- Chemoselective and Tandem Reduction of Arenes Using a Metal–Organic Framework-Supported Single-Site Cobalt Catalyst
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The development of heterogeneous, chemoselective, and tandem catalytic systems using abundant metals is vital for the sustainable synthesis of fine and commodity chemicals. We report a robust and recyclable single-site cobalt-hydride catalyst based on a porous aluminum metal–organic framework (DUT-5 MOF) for chemoselective hydrogenation of arenes. The DUT-5 node-supported cobalt(II) hydride (DUT-5-CoH) is a versatile solid catalyst for chemoselective hydrogenation of a range of nonpolar and polar arenes, including heteroarenes such as pyridines, quinolines, isoquinolines, indoles, and furans to afford cycloalkanes and saturated heterocycles in excellent yields. DUT-5-CoH exhibited excellent functional group tolerance and could be reusable at least five times without decreased activity. The same MOF-Co catalyst was also efficient for tandem hydrogenation–hydrodeoxygenation of aryl carbonyl compounds, including biomass-derived platform molecules such as furfural and hydroxymethylfurfural to cycloalkanes. In the case of hydrogenation of cumene, our spectroscopic, kinetic, and density functional theory (DFT) studies suggest the insertion of a trisubstituted alkene intermediate into the Co–H bond occurring in the turnover limiting step. Our work highlights the potential of MOF-supported single-site base–metal catalysts for sustainable and environment-friendly industrial production of chemicals and biofuels.
- Akhtar, Naved,Begum, Wahida,Chauhan, Manav,Manna, Kuntal,Newar, Rajashree,Rawat, Manhar Singh
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supporting information
(2022/01/19)
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- Lewis Acid Catalyzed Electrophilic Aminomethyloxygenative Cyclization of Alkynols with N, O-Aminals
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Lewis acid enables the electrophilic carbooxygenative cyclization of alkynols with N,O-aminals. The new process proceeds efficiently under very mild conditions via a pathway that is opposite to classical carbo-metalation. These reactions exhibit broad substrate generality and functional group compatibility, leading to a wide variety of 5-8-membered oxacycles bearing diverse functional groups. The cyclization products can be elaborated via simple functional group transformations to generate synthetically useful oxacycles.
- Chen, Anrong,Yu, Houjian,Yan, Jiaqi,Huang, Hanmin
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supporting information
p. 755 - 759
(2020/01/28)
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- Synthesis method for 3-aminomethyl tetrahydrofuran
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The invention provides a synthetic method for 3-aminomethyl tetrahydrofuran. A target product, namely the 3-aminomethyl tetrahydrofuran is prepared by taking 2,5-dihydrofuran as an initial raw material. In the whole synthesis process, the synthesis method has the advantages of green and environmentally-friendly used raw materials, mild and conveniently-controllable reaction conditions, safe production, low risk, simple process, high yield, and more applicability to industrial production.
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Paragraph 0054; 0058; 0061; 0065-0066; 0070-0071; 0075
(2020/07/14)
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- 3-aminomethyl tetrahydrofuran preparation method
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The invention provides a 3-aminomethyl tetrahydrofuran preparation method, which comprises: carrying out a condensation reaction by using tetrahydrofuran-3-one and nitromethane as raw materials to obtain 3-nitromethylene tetrahydrofuran, and carrying out catalytic hydrogenation reduction to obtain 3-aminomethyl tetrahydrofuran. According to the invention, the method has advantages of cheap and easily available raw materials, good stability, low cost, simple preparation steps, safe and simple operation, easy reaction achieving, little wastewater generation, environmental protection, few side reactions, high reaction selectivity, good atom economy, high product purity and high yield, and is suitable for industrial production.
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Paragraph 0060-0068
(2020/01/12)
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- A tetrahydrofuran -3 - preparation of method (by machine translation)
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The present invention provides a tetrahydrofuran - 3 - preparation of method, comprising the addition of raw materials, amination reaction, hydrogenation reaction. In order to tetrahydrofuran - 3 - formaldehyde as raw materials, water as a reaction solvent, in under the action of the supported bimetallic catalyst, and the liquid ammonia in the amination reaction, inject the hydrogen reduction reaction to obtain the tetrahydrofuran - 3 - methylamine, high purity 99.8%, yield up to 99.1%. The invention of the tetrahydrofuran - 3 - preparation of method, with high yield, less catalyst levels, the operation is simple, low cost, and is suitable for industrial production. (by machine translation)
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Paragraph 0026-0057
(2019/04/02)
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- Preparation method of 3-aminomethyl tetrahydrofuran
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The invention relates to a preparation method of 3-aminomethyl tetrahydrofuran, and the preparation method comprises the following steps: cyclizing compound 1 cis-butenediol to obtain a compound 2, namely 2,5-dihydrofuran, then formylating the 2,5-dihydrofuran to obtain a compound 3, namely 3-formyl tetrahydrofuran, and finally performing reductive amination to obtain a compound 4, namely the 3-aminomethyl tetrahydrofuran. The preparation method has the advantages of simple production process, high utilization rate of materials, large production capacity, high selectivity, durability and highefficiency of catalysts in each step. The preparation method is simple in route and easy to scale up in industrialization.
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Paragraph 0033-0036
(2019/11/20)
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- The invention relates to a benzofuran as raw materials for the synthesis of 3 - amino methyl tetrahydrofuran (by machine translation)
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The invention relates to a benzofuran as raw materials for the synthesis of 3 - amino methyl tetrahydrofuran, relates to the technical field of the synthesis intermediate for agricultural chemicals, to benzofuran as raw materials, obtained by the oxidation of the open loop 1, 4 - butene dialdehyde, and nitromethane by Michael addition, sodium borohydride reduction, dehydration cyclization and catalytic hydrogenation to five-step reaction to obtain 3 - amino methyl tetrahydrofuran. The present invention provides a benzofuran as raw materials for the synthesis of 3 - amino methyl tetrahydrofuran, the method cheap price of raw materials, synthetic route is short, low production cost, is suitable for mass production. (by machine translation)
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Paragraph 0050-0052
(2019/07/04)
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- Synthetic method of 3-aminomethyl tetrahydrofuran
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The invention discloses a synthetic method of 3-aminomethyl tetrahydrofuran and belongs to the technical field of organic chemistry. The synthetic method takes furan as a raw material and sequentiallycomprises the following steps: 1, bromination; 2, chloromethylation; 3, ammoniation; 4, deprotection; and 5, reduction so as to obtain the 3-aminomethyl tetrahydrofuran. The method has the advantagesthat the raw materials are easy to obtain, the reaction conditions of all steps are simple, virulent reagents or reagents with great potential safety hazards are not used, and a synthetic route for pesticide intermediates is enriched.
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Paragraph 0020; 0028-0030
(2018/09/08)
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- Preparation method of 3-aminomethyltetrahydrofuran serving as dinotefuran intermediate
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The invention relates to a preparation method of 3-aminomethyltetrahydrofuran serving as a dinotefuran intermediate. Specifically, the preparation method comprises the steps: firstly, carrying out a condensation reaction on cyanoacetate serving as a raw material and 1,2-dihaloethane to obtain 2-haloethyl-2-cyanoacetate serving as an intermediate; next, further carrying out reduction to obtain 2-haloethyl-2-cyanoethanol serving as an intermediate; then, cyclizing 2-haloethyl-2-cyanoethanol serving as the intermediate to obtain 3-cyanotetrahydrofuran serving as an intermediate; and finally, catalytically hydrogenating 3-cyanotetrahydrofuran to obtain 3-aminomethyltetrahydrofuran serving as the dinotefuran intermediate. The preparation method disclosed by the invention is available in raw material, simple in operation and relatively low in production cost so as to be suitable for industrialized mass production.
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- Preparation method of 3-methylamine tetrahydrofuran with high purity and low water content
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The invention discloses a preparation method of 3-methylamine tetrahydrofuran with high purity and low water content. The preparation method comprises the following steps: (1) reacting liquid ammoniawith 3-methanal tetrahydrofuran in the presence of absolute methanol to obtain an imine intermediate; and (2) in the presence of a catalyst, reacting the imine intermediate with hydrogen, cooling after the reaction is finished, filtering a reaction liquid to remove the catalyst, then transferring the solution into a distillation still, distilling and recycling ammonia gas and methyl alcohol, thenheating for distillation, and collecting fractions to obtain 3-methylamine tetrahydrofuran, wherein the internal temperature of the still is 75 to 80 DEG C, and the top temperature of the still is 65to 75 DEG C. Compared with the prior art, the prepared 3-methylamine tetrahydrofuran has higher purity and lower water content, the intermediate with high quality is provided for further synthesis ofother chemical products by using methanal tetrahydrofuran, the raw materials are also recycled, the production cost is reduced, the preparation method is energy-saving and environmentally-friendly, and the preparation method accords with current idea of green chemistry.
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Paragraph 0029; 0030; 0032
(2018/06/15)
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- Production technology of 3-aminomethyl tetrahydrofuran
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The invention discloses a production technology of 3-aminomethyl tetrahydrofuran, and belongs to the field of pesticide intermediate synthesis technology. The technology takes 2-butene-1,4-diol as a starting material, and the starting material is synthesized 3-aminomethyl tetrahydrofuran through dehydration cyclization, hydroformylation and reductive amination reaction. The production technology is mild in reaction conditions, and is low in cost, less in three wastes, and suitable for industrial production.
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Paragraph 0048; 0053; 0054; 0058
(2018/09/08)
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- A novel and practical method for the synthesis of dinotefuran through Michael addition of nitromethane to diethyl maleate
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A novel and practical synthesis of dinotefuran 1, featuring a new access to it from known key intermediate (tetrahydrofuran-3-yl)-methanamine 5, has been achieved through Michael addition reaction of nitromethane to diethyl maleate in 6 steps with 45.5% total yield. This synthesis is scalable and hence has high potential for application to further synthetic elaboration on such new neonicotinoid insecticide dinotefuran 1.
- Li, Haifeng,Wang, Lailai
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p. 336 - 340
(2017/12/11)
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- Synthesis method of 3-aminomethyltetrahydrofuran
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The invention relates to a synthesis method of 3-aminomethyltetrahydrofuran. According to the method, 2,5-dihydrofuran is taken as an initial raw material and subjected to two-step reactions including Rh-catalyzed hydroformylation and catalytic reduction amination, and 3-aminomethyltetrahydrofuran is synthesized. The synthesis method is high in reaction selectivity, a process is simple to operate, the synthesis route is short, the yield can reach 95% or above through the two-step reactions, and the method is suitable for industrial production.
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Paragraph 0020; 0022; 0024; 0026; 0028; 0030; 0032; 0034
(2018/01/11)
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- Novel synthesis technology for tetrahydrofuran-3-methylamine
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The invention discloses a novel synthesis technology for tetrahydrofuran-3-methylamine. The novel synthesis technology is used for solving the problems of the preparation technology in the prior art that the raw materials are expensive, the production cost is increased, a large amount of heat and flammable and explosive hydrogen are released in the production process and the safety risk is brought to the production. The novel synthesis technology comprises the following steps: (1) reacting 2,5-dihydrofuran with paraformaldehyde and hydrogen chloride in an organic solvent under the effect of catalyst A, thereby acquiring chloromethyl-2,5-dihydrofuran; (2) reacting chloromethyl-2,5-dihydrofuran with urotropine, thereby acquiring amine methyl-2,5-dihydrofuran hydrochloride, and then ionizing amine methyl-2,5-dihydrofuran by using a sodium hydroxide solution and distilling, thereby acquiring a crude product; and (3) reducing the crude product amine methyl-2,5-dihydrofuran by hydrogen under the effect of the catalyst, thereby acquiring 3-tetrahydrofuran methylamine, and then filtering and refining filtrate, thereby acquiring a purified product. The novel synthesis technology for tetrahydrofuran-3-methylamine has the advantages of low raw material cost, less three-waste emission and simple process.
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Paragraph 0032; 0036; 0040; 0044; 0048; 0052; 0056; 0060
(2017/09/18)
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- A synthetic method of the dinotefuran (by machine translation)
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The invention discloses a method for synthesis of dinotefuran, to γ - butyrolactone as raw materials, by Aldol condensation, also the original two-step by the reaction of 3 - hydroxy methyl tetrahydrofuran, then by the Gabriel synthesis of 3 - tetrahydrofuran methyl amine, dimethyl carbonate (DMC) as methylation reagent with the urea synthesis O - methyl isourea, re-nitration synthetic O - methyl - N - nitro-isourea, then with the methylamine reaction synthesis of 1, 3 - dimethyl - 2 - nitro-isourea, final 3 - tetrahydrofuran methylamine with 1, 3 - dimethyl - 2 - nitro-isourea through SN2 Bimolecular nucleophilic substitution reaction, one-step synthesis of dinotefuran. The present invention uses non of dimethyl carbonate as the methylating reagent, the methylation reaction yield ≥ 95%, O - methyl isourea content ≥ 96%, the by-product is carbon dioxide and methanol, process and environmental protection, the overall yield of the dinotefuran ≥ 50%. Synthetic method of this invention to reduce the production cost at the same time, with three wastes, after treatment is simple, the advantages of the environment friendly, and is suitable for industrial production, bring about significant economic benefits. (by machine translation)
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- Synthesis method of 3-tetrahydro-furanmethanamine
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The invention discloses a synthesis method of 3-tetrahydro-furanmethanamine. According to the method, maleic acid diester is used as a starting material to synthesize 3-tetrahydro-furanmethanamine via four steps of reaction of Michael addition, metal borohydride reduction, dehydration cyclization and catalytic hydrogenation reduction. The synthesis method provided by the invention has the advantages of mild reaction conditions, high product yield, less pollution discharge, simple process operation and suitability for industrialized production.
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Paragraph 0024-0025; 0028; 0032; 0036
(2017/12/30)
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- Preparation method of 3-aminomethyl tetrahydrofuran
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The invention relates to a preparation method of 3-aminomethyl tetrahydrofuran. Specifically the invention relates to a method of preparing 3-aminomethyl tetrahydrofuran through reducing 3-cyano-gamma-butyrolactone. A novel synthesis technology is adopted. Ethyl cyanoacetate and ethylene oxide carry out cyclization reactions under an alkaline condition to obtain 3-cyano-gamma-butyrolactone; then 3-cyano-gamma-butyrolactone is reduced to obtain 2-aminomethyl-1,4-butylene glycol, and finally 2-aminomethyl-1,4-butylene glycol carries out dehydration and cyclization reactions to obtain 3-aminomethyl tetrahydrofuran. The synthesis technology has the advantages of easily available raw materials, simple operation, mild reaction conditions, high yield and product purity, little environmental pollution, and low production cost, is suitable for industrial massive production, and has a wide application prospect.
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Paragraph 0031; 0032; 0033; 0043; 0044; 0052; 0053
(2017/08/29)
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- Preparation method of 3-aminomethyl tetrahydrofuran
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The invention relates to a preparation method of 3-aminomethyl tetrahydrofuran. Specifically the invention relates to a method of preparing 3-aminomethyl tetrahydrofuran through reducing 3-cyanotetrahydrofuran. A novel synthesis technology is adopted; gamma-butyrolactone and a halogen simple substance X2 are taken as the raw materials to prepare 3-X-gamma-butyrolactone; then 3-X-gamma-butyrolactone is reduced by a reducing agent to obtain 2-X-1,4-butylene glycol; 2-X-1,4-butylene glycol is dehydrated by a dehydrating agent to obtain 3-X tetrahydrofuran; 3-X tetrahydrofuran is converted into 3-cyanotetrahydrofuran in the presence of a cyaniding catalyst, and finally 3-cyanotetrahydrofuran is converted into 3-aminomethyl tetrahydrofuran in the presence of a hydrogenation catalyst. The synthesis technology has the advantages of easily available raw materials, simple operation, mild reaction conditions, high yield and product purity, little environmental pollution, and low production cost, is suitable for industrial massive production, and has a wide application prospect.
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Paragraph 0022; 0036-0038
(2017/07/12)
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- Preparation method for 3-aminomethyltetrahydrofuran
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The invention discloses a preparation method for 3-aminomethyltetrahydrofuran. The preparation method comprises the following steps: with acrylonitrile as a starting material, carrying out an addition reaction with 2-halogenated ethyl alcohol so as to obtain an intermediate 2-haloethyl-2-nitrile ethyl ether; then subjecting the intermediate 2-haloethyl-2-nitrile ethyl ether to cyclic condensation so as to obtain an intermediate 3-nitrile tetrahydrofuran; and finally subjecting the intermediate 3-nitrile tetrahydrofuran to catalytic hydrogenation so as to obtain 3-aminomethyltetrahydrofuran. The preparation method provided by the invention has the advantages of cheap and easily-available starting material, short synthetic route, simple process operation, low production cost, little pollution to the human body and the environment, good yield and applicability to large-scale industrial production.
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Paragraph 0013; 0020; 0024; 0025
(2017/02/24)
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- Synthesis method of tetrahydrofuran-3-methylamine
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The invention discloses a synthesis method of tetrahydrofuran-3-methylamine. The problems that the synthesis of the tetrahydrofuran-3-methylamine has the disadvantages of fussy route process, higher cost and harsh reaction condition in the prior art are solved. The synthesis method comprises the following steps of (1), in an organic solvent I, making acrylonitrile and epoxy ethane react to generate 3-cyano-tetrahydrofuran in a condition that a catalyst A exists; (2), purifying the 3-cyano-tetrahydrofuran, and then reducing the purified 3-cyano-tetrahydrofuran to obtain tetrahydrofuran-3-methylamine in conditions of an organic solvent II and a catalyst B. By using the synthesis method, the process flow and the production period are greatly shortened; raw materials are easily obtained; the synthesis method is green and environment-friendly, is low in cost, is simple to operate, is high in yield, and has obvious socioeconomic benefit and commercial application value.
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Paragraph 0014; 0028; 0030
(2017/09/01)
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- Method of synthesizing dinotech
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The invention relates to a method of synthesizing dinotech which comprises the steps of using the dihydrofuran as the raw material, using Vilsmeier Haack reaction to obtain the dihydrofuran-3-formaldehyde, reducing and aminating with the help of catalyst to get the 3-aminomethyltetrahydrofuran, at last condensing with 1,3-dimethyl-2-nitroisourea to obtain the compound dinotech. The method creatively applies the Vilsmeier Haack reaction to the synthesizing of dinotech, uses the generated intermediates of aldehyde group to run the aldehyde reduction and double bond reduction simultaneously, thereby reduces the reaction steps and lowers the operation complexity and greatly shortens the synthetic steps of the intermediate, reduces the costs. Besides in the aspect of material selection both the 2,3-dihydrofuran and the 2,5-dihydrofuran can all be used for the synthesizing of aldehyde group. The material selection is in wide scope which makes this method more practical in application.
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Paragraph 0005; 0018
(2017/02/09)
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- Synthetic method of 3-aminomethyl tetrahydrofuran
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The invention discloses a synthetic method of 3-aminomethyl tetrahydrofuran. The synthetic method comprises the following steps: (1) carrying out cyclization reaction on 1,4-butylene glycol under the action of a fixed acid catalyst, so as to generate 2,5-dihydrofuran; (2) carrying out hydroformylation reaction on 2,5-dihydrofuran under the action of a homogeneous catalyst HRhCO[P(PhX)3]3, so as to obtain 3-formaldehyde tetrahydrofuran; (3) reacting by virtue of 3-formaldehyde tetrahydrofuran and hydroxylamine compounds, so as to obtain 3-formoxime tetrahydrofuran; and (4) carrying out hydrogenation on 3-formoxime tetrahydrofuran, so as to obtain 3-aminomethyl tetrahydrofuran. The synthetic method disclosed by the invention is environmentally friendly and has the beneficial effects that the process is simple, the steps are short, the total yield is very high, the cost is low, the yield of products in each step is higher than 90%, and the total yield of the finally prepared 3-aminomethyl tetrahydrofuran is higher than 80%.
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Paragraph 0036; 0048; 0055; 0062; 0069; 0076
(2017/07/20)
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- FUNGICIDAL AMINES
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Disclosed are compounds of Formula 1, N-oxides, and salts thereof, wherein R1, R2, R9a, R9b, G, W, X, Y, and Z are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (1) and methods for controlling plant disease caused by a fungal pathogen comprising applying an effective amount of a compound or a composition of the invention.
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Page/Page column 44
(2009/06/27)
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- METHOD FOR PRODUCING 3-AMINOMETHYLTETRAHYDROFURAN DERIVATIVE
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An object of the present invention is to provide a process for producing a 3-cyanotetrahydrofuran derivative in a high yield from inexpensive industrial materials. According to the present invention, a 3-aminomethyltetrahydrofuran derivative is produced by preparing a 3-cyanotetrahydrofuran derivative in a high yield from an inexpensive and industrially easily available malic acid derivative, and reducing the cyano group of the 3-cyanotetrahydrofuran derivative.
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- METHOD FOR PRODUCING 3-AMINOMETHYLTETRAHYDROFURAN DERIVATIVE
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Disclosed is a method for highly efficiently producing a 3-aminomethyltetrahydrofuran derivative from a low-cost industrial raw material. Specifically, a 3-cyanotetrahydrofuran derivative is produced at high yield from a low-cost, industrially easily-available malic acid derivative, and then a 3-aminomethyltetrahydrofuran derivative is produced by reducing the cyano group of the 3-cyanotetrahydrofuran derivative.
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Page/Page column 27-28
(2008/06/13)
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- CB1 MODULATOR COMPOUNDS
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Novel compounds of structural formula (I) are disclosed. As modulators of the Cannabinoid-1 (CB1) receptor, these compounds are useful in the treatment, prevention and suppression of diseases mediated by the CB1 receptor. As such, compounds of the present invention are useful as in the treatment, prevention and suppression of psychosis, memory deficits, cognitive disorders, migraine, neuropathy, neuro-inflammatory disorders (e.g., multiple sclerosis, Guillain-Barre syndrome and the inflammatory sequelae of viral encephalitis), cerebral vascular accidents, head trauma, anxiety disorders, stress, epilepsy, Parkinson's disease, and schizophrenia. The compounds are also useful for the treatment of substance abuse disorders, particularly to opiates, alcohol, and nicotine. The compounds are also useful for the treatment of obesity or eating disorders associated with excessive food intake and complications associated therewith.
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Page/Page column 68-69
(2008/06/13)
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- Furanyl insecticide
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The present invention relates to novel (tetrahydro-3-furanyl)methylamino derivatives of the following formula (1): STR1 wherein the variables are defined in the specification, which are useful as insecticides.
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