Geometrical isomerism and 13C spectra of the β-substituted Enones R1?C(1)O?C(2)HC(3)H?R2

The ¹³C chemical shifts of the unsaturated carbons were measured in 31 cis and trans pairs of β-substituted enones R₁? C(1)O? C(2)H?C(3)H? R₂. In these polarized ethylenes the chemical shifts of the olefinic carbons are simply related by the equation δ_c=δ_t+A. The steric and electronic effects introduced by the R₁ and R₂ substituents influence the chemical shifts of C-2 and C-3 in both isomers. It is shown that the sign and magnitude of the intercept A mainly reflect the π-charge electronic density changes which arise in the cis isomer and are transmitted via the π-framework. The effect of the steric interaction on the chemical shift of C-3 in the cis isomers is postulated to be related to the symmetry of the substituents. Therefore, the differential shielding of C-3 is indicative of the conformational structure of the cis molecule.     

Déplacements chimiques induits en RMN par un réactif lanthanidique: I—Application á l'analyse conformationnelle de sulfites cycliques

The chemical shifts induced by Eu(fod)₃ in several series of 6-membered cyclic sulfites give the parameters K_c and Δ_SR of the complexation equilibrium for an assumed 1:1 stoicheiometry. The equilibrium constant K_c decreases with increasing bulk of the C-4 and C-6 substituents and polarity of the C-5 substituent, which corresponds to the increase of the i.r. stretching frequency vS?O. Thus axial S?O will be more tightly complexed than equatorial S?O. It can be predicted that when a conformational equilibrium exists without shift reagent, displacement towards an axial S?O form will occur with the reagent. Use of the Δ_SR pseudocontact equation confirms the following: (i) ax S?O chair forms are stabilized; (ii) eq S?O chairs with two eq C-4 and C-6 substituents show an equilibrium with a few percent of the ax S?O flexible conformation, particularly in the absence of an ax C-5 substituent; (iii) twist forms with a 2–5 axis, intermediate S?O and trans-4, 6-di-tert-Bu substituents give a boat form with O at the prow and ax S?O; (iv) the conformational equilibrium of trans-5-tert-butyl-2-oxo-1, 3, 2-dioxathiane (chair with ax tert-Bu and S?O ? 70%) is completely displaced towards that form; (v) cis-4,4,6-trimethyl-2-oxo-1,3,2-dioxathiane, which exists as an equilibrium in which the three types of S?O occur, is complexed essentially in the twist form with a 1–4 axis and ax S?O. Most of these results are supported by the coupling constants analysis for the ratio R₀/S₀ = 1.     

1H- und 13C-NMR-Untersuchungen zur Struktur N-substituierter Tetrazole—Die Strukturen des N-Methoxycarbonyl-, N-Acetyl- und N-(Tri-n-butylstannyl)-tetrazols sowie Substituenteneffekte auf δ13C und 1J(CH)

The ¹H and ¹³C NMR spectra of several isomeric N-substituted tetrazoles have been investigated. ¹³C NMR is shown to be more useful for distinguishing between structural isomers of N-substituted tetrazoles except for those carrying electropositive substituents like SnBu₃. Correlations of δC-5 (inverse) and ¹J(C-5,H) with s?₁ found for 1-substituted tetrazole allowed the identification of the N SnBu₃ derivative as 1-(tri-n-butylstannyl)tetrazole. The phenyl carbon chemical shift difference ΔC′ = δC-3′-δC-2′ is insignificant for structure elucidation and conformational studies of N-substituted 5-phenyltetrazoles; ΔH′ from ¹H NMR spectra seems to be more useful.     

Conformational Analysis. XIX properties and reactions of 1,3-oxathianes VIII A 1H NMR conformational study of methyl-substituted derivatives

The addition of thioacetic acid to unsaturated alcohols or acids was utilized to obtain mercaptoalkanols which were condensed with suitable carybonyl compounds to prepare 24 methyl-substituted 1,3-oxathianes. The ¹H NMR spectra of the 1,3-oxathiane products were recorded at 60, 100 and/or 300 MHz and fully analysed. The results are best explained by a chair form which is completely staggered in the C-4? C-5? C-6 moiety ψ₄₅ or (ψ₅₆=60±1°). 1,3-Oxathianes having syn-axial 2,4- (and/or 2,6-) methyl-methyl interactions exist appreciably, if not exclusively, in twist forms. The vicinal coupling constants lead to the conformational free energies of axial methyl groups at C-4, ΔG°=7.4±0.4 kJ mol^?1, and at C-5, ΔG°=3.7±0.3 kJ mol^?1, in good agreement with previous estimates. They also show that both r-4,cis-5,trans-6- and r-4,trans-5,trans-6- trimethyl-1,3-oxathianes greatly favour the chiar form where the methyl group at C-4 is axial. The chair-twist energy parameters are reestimated at ΔH°_CT 27.0 kJ mol^?1, ΔS°_CT 11.6J mol^?1K^?1, and ΔG°_CT(298) 23.5 kJ mol^?1 for a 2,5-twist form.     

Perhydroxylated 1,7-Dioxaspiro[5.5]undecanes (“Spiro Sugars”): Synthesis,Stereochemistry, and Structure

As spiro sugars is an apt way of considering perhydroxylated 1,7-dioxaspiro[5.5]undecanes–a class of compounds which has not been found in nature up to now. The crystal structure of such a spiroacetal, in which the two pyran rings show the β-D -manno configuration, is depicted. Note that the all-trans arrangement of C-6, C,-5, O_pyr, C_spiro, O_pyr^′, C-5′, and C-6′ does not allow any of the stereoelectronic effects that are typical of carbohydrates.     

Conformational study of phosphothreonine in aqueous solution. H and 13C NMR results

The 270 MHz ¹H and 22.6 MHz ¹³C NMR spectra of DL -phosphothreonine in D₂O have been measured and analysed as a function of pD. The trans-trans conformation of the fragment H-α? C-α? C-β? O? P predominates at all pD values. The C-β—O gauche contribution is notably larger for pD values in the range 7≤pD<10 than for acidic or more basic solutions which is in accordance with earlier results for phosphoserine (PSer).     

Conformational analysis. Part 20—conformational analysis of 4-deoxy-4-fluoro-D-glucose and 6-deoxy-6-fluoro-D-galactose in solution

The ¹H and ¹⁹F NMR spectra of the α- and β-pyranose anomers of 4-deoxy-4-fluoro-D -glucose (4FG) and 6-deoxy-6-fluoro-D -galactose (6FGA) in methanol-d₄, DMSO-d₆, acetone-d₆ and D₂O solution are reported. Computer analysis of the ABMX spectra of the CH CH₂F fragments gives accurate vicinal HH and HF coupling constants. An iterative computational analysis of the observed vicinal couplings in this fragment for 6FG, 6FGA and other molecules allows the determination of both the individual rotamer couplings and the rotamer populations. Consideration of the derived rotamer couplings strongly suggests that the correct assignment for the prochiral C-6 methylene protons in 6FG is that with the 6S proton having the larger coupling to H-5. This is the reverse of the assignment of these protons in D -glucose. In contrast, the assignment of these protons in 6FGA follows that given previously for D -galactose. The relative energies for the conformations about the C-5 C-6 bond for 4FG, 6FG and 6FGA are given from the derived rotamer populations. For 6FGA the rotamer in which the fluorine is antiperiplanar to C-4 is particularly favoured. For 4FG the rotamer with OH anti-periplanar to the ring O is highly unfavoured, but the other two rotamers are of almost equal energy. Consideration of the effect of replacing hydroxyl by fluorine in these molecules indicates that any hydrogen bonding involving the C-4 or C-6 hydroxyls plays little part in determining the conformer energies of glucose or galactose in polar solutions.     

Substitution of 2-phosphaindolizines by bromine and by chlorophosphines

Bromine does not add to phosphorus in a 2-phosphaindolizine 1 but substitutes its 1-position. The 1-bromo derivatives 2 are best prepared with Br₂/NEt₃ or N-bromosuccinimide. Their hydrolysis is remarkable; it involves a debromination of C-1, an oxidation of P and a selective opening of the P/C-3 bond. PCl₃ also causes a substitution of the 1-position. The resulting 1-dichlorophosphino derivatives 5 easily undergo a substituent exchange at the exocyclic phosphorus. More 1-phosphino derivatives are formed in the reaction of 1 with phenyl and diazaphospholyl dichlorophosphine.     

The nominal butyl ester ion in the mass spectra of long-chain n-alkyl esters: A postscript

n-Octadecyl benzoate, taken as a model for long-chain n-alkyl carboxylates generally, loses C₁₄H₂₈ under electron impact to yield a product with the same elemental composition as the butyl benzoate molecular ion. This product retains quantitatively one hydrogen from C-6, and seems to be formed as an oxygen-protonated 4-benzoyloxybutyl radical. It reacts further to lose H₂O, in which deuterium labeling demostrates that the second hydrogen atom comes predominantly from C-4. The intermediate reorganization, for which the driving force is presumably furnished by the instability associated with a primary radical, is pictured in terms of cyclization via bonding between the C-4 radical site and the benzoyl carbon concerted with hydrogen migration via a 4-membered quasicyclic transition state.     

STUDY ON CATIONIC RING-OPENING COPOLYMERIZATION OF 1,4-ANHYDRO-2,3-DI-O-BENZYL-α-D-RIBOPYRANOSE WITH 1,4-ANHYDRO-2,3-O-ISOPROPYLIDENE-α-D-RIBOPYRANOSE

Cationic ring-opening copolymerization of 1, 4-anhydro-2, 3-O-isopropylidene-α-D-ribo-pyranose (AIRP) with 1,4-anhydro-2,3-di-O-benzyl-α-D-ribopyranose (ADBR) preparedfrom D-ribose was studied. Copolymerization using SbCl_5 or BF_3 OEt_2 as catalyst atlow temperature gave stereoregular (1→4)β-D-ribofuranan (C-1 and C-4 ring cleavagesee Scheme 1) or (1→5) α-D-ribofuranan (C-1 and C-5 ring cleavage) respectively. Theeffects of catalysts, reaction time and temperatures on yield and stereoregularity of the ob-tained polymers were studied. Polymers were characterized by molecular weight, ~1HNMR,~(13)CNMR and optical rotation.     

The assignment of the 1H and the 13C NMR chemical shifts of N-phenyl-2,4-dimethylbuta-1,3-diene-1,4-sultam

The assignment of the signals in the ¹³C and ¹H NMR spectra of N-phenyl-2,4-dimethylbuta-1,3-diene-1,4-sultam is difficult for the signal pairs C-2 and C-4, C-1 and C-3, (C-1)? H, (C-2)? CH₃ and (C-4)? CH₃. The ¹³C NMR spectrum recorded under gated decoupling conditions provide long-range couplings which make possible an unambiguous assignment of the ¹³C NMR signal pairs. Application of the ¹H CW off-resonance decoupling technique in recording the ¹³C NMR spectra enables the assignment information from the ¹³C NMR spectrum to be transferred to the ¹H NMR spectrum.     

Carbon-13 n.m.r. study of 31P?13C spin–spin coupling constants in dichloro- and monochloro-vinyl phosphate derivatives

Carbon-13 chemical shifts and J(PC) coupling constants of 29 vinyl phosphate derivatives are presented. In the series of compounds (R₁O)₂P(O)OC¹(R)?C²X₂ (where 3 in R indicates the first carbon of the R₂ substituent) large differences were found between the ³J(P, O, C-1, C-3) and ³J(P, O, C-1, C-2) coupling constants of the chlorinated (X?CI) and the unsubstituted (X?H) derivatives. A possible explanation of this phenomenon is given on the basis of Jameson's s bond character theory. Strong stereospecificity of ³J(P, O, C-1, C-3) coupling constants was observed in the series of compounds (R₁O)₂ P(O)OC¹(R)?C²HR₃. Coupling constants varied between 3.2–4.9 Hz in the E isomers, while peaks could not be resolved in the Z isomers. The ³J(P, O, C-1, C-2) coupling constants were regularly 20–30% greater in the Z than in the E isomers.     

Cellulose organic solutions: A nuclear magnetic resonance investigation

Four solvents of cellulose have been studied by using ¹³C-NMR spectroscopy. All these solvents, N-methyl morpholine-N-oxide, methylamine, hydrazine, and paraformaldehyde (PF), contained dimethyl sulfoxide (DMSO) as a cosolvent. Oligomers of cellulose of DP = 10 soluble in hot DMSO have been used as model compounds. ¹³C chemical shifts and line shapes show that three of the mentioned solvents are “true solvents” of cellulose. On the other hand, dissolution of cellulose in DMSO-PF system occurs by the formation of a statistical derivative of cellulose. Enriched ¹³C bacterial cellulose on C-1 and C-6 positions have been used to identify the ¹³C positions mainly in DMSO-N-methyl morpholine-N-oxide system. This solvent has been found to be degradative for the macromolecule when the solution is kept at 100°C over a long period. Viscosity measurements show a reduction of the molecular weight in these conditions. Polarimetry indicates that no glucose is present in solution and hence there is a statistical break of the chain. Enriched cellulose solution in DMSO–N-methyl morpholine-N-oxide has been also used for relaxation time (T₁) determination both of the solvent and of the enriched carbons of the polymer. Nuclear Overhauser enhancement (NOE) was found to be 1.8 for C-1 and 2.1 for C-6 showing that relaxation phenomenon is not purely dipolar. T₁ values of 97 and 65 msec are found for C-1 and C-6 of cellulose, in good agreement with the values known for polysaccharides. Determination of T₁ for the different carbon atoms of the solvent DMSO-N-methyl morpholine-N-oxide with and without cellulose shows a large reduction of T₁ for N-methyl morpholine-N-oxide molecule. This denotes a slower molecular motion of this molecule and a preferential interaction with the cellulose macromolecule.     

Regiospecificity of intramolecular hydrogen transfer in cyclohexanol following chemical ionization

Both H₂O and HDO are eliminated from protonated d₁₁-cyclohexanol under chemical ionization conditions using methane as the reagent gas. The elimination of H₂O and HDO from the [M+H]⁺ ions of cyclohexanol specifically labeled with deuterium in the 1; 2,6; 3,5; and 4 positions has been measured. It is found that there is considerable selectivity as to the position from which deuterium is lost in the elimination of HDO. That is, transfer from C-4 is favored, some transfer from C-3(5) occurs, little deuterium is lost from C-2(6) and none is lost from C-1. A mechanism involving ring protonation and ring opening followed by deuterium transfer to oxygen with subsequent loss of HDO is proposed to account for these observations.     

The Role of the C-3 Substituent in the Asymmetric Dihydroxylation of Hexo-5-Enofuranosides

ABSTRACT

Asymmetric dihydroxylation of vinyl furanosides 1-6 by use of OsO₄, AD-mix-α® and β® is described yielding the corresponding hexofuranose sugars. Vinyl furanosides 2 and 3, with an ester group at C-3, and vinyl manno furanoside 5 on asymmetric dihydroxylation with AD-mix α® exhibited high R diastereoselectivity at C-5. Reversal in diastereoselectivity at C-5 was observed for the 3-deoxy vinyl furanoside 6 giving furanosaccharide 6S with the S configuration at C-5.     

The Effects of pH and Ionic Strength on the Aggregation of Bacteriochlorophyll c in Aqueous Organic Media: The Possibility of Two Kinds of Aggregates

The aggregation behavior of two homologs of bacteriochlorophyll c (BChl c) in various media was investigated for the effects of pH and salt, and the corresponding structures were analyzed by Fourier transform (FT)-IR spectroscopy. R-[P, E] BChl c_F (3¹-R-form of BChl c with a propyl group at the C-8 position and an ethyl group at the C-12 position) and R-[E, E] BChl c_F (3¹-R-form of BChl c with two ethyl groups at positions C-8 and C-12) were isolated from the green sulfur bacterium Chloro-bium limicola. Aggregates of each homolog showed a pH-dependent shift of the absorption maximum; at low pH, the peak moved to the red. This tendency was also revealed by circular dichroic spectra. A similar red shift of the peak was also induced by a high concentration of salt (NaCl) or buffer for both homologs. The FT-IR spectrum indicates that at low pH, both homologs formed a rather amorphous aggregate. On the other hand, a regular structure of R-[P, E] BChl c_F was indicated in an acetone-water mixture. This structure was stabilized by a triangular interaction among three pigment molecules through the Mg-OH (3>) O = C (13¹) linkage. This structure was not found for R-[E, E] BChl c_F. These results indicate that the replacement of the side chain at the C-8 position on the macrocycle induces a change in aggregation behavior. A possible heterogeneity of the in vivo rod structure of chlorosomes in green sulfur bacteria is discussed based on the above results.     

Lanthanide-induced shifts in proton NMR spectra of cyclohexanones

The lanthanide-induced shifts (LIS) of the lanthanide shift reagent (LSR) Eu(FOD)₃ are reported for a large number of cyclohexanones, especially those which are highly substituted. The following compounds were synthesized and characterized: 3-(aryl)-3,5,5-trimethylcyclohexanones, in which aryl = 1-naphthyl, phenyl, o-anisyl, m-anisyl, p-anisyl and p-chlorophenyl. Some analogous compounds were also studied: 3,5,5-trimethylcyclohexanone, 4-tert-butyl-cyclohexanone, 3,3,5,5-tetramethylcyclohexanone 3-(1-naphthyl)5,5-dimethylcyclohexanone and para-tert-butyl-anisole. A method for the regression analysis of the concentration dependence of the LIS of these substrates is developed and reported, and used to derive the limiting incremental LIS (Δ₂) for the LS₂ complex and to evaluate the proton chemical shifts (δ₀) in the absence of LSR. An ‘incremental dilution’ technique was found to be most appropriate to insure constant substrate concentrations, needed to extract both Δ₂ and δ₀. The conformations of the 3-(aryl)-type systems and analogous compounds were studied via LIS and found to conform to:—(i) an axially disposed aryl substituent in the 3,3,5,5-tetra-substituted cyclohexanones and (ii) a flattened chair form of the cyclohexanone ring with distortions in this chair form being an increase in the syn-diaxial (C-3, C-5) substituent distance (C-3 and C-5 substituents still eclipsed). The LIS were fully compatible with these structural assumptions.     

Investigation of benzimidazoles. III—transmission of the substituent effects in 2-substituted 1-methylbenzimidazoles studied by 13C nuclear magnetic resonance

The influence of substituents on the ¹³C NMR chemical shifts of 2-substituted 1-methylbenzimidazoles has been investigated. The electronic effects of the substituents are transmitted to C-4 and C-7 mainly by the resonance mechanism, and to C-5, C-6 and N-CH₃, by approximately equal contributions of the resonance and inductive components. A critical analysis of the share in the transmission of substituent effects through the ‘pyridine-type’ and ‘pyrrole-type’ nitrogen atoms is given.     

Solution conformation and dynamics of L-6-methylperhydroimidazo[1,5-c]thiazole-5,7-dione (γ-thiaprolinehydantoin). A 1H and 13C NMR study

The solution conformation of L-6-methylperhydroimidazo[1,5-c]thiazole-5,7-dione (γ-thiaprolinehydantoin) has been determined from an extensive ¹H and ¹³C NMR study, allowing the extraction of vicinal inter-proton and carbon-hydrogen coupling constants. The major conformation of the thiazolidine ring is an envelope with C-δ as the flap exo (δ^?). In solution the preferred solid state (twist) conformer with C-α exo and C-β endo (_α^βT) is only a minor contributor. ¹³C spin–lattice relaxation data reveal the flexibility of the thiazolidine ring.     

Carbon-carbon coupling in [3-13C1]tryptophan

Carbon-carbon coupling constants have been observed in [90% 3-¹³C₁]tryptophan and used to assign the ¹³C resonances of the indole ring. The results support a reassignment of C-5 and C-6 recently suggested on the basis of the reassigment of the corresponding resonances in indole. Coupling constants are compared with theoretical values obtained using a finite perturbation theory Blizzard-Santry program, and excellent agreement is obtained for the ¹J(CC) values. The calculations predict that the Fermi contact contribution is dominant for all ⁿJ(CC) couplings to C-3.