Absolute Configuration of Scopolamine N-Oxide and of Related Compounds

1971 ◽  
Vol 49 (20) ◽  
pp. 3258-3271 ◽  
Author(s):  
Carol Saunderson Huber ◽  
Gabor Fodor ◽  
Nagabhushanam Mandava
Keyword(s):  
Absolute Configuration ◽  
Chemical Shifts ◽  
Complete Agreement ◽  
Anomalous Scattering ◽  
Product Analysis ◽  
X Ray Crystallography ◽  
Chemical Correlation ◽  
A Minor ◽  
First Time ◽  
Related Compounds

Structure analysis of (−) scopolamine N-oxide (1) hydrobromide monohydrate by X-ray crystallography has proven that the N-methyl group is axial and the amineoxide function is equatorial. The absolute configuration of the tropic acid residue has also been determined by anomalous scattering as being S, in complete agreement with chemical correlation experiments.The N-stereoisomer of 1 has also been detected as a minor product 2 for the first time, as a result of using 100 MHz n.m.r. spectroscopy in the product analysis of the oxidation of (−) scopolamine with hydrogen peroxide in ethanol. A similar n.m.r. study was undertaken with atropine and tropine and correlation of chemical shifts with N-configuration in the N-oxides, 3–6, was attempted. N-oxidation of scopolamine, and by analogy of related tropane bases, has taken a preferentially equatorial course, similar to other quaternization reactions.

Preparation, structure, and electrochemistry of porphyrinato titanium (IV) benzenedithiolates with a trithiole ring, a dithiin ring, and two 2-cyanoethylthio groups

2018 ◽  
Vol 22 (01n03) ◽  
pp. 157-164
Author(s):  
Takeshi Kimura ◽  
Yusuke Muraoka ◽  
Kaori Amano ◽  
Toshiyuki Fujio ◽  
Takao Nishikawa ◽  
...  
Keyword(s):  
Gold Electrode ◽  
Chemical Shifts ◽  
Energy Levels ◽  
Dft Method ◽  
Similar Reaction ◽  
X Ray Crystallography ◽  
Cesium Hydroxide ◽  
Homo And Lumo ◽  
Related Compounds ◽  
Homo And Lumo Energy

The reaction of tetra([Formula: see text]-tolyl)porphyrinato titanium (IV) oxide (2) with 4,7-diethyl-5,6-dimercaptobenzo[1,2,3] trithiole (3a) produced the corresponding titanium (IV) complex, tetra([Formula: see text]-tolyl)porphyrinato titanium (IV) trithiolobenzenedithiolate (4a), fused with a trithiole ring. Related compounds 4b and 4c were prepared by a similar reaction of 2 with 5,8-diethyl-6,7-dimercaptobenzo[1,4]dithiin (3b) and 3,6-diethyl-4,5-dimercapto-1,2-bis(2-cyanoethylthio)benzene (3c). The structure of 4b was determined by X-ray crystallography. Compound 4c was further treated with cesium hydroxide to produce the corresponding dithiolate anion 4c2S, which was deposited on the gold electrode. The electrochemical property of the gold electrode was determined by cyclic voltammetry. The structure of simplified model compound 4b[Formula: see text] was optimized using the DFT method with the Gaussian 09 program. The optimized structure was utilized to calculate the NMR chemical shifts, the HOMO and LUMO energy levels, and the electronic transition in the absorption spectrum.

Beiträge zur Chemie des Phosphors, 621 Zur Frage des 31P-kernresonanzspektroskopischen Nachweises von monomerem und dimerem Phenylphosphor und der Ringgröße von Organyl-cyclophosphanen.

1976 ◽  
Vol 31 (5) ◽  
pp. 558-564 ◽  
Author(s):  
Marianne Baudler ◽  
Burkhard Carlsohn ◽  
Wolfgang Böhm ◽  
Goswin Reuschenbach
Keyword(s):  
Spectroscopic Investigation ◽  
Chemical Shifts ◽  
High Yield ◽  
Ring Size ◽  
Nmr Spectrum ◽  
Spectroscopic Evidence ◽  
Nmr Parameters ◽  
Similar Chemical ◽  
First Time ◽  
Related Compounds

The weak resonances at + 22 and + 49 ppm appearing in the 31P NMR spectrum of melts or solutions of (PPh)5 that have been attributed previously in the literature to “dimeric” and “monomeric phenylphosphorus” are caused by (PPh)6 and (PPh)4, respectively. This was proved by comparison with the 31P NMR parameters of related compounds and by 31P NMR spectroscopic investigation of authentic samples of (PPh)6 and (PPh)4, the latter of which was prepared in high yield from (Me3Si)PhP–PPh–PPh(SiMe3) and PhPCl2. (PEt)4 and mixed-substituted phenyl-ethyl-cyclotetraphosphanes exhibit similar chemical shifts as (PPh)4, corresponding mixed-substituted cyclohexaphosphanes have similar chemical shifts as (PPh)6. Generally, cyclophosphanes establish an equilibrium between (PR)n-species of different ring-size. Probably, the ring-interconversion proceeds via a multi-center mechanism. No 31P NMR spectroscopic evidence for the existence of free PPh or P2Ph2 under the conditions described could be detected. On thermolysis of (PEt)4 the existence of (PEt)3 was proved for the first time.

Structures and Synthesis of 4a-Homo-7,19-dinorsteroids, X-Ray Crystallography and NMR Spectroscopy

1999 ◽  
Vol 64 (12) ◽  
pp. 2019-2034 ◽  
Author(s):  
Alexander Kasal ◽  
Miloš Buděšínský ◽  
Jan Pelnař ◽  
Michael A. Bruck ◽  
Michael F. Brown
Keyword(s):  
Nmr Spectroscopy ◽  
Absolute Configuration ◽  
Starting Material ◽  
Nmr Analysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
X Ray Crystallography ◽  
Leaving Group ◽  
The Absolute ◽  
Related Compounds

X-Ray diffraction revealed the absolute configuration of 4aβ-methyl-4a-homo-7,19-dinor- 5α,10α-androstane-3,17-dione. Detailed NMR analysis suggested that the 5α configuration existed in the starting material, 3β-acetoxy-4a-methylidene-4a-homo-7,19-dinor- 5α-androst-9-en-17-one, and related compounds. Thus 5-methyl-5β-estr-9-ene derivatives with a leaving group in position 6β were found to react with nucleophiles to form rearranged 4a-homo-7,19-dinorandrostane derivatives with a 5α configuration.

scholarly journals Absolute Configuration of a New Phenethylcyclohexanetriol and a New Natural Bibenzyl From Amomum celsum

2019 ◽  
Vol 14 (5) ◽  
pp. 1934578X1984361 ◽  
Author(s):  
Phan Minh Giang ◽  
Lai Anh Tu ◽  
Vu Minh Trang ◽  
Nguyen Quoc Binh ◽  
Tadashi Hyodo ◽  
...  
Keyword(s):  
Absolute Configuration ◽  
Human Cancer ◽  
Ionization Mass ◽  
Hep G2 ◽  
Cytotoxic Assay ◽  
Human Cancer Cell Lines ◽  
X Ray Crystallography ◽  
Sulforhodamine B ◽  
First Time ◽  
Mcf 7

Methanol extracts of the rhizomes or fruit of Amomum celsum Lamxay & M.F. Newman (Zingiberaceae) yielded 5 compounds one of which, 1,3 S,5 S-trihydroxy-1-(4-hydroxyphenylethyl)cyclohexane (2), is new and one, 4-hydroxybibenzyl (1), is reported as a natural product for the first time. In addition, 3 known compounds, 5-hydroxy-3,7,3′,4′-tetramethoxyflavone (3), 3,5-diacetoxy-1,7- bis(3,4-dihydroxyphenyl)heptane (4), and 1,4-hydroquinone (5), were also isolated. Their structures were determined by performing extensive analysis of high-resolution electrospray ionization-mass spectrometry and nuclear magnetic resonance spectroscopic data. The absolute configuration of 2 was unambiguously established by X-ray crystallography and Mosher’s method. Cytotoxicity of compounds 1 and 2 against MCF-7 and Hep-G2 human cancer cell lines were tested in the sulforhodamine B cytotoxic assay. A plausible biosynthesis of 1 and 2 in A. celsum was proposed.

Absolute configuration at C(20) of the derivatives of 21-nor-5α-cholane-20,24-diol

1980 ◽  
Vol 45 (9) ◽  
pp. 2443-2451
Author(s):  
Vladimír Pouzar ◽  
Miroslav Havel
Keyword(s):  
Absolute Configuration ◽  
Side Chain ◽  
Chemical Correlation ◽  
The Absolute ◽  
Derivatives Of

Derivatives of 21-nor-5α-cholane-20,24-diol XI and XIX were prepared by stepwise construction of the side-chain in the position 17β. Their absolute configuration at C(20) was determined on the basis of chemical correlation with the derivatives of 21-nor-5α-cholan-20-ol, XVI and XXIV. The absolute configuration of alcohols XVI and XXIV was determined from the ratio of the yields in which they are formed during the reduction of ketone X and using the benzoate rule. To compounds XI-XVIII the configuration 20R and to compounds XIX-XXVI the configuration 20S has been assigned.

Preparation and absolute configuration at C(20) of 21-nor-5α-chol-22-en-24→20-olide derivatives

1981 ◽  
Vol 46 (4) ◽  
pp. 917-925 ◽  
Author(s):  
Vladimír Pouzar ◽  
Miroslav Havel
Keyword(s):  
Absolute Configuration ◽  
Nmr Spectra ◽  
Lithium Salt ◽  
H Nmr ◽  
Chemical Correlation ◽  
Unsaturated Lactones

Reaction of the aldehyde I with the lithium salt of 1-(2-tetrahydropyranyloxy)-2-propyne yielded the compounds II and IV. From the compound II the lactone XII was prepared via the intermediates III and X, the lactone XVIII was prepared from the substance IV via the intermediates V and XVI. The unsaturated lactones XII and XVIII were also prepared by sulfenylation and dehydrosulfenylation of the saturated lactones XIII and XIX. Based on chemical correlation and 1H-NMR spectra analyses of the compounds II and IV, the lactone XII was assigned the 20R-configuration whereas the lactone XVIII was allotted the 20S-configuration.

Preparation and absolute configuration at C(22) of 21,26,27-trinor-5α-cholestane-22,25-diol derivatives

1983 ◽  
Vol 48 (8) ◽  
pp. 2423-2435 ◽  
Author(s):  
Vladimír Pouzar ◽  
Soňa Vašíčková ◽  
Pavel Drašar ◽  
Ivan Černý ◽  
Miroslav Havel
Keyword(s):  
Absolute Configuration ◽  
Lithium Salt ◽  
Nickel Acetylacetonate ◽  
Cotton Effects ◽  
Chemical Correlation

Reaction of 5α-pregnan-21-al (V), obtained from ester of the corresponding acid III via the alcohol IV, with lithium salt of 1-methoxymethoxy-2-propyne afforded both the isomeric 25-methoxymethoxy-21,26,27-trinor-5α-cholest-23-yn-22-ols (VI and VIII) which were converted into two 21,26,27-trinor-5α-cholestane-22,25-diols (XI, XV). Absolute configuration of the alcohols X and XIV was assigned by chemical correlation with derivatives XXVI and XXVII of known absolute configuration at C(20). The correlation was based on reduction of thiocarbonates derived from the diols XXII and XXIV for which also Cotton effects of their complexes with nickel acetylacetonate were studied. Both diols were prepared from 5α-pregnan-20-one (XVIII) via 5α-pregn-20-yne (XIX) and the 21,26,27-trinor-5α-cholest-20-ene derivative XXI.

The High Resolution NMR Spectra of Pesticides. II. The DDT-Type Compounds

1969 ◽  
Vol 52 (5) ◽  
pp. 1074-1092 ◽  
Author(s):  
L H Keith ◽  
A L Alford ◽  
A W Garrison
Keyword(s):  
Nuclear Magnetic Resonance ◽  
High Resolution ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Aromatic Rings ◽  
Nuclear Magnetic Resonance Spectra ◽  
High Resolution Nmr ◽  
Related Compounds ◽  
Deshielding Effect

Abstract The high resolution nuclear magnetic resonance spectra of the DDT class of pesticides and related compounds are discussed, including a study of the resonances of the aromatic protons as they are affected by various substiluents. The CCl3 moiety on the α-carbon strongly deshields the ortho protons on the aromatic rings, and this deshielding effect is greatly enhanced by substitution of a chlorine ortho rather than para on the aromatic ring. These deshielding effects are explained by a consideration of the electronegativity of the substituents and the stereochemistry of the molecule. The chemical shifts and coupling constants are tabulated.

scholarly journals The Impact of Metabolic Scion–Rootstock Interactions in Different Grapevine Tissues and Phloem Exudates

Metabolites ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 349
Author(s):  
Sara Tedesco ◽  
Alexander Erban ◽  
Saurabh Gupta ◽  
Joachim Kopka ◽  
Pedro Fevereiro ◽  
...  
Keyword(s):  
Agronomic Traits ◽  
Phloem Exudate ◽  
Graft Union ◽  
Reciprocal Effect ◽  
Metabolic Markers ◽  
Interaction Studies ◽  
Metabolic Interactions ◽  
A Minor ◽  
The Impact ◽  
Related Compounds

In viticulture, grafting is used to propagate Phylloxera-susceptible European grapevines, thereby using resistant American rootstocks. Although scion–rootstock reciprocal signaling is essential for the formation of a proper vascular union and for coordinated growth, our knowledge of graft partner interactions is very limited. In order to elucidate the scale and the content of scion–rootstock metabolic interactions, we profiled the metabolome of eleven graft combination in leaves, stems, and phloem exudate from both above and below the graft union 5–6 months after grafting. We compared the metabolome of scions vs. rootstocks of homografts vs. heterografts and investigated the reciprocal effect of the rootstock on the scion metabolome. This approach revealed that (1) grafting has a minor impact on the metabolome of grafted grapevines when tissues and genotypes were compared, (2) heterografting affects rootstocks more than scions, (3) the presence of a heterologous grafting partner increases defense-related compounds in both scion and rootstocks in shorter and longer distances from the graft, and (4) leaves were revealed as the best tissue to search for grafting-related metabolic markers. These results will provide a valuable metabolomics resource for scion–rootstock interaction studies and will facilitate future efforts on the identification of metabolic markers for important agronomic traits in grafted grapevines.

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