38results about "Cyano group formation/introduction" patented technology

A ligand which contains arsenic and has the formula (I): where n is 2 and the ligand is bidentate; each X is O or NH; and Ar1 and Ar2 may be the same or different and each is an aryl group, provided that each Ar1 group connected to the same As atom may be combined to form a single aryl group.

This invention relates to a process for producing cyanoacetates using asparagine as a precursor to cyanoacetamide, a staring material to form the cyanoacetates.

The embodiment of the invention provides a bromo-ethyl difluoroacetate-mediated novel amide dehydration cyaniding method, which comprises the following steps of: heating and reacting 0.2 mmol and 1.0 equivalent weight of amide compound and 0.6 mmol and 3.0 equivalent weight of bromo-ethyl difluoroacetate for 24 hours under an oil bath condition of 90 DEG C to generate an experimental reactant; concentrating the experimental reactant under reduced pressure to obtain a residue; and purifying the residue by silica gel rapid column chromatography to obtain the target product nitrile compound. According to the scheme, the process reaction conditions are mild, a strict anhydrous and anaerobic environment is not needed, the harsh requirements on equipment and operation are greatly reduced, and the production safety and practicability are improved. Acetone is used as a solvent, so that high-efficiency reaction can be realized, the solvent after reaction is convenient to recycle and recycle, the production cost and the environmental burden are remarkably reduced, and the remarkable green chemical engineering characteristic is embodied.

The present invention relates to the field of organic synthesis, and in particular, to a method for preparing a malononitrile oxime ether compound. The malononitrile oxime ether compound has a structure shown in formula (VII), and W is selected from an aromatic group or a heteroaromatic group; the preparation method is as follows: a raw material (VI) reacts with a dehydrating agent at 0 to 40° C. in the presence of a solvent to obtain a malononitrile oxime ether compound shown in formula (VII). The above-mentioned preparation method is beneficial to improving the yield of malononitrile oxime ether and reducing the process cost.

The invention discloses a method for preparing an aromatic nitrile compound by photo-initiation of nitro-cyanation of nitro-aromatic hydrocarbon, and belongs to the technical field of organic synthesis. The method comprises the following steps: mixing nitro-aromatic hydrocarbon, a cyanation reagent and villiaumite in an organic solvent, and reacting at 25-55 DEG C under the irradiation of light with the wavelength of 365-450 nm to obtain the aromatic nitrile compound. According to the method disclosed by the invention, the denitrification cyanation of the nitro compound is realized through photo-initiation, the reaction conditions are simple, the used raw material reagents are few, the method has step economy and atom economy, the compatibility of substrate functional groups is good, and further derivatization of a converted product is facilitated to prepare complex functional molecules.

A ligand which contains arsenic and has the formula (I): where n is 2 and the ligand is bidentate; each X is O or NH; and Ar1 and Ar2 may be the same or different and each is an aryl group, provided that each Ar1 group connected to the same As atom may be combined to form a single aryl group.

A ligand which contains arsenic and has the formula (I): where n is 2 and the ligand is bidentate; each X is O or NH; and Ar1 and Ar2 may be the same or different and each is an aryl group, provided that each Ar1 group connected to the same As atom may be combined to form a single aryl group.

Positron emission tomography and magnetic resonance imaging are among the most widely used modalities, requiring isotopic labeling of bioactive molecules to generate the desired imaging probes. This method was applied to a wide range of aliphatic carboxylic acids, including complex and functionalized drug molecules, amino acids and short peptides. For non-stabilized radicals derived from benzylic and non-benzylic carboxylic acids, a copper co-catalyst was introduced to obtain the labeled nitriles, whereas metal-free conditions were applied to nitrogen-stabilized radical derived from a-amino acids and peptides to form the radiolabeled a-amino nitriles. These radiolabeled nitriles were then easily converted back to radiolabeled carboxylic acids.

The invention provides a synthesis method of an alpha-aminonitrile compound, and relates to the technical field of organic synthesis. The synthesis method provided by the invention comprises the following step: in an acidic solvent environment, under the action of a photocatalyst and a reducing agent, reacting a fatty amine compound I, a fatty aldehyde / ketone compound II and a cyano donor under illumination to generate the alpha-aminonitrile compound III. The raw materials are easy to obtain, the reaction conditions are mild, the compatibility of functional groups is good, the application range of substrates is wide, and the pollution to the environment is small.

The invention relates to a green and efficient preparation method and application of beta-carbonyl nitrile. The invention belongs to the technical field of fine chemical synthesis. The invention aims to solve the technical problems that the existing method for synthesizing beta-carbonyl nitrile needs to use a large amount of organic solvent and the catalyst is difficult to recover. According to the method, alpha, beta-unsaturated ketone is taken as a substrate, acetone cyanohydrin is taken as a cyaniding reagent, and beta-carbonyl nitrile is synthesized under the action of ionic liquid. According to the method disclosed by the invention, alpha, beta-unsaturated ketone is taken as a raw material, low-toxicity and low-price acetone cyanohydrin is taken as a cyanogen source, beta-carbonyl nitrile can be efficiently synthesized at room temperature without tedious anhydrous and anaerobic operation under the action of green, pollution-free and recyclable ionic liquid, and beta-carbonyl nitrile can be obtained by selecting the ionic liquid. And meanwhile, the ratio of the substances is reasonably controlled in a synergistic manner, so that the side reaction is inhibited to the maximum extent, the efficient synthesis of the high-purity beta-carbonyl nitrile is realized, and the industrial production process of the beta-carbonyl nitrile is promoted.

The present invention relates to a method for the iron-catalyzed decarboxylation / cyanoalkylation of cinnamic acid with a cyclic ketoxime. The method comprises the following steps: using a cinnamic acid compound and a cyclic ketoxime compound as raw materials, using an iron salt as a catalyst, and reacting them in a solvent at 90-150°C for 10-20 hours under a nitrogen atmosphere to prepare a remote cyanoalkyl olefin. The present invention provides a simple and effective iron-catalyzed decarboxylation / cyanoalkylation reaction of cinnamic acid for the production of remote cyanoalkyl olefins using cyclic ketoxime as a free radical precursor. Compared to the prior art, the present invention does not require an additional reducing agent and exhibits excellent radical tolerance. The reaction is applicable to a variety of cyclic ketoxime and cinnamic acid compounds, providing the corresponding products under mild, redox-neutral conditions.

The application relates to an industrialized preparation method and application of high-purity alpha-amino nitrile. The application belongs to the technical field of fine chemical synthesis. The purpose of the application is to solve the technical problems of low yield and purity, high cost and unsuitability for industrialized production of the existing alpha-amino nitrile synthesis method. The method of the application is as follows: taking imine as a substrate, alpha-amino nitrile is synthesized by reacting with acetone cyanohydrin under the action of an ionic liquid. The method of the application synthesizes a nucleophilic addition cyanyl product of a carbon-nitrogen double bond in one step at room temperature. By selecting the ionic liquid and reasonably controlling the proportioning of various substances, the reaction process is greatly accelerated, the high-efficiency synthesis of alpha-amino nitrile is realized, the purity of alpha-amino nitrile is remarkably improved, the substrate adaptability is good, and the method can be widely applied to the synthesis in the fields of medicines and the like in the industry and the academia.

The invention discloses a method for organic catalytic synthesis of beta-alkyl-nitrile compounds, and relates to the field of synthesis of beta-alkyl-nitrile compounds, and the method comprises the following steps: taking 5 mol percent of thiophene-2-formic acid cuprous as a catalyst, 6 mol percent of 4, 4 ', 6, 6'-tetramethyl-2, 2 '-dipyridyl as a ligand, 1, 2, 3, 3, 3-tetramethyl-1, 3, 3, 3-tetramethyl-1, 3, 3-tetramethyl-1, 3, 3-tetramethyl-1, 3, 3-tetramethyl-1, 3, 3-tetramethyl-1, 3, 3-tetramethyl-1, 3-tetramethyl-1, the method comprises the following steps: by taking 1, 2-dichloroethane as a reaction solvent, lauroyl peroxide with equivalent weight of 1.5 as an oxidizing agent and an alkyl source and trimethylsilyl cyanide with equivalent weight of 1.5 as a cyano source, reacting at room temperature for six hours; according to the method for preparing the beta-alkyl nitrile compound, the target product can be finally obtained at the separation yield of 80%.

Positron emission tomography and magnetic resonance imaging are among the most widely used modalities, requiring isotopic labeling of bioactive molecules to generate the desired imaging probes. This method was applied to a wide range of aliphatic carboxylic acids, including complex and functionalized drug molecules, amino acids and short peptides. For non-stabilized radicals derived from benzylic and non-benzylic carboxylic acids, a copper co-catalyst was introduced to obtain the labeled nitriles, whereas metal-free conditions were applied to nitrogen-stabilized radical derived from a-amino acids and peptides to form the radiolabeled a-amino nitriles. These radiolabeled nitriles were then easily converted back to radiolabeled carboxylic acids.

The invention discloses a photoinduced EDA-based aryl nitrile compound synthesis method, which comprises: in an air atmosphere, dissolving electron-rich methoxy aromatic hydrocarbon, 1, 4-dicyanobenzene and an inorganic alkali in a solvent to form a homogeneous reaction system; a light source containing ultraviolet light with the wavelength ranging from 200 nm to 780 nm is adopted to irradiate the homogeneous reaction system so as to excite the electron-rich methoxy aromatic hydrocarbon and the 1, 4-dicyanobenzene to form an EDA compound; generating an aryl cation free radical intermediate through light-induced single electron transfer, and triggering 1, 4-dicyanobenzene to release cyanide ions; and carrying out nucleophilic substitution reaction on the aryl cation free radical and cyanide ions to break a C (sp2)-O bond and construct a C-N bond to generate the aryl nitrile compound. And efficient and green synthesis of the aryl nitrile compound can be realized.

A ligand containing arsenic and having formula (I): wherein n is 2 and the ligand is bidentate; each X is O or NH; and Ar1 and Ar2 may be the same or different and each is an aryl group, with the proviso that each Ar1 group attached to the same As atom may combine to form a single aryl group. # imgabs0 #

According to the alkenyl nitrile compound and the preparation method thereof, the structural formula of the alkenyl nitrile compound is # imgabs0, in the formula, R1 is a group containing carboxylic acid, an ester group and phosphine, or an electron-withdrawing substituent, phenyl, naphthyl, an aromatic substituent containing electron donating, an aromatic substituent containing an electron-withdrawing group, and heteroaryl; r2 is a cyano group, an aryl group or a heteroaryl group; and R3 is aryl or alkyl. According to the preparation method of the alkenyl nitrile compound, provided by the invention, under simple and mild conditions, the alkenyl nitrile reaction which is difficult to realize by a traditional method is realized in one step by utilizing a photocatalytic multi-component reaction, and the prepared alkenyl nitrile compound is high in additional value, diversified in form and rich in substituent group variety, and has an important application prospect.

The invention discloses a method for preparing nitrile compounds by deoxidizing and aminating carboxylic acid compounds. The invention provides a preparation method of a nitrile compound, which comprises the following steps: in an organic solvent, heating and reacting a carboxylic acid compound as shown in a formula I with a nitriding reagent and a catalyst to obtain the nitrile compound as shown in a formula II, the preparation method provided by the invention can realize direct conversion from polyfunctional group complex carboxylic acid to nitrile by using a simple and cheap reagent and simple operation, and is very suitable for later modification of complex molecules containing sensitive functional groups.

This disclosure provides functional templates that direct Pd to functionalize multiple C—H bonds in polycyclic aza-arenes such as quinolines and related heterocycles at locations that are difficult to isolate and reach for substitution. Herein disclosed are two conceptually distinct directing templates (T) that enable site-selective C6 and C7-H activation of polycyclic aza-arenes. These catalytic pyridine-based templates recruit the aza-arene substrate through N-coordination, enabling the directing arm to deliver the catalyst and precisely activate remote and adjacent C6 or C7-H bond (FIG. 1d). In parallel, we discovered that the use of a simple and readily prepared template chaperone (TC) can turn over the directing template, allowing it to be used catalytically for the first time. Notably, chiral recognition is vital in the granular discrimination between competing C3 and C7-H bonds when the differentiation via distance and geometry is insufficient. Thus, precise recognition of a directing template's distance, geometry and chirality now enables the iterative C—H editing of quinoline and related pharmacophores at any desired site and order. The methods disclosed herein can also be used for diverse and late-stage modification of heterocycle-based drug molecules and pharmacophores.

The invention relates to a reaction method for decarboxylation / cyanoalkylation of cinnamic acid and cyclic ketoxime under the catalysis of iron, which comprises the following steps: in a nitrogen atmosphere, taking a cinnamic acid compound and a cyclic ketoxime compound as raw materials, taking iron salt as a catalyst, and reacting for 10-20 hours in a solvent at 90-150 DEG C to prepare far-end cyanoalkyl olefin. The invention provides a simple and effective iron-catalyzed cinnamic acid decarboxylation cyanoalkylation reaction which is used for constructing far-end cyano alkyl olefin taking cyclic ketoxime as a free radical precursor. Compared with the prior art, the method does not need an additional reducing agent, and has good group tolerance. The reaction is suitable for various cyclic ketoxime compounds and cinnamic acid compounds, and corresponding products are provided under mild and neutral redox conditions.

The invention discloses a synthesis method of a copper-catalyzed aryl nitrile compound. Specifically, the method comprises the following steps: cuprous cyanide, aryl halide, ligand and alkali are placed in an organic solvent, heating and stirring reaction are performed to obtain the aryl nitrile compound, the reaction process is shown in the specification, and the definition of each group is shown in the specification. The synthesis method has the advantages of cheap and easily available raw materials, low catalyst cost, mild reaction conditions, low production cost, high raw material conversion rate, good selectivity, good product purity, stability, high efficiency, simple operation, compatibility with almost all common functional groups, and good industrial production prospect.

The invention provides a method for preparing nitrile compounds by oxidizing and breaking carbon-carbon (C-C) bonds of alcohol compounds. The method comprises the following steps: adding an alcohol compound, a porous nitrogen-doped carbon nonmetal catalyst, a nitrogen source and a reaction solvent into a round-bottom flask, then transferring into a stainless steel high-pressure reaction kettle, introducing oxygen source gas of 0.3-1.0 MPa, putting the reaction kettle into an oil bath pan of 110-150 DEG C, and reacting for 8-24 hours, so that a C-C bond is oxidized and broken into a corresponding nitrile compound. The system disclosed by the invention has the advantages of high catalyst activity, wide application range, easiness in control of reaction conditions, recyclability of the catalyst, simple post-treatment and the like, and has a very good application prospect.

The invention belongs to the technical field of organic synthesis methodology, and particularly relates to a method for synthesizing allene nitrile compounds based on a visible light / metal copper dual-catalysis strategy and application of the allene nitrile compounds. According to the method, substituted sulfonium salt and substituted enyne are used as raw materials, trimethylsilyl cyanide is used as a cyano source, alkali is used as an additive, and an organic solvent is added; and reacting in inert gas at a certain temperature, and preparing the allene nitrile compound under the dual catalytic action of the photocatalyst and the metal copper / ligand catalyst. The method does not need harsh reaction conditions, the reaction can be completed in one step, the reaction conditions are mild, and the method is green and environment-friendly. The allene nitrile compound and the derivative thereof prepared by the method are expected to serve as lead compounds to be applied to the research and development fields of anti-cancer, antiviral and antibacterial drugs and the like.

The invention provides a method for preparing nitrile compounds by oxidizing and breaking carbon-nitrogen bonds (C-N) of nitrogen-containing compounds. The method comprises the following steps: adding a nitrogen-containing compound, an ammonia source, a nitrogen-doped microporous carbon-loaded zinc-based catalyst and a solvent into a reaction tube, then transferring the reaction tube into a stainless steel high-pressure reaction kettle, introducing oxygen source gas with the pressure of 0.2-2.0 MPa, putting the reaction kettle into an oil bath pan with the temperature of 130-160 DEG C, and reacting for 12-24 hours, so that the carbon-nitrogen bond is oxidized and broken to generate the corresponding nitrile compound. The system disclosed by the invention can be used for efficiently preparing the nitrile compound at low cost, the catalyst is high in activity, the catalyst can be recycled, the substrate range is wide, the used oxygen is cheap, green and rich, the environment is not polluted, and the system has important significance for developing a green and economical catalytic oxidation method.

The invention provides a method for cyanation of a carbon-sulfur bond in a sulfur-containing compound. The method comprises the following steps: adding a sulfur-containing compound, an ammonia source and a nitrogen-doped mesoporous carbon-loaded iron-based monatomic catalyst into a solvent, putting into a pressure container, sealing, introducing oxygen source gas of 0.2-2.0 MPa, and reacting at 100-180 DEG C for 6-30 hours, so as to oxidize and break a carbon-sulfur bond into the corresponding nitrile compound. The system has the advantages that the catalyst activity is high, the method is wide in application range, reaction conditions are easy to control, the catalyst can be recycled, post-treatment is simple and the like, and the system has a good application prospect.

The invention relates to an industrial preparation method and application of high-purity alpha-aminonitrile. The invention belongs to the technical field of fine chemical synthesis. The invention aims to solve the technical problems that the existing alpha-aminonitrile synthesis method is low in yield and purity, high in cost and not suitable for industrial production. According to the method disclosed by the invention, imine is taken as a substrate and reacts with acetone cyanohydrin under the action of ionic liquid to synthesize alpha-aminonitrile. According to the method disclosed by the invention, the nucleophilic addition cyanidation product of carbon-nitrogen double bonds is synthesized in one step at room temperature. The method has the advantages that the reaction process is greatly accelerated by selecting the ionic liquid and synergistically reasonably controlling the ratio of the substances, the efficient synthesis of the alpha-aminonitrile is realized, the purity of the alpha-aminonitrile is obviously improved, the substrate adaptability is good, and the method can be widely applied to the synthesis of the fields such as medicines in the industrial circle and the academic circle.

This invention discloses an iron-catalyzed C-H bond cyanotylation method for aromatic compounds. The method includes the following steps: in a solvent, using trimethylcyanosilane as the cyano source, peroxide as the oxidant, iron as the catalyst, amino acids and their derivatives as ligands, and a base as an additive, the aromatic ring of an aromatic compound undergoes a C-H bond cyanotylation reaction to generate a cyano-substituted aromatic compound. This invention offers advantages such as a widely available, inexpensive, and environmentally friendly catalyst; a widely available and inexpensive oxidant; mild reaction conditions and high selectivity; a relatively inexpensive and low-toxicity cyano source; good reactivity with heterocyclic aromatic compounds; good compatibility with substrate functional groups and a wide range of substrate applications; compatibility with drug molecules and drug molecule derivatives, enabling effective cyanotylation of aromatic rings. Under optimized reaction conditions, the yield of the target product after separation can reach 90%.

A method for preparing nitriles by oxidative cleavage of alcohols. The present invention provides a novel method for oxidative cleavage of alcohols into nitriles, specifically a method using a manganese oxide compound synthesized by potassium permanganate and manganese sulfate in an alkaline solution as a catalyst for the continuous oxidative cleavage of alcohols into nitriles. This method facilitates the synthesis of aromatic nitriles, heteroatom aromatic nitriles, and aliphatic nitrile compounds under mild reaction conditions, using air or oxygen as the oxygen source without the addition of any additives. The method is characterized by simple operation, a highly adaptable catalytic system, and high yield and selectivity.

The invention provides a method for preparing nitrile compounds by oxidizing and breaking carbon-sulfur bonds (C-S) of sulfur-containing compounds. The method comprises the following steps: adding a sulfur-containing compound, a nitrogen source and a nitrogen-doped mesoporous carbon supported cobalt-based catalyst into a solvent, putting the mixture into a pressure container, sealing, introducing 1.0 MPa oxygen source gas, and reacting at 150-170 DEG C for 6-48 hours, so as to oxidize and break a carbon-sulfur bond into a corresponding nitrile compound. The reaction system disclosed by the invention has the advantages of good functional group compatibility and substrate universality, high catalyst activity, recyclability, easiness in control of reaction conditions, simple post-treatment, accordance with green and sustainable chemical concepts and the like, and has a very good application prospect.