Ring opening of cyclobutene-1,2-dione and 3-trimethylsilylcyclobutene-1,2-dione. Dimerization/decarbonylation of a bisketene to a ketenylbutenolide

1999 ◽  
Vol 77 (5-6) ◽  
pp. 802-805 ◽  
Author(s):  
Annette D Allen ◽  
Thomas T Tidwell
Keyword(s):  
Ring Opening ◽  
H Nmr ◽  
First Time ◽  
Hydrolysis Of ◽  
Ketene Dimerization

Hydrolysis of 3-trimethylsilyl-4,4-dichlorocyclobut-2-ene-1-one (4) in H2SO4 gave small amounts of cyclobutene-1,2-dione (2a) and 3-trimethylsilylcyclobutene-1,2-dione (2d). Photolysis of 2a gave evidence for the formation of the bisketene (CH=C=O2) (1a) in solution for the first time, as identified by the IR band at 2120 cm-1 and the 1H NMR signal at δ 3.20. Thermolysis of 2d gave evidence for the intermediacy of O=C=CHC(SiMe3)=C=O (1d), with an 1H NMR signal at δ 3.43, and the isolation of the unusual ketenyl lactone 6, which could arise by formation of an unsymmetrical [2+2] ketene dimer from 1d, followed by rearrangement and decarbonylation.Key words: bisketenes, cyclobutenediones, ketene dimerization.

scholarly journals The hydrolysis of geminal ethers: a kinetic appraisal of orthoesters and ketals

2016 ◽  
Vol 12 ◽  
pp. 1467-1475 ◽  
Author(s):  
Sonia L Repetto ◽  
James F Costello ◽  
Craig P Butts ◽  
Joseph K W Lam ◽  
Norman M Ratcliffe
Keyword(s):  
Water Contamination ◽  
Jet Fuel ◽  
Computational Studies ◽  
Water Interface ◽  
H Nmr ◽  
Novel Approach ◽  
Rapid Hydrolysis ◽  
First Time ◽  
Hydrolysis Of ◽  
Hydrolysis Reactions

A novel approach to protecting jet fuel against the effects of water contamination is predicated upon the coupling of the rapid hydrolysis reactions of lipophilic cyclic geminal ethers, with the concomitant production of a hydrophilic acyclic hydroxyester with de-icing properties (Fuel Dehydrating Icing Inhibitors - FDII). To this end, a kinetic appraisal of the hydrolysis reactions of representative geminal ethers was undertaken using a convenient surrogate for the fuel–water interface (D2O/CD3CN 1:4). We present here a library of acyclic and five/six-membered cyclic geminal ethers arranged according to their hydroxonium catalytic coefficients for hydrolysis, providing for the first time a framework for the development of FDII. A combination of 1H NMR, labelling and computational studies was used to assess the effects that may govern the observed relative rates of hydrolyses.

Cardenolide aus Ornithogalum nutans (2 n = 28), 1. Mitteilung / Cardenolides from Ornithogalum nutans (2 n = 28), Part

1992 ◽  
Vol 47 (10) ◽  
pp. 1444-1458 ◽  
Author(s):  
Roland Ferth ◽  
Andreas Baumann ◽  
Wolfgang Robien ◽  
Brigitte Kopp
Keyword(s):  
Acid Hydrolysis ◽  
Column Chromatography ◽  
Structure Elucidation ◽  
European Species ◽  
H Nmr ◽  
First Time ◽  
Hydrolysis Of ◽  
C Nmr

From leaves and bulbs of Ornithogalum nutans L. (2 n = 28), seventeen cardenolides were isolated by column chromatography, DCCC and TLC. The structure elucidation was performed by means of 1H NMR, 13C NMR, HH-Cosy, HC-Cosy and FAB-MS studies and identification of the sugar moieties by GLC after acid hydrolysis of the cardenolides. Sugar compounds were identified as digitoxose, 3-acetyl-digitoxose, 2-deoxy-allose, 6-deoxy-allose, rhamnose, xylose and apiose. Glycosides of 7β,15β, 16 α-trihydroxy-uzarigenin, 8β,16 α-dihy-droxy, 15-oxo-uzarigenin, 3 β, 11β-dihydroxy, 12-oxo, 18-nor-5 α-card-13-enolid, 11 α-hydroxygitoxigenin, 12-oxo,8, 14β-epoxy-uzarigenin, 8β-hydroxy, 15-oxo-uzarigenin and 12β-hydroxy-oleandrigenin are described for the first time, the presence of oleandrigenin-glycosides in the genus Ornithogalum was not known until now. Ornithogalum nutans L. shows a different cardenolide pattern from the second European species of the section Myogalum (LINK) PETERM. - Ornithogalum boucheanum (KUNTH) ASCHERS.

scholarly journals Synthesis and characterization of different soybean oil-based polyols with fatty alcohol and aromatic alcohol

e-Polymers ◽  
2021 ◽  
Vol 21 (1) ◽  
pp. 491-499
Author(s):  
Fukai Yang ◽  
Hao Yu ◽  
Yuyuan Deng ◽  
Xinyu Xu
Keyword(s):  
Molecular Weight ◽  
Soybean Oil ◽  
Retention Time ◽  
Ring Opening ◽  
Isoamyl Alcohol ◽  
Synthesis And Characterization ◽  
Intermolecular Force ◽  
H Nmr ◽  
Epoxy Groups

Abstract In this article, five kinds of soybean oil-based polyols (polyol-E, polyol-P, polyol-I, polyol-B, and polyol-M) were prepared by ring-opening the epoxy groups in epoxidized soybean oil (ESO) with ethyl alcohol, 1-pentanol, isoamyl alcohol, p-tert-butylphenol, and 4-methoxyphenol in the presence of tetrafluoroboric acid as the catalyst. The SOPs were characterized by FTIR, 1H NMR, GPC, viscosity, and hydroxyl numbers. Compared with ESO, the retention time of SOPs is shortened, indicating that the molecular weight of SOPs is increased. The structure of different monomers can significantly affect the hydroxyl numbers of SOPs. Due to the large steric hindrance of isoamyl alcohol, p-hydroxyanisole, and p-tert-butylphenol, SOPs prepared by these three monomers often undergo further dehydration to ether reactions, which consumes the hydroxyl of polyols, thus forming dimers and multimers; therefore, the hydroxyl numbers are much lower than polyol-E and polyol-P. The viscosity of polyol-E and polyol-P is much lower than that of polyol-I, polyol-B, and polyol-M. A longer distance between the molecules and the smaller intermolecular force makes the SOPs dehydrate to ether again. This generates dimer or polymers and makes the viscosity of these SOPs larger, and the molecular weight greatly increases.

scholarly journals Optimisation of Recombinant Myrosinase Production in Pichia pastoris

2021 ◽  
Vol 22 (7) ◽  
pp. 3677
Author(s):  
Zuzana Rosenbergová ◽  
Kristína Kántorová ◽  
Martin Šimkovič ◽  
Albert Breier ◽  
Martin Rebroš
Keyword(s):  
Pichia Pastoris ◽  
Plant Defence ◽  
Plant Secondary Metabolites ◽  
Specific Productivity ◽  
Fermentation Conditions ◽  
Threefold Increase ◽  
Dry Cell Weight ◽  
First Time ◽  
Hydrolysis Of ◽  
Dry Cell

Myrosinase is a plant defence enzyme catalysing the hydrolysis of glucosinolates, a group of plant secondary metabolites, to a range of volatile compounds. One of the products, isothiocyanates, proved to have neuroprotective and chemo-preventive properties, making myrosinase a pharmaceutically interesting enzyme. In this work, extracellular expression of TGG1 myrosinase from Arabidopsis thaliana in the Pichia pastoris KM71H (MutS) strain was upscaled to a 3 L laboratory fermenter for the first time. Fermentation conditions (temperature and pH) were optimised, which resulted in a threefold increase in myrosinase productivity compared to unoptimised fermentation conditions. Dry cell weight increased 1.5-fold, reaching 100.5 g/L without additional glycerol feeding. Overall, a specific productivity of 4.1 U/Lmedium/h was achieved, which was 102.5-fold higher compared to flask cultivations.

scholarly journals Synthesis and Characterization of Polyphosphazenes Modified with Hydroxyethyl Methacrylate and Lactic Acid

2013 ◽  
Vol 2013 ◽  
pp. 1-7 ◽  
Author(s):  
Evelyn Carolina Martínez Ceballos ◽  
Ricardo Vera Graziano ◽  
Gonzalo Martínez Barrera ◽  
Oscar Olea Mejía
Keyword(s):  
Lactic Acid ◽  
Ring Opening ◽  
Room Temperature ◽  
Block Structure ◽  
Ring Opening Polymerization ◽  
Synthesis And Characterization ◽  
Poly Lactic Acid ◽  
Hydroxyethyl Methacrylate ◽  
H Nmr

Poly(dichlorophosphazene) was prepared by melt ring-opening polymerization of the hexachlorocyclotriphosphazene. Poly[bis(2-hydroxyethyl-methacrylate)-phosphazene] and poly[(2-hydroxyethyl-methacrylate)-graft-poly(lactic-acid)-phosphazene] were obtained by nucleophilic condensation reactions at different concentrations of the substituents. The properties of the synthesized copolymers were assessed by FTIR,1H-NMR and31P-NMR, thermal analysis (DSC-TGA), and electron microscopy (SEM). The copolymers have a block structure and show twoTg's below room temperature. They are stable up to a temperature of 100°C. The type of the substituents attached to the PZ backbone determines the morphology of the polymers.

scholarly journals Biosynthesis of anandamide and N-palmitoylethanolamine by sequential actions of phospholipase A2 and lysophospholipase D

2004 ◽  
Vol 380 (3) ◽  
pp. 749-756 ◽  
Author(s):  
Yong-Xin SUN ◽  
Kazuhito TSUBOI ◽  
Yasuo OKAMOTO ◽  
Takeharu TONAI ◽  
Makoto MURAKAMI ◽  
...  
Keyword(s):  
Biosynthetic Pathway ◽  
Brain Homogenate ◽  
Wide Distribution ◽  
Rat Tissues ◽  
Lysophospholipase D ◽  
Pla2 Enzyme ◽  
First Time ◽  
Hydrolysis Of ◽  
The Brain

Anandamide (an endocannabinoid) and other bioactive long-chain NAEs (N-acylethanolamines) are formed by direct release from N-acyl-PE (N-acyl-phosphatidylethanolamine) by a PLD (phospholipase D). However, the possible presence of a two-step pathway from N-acyl-PE has also been suggested previously, which comprises (1) the hydrolysis of N-acyl-PE to N-acyl-lysoPE by PLA1/PLA2 enzyme(s) and (2) the release of NAEs from N-acyllysoPE by lysoPLD (lysophospholipase D) enzyme(s). In the present study we report for the first time the characterization of enzymes responsible for this pathway. The PLA1/PLA2 activity for N-palmitoyl-PE was found in various rat tissues, with the highest activity in the stomach. This stomach enzyme was identified as group IB sPLA2 (secretory PLA2), and its product was determined as N-acyl-1-acyl-lysoPE. Recombinant group IB, IIA and V of sPLA2s were also active with N-palmitoyl-PE, whereas group X sPLA2 and cytosolic PLA2α were inactive. In addition, we found wide distribution of lysoPLD activity generating N-palmitoylethanolamine from N-palmitoyl-lysoPE in rat tissues, with higher activities in the brain and testis. Based on several lines of enzymological evidence, the lysoPLD enzyme could be distinct from the known N-acyl-PE-hydrolysing PLD. sPLA2-IB dose dependently enhanced the production of N-palmitoylethanolamine from N-palmitoyl-PE in the brain homogenate showing the lysoPLD activity. N-Arachidonoyl-PE and N-arachidonoyl-lysoPE as anandamide precursors were also good substrates of sPLA2-IB and the lysoPLD respectively. These results suggest that the sequential actions of PLA2 and lysoPLD may constitute another biosynthetic pathway for NAEs, including anandamide.

Synthesis and characterization of meso-to-meso directly linked porphyrin-diazaporphyrin triads

2018 ◽  
Vol 22 (09n10) ◽  
pp. 814-820
Author(s):  
Yingying Jia ◽  
Ling Xu ◽  
Bangshao Yin ◽  
Mingbo Zhou ◽  
Jianxin Song
Keyword(s):  
Nickel Complex ◽  
High Resolution Mass Spectrometry ◽  
Dihedral Angles ◽  
X Ray Diffraction ◽  
Extinction Coefficients ◽  
X Ray ◽  
H Nmr ◽  
First Time ◽  
Molar Extinction Coefficients

Beginning with 5,10,15-triarylporphyrin-nickel complex, five meso-to-meso directly linked porphyrin-diazaporphyrin triads were successfully prepared for the first time through a series of reactions including formylation via Vilsmeier–Haack reaction, condensation with pyrrole, bromination with [Formula: see text]-Bromosuccinimide (NBS), oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), metal-templated cyclization of dibromodipyrrin-metal complexes with NaN[Formula: see text] and demetalization. All these triads were comprehensively characterized by [Formula: see text]H NMR, high-resolution mass spectrometry and UV-vis absorption. In addition, the structure of compound 6Ni was unambiguously determined by X-ray diffraction analysis, which showed that the two dihedral angles are both 86.65 (4)[Formula: see text] between each mean plane of porphyrin and that of central diazaporphyrin The UV-vis absorption spectra disclosed that the longest wavelengths of Soret bands and Q bands for these triads were observed at 429 and 642 nm, respectively. In contrast to diazaporphyrin-porphyrin dyads, diazaporphyrin dimers and diazaporphyrin monomers reported previously the molar extinction coefficients, particularly for triad 8Ni are much higher.

Enzyme system of Clostridium stercorarium for hydrolysis of arabinoxylan: reconstitution of the in vivo system from recombinant enzymes

Microbiology ◽  
2004 ◽  
Vol 150 (7) ◽  
pp. 2257-2266 ◽  
Author(s):  
Helmuth Adelsberger ◽  
Christian Hertel ◽  
Erich Glawischnig ◽  
Vladimir V. Zverlov ◽  
Wolfgang H. Schwarz
Keyword(s):  
Extracellular Enzymes ◽  
Enzyme System ◽  
Thermophilic Bacterium ◽  
Recombinant Enzymes ◽  
Type Mode ◽  
Complete Set ◽  
First Time ◽  
Hydrolysis Of

Four extracellular enzymes of the thermophilic bacterium Clostridium stercorarium are involved in the depolymerization of de-esterified arabinoxylan: Xyn11A, Xyn10C, Bxl3B, and Arf51B. They were identified in a collection of eight clones producing enzymes hydrolysing xylan (xynA, xynB, xynC), β-xyloside (bxlA, bxlB, bglZ) and α-arabinofuranoside (arfA, arfB). The modular enzymes Xyn11A and Xyn10C represent the major xylanases in the culture supernatant of C. stercorarium. Both hydrolyse arabinoxylan in an endo-type mode, but differ in the pattern of the oligosaccharides produced. Of the glycosidases, Bxl3B degrades xylobiose and xylooligosaccharides to xylose, and Arf51B is able to release arabinose residues from de-esterified arabinoxylan and from the oligosaccharides generated. The other glycosidases either did not attack or only marginally attacked these oligosaccharides. Significantly more xylanase and xylosidase activity was produced during growth on xylose and xylan. This is believed to be the first time that, in a single thermophilic micro-organism, the complete set of enzymes (as well as the respective genes) to completely hydrolyse de-esterified arabinoxylan to its monomeric sugar constituents, xylose and arabinose, has been identified and the enzymes produced in vivo. The active enzyme system was reconstituted in vitro from recombinant enzymes.

Design, synthesis and evaluation of structurally diverse ortho-acylphenol-diindolylmethane hybrids as anticancer agents

2022 ◽  
Author(s):  
Zhi-Gang Yin ◽  
Xiong-Wei Liu ◽  
Hui-Juan Wang ◽  
Min Zhang ◽  
Xiong-Li Liu ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Anticancer Agents ◽  
Nucleophilic Addition ◽  
Ring Opening ◽  
Building Blocks ◽  
Efficient Synthesis ◽  
Design Synthesis ◽  
Pyrone Ring ◽  
Ring Opening Reaction ◽  
First Time

A highly efficient synthesis of structurally diverse ortho-acylphenol–diindolylmethane hybrids 3 using carboxylic acid-activated chromones as versatile synthetic building blocks is reported here for the first time, through 1,4-nucleophilic addition and followed by a decarboxylation and pyrone ring opening reaction process.

scholarly journals NH<sub>3</sub>-promoted hydrolysis of NO<sub>2</sub> induces explosive growth in HONO

2018 ◽  
Author(s):  
Wanyun Xu ◽  
Ye Kuang ◽  
Chunsheng Zhao ◽  
Jiangchuan Tao ◽  
Gang Zhao ◽  
...  
Keyword(s):  
North China Plain ◽  
North China ◽  
Ph Value ◽  
Primary Source ◽  
Field Measurements ◽  
Oh Radicals ◽  
The North ◽  
The North China Plain ◽  
First Time ◽  
Hydrolysis Of

Abstract. The study of atmospheric nitrous acid (HONO), which is the primary source of OH radicals, is crucial to atmospheric photochemistry and heterogeneous chemical processes. The heterogeneous NO2 chemistry under haze conditions was pointed out to be one of the missing sources of HONO on the North China Plain, producing sulfate and nitrate in the process. However, controversy exists between various proposed mechanisms, mainly debating on whether SO2 directly takes part in the HONO production process and what roles NH3 and the pH value play in it. In this paper, never before seen explosive HONO production (maximum rate: 16 ppb/hour) was reported and evidence was found for the first time in field measurements during fog episodes (usually with pH > 5) and haze episodes under high relative humidity (usually with pH 

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