Configurationally and conformationally homogeneous cyclicN-aryl sulfimides. I. Synthesis and mechanism of formation

Reactions of thianes andcis-andtrans-1-thiadecalins with 4-chloroaniline andN-chlorsuccinimide ortert-butylhypochlorite gave configurationally homogeneous cyclicN-4-chlorophenyl sulfimides. With appropriately substituted sulfides conformationally homogeneous thiane-and cis-1-thiadecalin-1-imides were obtained. Formation of sulfimides with axially oriented S–N bond is strongly disfavoured. Reactions with conformationally rigid ring systems yielded only sulfimides with equatorial S–N bond; two isomeric sulfimides, both with equatorial S–N bond, were obtained with the mobilecis-1-thiadecalin. Sulfimides with axial S–N bond were prepared from conformationally rigid sulfoxides with equatorial S–O bond. It is assumed that formation of sulfimides with rigid ring systems proceeds viaN-chloroanilines, while reactions of conformationally mobile systems withN-chlorosuccinimide may also occur via intermediate succinimidyl sulfonium ions.

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Konfigurativ und konformationell einheitliche cyclische N-Aryl-sulfimide.I. Synthese und Bildungsmechanismus

Zusammenfassung Durch Umsetzung von Thianen und voncis- undtrans-1-Thiadekalinen mit 4-Chloranilin undN-Chlorsuccinimid odertert-Butylhypochlorit wurden konfigurativ einheitliche cyclischeN-4-Chlorphenylsulfimide dargestellt. Bei geeigneter Substitution am Heteroring wurden konformativ einheitliche Thianundcis-1-Thiadekalin-1-imide erhalten. Die Bildung von Sulfimiden mit axial orientieter S–N-Bindung ist stark benachteiligt. Konformativ starre Ringsysteme führen praktisch ausschließlich zu den Sulfimiden mit äquatorialer S–N-Bindung; aus dem konformativ beweglichencis-1-Thiadekalin werden bei der Umsetzung mittert-Butylhypochlorit zwei isomere Sulfimide, beide mit äquatorialer S–N-Bindung, erhalten. Sulfimide mit axialer S–N-Bindung wurden aus konformativ starren Sulfoxiden mit äquatorialer S–O-Bindung erhalten. Es wird angenommen, daß die Sulfimidbildung bei konformativ starren Ringsystemen weitgehend überN-Chloraniline, bei Umsetzung von beweglichen Ringsystemen mitN-Chlorsuccinimid auch über Succinimidylsulfoniumionen verläuft.

     

Configurationally and conformationally homogeneous cyclic n-aryl sulfimides—III : Stereochemistry of rearrangement

Configurationally and conformationally homogeneous thiane- and trans- and cis-1-thiadecalin-1-N-p-chlorophenyl imides were rearranged to the corresponding 2-(2'-amino-5'-chlorophenyl)-sulfides and the configurations of the products were assigned by ^1H-NMR spectroscopy. If sterically unhindered, rearrangements proceeded with a high degree (95%) of stereospecifity: sulfimides with equatorial S-N-bond gave rearranged products with axial, sulfimides with axial S-N-bond gave rearranged products with equatorial aryl substituent. The proposed concerted mechanism via a cyclic transition state is supported by these results.     

Configurationally and conformationally homogeneous aryl-cis-1-thiadecalins

The structure of aryl-substituted cis-1-thiadecalins formed together with 5,6-tetramethylenethiopyrylium salts in disproportionation reactions of condensed 4H-, 6H-thiopyrans and dihydrothiopyrans with CF₃COOH, as well as in the ionic reduction of the latter by the ion pair trifluoroacetic acid-triethylsilane, was studied. It was shown that the reduction proceeds stereospecifically with the formation of configurationally and conformationally homogeneous aryl-cis-1-thiadecalins possessing 2-R¹- and 2-R¹-4-R²-configurations. The configurational and conformational assignments were made by the ¹³C NMR method.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 898–904, July, 1984.     

Configurationally and conformationally homogeneous cyclic n-aryl sulfimides—IV : Synthesis,configuration and stereochemistry of the rearrangement of 1,3-di-thiane-1-N-p-chlorophenylimides

1,3-Dithiane-1-N-p-chlorophenylimides (1,4-9) were prepared and their configuration and conformation was determined by ¹H and ¹³C NMR. The compounds were rearranged to the corresponding 2-(2'-amino-5'-chlorophenyl)-1, 3-dithianes (1U,4U,9U). The rearrangement reactions took place with ?95% stereospecifity. The mechanism of the reaction was investigated with the aid of analogs specifically deuterated at C-2.     

1H and 13C NMR spectra of N-vinylpyrroles

The position of the substituants in 2, 3-dialkyl-1-vinylpyrroles and 7-methyl-1 vinyl-4,5,6,7-tetrahydroindole was established on the basis of the ¹H and ¹³C NMR spectra. It was found that the S-trans conformation of the N-vinyl group is preferred. It is shown that the condensation of ketoximes with acetylene proceeds through the formation of free pyrroles and that vinyl oximes are not intermediates in the condensation.     

1H and 13C NMR spectra of benzyl compounds

Proton and carbon-13 spectra of benzyl compounds of the general formula (C₆H₅CH₂)_nX with a large variety of X substituents have been measured. While a linear relationship between the CH₂ chemical shift and the substituent electronegativity was found both for ¹H and ¹³C, large deviations from linearity were observed for transition metals such as titanium and zirconium. These later results are correlated with the X-ray studies of the latter compounds.     

1H and 13C NMR spectra of N-substituted morpholines

(1)H and (13)C NMR data for N-substituted morpholines 1-20 were measured using 1D (DEPT, 1D NOE difference) and 2D NMR spectroscopic methods including (1)H-(1)H COSY, long-range (1)H-(1)H COSY, NOESY, gHMBC and gHMQC experiments. At room temperature the (1)H NMR spectra of protonated compounds 2 and 9 show the chair conformation for the morpholine ring. Spin-spin coupling constants were deduced from the resolution-enhanced proton spectra.     

1H and13C NMR spectra of polycyclic compounds

Using 2D¹H and¹³C correlation NMR spectroscopy, all signals in the¹H and¹³C NMR spectra of five stereoisomeric bicyclo[2.2.1]heptadiene trimers, decacyclo[9.9.1.0^2.10.0^3.8.0^4.6.0^5.9.0^12.20.0^13.18.0^14.16.0^15.19]heneicosanes, obtained by Pd-catalyzed codimerization of norbornadiene dimer with quadricyclane followed by homocyclotrimerization of the latter were assigned unambiguously. Independent stereochemical identification of the trimers was performed using data on the nuclear Overhauser effect.     

1H and 13c NMR spectra of 8- hydroxyquinoline

The ¹H and ¹³C NMR spectra of 8-hydroxyquinoline were analyzed. The assignment of the signals was established unambiguously by ¹³C-{¹H} double-resonance experiments and investigation of the ¹³C NMR spectrum without decoupling from the protons.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1235–1236, September, 1977.     

1H and 13C NMR spectra of Strychnos alkaloids: Selected NMR updates

The PBE0/pcSseg-2//pcseg-2 calculations of ¹H and ¹³C NMR chemical shifts were performed for a classical series of 12 Strychnos alkaloids (except for the earlier studied parent strychnine), namely akuammicine, isostrychnine, rosibiline, tsilanine, spermostrychnine, diaboline, cyclostrychnine, henningsamide, strychnosilidine, strychnobrasiline, holstiine, and icajine. It was found that the calculated ¹H and ¹³C NMR chemical shifts show markedly good correlations with available experimental data, as characterized by a mean absolute error of 0.22 ppm for the range of 8 ppm for protons and 1.97 ppm for the range of 180 ppm for carbons. Complementarily, the present results provide essential NMR update and fill a gap in the NMR data of this distinguished group of vitally important natural products.     

1H and 13C NMR spectra of condensed benzimidazole and imidazobenzodiazepines

Benzimidazoles are heterocyclic compounds that have awakened great interest during the last few years because of their proven biological activity as antiviral, antimicrobial, and antitumoral agents. For this reason, the development of a systematic NMR study of condensed benzimidazole compounds constitutes a significant tool in understanding the molecular dynamics and the structural parameters that govern their behavior. The ¹H and ¹³C NMR spectra of new imidazobenzodiazepines were investigated. Based on the study of NMR chemical shifts, we discuss the environmental effect of the nucleus ¹³C. The correlation ¹H–¹³C proved to be a useful method for distinguishing the assignment of carbon.     

1H and13C NMR spectra of C- and N-substituted oxazolidines

An interrelationship between the structure of oxazolidines and the character of their¹H and¹³C NMR spectra was ascertained, and the most characteristic signals of the individual groups, which make it possible to establish the structure of the investigated compounds, were found.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 900–903, July, 1982.     

1H, 13C and 15N NMR spectra of ciprofloxacin

1H NMR assignment, including the values of delta(H) and J(H,H) for the cyclopropane moiety, and 13C NMR and 15N NMR spectral data for ciprofloxacin are presented.     

1H and13C NMR spectra of 1,5-disubstituted 1,3,4-oxadiazoles

The¹H and¹³C NMR spectra of 2, 5-disubstituted 1,3,4-oxadiazoles with aliphatic, aromatic, and hetero-aromatic substituents have been described and interpreted. The electronic effect of the 1,3,4-oxadiazole group as a benzene ring substituent was evaluated using¹³C NMR spectroscopy.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 834–842, June, 1994. Original article submitted April 8, 1994.     

13C and1H NMR spectra of spiropiperidine alkaloids of Nitraria

A detailed interpretation is given of the¹³C and¹H NMR spectroscopy of the spiropiperidine alkaloids of the nitramine group, and the results are generalized. The assignment has been made of the carbon-13 resonance lines in the spectra of five natural compounds. A dependence of the parameters on the spatial structures of the compounds of this series has been found. The overall PMR spectra of seven natural alkaloids and some of their derivatives are discussed. The conformations of acyl derivatives have been established.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 82–91, January–February, 1988.     

1H, 13C,and 29Si NMR spectra of 1-methylazasilatrane

Considerable shielding of the ¹H and ²⁹Si nuclei due to transannular nitrogen-silicon coupling, which is expressed more clearly than in the case of silatranes, was established on the basis of ¹H, ¹³C, and ²⁹Si NMR data for the methylsilyl group in 1-methyl-2,5,8,9-tetraaza-1-silatricyclo[3.3.3.0^1,5]undecane (1-methylazasilatrane) and a comparison of these data with the data for the methyl[tris(dimethylamino)]silane model. It is shown that the change in the hybridization of the silicon atom associated with the increase in its coordination number is not only reflected in the chemical shifts but also leads to an increase in ¹J_CH and ²J_SiH.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1063–1064, August, 1977.