The 1H NMR spectra of exo- and endo-3-thiatricylo[4.2.1.02,5]non-7-ene 3,3-dioxide. The shielding effect of the sulfone group

The proton spectra of exo- and endo-3-thiatricyclo[4.2.1.0^2,5]non-7-ene 3,3-dioxide have been analysed and completely assigned. Considerations of coupling constants indicate that the thietane ring is nonplanar and that the norbornene residue is significantly distorted from the geometry of norbornene itself. The sulfone group induces significant changes in the shielding of the proximate olefinic proton in the endo isomer and the bridge protons in the exo isomer. These shifts appear to be the result of the electrostatic effects and effects associated with the diagmagnetic anisotropy of the sulfone group.     

An NMR study of 2-alkoxy-1,3,2-dioxaphospholanes. I—13C chemical shifts

Measurements of the ¹³C chemical shifts of 2-alkoxy-1,3,2-dioxaphospholanes have allowed the determination of the contribution of the substituent to the α-, β- and γ-carbon chemical shifts of attached alkyl groups. The preliminary assignments of the signals were made using the following information; relative intensities, variations in coupling constants J(³¹P¹³C) and the existence of linear correlations between the shifts of carbon atoms in the P-alkoxy groups and the degree of substitution of the observed carbon or of its neighbours.     

13C, 13C coupling constants in phenyl substituted ethylene,naphthalene, phenanthrene and cyclopentadienone. Dependence on dihedral angles. Determination of signs by the symmetrical double labelling (SDL) method. IV

Carbon-13, carbon-13 coupling constants and carbon-13 chemical shifts have been measured in a series of phenyl substituted ethylenes and aromatics all doubly labelled with ¹³C at the olefinic positions (α,β-) or at neighbouring aromatic positions, tetraphenylcyclopentadienone labelled at the 3,4-positions, and dichlorodiphenylmethane labelled at the α-carbon. Signs of coupling constants were determined by the symmetrical double labelling (SDL) method. Coupling constants over as many as five bonds are reported. Two-bond couplings between carbons in the aromatic skeleton belong to different classes according to the nature of the coupling path. The magnitudes of three-bond coupling constants between such carbons correlate linearly with π-bond orders and a separation of the δ- and π-contributions is evident. The three-bond couplings between the 2-position in a phenyl substituent and the olefinic β-position or a corresponding aromatic position depend on the out-of-plane twist of the phenyl ring and may lead to information about the twist angle. Contrary to findings with aromatic carbonyl compounds two- and three-bond couplings to the α-carbon in the present compounds are fairly constant. The reported data suggest that the signs of coupling constants over more than two bonds alternate in aromatic systems. Carbon-13, carbon-13 coupling constants in naphthalene have been calculated by the INDO-SOS method.     

Fluorine-containing carbocations. III. Alkylation of polyfluorobenzenes with polyfluorinated α,α-difluorobenzyl cations and generation of polyfluorinated α-fluorodiphenylmethyl cations

Alkylation of incompletely fluorinated benzenes with polyfluorinated α,α-difluorobenzyl cations in an SbF₅ medium results in the formation of polyfluorinated α-fluorodiphenylmethyl cations whose precursors are the primary products of alkylation, i.e. the corresponding polyfluorinated α,α-difluorodiphenylmethanes. The influence of substituents on the ¹⁹F chemical shifts and spin-spin coupling constants J(FF) has been analysed in terms of their effects on contributions of the resonance structures controlling the positive charge distrubution on the coplanarity of the phenyl rings and the plane of the α-carbon bonds.     

Scope and Limitations in the Use of α-Silyl and α-Stannyl Sulfones as Latent α-Sulfonyl Anions

Three methods for the regeneration of α-sulfonyl anions from α-silyl sulfones and α-stannyl sulfones are investigated. These methods include: (1) treatment of α-silyl sulfones with electrophiles (aldehydes and acid halides) in the presence of fluoride ion; (2) reaction of α-silyl sulfones with n-butyllithium which produces an α-silyl anion via a migration of the -SiMe₃ group from the α-position to the ortho-position of the phenyl sulfones; and (3) direct transmetalation of α-stannyl sulfone by treatment with n-butyllithium. The addition of cerium [III] chloride is shown to substantially decrease enolization problems associated with addition of α-sulfonyl anions to carbonyl compounds bearing enolizable protons.     

Carbon-13 NMR spectra of DDT,its analogues and related compounds

Carbon-13 NMR spectra of mono- and disubstituted aromatic compounds including DDT, its analogues, homologues, derivatives and certain model compounds have been studied. The Savitsky scheme of carbon chemical shifts in disubstituted benzenes is applicable to these compounds. The data obtained show that in mono- and disubstituted aromatic compounds containing two different substituents in the α- and β-positions of the side chain, the substituted ring carbon atom shifts follow the additivity rule and can be calculated from substituent increments. Mutual effects of substituents in the ring and in the side chains are analysed. The chlorine atoms in α-position to the phenyl ring give rise to an additive α-effect of about 25 ppm, as in perchloroalkanes. The influence of a β-chlorine atom in the side chain on the substituted carbon atom in the ring is, however, only 3 ppm as against the usual value of about 10 ppm for the β-effect in alkyl chains. Moreover, the first β-chlorine substituent has no noticeable influence on the substituted ring carbon chemical shift: the effect of 3 ppm is transferred to the para-carbon atom almost without attenuation. The ring substituted carbon atom signal shifts caused by the γ-effect of chlorine in the side chain are similar to those observed in aliphatic chains. The ortho-chlorine substituents shift the side chain α-carbon atom signal by 3.6-5.2 ppm to high field compared to para-chlorophenyl compounds. This is similar to the chlorine γ-effect in aliphatic chains.     

13C NMR spectra of a number of penta- and hexacyclic triterpenoids derived from glycyrrhetic acid

The¹³C NMR spectra of 22 derivatives of 18α- and 18β-glycyrrhetic acids that have been investigated and an assignment of the signals has been made. It has been shown that a modification of the carboxy group of glycyrrhetic acid leads mainly to a change in the chemical shifts of the α-, β-, and γ-carbon atoms of ring E. The assignment of a number of signals has been confirmed by the use of the shift reagent Eu(fod)_s. It has been established that the C₂₈ and C₁₆ signals are the most sensitive to a change in the C₁₈ configuration in the spectra of glycyrrhetic acid derivatives.

     

Isoprene functionalisation : Chlorination of C10-isoprenoid sulfones with hexachloro-ethane

Lithiation of the sulfones 1–3 in THF at ?78° with lithium diisopropyl amide (LDA) is regioselective, since deuteration of the α-lithiosulfone 4 results in formation of the α-monodeuteriated sulfone 7. Higher temperature causes an intramolecular 1,4-addition of the lithiated sulfone 4 to the lithiated cyclic sulfone 19 and an intermolecular 1,4-addition of the lithiated sulfones 5 and 6. The cyclisation of Z-sulfone 1 has been used for the isolation of the isomeric E-sulfone 2 from mixtures of 1 and 2. The lithiated sulfones 4–6 are chlorinated with hexachloroethane (HCE). Due to acid/base reactions the α,α-dichlorinated cyclic sulfone 23 and α,α'-dichlorinated butadienyl sulfones 13–15 are formed in small amounts.     

1H and 13C NMR of platinum porphyrins—II. Platinum complexes of meso-tetrakis(3,5-di-t-butyl-4-hydroxyphenyl) porphyrin and 2,3,7,8,12,13,17,18-octaethylporphyrin

The ¹H and ¹³C NMR spectra of the title compounds are reported. In both porphyrins, long-range spin-spin coupling is observed between platinum and the porphyrin protons and carbon atoms. Two-bond Pt-“α-pyrrole” carbon couplings are less than the three-bond Pt-“fβ-pyrrole” carbon and Pt-“meso-carbon” couplings. Also, large upfield shifts of the pyrrole α-carbon resonances are noted. The coupling mechanism appears to proceed via Fermi contact through the porphyrin σ-framework for the carbons, and the π-system for the protons.     

About the structure of phosphorus ylids: Electron distribution and geometry

Using ¹³C-chemical shifts as a probe for the electronic environment of carbon centers, triphenylphosphoniomethanide, the model case of a “reactive” phosphorus ylid, was found to have much more zwitterion than PC double bond character (resonance structure 1a being dominant). Triphenylphosphonio-propenide (“triphenylphosphonium-allylid”), a “moderated” ylid, accumulates electron excess mainly at the α-carbon atom (resonance structure 6a being dominant) whereas triphenylphosphonio-ethenoate (formyl-methylene-triphenylphosphorane) and other “stabilized” ylids carry roughly equal fractions of negative charge at the α-carbon and the oxygen atom (resonance formulas a and b being of comparable importance). The one-bond C,H coupling constant of triphenylphosphonio-methanide ( 1 ) argues against a perfectly planar ylid center. The three-bond P,C coupling constants permit the assignment of endo- or exo-configurations to ylids having an allyl-type side-chain.     

Polymerization of thietane

Grignard reagent-initiated polymerization of thietane gave a soluble crystalline polymer melting at 59°C. Oxidation of the polymer with one or two equivalents of hydrogen peroxide gave the sulfoxide and sulfone, respectively. The sulfoxide was noncrystalline and insoluble in all common solvents at room temperature and softened at 185–200°C. The sulfone was partially crystalline and insoluble.     

Studies in tertiary amine oxides part II—carbon-13 nuclear magnetic resonance spectra of selected acetylenic amines,their N-oxides and the Meisenheimer rearrangement products

Carbon-13 NMR chemical shifts and ¹J(CH), ²J(CH) and ³J(CH) coupling constants of selected saturated nitrogen heterocyclic molecules containing the acetylenic moiety have been determined. These NMR parameters have also been determined for the corresponding N-oxides and the Meisenheimer rearrangement products, the O-allenylhydroxylamines. The effect of the N-oxidation on the chemical shifts of the ring and the acetylenic carbon atoms is discussed.     

15N-NMR. Studies of Aminopyridines,Aminopyrimidines and of Some Diazine N-Oxides

¹⁵N-NMR. spectra of mono- and diaminopyridines, and mono-, di- and triaminopyrimidines including trimethoprim and other dihydrofolate reductase inhibitors have been studied in neutral and acidic media. Complete chemical shift assignments are given. Ring-nitrogen shifts are discussed in terms of β-, χ- and δ-substituent effects of amino and alkyl groups. Protonation states in TFA- and FSO₃H-solution and protonation increments for the ¹⁵N-shifts of ring and amino N-atoms are determined. A linear correlation is observed between amino substituent effects (Δδ(¹⁵N)) on the ring N-atom in aminopyridines and corresponding Δδ (¹³C) values in aminobenzenes and, similarly, between Δδ(¹⁵N) values in aminopyrimidines and Δδ(¹³C) values in aminopyridines. Assignment of the ¹⁵N-NMR. spectra of pyrimidine N-oxides, pyrazine N-oxides and pyridazine N-oxides is achieved by comparison with ¹⁴N-NMR. data and with the aid of Yb(fod)₃-induced shifts. One-bond ¹⁵N, ¹H-coupling constants are reported for aminopyridines and aminopyrimidines and discussed in terms of conjugative interaction between NH₂-group and ring system.     

Cationic polymerization of α,β-disubstituted olefins. VI. Steric structure of poly(methyl propenyl ether) obtained by cationic catalysts

The steric structure of poly(methyl propenyl ether) obtained by cationic polymerization was studied by NMR spectra. From the analysis of β-methyl and α-methoxyal spectra, it was found that the tacticities of the α-carbon were different from those of the β-carbon in all polymers obtained. In the crystalline polymers obtained from the trans isomer by homogeneous catalysts, BF₃·O(C₂H₅)₂ or Al(C₂H₅)Cl₂, and from the cis isomer by a heterogeneous catalyst, Al₂(SO₄)₃–H₂SO₄ complex, the structure of polymers was threo-di-isotactic. Though the configurations of all α-carbons were isotactic, a small amount of syndiotactic structure was observed in the β-carbon. On the other hand, in the amorphous polymer obtained from cis isomer by the homogeneous catalyst, the configuration of the α-carbon was isotactic, but that of the β-carbon was atactic. These facts suggest that the type of opening of a monomeric double bond is complicated, or that carbon–carbon double bond in an incoming monomer rotates in the transition state. From these experimental results, a probability treatment was proposed from the diad tacticity of α,β-disubstituted polymers. It shows that the tacticity is decided by a polymerization mechanism different from that proposed by Bovey.     

Chemistry of trifluorostyrenes and their dimers: 2. Synthesis of substituted α, β, β-trifluorostyrenes and α, β, β-trifluoroethenylnaphthalenes. Hammett correlations of their NMR parameters and the concept of “distorted π-electron clouds”

Six α, β, β-trifluorostyrenes with the following substituents, viz., p-MeO, p-Me, m-Me, p-Cl, m-Cl, and m-CF₃, were synthesized by the reaction of the corresponding Grignard reagents with tetrafluoroethylene in tetrahydrofuran. Similarly, α-and β-trifluoroethenylnaphthalenes were prepared. The substituent electronic effects on the ¹⁹F-NMR parameters were investigated for the trifluorostyrenes (I). Linear correlations between the Hammett σ constants and the following ¹⁹F-NMR parameters were established, namely, chemical shifts δ. (F¹) and δ (F²), coupling constants J₁₂, differences of chemical shifts Δδ_3-1 (δ (F³)—δ(f¹) or Δδ_3-2. The results are consistent with previous expectations based on the simple concept of “distorted π-electron clouds”. Facts are presented which indicate that the Δδ_3-1 (or Δδ_3-2) values may serve as empirical measures of the degree of polarization of the π bonds of these fluoroolefins.     

Allylic Sulfones Containing Triene Moieties as Key Synthons for Carotenoid Synthesis

An efficient synthetic method for the allylic sulfone 2 containing a conjugated triene moiety has been proposed involving i) coupling of allylic sulfones 4 with the C₅ bromoallylic sulfide 5 , ii) base‐promoted dehydrosulfonation in the presence of allylic sulfide, and iii) selective oxidation of the resulting trienyl sulfide to the corresponding sulfone. Total synthesis of lycopene starting from the C₁₅ allylic sulfone 2b has been described, where the new C₁₀ bis(chloroallylic) sulfone 11 proved to be a useful substitute for the C₁₀ bis(chloroallylic) sulfide 3 , which did not require the problematic chemoselective sulfur oxidation in a conjugated polyene.     

Fluorine-containing carbocations. II. Polyfluorinated benzyl cations

When dissolved in SbF₅, polyfluorinated trifluoromethylbenzenes produce polyfluorinated α,α-difluorobenzyl ions. The ¹⁹F chemicals shifts and spin-spin coupling constants J(FF) have been analysed in terms of the resonance structures which contribute to the overall positive charge distribution. The influence of halogen atoms situated at position 4 on the downfield signal shift of α-fluorines follows the sequence F > Cl > Br which is opposite to that observed for 4-XC₆H₄CF₂⁺ ions.     

Carbon-13 NMR spectra of polybromoalkanes and polychlorobromoalkanes. Structural increments of halogens in polyhalogenated groups

The ¹³C NMR spectra of 48 polychlorobromoalkanes have been studied. Unlike the ¹³C signals of chlorine-containing groups (38–105 ppm), those of bromine-containing fragments, with the exception of CBr₂ (60–70 ppm), appear in a rather narrow range (25–50 ppm) and are shifted to higher field in relation to similar chlorine-containing groups. The spin–spin coupling constants in similar bromine- and chlorine-containing groups practically coinciEN. Calculation of the chemical shifts for the polyhaloalkanes under study according to the additivity scheme, as previously observed for polychloroalkanes, renders values which are in considerable discord with experimental values (up to –32 ppm for CBr₃). These discrepancies may be compensated for by corrections for the binary interaction of halogen atoms by grouping the halogen-containing fragments according to the geminal, vicinal, 1,3-, 1,3,5- and 1,2,3-arrangement of halogen atoms, and by introducing an increment for the position of the halogen at the secondary atom. It is established that as compared to 1-monohaloalkanes: (a) in the case of the geminal arrangement of halogen atoms the α- and γ-effects diminish (Δ α from –3.2 to –8 ppm; Δγ = 2.6 ppm), while the β-effect increases slightly (from 0 to 1.2 ppm); (b) in the case of a vicinal arrangement both the α- and β-effects diminish (by about –3.5 ppm) and the γ-effect remains constant, as if the vicinal system of the halogens was topologically insulated; (c) for the 1,3- and 1,3,5-arrangement of halogens their mutual influence is weak (about –0.5 ppm for each halogen atom in the α- and γ-positions); (d) the 1,2,3 system (serial arrangement of halogen atoms) is the sum of two vicinal fragments and hardly deviates from the additivity scheme; (e) the arrangement of a halogen at the secondary C atom enhances the α-effect (Δα = 2.8 and 1.0 for methyl and methylene, respectively, in the case of Cl, and 3.5 and 3.7 ppm in the case of Br); the variation of the β-effect has a different sign in relation to CH₃ and CH₂ groups (+1.2 and –1.7 for Cl, and +2.5 and –1.0 for Br). More distant effects of halogens (δ and ?) were not considered. The determined increments (Δα, Δβ and Δγ) for the α-, β- and γ-effects of chlorine and bromine atoms allow the prediction of the 13^C chemical shifts in polyhaloalkanes with an accuracy up to ±1.5 ppm. Some deviations of up to ±5 ppm may be connected with the influence of a three particle interaction of halogen atoms, which was taken into account only in the case of a geminal arrangement of halogen atoms.     

Structure of sulfur-stabilized carbanions. A 13C NMR study of some α-lithio-sulfoxides and sulfones

¹³C chemical shifts and ¹J(¹³CH) coupling constants provide information on the structures of some α-lithio-sulfoxides and sulfones.     

The NMR Coupling Constants,and Conformational and Structural Properties of Flexible Aldopyranosyl Rings: α- and β-D-Idopyranose

ABSTRACT

The flexible ring structures of α- and β-D-idopyranose have been investigated by conformational analysis using structures generated by MacroModel and GMMX search protocols. The lowest energy structures found during the conformer search for the ⁴ C ₁, ¹ C ₄, ^O S ₂ and the ³ S ₁ structures were then examined by AM1 and Gaussian ab initio methods at the HF/6-311G** and HF/6-31+G* levels. The B _2,5 conformer found for β-D-idopyranose at 14 kJ/mol by GMMX and 29.5 kJ/mol for α-D-idopyranose by MacroModel would not contribute to Boltzmann-averaged ¹H NMR coupling constants. The Merck MMFF force field tends to overweight the ¹ C ₄ structures, making these the lowest energy conformers for both anomers. Boltzmann-averaged coupling constants are heavily weighted by this structure in the MMFF search conformer ensemble. Averaged proton coupling constants determined using MMFF fit very well for α-D-idopyranose compared to the observed values, but fit poorly for the β-anomer. Ab initio results place the ¹ C ₄ conformer at lowest energy for the α-anomer and place the ⁴ C ₁ conformer at lowest energy for the β-anomer. The GMMX and MM3* force fields find the ⁴ C ₁ conformer to have the lowest energies for both anomers.