- PRODUCTION METHOD OF PRIMARY AMINE COMPOUND
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PROBLEM TO BE SOLVED: To provide a simple production method of a primary amine compound unnecessary for complicated procedures and toxic sodium azide or the like. SOLUTION: A production method of a primary amine compound includes a step for reacting a ketone compound and an oxime compound in the presence of alcohol and an acid catalyst. Preferably, the acid catalyst is hydrochloric acid, sulfuric acid, methanesulfonic acid, camphorsulfonic acid, a tosyl acid hydrate, trifluoromethane sulfonic acid or a boron trifluoride diethyl ether complex. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0029
(2019/09/20)
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- Deacetylative Amination of Acetyl Arenes and Alkanes with C-C Bond Cleavage
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The Br?nsted acid-catalyzed synthesis of primary amines from acetyl arenes and alkanes with C-C bond cleavage is described. Although the conversion from an acetyl group to amine has traditionally required multiple steps, the method described herein, which uses an oxime reagent as an amino group source, achieves the transformation directly via domino transoximation/Beckmann rearrangement/Pinner reaction. The method was also applied to the synthesis of γ-aminobutyric acids, such as baclophen and rolipram.
- Hyodo, Kengo,Hasegawa, Genna,Maki, Hiroya,Uchida, Kingo
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supporting information
p. 2818 - 2822
(2019/04/25)
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- Metal-free Semiconductor Photocatalysis for sp2 C?H Functionalization with Molecular Oxygen
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Designing metal-free catalysts for solar energy conversion is a long-standing challenge in semiconductor photoredox catalysis (SPC). With visible-light-responsive hexagonal boron carbon nitride (h-BCN) as a non-metal photocatalyst, this system affords C?H/N?H coupling products with broad substitution tolerance and high efficiency with molecular oxygen as the terminal oxidant. The catalyst exhibits remarkable performance for the selective C?H functionalization of electron-rich arenes to C?N products (yields up to 95 %) and good stability (6 recycles). Both nitrogen heteroarenes and amine salts are competent coupling nucleophiles. Mechanically, the reactive oxygen species are superoxide anion radical (O2?.) and H2O2, which are proved by electron spin resonance (ESR) data, KI-starch, and control experiments. In addition, kinetic isotope effect (KIE) experiments indicate that C?H bond cleavage is not involved in the rate limiting step. This semiconductor-based photoredox system allows for C?H amination free of any metals, ligands, strong oxidants, and additives. It provides a complementary avenue to C?H functionalizations and enables synthetic applications efficiently in a sustainable manner.
- Zheng, Meifang,Ghosh, Indrajit,K?nig, Burkhard,Wang, Xinchen
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p. 703 - 706
(2019/01/04)
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- Highly selective reduction of nitrobenzenes to azoxybenzenes with a copper catalyst
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A convenient protocol for highly selective delivery of azoxybenzenes from reduction of nitrobenzenes was developed by utilizing a copper catalyst. A variety of functional groups and substitution were well tolerated.
- Chen, Zhichao,Qiu, Yatao,Wu, Xiaoxing,Ni, Yong,Shen, Li,Wu, Jun,Jiang, Sheng
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supporting information
p. 1382 - 1384
(2018/03/06)
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- Method of preparing arylamine by photo-catalyzing C-H activation with semiconductor
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The invention discloses a method of preparing arylamine by photo-catalyzing C-H activation with a semiconductor. The method comprises the following steps of by taking an aromatic compound as a substrate and boron-nitrogen-carbon as a photocatalyst, adding an amino source, a solvent and alkali, performing stirring reaction for 48h under the condition of visible light radiation at room temperature in an oxygen atmosphere, and synthesizing an arylamine compound. The boron-nitrogen-carbon (h-BCN) is a semiconductor polymer photocatalyst which responds to visible light and does not contain metallicelements and has the advantages of low cost, availability, good chemical stability, non toxicity, innocuousness, proper forbidden band width and energy band position and the like. The catalyst is used for synthesizing the arylamine compound, is simple in operation in reaction process, is performed under the visible light, is mild in condition and good in catalytic effect and has the yield, to a target product, reaching 72 percent. The method provided by the invention is simple in technology and low in cost, accords with the actual production needs and has relatively large application potential.
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Paragraph 0014
(2018/10/04)
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- Fe-Catalyzed Amination of (Hetero)Arenes with a Redox-Active Aminating Reagent under Mild Conditions
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A novel and efficient Fe-catalyzed direct C?H amination (NH2) of arenes is reported using a new redox-active aminating reagent. The reaction is simple, and can be performed under air, mild, and redox-neutral conditions. This protocol has a broad substrate scope and could be used in the late-stage modification of bioactive compounds. Mechanistic studies demonstrate that a radical pathway could be involved in this transformation.
- Liu, Jianzhong,Wu, Kai,Shen, Tao,Liang, Yujie,Zou, Miancheng,Zhu, Yuchao,Li, Xinwei,Li, Xinyao,Jiao, Ning
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supporting information
p. 563 - 567
(2017/01/18)
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- Assembly of Primary (Hetero)Arylamines via CuI/Oxalic Diamide-Catalyzed Coupling of Aryl Chlorides and Ammonia
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A general and practical catalytic system for aryl amination of aryl chlorides with aqueous or gaseous ammonia has been developed, with CuI as the catalyst and bisaryl oxalic diamides as the ligands. The reaction proceeds at 105-120°C to provide a diverse set of primary (hetero)aryl amines in high yields with various functional groups.
- Fan, Mengyang,Zhou, Wei,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 5934 - 5937
(2015/12/11)
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- Transition-metal-free access to primary anilines from boronic acids and a common +NH2 equivalent
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Diversely substituted anilines are prepared by treatment of functionalized arylboronic acids with a common, inexpensive source of electrophilic nitrogen (H2N-OSO3H, HSA) under basic aqueous conditions. Electron-rich substrates are found to be the most reactive by this method. However, even moderately electron-poor substrates are well tolerated under the room temperature conditions. Sterically hindered substrates appear to be equally effective compared to unhindered ones. Highly electron-deficient substrates afford product in very low yields at room temperature, but moderate to good yields are obtained at refluxing temperatures. Our method is also amenable to electrophilic amination of several common boronic acid derivatives (e.g., pinacol esters). We demonstrate that it can be combined with metal-halogen exchange reactions or a variety of directed ortho metalation protocols in a "one-pot" sequence for the synthesis of aromatic amines with unique substitution patterns. DFT studies, in combination with experimental results, suggest that the reaction occurs via base-mediated activation of HSA, followed by 1,2 aryl B-N migration. This mode of activation appears to be critical for the success of the reaction and allows, for the first time, a general, electrophilic amination of boronic acids at ambient temperature.
- Voth, Samantha,Hollett, Joshua W.,Mccubbin, J. Adam
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p. 2545 - 2553
(2015/03/18)
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- Silicon analogues of the nonpeptidic GnRH antagonist AG-045572: Syntheses, crystal structure analyses, and pharmacological characterization
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AG-045572 (CMPD1, 1a) is a nonpeptidic gonadotropin-releasing hormone (GnRH) antagonist that has been investigated for the treatment of sex hormone-related diseases. In the context of systematic studies on sila-substituted drugs, the silicon analogue disila-AG-045572 (1b) and its derivative 2 were prepared in multi-step syntheses and characterized by elemental analyses (C, H, N), NMR spectroscopic studies (1H, 13C, 29Si), and single-crystal X-ray diffraction. The pharmacological properties of compounds 1a, 1b, and 2 were compared in terms of their in vitro potency at cloned human and rat GnRH receptors. Compounds 1a and 2 were also examined in regard to their pharmacokinetics and in vivo efficacy in both castrated rat (luteinizing hormone (LH) suppression) and intact rat (testosterone suppression) models. The efficacy and pharmacokinetic profiles of 1a and its silicon-containing analogue 2 appear similar, indicating that replacement of the 5,6,7,8-tetrahydronaphthalene ring system by the 1,3-disilaindane skeleton led to retention of efficacy. Therefore, the silicon compound 2 represents a novel drug prototype for the design of potent, orally available GnRH antagonists suitable for once-daily dosing.
- Barnes, Matthew J.,Burschka, Christian,Buettner, Matthias W.,Conroy, Richard,Daiss, Juergen O.,Gray, Ian C.,Hendrick, Alan G.,Tam,Kuehn, Diana,Miller, David J.,Mills, John S.,Mitchell, Philip,Montana, John G.,Muniandy, Parameswary A.,Rapley, Helen,Showell, Graham A.,Tebbe, David,Tacke, Reinhold,Warneck, Julie B.H.,Zhu, Bin
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experimental part
p. 2070 - 2080
(2012/06/30)
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- PIPERIDYL DERIVATIVES
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A compound of the formula (I): wherein R1, R2, R8, R9 and R10 are each as defined in the description, and -X- is -NH or -O-,Y is (II), (III), (IV), etc., and -Z- is bond or (V) in which R3, R4, R5, R6, R7, and R11 are each as defined in the description, or a salt thereof. The object compound of the present invention has pharmacological activities such as Tachykinin antagonism, and is useful for manufacture of a medicament for treating or preventing Tachykinin-mediated diseases.
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- HETEROCYCLIC SILICON COMPOUNDS AND THEIR USE IN THE TREATMENT OF DISEASES OR CONDITIONS ASSOCIATED WITH GNRH (GONADOTROPIN-RELEASING HORMONE)
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A compound of formula (I) wherein one of X and Y is silicon, and the other is carbon or silicon; Z is oxygen, sulphur or -N(R)-, wherein R is hydrogen or alkyl; R1 is hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxy or cycloalkyl; and R2 is alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, -alkyl-cycloalkyl, -alkyl-heterocycloalkyl, -alkyl-aryl or -alkyl-heteroaryl; or a pharmaceutically acceptable salt thereof. The compounds are used in the manufacture of a medicament for the treatment or prevention of a disease or condition associated with GnRH (gonadotropin-releasing hormone), e.g. for the treatment or prevention of progression of cancer (e.g. leukaemia therapy), of a fertility disorder, of HIV infection or AIDS, of Alzheimer’s disease of fibrosis, of endometriosis, of uterine fibroids or of uterine leiomyoma.
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Page/Page column 16,17
(2010/02/07)
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- Amination of arenes with N,N-dimethyl-2-imidazolidinone O-methoxyacetyloxime
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Treatment of nucleophilic arenes with N,N-dimethyl-2imidazolidinone O-methoxyacetyloxime and SnCl4 produced the corresponding N-arylimines, which were converted to anilines by hydrolysis with CsOH and to N-methylanilines by LiAlH4 reduction.
- Baldovini, Nicolas,Kitamura, Mitsuru,Narasaka, Koichi
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p. 548 - 549
(2007/10/03)
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- Heterocyclic-substituted alkylamide acat inhibitors
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Pharmaceutically useful compounds having ACAT inhibitory activity of the formula wherein n is 0, 1, or 2, for X other than tetrazole and n = 2 then R2 = R3 = H; R1 is phenyl, substituted phenyl, naphthyl, substituted naphthyl, a heteroaromatic group or a hydrocarbon group having from one to 18 carbon atoms; R2 and R3 are hydrogen, halo, hydroxy, alkyl, alkenyl, cycloalkyl, phenyl, substituted phenyl, a heteroaryl, or form a spiroalkyl group; x is a 5-membered heteromonocyclic group containing at least one to four heteroatoms selected from the group consisting of isothiazole, oxazole, thiazole, imidazole, furan, thiophene, pyrrole, tetrazole, 1,2,3-triazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,2,4-triazole, and 1,2,4-oxadiazole said heteromonocyclic group being unsubstituted or substituted at any available position along the ring,
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- Synthesis, Molecular Structure, Fluxional Behavior, and Tricarbonyliron Transfer Reactions of (η4-1-Azabuta-1,3-diene)tricarbonyliron Complexes
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The η4-1-azabuta-1,3-diene)tricarbonyliron complexes 10 are easily prepared in high yield by condensation of the corresponding arylamines 7 with the cinnamaldehydes 8 and subsequent ultrasound-promoted complexation of the resulting 1-azabuta-1,3-dienes 9 with nonacarbonyldiiron. The complexes 10 are shown to represent excellent reagents for the transfer of the tricarbonyliron fragment onto cyclohexa-1,3-diene (1a). The structural characterization for the complexes 10 is achieved by IR, 1H-NMR, and 13C-NMR spectroscopy, as well as X-ray crystallography of 10b, 10c, and 101. Using variable temperature 13C-NMR spectroscopy the fluxionality of the complexes 10a, 10b, 10c, 10e, and 2 is investigated and the activation barrier for the turnstile rotation of the tricarbonyliron fragment is determined. The transfer reaction and the structural factors influencing the transfer of the tricarbonyliron fragment are extensively investigated.
- Knoelker, Hans-Joachim,Baum, Gerhard,Foitzik, Norbert,Goesmann, Helmut,Gonser, Peter,Jones, Peter G.,Roettele, Herbert
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p. 993 - 1007
(2007/10/03)
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- Synthesis of aromatic amines from electron-rich arenes and bis(2,2,2-trichloroethyl) azodicarboxylate
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Electron-rich arenes react with bis(2,2,2-trichloroethyl) azodicarboxylate in 3 M lithium perchlorate-diethylether or acetone solution to produce para-substituted aryl hydrazides in high yields. The corresponding aromatic amines are readily obtained by reducing the hydrazides with zinc in acetic acid.
- Zaltsgendler,Leblanc,Bernstein
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p. 2441 - 2444
(2007/10/02)
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- Screw Sense Selective Polymerization of Achiral Isocyanides Catalysed by Optically Active Nickel(II) Complexes
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Poly(isocyanides), (RN=Cn, can be prepared from isocyanides, , by the catalytic action of nickel(II) compounds.The main chain of these polymers is a rigid helix.This helical conformation results from a restricted rotation around the single bonds that connect the main-chain carbon atoms.Polymerization of achiral isocyanides generally gives a racemic mixture of left- and right-handed helices, whereas polymerization of optically active isocyanides results in helices with an excess of one screw sense.We describe a procedure for obtaining poly(isocyanides) with predominantly one screw sense, starting from an achiral monomer.A catalyst is prepared by adding an optically active amine to a tetrakis(isocyanide)nickel(II) perchlorate complex.Polymerization of various achiral isocyanides with this catalist yields optically active polymers with an enantiomeric excess up to 83percent.
- Kamer, Paul C. J.,Nolte, Roeland J. M.,Drenth, Wiendelt
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p. 6818 - 6825
(2007/10/02)
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- Preparation of Some 2-(Methoxyphenyl)-2H-benzotriazoles and the Corresponding Hydroxyphenyl Compounds
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The reaction of several substituted o-nitronitrosobenzenes with o- and p-anisidine, and 2,4-dimethoxyaniline in acetic acid gives in good yield the corresponding o-nitroazobenzenes which are readily reduced with thiourea dioxide (formamidinesulfinic acid) to the corresponding 2-(methoxyphenyl)-2H-benzotriazoles, demethylation of which furnished the corresponding 2-(hydroxyphenyl)-2H-benzotriazoles.Demethylation of the dimethoxy derivatives was best accomplished with boron tribromide in methylene chloride, the methoxy group located ortho to the benzotriazole ring beingdemethylated more readily than is the para-methoxy group.The reaction of 0-nitroazobenzenes containing a methoxy group with hydrobromic acid in acetic acid results in cleavage of the azo bond and also partial bromination to give o-nitroaniline and some of its brominated derivatives.
- Rosevear, Judi,Wilshire, John F. K.
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p. 1663 - 1673
(2007/10/02)
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