show the complementarity of these reactions with the metal-hydrogen exchange reaction. In fact, monometallation of bromo(methylthio)benzenes afforded products substituted in para or meta or ortho to the thioethereal function while bimetallation led to αS,para, αS,meta and αS,ortho disubstituted products. Analogously, the monometallation of 4-bromo-(isopropylthio)benzene afforded para-monosubstituted and ortho,para-disubstituted products.     

Separating Para and Ortho Water

Water exists as two nuclear‐spin isomers, para and ortho, determined by the overall spin of its two hydrogen nuclei. For isolated water molecules, the conversion between these isomers is forbidden and they act as different molecular species. Yet, these species are not readily separated, and no pure para sample has been produced. Accordingly, little is known about their specific physical and chemical properties, conversion mechanisms, or interactions. The production of isolated samples of both spin isomers is demonstrated in pure beams of para and ortho water in their respective absolute ground state. These single‐quantum‐state samples are ideal targets for unraveling spin‐conversion mechanisms, for precision spectroscopy and fundamental symmetry‐breaking studies, and for spin‐enhanced applications, for example laboratory astrophysics and astrochemistry or hypersensitized NMR experiments.     

Analysis of the 13C-n.m.r. spectra of mono- and dimethylamphetamines

The ¹³C-n.m.r. spectra of the three monomethylainphetainines and the six dimethyl-amphetanunes and their hydrochlorides were determined. Spectra were distinctive and suitable for identification and authentication purposes. Signals were assigned by a self-consistent analysis of chemical shift differences between differently-substituted compounds in the series of both the bases and the salts. Determination of the effects of N-protonation on the chemical shifts of aromatic ¹³C signals was a valuable aid in resolving some ambiguities: C-1 shifted upfield by about 0.9 ppm, and methylated carbons ortho, meta, and para to the isopropylamine side-chain shifted downfield by about 3.3, 3.7, and 4.4 ppm, respectively. The data are useful in the authentication of reference materials employed in forensic analysis.     

Radical copolymerization of methyl 2-chloroacrylate with carbonyl-containing phenyl methacrylates

New chlorinated and carbonyl-containing polymethacrylates were prepared via the radical copolymerization of methyl 2-chloroacrylate with ortho- and para-acetylphenyl methacrylates or ortho- and para-formylphenyl methacrylates. It was shown that the reactivity ratios and the yields of copolymers of the ortho phenyl methacrylate isomers are lower than those for the corresponding para isomers because to the steric hindrance created by the substituents on the phenyl ring. Some mechanical parameters (ultimate tensile strength, compressive strength, flexural strength, and the Vicat softening point) of the copolymers are better than those of poly(methyl methacrylate).     

Synthesis and spectroscopic properties for six 7,16-dibenzoylated tetraaza[14]annulene nickel(II) complexes

The condensation reaction between tetraaza[14]annulene nickel(II) complex and a series of para-substituted benzoyl chlorides gave the corresponding 7,16-dibenzoylated products in 53–98% yields. The mass spectra exhibit molecular ion peaks ascribed to the 7,16-dibenzoylated products. The intense ir band due to the C?O stretching mode in these nickel(II) complexes is present in the 1650–1658 cm^?1 range upon the benzoylation. Even though the ligand moiety of these six complexes is changed by benzoylation, the electronic spectra hardly vary. These nickel(II) complexes assume roughly the square-planar coordinations as judged by the ligand-field transition bands. The olefinic proton peaks at the 7- and 16-positions vanish on benzoylation in the proton nmr spectra and the proton signals of the para-substituted benzoyl groups are observed in the 2.4–8.4 ppm region. The results of the carbon-13 nmr spectra are compatible with those for the proton nmr spectra.