- Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
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We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
- Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
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supporting information
p. 5317 - 5324
(2020/09/17)
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- A preparation method of Ranolazine
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The present invention relates to the technical field of ranolazine, in particular to a ranolazine preparation method, the method comprises the following steps: piperazine through the hydroformylation reaction to obtain the 1 - formyl piperazine, then with 2 - chloro - N - (2, 6 - dimethyl-phenyl) acetamide for carrying out the alkylation reaction to obtain N - (2, 6 - dimethyl-phenyl) - 2 - (4 - formyl piperazine) acetamide, then through hydrolytic reaction to obtain N - (2, 6 - dimethyl-phenyl) - 2 - (1 - piperazinyl) acetamide, finally with 2 - (2 - methyl-phenoxymethyl) oxirane ring opening reaction to obtain the ranolazine. The invention preparation of the ranolazine purity is good, high yield.
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Paragraph 0038; 0041; 0043
(2019/03/28)
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- Sustainable Co-Synthesis of Glycolic Acid, Formamides and Formates from 1,3-Dihydroxyacetone by a Cu/Al2O3 Catalyst with a Single Active Sites
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Glycolic acid (GA), as important building block of biodegradable polymers, has been synthesized for the first time in excellent yields at room temperature by selective oxidation of 1,3-dihyroxyacetone (DHA) using a cheap supported Cu/Al2O3 catalyst with single active CuII species. By combining EPR spin-trapping and operando ATR-IR experiments, different mechanisms for the co-synthesis of GA, formates, and formamides have been derived, in which .OH radicals formed from H2O2 by a Fenton-like reaction play a key role.
- Dai, Xingchao,Adomeit, Sven,Rabeah, Jabor,Kreyenschulte, Carsten,Brückner, Angelika,Wang, Hongli,Shi, Feng
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supporting information
p. 5251 - 5255
(2019/03/07)
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- Ru/ceria-catalyzed direct formylation of amines and CO to produce formamides
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We herein report a new strategy of directly converting amines and CO to formamides with 100% atom utilization efficiency. It is suitable for up to 25 amine substrates with no additives. Ru/ceria is found to be an excellent catalyst for this reaction due the efficient co-activation of CO and amine on Ru species.
- Wang, Yehong,Zhang, Jian,Chen, Haijun,Zhang, Zhixin,Zhang, Chaofeng,Li, Mingrun,Wang, Feng
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- Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions
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A simple and efficient Au/Al2O3 catalyst was prepared by the co-precipitation method for the oxidative N-formylation of amines with paraformaldehyde. Under the optimized reaction conditions, excellent amine conversion and N-formamide selectivity can be obtained with up to 97% yield with water as the solvent under ambient conditions. This catalyst tolerated a wide range of primary amines and second amines, and it can be reused for at least five runs without obvious deactivation.
- Ke, Zhengang,Zhang, Yan,Cui, Xinjiang,Shi, Feng
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p. 808 - 816
(2016/02/12)
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- C-N and N-H Bond Metathesis Reactions Mediated by Carbon Dioxide
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Herein, we report CO2-mediated metathesis reactions between amines and DMF to synthesize formamides. More than 20 amines, including primary, secondary, aromatic, and heterocyclic amines, diamines, and amino acids, are converted to the corresponding formamides with good-to-excellent conversions and selectivities under mild conditions. This strategy employs CO2 as a mediator to activate the amine under metal-free conditions. The experimental data and in situ NMR and attenuated total reflectance IR spectroscopy measurements support the formation of the N-carbamic acid as an intermediate through the weak acid-base interaction between CO2 and the amine. The metathesis reaction is driven by the formation of a stable carbamate, and a reaction mechanism is proposed.
- Wang, Yehong,Zhang, Jian,Liu, Jing,Zhang, Chaofeng,Zhang, Zhixin,Xu, Jie,Xu, Shutao,Wang, Fangjun,Wang, Feng
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p. 2066 - 2072
(2015/06/30)
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- K3PO4-catalyzed carbonylation of amines to formamides
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Synthesis of formamides from the catalytic carbonylation of amines with CO is of great interest due to their wide applications of formamides as synthetic intermediates and aprotic polar solvents. Up to now, the most commonly used catalysts are either expensive noble metal compounds or difficult-to-handle alkali metal alkoxides. We have found that a solid base, K3PO4 is a highly active and selective catalyst for the carbonylation of primary and cyclic secondary amines, producing corresponding formaldehydes in yields up to 99% at relatively mild conditions. Spectroscopic and quantum mechanical calculation results indicate that such high activity of K3PO4 is closely related to the strong hydrogen bonding ability of PO43- with the amino group of an amine, thereby enhancing the nucleophilicity of the amino group enough to interact with a neutral molecule, CO and mediating proton transfer from the amino group to the carbonyl group. Characterization of spent catalyst by FT-IR and XRD implies that small portion of K3PO4 is converted into less active K2HPO4 during the carbonylation reaction.
- Kim, Young Jin,Lee, Ji Woo,Lee, Hyun Ji,Zhang, Shuyao,Lee, Je Seung,Cheong, Minserk,Kim, Hoon Sik
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p. 126 - 133
(2015/09/28)
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- Copper-diphosphine complex catalysts for N-formylation of amines under 1 atm of carbon dioxide with polymethylhydrosiloxane
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N-formylation of a wide range of amines proceeded using copper-diphosphine complexes as homogeneous catalysts with polymethylhydrosiloxane (PMHS) under 1 atm of CO2. In the reaction of piperidine, for example, the turnover number (TON) reached 11700 in 23 h with 90% yield of the formylated product. This TON value is much higher than those of the reported catalysts for the formylation of amines under 1 atm of CO2 with hydrosilanes. The Cu complexes with phosphines having ortho-phenylene structures acted as good ligands for the formylation, as compared to a bidentate ligand connected with a propyl chain and a monodentate ligand. Among these diphosphines, ligands with alkyl functionalities, such as isopropyl and cyclohexyl groups, produced better results than the phenyl group. Not only cyclic secondary amines, but also linear secondary amines and aromatic and aliphatic primary amines were found to be reactive substrates. In the case of 2,2,6,6-tetramethylpiperidin-4-amine, the formylation proceeded regioselectively. A catalytic reaction pathway was proposed from a separate experiment using [Me2NCO2] [Me2NH2]. The Royal Society of Chemistry 2013.
- Motokura, Ken,Takahashi, Naoki,Kashiwame, Daiki,Yamaguchi, Sho,Miyaji, Akimitsu,Baba, Toshihide
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p. 2392 - 2396
(2013/09/02)
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- Aralkyl-ketone piperazine derivatives and their uses as new antalgic or ataractic agent
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Arylalkyl ketone piperazine derivatives of the formula: and pharmaceutical compositions comprising the same. Also dislcosed are methods for using the compounds as analgesic and sedative agents. The compounds of the present invention have good analgesic and sedative activities but few side effects.
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Page/Page column 7
(2008/06/13)
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- ARALKYL FORMYL-ALKYL PIPERAZINE DERIVATIVES AND THEIR USES AS CEREBRAL NERVE PROTECTIVE AGENT
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The invention relates to aralkyl formyl-alkyl piperazine derivatives, and the use of its comnositions in the manufacture of medicaments for preventing or treating cerebral ischemic apoplexy and nerve protection, acting as central system excitable amino acid (N-methy-D-aspartic acid) antagonists (NMDA). The pharmacological experiments show that they display favorable full or ischemic anti-apoplexy activity, nerve protective activity and low side effects.
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Page/Page column 11
(2008/06/13)
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- Pharmaceutical compositions comprising iron chelators for the treatment of neurodegenerative disorders and some novel iron chelators
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Use of a compound of formula (I), wherein R1 is H or hydrocarbyl; R2 is a hydrophobic radical; R3 is 3-(C2-C6)acyl-4-hydroxyphenyl, 3-hydroxyimino (C2-C6)-alkyl-4-hydroxyphenyl, or COOZ, wherein Z is H, (C1-C6) alkyl, aryl, aryl or ar(C1-C6) alkyl; and n is 1-20; and of a compound of formula (II), wherein R4 is (C1-C6) alkyl, cyano (C1-C6) alkyl, (C1-C6) alkoxy (C1-C6) alkyl or —CH2NR7R8, wherein R7 and R8, the same or different, is each H or (C1-C6) alkyl, or together with the N atom form a saturated or unsaturated 5-7 membered ring optionally containing a further heteroatom selected from N, O or S, the further N atom being optionally substituted, and either R5 is H and R6 is (C2-C6) acyl or hydroxyimino (C2-C6) alkyl, or R5 and R6 together with the phenyl ring form a quinoline, a 1,2,3,4-tetrahydroquinoline or a perhydroquinoline ring, for the preparation of pharmaceutical compositions for the treatment of Parkinson's disease or stroke.
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Page/Page column 14
(2010/02/10)
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- Convenient N-Formylation of Secondary Amines: KF-Al2O 3-Promoted Synthesis of Formamide Derivatives via Dichlorocarbene Generated from Chloroform
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The treatment of secondary amines with chloroform in the presence of KF-Al2O3 in acetonitrile brought about highly facile and efficient N-formylation to give the corresponding formamides in good to excellent yields. The N-formylation reaction not only involves mild conditions, simple operations and high yields but high chemoselectivity as well.
- Mihara, Masatoshi,Ishino, Yoshio,Minakata, Satoshi,Komatsu, Mitsuo
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p. 2317 - 2320
(2007/10/03)
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- Multifunctional ligand for use as a diagnostic or therapeutic pharmaceutical
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A compound and method of making a compound for use as a diagnostic or therapeutic pharmaceutical comprises either a phosphorous or germanium core and at least two hydrazine groups forming a ligand for bonding to a metal extending from the phosphorous or germanium core.
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- Rutheniumcluster als Katalysatoren fuer die Carbonylierung von cyclischen Aminen
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The tri- and tetra-nuclear ruthenium clusters Ru3(CO)12, - and - have been found to catalyse the carbonylation of cyclic amines such as piperidine, 3-methylpiperidine, pyrrolidine, heptamethylene imine, morpholine and piperazine to give the corresponding formamides.The catalytic reaction works with only carbon monoxide or a mixture of carbon dioxide and hydrogen.In the case of the neutral catalyst precursor, carbamoyl clusters of the type (μ2-H)Ru3(CO)10(μ2,η2-OCNR2) have been isolated from the reaction mixture.
- Suess-Fink, Georg,Langenbahn, Meinhard,Jenke, Thomas
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p. 103 - 110
(2007/10/02)
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