1-(Arylsulfonyl)cyclopropanol, a new cyclopropanone equivalent and its application to prepare 1-alkynyl cyclopropylamine

Cyclopropanone derivative 1-(arylsulfonyl)cyclopropanol 4 simply prepared from the reaction of cyclopropanone ethyl hemiacetal 3 with sodium arylsufinate in the presence of formic acid is a new cyclopropanone equivalent to react with terminal acetylenes, and disubstituted amines in water catalyzed by AuCl₃, to provide an unprecedented synthesis of 1-alkynyl cyclopropylamines in moderate yields.     

A new convenient synthetic method for 3,4-diaryl-2,6-piperidinediones

A one-pot reaction for the preparation of 3,4-diaryl-2,6-piperidinediones through acid hydrolysis of the corresponding ethyl 3,4-diaryl-4-cyanobutyrates is described.

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Ein neuer einfacher Syntheseweg für 3,4-Diaryl-2,6-piperidindione

Zusammenfassung Durch saure Hydrolyse der entsprechenden Ethyl-3,4-diaryl-4-cyanobutyrate wurden in einem Schritt (Eintopfreaktion) die 3,4-Diaryl-2,6-piperidindione dargestellt.

     

A new synthetic route to substituted 1-fluoro-1-cyclopropanecarboxylates

Substituted 6-fluoro-2,4-dioxo-3-azabicyclo[3.1.0]hexane-6-carboxylates were obtained as a mixture of the exo- and endo-isomers by reaction of substituted 6,8-dioxo-2,3,7-triazabicyclo[3.3.0]oct-3-en-4-carboxylates with N-fluoropyridinium tetrafluoroborate.     

A facile method to prepare graphene-coat cotton and its application for lithium battery

The free-standing and binder-free electrode materials, cotton/graphene (CGN) composites were prepared via a simple “dipping and freeze-drying” process using raw cotton as the supporting body (platform) and graphene oxide (GO) as the suspension. Then the cotton/GO (CGO) composites were annealed at 1000 °C under an Ar flow conditions to obtain CGN composites. The results show that the CGN structure can protect the cotton framework and have better thermal stable property than the cotton alone. Galvanostatic charge–discharge tests demonstrated that the GO concentration had great effects on their electrochemical performances. The CGN (for the GO with 3 and 5 mg ml^?1) provide reversible discharge capacity of 160 mAh g^?1 after 100 cycles, which is about 1.5 times higher than that of the cotton alone (115 mAh g^?1 after 100 cycles). Excellent electrochemical properties of CGN can be ascribed to its controllable structure with more lithium ion storage sites, high electronic conductivity, and fast ion diffusion velocity. The results suggest that this work develops a simple, cheap, and suitable large-scale production method in the lithium-ion batteries.     

A novel oxidative reaction of 2-nitro-1-phenylpropane with sodium nitrite. A new approach to prepare 1-oximino-1-phenylacetones

A useful method for preparation of 1-oximino-1-phenylacetones via a novel oxidative reaction of 2-nitro-1-phenylpropanes with sodium nitrite was reported.     

A versatile method to prepare difluorinated primary alcohols and its application to the syntheses of novel acyclic fluorinated nucleosides

The addition of fluorine to a molecule often leads to intriguing changes in the properties of the molecule. Many novel drug leads and drug candidates are the results of the incorporation of fluorine. This Letter presents a versatile method to create molecules with the general structure R₁R₂CHCF₂CH₂OH from ketone R₁(CO)R₂. The key steps of this synthetic method involve the formation of a cyclic thiocarbonate and the regioselective radical opening of the thiocarbonate to yield the corresponding primary alcohol –CF₂CH₂OH. Using this synthetic method, novel fluorinated analogs of ganciclovir and penciclovir have been prepared.     

A new synthetic method of 3-acyltetronic acid derivatives and its application to the synthesis of isoaspertetronin a (isogregatin A)

A new synthetic method of 3-acyltetronic acid derivatives from the corresponding 3-bromo compound via lithiation with n-BuLi followed either by acylation with acid chloride or better by first reacting with aldehyde and then subsequent oxidation with active MnO₂ is described. A revised structure $\text{10}$ for aspertetronin A(gregatin A) was presented based on the synthesis of the proposed structure $\text{8}$ and spectral comparison of a model compound $\text{12}$ with the natural product.     

A new asymmetric synthetic route to substituted piperidines

An asymmetric synthesis of substituted piperidines has been described. β-Cyclodextrin- or oxazaborolidine-catalyzed asymmetric reduction of α-azido aryl ketones to the corresponding alcohols has been employed as the key step along with ring closing metathesis and selective dihydroxylation.     

The green synthetic approach to prepare PbS/chitosan nanocomposites and its new optical sensing active properties for 2-isonaphthol

PbS nanoparticles were successfully synthesized in the presence of chitosan (CS) through an in situ method. This method is an effective, simple, and green synthetic approach to preparing nanomaterial films. The structure, morphology, and stability of the materials were examined via Fourier transform infrared spectroscopy, and the characteristic peak of the NH₂ group shifted from 1554 to 1598 cm^-1 after PbS was formed in the film. The Pb–S bond exhibited a vibrational absorption peak at 605 cm^-1, which further confirmed the generation of PbS nanoparticles. Differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) procedures were performed as well; well-defined nanoparticles were detected in the CS matrix by SEM. As per DSC findings, the thermal stabilities of the PbS/CS film were 50°C higher than those of pure CS. Moreover, the fluorescence emission of the films was sensitive to the presence of 2-isonaphthol. The effect of 2-isonaphthol concentration on the emission of films increases significantly with an increase in this concentration. The concentration-dependent fluorescence can be described by a correlation equation when 2-isonaphthol concentration ranges from 0 to 12.56 mg/L, and fluorescence results revealed that the PbS/CS nanoparticles were sensitive to 2-isonaphthol in the liquid phase. The proposed method may be applied to detect 2-isonaphthol in the environment and in the chemical industry.     

A new synthetic route to tyromycin A and its analogue from renewable resources

The synthesis of tyromycin A and that of the non-natural lower homologue, involving as featuring steps a transition metal catalyzed atom transfer radical cyclization and a functional rearrangement of the polyhalogenated 2-pyrrolidinones thus obtained, are described. Both routes use 10-undecenoic acid, a renewable source from castor oil, as starting material for the preparation of the pivotal intermediates α,α,α′,α′-tetrachlorodicarboxylic acids.     

A convenient hydroiodination of alkynes using I2/PPh3/H2O and its application to the one-pot synthesis of trisubstituted alkenes via iodoalkenes using Pd-catalyzed cross-coupling reactions

A facile hydroiodination of alkynes using readily-available reagents such as I₂, PPh₃, and H₂O has been developed. This is extended to the one-pot synthesis of trisubstituted alkenes from alkynes via iodoalkenes using Pd-catalyzed cross-coupling and related methods such as the Suzuki–Miyaura cross-coupling, Sonogashira cross-coupling reaction, and Mizoroki–Heck reaction.     

A new kinetic method for the determination of magnesium and its application to natural waters

A kinetic method is described for the determination of trace amounts of magnesium in the presence of calcium. The procedure is based on the inhibition of the manganese(II) catalyzed aerial oxidation of 1,4-dihydroxyphthalimide dithiosemicarbazone reaction by

2. Effect of Transition Metals^a

Transition metal	Concentration (M)	Percentage inhibition	Mg(II) found (×l05M)
Fe(II)	3.6.10?5	54.1	4.62
Fe(III)	3.6.10?5	47.8	4.48
Co(II)	3.4.10?5	50.0	4.53
Ni(II)	3.4.10?5	50.0	4.53
Cu(II)	3.1.10?5	52.0	4.56
Zn(II)	3.0.10?5	54.1	4.62
Cd(II)	1.7.10?5	52.0	4.56
Hg(II)	9.9.10?6	45.8	4.44
Sn(II)	2.1.10?6	50.0	4.52
Pb(II)	1.2.10?6	54.1	4.62

a

Conditions: 4.53.10^?5M Mg(II), 35 ng Mn ml^?1, 0.429 M ammonia, 1.6.10^?4M OH-PDT.

3. Determination of Magnesium in Natural Waters

			Mg(II) found (M)b
Natural water	Ca(II) presenta		Atomic absorption
sample	M	Kinetic absorption	method
Commercial	3.45 · 10?4	1.65 · 10?3	1.74 · 10?3
Commercial	5.46 · 10?4	1.57 · 10?4	1.81 · 10?4
Untreated	6.13 · 10?4	2.16 · 10?4	2.40 · 10?4
Treated	4.95 · 10?4	1.93 · 10?4	2.17 · 10?4

a

EDTA titration less the magnesium.

b

Average of three separate determinations. traces of magnesium(II). The reaction is followed spectrophotometrically by measuring the rate of change in absorbance at 594 nm. The calibration graph (percentage inhibition vs magnesium concentration) is linear in the range 329–535 · 10^?5M with an accuracy and precision of 1.2%. The method has been applied to the determination of magnesium in natural waters at low concentrations.

     

On the reaction between alkyl isocyanides and 3-benzylidene-2,4-pentanedione. A convenient synthetic route to densely functionalized furans

Summary Alkyl isocyanides undergo a formal [1+4] cycloaddition reaction with 3-benzylidene-2,4-pentanedione yielding multiply functionalized furan ring systems in fairly high yields. The¹H NMR spectrum of 4-acetyl-2-(N-benzylamino)-5-methyl-3-phenylfuran shows an AB pattern for the benzylic methylene protons as a result of a restricted rotation about the bond between the acetyl group and the furan ring, thus giving rise to perpendicular disymmetric planes.

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Eine einfache Synthese von hochfunktionalisierten Furanen durch Reaktion von Alkylisocyaniden mit 3-Benzyliden-2,4-pentadion

Zusammenfassung Alkylisocyanide gehen mit 3-Benzyliden-2,4-pentadion eine formale [1+4]-Cycloaddition ein, die in relativ hohen Ausbeuten zu mehrfach funktionalisierten Furansystemen führt. Das¹H-NMR-Spektrum von 4-Acetyl-2-(N-benzylamino)-5-methyl-3-phenylfuran zeigt für die benzylischen Methylenprotonen ein AB-System, da das Molekül durch die sterische Hinderung der Rotation der Acetylgruppe asymmetrisch wird.

     

Development of new synthetic methods and its application to total synthesis of nitrogen-containing bioactive natural products

A group of naturally occurring substances containing nitrogen is widely distributed in plants as well as in fungi, animal, marine organisms, and insects, and many exhibit significant biological activity. These natural products with a huge variety of chemical structures include antibiotics, antitumor agents, immunostimulants, drugs affecting the cardiovascular and central nervous systems, analgesics etc. The diverse activities and low natural abundance of this group of natural products when coupled with their molecular complexity warrant development of new and efficient synthetic methods and strategy for the total synthesis of these products, in particular alkaloids. The purpose of this review is to describe some of our achievements in the total synthesis of the naturally-occurring bases including the Dendrobatid alkaloids pumiliotoxin B and allopumiliotoxin A, the anitibiotic streptazolin, the tricyclic marine alkaloids isolated from the ascidians such as fasicularin, lepadiformine, and cylindricine C, and the dimeric monoterpene alkaloid incarvillateine as well as the formal total synthesis of the spirocyclic marine alkaloids halichlorine and pinnaic acid, which are isolated from the Japanese marine sponge and the Okinawan bivalve, respectively.     

A novel and convenient route for the construction of 5-((1H-1,2,4-triazol-1-yl)methyl)-1H-indoles and its application in the synthesis of Rizatriptan

In this study, a novel and convenient route for the construction of 5-((1H-1,2,4-triazol-1-yl)methyl)-1H-indoles (8) is presented starting from (1H-1,2,4-triazol-1-yl)methanol (5) and indolines (6) under 98% H₂SO₄ at room temperature for 4–24 h, followed by deacetylation and dehydrogenation. Based on this finding, a novel route to synthesize Rizatriptan starting from tryptamine was designed and accomplished with 48.5% overall yield in 6 steps. Compared with operational art, the new route afforded higher yield and more pure products requiring no chromatographic purification, which may further be applied in industrialization.     

A novel synthetic route to 2-alkylpropane-1,3-sultones and its application to the synthesis of 2-alkyl derivatives of tramiprosate

A practical synthetic route to various 2-alkylpropane-1,3-sultones, the key intermediates for the preparation of 2-substituted homotaurines as analogs of tramiprosate, was developed.     

A new method to assay hypoxia-inducible factor-1 based on small molecule binding DNA

Hypoxia-inducible factor-1 (HIF-1) is among the most important indicators of hypoxia in evaluating severity of many diseases. In this work, a novel method for HIF-1 detection is proposed by using electrochemical techniques based on small molecule binding DNA. In this method, since the designed DNA sequence can specifically bind with either an electroactive small molecule or HIF-1, the signal readout is inversely proportional to HIF-1 concentration, thus a simple and easily-operated method for HIF-1 detection can be developed. With the proposed method, HIF-1 can be determined in a linear range from 5 to 25 nM with a detection limit of 2.8 nM. Furthermore, the proposed method can be directly used to assay HIF-1 in placenta tissue, and the assay results can reliably reflect the severity of preeclampsia, a very dangerous condition during pregnancy. The proposed method also shows desirable sensitivity, high selectivity and excellent reproducibility, so this method can have potential applications in clinical practice.     

A new direct current method for resistance measurements of ionic membranes and its application to composite membranes

The present paper deals with a D.C. method for measuring membrane electrical resistance making use of a constant current pulse, automated measuring equipment and taking into account polarization phenomena. The potential transient, subsequent to application of current, is analyzed, and membrane electrical resistance is determined by extrapolation to zero time of the potential differences measured after the current step. Experimental results obtained with commercial ion-exchange membranes were in good agreement with those computed from the diffusion equation. The method developed gives values with a standard deviation lower than traditional techniques. As an application example, the current pulse technique allows measurement of electrical resistance of composite silicafouled membranes in the electrodialysis process in both current directions. In this case the different response of the system, after the current pulse, gives useful information about membrane structure and ion distribution on the double layers surrounding the membrane.     

A new method for the preparation of 2-chlorotrityl resin and its application to solid-phase peptide synthesis

2-Chlorotritylchloride (2-CTC) resin was prepared efficiently from 1% DVB-crosslinked polystyrene resin and 1-chloro-2-(dichloro(phenyl)methyl)benzene, which was easily obtained from 2-chlorobenzophenone. This 2-CTC resin showed excellent properties as a support for solid-phase peptide synthesis. Four peptide fragments were obtained in high purity using the resin.