Enamines of 2,2-bis(ethylthio)ethanal: a convenient route to γ-keto crotonate derivatives

1983 ◽  
Vol 61 (11) ◽  
pp. 2466-2475 ◽  
Author(s):  
Gordon S. Bates ◽  
S. Ramaswamy
Keyword(s):  
Potassium Salt ◽  
Alkylating Agents ◽  
High Yield ◽  
Convenient Route ◽  
High Yields ◽  
Hydrolysis Of ◽  
Potential Precursor ◽  
Chiral Potential

A new α-oxoaldehyde reagent, 2,2-bis(ethylthio)ethanal 1, has been prepared in high yield from ethanedial. Alkylation of the potassium salt of the enamines of 1 with various alkylating agents followed by insitu hydrolysis of the intermediate imine afforded high yields of the alkylation products of 1. This new reagent was used in the synthesis of a chiral potential precursor of the macrocyclic fragment of cytochalasins A, B, and F, as well as in the syntheses of the physiologically active diolides pyrenophorin and norpyrenophorin.

2,2-Bis(ethylthio)ethanenitrile: preparation and use as a one or two carbon nucleophile

1983 ◽  
Vol 61 (9) ◽  
pp. 2006-2009 ◽  
Author(s):  
Gordon S. Bates ◽  
S. Ramaswamy
Keyword(s):  
Potassium Salt ◽  
Alkylating Agents ◽  
Conjugate Addition ◽  
Carbon Chain ◽  
Chain Extension ◽  
High Yield ◽  
Unsaturated Ketones ◽  
High Yields

2,2-Bis(ethylthio)ethanenitrile 1 was prepared in high yield from 2,2-bis(ethylthio)ethanal 2. Alkylation of the potassium salt of 1 with various alkylating agents and conjugate addition to cyclic α,β-unsaturated ketones provided high yields of the alkylation products of 1. The potential one and two carbon chain extension capability of this new reagent has been demonstrated.

Enolic Ortho Esters. I. Preparation and Birch Reduction of Some Coumarinoid Ortho Esters

1989 ◽  
Vol 42 (8) ◽  
pp. 1235 ◽  
Author(s):  
DJ Collins ◽  
LM Downes ◽  
AG Jhingran ◽  
SB Rutschmann ◽  
GJ Sharp
Keyword(s):  
Carbon Tetrachloride ◽  
Acid Hydrolysis ◽  
Boron Trifluoride ◽  
Boron Trifluoride Etherate ◽  
High Yield ◽  
Ortho Ester ◽  
Birch Reduction ◽  
High Yields ◽  
Ortho Esters ◽  
Hydrolysis Of

Phenolic ortho esters such as 4′,4′-dimethylspiro[2H-1-benzopyran-2,2′-[1,3]dioxolan] (7b) and 4′,4′-dimethyl-3,4-dihydrospiro[2H-1-benzopyran-2,2′-[1,3]dioxolan] (9c) were prepared in low yields by reaction of 2H-1-benzopyran-2-one (5) or 3,4-dihydro-2H-1-benzopyran-2-one (8a) with 2,2-dimethyloxiran in carbon tetrachloride in the presence of boron trifluoride etherate. 3,4-Dihydrospiro[2H-1-benzopyran-2,2′-[1,3] dioxoan ] (9a) and the corresponding 7-methoxy compound (9e) were obtained in high yield by reaction of (8a) or its 7-methoxy analogue (8b) with 1,2-bis(trimethylsily1oxy)ethane (10) in the presence of trimethylsilyl trifluoromethane-sulfonate . Birch reduction of phenolic ortho esters such as (9c) and (9e) afforded the enolic ortho esters 4′,4′-dimethyl-3,4,5,8-tetrahydrospiro[2H-1-benzopyran-2,2′-[1,3] dioxola n] (11a) and 7-methoxy-3,4,5,8-tetrahydrospiro[2H-1-benzopyran-2,2′-[1,3]dioxolan] (llc) in high yields. Birch reduction of 4′,4′,5′,5′-tetramethylspiro[2H-1-benzopyran-2,2′-[1,3]dioxolan] (7c) gave a 1 : 3 mixture of 4′,4′,5′,5′-tetramethyl-3,4-dihydrospiro[2H-1-benzopyran-2,2′-[l,3] dioxolan ] (9d) and the corresponding 3,4,5,8-tetrahydro compound (11b). Acid hydrolysis of the enolic ortho ester (11a) gave 67% of 2-hydroxy-2-methylpropyl 3-(2-oxocyclohex-3-enyl) propanoate (20).

Cycloaddition reactions of acetylenic iminium salts and diazoacetates leading to pyrazole iminium salts

2019 ◽  
Vol 74 (4) ◽  
pp. 347-355
Author(s):  
Holger Gerster ◽  
Michael Keim ◽  
Gerhard Maas
Keyword(s):  
General Formula ◽  
Michael Addition ◽  
Equimolar Amount ◽  
High Yield ◽  
Cycloaddition Reactions ◽  
Iminium Salts ◽  
Iminium Salt ◽  
Hydride Reduction ◽  
High Yields ◽  
Hydrolysis Of

AbstractAcetylenic iminium triflates with the general formula [R–C≡ C–C(Ar)=N+R2 TfO−] were found to be excellent dipolarophiles in [3+ 2] cycloaddition reactions with diazoacetates leading to (1H-pyrazol-3(5)-yl)methanaminium triflates in high yields. The terminal acetylenic iminium salt (propyne iminium salt) [HC≡C–C(Ph)=N+Me2 TfO−] reacted with an equimolar amount of methyl diazoacetate instantaneously at 20°C to form the expected pyrazole in almost quantitative yield. When a 2:1 stoichiometry was applied, subsequent Michael addition of the pyrazole at the alkyne occurred and the bis(iminium) ditriflate 4 was obtained in high yield. By hydride reduction or hydrolysis of the iminium group, some of the highly hygroscopic pyrazole iminium salts were converted into neutral, twofold functionalized, di- and tri-C-substitued 1H-pyrazoles.

Evaluation of germ plasm for resistant to Soybean mosaic virus (SMV)

2020 ◽  
Vol 21 (1) ◽  
pp. 6-9
Author(s):  
Wuye Ria Andayanie
Keyword(s):  
Abiotic Stress ◽  
Environmental Factors ◽  
Mosaic Virus ◽  
Polyclonal Antibody ◽  
Symptom Severity ◽  
Germ Plasm ◽  
Polyclonal Antibodies ◽  
Soybean Mosaic Virus ◽  
High Yield ◽  
High Yields

Soybean superior varieties with high yields and are resistant to abiotic stress have been largely released, although some varieties grown in the field are not resistant to SMV. In addition, the opportunity to obtain lines of hope as prospective varieties with high yield and resistance to SMV is very small. The method for evaluating soybean germplasm is based on serological observations of 98 accessions of leaf samples from SMV inoculation with T isolate. The evaluation results of 98 accessions based on visual observations showed 31 genotypes reacting very resistant or healthy to mild resistant category to SMV T isolate  with a percentage of symptom severity of 0 −30 %. Among 31 genotypes there are 2 genotypes (PI 200485; M8Grb 44; Mlg 3288) with the category of visually very resistant and resistant, respectively and  Mlg 3288  with the category of mild resistant.  They have a good agronomic appearance with a weight of 100 seeds (˃10 g) and react negatively with polyclonal antibodies to SMV, except Mlg 3288 reaction is not consistent, despite the weight of 100 seeds (˃ 10 g). Leaf samples from 98 accessions revealed various symptoms of SMV infection in the field. This diversity of symptoms is caused by susceptibility to accession, when infection occurs, and environmental factors. Keywords—: soybean; genotipe; Soybean mosaic virus (SMV); disease severity; polyclonal  antibody

scholarly journals Performance of Strawberry Varieties Developed for Perennial Matted-Row Production in Annual Plasticulture in a Cold Climate Region

Agronomy ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 1407
Author(s):  
Courtney A. Weber
Keyword(s):  
Large Scale ◽  
Fruit Size ◽  
Weather Conditions ◽  
Cold Climate ◽  
Annual Production ◽  
High Yield ◽  
Production Cycle ◽  
Late Season ◽  
Berry Weight ◽  
High Yields

Annual plasticulture production of strawberries promises superior weed control, fruit quality and yields. However, strawberry varieties adapted for perennial, matted-row production and local markets in cold climate regions have not been widely tested for adaptation to an annual production cycle. Productivity of seven short-day varieties developed for matted-row and/or annual production was examined in an annual plasticulture system in two consecutive trials in central NY (lat. 42.87° N, long. 76.99° W) harvested in 2013 and 2014. ‘Flavorfest’ demonstrated good performance in Trial 1 with high yield (390 g/plant) and large fruit size (13.9 g mean berry weight). ‘Jewel’ was shown to be well adapted to the annual plasticulture system with consistently high yields (330 and 390 g/plant) that equaled or surpassed other varieties and had moderate fruit size. ‘Chandler’ performed similarly to previous trials conducted in warmer regions with yield (340 g/plant) and fruit size (9.8 g mean berry weight) similar to ‘Jewel’. ‘Clancy’ yielded less but was consistent from year to year. The late season varieties Seneca and Ovation showed marked variability between years, possibly due to drastically different temperatures during flowering and fruit development in Trial 1 compared to Trial 2. High temperatures in Trial 1 likely caused higher early fruit yield, a compressed season and a precipitous decline in fruit size in the later season, thus reducing yield in the late season. Survival after a second dormant period was poor resulting in a small second harvest and reduced fruit size. Overall, the system demonstrated many of the expected benefits but may be more sensitive to weather conditions in the region. While many varieties developed for matted-row production may work well in an annual plasticulture system, not all varieties are equally adapted. Performance of each variety should be determined independently before large scale adoption by growers.

Direct conversion of cellulose to high-yield methyl lactate over Ga-doped Zn/H-nanozeolite Y catalysts in supercritical methanol

2017 ◽  
Vol 19 (8) ◽  
pp. 1969-1982 ◽  
Author(s):  
Deepak Verma ◽  
Rizki Insyani ◽  
Young-Woong Suh ◽  
Seung Min Kim ◽  
Seok Ki Kim ◽  
...  
Keyword(s):  
Lignocellulosic Biomass ◽  
Value Added ◽  
Direct Conversion ◽  
High Yield ◽  
Supercritical Methanol ◽  
Methyl Lactate ◽  
High Yields

For realizing sustainable bio-based refineries, it is crucial to obtain high yields of value-added chemicalsviadirect conversion of cellulose and lignocellulosic biomass.

scholarly journals Multi-curie production of gallium-68 on a biomedical cyclotron and automated radiolabelling of PSMA-11 and DOTATATE

2021 ◽  
Vol 6 (1) ◽  
Author(s):  
Helge Thisgaard ◽  
Joel Kumlin ◽  
Niels Langkjær ◽  
Jansen Chua ◽  
Brian Hook ◽  
...  
Keyword(s):  
Radiochemical Purity ◽  
High Yield ◽  
Clinical Use ◽  
Automated Production ◽  
Automated Method ◽  
Gallium 68 ◽  
High Yields ◽  
High Level ◽  
Mev Protons ◽  
Very High

Abstract Background With increasing clinical demand for gallium-68, commercial germanium-68/gallium-68 ([68Ge]Ge/[68Ga]Ga) generators are incapable of supplying sufficient amounts of the short-lived daughter isotope. In this study, we demonstrate a high-yield, automated method for producing multi-Curie levels of [68Ga]GaCl3 from solid zinc-68 targets and subsequent labelling to produce clinical-grade [68Ga]Ga-PSMA-11 and [68Ga]Ga-DOTATATE. Results Enriched zinc-68 targets were irradiated at up to 80 µA with 13 MeV protons for 120 min; repeatedly producing up to 194 GBq (5.24 Ci) of purified gallium-68 in the form of [68Ga]GaCl3 at the end of purification (EOP) from an expected > 370 GBq (> 10 Ci) at end of bombardment. A fully automated dissolution/separation process was completed in 35 min. Isolated product was analysed according to the Ph. Eur. monograph for accelerator produced [68Ga]GaCl3 and found to comply with all specifications. In every instance, the radiochemical purity exceeded 99.9% and importantly, the radionuclidic purity was sufficient to allow for a shelf-life of up to 7 h based on this metric alone. Fully automated production of up to 72.2 GBq [68Ga]Ga-PSMA-11 was performed, providing a product with high radiochemical purity (> 98.2%) and very high apparent molar activities of up to 722 MBq/nmol. Further, manual radiolabelling of up to 3.2 GBq DOTATATE was performed in high yields (> 95%) and with apparent molar activities (9–25 MBq/nmol) sufficient for clinical use. Conclusions We have developed a high-yielding, automated method for the production of very high amounts of [68Ga]GaCl3, sufficient to supply proximal radiopharmacies. The reported method led to record-high purified gallium-68 activities (194 GBq at end of purification) and subsequent labelling of PSMA-11 and DOTATATE. The process was highly automated from irradiation through to formulation of the product, and as such comprised a high level of radiation protection. The quality control results obtained for both [68Ga]GaCl3 for radiolabelling and [68Ga]Ga-PSMA-11 are promising for clinical use.

High yield and greener C–H difluoromethylation reactions using copper iodide nanoparticles/boron nitride nanosheets as a versatile and recyclable heterogeneous catalyst

2021 ◽  
Author(s):  
Udayakumar Veerabagu ◽  
Gowsika Jaikumar ◽  
Fushen Lu ◽  
Franck Quero
Keyword(s):  
Boron Nitride ◽  
Heterogeneous Catalyst ◽  
High Efficiency ◽  
High Yield ◽  
Copper Iodide ◽  
Boron Nitride Nanosheets ◽  
Greener Synthesis ◽  
High Yields ◽  
Recyclable Heterogeneous Catalyst

The 3 wt% CuI/BNNS catalyst exhibited high efficiency for C–H difluoromethylation reactions and enabled greener synthesis at high yields using cyrene as a solvent. Furthermore, the catalyst could be easily recovered and recycled for at least five cycles.

Zur Chemie des Bis(methylsulfonyl)-amins (Dimesylamins), V [1] N-Chlorsulfonyl-methansulfonamid: Ein Produkt der Reaktion von Tetramethylsilan mit Imido-bis(schwefelsäurechlorid) / Investigations on Bis(methylsulphonyl)-amine (Dimesylamine), V [1] N-Chlorosulphonyl-methanesulphonamide: A Reaction Product from Tetramethylsilane and Imido-bis(sulphuryl chloride)

1983 ◽  
Vol 38 (6) ◽  
pp. 793-794 ◽  
Author(s):  
Armand Blaschette ◽  
Gerlinde Seurig
Keyword(s):  
High Yield ◽  
Reaction Conditions ◽  
Product Mixture ◽  
Moisture Sensitive ◽  
Hydrolysis Of ◽  
Complex Manner

AbstractTetramethylsilane reacts with HN(SO2Cl)2 (1) in a complex manner, the nature of the product mixture depending strongly on the reaction conditions. Refluxing 1 with TMS in excess, using CH2Cl2 as a diluent, affords in high yield the new compound HN(SO2Cl)(SO2Me) (2) according to eq. (3). Hydrolysis of the crystal-line, moisture sensitive compound 2 is described by eq. (4).

scholarly journals Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

2018 ◽  
Vol 14 ◽  
pp. 2897-2906 ◽  
Author(s):  
Stanislav V Lozovskiy ◽  
Alexander Yu Ivanov ◽  
Olesya V Khoroshilova ◽  
Aleksander V Vasilyev
Keyword(s):  
Dft Calculations ◽  
Reaction Mechanisms ◽  
Dft Study ◽  
Bronsted Acids ◽  
Allyl Alcohols ◽  
High Yields ◽  
Hydrolysis Of

In strong Brønsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2–CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO–CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation of (arysulfonyl)butadienes (for instance, ArSO2–CR1=C–C(Me)=CH2, for R2 = R3 = Me, yields of 87–98%). Reactions of (arysulfonyl)allenes in the system TfOH (0.1 equiv)–HFIP (hexafluoropropan-2-ol) followed by hydrolysis give rise to allyl alcohols (ArSO2–CR1=CH–C(OH)R2R3, yields of 78–99%). Reflux of solutions of (arysulfonyl)allenes in the presence of TfOH (1 equiv) in 1,2-dichlorobenzene leads to the cyclization into thiochromene 1,1-dioxides in high yields. Under the action of TfOH or AlX3 (X = Cl, Br) followed by hydrolysis of reaction mixtures, (arylsulfinyl)allenes give allyl alcohols (ArSO2–CR1=CH–C(OH)R2R3). Plausible reaction mechanisms have been proposed for all studied reactions.

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