63 results about "Trimethylsilylacetylene" patented technology

The invention belongs to the technical field of organic supermolecules and specifically relates to a 3,4-ethylenedioxythiophene polymer which can be super-assembled with a carbon-based material and a preparation method thereof. The polymer of the invention is a high molecular polymer with 3,4-ethylenedioxythiophene-2-acetylene as a main chain and an alkoxy group as a side chain. The preparation method comprises the following steps: 3,4-ethylenedioxythiophene, which is used as a starting material, is subjected to a bromination reaction to obtain 2,5-dibromo-3,4-vinyldioxythiophene; then, 2,5-dibromo-3,4-vinyldioxythiophene reacts with trimethylsilylacetylene to obtain a bistrimethylsilyl3,4-vinyldioxythiophene intermediate; after removal of theTMS protecting group, a Sonogashira reaction between the above reaction product and 2,5-dibromo-3,4-vinyldioxythiophene is carried out to obtain the 3,4-ethylenedioxythiophene polymer. The polymer and carbon nanotubes can form a super-assembly system with main chain Pi-Pi adsorption and side chain winding. The 3,4-vinyldioxythiophene polymer/carbon nanotube composite formed by the super-assembly system has good stability and has a broad application prospect in composite materials.

The invention discloses (S)-/(R)-difurodinaphthalene as well as derivatives thereof and a preparation method. The compounds have two spatial configurations which are (S)-/(R)-, and in the structure, the site 2 of furan has substituent groups which are hydrogen, and linear or branched alkyl groups or phenyl groups of C4 or below. The preparation method comprises the following steps of: reacting (S)-/(R)-binaphthol as a raw material and potassium carbonate as alkali with iodomethane in acetone so as to obtain (S)-/(R)-2, 2'-dimethoxy-1, 1'-dinaphthalene; then carrying out diiodo-reaction of a product obtained in the previous step, removing protecting groups of phenolic hydroxyl groups, and esterifying with acetic anhydride, thus obtaining (S)-/(R)-3, 3'-diiodo-2, 2'-diacetoxy-1, 1'-dinaphthalene; carrying out Sonogashira coupled reaction of (S)-/(R)-3, 3'-diiodo-2, 2'-diacetoxy-1, 1'-dinaphthalene with alkyne under the catalysis action of palladium to obtain a series of (S)-/(R)-3, 3'-di(trimethylsilylacetylene, hexynyl or phenyl ethynyl)-2, 2'-diacetoxy-1, 1'- dinaphthalene; and finally under the action of cesium carbonate, carrying out ring closing reaction to obtain the (S)-/(R)-double furodinaphthalene and derivatives thereof. A series of compounds provided by the invention broaden the range of organic electroluminescence materials.

The invention provides a continuous synthesis system and a continuous synthesis method of trimethylsilylacetylene. The continuous system comprises a Grignard reagent continuous preparation unit, an acetylene Grignard reagent continuous synthesis unit and a trimethylsilylacetylene continuous preparation device, wherein the Grignard reagent continuous preparation unit is provided with a first feeding port and a Grignard reagent outlet; the acetylene Grignard reagent continuous synthesis unit is provided with a Grignard reagent inlet, an acetylene solution inlet and an acetylene Grignard reagentoutlet, and the Grignard reagent inlet is communicated with the Grignard reagent outlet through a Grignard reagent transfer pipe; the trimethylsilylacetylene continuous preparation device is providedwith a trimethylhalosilane inlet, an acetylene Grignard reagent inlet and a trimethylsilylacetylene outlet, the acetylene Grignard reagent inlet is communicated with the acetylene Grignard reagent outlet through an acetylene Grignard reagent transfer pipe. By adopting the continuous synthesis system for preparing trimethylsilylacetylene, the production cost can be reduced, the period can be shortened, and safety of the whole process can also be improved.

The invention relates to an organic microporous material with metal coordination containing heteroatoms and preparation and application thereof. An organic conjugated precursor of the organic microporous material has a structural formula of I or II. The preparation comprises the steps of preparation of 4-trimethylsilylacetylene-2-bromopyridine or 5-trimethylsilylacetylene-3-bromopyridine, preparation of 4-ethynyl-2-bromopyridine or 5-ethynyl-3-bromopyridine, preparation of bis(2-bromopyridine) acetylene or bis(3-bromopyridine) acetylene, preparation of bis(2-thiophene pyridine) acetylene or bis(3-thiophene pyridine) acetylene, preparation of the organic conjugated precursor, and preparation of the organic microporous material with the metal coordination containing the heteroatoms. The organic microporous material has a controllable form and structure, thereby having different properties and functions, and can be applied to the development of novel functional materials such as gas adsorption and storage, molecular separation, catalysis, sustained release of drugs and the like.

The invention belongs to the technical field of organic photoelectric materials, and concretely relates to synthesis and application of porphyrin metal complexes with different frameworks. The complexes are obtained through coordination of porphyrin rings with different structures and a metal, and the structure general formula is shown in the specification. A porphyrin compound is synthesized from pyrrole, pentafluorobenzaldehyde and trimethylsilylacetylene, and then porphyrin complexes are formed through coordination of the porphyrin compound and different metals. TTA (triplet-triplet annihilation) transition phenomenon is generated when the prepared target metal complex is combined with an acceptor, and the metal complexes have good application prospects on solar cells and cell imaging. Additionally, the porphyrin metal complexes can generate single oxygen quantum dot with extremely high efficiency, and possesses potential application prospect on anoxia detection and photodynamic therapy. The prepared target complexes are shown in the specification.

The invention provides a synthetic method for silthiopham, which belongs to the technical field of organic synthesis. The objective of the invention is to overcome the problems of complicated synthesis process, a great number of byproducts and severe environmental pollution of conventional synthetic methods for silthiopham. The synthetic method provided by the invention comprises the following steps: (1) with trimethylsilylacetylene as a raw material, under the protection of inert gas, reacting trimethylsilylacetylene with methyl chloroformate under the action of organic base so as to obtain methyl (trimethylsilyl)propiolate; (2) reacting methyl (trimethylsilyl)propiolate with allyl amine in a solvent under the action of a catalyst so as to obtain N-allyl-3-(trimethylsilyl)propiolamide; and (3) subjecting N-allyl-3-(trimethylsilyl)propiolamide with 3-mercapto-2-butanone to a heating reflux reaction under the action of an alkali catalyst and carrying out dehydration so as to obtain the final product silthiopham. The method has the advantages of usage of cheap and easily available raw materials, simple route, high yield and no usage of reagents severely polluting the environment, e.g., t-butyl nitrous acid and thionyl chloride.

The invention discloses a method for preparing the CDK46 kinase inhibitor Palbociclib. The method includes the following steps that 1, the compound N-cyclopentyl-5-methyl-2-[[5-(1-piperazinyl)-2-pyridyl]amino]-6- bromopyridine -[2,3-d]-pyrimidine-7(8H)-ketone shown in the formula (I) reacts with trimethylsilylacetylene in the presence of cuprous bromide and potassium tert-butoxide to generate the compound N-cyclopentyl-5-methyl-6-acetenyl-2-[[5-(1-piperazinyl)-2-pyridyl]amino]pyridino-[2,3-d] pyrimidine-7(8H)-ketone shown in the formula (II); 2, the compound N-cyclopentyl-5-methyl-6-acetenyl-2-[[5-(1-piperazinyl)-2-pyridyl]amino]pyridino-[2,3-d] pyrimidine-7(8H)-ketone shown in the formula (II) and obtained in the step 1 is hydrolyzed in an acid water solution to obtain Palbociclib. By means of the method, a new way for preparing Palbociclib is developed, conditions are mild, and the yield is high.

The invention discloses a preparation method of erlotinib and derivatives of erlotinib. The preparation method is characterized in that a compound II (when R2=H, the compound II is 6,7-(2-methoxyl-oxethyl)-quinoline-4-amine and a compound III (when R1=SiMe and R3=I, the compound III is 3- trimethylsilylacetylene-iodobenzene have a coupling reaction in an organic solvent under the actions of alkali, elementary substance copper and/or copper salt to obtain erlotinib and derivatives of erlotinib. The elementary substance copper and/or copper salt or palladium reagent is used as the base of the catalytic reaction, the N-(3-phenylacetylene)-6,7-di(2-methoxyl oxethyl)-4-quinoline amino acid salt (erlotinib, I) and the derivatives of erlotinib are prepared from midbody compoundS II and III. The preparation method has the advantages of use of low-price and easily available raw materials, , moderate reaction conditions, few side reaction, high yield and small environmental pollution and is applicable to the industrial production.

The invention discloses a method for preparing 3-ethyl-4-methylol acetophenone. The method includes steps of S1, carrying out coupling reaction on 4-methylol-3-bromoacetophenone and trimethylsilylacetylene or ethynyltriisopropylsilane to generate 3-trimethyl silicon acetenyl-4-methylol acetophenone; S2, hydrolyzing the 3-trimethyl silicon acetenyl-4-methylol acetophenone under alkaline conditionsto generate 3-acetenyl-4-methylol acetophenone; S3, carrying out reduction on the 3-acetenyl-4-methylol acetophenone under the conditions of hydrogen, palladium and carbon to obtain the 3-ethyl-4-methylol acetophenone. The method has the advantages that the yield of the 3-ethyl-4-methylol acetophenone can be greatly increased, the highest yield of the 3-ethyl-4-methylol acetophenone can reach 55%at least, the method includes simple reaction steps and is easy to control, and reaction procedures are mild.

The invention discloses a fluorescent film sensor for fluoride ion detection and a preparation method of the fluorescent film sensor and relates to the field of fluorescent molecular sensors. According to the fluoride ion detecting fluorescent film sensor and the preparation method thereof, firstly, an electropolymerizable fluorescent sensing material monomer is prepared from 2-bromo-9,9-(N-carbazole-hexyl) fluorene and trimethylsilylacetylene through a reaction; then the fluorescent film sensor poly1,4-bis(4-(9,9-bis(N-carbazole-hexyl) fluorenyl)-1,2,3-triazolyl) benzene is obtained from the fluorescent sensing material monomer through electrochemical polymerization, and Fe<3+> can be added to the obtained fluorescent film sensor to enhance the detection performance of the sensor. The fluorescent film sensor can effectively guarantee fast diffusion of metal ions in a film and improves the film detection sensitivity, the used fluorescent sensing raw materials are cheap and available, the synthetic method is relatively simple, and a constructed device is good in reversibility and high in practicability.

The invention discloses a preparation method of a five-membered ring polymer used for OLED. The preparation method comprises following steps: 2,5-dibromoaniline is dissolved in acetate acid gracial, a NaNO2 aqueous solution is added, a urea aqueous solution is added dropwise, a KI aqueous solution is added drop by drop, extraction is carried out, and an obtained product 1 is mixed with a derivative of R molecular containing terminal alkynyl; the product 1 is dissolved in a mixed solution of tetrahydrofuran and triethylamine, argon is introduced, ultrasonic treatment is carried out, dichlorobispalladium and cuprous iodide are added, purification is carried out, and an obtained product 2 is dissolved in 1,4-dioxane, argon is introduced, ultrasonic treatment is carried out, an obtained product 3 is added into a mixture of hydroquinone, Cs2CO3, CsF, Pd2(dba)3, and P(tBu)3; purification is carried out, an obtained product 4 is dissolved in a mixed solution of tetrahydrofuran and triethylamine, argon is introduced, ultrasonic treatment is carried out, trimethylsilylacetylene is added, dichlorobispalladium and cuprous iodide are added, separation purification is carried out, an obtained product 5 is dissolved in a mixture of absolute methanol and tetrahydrofuran; separation purification is carried out, an obtained product 6 is dissolved in a mixed solution of methylbenzene and tetramethyl ethylenediamine; cuprous chloride is added, and separation purification is carried out so as to obtain a finished product. The five-membered ring polymer is capable of improving the stability and prolonging the service life of OLED.

The invention discloses a carbon nanotube dispersing phenylacetylene-based polyfunctional group polymer and a preparation method thereof. The backbone chain of the carbon nanotube dispersing phenylacetylene-based polyfunctional group polymer is phenylacetylene, and the side chain of the carbon nanotube dispersing phenylacetylene-based polyfunctional group polymer is alkoxy. The preparation methodof the carbon nanotube dispersing phenylacetylene-based polyfunctional group polymer comprises taking 1, 4-dialkoxy substituted bisphenol ether 1 as the raw material for bromination to obtain dibromo-bisphenol ether 2, subjecting the dibromo-bisphenol ether 2 to reaction with trimethylsilylacetylene to obtain an intermediate 3, removing TMS (trimethylsilyl) of the intermediate 3 to obtain terminalalkyne 4, subjecting the terminal alkyne 4 to Sonogashira reaction with the dibromo-bisphenol ether 2 to produce a high-molecular polyfunctional group polymer containing functional backbone and sidechains. The prepared carbon nanotube dispersing phenylacetylene-based polyfunctional group polymer can produce backbone chain pi-pi adsorption and side chain entanglement with carbon nanotubes to achieve well dispersion of the carbon nanotubes under the premise of not damaging the carbon nanotubes; according to difference in the structure of the carbon nanotube dispersing phenylacetylene-based polyfunctional group polymer and the sizes of the carbon nanotubes, the dispersion degrees ranges between 2% and 7%.

The invention discloses a production process of trimethylsilylacetylene, comprises the following steps: (1) adding the measured tetrahydrofuran and magnesium metal into a reaction still, adding iodine and 1,2-dibromoethane, warming to 50-60 DEG.C, introducing the measured chloroethylene, heat-insulating for 3 hours, cooling to 20-30 DEG.C, adding a catalyst, stirring, and then adding the measured mixed solution of tetrahydrofuran and trimethylchlorosilane, warming to 50-60 DEG.C, heat-insulating for 5 hours; distilling the produced vinyl trimethylsilyl to be dissolved in methanol, controlling temperature at 15-20 DEG.C, dropwise adding equal bromine, reacting until floor fading, slowly dropwise adding equal alkaline methanol solution, controlling temperature at 30-40 DEG.C, reacting HPLC monitoring until the reaction is finished, adding dichloromethane, filtering to remove salt, and concentrating to obtain a finished product. The raw materials adopted by the invention are available and low in price, the production cost is low, the product quality is high, the reaction condition is mild, the yield is high, and the production process is capable of producing the trimethylsilylacetylene on large scale.

The invention relates to a synthetic method of 7-azaindole-5-chloro-6-carboxylic acid, which mainly solves the technical problem that no effective synthetic method suitable for the industrialization is provided. The synthetic method comprises the following steps: dissolving 3,6-dichloropyridine-2-carboxylic acid in a solvent of tertiary butanol and pyridine, adding paratoluensulfonyl chloride, obtaining a compound 1, wherein the product is unnecessary to purify; coupling the compound 1 and diphenyl amine under the catalysis of Pd2(dba)3 and xant-Phos, adding hydroxylamine hydrochloride, and purifying a crude product by virtue of column chromatography, thus obtaining a compound 2; dissolving the compound 2 in acetic acid, adding NIS, heating to facilitate the reaction, and purifying a crudeproduct by virtue of column chromatography to obtain a compound 3; dissolving the compound 3 in tetrahydrofuran, adding trimethylsilylacetylene, cuprous iodide, Pd(PPh3)2Cl2 and triethylamine, and reacting under the protection of nitrogen, thus obtaining a product 4 which does not require to be purified; and dissolving the compound 4 in dry N-methyl pyrrolidone, adding potassium tert-butoxide, heating, reacting, standing overnight, washing a crude product by using acetate, and filtering to obtain a target product.

The invention discloses a method for synthesizing second-level trifluoromethyl propargyl alcohol. The method comprises the following steps: enabling 2-iodo benzoic acid and sodium periodate to react so as to generate 1-(hydroxyl)-1,2-iodobenzoyl-3(1H)-ketone (BIOH), generating trimethylsilylacetylene and triisopropylchlorosilane to generate trimethylsilyl (triisopropyl silicon) acetylene, synthesizing 1-[(triisopropyl silicon) acetylene]-1,2-iodobenzoyl-3(1H)-ketone from BIOH and trimethylsilyl (triisopropyl silicon) acetylene, enabling 1-[(triisopropyl silicon) acetylene]-1,2-iodobenzoyl-3(1H)-ketone and trifluoroethylamine hydrochloride and sodium nitrite to synthesize 1-[(triisopropyl silicon) acetylene]-1,2-iodobenzoyl-3(1H)-ketone, and finally performing hydrolysis, thereby synthesizing a target product. The trifluoromethyl propargyl alcohol prepared by using the method is an important fluorine-containing building block molecule, and has very great significances for synthesis of fluorine-containing functional organic molecules and medicinal intermediates.

The invention discloses a marine natural product (+)-(4E, 15Z)-4, 15- docosadienoic-1- alkyne-3-alcohol and a synthetic method of an enantiomer thereof, and belongs to the field of chemical synthesis. With propargyl alcohol as an initial raw material, the method provided by the invention comprises multiple reactive synthesis steps, such as coupling, triple bond transposition, oxidation, selective reduction, asymmetric alkynylation, esterification and hydrolysis and the like, and the key step is to carry out an asymmetric addition reaction on trimethylsilylacetylene and aldehyde to directly obtain a chiral propargyl alcohol structure. The synthetic method disclosed by the invention has the advantages of simple steps, high total yield and high optical purity of the product.

The invention relates to a synthetic method of di(trimethyl silicon-based)acetylene. The method comprises the following steps: 1. taking diacetylenes metal salt and trimethyl halogenosilane as raw materials, wherein the mole mass ratio of diacetylenes metal salt to trimethyl halogenosilane is 1:2.0-1:2.2, suspending diacetylenes metal salt in toluene, adding trimethyl halogenosilane drop by drop, heating to the temperature of 50-60 DEG C after dripping is finished and reacting for 2 hours, wherein the diacetylenes metal salt is acetylene disodium and/or acetylene dibromo; 2, terminating the reaction by water, extracting, drying, reducing the pressure, concentrating, vacuum rectifying to obtain the di(trimethyl silicon-based)acetylene with the purity of more than 99%, wherein the yield is more than 90%. The synthetic method omits the preparation of a Grignard reagent, so that toluene which has advantages of cheap price and convenient recovery is capable of replacing tetrahydrofuran with expensive price, so that the synthesis cost is substantially reduced, because the toluene solvent used in the method of the invention has high recovery rate, so that the generation and discharge of toxic waste can be substantially minimized, and the toluene solvent is in favor of environmental protection.

The invention relates to a synthesizing method of (E)-5-methyl-1H-pyrrolo-[2,3-b] pyridine-3-formaldoxime, which solves the technical problem that an effective synthesizing method is not discovered at present. The synthesizing method provided by the invention comprises the following steps: brominating 2-amino-5-picoline, so as to obtain a compound 1; performing a reaction on the compound 1 and trimethylsilylacetylene under a condition of a Sonogashira coupling reaction, so as to generate a compound 2; performing a reaction on the compound 2 and sodium hydride to form a pyrrole ring, so as to generate a compound 3; performing a reaction on the compound 3 and urotropine, so as to generate a compound 4; performing the compound 4, hydroxylamine hydrochloride and sodium acetate, so as to obtain the target product (E)-5-methyl-1H-pyrrolo-[2,3-b] pyridine-3-formaldoxime. As a sodium acetate, the (E)-5-methyl-1H-pyrrolo-[2,3-b] pyridine-3-formaldoxime is widely applied in the pharmaceutical industry.

The invention relates to a method for synthesizing 6-chlorofuro[3,2-B]pyridine. Mainly solve the technical problem of its synthetic method. The synthetic method of the present invention comprises the following steps: 5-chloro-3-hydroxypyridine reacts with iodine and sodium carbonate at room temperature to generate compound 1; compound 1 reacts with trimethylethynyl silicon to generate compound under the conditions of the scorpion coupling reaction 2; Compound 2 reacted with tetrabutylammonium fluoride at room temperature to generate target compound 3. The reaction formula is as follows: , as an expensive pharmaceutical intermediate, 6-chlorofuro[3,2-B]pyridine is widely used in the pharmaceutical industry.

The invention relates to a triazole-functionalized 4,4'-difluorodiphenyl sulfone compound and a preparation method thereof. The structural formula of the compound is: . This kind of compound is synthesized from 4,4'-difluorodiphenyl sulfone through bromination, coupling, click and other reactions. It is divided into four steps, including 3,3'-dibromo-4,4'-difluoro Synthesis of Diphenylsulfone, Synthesis of 3,3'-Ditrimethylsilylethynyl-4,4'-Difluorodiphenylsulfone, 3,3'-Diethynyl-4,4'-Difluorodiphenyl Synthesis of sulfones, synthesis of triazole-functionalized 4,4'-difluorodiphenylsulfone. The compound synthesized in the present invention can be polycondensed with bisphenol compounds to obtain polymer polysulfone material. The skeleton structure of polysulfone makes it have excellent alcohol resistance effect, anti-oxidation, anti-acid catalytic hydrolysis performance, and excellent mechanical properties and thermal stability, and the triazole basic functional group provides proton defects, which can be used to prepare acid-base amphoteric high-temperature proton conductive materials.