55 results about "Dehydrogenative coupling of silanes" patented technology

Compounds and method of preparation of Si—X and Ge—X compounds (X═N, P, As and Sb) via dehydrogenative coupling between the corresponding unsubstituted silanes and amines (including ammonia) or phosphines catalyzed by metallic catalysts is described. This new approach is based on the catalytic dehydrogenative coupling of a Si—H and a X—H moiety to form a Si—X containing compound and hydrogen gas (X═N, P, As and Sb). The process can be catalyzed by transition metal heterogenous catalysts such as Ru(0) on carbon, Pd(0) on MgO) as well as transition metal organometallic complexes that act as homogeneous catalysts. The —Si—X products produced by dehydrogenative coupling are inherently halogen free. Said compounds can be useful for the deposition of thin films by chemical vapor deposition or atomic layer deposition of Si-containing films.

Methods are disclosed of making linear and cross-linked, HMW (high molecular weight) polysilanes and polygermanes, polyperhydrosilanes and polyperhydrogermanes, functional liquids containing the same, and methods of using the liquids in a range of desirable applications. The silane and germane polymers are generally composed of chains of Si and / or Ge substituted with R′ substituents, where each instance of R′ is, for example, independently hydrogen, halogen, alkenyl, alkynyl, hydrocarbyl, aromatic hydrocarbyl, heterocyclic aromatic hydrocarbyl, SiR″3, GeR″3, PR″2, OR″, NR″2, or SR″; where each instance of R″ is independently hydrogen or hydrocarbyl. The cross-linked polymers can be synthesized by dehalogenative coupling or dehydrocoupling. The linear polymers can be synthesized by ring-opening polymerization. The polymers can be further modified by halogenation and / or reaction with the source of hydride to furnish perhydrosilane and perhydrogermane polymers, which are used in liquid ink formulations. The synthesis allows for tuning of the liquid properties (e.g., viscosity, volatility, and surface tension). The liquids can be used for deposition of films and bodies by spincoating, inkjetting, dropcasting, etc., with or without the use of UV irradiation. The deposited films can be converted into amorphous and polycrystalline silicon or germanium, and silicon or germanium oxide or nitride by curing at 400-600 DEG C. and (optionally) laser- or heat-induced crystallization (and / or dopant activation, when dopant is present).

The invention discloses a synthetic method of a covalent organic framework (COF) material. The method comprises the following steps: after mixing 1,3,5-benzenetricarboxaldehyde with 2,5-di(N,N-dimethyl)amino-1,4-benzdihydrazide uniformly in an organic solvent, reacting in the presence of a catalyst acetic acid to obtain the COF material, wherein the mole ratio of 1,3,5-benzenetricarboxaldehyde to 2,5-di(N,N-dimethyl)amino-1,4-benzdihydrazide is 1:(0.5-3). The COF material obtained by adopting the method has relatively large specific surface area and regular open framework structure with adjustable diameter, thus being beneficial for mass transfer of reactants and products in photoabsorption and catalytic processes; the material can serve as a photocatalyst and can increase the yield of the dehydrogenative coupling reaction between 2-phenyl-1,2,3,4-tetrahydroisoquinoline and nitromethane from 39% in the absence of catalysts to 89%.

The present invention discloses 2,2'-bipyridine, a catalytic coupling synthesis method and applications thereof. According to the method, Raney nickel is adopted as a catalyst and a reaction aid is added to an autoclave to catalyze pyridine to be subjected to dehydrogenation so as to directly couple to synthesize 2,2'-bipyridine, wherein the chemical formula of the reaction aid is represented by R-X, R represents alkyl or alkoxy or amino, and X represents an alkali metal or third main group element. According to the present invention, the pyridine is adopted as the raw material and the dehydrogenation coupling is performed to obtain the 2,2'-bipyridine, such that the raw material is easy to obtain, the pyridine chlorination process is eliminated, the process is simple, the production cost is substantially reduced, the use of halogenated pyridine is avoided, the production pollution is reduced, and the environmental protection is provided; the used catalyst has the cheap price and effectively replaces the expensive precious metal so as to reduce the catalyst cost; and the reaction aid is added during the reaction process so as to effectively improve the pyridine raw material conversion rate and improve the 2,2'-bipyridine yield, and the method is suitable for factory scale production.

Compounds and method of preparation of Si—X and Ge—X compounds (X═N, P, As and Sb) via dehydrogenative coupling between the corresponding unsubstituted silanes and amines (including ammonia) or phosphines catalyzed by metallic catalysts is described. This new approach is based on the catalytic dehydrogenative coupling of a Si—H and a X—H moiety to form a Si—X containing compound and hydrogen gas (X═N, P, As and Sb). The process can be catalyzed by transition metal heterogenous catalysts such as Ru(0) on carbon, Pd(0) on MgO) as well as transition metal organometallic complexes that act as homogeneous catalysts. The —Si—X products produced by dehydrogenative coupling are inherently halogen free. Said compounds can be useful for the deposition of thin films by chemical vapor deposition or atomic layer deposition of Si-containing films.

The invention belongs to the technical field of fine chemical engineering. The invention discloses a preparation method and application of a metal-organic framework structure compound with a chiral pore channel structure. In the preparation method, a right-handed spiral chiral metal-based ligand Ir (III) complex L1 or a left-handed spiral chiral metal-based ligand Ir (III) complex L2 is used as abasic construction module; Cu<+> with tetrahedral coordination configuration in a transition metal salt is used as a metal node, and the metal-organic framework structure compound with the chiral porechannel structure is prepared through reaction. The metal-organic framework structure compound having the chiral pore channel structure and prepared by the method is low in raw material price, high in yield and easy to put into practical application. The metal-organic framework structure compound is used as a compound Cu-L1 or Cu-L2 applied to catalysis of asymmetric oxidative dehydrogenation coupling (CDC) reaction of N-phenyl tetrahydroisoquinoline and phenylacetylene molecules, the highest yield can reach 80%, and the enantioselectivity is greater than 50%.

The invention relates to a method for preparing ethylene glycol by photocatalytic methanol dehydrogenation coupling, belonging to the chemical field, which comprises the following steps: adding additive and photocatalyst into a solvent, uniformly dispersing, removing oxygen in the system, and then carrying out photocatalytic reaction to prepare ethylene glycol, wherein the solvent is methanol or methanol-water system, wherein the additive comprises at least one of an aromatic organic substance, a fluorine-containing organic compound and a fluorinated salt, and the photocatalyst is a semiconductor catalyst or a modified semiconductor catalyst. Using a small amount of additives can significantly promote methanol photocatalytisis to prepare ethylene glycol. The reaction is carried out in an inert atmosphere and has the characteristics of high catalytic activity, high product selectivity, mild reaction conditions and the like.

The present invention relates to a method for preparation of carboxamides using alcohols and amines as starting materials in a dehydrogenative coupling reaction catalyzed by a ruthenium N-heterocyciic carbene (NHC) complex, which may be prepared in situ.

The invention discloses an HMS@NiPt@Beta core-shell structure catalytic material and a preparation method and application thereof. According to the catalytic material, a microporous Beta molecular sieve serves as a core, a mesoporous HMS molecular sieve serves as a shell, NiPt bimetallic nanoparticles are evenly distributed on the surface of the microporous Beta molecular sieve, the core of the microporous Beta molecular sieve is prepared through a hydrothermal synthesis method, niPt bimetallic nanoparticles are loaded on the surface of the microporous Beta molecular sieve through a low-temperature oxygen plasma treatment technology, the mesoporous HMS molecular sieve shell is prepared through a vapor phase crystal transformation method, and based on the total mass of the catalytic material, nickel accounts for 10-30 wt%, platinum accounts for 0.01-5 wt%, the microporous Beta molecular sieve core accounts for 40-60 wt%, and the balance is the mesoporous HMS molecular sieve shell. The catalytic material is applied to a reaction for catalyzing dehydrogenation coupling of pyridine to synthesize 2, 2'-dipyridyl, has the advantages of low dosage, few side reactions, short process and the like, and has a good application prospect in the fields of adsorption separation, petrochemical engineering, fine chemical production and the like.

The invention provides gold nanowires with mixed optional arrangement of various close-packed structures and their preparation method and application. The preparation method comprises the steps of 1)dispersing a gold precursor, a copper salt and an etching agent in oleylamine to obtain a reaction liquid; 2) allowing the reaction liquid of step 1) to react at 100-210 DEG C, centrifuging after reaction, and washing to obtain the gold nanowires with mixed optional arrangement of various close-packed structures. The gold nanowires prepared by the preparation method have an average diameter of 13.2 nanometers and can be supported on activated carbon, silicon dioxide, titanium dioxide or alumina to act as a catalyst to catalyze dehydrogenative coupling reaction and electrocatalytic reduction ofcarbon dioxide. The gold nanowires have high-density defect structure, and exhibits enhanced catalytic performance in catalytic reaction, particularly in dehydrogenative coupling reaction of silane and water (and hydroxy compounds).

The invention discloses a three-dimensional hollow high-dispersion metal catalyst and a preparation method thereof, and belongs to the technical field of industrial catalysis. The preparation method comprises the following steps of: preparing a three-dimensional hollow bimetallic oxide by a microwave hydrothermal method; carrying out oxygen plasma based modification and silane coupling agent basedsurface hydrophobic modification on the bimetallic oxide to obtain a modified three-dimensional hollow bimetallic oxide carrier; adding an active component nickel salt, an auxiliary agent group IVA element metal salt and a rare earth element metal salt; loading the active component and the auxiliary agent metal on the modified carrier by adopting a photodeposition technology; and carrying out roasting in an air flow at 400-600 DEG C to obtain the three-dimensional hollow high-dispersion metal catalyst. Based on the total mass of the catalyst, the catalyst comprises 20-40wt% of nickel, 0.01-5wt% of IVA group element metal and 0.01-5wt% of rare earth element metal. The catalyst is applied to catalyzing pyridine dehydrogenation coupling to synthesize 2, 2'-dipyridyl, has the advantages of low catalyst dosage, few side reactions, short process and the like, and has a good industrial application prospect.

The invention discloses a hierarchical pore molecular sieve packaged platinum-nickel bimetallic nano catalytic material and a preparation method and application thereof. The catalytic material is prepared from a modified silicon source, an aluminum source, a quaternary ammonium salt structure-directing agent and a PtNi bimetallic precursor through a hydrothermal synthesis method, and the modified silicon source is prepared by modifying nano silicon dioxide through a silane coupling agent. The PtNi bimetallic precursor is prepared by electrostatic self-assembly of an amine structure directing agent, Pt and Ni sources, and based on the total mass of the catalytic material, the mass percent of nickel is 0.1-20wt%, and the mass percent of platinum is 0.1-5wt%. A one-step method is adopted, a PtNi bimetallic precursor is introduced in situ in the process of synthesizing the hierarchical pore molecular sieve, and selective packaging of the PtNi bimetallic nanocluster in a hierarchical pore molecular sieve side cage is achieved. The catalytic material is applied to a reaction for catalyzing dehydrogenation coupling of pyridine to synthesize 2,2'-dipyridyl, has the advantages of low dosage, few side reactions, short process and the like, and has a good application prospect in the fields of adsorption separation, petrochemical engineering, fine chemical production and the like.

The invention discloses a method for synthesizing quinoline and quinazoline compounds through cobalt catalysis, benzene compounds with amino groups and hydroxyl groups and ketone compounds or cyanophenyl compounds are used as raw materials, the quinoline or quinazoline compounds are obtained through a receptor-free dehydrogenation coupling reaction in the presence of a catalyst and alkali, and the catalyst is cobalt acetate. According to the method, the acceptor-free dehydrogenation coupling reaction is efficiently catalyzed by directly using the cobalt acetate as the catalyst, metal cobalt does not need to be prepared into a corresponding metal complex, a ligand does not need to be used, the operation is simple, and the cost is low. The reaction system can catalyze synthesis of various quinoline and quinazoline compounds, the catalytic reaction has good functional group compatibility and high catalytic activity, products with high yield can be obtained, the reaction conditions are mild, and the method has good application prospects.

The invention discloses a method for synthesizing alpha-keto ester by dehydrogenation coupling reaction of 8-methyl quinoline derivatives and alpha-keto acid under palladium catalysis. According to the method, the 8-methyl quinoline derivatives and the alpha-keto acid are reacted under the catalysis action of tri-(benzylidene acetone) dipalladium to generate an alpha-keto ester derivative. The method had the advantages that reaction conditions are mild, peroxide is omitted, the alpha-keto ester and the air are compatible, gram-scale reaction is easily achieved under a palladium catalyst with low load amount and the like, the method overcomes the shortcomings that reaction conditions are rigorous, a lot of reagents unfriendly to the environments are needed, reaction steps are more, by-products are more and the like in the prior art, and the method for synthesizing the alpha-keto ester by dehydrogenation coupling reaction of the 8-methyl quinoline derivatives and the alpha-keto acid is firstly provided.

The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C—C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a hydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.

The invention discloses a method for preparing methyl heptanone. According to the method, 3-methyl-2-butene-1-ol and acetone undergoes a selective dehydrogenation coupling reaction under the action ofa rhodium catalyst, alkali and an optional assistant to generate methyl heptenone. Compared with the prior art, the method has the advantages that cheap and easily available 3-methyl-2-butene-1-ol and acetone are used as raw materials; the methyl heptenone with high additional value is prepared through a one-step reaction; and the method is high in atom utilization rate, low in generation of three wastes, mild in conditions and high in selectivity and yield.

The invention discloses a novel preparation method of 4, 4'-dinitrobibenzyl. According to the method, p-nitrotoluene is used as a reactant, oxygen is used as an oxidizing agent, ethanol is used as a solvent, transition metal doped FDU-12 mesoporous molecular sieve supported guanidine salt ionic liquid is used as a catalyst, and 4, 4 '-dinitrobibenzyl is prepared through high-selectivity oxidative dehydrogenation coupling reaction. After the reaction is finished, the catalyst phase and the product phase are easily subjected to heterogeneous separation and can be well recycled. The method has the advantages of simple operation, mild reaction conditions, small catalyst dosage, high reaction efficiency and selectivity, and small discharge of three wastes, and is a novel green and clean preparation method.

Disclosed is a method of making an aminosilane, the method comprising: forming a reaction mixture comprising a hydridosilane, an amine and a dehydrogenative coupling catalyst in a reactor; subjectingthe reaction mixture to conditions sufficient to cause a dehydrogenative coupling reaction between the hydridosilane and the amine to form the aminosilane and hydrogen gas; and venting the hydrogen gas; wherein the forming of the reaction mixture comprising the hydridosilane, the amine and the dehydrogenative coupling catalyst comprises continuously feeding the hydridosilane to the reactor containing the amine and the dehydrogenative coupling catalyst.

The invention belongs to the technical field of supramolecular chemistry, and relates to a preparation method and application of a cobalt organic macro-cyclic compound. The preparation method is characterized in that Co<2+> in a transition metal cobalt salt is used as a node, L is used as a ligand for reaction to prepare the metal organic macro-cyclic compound, and the synthetic route is as follows: Co<2+>+L-> Co-L; wherein the ligand L is selected from DTP; the transition metal cobalt salt is selected from one of cobalt chloride hexahydrate, cobalt nitrate hexahydrate, cobalt sulfate heptahydrate, cobalt tetrafluoroborate hexahydrate or cobalt perchlorate hexahydrate. The prepared cobalt organic macro-cyclic compound is low in raw material price and high in yield. The obtained compound isstable in chemical property, can catalyze an intra-molecular dehydrogenation coupling reaction of N-phenyl enamine, realizes efficient and green dehydrogenation, and has an important realistic meaning.

The present invention relates to a drainage aid composition and its use in pulp washing process. More particulary, this invention relates to drainage aid composition of silicone polyethers prepared via zinc catalized dehydrogenative coupling of alcohol terminated polyethers with silicone oligomers and polymers comprising of at least one silicon bonded hydrogen. The compostion of this invention exhibit excellent drainage properties.

The invention discloses a polysilyl ether and a method for synthesizing the polysilyl ether, and a series of polysilyl ethers with novel structures are obtained by catalyzing selective dehydrogenation coupling of prochiral silane and diol by taking a diphosphine ligand complex of cheap metal cobalt as a catalyst. The molar ratio of the cobalt complex to the monomer containing the hydroxyl silane is (0.005-0.020): 1. The reaction activity is high, and the maximum number-average molecular weight of the polysilyl ether can reach 3.23 * 10 < 4 >. The catalyst is convenient to prepare, simple and practical in reaction operation and mild in reaction condition; the synthesized polysilyl ether is derived from different types of monomers. In addition, the catalyst can be used for synthesizing polysilyl ether by a hydrosilylation / dehydrogenation coupling two-step one-pot method. When the chiral diphosphine ligand is used, chiral polysilyl ether can be obtained through the reaction. The synthesized chiral polysilyl ether has potential practical application value in the field of chiral separation.

A method of making an aminosilane, the method comprising: forming a reaction mixture comprising a hydridosilane, an amine and a dehydrogenative coupling catalyst in a reactor; subjecting the reaction mixture to conditions sufficient to cause a dehydrogenative coupling reaction between the hydridosilane and the amine to form the aminosilane and hydrogen gas; and venting the hydrogen gas; wherein the forming of the reaction mixture comprising the hydridosilane, the amine and the dehydrogenative coupling catalyst comprises continuously feeding the hydridosilane to the reactor containing the amine and the dehydrogenative coupling catalyst.

The invention provides a kaolin-loaded nano-iron catalyst and the application thereof in catalyzing cross dehydrogenation coupling reaction, and belongs to the technical field of catalysts. Accordingto the kaolin-loaded nano-iron catalyst provided in the invention, the kaolin-loaded nano-iron catalyst comprises a kaolin carrier and nano-iron loaded in the kaolin carrier. When the kaolin-loaded nano-iron catalyst provided by the invention is used for catalyzing cross dehydrogenation coupling reaction of cyclic ether C(sp3) H bonds and aromatic formic acid, activation and direct esterificationof the cyclic ether C(sp3) H bonds can be catalyzed, and a good catalytic effect is achieved. Meanwhile, the kaolin-loaded nano-iron catalyst provided by the invention is a heterogeneous catalyst, hasthe advantages of low cost, no toxicity and environmental sustainability, can be recycled for multiple times, and is very beneficial to application in modern industrial production.

The invention discloses a pincerlike manganese complex, a preparation method thereof, a ligand for preparation, a preparation method of the ligand, a catalyst composition taking the complex as an active component and application of the catalyst composition. According to the pincerlike manganese complex, a cycloalkyl ring is introduced into a ligand framework, and by regulating and controlling the cyclic tension, flexibility and steric hindrance of the cycloalkyl ring, the reactivity and stability of the manganese metal center can be effectively adjusted, and the catalytic activity and substrate applicability of a manganese metal system are remarkably improved. The catalyst composition taking the pincerlike manganese complex as an active component has the advantages of high catalyst activity, wide substrate application range, mild reaction conditions and the like in the process of preparing quinoline or pyridine derivatives by catalyzing dehydrogenation coupling reaction of o-amino aromatic alcohol or gamma-amino alcohol, ketone or secondary alcohol; and the synthesis advantages of low cost and stable performance are embodied, the operation is simple, and the yield is high.

The invention discloses the application of a carbon-supported ruthenium nanomaterial in catalyzing the reaction of aromatic amine and aromatic methanol. Specifically, the carbon-supported ruthenium metal nanometers of the present invention can catalyze the acceptor-free dehydrogenation coupling reaction to synthesize imines with aromatic methanol and aromatic amines as raw materials, and have the characteristics of high conversion efficiency, wide application range, mild reaction conditions and the like. After the conversion reaction, the catalyst was centrifuged out of the reaction system, and the next round of reaction was carried out after simple washing and drying. After 5 cycles, the catalyst remained stable and its catalytic activity did not decrease significantly.

The invention discloses a method for realizing the α-position methylation reaction of ketones under electrochemical conditions. This method adopts an electrochemical dehydrogenation coupling strategy to realize the direct conversion of ketones and methanol to ketones. α In the methylation reaction, under mild electrochemical oxidation conditions, methanol is used as a C-1 source, and ketones and methanol are directly ketones in an oxygen atmosphere under alkaline conditions. α The methylation reaction uses the solvent methanol as the methylation reagent, which has the advantages of environmental protection, atom economy and simple steps. The reaction avoids the use of transition metal catalysts and oxidants, and the operation is simple, the yield is high, and the raw materials are easily available and clean. Environmentally friendly, well in line with the concept of modern green chemistry.

The invention provides a novel catalytic direct dehydrogenation coupling method for synthesis of a thiophene structure-containing alkane compound. According to the method, based on a one-pot process, in the presence of a metal nickel salt as a catalyst, non-functional thiophene compounds containing different functional groups and fatty acid amide containing a positioning group as raw materials, an organic acid as a ligand, a high boiling point polar solvent, an inorganic salt as a base, a silver salt as an oxidizing agent and a phase transfer catalyst undergo a reaction at a temperature of 160 DEG C for 24h to produce a desired compound. Compared with the existing halogenation or lithium salt functionalization method, the method provided by the invention is free of thiophene compound pre-functionalization, greatly reduces intermediate steps, reduces a raw material cost and wastes produced in the reaction and has the characteristics of atom economy and high efficiency.

A high-stable defect-state cerium-zirconium double metal oxide catalyst, a preparation method and its application in light-driven methane molecular dehydrogenation coupling reactions belong to the technical field of methane dehydrogenation coupling. The present invention utilizes reducing metal powder to treat cerium-zirconium bimetallic oxide in a hydrogen atmosphere, and can obtain strongly basic anion-deficient state cerium-zirconium bimetallic oxide by controlling the ratio of cerium-zirconium bimetallic oxide and reducing metal powder material catalyst. The existence of inherent defects and adjustable strong basic sites can make the cerium-zirconium bimetallic oxide effectively adsorb and weaken the C-H bond in methane molecules, and realize the efficient dehydrogenation coupling of methane molecules driven by light at room temperature. The catalyst of the present invention drives methane activation by light, has high efficiency, energy saving, environmental protection, and high atom utilization rate. The design and construction of nano-catalysts and the modification of catalysts can achieve efficient methane dehydrogenation coupling under mild conditions, which can reduce energy consumption and reduce environmental pollution.

Disclosed is a method for preparing 2,2′-dipyridine and derivatives thereof. The method includes: using pyridine represented by formula I or a derivative thereof as a raw material to generate 2,2′-dipyridine represented by formula II by performing dehydrogenative coupling under the action of a supported catalyst in the presence of additives, where R is H, C1-C2 alkyl, Cl, or Br. The method of the present invention features wide adaptability to raw materials, high atomic utilization rate, high catalyst activity, long service life, and fewer by-products.