scholarly journals Efficient regio- and stereoselective access to novel fluorinated β-aminocyclohexanecarboxylates

2013 ◽  
Vol 9 ◽  
pp. 1164-1169 ◽  
Author(s):  
Loránd Kiss ◽  
Melinda Nonn ◽  
Reijo Sillanpää ◽  
Santos Fustero ◽  
Ferenc Fülöp
Keyword(s):  
Double Bond ◽  
Stereoselective Method ◽  
Aminocyclohexanecarboxylic Acid

A regio- and stereoselective method has been developed for the synthesis of novel fluorinated 2-aminocyclohexanecarboxylic acid derivatives with the fluorine attached to position 4 of the ring. The synthesis starts from either cis- or trans-β-aminocyclohex-4-enecarboxylic acids and involves regio- and stereoselective transformation of the ring C–C double bond through iodooxazine formation and hydroxylation, followed by hydroxy–fluorine or oxo–fluorine exchange.

scholarly journals NbCl5-Mg Reagent System in Regio- and Stereoselective Synthesis of (2Z)-Alkenylamines and (3Z)-Alkenylols from Substituted 2-Alkynylamines and 3-Alkynylols

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3722
Author(s):  
Rita N. Kadikova ◽  
Azat M. Gabdullin ◽  
Oleg S. Mozgovoj ◽  
Ilfir R. Ramazanov ◽  
Usein M. Dzhemilev
Keyword(s):  
Double Bond ◽  
Stereoselective Synthesis ◽  
Efficient Tool ◽  
Magnesium Metal ◽  
Methanesulfonyl Chloride ◽  
Homoallylic Alcohols ◽  
Homopropargylic Alcohols ◽  
Stereoselective Method ◽  
High Yields

The reduction of N,N-disubstituted 2-alkynylamines and substituted 3-alkynylols using the NbCl5–Mg reagent system affords the corresponding dideuterated (2Z)-alkenylamine and (3Z)-alkenylol derivatives in high yields in a regio- and stereoselective manner through the deuterolysis (or hydrolysis). The reaction of substituted propargylamines and homopropargylic alcohols with the in situ generated low-valent niobium complex (based on the reaction of NbCl5 with magnesium metal) is an efficient tool for the synthesis of allylamines and homoallylic alcohols bearing a 1,2-disubstituted double bond. It was found that the well-known approach for the reduction of alkynes based on the use of the TaCl5-Mg reagent system does not work for 2-alkynylamines and 3-alkynylols. Thus, this article reveals a difference in the behavior of two reagent systems—NbCl5-Mg and TaCl5-Mg, in relation to oxygen- and nitrogen-containing alkynes. A regio- and stereoselective method was developed for the synthesis of nitrogen-containing E-β-chlorovinyl sulfides based on the reaction of 2-alkynylamines with three equivalents of methanesulfonyl chloride in the presence of stoichiometric amounts of niobium(V) chloride and magnesium metal in toluene.

THE THYMOLYTIC ACTIVITY OF 6- AND 9-HALOCORTICOIDS AND RELATED STEROIDS

1965 ◽  
Vol 49 (2) ◽  
pp. 262-270 ◽  
Author(s):  
Ralph I. Dorfman ◽  
P. G. Holton ◽  
Fred A. Kind
Keyword(s):  
Double Bond ◽  
Subcutaneous Injection ◽  
Fluocinolone Acetonide ◽  
Relative Potency ◽  
Subcutaneous Route ◽  
Adrenalectomized Rats

ABSTRACT Adrenalectomized rats were used for the determination of the relative potency of various 6- and 9-halo substituted corticoids administered subcutaneously or by gavage using thymus weightas the endpoint. By subcutaneous injection, fluocinolone acetonide was the most active corticoid at 700 times that of cortisol. This compound was also the most active corticoid by the gavage route and was judged to be 570 times as active as the standard cortisol. The introduction of the 16,17-acetonide and 16,17-acetone 21-acetate groups into 17α,21-dihydroxy-9α,11β-dichloropregna-1,4-diene-3,20-dione increased the activity by a factor of 42 and 100, respectively. The introduction of the δ1 double bond into 6α-fluoroprogesterone 16,17-acetonide caused an increase of 10-fold in thymolytic activity assessed by the subcutaneous route

TRIGLYCERIDE COMPOSITION OF SIXTEEN STRAINS OF MARINE DIATOM

2013 ◽  
Vol 5 (1) ◽  
Author(s):  
Lily M.G. Panggabean ◽  
Abdullah Rasyid ◽  
Zarrah Duniani ◽  
Yana Meliana ◽  
Indah Kurniasih
Keyword(s):  
Mass Spectrometry ◽  
Fatty Acid ◽  
Double Bond ◽  
Unsaturated Fatty Acid ◽  
Ion Trap ◽  
Carbon Chain ◽  
Highly Unsaturated Fatty Acid ◽  
Marine Diatom ◽  
Ion Trap Mass Spectrometry ◽  
Spectra Analysis

Trigliceride or triacylglicerol (TAG) composition in crude oil of sixteen strain of marine diatom has been detected by spectra analyses on an Electrospray - Ion Trap – Mass Spectrometry (ESI-IT-MS) HCT Bruker-Daltonic GmbH instrument with AgNO3 used as coordination ionization agent. Biomass samples of each microalga strain were taken from early and late stationary cultures in f/2 enriched seawater and algal oils were extracted according to Bligh and Dyer. Results from spectra analysis showed that P-Pt-P (C16:0-C16:1-C16:0) were distinguished in TAG from diatom strains Chaetoceros sp.1, Chaetoceros sp.2, Thalasiossira sp.1, Thalasiossira sp.2, Thalasiossira sp.3, Navicula sp. 1, Navicula sp. 2, Navicula sp. 3, Navicula sp. 4, Nitzschia sp. 2 and Amphora sp. In contrast, TAGs in Melosira sp. included P-P-P (C16:0-C16:0-C16:0) and P-P-O (C16:0-C16:0-C18:1) were identified. TAGs from Chaetoceros sp. were the most varies among samples, i.e. P-Pt-P (C16:0-C16:1-C16:0), A-P-M (C20:4-C16:0-C14:0), P-Pt-Lt (C16:0-C16:1-C18:3), P-Pt-A (C16:0-C16:1-C20:4), D-P-P (C22:6-C16:0-C16:0), A-Ln-P (C20:4-C18:2-C16:0). Various TAGs were also detected in Nitzschia sp.2, i.e. P-Pt-M (C16:0-C16:1-C14:0), P-Pt-P (C16:0-C16:1-C16:0), P-Pt-S (C16:0-C16:1-C18:0), P-Pt-A (C16:0-C16:1-C20:4). TAGs composition in Skeletonema strains that similar to those in Nitzschia sp.1 has longer carbon, i.e. P-P-O (C16:0-C16:0-C18:1), P-O-O (C16:0-C18:1-C18:1) and O-O-O (C18:1-C18:1-C18:1). TAGs with longer carbon chain and more double bond including highly unsaturated fatty acid C20:4 were increased with culture age in diatoms Chaetoceros sp.1, Chaetoceros sp.2, Thalasiossira sp.2, Navicula sp.1 and Nitzschia sp. 2.Keywords: diatom, TAG, ESI-IT-MS, f/2, early and late stationary

Some Considerations Regarding the 1H and 13C Spectra of 4-(1-azulenyl)-2,6-bis(2-heteroaryl-vinyl)- pyrylium and Pyridinium and their Corresponding Pyridines

2018 ◽  
Vol 69 (1) ◽  
pp. 64-69
Author(s):  
Liviu Birzan ◽  
Mihaela Cristea ◽  
Constantin C. Draghici ◽  
Alexandru C. Razus
Keyword(s):  
Double Bond ◽  
13C Nmr ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Pyridinium Salts ◽  
13C Nmr Spectra ◽  
1H And 13C Nmr ◽  
Pyrylium Salts

The 1H and 13C NMR spectra of several 2,6-diheteroarylvinyl heterocycles containing 4-azulenyl moiety were recorded and their proton and carbon chemical shifts were compared with those of the compounds without double bond between the heterocycles. The influence of the nature of central and side heterocycles, molecule polarization and anisotropic effects were revealed. The highest chemical shifts were recorded for the pyrylium salts and the lowest at pyridines, but in the case of the pyridinium salts, the protons chemical shifts at the central heterocycle are more shielded due to a peculiar anisotropy of the attached vinyl groups.

Combinatorial Synthesis of Novel 9R-Acyloxyquinine Derivatives as Insecticidal Agents

2020 ◽  
Vol 23 (2) ◽  
pp. 111-118
Author(s):  
Zhiping Che ◽  
Jinming Yang ◽  
Di Sun ◽  
Yuee Tian ◽  
Shengming Liu ◽  
...  
Keyword(s):  
Natural Products ◽  
Double Bond ◽  
Insecticidal Activity ◽  
Structural Modification ◽  
Combinatorial Synthesis ◽  
Hydroxyl Group ◽  
Botanical Insecticide ◽  
Mythimna Separata ◽  
Lead Compounds

Background: It is one of the effective ways for pesticide innovation to develop new insecticides from natural products as lead compounds. Quinine, the main alkaloid in the bark of cinchona tree as well as in plants in the same genus, is recognized as a safe and potent botanical insecticide to many insects. The structural modification of quinine into 9R-acyloxyquinine derivatives is a potential approach for the development of novel insecticides, which showed more toxicity than quinine. However, there are no reports on the insecticidal activity of 9Racyloxyquinine derivatives to control Mythimna separata. Methods: Endeavor to discover biorational natural products-based insecticides, 20 novel 9Racyloxyquinine derivatives were prepared and assessed for their insecticidal activity against M. separata in vivo by the leaf-dipping method at 1 mg/mL. Results: Among all the compounds, especially derivatives 5i, 5k and 5t exhibited the best insecticidal activity with final mortality rates of 50.0%, 57.1%, and 53.6%, respectively. Conclusion: Overall, a free 9-hydroxyl group is not a prerequisite for insecticidal activity and C9- substitution is well tolerated; modification of out-ring double-bond is acceptable, and hydrogenation of double-bond enhances insecticidal activity; Quinine ring is essential and open of it is not acceptable. These preliminary results will pave the way for further modification of quinine in the development of potential new insecticides.

One-pot Synthesis of Pyrazolone Sulfones by Iodine-catalyzed Sulfenylation of Pyrazolones with Aryl Sulfonyl Hydrazides Followed by Oxidation in Water

2018 ◽  
Vol 15 (3) ◽  
pp. 380-387
Author(s):  
Xia Zhao ◽  
Xiaoyu Lu ◽  
Lipeng Zhang ◽  
Tianjiao Li ◽  
Kui Lu
Keyword(s):  
Double Bond ◽  
Efficient Method ◽  
Room Temperature ◽  
Sulfonyl Chloride ◽  
Antibacterial Activities ◽  
Oxidation Reactions ◽  
Reaction Conditions ◽  
One Pot ◽  
X Ray ◽  
Amide Form

Aim and Objective: Pyrazolone sulfones have been reported to exhibit herbicidal and antibacterial activities. In spite of their good bioactivities, only a few methods have been developed to prepare pyrazolone sulfones. However, the substrate scope of these methods is limited. Moreover, the direct sulfonylation of pyrazolone by aryl sulfonyl chloride failed to give pyrazolone sulfones. Thus, developing a more efficient method to synthesize pyrazolone sulfones is very important. Materials and Method: Pyrazolone, aryl sulphonyl hydrazide, iodine, p-toluenesulphonic acid and water were mixed in a sealed tube, which was heated to 100°C for 12 hours. The mixture was cooled to 0°C and m-CPBA was added in batches. The mixture was allowed to stir for 30 min at room temperature. The crude product was purified by silica gel column chromatography to afford sulfuryl pyrazolone. Results: In all cases, the sulfenylation products were formed smoothly under the optimized reaction conditions, and were then oxidized to the corresponding sulfones in good yields by 3-chloroperoxybenzoic acid (m-CPBA) in water. Single crystal X-ray analysis of pyrazolone sulfone 4aa showed that the major tautomer of pyrazolone sulfones was the amide form instead of the enol form observed for pyrazolone thioethers. Moreover, the C=N double bond isomerized to form an α,β-unsaturated C=C double bond. Conclusion: An efficient method to synthesize pyrazolone thioethers by iodine-catalyzed sulfenylation of pyrazolones with aryl sulfonyl hydrazides in water was developed. Moreover, this method was employed to synthesize pyrazolone sulfones in one-pot by subsequent sulfenylation and oxidation reactions.

A Novel Scheme for the Synthesis of 21-Acetoxypregna-1,4,9(11)-triene- 17α,21-diol-3,20-dione from 9α-Hydroxyandrostenedione

2020 ◽  
Vol 16 (5) ◽  
pp. 606-610
Author(s):  
Nguyen T. Diep ◽  
Luu D. Huy
Keyword(s):  
Double Bond ◽  
Chemical Synthesis ◽  
Economic Efficiency ◽  
Final Stage ◽  
Side Chain ◽  
Entire Process ◽  
Drug Synthesis ◽  
First Time

Background: Vietnam currently imports up to 90% of the pharmaceuticals it consumes and 100% of the steroid-based pharmaceuticals. The ability for efficient chemical synthesis of the steroids could create commercial opportunities to address this issue. Synthesis of 21-acetoxypregna-1,4,9(11)- triene-17α,21-diol-3,20-dione is considered a key intermediate in the scheme of steroidal drug synthesis. Previous synthesis attempts of such steroids (corticoids) introduce a double bond at C-1(2) in the final stage of synthesis, which delivers a poor yield and reduces the economic efficiency of the process. Objective: To study and develop a novel and effective method for the synthesis of 21-acetoxypregna- 1,4,9(11)-triene-17α,21-diol-3,20-dione. Methods: Using 9α-hydroxyandrostenedione as a substrate chemical synthesis was performed as follows: pregnane side chain construction at C-17 (acetylene method), introduction of C-1(2) double bond (using SeO2), epimerization of C-17 (via 17-ONO2 ester) and Stork’s iodination. Results: 21-acetoxypregna-1,4,9(11)-triene-17α,21-diol-3,20-dione was prepared from 9α- hydroxyandrostenedione with an improved yield compared to previous attempts. Conclusion: Here, 21-acetoxypregna-1,4,9(11)-triene-17α,21-diol-3,20-dione has been synthesized from 9α-hydroxyandrostenedione based on a novel, effective and commercially feasible scheme. The introduction of the C-1(2) double bond at an earlier stage of the synthesis has increased the economic efficiency of the entire process. For the first time, the indirect epimerization mechanism has been clarified along with the configuration of the C-17 stereo-center which has been confirmed using NOESY data.

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