- Photocatalytic C-H Amination of Aromatics Overcoming Redox Potential Limitations
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We report the photocatalytic C-H amination of aromatics overcoming redox potential limitations. Radical cations of aromatic compounds are generated photocatalytically using Ru(phen)3(PF6)2, which has a reduction potential at a high oxidation state (Ered(RuIII/RuII) = +1.37 V vs SCE) lower than the oxidation potentials of aromatic substrates (Eox = +1.65 to +2.27 V vs SCE). The radical cations are trapped with pyridine to give N-arylpyridinium ions, which were converted to aromatic amines.
- Ikarashi, Gun,Kano, Naokazu,Morofuji, Tatsuya
-
supporting information
p. 2822 - 2827
(2020/04/16)
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- MONO AMINE DERIVATIVES AND ORGANIC ELECTROLUMINESCENT DEVICE INCLUDING THE SAME
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An organic electroluminescent device includes a monoamine derivative represented by Formula 1: In Formula 1, Ar1 may be represented by Formula 2; Ar2 may be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, wherein the substituent of Ar2 is an unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring; Ar1 and Ar2 may be different from each other; m may be an integer from 0 to 4; and R1 may be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, and when m is 2 or more, a plurality of R1 may combine to form a ring:
- -
-
Paragraph 0091-0094; 0161-0165
(2020/12/14)
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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
-
supporting information
p. 2818 - 2822
(2019/04/25)
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- 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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- Cobalt-Catalyzed Direct Carbonylative Synthesis of Free (NH)-Benzo[ cd]indol-2(1 H)-ones from Naphthylamides
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A cobalt-catalyzed C-H carbonylation of naphthylamides for the synthesis of benzo[cd]indol-2(1H)-one scaffolds has been developed. The reaction employs a traceless directing group and uses benzene-1,3,5-triyl triormate as the CO source, affording various free (NH)-benzo[cd]indol-2(1H)-ones in moderate to high yields (up to 88%). Using this protocol, the total synthesis of BET bromodomain inhibitors A and B was accomplished as well.
- Ying, Jun,Fu, Lu-Yang,Zhong, Guoqiang,Wu, Xiao-Feng
-
supporting information
p. 5694 - 5698
(2019/07/08)
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- Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium
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Primary anilines are essential building blocks to synthesize various pharmaceuticals, agrochemicals, pigments, electronic materials, and others. To date, the syntheses of primary anilines mostly rely on the reduction of nitroarenes or the transition-metal-catalyzed Ullmann, Buchwald-Hartwig and Chan-Lam cross-coupling reactions with ammonia, in which non-renewable petroleum-based chemicals are typically used as feedstocks via multiple step syntheses. A long-standing scientific challenge is to synthesize various primary anilines directly from renewable sources. Herein, we report a general method to directly convert a broad range of phenols into the corresponding primary anilines with the cheap and widely available hydrazine as both amine and hydride sources with simple Pd/C as the catalyst.
- Qiu, Zihang,Lv, Leiyang,Li, Jianbin,Li, Chen-Chen,Li, Chao-Jun
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p. 4775 - 4781
(2019/05/16)
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- Aryl amine derivatieves and organic electroluminescent device including the same
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Provided is an arylamine derivative that effectively absorbs a high-energy external light source in a UV region and minimizes damage to organic matter inside an organic electroluminescent device, thereby contributing to a substantial improvement in the lifespan of the organic electroluminescent device. An organic electroluminescent device according to the present invention comprises a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode. The organic material layer contains an arylamine derivative representedby chemical formula 1. In the chemical formula 1, the definition of each substituent is the same as the definition in the specific embodiment of the invention.
- -
-
Paragraph 0152; 0153; 0154; 0155
(2019/08/12)
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- Material for organic electroluminescent device and organic electroluminescent device using the same
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A material for an organic electroluminescent device and an organic electroluminescent device including the same, the material including a monoamine compound represented by the following Formula 1:
- -
-
Page/Page column 62
(2019/07/12)
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- Material for organic electroluminescent device and organic electroluminescent device using the same
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A novel and improved material for an organic electroluminescent device includes at least one monoamine compound represented by any one of the following Formulae I to III: In Formulae I to III, Ar is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms for forming a ring. The organic electroluminescent device including the material may have improved emission life.
- -
-
Page/Page column 29
(2019/07/19)
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- Ruthenium-catalyzed hydrogenation of carbocyclic aromatic amines: Access to chiral exocyclic amines
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The first highly enantioselective hydrogenation of carbocyclic aromatic amines has been successfully realized using in situ-generated chiral ruthenium complex as catalyst, affording facile access to chiral exocyclic amines with up to 98% ee.
- Yan, Zhong,Xie, Huan-Ping,Shen, Hong-Qiang,Zhou, Yong-Gui
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p. 1094 - 1097
(2018/02/23)
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- AMINATION AND HYDROXYLATION OF ARYLMETAL COMPOUNDS
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In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.
- -
-
Paragraph 0098; 0134; 0135; 0150
(2018/03/25)
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- Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds
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Arylmetals are highly valuable carbon nucleophiles that are readily and inexpensively prepared from aryl halides or arenes and widely used on both laboratory and industrial scales to react directly with a wide range of electrophiles. Although C-C bond formation has been a staple of organic synthesis, the direct transfer of primary amino (-NH2) and hydroxyl (-OH) groups to arylmetals in a scalable and environmentally friendly fashion remains a formidable synthetic challenge because of the absence of suitable heteroatom-transfer reagents. Here, we demonstrate the use of bench-stable N-H and N-alkyl oxaziridines derived from readily available terpenoid scaffolds as efficient multifunctional reagents for the direct primary amination and hydroxylation of structurally diverse aryl- and heteroarylmetals. This practical and scalable method provides one-step synthetic access to primary anilines and phenols at low temperature and avoids the use of transition-metal catalysts, ligands and additives, nitrogen-protecting groups, excess reagents and harsh workup conditions.
- Gao, Hongyin,Zhou, Zhe,Kwon, Doo-Hyun,Coombs, James,Jones, Steven,Behnke, Nicole Erin,Ess, Daniel H.,Kürti, László
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p. 681 - 688
(2017/06/30)
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- MATERIAL FOR ORGANIC ELECTROLUMINESCENT DEVICE AND ORGANIC ELECTROLUMINESCENT DEVICE INCLUDING THE SAME
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The material for an organic electroluminescent device includes a monoamine derivative represented by Formula 1. An organic electroluminescent device including the material can exhibit low driving voltage and improved emission efficiency. The material can be included in at least one layer positioned between an emission layer and an anode of the organic electroluminescent device.
- -
-
Paragraph 0053; 0054
(2016/08/03)
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- MONOAMINE DERIVATIVE AND ORGANIC ELECTROLUMINESCENT ELEMENT
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PROBLEM TO BE SOLVED: To provide a compound that gives an organic electroluminescent element having improved emission lifetime. SOLUTION: The monoamine derivative is represented by formula (1). [R1 and R2 are each independently H, a halogen atom, a substituted/unsubstituted 1-15C alkyl group, a 6-30C aryl group or a 1-30C heteroaryl group; a and b are each independently an integer of 1 to 4; and Ar1 is a substituent of formula (2)(Ar2 to Ar4 are each independently an unsubstituted 6-50C aryl group; and a sum of l and m is integer of 0 to 2)] SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2016,JPOandINPIT
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-
Paragraph 0082; 0083
(2017/01/31)
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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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- An electroluminescent compound and an electroluminescent device comprising the same
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The present invention relates to organic light emitting compounds represented by chemical formula 1-1 to chemical formula 1-2. An organic electroluminescent device using the same has excellent light emitting efficiency and can be driven at low voltage, thereby having improved power efficiency and long life characteristics.COPYRIGHT KIPO 2015
- -
-
Paragraph 0662-0668
(2020/12/25)
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- Synthesis of triaryls: Hydroxy and amine dinaphthyl and diphenanthryl aryls by one-pot electron-transfer nucleophilic substitution reactions
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A new one-pot synthetic route to achieve the preparation of hydroxy and amine binaphthyl and biphenanthryl aryls is here reported. This approach involves the reaction of 1,4-bromoiodobenzene, 4,4′-diiodobiphenyl, and 1,4- and 1,5-diiodonaphthalene with the anions of 2-naphthylamine, 2-naphthol, and 9-phenanthrylamine under irradiation in liquid ammonia. The reactions proceed to afford triaryl derivatives in moderate to good yields (～45% of 1,4-phenylene- and 1,4-naphthylene-1,1′-dinaphthalen-2-ols as well as 1,4-phenylene-1,1′-dinaphthalen-2-amine and 10,10′-diphenanthren-9- amine). Lower yields (27%) of polyaryl derivatives are obtained by reaction of 4,4′-diiodobiphenyl with anions of 2-naphthol and 9-phenanthrylamine.
- Jimenez, Liliana B.,Torres, Natalia V.,Borioni, José L.,Pierini, Adriana B.
-
supporting information
p. 3614 - 3620
(2014/05/20)
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- Mild and highly selective palladium-catalyzed monoarylation of ammonia enabled by the use of bulky biarylphosphine ligands and palladacycle precatalysts
-
A method for the Pd-catalyzed arylation of ammonia with a wide range of aryl and heteroaryl halides, including challenging five-membered heterocyclic substrates, is described. Excellent selectivity for monoarylation of ammonia to primary arylamines was achieved under mild conditions or at rt by the use of bulky biarylphosphine ligands (L6, L7, and L4) as well as their corresponding aminobiphenyl palladacycle precatalysts (3a, 3b, and 3c). As this process requires neither the use of a glovebox nor high pressures of ammonia, it should be widely applicable.
- Cheung, Chi Wai,Surry, David S.,Buchwald, Stephen L.
-
supporting information
p. 3734 - 3737
(2013/08/23)
-
- Elusive metal-free primary amination of arylboronic acids: Synthetic studies and mechanism by density functional theory
-
Herein, we disclose the first metal-free synthesis of primary aromatic amines from arylboronic acids, a reaction that has eluded synthetic chemists for decades. This remarkable transformation affords structurally diverse primary arylamines in good chemical yields, including a variety of halogenated primary anilines that often cannot be prepared via transition-metal-catalyzed amination. The reaction is operationally simple, requires only a slight excess of aminating agent, proceeds under neutral or basic conditions, and, importantly, can be scaled up to provide multigram quantities of primary anilines. Density functional calculations reveal that the most likely mechanism involves a facile 1,2-aryl migration and that the presence of an ortho nitro group in the aminating agent plays a critical role in lowering the free energy barrier of the 1,2-aryl migration step.
- Zhu, Chen,Li, Gongqiang,Ess, Daniel H.,Falck, John R.,Kürti, László
-
supporting information
p. 18253 - 18256
(2013/01/15)
-
- Different behavior of nitrenes and carbenes on photolysis and thermolysis: Formation of azirine, ylidic cumulene, and cyclic ketenimine and the rearrangement of 6-phenanthridylcarbene to 9-phenanthrylnitrene
-
Flash vacuum thermolysis (FVT) of 9-azidophenanthrene 8, 6-(5-tetrazolyl)phenanthridine 18, and [1,2,3]triazolo[l,5-f]phenanthridine 19 yields 9-cyanofluorene 12 as the principal product and 4-cyanofluorene as a minor product. In all cases, when the product is condensed at or below 77 K, the seven-membered ring ketenimine 24 is detectable by IR spectroscopy (1932 cm-1) up to 200 K. Photolysis of Ar matrix isolated 8 at λ = 308 or 313 nm generates at first the azirine 26, rapidly followed by the ylidic cumulene 27. The latter reverts to azirine 26 at λ > 405 nm, and the azirine reverts to the ylidic cumulene at 313 nm. Nitrene 9 is observed by ESR spectroscopy following FVT of either azide 8, tetrazole 18, or triazole 19 with Ar matrix isolation of the products. Nitrene 9 and carbene 21 are observed by ESR spectroscopy in the Ar matrix photolyses of azide 8 and triazole 19, respectively.
- Kvaskoff, David,Bednarek, Pawel,George, Lisa,Pankajakshan, Sreekumar,Wentrup, Curt
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p. 7947 - 7955
(2007/10/03)
-
- A different route to the synthesis of 9,10-disubstituted phenanthrenes
-
We here report the synthesis of 10-aryl-9-hydroxy- and 10-aryl-9- aminophenanthrenes by reaction of the anions of 9-phenanthrol and 9-aminophenanthrene, respectively, with aryl halides (iodobenzene, 4-iodoanisole, 9-bromophenantrene). Good yields of 9,10-disubstituted phenanthrenes were obtained in these reactions (>75% and ～50% for the 9-amino and 9-hydroxyphenanthrene rings, respectively). Extension of the procedure to the reaction of both anions with o-dihalobenzenes leads to the synthesis of the ring closure products (aza- or oxa-indeno[1,2-l]phenanthrene), which bear a pentacyclic aromatic condensed ring system, although in lower overall yields (～35%).
- Tempesti, Tomas C.,Pierini, Adriana B.,Baumgartner, Maria T.
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p. 6508 - 6511
(2007/10/03)
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- Palladium-catalysed synthesis of dibenzo[de,g]quinolines. A novel approach to the B-ring system of aporphine-related heterocycles
-
Dibenzo[de,g]quinolines 5 were formed by the palladium-catalysed heteroannulation of disubstituted alkynes and 1-iodo-10- (dimethylamino)phenanthrene (3c). Symmetric alkynes led to high levels of regioselectivity. These reactions constitute a new synthesis of the B-ring system of aporphine heterocycles.
- Gies, Anne-Elisabeth,Pfeffer, Michel,Sirlin, Claude,Spencer, John
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p. 1957 - 1961
(2007/10/03)
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- Directed ortho metalation - Cross coupling connections. Remote lateral metalation - Cyclization of 2-Imino-2'-methyl biaryls to 9- aminophenanthrenes. A synthesis of the alkaloid piperolactam C+
-
2-Imino-2'-methyl biaryls, conveniently available by Suzuki cross coupling protocol, undergo lithium diethyl amide-mediated metalation - cyclization to give 9-aminophonanthrenes (Table 1). The application of this new general methodology to the first synthesis of the alkaloid piperolactam C (9) is described.
- Benesch, Lisbeth,Bury, Paul,Guillaneux, Denis,Houldsworth, Stephen,Wang,Snieckus, Victor
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p. 961 - 964
(2007/10/03)
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- Investigation of the reaction of 2-bromo-1,4-dimethoxynaphthalene and 9-bromophenanthrene with nitriles under aryne-forming conditions
-
The reaction of 2-bromo-1,4-dimethoxynaphthalene (1) and 9-bromophenanthrene (3) with nitriles 2 under base-mediated, aryne-forming conditions gives product distributions which depend upon the nature of the bromoarene, nitrile, base, and the reaction medium. Thus, treatment of 1 with arylacetonitriles 2a-d in the presence of LDA in THF or sodium amide in liquid ammonia supplies α-aryl-1,4-dimethoxy-2-naphthylacetonitriles 4a-d, presumably by the aryne arylation mechanism. In contrast, the reaction of 9-bromophenanthrene (3) and arylacetonitriles 2b-e with LDA in THF yields 10-arylmethyl-9-phenanthrenecarbonitriles 6b-e, most likely by the tandem addition-rearrangement pathway. When 3 reacts with 2a-c in the presence of sodium amide and liquid ammonia, α-aryl-9-phenanthrylacetonitriles 5a-c, rather than the rearranged nitriles 6a-c, are obtained. Both 1 and 3 react with alkylnitriles 2f-i and LDA-THF, sodium amide-liquid ammonia, or Caubere's sodamide base to afford aryne arylated nitriles (4f-i and 5f-i, respectively). An explanation in terms of the influence of reactants and solvent on the competition between the aryne arylation and tandem addition-rearrangement pathways is presented.
- Hansen,Khanapure,Fry,Swartling,Biehl
-
p. 957 - 960
(2007/10/02)
-
- Dehydroamination Reaction of 9-Amino-9,10-dihydrophenanthrene and Related Compounds by Thermolysis
-
Dehydroamination of 9-alkylamino-9,10-dihydrophenanthrene occurred at 190 - 250 deg C under non-basic conditions to give phenanthrene exclusively.The thermal reaction of cis-9-t-butylamino-10-methoxy-9,10-dihydrophenanthrene gave both 9-methoxyphenanthrene and 9-t-butylaminophenanthrene, while 9-aminophenanthrene was obtained from the thermal reaction of 9-amino-10-methoxy-9,10-dihydrophenanthrene.The thermal reaction of 9-amino-9,10-dihydroanthracene gave both anthracene and 9-aminoanthracene.Analysis of activation energies and frequency factors showed that the dehydroamination proceeds via an intramolecular proton transfer from C-10 to the amino group and subsequent C-N bond cleavage.
- Yasuda, Masahide,Harada, Takamitsu,Ansho, Yasuhiro,Shima, Kensuke
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p. 1451 - 1455
(2007/10/02)
-
- Direct Aromatic Amination by Azides: Reactions of Hydrazoic Acid and Butyl Azides with Aromatic Compounds in the Presence of Both Trifluoromethanesulfonic Acid and Trifluoroacetic Acid
-
Reactions of hydrazoic acid with aromatic compounds in the presence of both trifluoromethanesulfonic acid (TFSA) and trifluoroacetic acid (TFA) efficiently gave primary arylamines without diamine contaminants.The reactions provide mainly the ortho- and para-monoamines wven for readily oxidised aromatic compounds such as cumene, mesitylene, durene, isodurene and anisole.The mechanistic investigation demonstrates that the reactions proceed via a concerted process involving both arene attack on a conjugate acid of the azide and elimination of N2 from the conjugate acid.The reaction of butyl azide with benzene and mesitylene in the presence of both TFSA and TFA produced N-butylarylamines in low yields together with high yields of butanal via a butylnitrenium ion intermediate; a similar reaction with tert-butyl azide gave no tert-butylarylamines.
- Takeuchi, Hiroshi,Adachi, Taki,Nishiguchi, Hideaki,Itou, Katsutaka,Koyama, Kikuhiko
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p. 867 - 870
(2007/10/02)
-
- The Chemistry of Polycyclic Arene Imines. II. Photochemistry of Phenanthrene 9,10-Imine and of Its N-Butyl Derivative
-
The uv irradiation of phenanthrene-9,10-imine has been shown to give 9H-tetrabenzocarbazole as the major photo-product both in argon purged acetone and in dichloromethane.Phenanthrazine, N-9-phenanthrenyl-9-phenanthrenamine and phenanthrene were formed in smaller quantities. 9-Phenanthrenamine was found to be a minor by-product.N-Butylphenanthrene 9,10-imine yielded under similar conditions phenanthrene and N-butyl-9-phenanthrenamine as the only isolable polycyclic compounds.In the presence of air the substituted imine gave mainly 2-propylphenanthrooxazole.
- Weitzberg, Moshe,Avnir, David,Aizenshtat, Zeev,Blum, Jochanan
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p. 1019 - 1022
(2007/10/02)
-
