Showing papers on "Boron trifluoride published in 2017"

Boron Trifluoride-Catalyzed Synthesis of 3-Alkylidene-3H-indole N-Oxides via Tandem Reaction of Propargylic Alcohols and Nitrosobenzenes

Abstract: An atom-economical synthesis of 3-alkylidene-3H-indole N-oxides has been developed via a tandem reaction of propargylic alcohols and nitrosobenzenes in the presence of boron trifluoride etherate (BF3⋅Et2O) as catalyst. This method offers great potential for the synthesis of biologically important 3-alkylidene-3H-indole N-oxides and related derivatives.

Tuning the photophysical properties of BODIPY dyes through extended aromatic pyrroles

Abstract: Three new BODIPY dyes have been synthesized by a two-step synthetic route. This expands the series to nine different BODIPY dyes by this method. Naphtha[1,2-c]pyrrole was combined with 1-pyrenecarboxaldehyde to give a symmetric dipyrrin followed by reaction with boron trifluoride to give a symmetric highly conjugated BODIPY dye. Expanding this synthetic route to a more conjugated pyrrole fluorantho[2,3-c]pyrrole was combined with 1-pyrenecarboxaldehyde followed by reaction with boron trifluoride to give the asymmetric BODIPY dye (9). Dyes with the more highly conjugated fluoranthopyrrole resulted in a bathochromic shift of ca. 50 nm in the electronic absorption and showed greater stability of the LUMO energy, as determined by electrochemical measurements, compared to their naphthapyrrole analogs. All of the dyes synthesized by this method display molar absorptivities greater than 100 000 M−1 cm−1 with photoluminescence quantum efficiencies of 0.8–1.0. Excited state lifetimes of the dyes in dichloromethane are modest, ranging from 3.2 ns to 4.3 ns.

Pyreniporphyrins: Porphyrin Analogues That Incorporate a Polycyclic Aromatic Hydrocarbon Subunit within the Macrocyclic Framework

Abstract: The first examples of porphyrin analogues incorporating pyrene units are reported Acid-catalyzed condensation of a pyrene dialdehyde with a tripyrrane, followed by oxidation with DDQ, afforded a polycyclic aromatic hydrocarbon (PAH)–porphyrin hybrid in 38% yield Pyreniporphyrin proved to be devoid of global aromatic character, but upon protonation aromatic mono- and dicationic species were generated In the proton NMR spectrum for the dication, the internal CH was shifted upfield to approximately +3 ppm NICS calculations and ACID plots confirmed the diatropic nature of these structures Pyreniporphyrin reacted with palladium(II) acetate to give excellent yields of a palladium(II) complex that showed weakly diatropic properties Treatment of the pyrene dialdehyde with phenylmagnesium bromide generated a dicarbinol that reacted with excess pyrrole in the presence of boron trifluoride etherate to give a tripyrrane analogue Lewis acid catalyzed ring closure with a thiophene dialcohol in 2% ethanol–dichlor

Boron Complexes of Glyoxal-Derived Ugi Adducts as a New Class of Aggregation-Induced Emission Photoluminescent Materials.

Abstract: A series of O,O-chelated boron complexes was prepared through a four-component Ugi reaction followed by complexation of the resulting 1,3-dicarbonyl compounds with boron trifluoride diethyl etherate. The optical properties of these novel luminophores were investigated by UV/Vis spectroscopy and spectrofluorometry, revealing pronounced aggregation-induced emission (AIE) features.

A Stable N-Annulated Perylene-Bridged Bisphenoxyl Diradicaloid and the Corresponding Boron Trifluoride Complex.

Abstract: Organic π-extended radicals display unique electronic structures and could be used as promising functional materials. However, design and synthesis of stable radicals are challenging for chemists due to their intrinsic high reactivity. In this work, we synthesized a stable N-annulated perylene bridged bisphenoxyl diradicaloid, and its complex with Lewis acid boron trifluoride. Their ground-state geometric and electronic structures were systematically studied by various experimental methods including X-ray crystallographic analysis, variable temperature nuclear magnetic resonance, electron spin resonance and superconducting quantum interference device measurements, supported by density functional theory. Both of them were observed as open-shell singlet diradicaloids in the ground state. The former demonstrated string features of strong NIR absorption, closely packed π-dimer structure in crystals, amphoteric redox behavior with a small HOMO-LUMO energy band gap, as well as a rather small singlet-triplet gap, while the latter showed very different photophysical, electrochemical and magnetic properties. Our studies provide an efficient method to make stable diradicaloids by Lewis acid/base complexation.

1,5-Diaryl-3-oxo-1,4-pentadienes based on (4-oxopiperidin-1-yl)(aryl)methyl phosphonate scaffold: synthesis and antitumor properties

Abstract: Novel 3,5-bis(arylidene)-4-piperidones modified with diethyl[(aryl)methyl]phosphonate moiety attached to the piperidone nitrogen atom have been synthesized by crotonic condensation of aromatic aldehydes with diethyl[(4-oxopiperidin-1-yl)(aryl)methyl]phosphonates in the presence of LiClO4/Et3N system or acetonitrile solution of boron trifluoride etherate. The synthesized phosphonate derivatives of 3,5-bis(arylidene)-4-piperidone series displayed inhibitory properties toward RD, PC3, HCT116, and MCF7 human cancer cell lines with IC50 values in the range of 2.5–8.5 μM, as assessed by an in vitro 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay.

Preparation of [18F]-NHC-BF3 conjugates and their applications in PET imaging

Abstract: N-Heterocyclic carbene boron trifluoride (NHC-BF3) conjugates were successfully radiofluorinated by SnCl4-promoted 18F–19F isotopic exchange reaction in one labelling step. This method afforded in vivo stable PET agents that efficiently bound to targeted tumours yielding PET images with good tumour-to-background contrast.

Stereodivergent Mannich reaction of bis(trimethylsilyl)ketene acetals with N-tert-butanesulfinyl imines by Lewis acid or Lewis base activation, a one-pot protocol to obtain chiral β-amino acids

Abstract: We report a one-pot synthesis of chiral β2,2,3-amino acids by the Mannich addition of bistrimethylsilyl ketene acetals to N-tert-butanesulfinyl imines followed by the removal of the chiral auxiliary. The synthesis and isolation of pure β-amino acid hydrochlorides were conducted under mild conditions, without strong bases and this method is operationally simple. The stereoselective reaction was promoted by two different activation methods that lead to different stereoisomers: (1) Lewis Acid (LA) catalysis with boron trifluoride diethyl etherate and (2) Lewis Base (LB) catalysis with tetrabutylammonium difluorotriphenylsilicate. The reaction presented good diastereoselectivity with LB activation and moderate to good dr with LA catalysis. The exceptions in both protocols were imines with electron donating groups in the aromatic ring.

Boron trifluoride-mediated synthesis of N -aryl-substituted pyrrolidines from tetrahydrofuran and amines

Abstract: Boron trifluoride-mediated transformation of tetrahydrofuran to corresponding N-aryl-substituted pyrrolidines is conducted under mild reaction conditions, providing a practical synthetic method with reasonable yields Computational studies confirmed the reaction mechanism involving a fast Lewis acid-assisted ring-opening step, followed by the 7-membered intermediate formation and a ringclosing process as the rate-determining step

Preparation and application of boron-dipyrromethene-based diethyl chlorophosphate fluorescent probe

Abstract: The invention relates to a detection diethyl chlorophosphate (DCP) fluorescent probe compound based on boron dipyrromethene (BODIPY) and preparation and application of the detection diethyl chlorophosphate (DCP) fluorescent probe compound. The detection diethyl chlorophosphate (DCP) fluorescent probe compound has the structure shown in the formula I. A preparation method includes the steps that an acetonitrile solution containing 4-(4-hydroxyphenyl)benzonitrile, anhydrous magnesium chloride, paraformaldehyde and triethylamine is subjected to heating and refluxing under protection of nitrogen to obtain white solid III; the obtained solid III and pyrrole are mixed and dissolved in dichloromethane; grey white solid II is obtained under catalysis of trifluoroacetic acid; and the obtained grey white solid II is subjected to DDQ oxydehydrogenation and boron trifluoride diethyl etherate coupling to obtain orange solid I. The probe compound has very good selectivity and sensitivity for DCP, the detection limit is low, and the probe compound can be applied to DCP content measurement.

Near-infrared aza-BODIPY dye and microwave synthesis method thereof

Abstract: The invention belongs to the technical field of organic synthesis and particularly discloses near-infrared aza-BODIPY dye and a microwave synthesis method thereof. The compound structural formula of the aza-BODIPY fluorescent dye is shown in the abstract figure. The synthesis method comprises synthesis steps as follows: p-hydroxyacetophenone and p-cyanobenzaldehyde are taken as raw materials, and an alpha, beta-unsaturated ketone compound 1 containing conjugated double bonds is obtained; the compound 1 is subjected to heating reflux and Michael addition with nitromethane for nitrosation under the alkaline condition, and a compound 2 is obtained; the compound 2 reacts with ammonium acetate with a microwave method at the reaction temperature of 95 DEG C for 6 h, a tetraaryl-aza-dipyrromethene compound 3 is obtained; the compound 3 reacts with triethylamine and boron trifluoride to produce the near-infrared aza-BODIPY dye. The near-infrared aza-BODIPY dye and the synthesis method have the advantages that compared with a conventional heating method for synthesizing the fluorescent dye, the microwave method can greatly shorten the reaction time, reduce by-products and increase the reaction yield to a certain extent.

Preparation method of catalyzed synthesis of mesophase pitch

Abstract: The invention relates to a preparation method of catalyzed synthesis of mesophase pitch. The method comprises the steps that catalytic polymerization of purified pitch, a pure aromatic compound and boron trifluoride or boron trifluoride diethyl etherate, the catalyst boron trifluoride etherate or boron trifluoride are added into a low-temperature reaction kettle according to the reaction mass ratio being 1:100-1:200, the heating temperature is 100-260 DEG C, the pressure is controlled to 0.5-2 Mpa to perform a reaction, pyridine is added into a cooled solid phase component, the temperature is increased to 100-150 DEG C, solids generated in the reaction are filtered out, and boron trifluoride is removed to obtain high-purity polymerized pitch; then, further thermal polymerization and micromolecule removal are performed to obtain the mesophase pitch. The reaction controllability is good, the catalyst is good in safety, the pitch can be recycled, and a polytetrafluoroethylene liner and a graphite liner are adopted to obtain the high-quality synthesis mesophase pitch. The problem that a catalyst existing in an existing method of catalytic synthesis of mesophase pitch is large in toxin and hard to remove is solved.

Synthesis and Analysis of Glucuronic Acid-Conjugated Metabolites of 4-Bromo-2,5-Dimethoxyphenethylamine.

Abstract: In the study reported here, two glucuronic acid-conjugated metabolites of 4-bromo-2,5-dimethoxyphenethylamine (2C-B)-a ring-substituted psychoactive phenethylamine-were chemically synthesized for the first time and a method for analyzing them in urine was developed. β-D-Glucuronide of 4-bromo-2,5-dimethoxyphenylethylalcohol was successfully synthesized using methyl 2,3,4-tri-Ο-acetyl-1-O-(trichloroacetimidoyl)-α-D-glucuronate as a glucuronyl donor and boron trifluoride diethylether complex as a Lewis acid catalyst. β-D-Glucuronide of 4-bromo-2,5-dimethoxyphenylacetic acid was synthesized by condensing 4-bromo-2,5-dimethoxyphenylacetic acid and benzyl D-glucuronate followed by benzyl group deprotection based on catalytic hydrogenation. Two glucuronic acid-conjugated metabolites of 2C-B in urine were qualitatively and semiquantitatively evaluated via direct liquid chromatography/mass spectrometry (LC/MS) analysis of a diluted urine sample. The simple method proposed is expected to be useful for studying the metabolic fate of 2C-B.

Method for preparing resin through cationic polymerization and initiator system for method

Abstract: The invention discloses an initiator system for cationic polymerization. A Lewis acid in the initiator system is a solid powdery boron trifluoride complex and the particle sizes are 10-200 microns; the initiator system comprises an organic complex. The invention further discloses a method for preparing resin through applying an initiator or the initiator system to cationic polymerization. The method comprises the steps of firstly dispersing the solid powdery boron trifluoride complex or the initiator system into an organic solvent; adding a reaction monomer and filtering a reaction liquid for the first time after reaction is completed; and adding a flocculant or a basic inorganic matter to first filtrate, filtering for the second time, and carrying out the aftertreatment steps, such as distillation, on second filtrate to obtain the resin and a solvent, wherein the solvent can be recovered for use. The method for preparing the resin by adopting the initiator or the initiator system is safe in process, environment-friendly and high in productivity, and the Lewis acid and the solvent can be recycled.

Synthesis method of 2-hexenal

Abstract: The invention discloses a synthesis method of 2-hexenal. The method includes: adding a mixed solution of n-butanal and vinyl alkyl ether into a catalyst boron trifluoride diethyl etherate solution dropwise to carry out reaction, subjecting the obtained acetal to heating hydrolysis distillation under the catalytic action of a Lewis acid aqueous solution, and subjecting an obtained 2-hexenal crude product to continuous pressure reduction distillation, thus obtaining high purity 2-hexenal. The method provided by the invention has the characteristics of stable route and process and high yield, and the product has competitive edge.

Construction of Spiro[indeno[2,1-e]pyrrolo[3,4-b]pyridine-10,3′-indoline] and Indeno[1,2-b]pyrrolo[3,4-e]pyridine via Three-Component Reaction

Abstract: The three-component reaction of β-enamino imides, isatins and indan-1,3-dione in refluxing ethanol in the presence of triethylamine afforded functionalized spiro[indeno[2,1-e]pyrrolo[3,4-b]pyridine-10,3′-indolines] in good yields. The similar three-component reaction of β-enamino imides, aromatic aldehydes and indan-1,3-dione in methylene dichloride in the presence of boron trifluoride etherate resulted in the corresponding indeno[1,2-b]pyrrolo[3,4-e]pyridine derivatives.

Boron neutron capture treatingsystem and application of a-amino acid-like boron trifluoride inmanufacturing medicament for treating tumors

Abstract: As one aspect of the present invention, disclosed is a boron neutron capture therapy system, comprising: a boron neutron capture therapy device and an α-amino acid-like boron trifluoride; the α-amino acid-like boron trifluoride has a structure as shown in the formula (I) wherein R refers to hydrogen, methyl, isopropyl,1-methylpropyl, 2-methylpropyl, hydroxymethyl, 1-hydroxyethyl, benzylor hydroxybenzyl, and M refers to H or a metal atom; theenergy generated after a neutron beam generated by the boron neutron capture therapy device acts on the α-amino acid-like boron trifluoride can damage DNA of tumour cells. As another aspect of the present invention, disclosed also is the application of an α-amino acid-like boron trifluoride in manufacturing medicament for treating tumors.

Novel synthesis method of IDTT derivative

Abstract: The invention relates to the field of organic solar cells, in particular to a novel synthesis method of an IDTT derivative. Alkyl bromobenzene is dissolved in dehydrated tetrahydrofuran in a nitrogen environment, a hexane solution of n-butyllithium is added at minus 78- minus 80 DEG C, then, 2,5-dibromoterephthalate is added to react, the system reacts at the room temperature for 16-20 h, the reaction is quenched with water, extraction is performed with ethyl acetate, rotary drying is performed with anhydrous sodium sulfate, a crude product is dissolved with dichloromethane in the nitrogen environment, a boron trifluoride diethyl etherate solution is added, the system reacts at the room temperature, methyl alcohol is added, the reaction is quenched with water after the reaction ends, extraction is performed with dichloromethane, separation is performed with column chromatography, and IDTT and the IDTT derivative are obtained. Compared with methods reported in literature previously, the method has the advantages that aftertreatment is convenient, the yield of the obtained final product is higher, and the method has low environmental protection pressure, low energy consumption and high safety.

Boron nitride nanotube for hydrogen storage and synthesis method

Abstract: The invention provides a boron nitride nanotube for hydrogen storage and a synthesis method. The synthesis method comprises two steps as follows: step one, synthesizing a precursor of the boron nitride nanotube from a boron trifluoride etherate solution as raw material; step two, preparing the boron nitride nanotube with high specific surface area and high adsorption activity with a low-temperature chemical vapor deposition method under conditions of protective atmosphere and carrier gas. The boron nitride nanotube synthesized with the method has high purity and large specific surface area; the synthesis method is simple, reliable, cheap and suitable for large-scale synthesis. The hydrogen adsorption capacity of the synthesized boron nitride nanotube at the room temperature is up to 0.6 g per gram, 90% of the adsorption capacity is still maintained after the boron nitride nanotube is reused 70 times, and defects of low hydrogen storage capacity, low reuse efficiency and the like of common hydrogen storage materials are overcome, therefore, the boron nitride nanotube has broad prospect in the field of hydrogen energy application.

Erlotinib preparation method

Abstract: The invention relates to an erlotinib preparation method. The method for synthesizing erlotinib includes the steps: (1) reacting a compound 1 and paraformaldehyde under the condition of catalytic amount of boron trifluoride diethyl etherate to generate a compound 2; (2) reacting the compound 2 and ammonium hydroxide under the condition of catalytic amount of tetrabutylammonium bromide and ultrasound to generate a compound 3; (3) reacting the compound 3 and sulfoxide chloride to generate a compound 4; (4) reacting the compound 4 and aminophenylacetylene to generate erlotinib.

Preparation method for 3[alpha],7[alpha]-dihydroxyl-6[alpha]-ethyl cholanic acid

Abstract: The invention belongs to the technical field of pharmaceutical synthesis, and discloses a preparation method for 3[alpha],7[alpha]-dihydroxyl-6[alpha]-ethyl cholanic acid. The method comprises the steps: with 3[alpha]-hydroxyl-7-carbonyl cholanic acid as a raw material, carrying out methyl esterification, and under alkaline and low temperature conditions and with estersil as a catalyst, carrying out a reaction with halogenated silane to obtain 3[alpha],7-di(trimethyl siloxy)-6-en-methyl cholanate; then under conditions of low temperature and boron trifluoride acetonitrile, carrying out a reaction with Mukaiyama aldol, to obtain 3[alpha]-hydroxyl-6-ethidene-7-carbonyl methyl cholanate; and then with palladium carbon as a catalyst, carrying out catalytic hydrogenation and deprotection reaction in an alkaline alcohol/aqueous solution, acidifying to obtain 3[alpha]-hydroxyl-6[alpha]-ethyl-7-carbonyl cholanic acid; and finally reducing with sodium borohydride to obtain the target product. The method has the advantages of simple synthesis process, mild conditions and high yield, and is suitable for industrialization.

Hydrogenated isotopically enriched boront trifluoride dopant source gas composition

Abstract: A hydrogenated isotopically enriched boron trifluoride (BF3) dopant source gas composition. The composition contains (i) boron trifluoride isotopically enriched above natural abundance in boron of atomic mass 11 (UB), and (ii) hydrogen in an amount of from 2 to 6.99 vol.%, based on total volume of boron trifluoride and hydrogen in the composition. Also described are methods of use of such dopant source gas composition, and associated apparatus therefor.

Electrolytic liquor, electrolyte, polymer electrolyte as well as preparation method and application thereof

Abstract: The invention discloses electrolytic liquor, electrolyte, polymer electrolyte as well as a preparation method and application thereof. A method for preparing LiPBFO electrolytic liquor in the invention comprises the following steps: reacting lithium phosphate, lithium fluoride and boron trifluoride gas in an organic solvent under the protection of protective gases, thereby obtaining the product, wherein a mass ratio of lithium fluoride to lithium phosphate is (0.01:1)is similar to(5:1), and a mass ratio of boron trifluoride to lithium phosphate is (0.8:1)is similar to (13:1). The electrolyte disclosed by the invention is high in conductivity and low in price, and the preparation method is simple.

Preparation method of antitumor active compound

Abstract: The invention relates to a preparation method of antitumor active compound, belonging to the field of medicinal chemistry. The method comprises the steps of enabling commercialized fully-acetylated glucose serving as a starting raw material and methylene dichloride serving as a solvent to react with 3, 4-dimethoxyphenol under the catalytic action of boron trifluoride ether so as to form a glucose anomeric carbon position-substituted glycoside intermediate; then, removing acetyl under the alkaline condition of sodium methylate, and enabling the product to have a regioselective chemical reaction with benzoyl chloride prepared by using full benzyl-protected anhydrous gallic acid so as to obtain a key glycosyl intermediate; finally, carrying out palladium-carbon reduction to remove benzyl protection. The glycoside natural product 1 is formed in high yield by means of simple and efficient reactions in the four steps; the prepared glycoside natural product has good tumor cytotoxic activity. The structural formula of the glycoside natural product 1 is described in the description.